High-temperature Fe oxidation coupled with redistribution of framework cations in lobanovite, K₂Na(Fe²⁺₄Mg₂Na)Ti₂(Si₄O₁₂)₂O₂(OH)₄ – the first titanosilicate case

The high-temperature (HT) behaviour of lobanovite, K₂Na(Fe²⁺₄Mg₂Na)Ti₂(Si₄O₁₂)₂O₂(OH)₄, was studied using in situ powder X-ray diffraction in the temperature range 25–1000°C and ex situ single-crystal X-ray diffraction of 17 crystals quenched from different temperatures. HT iron oxidation associated with de­hydroxy­lation starts at 450°C, similar to other ferrous-hy­droxy-rich heterophyllosilicates such as astrophyllite and bafertisite. A prominent feature of lobanovite HT crystal chemistry is the redistribution of Fe and Mg+Mn cations over the M(2), M(3), M(4) sites of the octahedral (O) layer that accompanies iron oxidation and de­hydroxy­lation. This HT redistribution of cations has not been observed in titanosilicates until now, and seems to be triggered by the need to maintain bond strengths at the apical oxygen atom of the TiO₅ pyramid in the heteropolyhedral (H) layer during oxidation–de­hydroxy­lation. Comparison of the HT behaviour of lobanovite with five-coordinated Ti and astrophyllite with six-coordinated Ti shows that the geometry of the Ti polyhedron plays a key role in the HT behaviour of heterophyllosilicates. The thermal expansion, geometrical changes and redistribution of site occupancies which occur in lobanovite under increasing temperature are reported. A brief discussion is given of minerals in which the cation ordering (usually for Fe and Mg) occurs together with iron oxidation–de­hydroxy­lation at elevated temperatures: micas, amphiboles and tourmalines. Now this list is expanded by the inclusion of titanosilicate minerals.

Computing details

Data collection: CrysAlis PRO, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58) for lb300, (I), lb550, lb570-2, lb590, lb590-2, lb590-3, lb610, lb630, lb630-2, lb650, lb670, lb690, lb710; CrysAlis PRO 1.171.39.44a (Rigaku OD, 2018) for lb450, lb500, lb570_3m. Cell refinement: CrysAlis PRO, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58) for lb300, (I), lb550, lb570-2, lb590, lb590-2, lb590-3, lb610, lb630, lb630-2, lb650, lb670, lb690, lb710; CrysAlis PRO 1.171.39.44a (Rigaku OD, 2018) for lb450, lb500, lb570_3m. Data reduction: CrysAlis PRO, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58) for lb300, (I), lb550, lb570-2, lb590, lb590-2, lb590-3, lb610, lb630, lb630-2, lb650, lb670, lb690, lb710; CrysAlis PRO 1.171.39.44a (Rigaku OD, 2018) for lb450, lb500, lb570_3m. Program(s) used to solve structure: olex2.solve (Bourhis et al., 2015) for lb300; SHELXS (Sheldrick, 2008) for lb450; ShelXT (Sheldrick, 2015) for lb500, lb550, lb570_3m, lb570-2, lb590, lb590-2, lb610, lb630, lb630-2, lb650, lb670, lb690, lb710. For all structures, program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

(lb300)

Crystal data

0.5(Ca0.18F0.41Fe9.23H8K3.91Na3.74O60Si15.39Ti3.98)	F(000) = 1154
Mr = 1180.72	Dx = 3.115 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 5.3203 (2) Å	Cell parameters from 5124 reflections
b = 23.1311 (7) Å	θ = 1.8–36.6°
c = 10.3783 (4) Å	µ = 4.06 mm^−1
β = 99.687 (4)°	T = 293 K
V = 1259.00 (8) Å^3	0.22 × 0.18 × 0.11 mm
Z = 2

Data collection

Saxi-CrysAlisPro-abstract goniometer imported SAXI images diffractometer	3075 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2621 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ω scans	θmax = 36.6°, θmin = 1.8°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→8
Tmin = 0.794, Tmax = 1.000	k = −38→37
11739 measured reflections	l = −16→17

Refinement

Refinement on F^2	Primary atom site location: iterative
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Only H-atom coordinates refined
wR(F^2) = 0.068	w = 1/[σ^2(Fo^2) + (0.0173P)^2 + 5.1997P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
3075 reflections	Δρmax = 0.68 e Å^−3
136 parameters	Δρmin = −0.89 e Å^−3
2 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
M1	0.500000	0.500000	0.000000	0.0127 (5)	0.964 (8)
M2	1.000000	0.42540 (2)	0.000000	0.00823 (11)	0.938 (3)
M3	0.500000	0.35484 (2)	0.000000	0.00843 (13)	0.743 (3)
M4	1.000000	0.28603 (3)	0.000000	0.00914 (16)	0.625 (2)
D	0.93723 (8)	0.500000	0.28705 (4)	0.00569 (11)	0.994 (3)
T1	1.42126 (9)	0.28221 (2)	0.26388 (5)	0.00598 (14)	0.963 (4)
T2	0.57602 (10)	0.41434 (2)	0.72983 (5)	0.00593 (13)	0.960 (4)
A	1.000000	0.36167 (4)	0.500000	0.0260 (2)	0.978 (4)
BNA	0.500000	0.500000	0.500000	0.0145 (6)	0.908 (13)
BCA	0.500000	0.500000	0.500000	0.0145 (6)	0.092 (13)
O1	0.9035 (4)	0.500000	0.11764 (19)	0.0109 (3)
O2	0.6409 (3)	0.41777 (6)	0.88712 (13)	0.0107 (2)
O3	0.7977 (3)	0.44233 (7)	0.66117 (14)	0.0160 (3)
O4	0.6964 (3)	0.44232 (7)	0.32794 (15)	0.0173 (3)
O5	0.5534 (3)	0.34675 (6)	0.67736 (14)	0.0156 (3)
O6	1.3700 (3)	0.28228 (6)	0.10700 (13)	0.0094 (2)
O7	1.1868 (3)	0.25121 (6)	0.32174 (13)	0.0131 (3)
O8	0.8657 (3)	0.35210 (6)	0.10287 (13)	0.0116 (3)
F	1.000000	0.500000	0.500000	0.014 (3)*	0.206 (10)
H8	0.873 (5)	0.3632 (10)	0.1941 (18)	0.021*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
M1	0.0093 (8)	0.0118 (8)	0.0158 (9)	0.000	−0.0014 (6)	0.000
M2	0.00655 (18)	0.00757 (17)	0.01034 (18)	0.000	0.00078 (13)	0.000
M3	0.0076 (2)	0.0075 (2)	0.0105 (2)	0.000	0.00222 (16)	0.000
M4	0.0075 (3)	0.0085 (2)	0.0115 (3)	0.000	0.00186 (19)	0.000
D	0.00390 (18)	0.00616 (17)	0.00723 (18)	0.000	0.00158 (13)	0.000
T1	0.0060 (2)	0.0052 (2)	0.0068 (2)	−0.00013 (15)	0.00126 (16)	−0.00021 (15)
T2	0.0060 (2)	0.00494 (19)	0.0068 (2)	0.00009 (15)	0.00118 (16)	0.00020 (15)
A	0.0317 (4)	0.0257 (4)	0.0206 (4)	0.000	0.0038 (3)	0.000
BNA	0.0204 (9)	0.0129 (8)	0.0091 (8)	0.000	−0.0009 (5)	0.000
BCA	0.0204 (9)	0.0129 (8)	0.0091 (8)	0.000	−0.0009 (5)	0.000
O1	0.0100 (8)	0.0131 (8)	0.0099 (8)	0.000	0.0027 (6)	0.000
O2	0.0114 (6)	0.0124 (5)	0.0082 (5)	0.0002 (4)	0.0010 (4)	0.0005 (4)
O3	0.0151 (7)	0.0202 (7)	0.0134 (6)	−0.0083 (5)	0.0043 (5)	−0.0036 (5)
O4	0.0138 (7)	0.0224 (7)	0.0149 (6)	−0.0098 (5)	−0.0005 (5)	0.0031 (5)
O5	0.0285 (8)	0.0059 (5)	0.0117 (6)	0.0007 (5)	0.0015 (5)	0.0002 (4)
O6	0.0098 (6)	0.0100 (5)	0.0085 (5)	0.0001 (4)	0.0015 (4)	−0.0007 (4)
O7	0.0100 (6)	0.0182 (6)	0.0112 (6)	−0.0063 (5)	0.0020 (5)	−0.0006 (5)
O8	0.0123 (6)	0.0123 (6)	0.0101 (6)	0.0003 (5)	0.0017 (5)	0.0000 (4)

Geometric parameters (Å, º)

M1—M2^i	3.1708 (2)	D—O4^xv	1.9454 (15)
M1—M2^ii	3.1708 (2)	D—O4	1.9455 (15)
M1—M2^iii	3.1708 (2)	D—F	2.1789 (4)
M1—M2	3.1708 (2)	T1—O5^viii	1.6095 (14)
M1—M3	3.3576 (5)	T1—O6	1.6049 (14)
M1—M3^ii	3.3576 (5)	T1—O7	1.6381 (14)
M1—O1	2.284 (2)	T1—O7^xvi	1.6335 (14)
M1—O1^ii	2.284 (2)	T2—A^iii	3.7557 (6)
M1—O2^iv	2.4180 (14)	T2—A	3.7513 (6)
M1—O2^v	2.4180 (14)	T2—BNA	3.0748 (5)
M1—O2^vi	2.4180 (14)	T2—O2	1.6127 (14)
M1—O2^vii	2.4180 (14)	T2—O3	1.6128 (15)
M2—O1	2.2231 (12)	T2—O4^vii	1.6084 (16)
M2—O1^i	2.2231 (12)	T2—O5	1.6532 (14)
M2—O2^viii	2.0739 (14)	A—O3	2.8359 (16)
M2—O2^iv	2.0739 (14)	A—O3^viii	2.8359 (16)
M2—O8^ix	2.1869 (14)	A—O4^viii	2.8821 (17)
M2—O8	2.1868 (14)	A—O4	2.8820 (17)
M3—O2^iv	2.0853 (14)	A—O5^vii	3.2174 (16)
M3—O2^vii	2.0853 (14)	A—O5^xiv	3.2174 (16)
M3—O6^ix	2.1881 (14)	A—O5^viii	3.2596 (16)
M3—O6^iii	2.1881 (14)	A—O5	3.2596 (16)
M3—O8	2.0566 (14)	A—O7^viii	3.3995 (16)
M3—O8^x	2.0566 (14)	A—O7	3.3996 (16)
M4—O6^xi	2.1135 (14)	A—F	3.1996 (8)
M4—O6^xii	2.1135 (14)	BNA—O3^vii	2.4889 (16)
M4—O6^ix	2.0928 (13)	BNA—O3^vi	2.4889 (16)
M4—O6	2.0928 (13)	BNA—O3	2.4889 (16)
M4—O8	2.0599 (14)	BNA—O3^xv	2.4889 (16)
M4—O8^ix	2.0598 (14)	BNA—O4^vi	2.5863 (17)
D—A^xiii	3.8710 (7)	BNA—O4^vii	2.5863 (17)
D—A	3.8711 (7)	BNA—O4^xv	2.5863 (17)
D—BNA	3.4678 (4)	BNA—O4	2.5863 (17)
D—BNA^xiv	3.4091 (5)	BNA—F^iii	2.6602 (1)
D—O1	1.7370 (19)	BNA—F	2.6602 (1)
D—O3^xiii	1.9498 (15)	O8—H8	0.976 (15)
D—O3^viii	1.9498 (15)
M2^iii—M1—M2^i	180.000 (11)	O3—T2—BNA	53.78 (6)
M2^iii—M1—M2	114.062 (12)	O3—T2—O5	104.61 (8)
M2^i—M1—M2	65.938 (12)	O4^vii—T2—M1^xvii	81.54 (6)
M2^i—M1—M2^ii	114.062 (12)	O4^vii—T2—A	119.62 (6)
M2^iii—M1—M2^ii	65.938 (12)	O4^vii—T2—A^iii	46.04 (6)
M2^ii—M1—M2	180.0	O4^vii—T2—BNA	57.24 (6)
M2^iii—M1—M3^ii	122.969 (6)	O4^vii—T2—O2	112.55 (8)
M2^ii—M1—M3^ii	57.031 (6)	O4^vii—T2—O3	110.73 (9)
M2^i—M1—M3	122.969 (6)	O4^vii—T2—O5	104.28 (9)
M2^ii—M1—M3	122.969 (6)	O5—T2—M1^xvii	141.70 (6)
M2^iii—M1—M3	57.031 (6)	O5—T2—A	60.12 (6)
M2^i—M1—M3^ii	57.031 (6)	O5—T2—A^iii	58.51 (6)
M2—M1—M3^ii	122.969 (6)	O5—T2—BNA	111.17 (5)
M2—M1—M3	57.031 (6)	O3—A—T2^viii	119.33 (4)
M3^ii—M1—M3	180.0	O3^viii—A—T2^viii	23.49 (3)
O1—M1—M2^i	44.51 (3)	O3—A—O3^viii	97.73 (6)
O1^ii—M1—M2^iii	44.51 (3)	O3—A—O4	73.20 (5)
O1—M1—M2	44.51 (3)	O3^viii—A—O4	55.77 (4)
O1—M1—M2^ii	135.49 (3)	O3—A—O4^viii	55.77 (4)
O1^ii—M1—M2^i	135.49 (3)	O3^viii—A—O4^viii	73.20 (5)
O1^ii—M1—M2	135.49 (3)	O3—A—O5^xiv	97.74 (4)
O1^ii—M1—M2^ii	44.51 (3)	O3—A—O5^viii	141.98 (4)
O1—M1—M2^iii	135.49 (3)	O3^viii—A—O5^viii	49.58 (4)
O1^ii—M1—M3^ii	90.0	O3^viii—A—O5^vii	97.74 (4)
O1—M1—M3^ii	90.0	O3—A—O5	49.58 (4)
O1—M1—M3	90.0	O3—A—O5^vii	90.37 (4)
O1^ii—M1—M3	90.0	O3^viii—A—O5	141.98 (4)
O1—M1—O1^ii	180.0	O3^viii—A—O5^xiv	90.37 (4)
O1^ii—M1—O2^vii	85.35 (4)	O3^viii—A—O7^viii	171.93 (4)
O1—M1—O2^vi	94.65 (4)	O3^viii—A—O7	89.93 (4)
O1—M1—O2^vii	94.65 (4)	O3—A—O7	171.93 (4)
O1—M1—O2^v	85.35 (4)	O3—A—O7^viii	89.93 (4)
O1—M1—O2^iv	85.35 (4)	O3—A—F	48.86 (3)
O1^ii—M1—O2^iv	94.65 (4)	O3^viii—A—F	48.86 (3)
O1^ii—M1—O2^v	94.65 (4)	O4—A—T2^viii	74.34 (3)
O1^ii—M1—O2^vi	85.35 (4)	O4^viii—A—T2^viii	81.35 (4)
O2^vi—M1—M2^i	84.28 (3)	O4—A—O4^viii	99.33 (6)
O2^vi—M1—M2^iii	95.72 (3)	O4—A—O5^vii	49.57 (4)
O2^vii—M1—M2^i	139.15 (3)	O4—A—O5	91.87 (4)
O2^iv—M1—M2^i	95.72 (3)	O4^viii—A—O5^viii	91.87 (4)
O2^v—M1—M2^ii	84.28 (3)	O4^viii—A—O5^vii	141.94 (4)
O2^iv—M1—M2	40.85 (3)	O4—A—O5^viii	96.00 (4)
O2^vi—M1—M2	139.15 (3)	O4—A—O5^xiv	141.94 (4)
O2^iv—M1—M2^ii	139.15 (3)	O4^viii—A—O5	96.00 (4)
O2^v—M1—M2^iii	139.15 (3)	O4^viii—A—O5^xiv	49.57 (4)
O2^vi—M1—M2^ii	40.85 (3)	O4—A—O7^viii	129.72 (4)
O2^vii—M1—M2	84.28 (3)	O4^viii—A—O7^viii	109.51 (4)
O2^vii—M1—M2^iii	40.85 (3)	O4—A—O7	109.51 (4)
O2^iv—M1—M2^iii	84.28 (3)	O4^viii—A—O7	129.72 (4)
O2^vii—M1—M2^ii	95.72 (3)	O4^viii—A—F	49.67 (3)
O2^v—M1—M2	95.72 (3)	O4—A—F	49.67 (3)
O2^v—M1—M2^i	40.85 (3)	O5^vii—A—T2^viii	105.15 (3)
O2^vi—M1—M3^ii	38.13 (3)	O5—A—T2^viii	165.22 (3)
O2^vi—M1—M3	141.87 (3)	O5^xiv—A—T2^viii	78.95 (3)
O2^iv—M1—M3	38.13 (3)	O5^viii—A—T2^viii	26.09 (2)
O2^v—M1—M3^ii	38.13 (3)	O5^xiv—A—O5	110.45 (4)
O2^vii—M1—M3^ii	141.87 (3)	O5^vii—A—O5^viii	110.45 (4)
O2^v—M1—M3	141.87 (3)	O5—A—O5^viii	167.84 (5)
O2^vii—M1—M3	38.13 (3)	O5^vii—A—O5	68.15 (4)
O2^iv—M1—M3^ii	141.87 (3)	O5^vii—A—O5^xiv	167.68 (6)
O2^iv—M1—O2^vii	76.27 (6)	O5^xiv—A—O5^viii	68.15 (4)
O2^vi—M1—O2^vii	103.73 (6)	O5^vii—A—O7^viii	84.70 (4)
O2^vi—M1—O2^iv	180.00 (5)	O5^xiv—A—O7	84.70 (4)
O2^v—M1—O2^vii	180.0	O5^viii—A—O7	46.01 (3)
O2^vi—M1—O2^v	76.27 (6)	O5^xiv—A—O7^viii	86.05 (4)
O2^iv—M1—O2^v	103.73 (6)	O5^vii—A—O7	86.05 (4)
M1^xiv—M2—M1	114.062 (12)	O5—A—O7^viii	46.01 (3)
O1^i—M2—M1	81.31 (5)	O5^viii—A—O7^viii	122.36 (4)
O1—M2—M1	46.09 (5)	O5—A—O7	122.36 (4)
O1^i—M2—M1^xiv	46.09 (5)	O7^viii—A—T2^viii	148.45 (3)
O1—M2—M1^xiv	81.31 (5)	O7—A—T2^viii	68.65 (2)
O1^i—M2—O1	78.18 (8)	O7^viii—A—O7	82.54 (5)
O2^iv—M2—M1^xiv	137.69 (4)	F—A—T2^viii	71.052 (14)
O2^viii—M2—M1	137.69 (4)	F—A—O5^viii	96.08 (3)
O2^iv—M2—M1	49.69 (4)	F—A—O5^xiv	96.16 (3)
O2^viii—M2—M1^xiv	49.69 (4)	F—A—O5	96.08 (3)
O2^iv—M2—O1^i	91.82 (6)	F—A—O5^vii	96.16 (3)
O2^iv—M2—O1	95.76 (6)	F—A—O7^viii	138.73 (3)
O2^viii—M2—O1	91.82 (6)	F—A—O7	138.73 (3)
O2^viii—M2—O1^i	95.76 (6)	T2—BNA—T2^vii	99.755 (19)
O2^iv—M2—O2^viii	170.23 (8)	O3^vii—BNA—T2	99.31 (4)
O2^iv—M2—O8	82.19 (5)	O3—BNA—T2^vii	99.30 (4)
O2^iv—M2—O8^ix	90.23 (5)	O3^vi—BNA—T2	148.48 (3)
O2^viii—M2—O8	90.23 (5)	O3^vi—BNA—T2^vii	80.70 (4)
O2^viii—M2—O8^ix	82.18 (5)	O3^xv—BNA—T2^vii	148.48 (3)
O8^ix—M2—M1^xiv	94.52 (4)	O3^xv—BNA—T2	80.69 (4)
O8^ix—M2—M1	139.91 (4)	O3—BNA—T2	31.52 (3)
O8—M2—M1^xiv	139.91 (4)	O3^vii—BNA—T2^vii	31.52 (3)
O8—M2—M1	94.52 (4)	O3—BNA—O3^vii	115.18 (7)
O8^ix—M2—O1	174.00 (6)	O3—BNA—O3^xv	64.82 (7)
O8—M2—O1^i	174.00 (6)	O3—BNA—O3^vi	180.0
O8—M2—O1	102.07 (5)	O3^vii—BNA—O3^vi	64.82 (7)
O8^ix—M2—O1^i	102.07 (5)	O3^xv—BNA—O3^vi	115.18 (7)
O8—M2—O8^ix	78.33 (7)	O3^xv—BNA—O3^vii	180.00 (6)
O2^vii—M3—M1	45.73 (4)	O3^vi—BNA—O4^xv	62.93 (5)
O2^iv—M3—M1	45.73 (4)	O3—BNA—O4^vi	95.62 (5)
O2^vii—M3—O2^iv	91.46 (8)	O3^vii—BNA—O4^xv	95.62 (5)
O2^vii—M3—O6^iii	94.37 (5)	O3^vii—BNA—O4	62.93 (5)
O2^vii—M3—O6^ix	174.16 (5)	O3—BNA—O4	84.38 (5)
O2^iv—M3—O6^iii	174.16 (5)	O3—BNA—O4^vii	62.93 (5)
O2^iv—M3—O6^ix	94.37 (5)	O3—BNA—O4^xv	117.07 (5)
O6^iii—M3—M1	140.10 (4)	O3^xv—BNA—O4^vii	95.62 (5)
O6^ix—M3—M1	140.10 (3)	O3^xv—BNA—O4	117.07 (5)
O6^ix—M3—O6^iii	79.81 (7)	O3^vii—BNA—O4^vii	84.38 (5)
O8^x—M3—M1	91.77 (4)	O3^xv—BNA—O4^xv	84.38 (5)
O8—M3—M1	91.77 (4)	O3^vi—BNA—O4^vi	84.38 (5)
O8^x—M3—O2^iv	97.35 (5)	O3^vi—BNA—O4	95.62 (5)
O8^x—M3—O2^vii	85.13 (5)	O3^vi—BNA—O4^vii	117.07 (5)
O8—M3—O2^iv	85.13 (5)	O3^xv—BNA—O4^vi	62.93 (5)
O8—M3—O2^vii	97.35 (5)	O3^vii—BNA—O4^vi	117.07 (5)
O8^x—M3—O6^iii	83.54 (5)	O3^vi—BNA—F^iii	58.44 (3)
O8^x—M3—O6^ix	93.73 (5)	O3^xv—BNA—F	58.44 (3)
O8—M3—O6^ix	83.55 (5)	O3—BNA—F	58.44 (3)
O8—M3—O6^iii	93.73 (5)	O3^xv—BNA—F^iii	121.56 (3)
O8^x—M3—O8	176.47 (8)	O3—BNA—F^iii	121.56 (3)
O6^ix—M4—O6^xi	83.46 (5)	O3^vii—BNA—F	121.56 (3)
O6—M4—O6^ix	175.24 (8)	O3^vi—BNA—F	121.56 (3)
O6^ix—M4—O6^xii	92.98 (5)	O3^vii—BNA—F^iii	58.44 (3)
O6—M4—O6^xii	83.45 (5)	O4—BNA—T2	100.80 (4)
O6^xii—M4—O6^xi	83.23 (7)	O4^vi—BNA—T2^vii	148.47 (3)
O6—M4—O6^xi	92.98 (5)	O4^xv—BNA—T2^vii	79.20 (4)
O8—M4—O6	97.65 (5)	O4—BNA—T2^vii	31.53 (3)
O8—M4—O6^xi	96.29 (5)	O4^vi—BNA—T2	79.20 (4)
O8^ix—M4—O6^ix	97.65 (5)	O4^vii—BNA—T2	31.53 (3)
O8^ix—M4—O6^xii	96.29 (5)	O4^vii—BNA—T2^vii	100.80 (4)
O8—M4—O6^xii	178.82 (6)	O4^xv—BNA—T2	148.47 (3)
O8—M4—O6^ix	85.89 (5)	O4^vi—BNA—O4^xv	117.89 (7)
O8^ix—M4—O6	85.89 (5)	O4^vi—BNA—O4^vii	62.11 (7)
O8^ix—M4—O6^xi	178.82 (6)	O4^xv—BNA—O4^vii	180.00 (6)
O8^ix—M4—O8	84.21 (8)	O4^vii—BNA—O4	117.89 (7)
M1—D—A	118.218 (9)	O4^vi—BNA—O4	180.0
M1—D—A^xiii	118.218 (9)	O4^xv—BNA—O4	62.11 (7)
M1—D—BNA	97.060 (11)	O4^vi—BNA—F	121.35 (3)
A^xiii—D—A	111.491 (17)	O4^vi—BNA—F^iii	58.65 (3)
BNA^xiv—D—M1	161.579 (14)	O4^vii—BNA—F^iii	58.65 (3)
BNA^xiv—D—A^xiii	69.384 (8)	O4^vii—BNA—F	121.35 (3)
BNA—D—A	68.828 (8)	O4—BNA—F	58.65 (3)
BNA—D—A^xiii	68.827 (8)	O4^xv—BNA—F	58.65 (3)
BNA^xiv—D—A	69.384 (8)	O4—BNA—F^iii	121.35 (3)
BNA^xiv—D—BNA	101.361 (12)	O4^xv—BNA—F^iii	121.35 (3)
O1—D—M1	35.71 (7)	F—BNA—T2^vii	90.058 (10)
O1—D—A	124.206 (9)	F^iii—BNA—T2	90.058 (10)
O1—D—A^xiii	124.206 (9)	F—BNA—T2	89.942 (10)
O1—D—BNA	132.77 (7)	F^iii—BNA—T2^vii	89.942 (10)
O1—D—BNA^xiv	125.87 (7)	F^iii—BNA—F	180.0
O1—D—O3^viii	103.04 (7)	M2—O1—M1	89.40 (6)
O1—D—O3^xiii	103.04 (7)	M2^i—O1—M1	89.40 (6)
O1—D—O4^xv	105.14 (7)	M2—O1—M2^i	101.82 (8)
O1—D—O4	105.14 (7)	D—O1—M1	117.95 (10)
O1—D—F	177.15 (7)	D—O1—M2	124.18 (5)
O3^viii—D—M1	126.02 (5)	D—O1—M2^i	124.18 (5)
O3^xiii—D—M1	126.02 (5)	M2^xvii—O2—M1^xvii	89.46 (5)
O3^viii—D—A^xiii	114.78 (5)	M2^xvii—O2—M3^xvii	97.25 (6)
O3^viii—D—A	44.62 (5)	M3^xvii—O2—M1^xvii	96.14 (5)
O3^xiii—D—A	114.79 (5)	T2—O2—M1^xvii	119.88 (7)
O3^xiii—D—A^xiii	44.62 (5)	T2—O2—M2^xvii	126.57 (8)
O3^xiii—D—BNA	110.85 (5)	T2—O2—M3^xvii	119.89 (8)
O3^xiii—D—BNA^xiv	46.03 (5)	D^xiii—O3—A	106.50 (6)
O3^viii—D—BNA^xiv	46.03 (5)	D^xiii—O3—BNA	99.64 (6)
O3^viii—D—BNA	110.85 (5)	T2—O3—D^xiii	134.56 (9)
O3^xiii—D—O3^viii	86.34 (10)	T2—O3—A	112.01 (7)
O3^xiii—D—F	74.94 (5)	T2—O3—BNA	94.71 (7)
O3^viii—D—F	74.94 (5)	BNA—O3—A	102.59 (5)
O4—D—M1	79.38 (5)	D—O4—A	104.96 (6)
O4^xv—D—M1	79.38 (5)	D—O4—BNA	98.87 (6)
O4—D—A	46.00 (5)	T2^vii—O4—D	141.25 (10)
O4—D—A^xiii	116.04 (5)	T2^vii—O4—A	110.27 (7)
O4^xv—D—A^xiii	46.00 (5)	T2^vii—O4—BNA	91.23 (7)
O4^xv—D—A	116.04 (5)	BNA—O4—A	98.95 (5)
O4^xv—D—BNA	47.46 (5)	T1^viii—O5—T2	139.06 (10)
O4—D—BNA^xiv	113.41 (5)	T1^viii—O5—A^iii	109.06 (7)
O4—D—BNA	47.47 (5)	T1^viii—O5—A	106.83 (7)
O4^xv—D—BNA^xiv	113.41 (5)	T2—O5—A	93.80 (7)
O4—D—O3^viii	86.73 (7)	T2—O5—A^iii	95.50 (7)
O4^xv—D—O3^viii	151.81 (7)	A^iii—O5—A	110.45 (4)
O4^xv—D—O3^xiii	86.73 (7)	M4—O6—M3^xiv	92.77 (5)
O4—D—O3^xiii	151.81 (7)	M4^xii—O6—M3^xiv	98.48 (5)
O4^xv—D—O4	86.60 (10)	M4—O6—M4^xii	96.55 (5)
O4—D—F	76.87 (5)	T1—O6—M3^xiv	120.08 (7)
O4^xv—D—F	76.87 (5)	T1—O6—M4^xii	121.17 (7)
F—D—M1	147.143 (18)	T1—O6—M4	121.50 (8)
F—D—A	55.746 (9)	T1^xi—O7—T1	137.50 (10)
F—D—A^xiii	55.745 (9)	T1—O7—A	100.42 (6)
F—D—BNA	50.083 (9)	T1^xi—O7—A	104.00 (6)
F—D—BNA^xiv	51.278 (10)	M2—O8—H8	107.8 (16)
O5^viii—T1—O7^xvi	106.71 (8)	M3—O8—M2	94.65 (6)
O5^viii—T1—O7	106.71 (8)	M3—O8—M4	97.71 (6)
O6—T1—O5^viii	111.88 (7)	M3—O8—H8	112.1 (16)
O6—T1—O7	111.24 (7)	M4—O8—M2	98.73 (6)
O6—T1—O7^xvi	111.24 (7)	M4—O8—H8	137.5 (14)
O7^xvi—T1—O7	108.84 (6)	D—F—D^xiii	180.00 (2)
M1^xvii—T2—A^iii	119.919 (15)	D^xiii—F—A	90.0
M1^xvii—T2—A	148.565 (17)	D^xiii—F—A^xiii	90.0
A—T2—A^iii	90.262 (14)	D—F—A^xiii	90.0
BNA—T2—M1^xvii	103.766 (14)	D—F—A	90.0
BNA—T2—A	74.377 (14)	D^xiii—F—BNA^xiv	90.998 (12)
BNA—T2—A^iii	74.310 (14)	D^xiii—F—BNA	89.002 (12)
O2—T2—M1^xvii	36.66 (5)	D—F—BNA^xiv	89.002 (12)
O2—T2—A^iii	132.19 (6)	D—F—BNA	90.998 (12)
O2—T2—A	127.63 (6)	A^xiii—F—A	180.0
O2—T2—BNA	136.99 (5)	BNA^xiv—F—A	90.0
O2—T2—O3	112.31 (8)	BNA—F—A	90.0
O2—T2—O5	111.80 (7)	BNA^xiv—F—A^xiii	90.0
O3—T2—M1^xvii	108.50 (6)	BNA—F—A^xiii	90.0
O3—T2—A	44.50 (6)	BNA^xiv—F—BNA	180.0
O3—T2—A^iii	115.40 (6)

Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, −y+1, −z; (iii) x−1, y, z; (iv) x, y, z−1; (v) x, −y+1, z−1; (vi) −x+1, −y+1, −z+1; (vii) −x+1, y, −z+1; (viii) −x+2, y, −z+1; (ix) −x+2, y, −z; (x) −x+1, y, −z; (xi) x−1/2, −y+1/2, z; (xii) −x+5/2, −y+1/2, −z; (xiii) −x+2, −y+1, −z+1; (xiv) x+1, y, z; (xv) x, −y+1, z; (xvi) x+1/2, −y+1/2, z; (xvii) x, y, z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8···O3^viii	0.98 (2)	2.79 (2)	3.476 (2)	128 (2)
O8—H8···O4	0.98 (2)	2.57 (2)	3.366 (2)	139 (2)

Symmetry code: (viii) −x+2, y, −z+1.

(I)

Crystal data

0.5(Ca0.19F0.34Fe9.37H8K3.88Na3.79O60Si15.48Ti3.93)	F(000) = 1158
Mr = 1184.31	Dx = 3.077 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 5.3499 (3) Å	Cell parameters from 7312 reflections
b = 23.2681 (11) Å	θ = 2.5–36.3°
c = 10.4149 (4) Å	µ = 4.04 mm^−1
β = 99.658 (4)°	T = 293 K
V = 1278.09 (10) Å^3	Prism, brown
Z = 2	0.22 × 0.18 × 0.11 mm

Data collection

Saxi-CrysAlisPro-abstract goniometer imported SAXI images diffractometer	3040 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2727 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ω scans	θmax = 36.3°, θmin = 1.8°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→8
Tmin = 0.697, Tmax = 1.000	k = −37→38
10570 measured reflections	l = −17→17

Refinement

Refinement on F^2	2 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.033	Only H-atom coordinates refined
wR(F^2) = 0.083	w = 1/[σ^2(Fo^2) + (0.0435P)^2 + 2.3471P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
3040 reflections	Δρmax = 0.71 e Å^−3
136 parameters	Δρmin = −1.12 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
M1	0.500000	0.500000	0.000000	0.0129 (4)	0.992 (8)
M2	1.000000	0.42548 (2)	0.000000	0.00805 (9)	0.938 (3)
M3	0.500000	0.35482 (2)	0.000000	0.00879 (12)	0.760 (3)
M4	1.000000	0.28601 (2)	0.000000	0.00942 (14)	0.645 (2)
D	0.93685 (7)	0.500000	0.28677 (3)	0.00559 (10)	0.982 (3)
T1	1.42108 (8)	0.28222 (2)	0.26420 (4)	0.00594 (12)	0.970 (4)
T2	0.57591 (8)	0.41435 (2)	0.72938 (4)	0.00594 (12)	0.965 (4)
A	1.000000	0.36147 (3)	0.500000	0.0257 (2)	0.970 (4)
BNA	0.500000	0.500000	0.500000	0.0136 (5)	0.903 (12)
BCA	0.500000	0.500000	0.500000	0.0136 (5)	0.097 (12)
O1	0.9032 (3)	0.500000	0.11758 (15)	0.0103 (3)
O2	0.6403 (2)	0.41782 (5)	0.88715 (11)	0.0107 (2)
O3	0.7979 (2)	0.44246 (6)	0.66098 (12)	0.0148 (2)
O4	0.6964 (2)	0.44252 (6)	0.32876 (12)	0.0165 (3)
O5	0.5533 (3)	0.34676 (5)	0.67693 (12)	0.0162 (3)
O6	1.3699 (2)	0.28238 (5)	0.10691 (11)	0.0092 (2)
O7	1.1866 (2)	0.25128 (6)	0.32208 (12)	0.0141 (2)
O8	0.8655 (2)	0.35234 (5)	0.10302 (12)	0.0112 (2)
F	1.000000	0.500000	0.500000	0.008 (3)*	0.170 (9)
H8	0.876 (5)	0.3647 (9)	0.1990 (17)	0.012*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
M1	0.0096 (6)	0.0112 (7)	0.0171 (7)	0.000	−0.0007 (5)	0.000
M2	0.00614 (15)	0.00680 (15)	0.01066 (15)	0.000	−0.00016 (10)	0.000
M3	0.00774 (19)	0.00742 (19)	0.01120 (19)	0.000	0.00152 (13)	0.000
M4	0.0079 (2)	0.0078 (2)	0.0123 (2)	0.000	0.00101 (15)	0.000
D	0.00370 (15)	0.00560 (15)	0.00738 (15)	0.000	0.00070 (10)	0.000
T1	0.00575 (19)	0.00456 (18)	0.00728 (18)	0.00008 (12)	0.00046 (13)	−0.00019 (12)
T2	0.00584 (18)	0.00430 (18)	0.00742 (18)	0.00040 (12)	0.00036 (12)	0.00023 (12)
A	0.0316 (4)	0.0241 (3)	0.0210 (3)	0.000	0.0031 (2)	0.000
BNA	0.0207 (8)	0.0106 (7)	0.0079 (6)	0.000	−0.0017 (4)	0.000
BCA	0.0207 (8)	0.0106 (7)	0.0079 (6)	0.000	−0.0017 (4)	0.000
O1	0.0097 (6)	0.0117 (7)	0.0093 (6)	0.000	0.0009 (5)	0.000
O2	0.0116 (5)	0.0107 (5)	0.0094 (4)	0.0000 (4)	0.0008 (4)	0.0006 (4)
O3	0.0139 (5)	0.0181 (6)	0.0128 (5)	−0.0079 (4)	0.0034 (4)	−0.0026 (4)
O4	0.0122 (5)	0.0210 (6)	0.0154 (5)	−0.0088 (4)	−0.0006 (4)	0.0030 (4)
O5	0.0296 (7)	0.0058 (5)	0.0123 (5)	0.0000 (4)	0.0007 (5)	0.0000 (4)
O6	0.0093 (5)	0.0090 (5)	0.0091 (4)	0.0003 (3)	0.0012 (3)	0.0000 (3)
O7	0.0108 (5)	0.0192 (6)	0.0119 (5)	−0.0069 (4)	0.0012 (4)	−0.0011 (4)
O8	0.0109 (5)	0.0112 (5)	0.0113 (5)	0.0000 (4)	0.0014 (4)	−0.0003 (4)

Geometric parameters (Å, º)

M1—M2^i	3.1878 (2)	D—O4^xv	1.9552 (13)
M1—M2	3.1878 (2)	D—O4	1.9553 (13)
M1—M2^ii	3.1878 (2)	D—F	2.1895 (4)
M1—M2^iii	3.1878 (2)	T1—O5^viii	1.6191 (13)
M1—M3	3.3780 (4)	T1—O6	1.6149 (12)
M1—M3^ii	3.3780 (4)	T1—O7^xvi	1.6436 (13)
M1—O1^ii	2.2947 (16)	T1—O7	1.6459 (12)
M1—O1	2.2947 (16)	T2—A^i	3.7742 (5)
M1—O2^iv	2.4285 (12)	T2—A	3.7666 (5)
M1—O2^v	2.4285 (12)	T2—BNA	3.0851 (4)
M1—O2^vi	2.4285 (12)	T2—O2	1.6233 (12)
M1—O2^vii	2.4285 (12)	T2—O3	1.6213 (12)
M2—O1	2.2332 (10)	T2—O4^iv	1.6196 (13)
M2—O1^iii	2.2332 (10)	T2—O5	1.6626 (13)
M2—O2^vii	2.0874 (12)	A—O3^viii	2.8530 (14)
M2—O2^viii	2.0874 (12)	A—O3	2.8530 (14)
M2—O8	2.1964 (12)	A—O4^viii	2.8988 (15)
M2—O8^ix	2.1964 (12)	A—O4	2.8987 (15)
M3—O2^vii	2.0951 (12)	A—O5^iv	3.2317 (15)
M3—O2^iv	2.0951 (12)	A—O5^viii	3.2715 (14)
M3—O6^i	2.1966 (12)	A—O5	3.2715 (14)
M3—O6^ix	2.1966 (12)	A—O5^xiv	3.2317 (15)
M3—O8^x	2.0673 (12)	A—O7	3.4096 (14)
M3—O8	2.0673 (12)	A—O7^viii	3.4095 (14)
M4—O6^xi	2.1251 (12)	A—F	3.2233 (7)
M4—O6^ix	2.1035 (12)	BNA—O3	2.4993 (14)
M4—O6	2.1035 (12)	BNA—O3^xv	2.4993 (14)
M4—O6^xii	2.1251 (12)	BNA—O3^iv	2.4993 (14)
M4—O8^ix	2.0762 (12)	BNA—O3^v	2.4993 (14)
M4—O8	2.0762 (12)	BNA—O4	2.5890 (14)
D—A^xiii	3.8966 (6)	BNA—O4^v	2.5890 (14)
D—A	3.8966 (6)	BNA—O4^xv	2.5890 (14)
D—BNA	3.4836 (4)	BNA—O4^iv	2.5890 (14)
D—BNA^xiv	3.4298 (4)	BNA—F^i	2.6749 (1)
D—O1	1.7410 (16)	BNA—F	2.6749 (1)
D—O3^viii	1.9606 (12)	O8—H8	1.032 (15)
D—O3^xiii	1.9607 (12)
M2—M1—M2^i	114.094 (11)	O3—T2—O5	104.81 (7)
M2^i—M1—M2^iii	180.0	O4^iv—T2—A	119.66 (5)
M2—M1—M2^iii	65.906 (11)	O4^iv—T2—A^i	46.18 (5)
M2^iii—M1—M2^ii	114.092 (11)	O4^iv—T2—BNA	57.03 (5)
M2—M1—M2^ii	180.0	O4^iv—T2—O2	112.53 (7)
M2^i—M1—M2^ii	65.908 (11)	O4^iv—T2—O3	110.60 (8)
M2^iii—M1—M3	122.954 (5)	O4^iv—T2—O5	104.39 (8)
M2^ii—M1—M3^ii	57.046 (5)	O5—T2—A^i	58.46 (5)
M2^ii—M1—M3	122.954 (5)	O5—T2—A	60.07 (5)
M2^iii—M1—M3^ii	57.046 (5)	O5—T2—BNA	111.33 (5)
M2—M1—M3^ii	122.952 (5)	O3^viii—A—T2^viii	23.58 (3)
M2—M1—M3	57.048 (5)	O3—A—T2^viii	119.01 (3)
M2^i—M1—M3	57.046 (5)	O3—A—O3^viii	97.33 (5)
M2^i—M1—M3^ii	122.954 (5)	O3^viii—A—O4	55.75 (4)
M3^ii—M1—M3	180.0	O3—A—O4	72.75 (4)
O1^ii—M1—M2^i	44.47 (3)	O3^viii—A—O4^viii	72.75 (4)
O1^ii—M1—M2	135.53 (3)	O3—A—O4^viii	55.75 (4)
O1—M1—M2	44.47 (3)	O3—A—O5^iv	90.22 (4)
O1—M1—M2^ii	135.53 (3)	O3^viii—A—O5^iv	97.82 (4)
O1—M1—M2^iii	44.47 (3)	O3—A—O5^xiv	97.82 (4)
O1^ii—M1—M2^iii	135.53 (3)	O3^viii—A—O5^viii	49.71 (3)
O1—M1—M2^i	135.53 (3)	O3—A—O5^viii	141.71 (4)
O1^ii—M1—M2^ii	44.47 (3)	O3^viii—A—O5^xiv	90.22 (4)
O1^ii—M1—M3^ii	90.0	O3—A—O5	49.71 (3)
O1—M1—M3	90.0	O3^viii—A—O5	141.71 (4)
O1^ii—M1—M3	90.0	O3—A—O7^viii	90.17 (3)
O1—M1—M3^ii	90.0	O3^viii—A—O7	90.17 (3)
O1^ii—M1—O1	180.0	O3—A—O7	172.09 (4)
O1—M1—O2^iv	94.64 (4)	O3^viii—A—O7^viii	172.09 (4)
O1^ii—M1—O2^v	85.36 (4)	O3—A—F	48.66 (3)
O1—M1—O2^v	94.64 (4)	O3^viii—A—F	48.66 (3)
O1—M1—O2^vi	85.36 (4)	O4^viii—A—T2^viii	80.96 (3)
O1—M1—O2^vii	85.36 (4)	O4—A—T2^viii	74.46 (3)
O1^ii—M1—O2^iv	85.36 (4)	O4—A—O4^viii	98.83 (6)
O1^ii—M1—O2^vi	94.64 (4)	O4—A—O5^viii	96.22 (4)
O1^ii—M1—O2^vii	94.64 (4)	O4—A—O5^xiv	141.70 (4)
O2^v—M1—M2^iii	84.21 (3)	O4—A—O5	91.59 (4)
O2^v—M1—M2^ii	40.90 (3)	O4^viii—A—O5^viii	91.59 (4)
O2^vii—M1—M2	40.90 (3)	O4^viii—A—O5	96.22 (4)
O2^vii—M1—M2^i	84.21 (3)	O4^viii—A—O5^xiv	49.69 (3)
O2^vi—M1—M2^i	139.10 (3)	O4^viii—A—O5^iv	141.70 (4)
O2^iv—M1—M2^ii	95.79 (3)	O4—A—O5^iv	49.69 (3)
O2^iv—M1—M2^iii	139.10 (3)	O4—A—O7^viii	129.70 (3)
O2^v—M1—M2^i	95.79 (3)	O4^viii—A—O7	129.70 (3)
O2^vii—M1—M2^iii	95.79 (3)	O4^viii—A—O7^viii	109.86 (4)
O2^vii—M1—M2^ii	139.10 (3)	O4—A—O7	109.86 (4)
O2^vi—M1—M2^iii	40.90 (3)	O4^viii—A—F	49.42 (3)
O2^vi—M1—M2^ii	84.21 (3)	O4—A—F	49.42 (3)
O2^vi—M1—M2	95.78 (3)	O5^iv—A—T2^viii	105.34 (2)
O2^iv—M1—M2	84.22 (3)	O5^xiv—A—T2^viii	78.74 (2)
O2^v—M1—M2	139.10 (3)	O5—A—T2^viii	165.05 (3)
O2^iv—M1—M2^i	40.90 (3)	O5^viii—A—T2^viii	26.13 (2)
O2^v—M1—M3	141.94 (3)	O5^iv—A—O5	67.93 (4)
O2^vii—M1—M3^ii	141.94 (3)	O5^iv—A—O5^viii	110.70 (4)
O2^iv—M1—M3	38.06 (3)	O5^xiv—A—O5^viii	67.93 (4)
O2^v—M1—M3^ii	38.06 (3)	O5^xiv—A—O5	110.70 (4)
O2^vi—M1—M3	141.94 (3)	O5—A—O5^viii	167.99 (5)
O2^vi—M1—M3^ii	38.06 (3)	O5^iv—A—O5^xiv	167.84 (5)
O2^vii—M1—M3	38.06 (3)	O5^xiv—A—O7	84.64 (3)
O2^iv—M1—M3^ii	141.94 (3)	O5^iv—A—O7	86.22 (3)
O2^v—M1—O2^vii	180.0	O5^xiv—A—O7^viii	86.22 (3)
O2^v—M1—O2^vi	76.11 (5)	O5^viii—A—O7^viii	122.39 (4)
O2^vii—M1—O2^iv	76.11 (5)	O5^viii—A—O7	46.13 (3)
O2^vi—M1—O2^iv	180.0	O5^iv—A—O7^viii	84.64 (3)
O2^vii—M1—O2^vi	103.89 (5)	O5—A—O7	122.39 (4)
O2^v—M1—O2^iv	103.89 (5)	O5—A—O7^viii	46.13 (3)
M1^xiv—M2—M1	114.095 (11)	O7—A—T2^viii	68.81 (2)
O1—M2—M1	46.04 (4)	O7^viii—A—T2^viii	148.52 (3)
O1^iii—M2—M1	81.34 (4)	O7^viii—A—O7	82.47 (4)
O1—M2—M1^xiv	81.34 (4)	F—A—T2^viii	70.932 (12)
O1^iii—M2—M1^xiv	46.04 (4)	F—A—O5	96.01 (2)
O1^iii—M2—O1	78.13 (6)	F—A—O5^xiv	96.08 (3)
O2^viii—M2—M1^xiv	49.62 (3)	F—A—O5^iv	96.08 (3)
O2^vii—M2—M1	49.62 (3)	F—A—O5^viii	96.01 (2)
O2^viii—M2—M1	137.79 (3)	F—A—O7^viii	138.76 (2)
O2^vii—M2—M1^xiv	137.79 (3)	F—A—O7	138.76 (2)
O2^vii—M2—O1	95.64 (5)	T2^xv—BNA—T2^iv	180.0
O2^viii—M2—O1	91.96 (5)	O3^xv—BNA—T2^iv	148.41 (3)
O2^vii—M2—O1^iii	91.96 (5)	O3—BNA—T2^iv	99.19 (3)
O2^viii—M2—O1^iii	95.64 (5)	O3^xv—BNA—T2^xv	31.59 (3)
O2^vii—M2—O2^viii	170.20 (7)	O3—BNA—T2^xv	80.81 (3)
O2^viii—M2—O8^ix	82.08 (5)	O3^iv—BNA—T2^iv	31.59 (3)
O2^vii—M2—O8	82.08 (5)	O3^v—BNA—T2^iv	80.81 (3)
O2^vii—M2—O8^ix	90.31 (5)	O3^iv—BNA—T2^xv	148.41 (3)
O2^viii—M2—O8	90.31 (5)	O3^v—BNA—T2^xv	99.19 (3)
O8^ix—M2—M1	139.92 (3)	O3^iv—BNA—O3^v	64.79 (6)
O8—M2—M1	94.46 (3)	O3—BNA—O3^v	180.0
O8—M2—M1^xiv	139.92 (3)	O3^xv—BNA—O3^iv	180.00 (5)
O8^ix—M2—M1^xiv	94.46 (3)	O3^xv—BNA—O3^v	115.21 (6)
O8—M2—O1^iii	174.04 (5)	O3—BNA—O3^iv	115.21 (6)
O8^ix—M2—O1	174.04 (5)	O3—BNA—O3^xv	64.79 (6)
O8—M2—O1	102.04 (4)	O3^v—BNA—O4	95.82 (4)
O8^ix—M2—O1^iii	102.04 (4)	O3^xv—BNA—O4^iv	95.82 (4)
O8^ix—M2—O8	78.43 (6)	O3^iv—BNA—O4	63.12 (4)
O2^iv—M3—M1	45.61 (3)	O3^xv—BNA—O4^v	63.12 (4)
O2^vii—M3—M1	45.61 (3)	O3—BNA—O4^iv	63.12 (4)
O2^iv—M3—O2^vii	91.21 (7)	O3^v—BNA—O4^iv	116.88 (4)
O2^vii—M3—O6^i	174.27 (5)	O3^xv—BNA—O4	116.88 (4)
O2^vii—M3—O6^ix	94.51 (4)	O3^iv—BNA—O4^xv	95.82 (4)
O2^iv—M3—O6^ix	174.27 (4)	O3^v—BNA—O4^v	84.18 (4)
O2^iv—M3—O6^i	94.51 (4)	O3—BNA—O4^v	95.82 (4)
O6^i—M3—M1	140.12 (3)	O3—BNA—O4	84.18 (4)
O6^ix—M3—M1	140.12 (3)	O3—BNA—O4^xv	116.88 (4)
O6^ix—M3—O6^i	79.77 (6)	O3^xv—BNA—O4^xv	84.18 (4)
O8—M3—M1	91.60 (3)	O3^v—BNA—O4^xv	63.12 (4)
O8^x—M3—M1	91.60 (3)	O3^iv—BNA—O4^v	116.88 (4)
O8—M3—O2^vii	85.07 (5)	O3^iv—BNA—O4^iv	84.18 (4)
O8^x—M3—O2^iv	85.07 (5)	O3—BNA—F	58.33 (3)
O8^x—M3—O2^vii	97.19 (5)	O3^xv—BNA—F^i	121.67 (3)
O8—M3—O2^iv	97.19 (5)	O3^v—BNA—F	121.67 (3)
O8—M3—O6^i	93.89 (5)	O3—BNA—F^i	121.67 (3)
O8^x—M3—O6^i	83.64 (5)	O3^iv—BNA—F	121.67 (3)
O8—M3—O6^ix	83.64 (5)	O3^iv—BNA—F^i	58.33 (3)
O8^x—M3—O6^ix	93.89 (5)	O3^xv—BNA—F	58.33 (3)
O8^x—M3—O8	176.80 (7)	O3^v—BNA—F^i	58.33 (3)
O6—M4—O6^xi	93.11 (4)	O4—BNA—T2^xv	148.34 (3)
O6—M4—O6^xii	83.44 (5)	O4^iv—BNA—T2^iv	100.59 (3)
O6^xii—M4—O6^xi	83.03 (6)	O4^xv—BNA—T2^xv	100.59 (3)
O6^ix—M4—O6^xii	93.11 (4)	O4^v—BNA—T2^iv	148.34 (3)
O6—M4—O6^ix	175.41 (7)	O4^xv—BNA—T2^iv	79.41 (3)
O6^ix—M4—O6^xi	83.43 (5)	O4—BNA—T2^iv	31.66 (3)
O8—M4—O6^ix	85.78 (5)	O4^v—BNA—T2^xv	31.66 (3)
O8—M4—O6	97.65 (5)	O4^iv—BNA—T2^xv	79.41 (3)
O8^ix—M4—O6^xii	96.52 (5)	O4—BNA—O4^xv	62.21 (6)
O8—M4—O6^xi	96.52 (5)	O4^v—BNA—O4^xv	117.79 (6)
O8^ix—M4—O6	85.78 (5)	O4^xv—BNA—O4^iv	180.00 (5)
O8^ix—M4—O6^ix	97.65 (5)	O4—BNA—O4^iv	117.79 (6)
O8—M4—O6^xii	178.85 (5)	O4—BNA—O4^v	180.0
O8^ix—M4—O6^xi	178.85 (5)	O4^v—BNA—O4^iv	62.21 (6)
O8—M4—O8^ix	83.95 (7)	O4^v—BNA—F^i	58.57 (3)
M1—D—A	118.166 (7)	O4—BNA—F^i	121.43 (3)
M1—D—A^xiii	118.166 (7)	O4—BNA—F	58.57 (3)
M1—D—BNA	96.990 (9)	O4^v—BNA—F	121.43 (3)
A^xiii—D—A	111.624 (15)	O4^xv—BNA—F	58.57 (3)
BNA^xiv—D—M1	161.612 (11)	O4^iv—BNA—F^i	58.57 (3)
BNA—D—A	68.899 (7)	O4^iv—BNA—F	121.43 (3)
BNA—D—A^xiii	68.898 (7)	O4^xv—BNA—F^i	121.43 (3)
BNA^xiv—D—A^xiii	69.404 (7)	F^i—BNA—T2^xv	90.100 (8)
BNA^xiv—D—A	69.405 (7)	F^i—BNA—T2^iv	89.900 (8)
BNA^xiv—D—BNA	101.398 (10)	F—BNA—T2^xv	89.900 (8)
O1—D—M1	35.75 (5)	F—BNA—T2^iv	90.100 (8)
O1—D—A^xiii	124.139 (8)	F^i—BNA—F	180.0
O1—D—A	124.138 (8)	M2^iii—O1—M1	89.49 (5)
O1—D—BNA^xiv	125.86 (6)	M2—O1—M1	89.49 (5)
O1—D—BNA	132.74 (6)	M2—O1—M2^iii	101.87 (6)
O1—D—O3^viii	103.19 (5)	D—O1—M1	117.94 (8)
O1—D—O3^xiii	103.19 (5)	D—O1—M2	124.11 (4)
O1—D—O4	105.43 (6)	D—O1—M2^iii	124.11 (4)
O1—D—O4^xv	105.43 (6)	M2^xvii—O2—M1^xvii	89.48 (4)
O1—D—F	177.11 (6)	M2^xvii—O2—M3^xvii	97.30 (5)
O3^xiii—D—M1	126.20 (4)	M3^xvii—O2—M1^xvii	96.34 (4)
O3^viii—D—M1	126.20 (4)	T2—O2—M1^xvii	119.91 (6)
O3^viii—D—A	44.55 (4)	T2—O2—M2^xvii	126.39 (7)
O3^xiii—D—A	114.66 (4)	T2—O2—M3^xvii	119.86 (7)
O3^xiii—D—A^xiii	44.55 (4)	D^xiii—O3—A	106.62 (5)
O3^viii—D—A^xiii	114.66 (4)	D^xiii—O3—BNA	99.83 (6)
O3^xiii—D—BNA	110.79 (4)	T2—O3—D^xiii	134.66 (7)
O3^viii—D—BNA^xiv	45.89 (4)	T2—O3—A	111.69 (6)
O3^xiii—D—BNA^xiv	45.89 (4)	T2—O3—BNA	94.55 (6)
O3^viii—D—BNA	110.79 (4)	BNA—O3—A	102.80 (4)
O3^viii—D—O3^xiii	86.14 (8)	D—O4—A	105.13 (5)
O3^viii—D—F	74.76 (4)	D—O4—BNA	99.15 (6)
O3^xiii—D—F	74.76 (4)	T2^iv—O4—D	141.03 (8)
O4^xv—D—M1	79.58 (4)	T2^iv—O4—A	110.05 (7)
O4—D—M1	79.58 (4)	T2^iv—O4—BNA	91.31 (6)
O4—D—A	45.90 (4)	BNA—O4—A	99.35 (4)
O4^xv—D—A	115.84 (4)	T1^viii—O5—T2	139.12 (9)
O4—D—A^xiii	115.83 (4)	T1^viii—O5—A	106.67 (6)
O4^xv—D—A^xiii	45.90 (4)	T1^viii—O5—A^i	109.00 (7)
O4^xv—D—BNA	47.20 (4)	T2—O5—A	93.80 (6)
O4—D—BNA^xiv	113.24 (4)	T2—O5—A^i	95.53 (6)
O4^xv—D—BNA^xiv	113.24 (4)	A^i—O5—A	110.70 (4)
O4—D—BNA	47.20 (4)	M4^xii—O6—M3^xiv	98.60 (5)
O4—D—O3^viii	86.76 (6)	M4—O6—M3^xiv	92.92 (5)
O4^xv—D—O3^viii	151.38 (6)	M4—O6—M4^xii	96.56 (5)
O4^xv—D—O3^xiii	86.76 (6)	T1—O6—M3^xiv	120.12 (6)
O4—D—O3^xiii	151.38 (6)	T1—O6—M4^xii	121.00 (6)
O4^xv—D—O4	86.32 (9)	T1—O6—M4	121.42 (6)
O4—D—F	76.62 (4)	T1^xi—O7—T1	137.56 (8)
O4^xv—D—F	76.62 (4)	T1^xi—O7—A	104.01 (6)
F—D—M1	147.145 (14)	T1—O7—A	100.41 (6)
F—D—A	55.812 (7)	M2—O8—H8	106.7 (14)
F—D—A^xiii	55.812 (7)	M3—O8—M2	94.80 (5)
F—D—BNA	50.155 (8)	M3—O8—M4	97.60 (5)
F—D—BNA^xiv	51.243 (8)	M3—O8—H8	112.9 (13)
O5^viii—T1—O7^xvi	106.72 (7)	M4—O8—M2	98.81 (5)
O5^viii—T1—O7	106.76 (7)	M4—O8—H8	137.7 (12)
O6—T1—O5^viii	111.78 (6)	D^xiii—F—D	180.0
O6—T1—O7	111.27 (6)	D^xiii—F—A	90.0
O6—T1—O7^xvi	111.23 (6)	D^xiii—F—A^xiii	90.0
O7^xvi—T1—O7	108.85 (5)	D—F—A	90.0
A—T2—A^i	90.382 (12)	D—F—A^xiii	90.0
BNA—T2—A	74.629 (12)	D^xiii—F—BNA^xiv	90.909 (10)
BNA—T2—A^i	74.514 (12)	D—F—BNA^xiv	89.091 (10)
O2—T2—A^i	131.99 (5)	D—F—BNA	90.909 (10)
O2—T2—A	127.60 (5)	D^xiii—F—BNA	89.091 (10)
O2—T2—BNA	136.86 (5)	A^xiii—F—A	180.0
O2—T2—O5	111.78 (7)	BNA^xiv—F—A	90.0
O3—T2—A^i	115.70 (5)	BNA—F—A^xiii	90.0
O3—T2—A	44.73 (5)	BNA—F—A	90.0
O3—T2—BNA	53.86 (5)	BNA^xiv—F—A^xiii	90.0
O3—T2—O2	112.21 (7)	BNA^xiv—F—BNA	180.0

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z; (iii) −x+2, −y+1, −z; (iv) −x+1, y, −z+1; (v) −x+1, −y+1, −z+1; (vi) x, −y+1, z−1; (vii) x, y, z−1; (viii) −x+2, y, −z+1; (ix) −x+2, y, −z; (x) −x+1, y, −z; (xi) x−1/2, −y+1/2, z; (xii) −x+5/2, −y+1/2, −z; (xiii) −x+2, −y+1, −z+1; (xiv) x+1, y, z; (xv) x, −y+1, z; (xvi) x+1/2, −y+1/2, z; (xvii) x, y, z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8···O3^viii	1.03 (2)	2.75 (2)	3.4923 (18)	129 (2)
O8—H8···O4	1.03 (2)	2.54 (2)	3.3854 (18)	138 (2)

Symmetry code: (viii) −x+2, y, −z+1.

(lb450)

Crystal data

0.5(Ca0.16F0.39Fe9.26H8K3.88Na3.76O60Si15.17Ti3.85)	F(000) = 1148
Mr = 1173.87	Dx = 3.095 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 5.3279 (2) Å	Cell parameters from 3843 reflections
b = 23.1472 (8) Å	θ = 1.8–36.6°
c = 10.3619 (5) Å	µ = 4.04 mm^−1
β = 99.662 (4)°	T = 293 K
V = 1259.78 (9) Å^3	Prism, brown
Z = 2	0.22 × 0.18 × 0.11 mm

Data collection

Saxi-CrysAlisPro-abstract goniometer imported SAXI images diffractometer	3045 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2488 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ω scans	θmax = 36.5°, θmin = 1.8°
Absorption correction: multi-scan CrysAlisPro 1.171.39.44a (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→8
Tmin = 0.774, Tmax = 1.000	k = −31→37
9394 measured reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	Only H-atom coordinates refined
wR(F^2) = 0.108	w = 1/[σ^2(Fo^2) + (0.0474P)^2 + 3.866P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
3045 reflections	Δρmax = 0.86 e Å^−3
136 parameters	Δρmin = −0.83 e Å^−3
2 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
M1	0.500000	0.500000	0.000000	0.0142 (6)	0.959 (10)
M2	1.000000	0.42545 (2)	0.000000	0.01056 (14)	0.922 (4)
M3	0.500000	0.35491 (3)	0.000000	0.01065 (18)	0.745 (4)
M4	1.000000	0.28608 (3)	0.000000	0.0119 (2)	0.649 (3)
D	0.93686 (10)	0.500000	0.28657 (6)	0.00758 (15)	0.962 (5)
T1	1.42116 (12)	0.28224 (3)	0.26433 (6)	0.00781 (18)	0.947 (5)
T2	0.57593 (11)	0.41439 (3)	0.72930 (6)	0.00785 (18)	0.950 (5)
A	1.000000	0.36130 (5)	0.500000	0.0280 (3)	0.970 (6)
BNA	0.500000	0.500000	0.500000	0.0156 (8)	0.919 (16)
BCA	0.500000	0.500000	0.500000	0.0156 (8)	0.081 (16)
O1	0.9034 (5)	0.500000	0.1175 (2)	0.0141 (4)
O2	0.6402 (3)	0.41794 (8)	0.88702 (17)	0.0138 (3)
O3	0.7981 (3)	0.44240 (9)	0.66077 (18)	0.0174 (4)
O4	0.6960 (4)	0.44240 (9)	0.32864 (19)	0.0195 (4)
O5	0.5532 (4)	0.34678 (8)	0.67649 (18)	0.0190 (4)
O6	1.3707 (3)	0.28252 (7)	0.10715 (16)	0.0120 (3)
O7	1.1868 (3)	0.25134 (9)	0.32242 (18)	0.0172 (4)
O8	0.8653 (3)	0.35240 (7)	0.10311 (18)	0.0141 (3)
F	1.000000	0.500000	0.500000	0.017 (4)*	0.195 (13)
H8	0.860 (7)	0.3631 (12)	0.194 (2)	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
M1	0.0096 (9)	0.0147 (10)	0.0176 (11)	0.000	0.0003 (7)	0.000
M2	0.0062 (2)	0.0115 (2)	0.0134 (2)	0.000	0.00010 (16)	0.000
M3	0.0074 (3)	0.0116 (3)	0.0130 (3)	0.000	0.0019 (2)	0.000
M4	0.0081 (3)	0.0129 (3)	0.0143 (4)	0.000	0.0011 (2)	0.000
D	0.0034 (2)	0.0100 (2)	0.0093 (2)	0.000	0.00082 (16)	0.000
T1	0.0051 (3)	0.0086 (3)	0.0095 (3)	−0.00029 (19)	0.0007 (2)	−0.00006 (19)
T2	0.0053 (3)	0.0084 (3)	0.0096 (3)	0.00013 (19)	0.00069 (19)	0.0002 (2)
A	0.0303 (5)	0.0291 (5)	0.0242 (5)	0.000	0.0035 (4)	0.000
BNA	0.0187 (11)	0.0156 (11)	0.0109 (10)	0.000	−0.0021 (6)	0.000
BCA	0.0187 (11)	0.0156 (11)	0.0109 (10)	0.000	−0.0021 (6)	0.000
O1	0.0103 (10)	0.0176 (11)	0.0138 (10)	0.000	0.0006 (8)	0.000
O2	0.0123 (7)	0.0166 (8)	0.0123 (7)	0.0001 (6)	0.0010 (6)	0.0000 (6)
O3	0.0130 (8)	0.0231 (9)	0.0166 (8)	−0.0086 (6)	0.0040 (6)	−0.0033 (7)
O4	0.0120 (7)	0.0263 (10)	0.0189 (9)	−0.0098 (7)	−0.0010 (6)	0.0033 (7)
O5	0.0307 (10)	0.0108 (7)	0.0144 (8)	−0.0003 (7)	0.0001 (7)	0.0000 (6)
O6	0.0097 (7)	0.0149 (7)	0.0112 (7)	0.0004 (5)	0.0015 (5)	−0.0002 (5)
O7	0.0119 (7)	0.0251 (9)	0.0147 (8)	−0.0068 (7)	0.0023 (6)	−0.0009 (7)
O8	0.0113 (7)	0.0169 (8)	0.0136 (7)	0.0003 (6)	0.0008 (6)	−0.0003 (6)

Geometric parameters (Å, º)

M1—M2^i	3.1740 (3)	D—O4	1.9500 (18)
M1—M2^ii	3.1740 (3)	D—O4^xv	1.9501 (18)
M1—M2	3.1740 (3)	D—F	2.1804 (6)
M1—M2^iii	3.1740 (3)	T1—O5^viii	1.6119 (19)
M1—M3	3.3585 (6)	T1—O6	1.6056 (18)
M1—M3^iii	3.3584 (6)	T1—O7^xvi	1.6382 (18)
M1—O1	2.286 (2)	T1—O7	1.6387 (18)
M1—O1^iii	2.286 (2)	T2—A^ii	3.7582 (7)
M1—O2^iv	2.4145 (18)	T2—A	3.7500 (7)
M1—O2^v	2.4145 (18)	T2—BNA	3.0681 (6)
M1—O2^vi	2.4145 (18)	T2—O2	1.6146 (18)
M1—O2^vii	2.4145 (18)	T2—O3	1.6150 (19)
M2—O1^i	2.2218 (16)	T2—O4^iv	1.6086 (19)
M2—O1	2.2217 (16)	T2—O5	1.6556 (19)
M2—O2^vii	2.0790 (18)	A—O3^viii	2.839 (2)
M2—O2^viii	2.0790 (18)	A—O3	2.839 (2)
M2—O8	2.1848 (18)	A—O4	2.887 (2)
M2—O8^ix	2.1848 (18)	A—O4^viii	2.887 (2)
M3—O2^vii	2.0859 (18)	A—O5^iv	3.215 (2)
M3—O2^iv	2.0859 (18)	A—O5^viii	3.254 (2)
M3—O6^ii	2.1845 (18)	A—O5	3.254 (2)
M3—O6^ix	2.1845 (18)	A—O5^xiv	3.215 (2)
M3—O8	2.0580 (18)	A—O7	3.387 (2)
M3—O8^x	2.0580 (18)	A—O7^viii	3.387 (2)
M4—O6^xi	2.1178 (18)	A—F	3.2105 (11)
M4—O6	2.0986 (17)	BNA—O3^xv	2.488 (2)
M4—O6^ix	2.0986 (17)	BNA—O3^iv	2.488 (2)
M4—O6^xii	2.1178 (18)	BNA—O3^v	2.488 (2)
M4—O8^ix	2.0665 (19)	BNA—O3	2.488 (2)
M4—O8	2.0665 (19)	BNA—O4^v	2.577 (2)
D—A	3.8810 (9)	BNA—O4^xv	2.577 (2)
D—A^xiii	3.8810 (9)	BNA—O4^iv	2.577 (2)
D—BNA	3.4693 (6)	BNA—O4	2.577 (2)
D—BNA^xiv	3.4155 (6)	BNA—F^ii	2.6640 (1)
D—O1	1.731 (3)	BNA—F	2.6640 (1)
D—O3^viii	1.9521 (18)	O8—H8	0.975 (17)
D—O3^xiii	1.9521 (18)
M2^ii—M1—M2^i	180.000 (15)	O3—T2—BNA	53.94 (7)
M2^i—M1—M2^iii	114.137 (15)	O3—T2—O5	104.63 (11)
M2^ii—M1—M2^iii	65.863 (15)	O4^iv—T2—M1^xvii	81.57 (7)
M2^i—M1—M2	65.864 (15)	O4^iv—T2—A	119.75 (8)
M2^ii—M1—M2	114.136 (15)	O4^iv—T2—A^ii	46.15 (8)
M2^iii—M1—M2	180.0	O4^iv—T2—BNA	57.12 (8)
M2—M1—M3^iii	122.933 (8)	O4^iv—T2—O2	112.46 (10)
M2^iii—M1—M3	122.931 (8)	O4^iv—T2—O3	110.78 (11)
M2^i—M1—M3^iii	57.069 (8)	O4^iv—T2—O5	104.26 (11)
M2^i—M1—M3	122.931 (8)	O5—T2—M1^xvii	141.75 (7)
M2^iii—M1—M3^iii	57.069 (8)	O5—T2—A^ii	58.35 (8)
M2^ii—M1—M3	57.069 (8)	O5—T2—A	59.96 (8)
M2—M1—M3	57.067 (8)	O5—T2—BNA	111.21 (7)
M2^ii—M1—M3^iii	122.931 (8)	O3^viii—A—T2	118.89 (5)
M3^iii—M1—M3	180.0	O3—A—T2	23.58 (4)
O1—M1—M2	44.42 (4)	O3—A—O3^viii	97.20 (8)
O1^iii—M1—M2^i	135.58 (4)	O3—A—O4	72.67 (6)
O1^iii—M1—M2^iii	44.42 (4)	O3—A—O4^viii	55.79 (5)
O1—M1—M2^i	44.42 (4)	O3^viii—A—O4^viii	72.67 (6)
O1—M1—M2^ii	135.58 (4)	O3^viii—A—O4	55.79 (5)
O1—M1—M2^iii	135.58 (4)	O3^viii—A—O5	141.56 (6)
O1^iii—M1—M2^ii	44.42 (4)	O3^viii—A—O5^iv	97.86 (5)
O1^iii—M1—M2	135.58 (4)	O3—A—O5	49.71 (5)
O1^iii—M1—M3^iii	90.0	O3^viii—A—O5^viii	49.71 (5)
O1—M1—M3	90.0	O3—A—O5^viii	141.56 (6)
O1^iii—M1—M3	90.0	O3—A—O5^xiv	97.86 (5)
O1—M1—M3^iii	90.0	O3^viii—A—O5^xiv	90.09 (5)
O1—M1—O1^iii	180.0	O3—A—O5^iv	90.09 (5)
O1—M1—O2^iv	94.67 (6)	O3^viii—A—O7^viii	172.20 (5)
O1—M1—O2^vii	85.33 (6)	O3—A—O7	172.20 (5)
O1^iii—M1—O2^vi	94.67 (6)	O3^viii—A—O7	90.19 (5)
O1^iii—M1—O2^iv	85.33 (6)	O3—A—O7^viii	90.19 (5)
O1—M1—O2^vi	85.33 (6)	O3—A—F	48.60 (4)
O1—M1—O2^v	94.67 (6)	O3^viii—A—F	48.60 (4)
O1^iii—M1—O2^vii	94.67 (6)	O4^viii—A—T2	74.50 (4)
O1^iii—M1—O2^v	85.33 (6)	O4—A—T2	80.85 (4)
O2^iv—M1—M2	84.28 (4)	O4^viii—A—O4	98.88 (8)
O2^vii—M1—M2^ii	84.28 (4)	O4—A—O5^viii	96.28 (5)
O2^vi—M1—M2	95.72 (4)	O4^viii—A—O5^viii	91.43 (5)
O2^vii—M1—M2^iii	139.08 (4)	O4—A—O5	91.43 (5)
O2^vi—M1—M2^ii	139.08 (4)	O4—A—O5^xiv	141.63 (6)
O2^vi—M1—M2^iii	84.28 (4)	O4^viii—A—O5^iv	141.63 (6)
O2^iv—M1—M2^i	139.08 (4)	O4—A—O5^iv	49.60 (5)
O2^v—M1—M2	139.08 (4)	O4^viii—A—O5	96.28 (5)
O2^v—M1—M2^ii	95.72 (4)	O4^viii—A—O5^xiv	49.60 (5)
O2^v—M1—M2^i	84.28 (4)	O4^viii—A—O7^viii	109.89 (5)
O2^v—M1—M2^iii	40.92 (4)	O4^viii—A—O7	129.58 (5)
O2^vii—M1—M2^i	95.72 (4)	O4—A—O7	109.89 (5)
O2^iv—M1—M2^ii	40.92 (4)	O4—A—O7^viii	129.58 (5)
O2^vii—M1—M2	40.92 (4)	O4^viii—A—F	49.44 (4)
O2^vi—M1—M2^i	40.92 (4)	O4—A—F	49.44 (4)
O2^iv—M1—M2^iii	95.72 (4)	O5^iv—A—T2	78.60 (4)
O2^v—M1—M3^iii	38.12 (4)	O5^xiv—A—T2	105.44 (4)
O2^vi—M1—M3^iii	38.12 (4)	O5—A—T2	26.13 (3)
O2^vi—M1—M3	141.88 (4)	O5^viii—A—T2	164.90 (4)
O2^iv—M1—M3	38.12 (4)	O5^xiv—A—O5	110.91 (6)
O2^v—M1—M3	141.88 (4)	O5^iv—A—O5	67.76 (6)
O2^iv—M1—M3^iii	141.88 (4)	O5^iv—A—O5^xiv	168.00 (7)
O2^vii—M1—M3^iii	141.88 (4)	O5—A—O5^viii	168.14 (7)
O2^vii—M1—M3	38.12 (4)	O5^iv—A—O5^viii	110.91 (6)
O2^vii—M1—O2^iv	76.25 (8)	O5^xiv—A—O5^viii	67.76 (6)
O2^vi—M1—O2^iv	180.0	O5^viii—A—O7^viii	122.50 (5)
O2^v—M1—O2^vi	76.25 (8)	O5—A—O7	122.50 (5)
O2^v—M1—O2^vii	180.00 (5)	O5^xiv—A—O7^viii	86.40 (5)
O2^v—M1—O2^iv	103.75 (8)	O5—A—O7^viii	46.17 (4)
O2^vii—M1—O2^vi	103.75 (8)	O5^viii—A—O7	46.17 (4)
M1^xiv—M2—M1	114.135 (15)	O5^xiv—A—O7	84.58 (5)
O1—M2—M1^xiv	81.34 (6)	O5^iv—A—O7	86.41 (5)
O1—M2—M1	46.06 (6)	O5^iv—A—O7^viii	84.58 (5)
O1^i—M2—M1	81.34 (6)	O7^viii—A—T2	68.82 (3)
O1^i—M2—M1^xiv	46.06 (6)	O7—A—T2	148.63 (4)
O1—M2—O1^i	78.09 (10)	O7^viii—A—O7	82.55 (7)
O2^viii—M2—M1^xiv	49.53 (5)	F—A—T2	70.871 (18)
O2^vii—M2—M1	49.53 (5)	F—A—O5	95.93 (4)
O2^vii—M2—M1^xiv	137.74 (5)	F—A—O5^iv	96.00 (4)
O2^viii—M2—M1	137.74 (5)	F—A—O5^xiv	96.00 (4)
O2^viii—M2—O1	91.88 (8)	F—A—O5^viii	95.93 (4)
O2^vii—M2—O1	95.57 (8)	F—A—O7^viii	138.72 (3)
O2^viii—M2—O1^i	95.57 (8)	F—A—O7	138.72 (3)
O2^vii—M2—O1^i	91.88 (8)	T2—BNA—T2^iv	99.53 (2)
O2^vii—M2—O2^viii	170.40 (10)	O3—BNA—T2	31.66 (4)
O2^viii—M2—O8^ix	82.13 (7)	O3^v—BNA—T2^iv	80.87 (5)
O2^vii—M2—O8^ix	90.42 (7)	O3^iv—BNA—T2^iv	31.66 (4)
O2^viii—M2—O8	90.42 (7)	O3^xv—BNA—T2	80.87 (5)
O2^vii—M2—O8	82.13 (7)	O3^v—BNA—T2	148.34 (4)
O8^ix—M2—M1	139.94 (5)	O3—BNA—T2^iv	99.14 (4)
O8—M2—M1^xiv	139.94 (5)	O3^xv—BNA—T2^iv	148.34 (4)
O8^ix—M2—M1^xiv	94.37 (5)	O3^iv—BNA—T2	99.13 (5)
O8—M2—M1	94.37 (5)	O3^xv—BNA—O3^v	115.17 (8)
O8—M2—O1^i	174.00 (8)	O3^v—BNA—O3	180.0
O8—M2—O1	101.99 (7)	O3^iv—BNA—O3	115.17 (8)
O8^ix—M2—O1^i	101.99 (7)	O3^xv—BNA—O3	64.83 (8)
O8^ix—M2—O1	174.00 (8)	O3^xv—BNA—O3^iv	180.00 (8)
O8^ix—M2—O8	78.57 (9)	O3^iv—BNA—O3^v	64.83 (8)
O2^vii—M3—M1	45.61 (5)	O3^iv—BNA—O4^iv	84.09 (6)
O2^iv—M3—M1	45.61 (5)	O3^v—BNA—O4^iv	116.85 (6)
O2^iv—M3—O2^vii	91.23 (10)	O3—BNA—O4^v	95.91 (6)
O2^vii—M3—O6^ix	94.48 (7)	O3—BNA—O4^iv	63.15 (6)
O2^iv—M3—O6^ii	94.48 (7)	O3^iv—BNA—O4^v	116.85 (6)
O2^vii—M3—O6^ii	174.28 (7)	O3^xv—BNA—O4	116.85 (6)
O2^iv—M3—O6^ix	174.28 (7)	O3—BNA—O4^xv	116.85 (6)
O6^ii—M3—M1	140.09 (5)	O3^xv—BNA—O4^xv	84.09 (6)
O6^ix—M3—M1	140.09 (5)	O3^v—BNA—O4^v	84.09 (6)
O6^ix—M3—O6^ii	79.81 (9)	O3^v—BNA—O4	95.91 (6)
O8—M3—M1	91.62 (5)	O3^iv—BNA—O4	63.15 (6)
O8^x—M3—M1	91.62 (5)	O3^xv—BNA—O4^iv	95.91 (6)
O8—M3—O2^vii	85.10 (7)	O3^iv—BNA—O4^xv	95.91 (6)
O8^x—M3—O2^iv	85.10 (7)	O3^v—BNA—O4^xv	63.15 (6)
O8^x—M3—O2^vii	97.18 (7)	O3—BNA—O4	84.09 (6)
O8—M3—O2^iv	97.18 (7)	O3^xv—BNA—O4^v	63.15 (6)
O8—M3—O6^ii	93.78 (7)	O3—BNA—F^ii	121.75 (4)
O8^x—M3—O6^ii	83.73 (7)	O3^iv—BNA—F^ii	58.25 (4)
O8^x—M3—O6^ix	93.78 (7)	O3^v—BNA—F	121.75 (4)
O8—M3—O6^ix	83.73 (7)	O3—BNA—F	58.25 (4)
O8—M3—O8^x	176.77 (10)	O3^iv—BNA—F	121.75 (4)
O6^ix—M4—O6^xi	83.56 (7)	O3^xv—BNA—F^ii	121.75 (4)
O6—M4—O6^xii	83.56 (7)	O3^xv—BNA—F	58.25 (4)
O6^xii—M4—O6^xi	82.87 (9)	O3^v—BNA—F^ii	58.25 (4)
O6^ix—M4—O6	175.49 (10)	O4—BNA—T2	100.57 (5)
O6—M4—O6^xi	93.05 (6)	O4—BNA—T2^iv	31.61 (4)
O6^ix—M4—O6^xii	93.05 (6)	O4^iv—BNA—T2	31.61 (4)
O8^ix—M4—O6^ix	97.66 (7)	O4^iv—BNA—T2^iv	100.57 (5)
O8—M4—O6^xii	178.68 (7)	O4^v—BNA—T2^iv	148.39 (4)
O8^ix—M4—O6	85.71 (7)	O4^v—BNA—T2	79.43 (5)
O8—M4—O6^ix	85.71 (7)	O4^xv—BNA—T2	148.39 (4)
O8^ix—M4—O6^xi	178.68 (7)	O4^xv—BNA—T2^iv	79.43 (5)
O8^ix—M4—O6^xii	96.55 (7)	O4^v—BNA—O4^xv	117.70 (9)
O8—M4—O6	97.66 (7)	O4^iv—BNA—O4	117.70 (9)
O8—M4—O6^xi	96.55 (7)	O4^v—BNA—O4	180.0
O8—M4—O8^ix	84.05 (10)	O4^xv—BNA—O4^iv	180.00 (8)
M1—D—A	118.142 (11)	O4^v—BNA—O4^iv	62.30 (9)
M1—D—A^xiii	118.141 (11)	O4^xv—BNA—O4	62.30 (9)
M1—D—BNA	96.933 (13)	O4—BNA—F^ii	121.38 (4)
A—D—A^xiii	111.64 (2)	O4^xv—BNA—F^ii	121.38 (4)
BNA^xiv—D—M1	161.666 (18)	O4^iv—BNA—F	121.38 (4)
BNA^xiv—D—A^xiii	69.410 (10)	O4^xv—BNA—F	58.62 (4)
BNA—D—A	68.901 (10)	O4^iv—BNA—F^ii	58.62 (4)
BNA^xiv—D—A	69.410 (10)	O4^v—BNA—F^ii	58.62 (4)
BNA—D—A^xiii	68.901 (10)	O4—BNA—F	58.62 (4)
BNA^xiv—D—BNA	101.401 (15)	O4^v—BNA—F	121.38 (4)
O1—D—M1	35.83 (8)	F—BNA—T2^iv	90.107 (12)
O1—D—A	124.132 (12)	F—BNA—T2	89.892 (12)
O1—D—A^xiii	124.132 (12)	F^ii—BNA—T2	90.108 (12)
O1—D—BNA	132.76 (8)	F^ii—BNA—T2^iv	89.893 (12)
O1—D—BNA^xiv	125.84 (8)	F^ii—BNA—F	180.0
O1—D—O3^viii	103.28 (8)	M2—O1—M1	89.52 (7)
O1—D—O3^xiii	103.28 (8)	M2^i—O1—M1	89.52 (7)
O1—D—O4	105.45 (8)	M2^i—O1—M2	101.91 (10)
O1—D—O4^xv	105.45 (8)	D—O1—M1	117.86 (12)
O1—D—F	177.08 (9)	D—O1—M2^i	124.11 (7)
O3^xiii—D—M1	126.31 (6)	D—O1—M2	124.11 (7)
O3^viii—D—M1	126.31 (6)	M2^xvii—O2—M1^xvii	89.55 (7)
O3^xiii—D—A	114.60 (6)	M2^xvii—O2—M3^xvii	97.22 (7)
O3^viii—D—A	44.46 (6)	M3^xvii—O2—M1^xvii	96.26 (7)
O3^viii—D—A^xiii	114.60 (6)	T2—O2—M1^xvii	120.03 (10)
O3^xiii—D—A^xiii	44.45 (6)	T2—O2—M2^xvii	126.38 (10)
O3^viii—D—BNA	110.67 (6)	T2—O2—M3^xvii	119.83 (10)
O3^xiii—D—BNA^xiv	45.85 (6)	D^xiii—O3—A	106.75 (7)
O3^xiii—D—BNA	110.67 (6)	D^xiii—O3—BNA	99.89 (8)
O3^viii—D—BNA^xiv	45.85 (6)	T2—O3—D^xiii	134.47 (11)
O3^viii—D—O3^xiii	86.16 (12)	T2—O3—A	111.74 (9)
O3^xiii—D—F	74.65 (6)	T2—O3—BNA	94.40 (9)
O3^viii—D—F	74.65 (6)	BNA—O3—A	102.93 (6)
O4^xv—D—M1	79.53 (6)	D—O4—A	105.05 (8)
O4—D—M1	79.53 (6)	D—O4—BNA	99.11 (8)
O4—D—A	45.92 (6)	T2^iv—O4—D	141.03 (12)
O4^xv—D—A	115.82 (7)	T2^iv—O4—A	110.16 (10)
O4—D—A^xiii	115.82 (7)	T2^iv—O4—BNA	91.27 (9)
O4^xv—D—A^xiii	45.92 (6)	BNA—O4—A	99.38 (6)
O4—D—BNA	47.18 (6)	T1^viii—O5—T2	138.89 (13)
O4^xv—D—BNA	47.18 (6)	T1^viii—O5—A^ii	108.93 (9)
O4^xv—D—BNA^xiv	113.26 (6)	T1^viii—O5—A	106.63 (9)
O4—D—BNA^xiv	113.26 (6)	T2—O5—A^ii	95.65 (9)
O4^xv—D—O3^xiii	86.72 (9)	T2—O5—A	93.91 (9)
O4^xv—D—O3^viii	151.26 (8)	A^ii—O5—A	110.91 (6)
O4—D—O3^viii	86.72 (9)	M4^xii—O6—M3^xiv	98.66 (7)
O4—D—O3^xiii	151.26 (8)	M4—O6—M3^xiv	92.87 (7)
O4—D—O4^xv	86.26 (13)	M4—O6—M4^xii	96.44 (7)
O4—D—F	76.62 (6)	T1—O6—M3^xiv	120.35 (9)
O4^xv—D—F	76.62 (6)	T1—O6—M4^xii	121.00 (10)
F—D—M1	147.09 (2)	T1—O6—M4	121.29 (9)
F—D—A^xiii	55.818 (11)	T1^xi—O7—T1	137.45 (12)
F—D—A	55.818 (11)	T1—O7—A	100.55 (8)
F—D—BNA^xiv	51.248 (11)	T1^xi—O7—A	103.99 (8)
F—D—BNA	50.154 (11)	M2—O8—H8	110 (2)
O5^viii—T1—O7^xvi	106.68 (11)	M3—O8—M2	94.81 (7)
O5^viii—T1—O7	106.62 (11)	M3—O8—M4	97.63 (8)
O6—T1—O5^viii	111.79 (10)	M3—O8—H8	108 (2)
O6—T1—O7	111.48 (9)	M4—O8—M2	98.69 (8)
O6—T1—O7^xvi	111.22 (9)	M4—O8—H8	139.0 (17)
O7^xvi—T1—O7	108.82 (7)	D—F—D^xiii	180.0
M1^xvii—T2—A^ii	119.872 (19)	D^xiii—F—A^xiii	90.0
M1^xvii—T2—A	148.56 (2)	D—F—A	90.0
A—T2—A^ii	90.408 (18)	D—F—A^xiii	90.0
BNA—T2—M1^xvii	103.657 (18)	D^xiii—F—A	90.0
BNA—T2—A^ii	74.578 (18)	D^xiii—F—BNA^xiv	90.913 (15)
BNA—T2—A	74.702 (18)	D—F—BNA	90.913 (15)
O2—T2—M1^xvii	36.52 (7)	D^xiii—F—BNA	89.087 (15)
O2—T2—A	127.59 (7)	D—F—BNA^xiv	89.087 (15)
O2—T2—A^ii	131.95 (7)	A—F—A^xiii	180.0
O2—T2—BNA	136.80 (7)	BNA^xiv—F—A^xiii	90.0
O2—T2—O3	112.21 (10)	BNA^xiv—F—A	90.0
O2—T2—O5	111.96 (10)	BNA—F—A	90.0
O3—T2—M1^xvii	108.41 (7)	BNA—F—A^xiii	90.0
O3—T2—A	44.67 (7)	BNA^xiv—F—BNA	180.0
O3—T2—A^ii	115.74 (7)

Symmetry codes: (i) −x+2, −y+1, −z; (ii) x−1, y, z; (iii) −x+1, −y+1, −z; (iv) −x+1, y, −z+1; (v) −x+1, −y+1, −z+1; (vi) x, −y+1, z−1; (vii) x, y, z−1; (viii) −x+2, y, −z+1; (ix) −x+2, y, −z; (x) −x+1, y, −z; (xi) x−1/2, −y+1/2, z; (xii) −x+5/2, −y+1/2, −z; (xiii) −x+2, −y+1, −z+1; (xiv) x+1, y, z; (xv) x, −y+1, z; (xvi) x+1/2, −y+1/2, z; (xvii) x, y, z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8···O3^viii	0.98 (2)	2.84 (3)	3.474 (3)	124 (3)
O8—H8···O4	0.98 (2)	2.55 (2)	3.365 (3)	141 (2)

Symmetry code: (viii) −x+2, y, −z+1.

(lb500)

Crystal data

Ca0.17F0.44Fe9.33H8K3.87Na3.77O60Si15.18Ti3.89	F(000) = 1151
Mr = 2355.04	Dx = 3.029 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 5.3673 (5) Å	Cell parameters from 3432 reflections
b = 23.345 (2) Å	θ = 1.9–36.1°
c = 10.4559 (11) Å	µ = 3.97 mm^−1
β = 99.727 (11)°	T = 293 K
V = 1291.3 (2) Å^3	Prism, brown
Z = 1	0.22 × 0.18 × 0.11 mm

Data collection

Saxi-CrysAlisPro-abstract goniometer imported SAXI images diffractometer	3049 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2397 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
ω scans	θmax = 36.3°, θmin = 1.8°
Absorption correction: multi-scan CrysAlisPro 1.171.39.44a (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→8
Tmin = 0.819, Tmax = 1.000	k = −38→36
11684 measured reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.061	Only H-atom coordinates refined
wR(F^2) = 0.104	w = 1/[σ^2(Fo^2) + (0.0252P)^2 + 9.566P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max < 0.001
3049 reflections	Δρmax = 0.79 e Å^−3
136 parameters	Δρmin = −1.44 e Å^−3
2 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
M1	0.500000	0.500000	0.000000	0.0132 (8)	0.973 (12)
M2	1.000000	0.42559 (3)	0.000000	0.00878 (19)	0.904 (5)
M3	0.500000	0.35497 (4)	0.000000	0.0090 (2)	0.751 (4)
M4	1.000000	0.28621 (4)	0.000000	0.0098 (3)	0.678 (4)
D	0.93714 (14)	0.500000	0.28722 (7)	0.00545 (19)	0.973 (5)
T1	1.42163 (15)	0.28224 (4)	0.26406 (8)	0.0059 (2)	0.945 (6)
T2	0.57593 (16)	0.41426 (4)	0.72946 (8)	0.0062 (2)	0.952 (6)
A	1.000000	0.36145 (6)	0.500000	0.0262 (4)	0.967 (6)
BNA	0.500000	0.500000	0.500000	0.0131 (10)	0.913 (19)
BCA	0.500000	0.500000	0.500000	0.0131 (10)	0.087 (19)
O1	0.9040 (6)	0.500000	0.1179 (3)	0.0124 (6)
O2	0.6409 (4)	0.41775 (10)	0.8872 (2)	0.0127 (4)
O3	0.7978 (5)	0.44242 (11)	0.6607 (2)	0.0166 (5)
O4	0.6960 (5)	0.44239 (11)	0.3282 (2)	0.0185 (5)
O5	0.5533 (5)	0.34672 (10)	0.6771 (2)	0.0175 (5)
O6	1.3706 (4)	0.28246 (9)	0.1069 (2)	0.0101 (4)
O7	1.1884 (4)	0.25112 (11)	0.3219 (2)	0.0152 (5)
O8	0.8644 (4)	0.35264 (10)	0.1030 (2)	0.0135 (5)
F	1.000000	0.500000	0.500000	0.023 (6)*	0.219 (17)
H8	0.862 (9)	0.3650 (15)	0.194 (2)	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
M1	0.0110 (14)	0.0103 (13)	0.0166 (14)	0.000	−0.0029 (10)	0.000
M2	0.0055 (3)	0.0099 (3)	0.0108 (3)	0.000	0.0010 (2)	0.000
M3	0.0074 (4)	0.0088 (4)	0.0112 (4)	0.000	0.0027 (3)	0.000
M4	0.0075 (4)	0.0099 (4)	0.0122 (4)	0.000	0.0024 (3)	0.000
D	0.0020 (3)	0.0075 (3)	0.0072 (3)	0.000	0.0017 (2)	0.000
T1	0.0051 (4)	0.0065 (4)	0.0062 (4)	−0.0002 (3)	0.0014 (3)	−0.0007 (3)
T2	0.0048 (4)	0.0062 (4)	0.0078 (4)	0.0008 (3)	0.0019 (3)	0.0007 (3)
A	0.0296 (7)	0.0278 (7)	0.0211 (6)	0.000	0.0044 (5)	0.000
BNA	0.0171 (15)	0.0121 (14)	0.0086 (13)	0.000	−0.0017 (9)	0.000
BCA	0.0171 (15)	0.0121 (14)	0.0086 (13)	0.000	−0.0017 (9)	0.000
O1	0.0104 (14)	0.0151 (15)	0.0125 (14)	0.000	0.0041 (11)	0.000
O2	0.0113 (10)	0.0152 (10)	0.0114 (10)	0.0001 (8)	0.0013 (8)	−0.0002 (8)
O3	0.0135 (11)	0.0212 (12)	0.0157 (11)	−0.0091 (9)	0.0045 (9)	−0.0027 (9)
O4	0.0133 (11)	0.0249 (13)	0.0167 (11)	−0.0090 (9)	0.0011 (9)	0.0044 (9)
O5	0.0306 (14)	0.0090 (10)	0.0125 (10)	−0.0004 (9)	0.0029 (9)	−0.0004 (8)
O6	0.0089 (9)	0.0118 (10)	0.0099 (9)	0.0003 (8)	0.0025 (7)	0.0000 (8)
O7	0.0104 (10)	0.0219 (12)	0.0133 (10)	−0.0067 (9)	0.0021 (8)	−0.0003 (9)
O8	0.0127 (10)	0.0166 (12)	0.0119 (10)	0.0001 (8)	0.0037 (8)	−0.0005 (8)

Geometric parameters (Å, º)

M1—M2^i	3.1968 (4)	D—O4^xv	1.963 (2)
M1—M2^ii	3.1968 (4)	D—O4	1.963 (2)
M1—M2	3.1968 (4)	D—F	2.1931 (8)
M1—M2^iii	3.1968 (4)	T1—O5^viii	1.623 (2)
M1—M3	3.3858 (9)	T1—O6	1.620 (2)
M1—M3^iii	3.3857 (9)	T1—O7	1.648 (2)
M1—O1^iii	2.306 (3)	T1—O7^xvi	1.653 (2)
M1—O1	2.306 (3)	T2—A^ii	3.7849 (11)
M1—O2^iv	2.439 (2)	T2—A	3.7818 (10)
M1—O2^v	2.439 (2)	T2—BNA	3.0981 (9)
M1—O2^vi	2.439 (2)	T2—O2	1.629 (2)
M1—O2^vii	2.439 (2)	T2—O3	1.630 (2)
M2—O1^i	2.240 (2)	T2—O4^iv	1.621 (3)
M2—O1	2.240 (2)	T2—O5	1.667 (2)
M2—O2^vii	2.090 (2)	A—O3^viii	2.862 (3)
M2—O2^viii	2.090 (2)	A—O3	2.862 (3)
M2—O8^ix	2.203 (2)	A—O4^viii	2.910 (3)
M2—O8	2.203 (2)	A—O4	2.910 (3)
M3—O2^vii	2.101 (2)	A—O5^iv	3.242 (3)
M3—O2^iv	2.101 (2)	A—O5^viii	3.286 (3)
M3—O6^ii	2.204 (2)	A—O5	3.286 (3)
M3—O6^ix	2.204 (2)	A—O5^xiv	3.242 (3)
M3—O8^x	2.068 (2)	A—O7	3.429 (3)
M3—O8	2.068 (2)	A—O7^viii	3.429 (3)
M4—O6^xi	2.136 (2)	A—F	3.2345 (14)
M4—O6	2.112 (2)	BNA—O3^xv	2.505 (3)
M4—O6^ix	2.112 (2)	BNA—O3^iv	2.505 (3)
M4—O6^xii	2.136 (2)	BNA—O3^v	2.505 (3)
M4—O8	2.088 (2)	BNA—O3	2.505 (3)
M4—O8^ix	2.088 (2)	BNA—O4	2.604 (3)
D—A^xiii	3.9079 (12)	BNA—O4^v	2.604 (3)
D—A	3.9079 (12)	BNA—O4^xv	2.604 (3)
D—BNA	3.4955 (8)	BNA—O4^iv	2.604 (3)
D—BNA^xiv	3.4359 (9)	BNA—F^ii	2.6837 (3)
D—O1	1.749 (3)	BNA—F	2.6837 (3)
D—O3^xiii	1.966 (2)	O8—H8	0.992 (18)
D—O3^viii	1.966 (2)
M2^ii—M1—M2^i	180.00 (2)	O3—T2—O5	104.76 (13)
M2^i—M1—M2^iii	114.17 (2)	O4^iv—T2—A	119.78 (9)
M2^ii—M1—M2^iii	65.83 (2)	O4^iv—T2—A^ii	46.26 (10)
M2^iii—M1—M2	180.00 (2)	O4^iv—T2—BNA	57.17 (10)
M2^ii—M1—M2	114.17 (2)	O4^iv—T2—O2	112.44 (13)
M2^i—M1—M2	65.83 (2)	O4^iv—T2—O3	110.57 (14)
M2^iii—M1—M3	122.914 (11)	O4^iv—T2—O5	104.49 (14)
M2—M1—M3^iii	122.914 (11)	O5—T2—A^ii	58.49 (10)
M2—M1—M3	57.086 (11)	O5—T2—A	60.10 (9)
M2^iii—M1—M3^iii	57.086 (11)	O5—T2—BNA	111.36 (9)
M2^ii—M1—M3^iii	122.914 (11)	O3^viii—A—T2	119.06 (6)
M2^ii—M1—M3	57.086 (11)	O3—A—T2	23.60 (5)
M2^i—M1—M3	122.914 (11)	O3—A—O3^viii	97.32 (10)
M2^i—M1—M3^iii	57.086 (11)	O3^viii—A—O4	55.77 (7)
M3^iii—M1—M3	180.0	O3—A—O4	72.82 (8)
O1^iii—M1—M2^i	135.52 (5)	O3^viii—A—O4^viii	72.82 (8)
O1^iii—M1—M2^ii	44.48 (5)	O3—A—O4^viii	55.77 (7)
O1—M1—M2^ii	135.52 (5)	O3—A—O5^iv	90.21 (7)
O1—M1—M2	44.48 (5)	O3^viii—A—O5^iv	97.84 (7)
O1—M1—M2^iii	135.52 (5)	O3—A—O5^xiv	97.84 (7)
O1^iii—M1—M2^iii	44.48 (5)	O3^viii—A—O5^viii	49.68 (6)
O1—M1—M2^i	44.48 (5)	O3—A—O5^viii	141.74 (7)
O1^iii—M1—M2	135.52 (5)	O3^viii—A—O5^xiv	90.21 (7)
O1^iii—M1—M3^iii	90.0	O3—A—O5	49.68 (6)
O1—M1—M3	90.0	O3^viii—A—O5	141.74 (7)
O1^iii—M1—M3	90.0	O3—A—O7^viii	90.09 (6)
O1—M1—M3^iii	90.0	O3^viii—A—O7	90.09 (6)
O1^iii—M1—O1	180.0	O3—A—O7	172.20 (7)
O1—M1—O2^iv	94.70 (7)	O3^viii—A—O7^viii	172.20 (7)
O1^iii—M1—O2^v	85.30 (7)	O3—A—F	48.66 (5)
O1—M1—O2^v	94.70 (7)	O3^viii—A—F	48.66 (5)
O1—M1—O2^vi	85.30 (7)	O4^viii—A—T2	74.43 (5)
O1—M1—O2^vii	85.30 (7)	O4—A—T2	81.09 (6)
O1^iii—M1—O2^iv	85.30 (7)	O4—A—O4^viii	99.02 (11)
O1^iii—M1—O2^vi	94.70 (7)	O4—A—O5^viii	96.11 (7)
O1^iii—M1—O2^vii	94.70 (7)	O4—A—O5^xiv	141.76 (7)
O2^v—M1—M2^iii	40.84 (6)	O4—A—O5	91.69 (7)
O2^v—M1—M2	139.16 (6)	O4^viii—A—O5^viii	91.69 (7)
O2^vii—M1—M2^ii	84.33 (6)	O4^viii—A—O5	96.11 (7)
O2^vii—M1—M2^i	95.67 (6)	O4^viii—A—O5^xiv	49.63 (6)
O2^vi—M1—M2^i	40.84 (6)	O4^viii—A—O5^iv	141.76 (7)
O2^iv—M1—M2	84.33 (6)	O4—A—O5^iv	49.63 (6)
O2^iv—M1—M2^iii	95.67 (6)	O4—A—O7^viii	129.55 (6)
O2^v—M1—M2^i	84.33 (6)	O4^viii—A—O7	129.55 (6)
O2^vii—M1—M2^iii	139.16 (6)	O4^viii—A—O7^viii	109.79 (7)
O2^vii—M1—M2	40.84 (6)	O4—A—O7	109.80 (7)
O2^vi—M1—M2^iii	84.33 (6)	O4^viii—A—F	49.51 (5)
O2^vi—M1—M2	95.67 (6)	O4—A—F	49.51 (5)
O2^vi—M1—M2^ii	139.16 (6)	O5^iv—A—T2	78.79 (5)
O2^iv—M1—M2^ii	40.84 (6)	O5^xiv—A—T2	105.28 (5)
O2^v—M1—M2^ii	95.67 (6)	O5—A—T2	26.08 (4)
O2^iv—M1—M2^i	139.16 (6)	O5^viii—A—T2	165.10 (6)
O2^v—M1—M3	141.92 (5)	O5^iv—A—O5	68.02 (7)
O2^vii—M1—M3^iii	141.92 (5)	O5^iv—A—O5^viii	110.62 (7)
O2^iv—M1—M3	38.08 (5)	O5^xiv—A—O5^viii	68.02 (7)
O2^v—M1—M3^iii	38.08 (5)	O5^xiv—A—O5	110.62 (7)
O2^vi—M1—M3	141.92 (5)	O5—A—O5^viii	167.99 (9)
O2^vi—M1—M3^iii	38.08 (5)	O5^iv—A—O5^xiv	167.83 (9)
O2^vii—M1—M3	38.08 (5)	O5^xiv—A—O7	84.53 (6)
O2^iv—M1—M3^iii	141.92 (5)	O5^iv—A—O7	86.33 (6)
O2^v—M1—O2^vii	180.00 (9)	O5^xiv—A—O7^viii	86.33 (6)
O2^v—M1—O2^vi	76.17 (11)	O5^viii—A—O7^viii	122.53 (7)
O2^vii—M1—O2^iv	76.17 (11)	O5^viii—A—O7	45.99 (6)
O2^vi—M1—O2^iv	180.00 (9)	O5^iv—A—O7^viii	84.53 (6)
O2^vii—M1—O2^vi	103.83 (11)	O5—A—O7	122.53 (7)
O2^v—M1—O2^iv	103.83 (11)	O5—A—O7^viii	45.99 (6)
M1^xiv—M2—M1	114.17 (2)	O7—A—T2	148.61 (5)
O1^i—M2—M1	81.36 (8)	O7^viii—A—T2	68.66 (4)
O1—M2—M1	46.16 (8)	O7^viii—A—O7	82.63 (8)
O1^i—M2—M1^xiv	46.16 (8)	F—A—T2	70.97 (2)
O1—M2—M1^xiv	81.36 (8)	F—A—O5	96.00 (5)
O1—M2—O1^i	78.31 (12)	F—A—O5^xiv	96.09 (5)
O2^viii—M2—M1^xiv	49.73 (6)	F—A—O5^iv	96.09 (5)
O2^vii—M2—M1	49.73 (6)	F—A—O5^viii	96.01 (5)
O2^viii—M2—M1	137.86 (7)	F—A—O7^viii	138.68 (4)
O2^vii—M2—M1^xiv	137.86 (7)	F—A—O7	138.68 (4)
O2^vii—M2—O1^i	91.91 (11)	T2^xv—BNA—T2^iv	180.0
O2^viii—M2—O1^i	95.88 (11)	O3^iv—BNA—T2^iv	31.63 (5)
O2^vii—M2—O1	95.88 (11)	O3^xv—BNA—T2^iv	148.37 (5)
O2^viii—M2—O1	91.91 (11)	O3^iv—BNA—T2^xv	148.37 (5)
O2^vii—M2—O2^viii	169.95 (13)	O3^xv—BNA—T2^xv	31.63 (5)
O2^viii—M2—O8	90.34 (9)	O3^v—BNA—T2^iv	80.90 (6)
O2^vii—M2—O8^ix	90.33 (9)	O3—BNA—T2^iv	99.10 (6)
O2^vii—M2—O8	81.88 (9)	O3^v—BNA—T2^xv	99.10 (6)
O2^viii—M2—O8^ix	81.88 (9)	O3—BNA—T2^xv	80.90 (6)
O8—M2—M1	94.21 (6)	O3^v—BNA—O3	180.00 (10)
O8^ix—M2—M1	140.06 (6)	O3^xv—BNA—O3	64.90 (11)
O8^ix—M2—M1^xiv	94.21 (6)	O3^iv—BNA—O3^v	64.90 (11)
O8—M2—M1^xiv	140.06 (6)	O3^iv—BNA—O3	115.10 (11)
O8^ix—M2—O1	173.78 (10)	O3^xv—BNA—O3^v	115.10 (11)
O8—M2—O1^i	173.78 (10)	O3^xv—BNA—O3^iv	180.00 (10)
O8^ix—M2—O1^i	101.82 (9)	O3—BNA—O4	84.21 (8)
O8—M2—O1	101.81 (9)	O3^iv—BNA—O4^iv	84.21 (8)
O8—M2—O8^ix	78.75 (12)	O3^v—BNA—O4	95.79 (8)
O2^iv—M3—M1	45.75 (6)	O3^iv—BNA—O4^v	116.96 (8)
O2^vii—M3—M1	45.75 (6)	O3^xv—BNA—O4^iv	95.79 (8)
O2^iv—M3—O2^vii	91.51 (13)	O3—BNA—O4^iv	63.04 (7)
O2^vii—M3—O6^ii	174.06 (9)	O3^iv—BNA—O4	63.04 (7)
O2^vii—M3—O6^ix	94.41 (9)	O3^v—BNA—O4^xv	63.04 (8)
O2^iv—M3—O6^ix	174.06 (9)	O3—BNA—O4^v	95.79 (8)
O2^iv—M3—O6^ii	94.41 (9)	O3^xv—BNA—O4^v	63.04 (7)
O6^ii—M3—M1	140.17 (6)	O3^xv—BNA—O4	116.96 (8)
O6^ix—M3—M1	140.17 (6)	O3^xv—BNA—O4^xv	84.21 (8)
O6^ix—M3—O6^ii	79.67 (11)	O3^iv—BNA—O4^xv	95.79 (8)
O8—M3—M1	91.51 (7)	O3—BNA—O4^xv	116.96 (8)
O8^x—M3—M1	91.51 (7)	O3^v—BNA—O4^v	84.21 (8)
O8—M3—O2^vii	84.95 (9)	O3^v—BNA—O4^iv	116.96 (8)
O8^x—M3—O2^iv	84.95 (9)	O3^xv—BNA—F	58.35 (5)
O8^x—M3—O2^vii	97.17 (9)	O3^iv—BNA—F^ii	58.35 (5)
O8—M3—O2^iv	97.16 (9)	O3—BNA—F	58.35 (5)
O8—M3—O6^ii	93.85 (9)	O3^xv—BNA—F^ii	121.65 (5)
O8^x—M3—O6^ii	83.82 (9)	O3^v—BNA—F	121.65 (5)
O8—M3—O6^ix	83.83 (9)	O3^v—BNA—F^ii	58.35 (5)
O8^x—M3—O6^ix	93.85 (9)	O3^iv—BNA—F	121.65 (5)
O8^x—M3—O8	176.99 (14)	O3—BNA—F^ii	121.65 (5)
O6^ix—M4—O6^xi	83.42 (9)	O4—BNA—T2^xv	148.46 (6)
O6^ix—M4—O6^xii	93.01 (8)	O4^iv—BNA—T2^iv	100.66 (6)
O6^xii—M4—O6^xi	82.74 (12)	O4^xv—BNA—T2^xv	100.66 (6)
O6—M4—O6^xii	83.41 (9)	O4^v—BNA—T2^iv	148.46 (6)
O6^ix—M4—O6	175.25 (13)	O4^xv—BNA—T2^iv	79.34 (6)
O6—M4—O6^xi	93.01 (8)	O4—BNA—T2^iv	31.54 (6)
O8^ix—M4—O6	85.67 (9)	O4^v—BNA—T2^xv	31.54 (6)
O8^ix—M4—O6^ix	97.88 (9)	O4^iv—BNA—T2^xv	79.34 (6)
O8—M4—O6^xii	178.59 (9)	O4—BNA—O4^xv	62.19 (11)
O8^ix—M4—O6^xi	178.59 (9)	O4^v—BNA—O4^xv	117.81 (11)
O8—M4—O6^ix	85.67 (9)	O4^xv—BNA—O4^iv	180.00 (10)
O8—M4—O6	97.88 (9)	O4—BNA—O4^iv	117.81 (11)
O8^ix—M4—O6^xii	96.61 (8)	O4—BNA—O4^v	180.0
O8—M4—O6^xi	96.61 (8)	O4^v—BNA—O4^iv	62.19 (11)
O8^ix—M4—O8	84.06 (13)	O4^v—BNA—F^ii	58.63 (5)
M1—D—A	118.127 (15)	O4—BNA—F^ii	121.37 (5)
M1—D—A^xiii	118.127 (15)	O4—BNA—F	58.63 (5)
M1—D—BNA	97.003 (19)	O4^v—BNA—F	121.37 (5)
A^xiii—D—A	111.72 (3)	O4^xv—BNA—F	58.63 (5)
BNA^xiv—D—M1	161.51 (2)	O4^iv—BNA—F^ii	58.63 (5)
BNA—D—A	68.920 (13)	O4^iv—BNA—F	121.37 (5)
BNA—D—A^xiii	68.920 (13)	O4^xv—BNA—F^ii	121.37 (5)
BNA^xiv—D—A^xiii	69.480 (14)	F^ii—BNA—T2^xv	90.040 (17)
BNA^xiv—D—A	69.480 (14)	F^ii—BNA—T2^iv	89.960 (17)
BNA^xiv—D—BNA	101.49 (2)	F—BNA—T2^xv	89.960 (17)
O1—D—M1	35.82 (11)	F—BNA—T2^iv	90.040 (17)
O1—D—A^xiii	124.087 (15)	F^ii—BNA—F	180.0
O1—D—A	124.087 (15)	M2—O1—M1	89.35 (10)
O1—D—BNA^xiv	125.69 (11)	M2^i—O1—M1	89.35 (10)
O1—D—BNA	132.82 (11)	M2^i—O1—M2	101.69 (12)
O1—D—O3^xiii	103.04 (11)	D—O1—M1	117.83 (16)
O1—D—O3^viii	103.04 (11)	D—O1—M2^i	124.30 (9)
O1—D—O4	105.24 (11)	D—O1—M2	124.30 (9)
O1—D—O4^xv	105.24 (11)	M2^xvii—O2—M1^xvii	89.43 (8)
O1—D—F	177.04 (11)	M2^xvii—O2—M3^xvii	97.44 (9)
O3^viii—D—M1	126.10 (8)	M3^xvii—O2—M1^xvii	96.16 (9)
O3^xiii—D—M1	126.10 (8)	T2—O2—M1^xvii	119.86 (12)
O3^xiii—D—A	114.78 (8)	T2—O2—M2^xvii	126.50 (13)
O3^viii—D—A	44.57 (7)	T2—O2—M3^xvii	119.84 (13)
O3^viii—D—A^xiii	114.78 (8)	D^xiii—O3—A	106.60 (10)
O3^xiii—D—A^xiii	44.57 (7)	D^xiii—O3—BNA	99.72 (10)
O3^viii—D—BNA	110.84 (7)	T2—O3—D^xiii	134.57 (15)
O3^xiii—D—BNA^xiv	45.94 (8)	T2—O3—A	111.74 (12)
O3^viii—D—BNA^xiv	45.94 (8)	T2—O3—BNA	94.68 (11)
O3^xiii—D—BNA	110.84 (7)	BNA—O3—A	102.89 (8)
O3^xiii—D—O3^viii	86.25 (16)	D—O4—A	104.95 (10)
O3^xiii—D—F	74.86 (7)	D—O4—BNA	98.91 (11)
O3^viii—D—F	74.86 (7)	T2^iv—O4—D	141.40 (16)
O4^xv—D—M1	79.37 (8)	T2^iv—O4—A	110.01 (12)
O4—D—M1	79.37 (8)	T2^iv—O4—BNA	91.29 (11)
O4—D—A	46.01 (8)	BNA—O4—A	99.17 (8)
O4^xv—D—A	116.06 (8)	T1^viii—O5—T2	139.14 (16)
O4—D—A^xiii	116.06 (8)	T1^viii—O5—A	106.80 (12)
O4^xv—D—A^xiii	46.01 (8)	T1^viii—O5—A^ii	108.90 (12)
O4^xv—D—BNA	47.39 (8)	T2—O5—A	93.82 (11)
O4—D—BNA^xiv	113.49 (8)	T2—O5—A^ii	95.51 (11)
O4^xv—D—BNA^xiv	113.49 (8)	A^ii—O5—A	110.62 (7)
O4—D—BNA	47.39 (8)	M4^xii—O6—M3^xiv	98.79 (9)
O4—D—O3^xiii	151.71 (11)	M4—O6—M3^xiv	92.82 (9)
O4^xv—D—O3^xiii	86.80 (11)	M4—O6—M4^xii	96.59 (9)
O4^xv—D—O3^viii	151.71 (11)	T1—O6—M3^xiv	120.20 (12)
O4—D—O3^viii	86.79 (11)	T1—O6—M4^xii	120.94 (12)
O4^xv—D—O4	86.47 (16)	T1—O6—M4	121.31 (12)
O4—D—F	76.86 (8)	T1—O7—T1^xi	137.57 (16)
O4^xv—D—F	76.86 (8)	T1—O7—A	100.39 (11)
F—D—M1	147.14 (3)	T1^xi—O7—A	103.65 (11)
F—D—A	55.861 (15)	M2—O8—H8	108 (3)
F—D—A^xiii	55.861 (15)	M3—O8—M2	94.98 (9)
F—D—BNA	50.141 (16)	M3—O8—M4	97.62 (10)
F—D—BNA^xiv	51.348 (17)	M3—O8—H8	109 (3)
O5^viii—T1—O7	106.80 (13)	M4—O8—M2	98.60 (9)
O5^viii—T1—O7^xvi	106.69 (14)	M4—O8—H8	140.4 (19)
O6—T1—O5^viii	111.74 (12)	D—F—D^xiii	180.00 (4)
O6—T1—O7^xvi	111.14 (12)	D—F—A^xiii	90.0
O6—T1—O7	111.42 (12)	D—F—A	90.0
O7—T1—O7^xvi	108.82 (9)	D^xiii—F—A^xiii	90.0
A—T2—A^ii	90.36 (2)	D^xiii—F—A	90.0
BNA—T2—A^ii	74.52 (2)	D—F—BNA^xiv	88.99 (2)
BNA—T2—A	74.57 (2)	D^xiii—F—BNA^xiv	91.01 (2)
O2—T2—A	127.56 (9)	D^xiii—F—BNA	88.99 (2)
O2—T2—A^ii	132.09 (9)	D—F—BNA	91.01 (2)
O2—T2—BNA	136.83 (9)	A—F—A^xiii	180.0
O2—T2—O3	112.28 (13)	BNA^xiv—F—A^xiii	90.0
O2—T2—O5	111.78 (13)	BNA—F—A	90.0
O3—T2—A^ii	115.53 (9)	BNA—F—A^xiii	90.0
O3—T2—A	44.66 (9)	BNA^xiv—F—A	90.0
O3—T2—BNA	53.70 (10)	BNA^xiv—F—BNA	180.0

Symmetry codes: (i) −x+2, −y+1, −z; (ii) x−1, y, z; (iii) −x+1, −y+1, −z; (iv) −x+1, y, −z+1; (v) −x+1, −y+1, −z+1; (vi) x, −y+1, z−1; (vii) x, y, z−1; (viii) −x+2, y, −z+1; (ix) −x+2, y, −z; (x) −x+1, y, −z; (xi) x−1/2, −y+1/2, z; (xii) −x+5/2, −y+1/2, −z; (xiii) −x+2, −y+1, −z+1; (xiv) x+1, y, z; (xv) x, −y+1, z; (xvi) x+1/2, −y+1/2, z; (xvii) x, y, z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8···O3^viii	0.99 (2)	2.83 (4)	3.504 (4)	126 (4)
O8—H8···O4	0.99 (2)	2.54 (2)	3.387 (3)	143 (3)

Symmetry code: (viii) −x+2, y, −z+1.

(lb550)

Crystal data

0.5(Ca0.16F0.37Fe9.08K3.91Na3.8O60Si15.21Ti3.93)	F(000) = 1138
Mr = 1168.29	Dx = 3.057 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 5.3346 (4) Å	Cell parameters from 3731 reflections
b = 23.2193 (15) Å	θ = 1.7–36.2°
c = 10.3945 (8) Å	µ = 3.97 mm^−1
β = 99.706 (7)°	T = 293 K
V = 1269.09 (16) Å^3	Prism, browm
Z = 2	0.22 × 0.18 × 0.11 mm

Data collection

Saxi-CrysAlisPro-abstract goniometer imported SAXI images diffractometer	3059 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2370 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.059
ω scans	θmax = 36.5°, θmin = 1.8°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→8
Tmin = 0.896, Tmax = 1.000	k = −38→36
11732 measured reflections	l = −16→17

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: dual
R[F^2 > 2σ(F^2)] = 0.070	w = 1/[σ^2(Fo^2) + (0.0173P)^2 + 11.7263P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.108	(Δ/σ)max < 0.001
S = 1.17	Δρmax = 1.00 e Å^−3
3059 reflections	Δρmin = −1.08 e Å^−3
133 parameters

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
M1	0.500000	0.500000	0.000000	0.0144 (9)	0.983 (13)
M2	1.000000	0.42507 (3)	0.000000	0.0113 (2)	0.871 (5)
M3	0.500000	0.35509 (4)	0.000000	0.0101 (3)	0.736 (4)
M4	1.000000	0.28739 (5)	0.000000	0.0109 (3)	0.662 (4)
D	0.93789 (16)	0.500000	0.28740 (8)	0.0076 (2)	0.981 (6)
T1	1.42142 (18)	0.28213 (4)	0.26459 (9)	0.0076 (3)	0.949 (6)
T2	0.57521 (18)	0.41425 (4)	0.72910 (9)	0.0075 (3)	0.953 (6)
A	1.000000	0.36133 (6)	0.500000	0.0286 (4)	0.977 (7)
BNA	0.500000	0.500000	0.500000	0.0152 (11)	0.92 (2)
BCA	0.500000	0.500000	0.500000	0.0152 (11)	0.08 (2)
O1	0.9040 (7)	0.500000	0.1163 (4)	0.0154 (7)
O2	0.6404 (5)	0.41744 (11)	0.8875 (2)	0.0138 (5)
O3	0.7972 (5)	0.44251 (12)	0.6612 (3)	0.0180 (6)
O4	0.6966 (5)	0.44264 (12)	0.3282 (3)	0.0197 (6)
O5	0.5527 (6)	0.34671 (11)	0.6772 (3)	0.0179 (6)
O6	1.3709 (5)	0.28216 (10)	0.1070 (2)	0.0116 (5)
O7	1.1867 (5)	0.25143 (12)	0.3224 (2)	0.0163 (5)
O8	0.8619 (5)	0.35251 (11)	0.1014 (3)	0.0161 (5)
F	1.000000	0.500000	0.500000	0.018 (7)*	0.186 (18)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
M1	0.0125 (15)	0.0107 (15)	0.0186 (16)	0.000	−0.0014 (11)	0.000
M2	0.0082 (4)	0.0127 (4)	0.0121 (4)	0.000	−0.0007 (3)	0.000
M3	0.0096 (4)	0.0087 (4)	0.0122 (4)	0.000	0.0019 (3)	0.000
M4	0.0085 (5)	0.0122 (5)	0.0118 (5)	0.000	0.0007 (3)	0.000
D	0.0055 (3)	0.0076 (4)	0.0097 (4)	0.000	0.0008 (3)	0.000
T1	0.0078 (4)	0.0070 (4)	0.0076 (4)	0.0001 (3)	0.0007 (3)	0.0003 (3)
T2	0.0073 (4)	0.0063 (4)	0.0088 (4)	0.0014 (3)	0.0010 (3)	0.0009 (3)
A	0.0327 (8)	0.0263 (7)	0.0263 (7)	0.000	0.0040 (5)	0.000
BNA	0.0211 (17)	0.0127 (15)	0.0101 (15)	0.000	−0.0025 (10)	0.000
BCA	0.0211 (17)	0.0127 (15)	0.0101 (15)	0.000	−0.0025 (10)	0.000
O1	0.0130 (16)	0.0211 (18)	0.0114 (16)	0.000	−0.0001 (12)	0.000
O2	0.0133 (11)	0.0154 (11)	0.0122 (11)	0.0005 (9)	0.0008 (9)	0.0012 (9)
O3	0.0186 (13)	0.0204 (13)	0.0156 (12)	−0.0079 (10)	0.0044 (10)	−0.0033 (10)
O4	0.0153 (12)	0.0250 (14)	0.0174 (13)	−0.0106 (10)	−0.0009 (10)	0.0027 (10)
O5	0.0319 (15)	0.0089 (11)	0.0118 (11)	−0.0009 (10)	0.0009 (10)	0.0003 (9)
O6	0.0102 (10)	0.0126 (11)	0.0114 (10)	0.0012 (8)	0.0002 (8)	0.0003 (8)
O7	0.0144 (12)	0.0215 (13)	0.0126 (11)	−0.0071 (10)	0.0015 (9)	−0.0013 (10)
O8	0.0145 (11)	0.0172 (13)	0.0170 (12)	0.0001 (9)	0.0034 (9)	0.0016 (10)

Geometric parameters (Å, º)

M1—M2^i	3.1846 (5)	D—O3^viii	1.952 (3)
M1—M2^ii	3.1846 (5)	D—O4	1.948 (3)
M1—M2	3.1846 (5)	D—O4^xv	1.948 (3)
M1—M2^iii	3.1846 (5)	D—F	2.1786 (9)
M1—M3	3.3647 (10)	T1—O5^viii	1.614 (3)
M1—M3^ii	3.3647 (10)	T1—O6	1.614 (3)
M1—O1^ii	2.287 (4)	T1—O7^xvi	1.638 (3)
M1—O1	2.287 (4)	T1—O7	1.640 (3)
M1—O2^iv	2.429 (3)	T2—A^i	3.7594 (11)
M1—O2^v	2.429 (3)	T2—A	3.7598 (11)
M1—O2^vi	2.429 (3)	T2—BNA	3.0780 (10)
M1—O2^vii	2.429 (3)	T2—O2	1.626 (3)
M2—O1	2.227 (2)	T2—O3	1.616 (3)
M2—O1^iii	2.227 (2)	T2—O4^vii	1.613 (3)
M2—O2^vi	2.079 (3)	T2—O5	1.656 (3)
M2—O2^viii	2.079 (3)	A—O3^viii	2.854 (3)
M2—O8^ix	2.180 (3)	A—O3	2.854 (3)
M2—O8	2.180 (3)	A—O4^viii	2.898 (3)
M3—O2^vii	2.079 (3)	A—O4	2.898 (3)
M3—O2^vi	2.079 (3)	A—O5^vii	3.220 (3)
M3—O6^ix	2.200 (3)	A—O5	3.269 (3)
M3—O6^i	2.200 (3)	A—O5^viii	3.269 (3)
M3—O8^x	2.039 (3)	A—O5^xiv	3.220 (3)
M3—O8	2.039 (3)	A—O7^viii	3.396 (3)
M4—O6	2.104 (2)	A—O7	3.396 (3)
M4—O6^xi	2.140 (3)	A—F	3.2198 (15)
M4—O6^xii	2.140 (3)	BNA—O3^vii	2.492 (3)
M4—O6^ix	2.104 (2)	BNA—O3	2.492 (3)
M4—O8^ix	2.050 (3)	BNA—O3^xv	2.492 (3)
M4—O8	2.050 (3)	BNA—O3^v	2.492 (3)
D—A^xiii	3.8877 (13)	BNA—O4^xv	2.587 (3)
D—A	3.8876 (13)	BNA—O4^v	2.587 (3)
D—BNA^xiv	3.4119 (9)	BNA—O4	2.587 (3)
D—BNA	3.4758 (9)	BNA—O4^vii	2.587 (3)
D—O1	1.757 (4)	BNA—F^i	2.6673 (2)
D—O3^xiii	1.952 (3)	BNA—F	2.6673 (2)
M2^i—M1—M2^iii	180.00 (2)	O3—T2—A^i	115.85 (10)
M2^iii—M1—M2^ii	113.77 (2)	O3—T2—BNA	53.79 (11)
M2^i—M1—M2^ii	66.23 (2)	O3—T2—O2	112.09 (14)
M2^iii—M1—M2	66.23 (2)	O3—T2—O5	105.10 (15)
M2^i—M1—M2	113.77 (2)	O4^vii—T2—M1^xvii	81.25 (10)
M2^ii—M1—M2	180.0	O4^vii—T2—A	120.00 (11)
M2—M1—M3	56.883 (12)	O4^vii—T2—A^i	46.57 (11)
M2^ii—M1—M3^ii	56.884 (12)	O4^vii—T2—BNA	57.18 (11)
M2^iii—M1—M3	123.116 (12)	O4^vii—T2—O2	112.39 (15)
M2^iii—M1—M3^ii	56.884 (12)	O4^vii—T2—O3	110.62 (16)
M2^ii—M1—M3	123.116 (12)	O4^vii—T2—O5	104.80 (15)
M2^i—M1—M3^ii	123.116 (12)	O5—T2—M1^xvii	141.52 (10)
M2—M1—M3^ii	123.117 (12)	O5—T2—A^i	58.51 (10)
M2^i—M1—M3	56.884 (12)	O5—T2—A	60.17 (11)
M3—M1—M3^ii	180.0	O5—T2—BNA	111.58 (10)
O1^ii—M1—M2	135.63 (6)	O3^viii—A—T2^xiv	78.83 (6)
O1—M1—M2^iii	44.37 (6)	O3—A—T2^xiv	76.22 (6)
O1—M1—M2^ii	135.63 (6)	O3—A—O3^viii	97.31 (12)
O1^ii—M1—M2^iii	135.63 (6)	O3^viii—A—O4^viii	72.78 (9)
O1^ii—M1—M2^i	44.37 (6)	O3—A—O4	72.78 (9)
O1^ii—M1—M2^ii	44.37 (6)	O3^viii—A—O4	55.63 (8)
O1—M1—M2^i	135.63 (6)	O3—A—O4^viii	55.63 (8)
O1—M1—M2	44.37 (6)	O3—A—O5^viii	141.68 (8)
O1—M1—M3	90.0	O3^viii—A—O5^viii	49.66 (7)
O1^ii—M1—M3^ii	90.0	O3^viii—A—O5	141.68 (8)
O1—M1—M3^ii	90.0	O3—A—O5	49.65 (7)
O1^ii—M1—M3	90.0	O3—A—O5^xiv	97.75 (8)
O1^ii—M1—O1	180.0	O3—A—O5^vii	90.25 (7)
O1^ii—M1—O2^vii	85.12 (8)	O3^viii—A—O5^vii	97.75 (8)
O1^ii—M1—O2^vi	94.88 (8)	O3^viii—A—O5^xiv	90.25 (7)
O1—M1—O2^iv	85.12 (8)	O3^viii—A—O7	90.12 (7)
O1—M1—O2^vii	94.88 (8)	O3—A—O7^viii	90.12 (7)
O1^ii—M1—O2^iv	94.88 (8)	O3—A—O7	172.14 (8)
O1^ii—M1—O2^v	85.12 (8)	O3^viii—A—O7^viii	172.14 (8)
O1—M1—O2^vi	85.12 (8)	O3—A—F	48.66 (6)
O1—M1—O2^v	94.88 (8)	O3^viii—A—F	48.66 (6)
O2^vii—M1—M2	83.98 (6)	O4^viii—A—T2^xiv	23.84 (5)
O2^vi—M1—M2^i	83.98 (6)	O4—A—T2^xiv	119.26 (7)
O2^iv—M1—M2	96.02 (6)	O4—A—O4^viii	98.69 (12)
O2^vi—M1—M2^ii	139.24 (6)	O4^viii—A—O5^viii	91.72 (8)
O2^iv—M1—M2^i	139.24 (6)	O4^viii—A—O5	96.04 (8)
O2^iv—M1—M2^ii	83.98 (6)	O4^viii—A—O5^vii	141.58 (8)
O2^vii—M1—M2^iii	139.24 (6)	O4—A—O5^xiv	141.58 (8)
O2^v—M1—M2	139.24 (6)	O4—A—O5^vii	49.75 (7)
O2^v—M1—M2^i	96.02 (6)	O4—A—O5	91.72 (8)
O2^v—M1—M2^iii	83.98 (6)	O4^viii—A—O5^xiv	49.75 (7)
O2^v—M1—M2^ii	40.76 (6)	O4—A—O5^viii	96.04 (8)
O2^vi—M1—M2^iii	96.02 (6)	O4^viii—A—O7^viii	109.82 (7)
O2^vii—M1—M2^i	40.76 (6)	O4—A—O7	109.82 (7)
O2^vi—M1—M2	40.76 (6)	O4—A—O7^viii	129.80 (7)
O2^iv—M1—M2^iii	40.76 (6)	O4^viii—A—O7	129.80 (7)
O2^vii—M1—M2^ii	96.02 (6)	O4—A—F	49.35 (6)
O2^v—M1—M3	142.11 (6)	O4^viii—A—F	49.35 (6)
O2^iv—M1—M3	142.11 (6)	O5^vii—A—T2^xiv	165.38 (6)
O2^iv—M1—M3^ii	37.89 (6)	O5—A—T2^xiv	105.80 (5)
O2^vii—M1—M3^ii	142.11 (6)	O5^xiv—A—T2^xiv	26.01 (5)
O2^v—M1—M3^ii	37.89 (6)	O5^viii—A—T2^xiv	78.20 (5)
O2^vii—M1—M3	37.89 (6)	O5^vii—A—O5^xiv	167.90 (10)
O2^vi—M1—M3	37.89 (6)	O5^xiv—A—O5^viii	68.07 (8)
O2^vi—M1—M3^ii	142.11 (6)	O5^vii—A—O5	68.07 (8)
O2^vi—M1—O2^vii	75.77 (12)	O5^xiv—A—O5	110.58 (8)
O2^iv—M1—O2^vii	180.00 (10)	O5^vii—A—O5^viii	110.58 (8)
O2^v—M1—O2^iv	75.77 (12)	O5—A—O5^viii	168.08 (10)
O2^v—M1—O2^vi	180.00 (10)	O5—A—O7^viii	46.11 (6)
O2^v—M1—O2^vii	104.23 (12)	O5^vii—A—O7^viii	84.70 (7)
O2^vi—M1—O2^iv	104.23 (12)	O5^viii—A—O7^viii	122.49 (7)
M1^xiv—M2—M1	113.77 (2)	O5^viii—A—O7	46.11 (6)
O1^iii—M2—M1^xiv	45.89 (9)	O5^xiv—A—O7^viii	86.21 (7)
O1^iii—M2—M1	80.93 (9)	O5^vii—A—O7	86.21 (7)
O1—M2—M1	45.89 (9)	O5—A—O7	122.49 (7)
O1—M2—M1^xiv	80.93 (9)	O5^xiv—A—O7	84.70 (7)
O1^iii—M2—O1	77.25 (15)	O7^viii—A—T2^xiv	100.61 (5)
O2^viii—M2—M1^xiv	49.70 (7)	O7—A—T2^xiv	107.89 (5)
O2^vi—M2—M1	49.70 (7)	O7—A—O7^viii	82.57 (10)
O2^vi—M2—M1^xiv	137.72 (7)	F—A—T2^xiv	70.92 (3)
O2^viii—M2—M1	137.72 (7)	F—A—O5^xiv	96.05 (5)
O2^viii—M2—O1^iii	95.58 (12)	F—A—O5	95.96 (5)
O2^vi—M2—O1^iii	92.05 (12)	F—A—O5^viii	95.96 (5)
O2^viii—M2—O1	92.05 (12)	F—A—O5^vii	96.05 (5)
O2^vi—M2—O1	95.58 (12)	F—A—O7	138.72 (5)
O2^vi—M2—O2^viii	170.23 (15)	F—A—O7^viii	138.72 (5)
O2^viii—M2—O8	90.98 (10)	T2^xv—BNA—T2^vii	180.0
O2^vi—M2—O8	81.45 (10)	O3^v—BNA—T2^vii	80.85 (6)
O2^viii—M2—O8^ix	81.45 (10)	O3^xv—BNA—T2^xv	31.56 (6)
O2^vi—M2—O8^ix	90.98 (10)	O3^xv—BNA—T2^vii	148.44 (6)
O8—M2—M1	94.06 (7)	O3^vii—BNA—T2^vii	31.56 (6)
O8^ix—M2—M1^xiv	94.06 (7)	O3^vii—BNA—T2^xv	148.44 (6)
O8—M2—M1^xiv	140.66 (7)	O3—BNA—T2^vii	99.15 (6)
O8^ix—M2—M1	140.66 (7)	O3—BNA—T2^xv	80.85 (6)
O8^ix—M2—O1	173.44 (11)	O3^v—BNA—T2^xv	99.15 (6)
O8^ix—M2—O1^iii	102.34 (10)	O3^xv—BNA—O3^v	115.21 (12)
O8—M2—O1	102.34 (10)	O3^vii—BNA—O3^v	64.79 (12)
O8—M2—O1^iii	173.44 (11)	O3^xv—BNA—O3	64.79 (12)
O8—M2—O8^ix	78.82 (14)	O3^vii—BNA—O3	115.21 (12)
O2^vi—M3—M1	45.85 (7)	O3^v—BNA—O3	180.0
O2^vii—M3—M1	45.85 (7)	O3^xv—BNA—O3^vii	180.00 (11)
O2^vii—M3—O2^vi	91.70 (15)	O3^vii—BNA—O4	63.00 (9)
O2^vi—M3—O6^ix	94.50 (10)	O3^v—BNA—O4^vii	117.00 (9)
O2^vii—M3—O6^i	94.50 (10)	O3^vii—BNA—O4^v	117.00 (9)
O2^vi—M3—O6^i	173.78 (10)	O3^v—BNA—O4	95.60 (9)
O2^vii—M3—O6^ix	173.78 (10)	O3^xv—BNA—O4	117.00 (9)
O6^ix—M3—M1	140.35 (7)	O3—BNA—O4	84.40 (9)
O6^i—M3—M1	140.35 (7)	O3^xv—BNA—O4^xv	84.40 (9)
O6^ix—M3—O6^i	79.31 (13)	O3^xv—BNA—O4^v	63.00 (9)
O8—M3—M1	91.68 (8)	O3^v—BNA—O4^xv	63.00 (9)
O8^x—M3—M1	91.68 (8)	O3—BNA—O4^v	95.60 (9)
O8^x—M3—O2^vii	84.95 (10)	O3^xv—BNA—O4^vii	95.60 (9)
O8^x—M3—O2^vi	97.41 (10)	O3—BNA—O4^xv	117.00 (9)
O8—M3—O2^vi	84.94 (10)	O3^v—BNA—O4^v	84.40 (9)
O8—M3—O2^vii	97.41 (10)	O3—BNA—O4^vii	63.00 (9)
O8—M3—O6^i	93.77 (10)	O3^vii—BNA—O4^xv	95.60 (9)
O8^x—M3—O6^i	83.63 (10)	O3^vii—BNA—O4^vii	84.40 (9)
O8^x—M3—O6^ix	93.77 (10)	O3—BNA—F^i	121.53 (6)
O8—M3—O6^ix	83.63 (10)	O3^v—BNA—F^i	58.47 (6)
O8—M3—O8^x	176.63 (16)	O3^v—BNA—F	121.53 (6)
O6—M4—O6^ix	173.38 (15)	O3—BNA—F	58.47 (6)
O6—M4—O6^xii	92.18 (9)	O3^vii—BNA—F	121.53 (6)
O6^ix—M4—O6^xii	82.81 (10)	O3^xv—BNA—F^i	121.53 (6)
O6^ix—M4—O6^xi	92.18 (9)	O3^xv—BNA—F	58.47 (6)
O6^xi—M4—O6^xii	81.99 (14)	O3^vii—BNA—F^i	58.47 (6)
O6—M4—O6^xi	82.81 (10)	O4—BNA—T2^vii	31.59 (6)
O8—M4—O6^xi	177.67 (10)	O4^xv—BNA—T2^vii	79.29 (6)
O8^ix—M4—O6^ix	99.10 (10)	O4—BNA—T2^xv	148.41 (6)
O8^ix—M4—O6^xi	96.56 (10)	O4^v—BNA—T2^xv	31.59 (6)
O8—M4—O6	99.10 (10)	O4^xv—BNA—T2^xv	100.71 (6)
O8^ix—M4—O6^xii	177.67 (10)	O4^vii—BNA—T2^vii	100.71 (6)
O8—M4—O6^ix	85.82 (10)	O4^v—BNA—T2^vii	148.41 (6)
O8^ix—M4—O6	85.82 (10)	O4^vii—BNA—T2^xv	79.29 (6)
O8—M4—O6^xii	96.56 (10)	O4^xv—BNA—O4^vii	180.00 (11)
O8^ix—M4—O8	84.95 (15)	O4^xv—BNA—O4	61.96 (12)
M1—D—A^xiii	118.041 (16)	O4^v—BNA—O4	180.00 (10)
M1—D—A	118.041 (16)	O4^v—BNA—O4^vii	61.96 (12)
M1—D—BNA	96.91 (2)	O4^v—BNA—O4^xv	118.04 (12)
A—D—A^xiii	111.83 (3)	O4^vii—BNA—O4	118.04 (12)
BNA^xiv—D—M1	161.57 (3)	O4^xv—BNA—F	58.55 (6)
BNA^xiv—D—A^xiii	69.541 (14)	O4^v—BNA—F	121.45 (6)
BNA—D—A^xiii	68.937 (15)	O4—BNA—F	58.55 (6)
BNA—D—A	68.937 (15)	O4^xv—BNA—F^i	121.45 (6)
BNA^xiv—D—A	69.541 (14)	O4^v—BNA—F^i	58.55 (6)
BNA^xiv—D—BNA	101.52 (2)	O4—BNA—F^i	121.45 (6)
O1—D—M1	35.78 (12)	O4^vii—BNA—F	121.45 (6)
O1—D—A	124.037 (17)	O4^vii—BNA—F^i	58.55 (6)
O1—D—A^xiii	124.036 (17)	F^i—BNA—T2^xv	89.995 (18)
O1—D—BNA	132.69 (13)	F^i—BNA—T2^vii	90.005 (19)
O1—D—BNA^xiv	125.79 (13)	F—BNA—T2^vii	89.995 (18)
O1—D—O3^xiii	102.89 (12)	F—BNA—T2^xv	90.005 (19)
O1—D—O3^viii	102.89 (12)	F^i—BNA—F	180.0
O1—D—O4^xv	105.15 (12)	M2^iii—O1—M1	89.74 (11)
O1—D—O4	105.15 (12)	M2—O1—M1	89.74 (11)
O1—D—F	177.20 (13)	M2^iii—O1—M2	102.75 (15)
O3^viii—D—M1	125.95 (9)	D—O1—M1	117.53 (19)
O3^xiii—D—M1	125.95 (9)	D—O1—M2	123.76 (10)
O3^viii—D—A	44.74 (8)	D—O1—M2^iii	123.76 (10)
O3^xiii—D—A	114.99 (9)	M2^xvii—O2—M1^xvii	89.54 (9)
O3^viii—D—A^xiii	114.99 (9)	M3^xvii—O2—M1^xvii	96.26 (10)
O3^xiii—D—A^xiii	44.74 (8)	M3^xvii—O2—M2^xvii	97.38 (10)
O3^viii—D—BNA^xiv	46.06 (9)	T2—O2—M1^xvii	119.53 (13)
O3^xiii—D—BNA	111.05 (9)	T2—O2—M2^xvii	126.37 (15)
O3^xiii—D—BNA^xiv	46.06 (9)	T2—O2—M3^xvii	120.15 (14)
O3^viii—D—BNA	111.05 (9)	D^xiii—O3—A	106.49 (12)
O3^xiii—D—O3^viii	86.30 (18)	D^xiii—O3—BNA	99.61 (11)
O3^viii—D—F	75.12 (8)	T2—O3—D^xiii	135.09 (17)
O3^xiii—D—F	75.12 (8)	T2—O3—A	111.49 (13)
O4^xv—D—M1	79.26 (8)	T2—O3—BNA	94.65 (13)
O4—D—M1	79.26 (8)	BNA—O3—A	102.72 (9)
O4^xv—D—A^xiii	46.06 (8)	D—O4—A	104.99 (11)
O4—D—A^xiii	116.02 (9)	D—O4—BNA	99.09 (12)
O4^xv—D—A	116.02 (9)	T2^vii—O4—D	141.72 (18)
O4—D—A	46.06 (8)	T2^vii—O4—A	109.59 (13)
O4—D—BNA^xiv	113.57 (9)	T2^vii—O4—BNA	91.23 (13)
O4—D—BNA	47.31 (9)	BNA—O4—A	99.17 (9)
O4^xv—D—BNA^xiv	113.57 (9)	T1^viii—O5—T2	139.54 (17)
O4^xv—D—BNA	47.31 (9)	T1^viii—O5—A	106.45 (13)
O4^xv—D—O3^xiii	86.98 (12)	T1^viii—O5—A^i	108.93 (13)
O4—D—O3^viii	86.98 (12)	T2—O5—A^i	95.48 (12)
O4^xv—D—O3^viii	151.95 (12)	T2—O5—A	93.75 (12)
O4—D—O3^xiii	151.95 (12)	A^i—O5—A	110.58 (8)
O4^xv—D—O4	86.27 (19)	M4—O6—M3^xiv	92.00 (9)
O4^xv—D—F	76.83 (9)	M4^xi—O6—M3^xiv	99.35 (10)
O4—D—F	76.83 (9)	M4—O6—M4^xi	97.19 (10)
F—D—M1	147.02 (4)	T1—O6—M3^xiv	120.03 (13)
F—D—A	55.917 (17)	T1—O6—M4^xi	120.92 (13)
F—D—A^xiii	55.917 (16)	T1—O6—M4	121.19 (14)
F—D—BNA^xiv	51.410 (18)	T1^xii—O7—T1	137.54 (18)
F—D—BNA	50.109 (18)	T1^xii—O7—A	104.03 (12)
O5^viii—T1—O6	111.64 (14)	T1—O7—A	100.64 (12)
O5^viii—T1—O7^xvi	106.88 (15)	M3—O8—M2	95.45 (11)
O5^viii—T1—O7	106.78 (15)	M3—O8—M4	98.44 (11)
O6—T1—O7	111.38 (13)	M4—O8—M2	98.12 (11)
O6—T1—O7^xvi	111.01 (14)	D—F—D^xiii	180.0
O7^xvi—T1—O7	108.93 (10)	D—F—A	90.0
M1^xvii—T2—A^i	119.99 (3)	D^xiii—F—A^xiii	90.0
M1^xvii—T2—A	148.45 (3)	D^xiii—F—A	90.0
A^i—T2—A	90.38 (3)	D—F—A^xiii	90.0
BNA—T2—M1^xvii	103.59 (3)	D—F—BNA^xiv	88.91 (2)
BNA—T2—A	74.65 (3)	D^xiii—F—BNA	88.92 (2)
BNA—T2—A^i	74.65 (3)	D^xiii—F—BNA^xiv	91.08 (2)
O2—T2—M1^xvii	36.82 (9)	D—F—BNA	91.09 (2)
O2—T2—A^i	131.96 (10)	A—F—A^xiii	180.0
O2—T2—A	127.40 (10)	BNA^xiv—F—A^xiii	90.0
O2—T2—BNA	137.02 (10)	BNA^xiv—F—A	90.0
O2—T2—O5	111.36 (14)	BNA—F—A	90.0
O3—T2—M1^xvii	108.04 (10)	BNA—F—A^xiii	90.0
O3—T2—A	44.93 (10)	BNA^xiv—F—BNA	180.0

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z; (iii) −x+2, −y+1, −z; (iv) x, −y+1, z−1; (v) −x+1, −y+1, −z+1; (vi) x, y, z−1; (vii) −x+1, y, −z+1; (viii) −x+2, y, −z+1; (ix) −x+2, y, −z; (x) −x+1, y, −z; (xi) −x+5/2, −y+1/2, −z; (xii) x−1/2, −y+1/2, z; (xiii) −x+2, −y+1, −z+1; (xiv) x+1, y, z; (xv) x, −y+1, z; (xvi) x+1/2, −y+1/2, z; (xvii) x, y, z+1.

(lb570_3m)

Crystal data

0.5(Ca0.19F0.44Fe9.06K3.87Na3.78O60Si14.98Ti3.93)	F(000) = 1135
Mr = 1164.62	Dx = 3.044 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 5.3434 (6) Å	Cell parameters from 1962 reflections
b = 23.221 (3) Å	θ = 2.0–35.7°
c = 10.3740 (14) Å	µ = 3.96 mm^−1
β = 99.250 (13)°	T = 293 K
V = 1270.5 (3) Å^3	Prism, brown
Z = 2	0.22 × 0.18 × 0.11 mm

Data collection

Saxi-CrysAlisPro-abstract goniometer imported SAXI images diffractometer	3024 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2559 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.065
ω scans	θmax = 36.4°, θmin = 1.8°
Absorption correction: multi-scan CrysAlisPro 1.171.39.44a (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→8
Tmin = 0.521, Tmax = 1.000	k = −37→34
11330 measured reflections	l = −16→17

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: dual
R[F^2 > 2σ(F^2)] = 0.118	w = 1/[σ^2(Fo^2) + (0.004P)^2 + 32.282P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.169	(Δ/σ)max < 0.001
S = 1.36	Δρmax = 1.07 e Å^−3
3024 reflections	Δρmin = −1.43 e Å^−3
133 parameters

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
M1	0.500000	0.500000	0.000000	0.0197 (16)	0.99 (2)
M2	1.000000	0.42333 (8)	0.000000	0.0226 (5)	0.814 (8)
M3	0.500000	0.35513 (7)	0.000000	0.0138 (4)	0.761 (7)
M4	1.000000	0.29037 (8)	0.000000	0.0169 (5)	0.689 (7)
D	0.9398 (3)	0.500000	0.28875 (15)	0.0140 (4)	0.983 (10)
T1	1.4210 (3)	0.28186 (7)	0.26568 (16)	0.0128 (5)	0.941 (10)
T2	0.5730 (3)	0.41398 (7)	0.72803 (16)	0.0121 (5)	0.932 (10)
A	1.000000	0.36121 (12)	0.500000	0.0339 (7)	0.968 (12)
BNA	0.500000	0.500000	0.500000	0.0180 (18)	0.90 (4)
BCA	0.500000	0.500000	0.500000	0.0180 (18)	0.10 (4)
O1	0.9062 (13)	0.500000	0.1147 (7)	0.0288 (16)
O2	0.6379 (9)	0.4164 (2)	0.8874 (4)	0.0204 (9)
O3	0.7969 (9)	0.4428 (2)	0.6612 (5)	0.0249 (10)
O4	0.6983 (10)	0.4428 (2)	0.3292 (5)	0.0271 (11)
O5	0.5504 (10)	0.3469 (2)	0.6756 (5)	0.0248 (10)
O6	1.3705 (8)	0.2817 (2)	0.1076 (4)	0.0189 (9)
O7	1.1850 (8)	0.2518 (2)	0.3246 (4)	0.0213 (9)
O8	0.8541 (9)	0.3516 (2)	0.0976 (5)	0.0240 (10)
F	1.000000	0.500000	0.500000	0.022 (10)*	0.22 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
M1	0.019 (3)	0.013 (3)	0.026 (3)	0.000	−0.001 (2)	0.000
M2	0.0132 (7)	0.0325 (10)	0.0203 (8)	0.000	−0.0030 (6)	0.000
M3	0.0143 (7)	0.0128 (7)	0.0144 (7)	0.000	0.0024 (5)	0.000
M4	0.0136 (8)	0.0203 (9)	0.0166 (8)	0.000	0.0020 (6)	0.000
D	0.0076 (6)	0.0201 (8)	0.0142 (7)	0.000	0.0010 (4)	0.000
T1	0.0120 (7)	0.0143 (8)	0.0114 (7)	−0.0002 (6)	−0.0002 (5)	−0.0013 (6)
T2	0.0122 (8)	0.0126 (7)	0.0114 (8)	0.0012 (6)	0.0013 (5)	0.0006 (5)
A	0.0315 (12)	0.0350 (14)	0.0352 (14)	0.000	0.0057 (10)	0.000
BNA	0.021 (3)	0.019 (3)	0.012 (2)	0.000	−0.0009 (16)	0.000
BCA	0.021 (3)	0.019 (3)	0.012 (2)	0.000	−0.0009 (16)	0.000
O1	0.017 (3)	0.052 (5)	0.017 (3)	0.000	0.002 (2)	0.000
O2	0.021 (2)	0.024 (2)	0.0156 (19)	−0.0016 (17)	0.0005 (16)	−0.0006 (16)
O3	0.022 (2)	0.033 (3)	0.020 (2)	−0.0087 (19)	0.0032 (17)	−0.0001 (19)
O4	0.024 (2)	0.035 (3)	0.022 (2)	−0.011 (2)	0.0020 (18)	0.003 (2)
O5	0.038 (3)	0.015 (2)	0.020 (2)	0.0000 (18)	0.0009 (19)	0.0013 (16)
O6	0.0179 (19)	0.023 (2)	0.0155 (18)	0.0001 (16)	0.0013 (15)	0.0008 (16)
O7	0.018 (2)	0.029 (2)	0.0175 (19)	−0.0094 (18)	0.0041 (16)	0.0002 (18)
O8	0.019 (2)	0.035 (3)	0.018 (2)	0.0013 (19)	0.0039 (16)	0.0011 (19)

Geometric parameters (Å, º)

M1—M2^i	3.2106 (11)	D—O3^viii	1.944 (5)
M1—M2^ii	3.2106 (11)	D—O4	1.944 (5)
M1—M2	3.2106 (11)	D—O4^xv	1.944 (5)
M1—M2^iii	3.2106 (11)	D—F	2.1632 (16)
M1—M3^ii	3.3639 (17)	T1—O5^viii	1.626 (5)
M1—M3	3.3640 (17)	T1—O6	1.618 (5)
M1—O1	2.301 (7)	T1—O7	1.642 (5)
M1—O1^ii	2.301 (7)	T1—O7^xvi	1.643 (5)
M1—O2^iv	2.440 (5)	T2—A	3.747 (2)
M1—O2^v	2.440 (5)	T2—A^i	3.7607 (19)
M1—O2^vi	2.440 (5)	T2—BNA	3.0727 (17)
M1—O2^vii	2.440 (5)	T2—O2	1.634 (5)
M2—O1	2.242 (5)	T2—O3	1.620 (5)
M2—O1^iii	2.242 (5)	T2—O4^vii	1.620 (5)
M2—O2^vi	2.100 (4)	T2—O5	1.648 (5)
M2—O2^viii	2.100 (4)	A—O3^viii	2.854 (6)
M2—O8	2.158 (5)	A—O3	2.854 (6)
M2—O8^ix	2.158 (5)	A—O4	2.900 (6)
M3—O2^vii	2.051 (5)	A—O4^viii	2.900 (6)
M3—O2^vi	2.051 (5)	A—O5	3.257 (5)
M3—O6^ix	2.209 (5)	A—O5^vii	3.218 (5)
M3—O6^i	2.209 (5)	A—O5^viii	3.257 (5)
M3—O8	1.999 (5)	A—O5^xiv	3.218 (5)
M3—O8^x	1.999 (5)	A—O7^viii	3.364 (5)
M4—O6	2.121 (4)	A—O7	3.364 (5)
M4—O6^xi	2.185 (5)	A—F	3.223 (3)
M4—O6^xii	2.185 (5)	BNA—O3^xv	2.496 (5)
M4—O6^ix	2.121 (4)	BNA—O3	2.496 (5)
M4—O8^ix	1.977 (5)	BNA—O3^vii	2.496 (5)
M4—O8	1.977 (5)	BNA—O3^v	2.496 (5)
D—A^xiii	3.882 (2)	BNA—O4	2.575 (6)
D—A	3.881 (2)	BNA—O4^xv	2.575 (6)
D—BNA^xiv	3.4137 (15)	BNA—O4^vii	2.575 (6)
D—BNA	3.4614 (16)	BNA—O4^v	2.575 (6)
D—O1	1.786 (7)	BNA—F^i	2.6717 (3)
D—O3^xiii	1.944 (5)	BNA—F	2.6717 (3)
M2^i—M1—M2^iii	180.00 (6)	O3—T2—A^i	116.61 (18)
M2^iii—M1—M2^ii	112.64 (6)	O3—T2—BNA	54.10 (18)
M2^i—M1—M2^ii	67.36 (6)	O3—T2—O2	111.5 (3)
M2^iii—M1—M2	67.36 (6)	O3—T2—O4^vii	110.6 (3)
M2^i—M1—M2	112.64 (6)	O3—T2—O5	105.6 (3)
M2^ii—M1—M2	180.0	O4^vii—T2—M1^xvii	81.46 (19)
M2—M1—M3^ii	123.68 (3)	O4^vii—T2—A	120.2 (2)
M2^ii—M1—M3	123.68 (3)	O4^vii—T2—A^i	46.7 (2)
M2^iii—M1—M3^ii	56.32 (3)	O4^vii—T2—BNA	56.9 (2)
M2^iii—M1—M3	123.68 (3)	O4^vii—T2—O2	112.8 (3)
M2^ii—M1—M3^ii	56.32 (3)	O4^vii—T2—O5	104.8 (3)
M2^i—M1—M3	56.32 (3)	O5—T2—M1^xvii	141.93 (19)
M2—M1—M3	56.32 (3)	O5—T2—A^i	58.36 (18)
M2^i—M1—M3^ii	123.68 (3)	O5—T2—A	60.1 (2)
M3^ii—M1—M3	180.0	O5—T2—BNA	111.52 (18)
O1—M1—M2	44.30 (11)	O3^viii—A—T2^viii	23.86 (10)
O1^ii—M1—M2^iii	135.70 (11)	O3—A—T2^viii	118.72 (13)
O1^ii—M1—M2^ii	44.30 (11)	O3—A—O3^viii	96.9 (2)
O1—M1—M2^iii	44.30 (11)	O3—A—O4^viii	55.58 (14)
O1—M1—M2^i	135.70 (11)	O3—A—O4	72.44 (15)
O1—M1—M2^ii	135.70 (11)	O3^viii—A—O4^viii	72.44 (15)
O1^ii—M1—M2^i	44.30 (11)	O3^viii—A—O4	55.58 (14)
O1^ii—M1—M2	135.70 (11)	O3^viii—A—O5^xiv	90.08 (13)
O1^ii—M1—M3^ii	90.0	O3—A—O5^vii	90.08 (13)
O1—M1—M3	90.0	O3^viii—A—O5^vii	97.81 (13)
O1^ii—M1—M3	90.0	O3^viii—A—O5	141.24 (15)
O1—M1—M3^ii	90.0	O3^viii—A—O5^viii	49.90 (12)
O1—M1—O1^ii	180.0	O3—A—O5^xiv	97.82 (13)
O1—M1—O2^vii	94.86 (15)	O3—A—O5^viii	141.24 (15)
O1—M1—O2^vi	85.14 (15)	O3—A—O5	49.90 (13)
O1^ii—M1—O2^iv	94.86 (15)	O3—A—O7	172.08 (14)
O1^ii—M1—O2^vii	85.14 (15)	O3—A—O7^viii	90.65 (12)
O1—M1—O2^iv	85.14 (15)	O3^viii—A—O7^viii	172.08 (14)
O1—M1—O2^v	94.86 (15)	O3^viii—A—O7	90.65 (12)
O1^ii—M1—O2^vi	94.86 (15)	O3^viii—A—F	48.43 (11)
O1^ii—M1—O2^v	85.14 (15)	O3—A—F	48.43 (11)
O2^vii—M1—M2	82.77 (11)	O4—A—T2^viii	74.67 (11)
O2^vi—M1—M2^i	82.77 (11)	O4^viii—A—T2^viii	80.62 (12)
O2^iv—M1—M2	97.23 (11)	O4—A—O4^viii	98.4 (2)
O2^vi—M1—M2^ii	139.16 (11)	O4—A—O5^xiv	141.36 (15)
O2^iv—M1—M2^i	139.16 (11)	O4^viii—A—O5^vii	141.36 (15)
O2^iv—M1—M2^ii	82.77 (11)	O4—A—O5^vii	49.77 (12)
O2^vii—M1—M2^iii	139.16 (11)	O4—A—O5^viii	96.46 (14)
O2^v—M1—M2	139.16 (11)	O4^viii—A—O5	96.46 (14)
O2^v—M1—M2^i	97.23 (11)	O4^viii—A—O5^xiv	49.77 (12)
O2^v—M1—M2^iii	82.77 (11)	O4—A—O5	91.21 (13)
O2^v—M1—M2^ii	40.84 (11)	O4^viii—A—O5^viii	91.21 (13)
O2^vi—M1—M2^iii	97.23 (11)	O4—A—O7^viii	129.87 (13)
O2^vii—M1—M2^i	40.84 (11)	O4—A—O7	110.21 (13)
O2^vi—M1—M2	40.84 (11)	O4^viii—A—O7	129.87 (13)
O2^iv—M1—M2^iii	40.84 (11)	O4^viii—A—O7^viii	110.21 (13)
O2^vii—M1—M2^ii	97.23 (11)	O4^viii—A—F	49.20 (11)
O2^v—M1—M3^ii	37.28 (11)	O4—A—F	49.20 (11)
O2^iv—M1—M3^ii	37.28 (11)	O5^vii—A—T2^viii	105.69 (10)
O2^iv—M1—M3	142.72 (11)	O5^viii—A—T2^viii	26.04 (9)
O2^vii—M1—M3	37.28 (11)	O5^xiv—A—T2^viii	78.30 (9)
O2^v—M1—M3	142.72 (11)	O5—A—T2^viii	164.87 (12)
O2^vii—M1—M3^ii	142.72 (11)	O5^vii—A—O5^xiv	168.12 (19)
O2^vi—M1—M3^ii	142.72 (11)	O5^xiv—A—O5^viii	67.47 (14)
O2^vi—M1—M3	37.28 (11)	O5^vii—A—O5^viii	111.23 (14)
O2^vi—M1—O2^vii	74.6 (2)	O5^xiv—A—O5	111.23 (14)
O2^iv—M1—O2^vii	180.0	O5^vii—A—O5	67.47 (14)
O2^v—M1—O2^iv	74.6 (2)	O5^viii—A—O5	168.26 (19)
O2^v—M1—O2^vi	180.0	O5—A—O7^viii	46.60 (11)
O2^v—M1—O2^vii	105.4 (2)	O5^vii—A—O7^viii	84.65 (12)
O2^vi—M1—O2^iv	105.4 (2)	O5^viii—A—O7^viii	122.19 (13)
M1^xiv—M2—M1	112.64 (6)	O5^viii—A—O7	46.60 (11)
O1^iii—M2—M1^xiv	45.79 (18)	O5^xiv—A—O7^viii	86.39 (12)
O1^iii—M2—M1	79.44 (17)	O5^vii—A—O7	86.39 (12)
O1—M2—M1	45.79 (18)	O5^xiv—A—O7	84.65 (12)
O1—M2—M1^xiv	79.44 (17)	O5—A—O7	122.19 (13)
O1^iii—M2—O1	74.9 (3)	O5^xiv—A—F	95.94 (10)
O2^viii—M2—M1^xiv	49.47 (13)	O5^vii—A—F	95.94 (10)
O2^vi—M2—M1	49.47 (13)	O7^viii—A—T2^viii	148.23 (10)
O2^vi—M2—M1^xiv	137.31 (14)	O7—A—T2^viii	69.12 (8)
O2^viii—M2—M1	137.31 (14)	O7—A—O7^viii	81.97 (17)
O2^viii—M2—O1^iii	95.3 (2)	F—A—T2^viii	70.91 (5)
O2^vi—M2—O1^iii	91.7 (2)	F—A—O5^viii	95.87 (9)
O2^viii—M2—O1	91.7 (2)	F—A—O5	95.87 (9)
O2^vi—M2—O1	95.3 (2)	F—A—O7^viii	139.02 (8)
O2^vi—M2—O2^viii	171.2 (3)	F—A—O7	139.02 (8)
O2^viii—M2—O8^ix	80.32 (18)	T2^xv—BNA—T2^vii	180.0
O2^vi—M2—O8^ix	92.85 (19)	O3^vii—BNA—T2^vii	31.73 (11)
O2^viii—M2—O8	92.85 (19)	O3—BNA—T2^xv	80.90 (12)
O2^vi—M2—O8	80.32 (18)	O3—BNA—T2^vii	99.10 (12)
O8^ix—M2—M1	142.28 (12)	O3^v—BNA—T2^xv	99.10 (12)
O8—M2—M1^xiv	142.28 (13)	O3^v—BNA—T2^vii	80.90 (12)
O8^ix—M2—M1^xiv	93.70 (13)	O3^vii—BNA—T2^xv	148.27 (11)
O8—M2—M1	93.70 (13)	O3^xv—BNA—T2^xv	31.73 (12)
O8—M2—O1	103.6 (2)	O3^xv—BNA—T2^vii	148.27 (12)
O8—M2—O1^iii	171.8 (2)	O3^v—BNA—O3	180.0
O8^ix—M2—O1	171.8 (2)	O3^xv—BNA—O3	64.4 (2)
O8^ix—M2—O1^iii	103.6 (2)	O3^vii—BNA—O3^v	64.4 (2)
O8^ix—M2—O8	79.0 (3)	O3^vii—BNA—O3	115.6 (2)
O2^vi—M3—M1	46.10 (14)	O3^xv—BNA—O3^v	115.6 (2)
O2^vii—M3—M1	46.10 (14)	O3^xv—BNA—O3^vii	180.0 (2)
O2^vii—M3—O2^vi	92.2 (3)	O3^vii—BNA—O4^vii	84.21 (16)
O2^vi—M3—O6^ix	94.41 (18)	O3^v—BNA—O4^xv	63.37 (16)
O2^vii—M3—O6^i	94.41 (18)	O3^vii—BNA—O4	63.37 (16)
O2^vi—M3—O6^i	173.38 (19)	O3^v—BNA—O4^vii	116.63 (16)
O2^vii—M3—O6^ix	173.38 (19)	O3^xv—BNA—O4^vii	95.79 (16)
O6^ix—M3—M1	140.51 (12)	O3—BNA—O4^vii	63.37 (16)
O6^i—M3—M1	140.51 (12)	O3^xv—BNA—O4^v	63.37 (16)
O6^ix—M3—O6^i	79.0 (2)	O3^xv—BNA—O4	116.63 (16)
O8^x—M3—M1	92.33 (16)	O3^v—BNA—O4^v	84.21 (16)
O8—M3—M1	92.33 (16)	O3—BNA—O4	84.21 (16)
O8—M3—O2^vii	97.88 (19)	O3^xv—BNA—O4^xv	84.21 (16)
O8—M3—O2^vi	85.37 (19)	O3—BNA—O4^v	95.79 (16)
O8^x—M3—O2^vi	97.88 (19)	O3^v—BNA—O4	95.79 (16)
O8^x—M3—O2^vii	85.37 (19)	O3—BNA—O4^xv	116.63 (16)
O8^x—M3—O6^i	82.92 (19)	O3^vii—BNA—O4^v	116.63 (16)
O8—M3—O6^i	93.47 (19)	O3^vii—BNA—O4^xv	95.79 (16)
O8—M3—O6^ix	82.92 (19)	O3—BNA—F^i	121.87 (11)
O8^x—M3—O6^ix	93.47 (19)	O3^v—BNA—F^i	58.13 (11)
O8^x—M3—O8	175.3 (3)	O3^v—BNA—F	121.87 (11)
O6—M4—O6^xii	90.22 (16)	O3—BNA—F	58.13 (11)
O6^ix—M4—O6^xi	90.22 (16)	O3^vii—BNA—F	121.87 (11)
O6^xi—M4—O6^xii	80.0 (2)	O3^xv—BNA—F^i	121.87 (11)
O6—M4—O6^ix	169.1 (3)	O3^xv—BNA—F	58.13 (11)
O6^ix—M4—O6^xii	81.43 (18)	O3^vii—BNA—F^i	58.13 (11)
O6—M4—O6^xi	81.43 (18)	O4^vii—BNA—T2^vii	100.32 (12)
O8—M4—O6	102.13 (19)	O4^v—BNA—T2^vii	148.18 (11)
O8^ix—M4—O6^xi	96.10 (19)	O4^vii—BNA—T2^xv	79.68 (12)
O8—M4—O6^ix	85.77 (19)	O4—BNA—T2^xv	148.18 (11)
O8^ix—M4—O6	85.77 (19)	O4^v—BNA—T2^xv	31.82 (11)
O8^ix—M4—O6^xii	174.8 (2)	O4^xv—BNA—T2^vii	79.68 (12)
O8—M4—O6^xi	174.8 (2)	O4—BNA—T2^vii	31.82 (11)
O8^ix—M4—O6^ix	102.13 (19)	O4^xv—BNA—T2^xv	100.32 (12)
O8—M4—O6^xii	96.10 (19)	O4^v—BNA—O4^xv	117.9 (2)
O8^ix—M4—O8	88.0 (3)	O4^v—BNA—O4^vii	62.1 (2)
M1—D—A^xiii	117.83 (3)	O4—BNA—O4^vii	117.9 (2)
M1—D—A	117.83 (3)	O4—BNA—O4^xv	62.1 (2)
A—D—A^xiii	112.26 (6)	O4—BNA—O4^v	180.0
BNA—D—M1	96.38 (4)	O4^xv—BNA—O4^vii	180.0 (2)
BNA^xiv—D—M1	161.61 (5)	O4^v—BNA—F	121.48 (11)
BNA—D—A^xiii	69.24 (3)	O4—BNA—F	58.52 (11)
BNA^xiv—D—A	69.70 (3)	O4^vii—BNA—F	121.48 (11)
BNA—D—A	69.24 (3)	O4^v—BNA—F^i	58.52 (11)
BNA^xiv—D—A^xiii	69.70 (3)	O4—BNA—F^i	121.48 (11)
BNA^xiv—D—BNA	102.01 (4)	O4^vii—BNA—F^i	58.52 (11)
O1—D—M1	35.8 (2)	O4^xv—BNA—F	58.52 (11)
O1—D—A	123.83 (3)	O4^xv—BNA—F^i	121.48 (11)
O1—D—A^xiii	123.83 (3)	F^i—BNA—T2^xv	90.18 (3)
O1—D—BNA^xiv	125.8 (2)	F^i—BNA—T2^vii	89.82 (3)
O1—D—BNA	132.2 (2)	F—BNA—T2^vii	90.18 (3)
O1—D—O3^xiii	102.8 (2)	F—BNA—T2^xv	89.82 (3)
O1—D—O3^viii	102.8 (2)	F^i—BNA—F	180.0
O1—D—O4	104.8 (2)	M2^iii—O1—M1	89.9 (2)
O1—D—O4^xv	104.8 (2)	M2—O1—M1	89.9 (2)
O1—D—F	177.3 (2)	M2^iii—O1—M2	105.1 (3)
O3^xiii—D—M1	125.90 (15)	D—O1—M1	117.1 (4)
O3^viii—D—M1	125.90 (15)	D—O1—M2	122.80 (18)
O3^viii—D—A	44.85 (16)	D—O1—M2^iii	122.80 (18)
O3^xiii—D—A	115.22 (16)	M2^xvii—O2—M1^xvii	89.69 (17)
O3^xiii—D—A^xiii	44.85 (16)	M3^xvii—O2—M1^xvii	96.61 (19)
O3^viii—D—A^xiii	115.22 (16)	M3^xvii—O2—M2^xvii	96.86 (19)
O3^viii—D—BNA	111.52 (16)	T2—O2—M1^xvii	118.7 (2)
O3^xiii—D—BNA^xiv	46.09 (15)	T2—O2—M2^xvii	126.3 (3)
O3^viii—D—BNA^xiv	46.09 (15)	T2—O2—M3^xvii	121.0 (3)
O3^xiii—D—BNA	111.52 (16)	D^xiii—O3—A	106.4 (2)
O3^xiii—D—O3^viii	86.2 (3)	D^xiii—O3—BNA	99.8 (2)
O3^xiii—D—F	75.30 (15)	T2—O3—D^xiii	136.1 (3)
O3^viii—D—F	75.30 (15)	T2—O3—A	110.7 (2)
O4^xv—D—M1	78.86 (15)	T2—O3—BNA	94.2 (2)
O4—D—M1	78.86 (15)	BNA—O3—A	102.78 (16)
O4—D—A	46.26 (16)	D—O4—A	104.8 (2)
O4^xv—D—A	116.30 (17)	D—O4—BNA	99.0 (2)
O4—D—A^xiii	116.30 (17)	T2^vii—O4—D	142.1 (3)
O4^xv—D—A^xiii	46.26 (16)	T2^vii—O4—A	109.3 (2)
O4^xv—D—BNA	47.28 (17)	T2^vii—O4—BNA	91.3 (2)
O4^xv—D—BNA^xiv	113.92 (16)	BNA—O4—A	99.57 (16)
O4—D—BNA^xiv	113.92 (16)	T1^viii—O5—T2	139.2 (3)
O4—D—BNA	47.28 (17)	T1^viii—O5—A	105.7 (2)
O4^xv—D—O3^xiii	87.3 (2)	T1^viii—O5—A^i	109.3 (2)
O4^xv—D—O3^viii	152.4 (2)	T2—O5—A^i	95.8 (2)
O4—D—O3^viii	87.3 (2)	T2—O5—A	93.8 (2)
O4—D—O3^xiii	152.4 (2)	A^i—O5—A	111.23 (14)
O4^xv—D—O4	86.2 (3)	M4—O6—M3^xiv	90.14 (17)
O4^xv—D—F	77.13 (16)	M4^xi—O6—M3^xiv	100.50 (19)
O4—D—F	77.13 (16)	M4—O6—M4^xi	98.57 (18)
F—D—M1	146.89 (6)	T1—O6—M3^xiv	119.7 (2)
F—D—A^xiii	56.13 (3)	T1—O6—M4	121.5 (3)
F—D—A	56.13 (3)	T1—O6—M4^xi	120.3 (2)
F—D—BNA^xiv	51.50 (3)	T1—O7—T1^xii	136.8 (3)
F—D—BNA	50.51 (3)	T1^xii—O7—A	104.5 (2)
O5^viii—T1—O7^xvi	106.2 (3)	T1—O7—A	101.0 (2)
O5^viii—T1—O7	106.6 (3)	M3—O8—M2	96.6 (2)
O6—T1—O5^viii	111.8 (3)	M4—O8—M2	96.5 (2)
O6—T1—O7	111.3 (2)	M4—O8—M3	100.9 (2)
O6—T1—O7^xvi	111.6 (2)	D—F—D^xiii	180.0
O7—T1—O7^xvi	108.93 (19)	D^xiii—F—A^xiii	90.0
M1^xvii—T2—A	147.84 (6)	D—F—A	90.0
M1^xvii—T2—A^i	120.25 (5)	D^xiii—F—A	90.0
A—T2—A^i	90.75 (5)	D—F—A^xiii	90.0
BNA—T2—M1^xvii	103.35 (5)	D^xiii—F—BNA	89.19 (4)
BNA—T2—A^i	74.80 (5)	D—F—BNA	90.81 (4)
BNA—T2—A	75.01 (5)	D^xiii—F—BNA^xiv	90.81 (4)
O2—T2—M1^xvii	37.33 (17)	D—F—BNA^xiv	89.19 (4)
O2—T2—A	126.72 (18)	A—F—A^xiii	180.0
O2—T2—A^i	131.78 (18)	BNA^xiv—F—A^xiii	90.0
O2—T2—BNA	137.42 (19)	BNA^xiv—F—A	90.0
O2—T2—O5	111.0 (3)	BNA—F—A	90.0
O3—T2—M1^xvii	107.00 (19)	BNA—F—A^xiii	90.0
O3—T2—A	45.45 (19)	BNA^xiv—F—BNA	180.0

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z; (iii) −x+2, −y+1, −z; (iv) x, −y+1, z−1; (v) −x+1, −y+1, −z+1; (vi) x, y, z−1; (vii) −x+1, y, −z+1; (viii) −x+2, y, −z+1; (ix) −x+2, y, −z; (x) −x+1, y, −z; (xi) −x+5/2, −y+1/2, −z; (xii) x−1/2, −y+1/2, z; (xiii) −x+2, −y+1, −z+1; (xiv) x+1, y, z; (xv) x, −y+1, z; (xvi) x+1/2, −y+1/2, z; (xvii) x, y, z+1.

(lb570-2)

Crystal data

0.5(Ca0.23F0.38Fe9.05K3.86Na3.71O60Si15.15Ti3.95)	F(000) = 1136
Mr = 1166.43	Dx = 3.059 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 5.3369 (5) Å	Cell parameters from 3351 reflections
b = 23.2155 (14) Å	θ = 1.7–35.7°
c = 10.3600 (11) Å	µ = 3.98 mm^−1
β = 99.401 (9)°	T = 293 K
V = 1266.4 (2) Å^3	Prism, browm
Z = 2	0.22 × 0.18 × 0.11 mm

Data collection

Saxi-CrysAlisPro-abstract goniometer imported SAXI images diffractometer	2993 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2302 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.085
ω scans	θmax = 36.2°, θmin = 1.8°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→8
Tmin = 0.825, Tmax = 1.000	k = −37→37
10198 measured reflections	l = −16→15

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: dual
R[F^2 > 2σ(F^2)] = 0.104	w = 1/[σ^2(Fo^2) + 34.8374P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.156	(Δ/σ)max < 0.001
S = 1.27	Δρmax = 1.75 e Å^−3
2993 reflections	Δρmin = −1.61 e Å^−3
133 parameters

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
M1	0.500000	0.500000	0.000000	0.0133 (14)	0.97 (2)
M2	1.000000	0.42325 (7)	0.000000	0.0180 (5)	0.805 (8)
M3	0.500000	0.35521 (6)	0.000000	0.0122 (4)	0.776 (7)
M4	1.000000	0.29030 (7)	0.000000	0.0127 (5)	0.682 (7)
D	0.9389 (3)	0.500000	0.28800 (15)	0.0114 (4)	0.987 (9)
T1	1.4213 (3)	0.28187 (6)	0.26655 (15)	0.0093 (4)	0.948 (10)
T2	0.5728 (3)	0.41409 (6)	0.72732 (16)	0.0091 (4)	0.945 (10)
A	1.000000	0.36099 (10)	0.500000	0.0295 (7)	0.966 (11)
BNA	0.500000	0.500000	0.500000	0.0164 (17)	0.88 (3)
BCA	0.500000	0.500000	0.500000	0.0164 (17)	0.12 (3)
O1	0.9055 (12)	0.500000	0.1149 (7)	0.0257 (15)
O2	0.6377 (8)	0.41638 (18)	0.8872 (4)	0.0162 (8)
O3	0.7963 (8)	0.44275 (19)	0.6611 (5)	0.0213 (9)
O4	0.6984 (8)	0.44269 (19)	0.3296 (5)	0.0226 (10)
O5	0.5507 (9)	0.34670 (17)	0.6749 (4)	0.0199 (9)
O6	1.3706 (7)	0.28176 (17)	0.1082 (4)	0.0133 (7)
O7	1.1854 (8)	0.25206 (19)	0.3255 (4)	0.0188 (9)
O8	0.8544 (8)	0.3519 (2)	0.0973 (5)	0.0202 (9)
F	1.000000	0.500000	0.500000	0.023 (12)*	0.19 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
M1	0.013 (2)	0.0035 (19)	0.022 (3)	0.000	−0.0022 (17)	0.000
M2	0.0105 (7)	0.0233 (9)	0.0187 (8)	0.000	−0.0016 (5)	0.000
M3	0.0122 (6)	0.0069 (6)	0.0180 (8)	0.000	0.0041 (5)	0.000
M4	0.0105 (7)	0.0126 (8)	0.0148 (9)	0.000	0.0013 (5)	0.000
D	0.0071 (5)	0.0109 (6)	0.0165 (7)	0.000	0.0027 (4)	0.000
T1	0.0101 (7)	0.0071 (6)	0.0107 (8)	0.0008 (5)	0.0016 (5)	−0.0004 (5)
T2	0.0093 (7)	0.0054 (6)	0.0129 (8)	0.0008 (5)	0.0022 (5)	0.0009 (5)
A	0.0286 (11)	0.0240 (11)	0.0367 (14)	0.000	0.0072 (9)	0.000
BNA	0.020 (2)	0.013 (2)	0.015 (3)	0.000	−0.0006 (16)	0.000
BCA	0.020 (2)	0.013 (2)	0.015 (3)	0.000	−0.0006 (16)	0.000
O1	0.014 (3)	0.042 (4)	0.023 (4)	0.000	0.006 (2)	0.000
O2	0.0179 (18)	0.0141 (17)	0.017 (2)	−0.0011 (14)	0.0040 (15)	−0.0005 (15)
O3	0.018 (2)	0.023 (2)	0.023 (2)	−0.0083 (16)	0.0035 (17)	−0.0008 (17)
O4	0.018 (2)	0.021 (2)	0.029 (3)	−0.0074 (16)	0.0039 (17)	0.0011 (18)
O5	0.029 (2)	0.0096 (17)	0.021 (2)	0.0006 (15)	0.0033 (17)	0.0013 (15)
O6	0.0132 (16)	0.0123 (16)	0.0144 (19)	0.0023 (13)	0.0022 (13)	0.0007 (14)
O7	0.0139 (18)	0.022 (2)	0.022 (2)	−0.0081 (15)	0.0049 (15)	−0.0011 (17)
O8	0.0168 (18)	0.023 (2)	0.022 (2)	0.0015 (16)	0.0069 (16)	0.0004 (17)

Geometric parameters (Å, º)

M1—M2	3.2086 (9)	D—O3^viii	1.949 (4)
M1—M2^i	3.2087 (9)	D—O4^xv	1.945 (4)
M1—M2^ii	3.2087 (9)	D—O4	1.945 (4)
M1—M2^iii	3.2087 (9)	D—F	2.1670 (16)
M1—M3	3.3614 (14)	T1—O5^viii	1.621 (4)
M1—M3^ii	3.3615 (14)	T1—O6	1.619 (4)
M1—O1^ii	2.293 (7)	T1—O7	1.640 (4)
M1—O1	2.293 (7)	T1—O7^xvi	1.643 (4)
M1—O2^iv	2.440 (4)	T2—A	3.7439 (18)
M1—O2^v	2.440 (4)	T2—A^iii	3.7497 (18)
M1—O2^vi	2.440 (4)	T2—BNA	3.0620 (16)
M1—O2^vii	2.440 (4)	T2—O2	1.637 (5)
M2—O1	2.246 (4)	T2—O3	1.613 (5)
M2—O1^i	2.246 (4)	T2—O4^vii	1.614 (5)
M2—O2^vi	2.095 (4)	T2—O5	1.654 (4)
M2—O2^viii	2.095 (4)	A—O3	2.857 (5)
M2—O8	2.150 (5)	A—O3^viii	2.857 (5)
M2—O8^ix	2.149 (5)	A—O4^viii	2.894 (5)
M3—O2^vii	2.050 (4)	A—O4	2.894 (5)
M3—O2^vi	2.050 (4)	A—O5	3.250 (5)
M3—O6^ix	2.212 (4)	A—O5^vii	3.208 (5)
M3—O6^iii	2.212 (4)	A—O5^viii	3.250 (5)
M3—O8^x	1.994 (4)	A—O5^xiv	3.208 (5)
M3—O8	1.994 (4)	A—O7	3.351 (5)
M4—O6^ix	2.117 (4)	A—O7^viii	3.351 (5)
M4—O6^xi	2.187 (4)	A—F	3.227 (2)
M4—O6^xii	2.187 (4)	BNA—O3	2.488 (5)
M4—O6	2.117 (4)	BNA—O3^v	2.488 (5)
M4—O8	1.981 (5)	BNA—O3^xv	2.488 (5)
M4—O8^ix	1.981 (5)	BNA—O3^vii	2.488 (5)
D—A	3.887 (2)	BNA—O4	2.572 (5)
D—A^xiii	3.887 (2)	BNA—O4^xv	2.572 (5)
D—BNA^xiv	3.4120 (15)	BNA—O4^vii	2.572 (5)
D—BNA	3.4629 (15)	BNA—O4^v	2.572 (5)
D—O1	1.773 (7)	BNA—F^iii	2.6685 (3)
D—O3^xiii	1.949 (4)	BNA—F	2.6685 (3)
M2—M1—M2^iii	112.54 (5)	O3—T2—O2	111.6 (2)
M2^iii—M1—M2^i	180.00 (5)	O3—T2—O4^vii	110.9 (3)
M2—M1—M2^i	67.46 (5)	O3—T2—O5	105.6 (2)
M2^i—M1—M2^ii	112.54 (5)	O4^vii—T2—A^iii	46.77 (18)
M2—M1—M2^ii	180.0	O4^vii—T2—A	120.49 (19)
M2^iii—M1—M2^ii	67.46 (5)	O4^vii—T2—BNA	57.14 (18)
M2^i—M1—M3^ii	56.27 (2)	O4^vii—T2—O2	112.7 (2)
M2^ii—M1—M3	123.73 (2)	O4^vii—T2—O5	104.9 (2)
M2^ii—M1—M3^ii	56.27 (2)	O5—T2—A^iii	58.37 (17)
M2^i—M1—M3	123.73 (2)	O5—T2—A	60.01 (17)
M2—M1—M3	56.27 (2)	O5—T2—BNA	111.72 (17)
M2—M1—M3^ii	123.73 (2)	O3^viii—A—T2	118.53 (11)
M2^iii—M1—M3^ii	123.73 (2)	O3—A—T2	23.78 (9)
M2^iii—M1—M3	56.27 (2)	O3^viii—A—O3	96.74 (19)
M3—M1—M3^ii	180.0	O3^viii—A—O4^viii	72.19 (14)
O1^ii—M1—M2^iii	44.41 (11)	O3—A—O4	72.19 (14)
O1^ii—M1—M2	135.59 (11)	O3—A—O4^viii	55.60 (13)
O1—M1—M2	44.41 (11)	O3^viii—A—O4	55.60 (13)
O1—M1—M2^ii	135.59 (11)	O3^viii—A—O5^xiv	89.87 (12)
O1—M1—M2^i	44.41 (11)	O3^viii—A—O5^vii	98.03 (13)
O1^ii—M1—M2^i	135.59 (11)	O3^viii—A—O5^viii	49.94 (11)
O1—M1—M2^iii	135.59 (11)	O3^viii—A—O5	141.19 (13)
O1^ii—M1—M2^ii	44.41 (11)	O3—A—O5^vii	89.87 (12)
O1^ii—M1—M3	90.0	O3—A—O5^xiv	98.03 (13)
O1—M1—M3^ii	90.0	O3—A—O5	49.94 (11)
O1^ii—M1—M3^ii	90.0	O3—A—O5^viii	141.19 (13)
O1—M1—M3	90.0	O3^viii—A—O7^viii	172.17 (13)
O1^ii—M1—O1	180.0	O3^viii—A—O7	90.69 (11)
O1—M1—O2^vii	94.82 (14)	O3—A—O7	172.17 (13)
O1^ii—M1—O2^v	85.18 (14)	O3—A—O7^viii	90.69 (11)
O1—M1—O2^v	94.82 (14)	O3^viii—A—F	48.37 (10)
O1—M1—O2^iv	85.18 (14)	O3—A—F	48.37 (10)
O1—M1—O2^vi	85.18 (14)	O4^viii—A—T2	74.67 (10)
O1^ii—M1—O2^vii	85.18 (14)	O4—A—T2	80.37 (11)
O1^ii—M1—O2^iv	94.82 (14)	O4^viii—A—O4	98.10 (19)
O1^ii—M1—O2^vi	94.82 (14)	O4—A—O5	91.11 (12)
O2^v—M1—M2^i	82.75 (10)	O4^viii—A—O5^viii	91.11 (12)
O2^v—M1—M2^ii	40.77 (10)	O4—A—O5^vii	49.94 (11)
O2^vi—M1—M2	40.77 (10)	O4—A—O5^viii	96.57 (13)
O2^vi—M1—M2^iii	82.75 (10)	O4^viii—A—O5^vii	141.19 (13)
O2^iv—M1—M2^iii	139.23 (10)	O4^viii—A—O5^xiv	49.94 (11)
O2^vii—M1—M2^ii	97.25 (10)	O4—A—O5^xiv	141.18 (13)
O2^vii—M1—M2^i	139.23 (10)	O4^viii—A—O5	96.57 (13)
O2^v—M1—M2^iii	97.25 (10)	O4—A—O7	110.45 (12)
O2^vi—M1—M2^i	97.25 (10)	O4^viii—A—O7	129.79 (11)
O2^vi—M1—M2^ii	139.23 (10)	O4—A—O7^viii	129.79 (12)
O2^iv—M1—M2^i	40.77 (10)	O4^viii—A—O7^viii	110.45 (12)
O2^iv—M1—M2^ii	82.75 (10)	O4—A—F	49.05 (10)
O2^iv—M1—M2	97.25 (10)	O4^viii—A—F	49.05 (10)
O2^vii—M1—M2	82.75 (10)	O5^vii—A—T2	78.08 (8)
O2^v—M1—M2	139.23 (10)	O5^viii—A—T2	164.76 (10)
O2^vii—M1—M2^iii	40.77 (10)	O5—A—T2	26.16 (8)
O2^v—M1—M3^ii	37.29 (10)	O5^xiv—A—T2	105.94 (9)
O2^vi—M1—M3	37.29 (10)	O5^vii—A—O5^viii	111.47 (13)
O2^vii—M1—M3^ii	142.71 (10)	O5^vii—A—O5	67.22 (14)
O2^v—M1—M3	142.71 (10)	O5^viii—A—O5	168.28 (17)
O2^iv—M1—M3^ii	37.29 (10)	O5^vii—A—O5^xiv	168.13 (17)
O2^iv—M1—M3	142.71 (10)	O5^xiv—A—O5	111.47 (13)
O2^vi—M1—M3^ii	142.71 (10)	O5^xiv—A—O5^viii	67.22 (14)
O2^vii—M1—M3	37.29 (10)	O5^vii—A—O7	86.63 (11)
O2^v—M1—O2^vi	180.00 (18)	O5^viii—A—O7^viii	122.24 (12)
O2^v—M1—O2^iv	74.6 (2)	O5^xiv—A—O7^viii	86.63 (11)
O2^vi—M1—O2^vii	74.6 (2)	O5^vii—A—O7^viii	84.42 (11)
O2^iv—M1—O2^vii	180.00 (18)	O5—A—O7	122.24 (12)
O2^vi—M1—O2^iv	105.4 (2)	O5—A—O7^viii	46.56 (10)
O2^v—M1—O2^vii	105.4 (2)	O5^xiv—A—O7	84.42 (11)
M1^xiv—M2—M1	112.54 (5)	O5^viii—A—O7	46.56 (10)
O1—M2—M1	45.62 (17)	O5^vii—A—F	95.94 (8)
O1^i—M2—M1	79.53 (15)	O5^xiv—A—F	95.94 (8)
O1—M2—M1^xiv	79.53 (15)	O7^viii—A—T2	69.23 (7)
O1^i—M2—M1^xiv	45.62 (17)	O7—A—T2	148.40 (9)
O1^i—M2—O1	75.0 (3)	O7^viii—A—O7	82.00 (16)
O2^viii—M2—M1^xiv	49.50 (12)	F—A—T2	70.78 (4)
O2^vi—M2—M1	49.50 (12)	F—A—O5	95.86 (8)
O2^viii—M2—M1	137.22 (13)	F—A—O5^viii	95.86 (8)
O2^vi—M2—M1^xiv	137.22 (13)	F—A—O7^viii	139.00 (8)
O2^vi—M2—O1	95.1 (2)	F—A—O7	139.00 (8)
O2^viii—M2—O1	91.8 (2)	T2^xv—BNA—T2^vii	180.0
O2^vi—M2—O1^i	91.8 (2)	O3^xv—BNA—T2^vii	148.30 (10)
O2^viii—M2—O1^i	95.1 (2)	O3^v—BNA—T2^xv	98.91 (11)
O2^vi—M2—O2^viii	171.3 (2)	O3^v—BNA—T2^vii	81.09 (11)
O2^viii—M2—O8^ix	80.30 (17)	O3^xv—BNA—T2^xv	31.70 (10)
O2^vi—M2—O8	80.30 (17)	O3—BNA—T2^xv	81.09 (11)
O2^vi—M2—O8^ix	92.94 (17)	O3^vii—BNA—T2^vii	31.70 (10)
O2^viii—M2—O8	92.94 (17)	O3—BNA—T2^vii	98.91 (11)
O8^ix—M2—M1	142.40 (12)	O3^vii—BNA—T2^xv	148.30 (10)
O8—M2—M1	93.64 (11)	O3—BNA—O3^vii	115.4 (2)
O8—M2—M1^xiv	142.40 (12)	O3^vii—BNA—O3^v	64.6 (2)
O8^ix—M2—M1^xiv	93.64 (11)	O3^xv—BNA—O3^vii	180.00 (18)
O8—M2—O1^i	171.8 (2)	O3—BNA—O3^v	180.0
O8^ix—M2—O1	171.8 (2)	O3—BNA—O3^xv	64.6 (2)
O8—M2—O1	103.47 (18)	O3^xv—BNA—O3^v	115.4 (2)
O8^ix—M2—O1^i	103.47 (18)	O3^v—BNA—O4	95.96 (15)
O8^ix—M2—O8	79.2 (2)	O3—BNA—O4^vii	63.33 (14)
O2^vii—M3—M1	46.15 (12)	O3^xv—BNA—O4	116.67 (14)
O2^vi—M3—M1	46.15 (12)	O3^vii—BNA—O4^xv	95.96 (15)
O2^vii—M3—O2^vi	92.3 (2)	O3^vii—BNA—O4^v	116.67 (14)
O2^vi—M3—O6^iii	173.42 (17)	O3^v—BNA—O4^xv	63.33 (14)
O2^vii—M3—O6^iii	94.28 (16)	O3—BNA—O4	84.04 (15)
O2^vii—M3—O6^ix	173.42 (17)	O3^v—BNA—O4^vii	116.67 (14)
O2^vi—M3—O6^ix	94.28 (16)	O3^vii—BNA—O4	63.33 (14)
O6^iii—M3—M1	140.43 (11)	O3^xv—BNA—O4^vii	95.96 (15)
O6^ix—M3—M1	140.43 (11)	O3^v—BNA—O4^v	84.04 (15)
O6^ix—M3—O6^iii	79.1 (2)	O3—BNA—O4^v	95.96 (15)
O8^x—M3—M1	92.20 (14)	O3—BNA—O4^xv	116.67 (14)
O8—M3—M1	92.20 (14)	O3^xv—BNA—O4^v	63.33 (14)
O8—M3—O2^vi	85.19 (18)	O3^vii—BNA—O4^vii	84.04 (15)
O8—M3—O2^vii	97.88 (18)	O3^xv—BNA—O4^xv	84.04 (15)
O8^x—M3—O2^vii	85.19 (18)	O3^v—BNA—F^iii	58.26 (10)
O8^x—M3—O2^vi	97.88 (18)	O3^xv—BNA—F^iii	121.74 (10)
O8^x—M3—O6^ix	93.61 (17)	O3^vii—BNA—F	121.74 (10)
O8—M3—O6^iii	93.61 (17)	O3^v—BNA—F	121.74 (10)
O8^x—M3—O6^iii	82.99 (17)	O3^xv—BNA—F	58.26 (10)
O8—M3—O6^ix	82.98 (17)	O3^vii—BNA—F^iii	58.26 (10)
O8—M3—O8^x	175.6 (3)	O3—BNA—F	58.26 (10)
O6^ix—M4—O6^xii	81.60 (17)	O3—BNA—F^iii	121.74 (10)
O6^ix—M4—O6^xi	90.17 (14)	O4—BNA—T2^xv	148.19 (10)
O6—M4—O6^xii	90.17 (14)	O4^xv—BNA—T2^vii	79.86 (11)
O6—M4—O6^xi	81.60 (17)	O4—BNA—T2^vii	31.81 (10)
O6^ix—M4—O6	169.3 (2)	O4^v—BNA—T2^vii	148.19 (10)
O6^xi—M4—O6^xii	80.2 (2)	O4^xv—BNA—T2^xv	100.14 (11)
O8^ix—M4—O6^ix	102.03 (17)	O4^vii—BNA—T2^vii	100.14 (11)
O8—M4—O6^ix	85.80 (17)	O4^v—BNA—T2^xv	31.81 (10)
O8^ix—M4—O6^xi	96.23 (16)	O4^vii—BNA—T2^xv	79.86 (11)
O8—M4—O6^xii	96.23 (16)	O4^v—BNA—O4^vii	62.3 (2)
O8^ix—M4—O6	85.80 (17)	O4—BNA—O4^xv	62.3 (2)
O8—M4—O6	102.03 (17)	O4—BNA—O4^vii	117.7 (2)
O8—M4—O6^xi	174.99 (17)	O4—BNA—O4^v	180.0
O8^ix—M4—O6^xii	174.99 (17)	O4^v—BNA—O4^xv	117.7 (2)
O8—M4—O8^ix	87.5 (3)	O4^xv—BNA—O4^vii	180.00 (17)
M1—D—A	117.84 (3)	O4^xv—BNA—F^iii	121.58 (10)
M1—D—A^xiii	117.84 (3)	O4—BNA—F	58.42 (10)
A^xiii—D—A	112.24 (5)	O4^vii—BNA—F	121.58 (10)
BNA—D—M1	96.51 (3)	O4^v—BNA—F^iii	58.42 (10)
BNA^xiv—D—M1	161.64 (5)	O4^v—BNA—F	121.58 (10)
BNA—D—A	69.18 (3)	O4^vii—BNA—F^iii	58.42 (10)
BNA^xiv—D—A^xiii	69.67 (2)	O4^xv—BNA—F	58.42 (10)
BNA—D—A^xiii	69.18 (3)	O4—BNA—F^iii	121.58 (10)
BNA^xiv—D—A	69.67 (2)	F—BNA—T2^vii	90.08 (3)
BNA^xiv—D—BNA	101.84 (4)	F—BNA—T2^xv	89.92 (3)
O1—D—M1	35.9 (2)	F^iii—BNA—T2^xv	90.08 (3)
O1—D—A^xiii	123.83 (3)	F^iii—BNA—T2^vii	89.92 (3)
O1—D—A	123.83 (3)	F^iii—BNA—F	180.0
O1—D—BNA^xiv	125.7 (2)	M2^i—O1—M1	90.0 (2)
O1—D—BNA	132.4 (2)	M2—O1—M1	90.0 (2)
O1—D—O3^xiii	102.9 (2)	M2—O1—M2^i	105.0 (3)
O1—D—O3^viii	102.9 (2)	D—O1—M1	117.1 (3)
O1—D—O4	105.3 (2)	D—O1—M2^i	122.82 (19)
O1—D—O4^xv	105.3 (2)	D—O1—M2	122.82 (19)
O1—D—F	177.2 (2)	M2^xvii—O2—M1^xvii	89.72 (16)
O3^viii—D—M1	126.08 (15)	M3^xvii—O2—M1^xvii	96.56 (17)
O3^xiii—D—M1	126.08 (15)	M3^xvii—O2—M2^xvii	96.84 (18)
O3^viii—D—A^xiii	115.04 (15)	T2—O2—M1^xvii	118.7 (2)
O3^xiii—D—A	115.04 (15)	T2—O2—M2^xvii	126.2 (2)
O3^viii—D—A	44.83 (14)	T2—O2—M3^xvii	121.2 (2)
O3^xiii—D—A^xiii	44.83 (14)	D^xiii—O3—A	106.43 (19)
O3^viii—D—BNA^xiv	45.94 (15)	D^xiii—O3—BNA	99.82 (19)
O3^viii—D—BNA	111.35 (15)	T2—O3—D^xiii	136.0 (3)
O3^xiii—D—BNA^xiv	45.94 (14)	T2—O3—A	110.6 (2)
O3^xiii—D—BNA	111.35 (15)	T2—O3—BNA	94.2 (2)
O3^xiii—D—O3^viii	86.0 (3)	BNA—O3—A	102.93 (16)
O3^xiii—D—F	75.13 (15)	D—O4—A	105.19 (19)
O3^viii—D—F	75.13 (15)	D—O4—BNA	99.14 (19)
O4^xv—D—M1	79.28 (15)	T2^vii—O4—D	141.7 (3)
O4—D—M1	79.28 (15)	T2^vii—O4—A	109.2 (2)
O4^xv—D—A^xiii	45.93 (14)	T2^vii—O4—BNA	91.1 (2)
O4—D—A	45.93 (14)	BNA—O4—A	99.83 (16)
O4—D—A^xiii	116.10 (16)	T1^viii—O5—T2	139.3 (3)
O4^xv—D—A	116.10 (16)	T1^viii—O5—A	105.8 (2)
O4—D—BNA^xiv	113.50 (15)	T1^viii—O5—A^iii	109.1 (2)
O4^xv—D—BNA^xiv	113.50 (15)	T2—O5—A	93.84 (19)
O4—D—BNA	47.17 (15)	T2—O5—A^iii	95.59 (19)
O4^xv—D—BNA	47.17 (15)	A^iii—O5—A	111.47 (13)
O4—D—O3^xiii	151.9 (2)	M4^xi—O6—M3^xiv	100.32 (17)
O4^xv—D—O3^xiii	87.1 (2)	M4—O6—M3^xiv	90.09 (15)
O4—D—O3^viii	87.1 (2)	M4—O6—M4^xi	98.40 (17)
O4^xv—D—O3^viii	151.9 (2)	T1—O6—M3^xiv	119.9 (2)
O4—D—O4^xv	86.3 (3)	T1—O6—M4	121.6 (2)
O4—D—F	76.75 (16)	T1—O6—M4^xi	120.4 (2)
O4^xv—D—F	76.75 (16)	T1—O7—T1^xii	136.8 (3)
F—D—M1	146.91 (6)	T1^xii—O7—A	104.57 (19)
F—D—A^xiii	56.12 (3)	T1—O7—A	101.23 (19)
F—D—A	56.12 (3)	M3—O8—M2	96.8 (2)
F—D—BNA	50.40 (3)	M4—O8—M2	96.63 (18)
F—D—BNA^xiv	51.44 (3)	M4—O8—M3	100.9 (2)
O5^viii—T1—O7	106.4 (2)	D^xiii—F—D	180.0
O5^viii—T1—O7^xvi	106.6 (2)	D^xiii—F—A	90.0
O6—T1—O5^viii	111.8 (2)	D—F—A	90.0
O6—T1—O7^xvi	111.5 (2)	D^xiii—F—A^xiii	90.0
O6—T1—O7	111.4 (2)	D—F—A^xiii	90.0
O7—T1—O7^xvi	108.88 (18)	D—F—BNA	90.87 (4)
A—T2—A^iii	90.83 (4)	D^xiii—F—BNA	89.13 (4)
BNA—T2—A^iii	75.11 (4)	D—F—BNA^xiv	89.13 (4)
BNA—T2—A	75.20 (4)	D^xiii—F—BNA^xiv	90.87 (4)
O2—T2—A	126.69 (16)	A^xiii—F—A	180.0
O2—T2—A^iii	131.47 (16)	BNA^xiv—F—A	90.0
O2—T2—BNA	137.43 (16)	BNA^xiv—F—A^xiii	90.0
O2—T2—O5	110.8 (2)	BNA—F—A^xiii	90.0
O3—T2—A^iii	116.88 (18)	BNA—F—A	90.0
O3—T2—A	45.57 (17)	BNA^xiv—F—BNA	180.0
O3—T2—BNA	54.14 (18)

Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, −y+1, −z; (iii) x−1, y, z; (iv) x, −y+1, z−1; (v) −x+1, −y+1, −z+1; (vi) x, y, z−1; (vii) −x+1, y, −z+1; (viii) −x+2, y, −z+1; (ix) −x+2, y, −z; (x) −x+1, y, −z; (xi) −x+5/2, −y+1/2, −z; (xii) x−1/2, −y+1/2, z; (xiii) −x+2, −y+1, −z+1; (xiv) x+1, y, z; (xv) x, −y+1, z; (xvi) x+1/2, −y+1/2, z; (xvii) x, y, z+1.

(lb590)

Crystal data

0.5(Ca0.16F0.32Fe8.88K3.83Na3.84O60Si14.99Ti3.89)	F(000) = 1127
Mr = 1156.94	Dx = 3.097 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 5.3003 (5) Å	Cell parameters from 2317 reflections
b = 23.066 (3) Å	θ = 1.8–35.9°
c = 10.284 (1) Å	µ = 3.99 mm^−1
β = 99.338 (9)°	T = 293 K
V = 1240.6 (2) Å^3	Prism, brown
Z = 2	0.22 × 0.18 × 0.11 mm

Data collection

Saxi-CrysAlisPro-abstract goniometer imported SAXI images diffractometer	3001 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2182 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.090
ω scans	θmax = 36.4°, θmin = 1.8°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→8
Tmin = 0.870, Tmax = 1.000	k = −36→38
11359 measured reflections	l = −17→17

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: dual
R[F^2 > 2σ(F^2)] = 0.115	w = 1/[σ^2(Fo^2) + 26.0508P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.142	(Δ/σ)max < 0.001
S = 1.26	Δρmax = 1.24 e Å^−3
3001 reflections	Δρmin = −1.32 e Å^−3
132 parameters

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
M1	0.500000	0.500000	0.000000	0.0168 (10)
M2	1.000000	0.42222 (8)	0.000000	0.0204 (5)	0.777 (7)
M3	0.500000	0.35525 (7)	0.000000	0.0107 (4)	0.769 (6)
M4	1.000000	0.29117 (8)	0.000000	0.0116 (5)	0.673 (6)
D	0.9394 (3)	0.500000	0.28763 (14)	0.0098 (4)	0.973 (8)
T1	1.4211 (3)	0.28202 (7)	0.26717 (15)	0.0089 (4)	0.944 (9)
T2	0.5720 (3)	0.41403 (7)	0.72659 (15)	0.0084 (4)	0.930 (9)
A	1.000000	0.36082 (10)	0.500000	0.0276 (7)	0.956 (10)
BNA	0.500000	0.500000	0.500000	0.0128 (16)	0.92 (3)
BCA	0.500000	0.500000	0.500000	0.0128 (16)	0.08 (3)
O1	0.9062 (13)	0.500000	0.1136 (7)	0.0282 (16)
O2	0.6375 (8)	0.41630 (18)	0.8869 (4)	0.0160 (8)
O3	0.7970 (8)	0.44259 (19)	0.6603 (4)	0.0201 (9)
O4	0.6988 (8)	0.44271 (19)	0.3305 (5)	0.0214 (10)
O5	0.5501 (9)	0.34677 (18)	0.6739 (4)	0.0206 (9)
O6	1.3698 (7)	0.28150 (17)	0.1080 (4)	0.0136 (8)
O7	1.1846 (8)	0.2524 (2)	0.3252 (4)	0.0186 (9)
O8	0.8520 (8)	0.3518 (2)	0.0958 (4)	0.0202 (9)
F	1.000000	0.500000	0.500000	0.020 (14)*	0.16 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
M1	0.015 (2)	0.010 (2)	0.025 (3)	0.000	−0.0006 (19)	0.000
M2	0.0079 (8)	0.0301 (11)	0.0213 (9)	0.000	−0.0036 (6)	0.000
M3	0.0099 (6)	0.0093 (7)	0.0131 (7)	0.000	0.0028 (5)	0.000
M4	0.0082 (7)	0.0149 (9)	0.0118 (8)	0.000	0.0016 (5)	0.000
D	0.0048 (6)	0.0131 (7)	0.0115 (6)	0.000	0.0012 (4)	0.000
T1	0.0075 (7)	0.0093 (7)	0.0098 (7)	−0.0009 (5)	0.0012 (5)	−0.0014 (5)
T2	0.0074 (7)	0.0082 (7)	0.0094 (7)	0.0013 (5)	0.0010 (5)	0.0005 (5)
A	0.0256 (11)	0.0254 (11)	0.0328 (12)	0.000	0.0073 (9)	0.000
BNA	0.015 (2)	0.014 (2)	0.010 (2)	0.000	−0.0001 (15)	0.000
BCA	0.015 (2)	0.014 (2)	0.010 (2)	0.000	−0.0001 (15)	0.000
O1	0.015 (3)	0.053 (5)	0.016 (3)	0.000	0.002 (2)	0.000
O2	0.0145 (19)	0.019 (2)	0.0140 (18)	−0.0010 (15)	0.0016 (15)	0.0009 (15)
O3	0.015 (2)	0.024 (2)	0.022 (2)	−0.0052 (17)	0.0048 (16)	0.0007 (17)
O4	0.016 (2)	0.021 (2)	0.027 (2)	−0.0090 (17)	0.0029 (17)	−0.0008 (18)
O5	0.031 (2)	0.015 (2)	0.0148 (18)	0.0006 (17)	0.0018 (17)	0.0022 (15)
O6	0.0111 (17)	0.0136 (18)	0.0157 (18)	0.0017 (14)	0.0012 (14)	−0.0026 (15)
O7	0.0143 (19)	0.024 (2)	0.0173 (19)	−0.0097 (16)	0.0026 (15)	−0.0041 (17)
O8	0.0159 (19)	0.028 (2)	0.0168 (19)	0.0032 (18)	0.0029 (16)	−0.0009 (18)

Geometric parameters (Å, º)

M1—M2	3.2004 (10)	D—O3^viii	1.937 (4)
M1—M2^i	3.2004 (10)	D—O4	1.936 (4)
M1—M2^ii	3.2004 (10)	D—O4^xv	1.936 (4)
M1—M2^iii	3.2004 (10)	D—F	2.1553 (15)
M1—M3	3.3388 (15)	T1—O5^viii	1.609 (4)
M1—M3^ii	3.3389 (15)	T1—O6	1.616 (4)
M1—O1	2.277 (7)	T1—O7	1.625 (5)
M1—O1^ii	2.277 (7)	T1—O7^xvi	1.632 (4)
M1—O2^iv	2.426 (4)	T2—A	3.7145 (18)
M1—O2^v	2.426 (4)	T2—A^iii	3.7197 (18)
M1—O2^vi	2.426 (4)	T2—BNA	3.0363 (16)
M1—O2^vii	2.426 (4)	T2—O2	1.630 (4)
M2—O1	2.240 (4)	T2—O3	1.608 (5)
M2—O1^i	2.240 (4)	T2—O4^vii	1.603 (5)
M2—O2^vi	2.083 (4)	T2—O5	1.641 (5)
M2—O2^viii	2.083 (4)	A—O3	2.830 (5)
M2—O8^ix	2.116 (5)	A—O3^viii	2.830 (5)
M2—O8	2.116 (5)	A—O4	2.873 (5)
M3—O2^vii	2.035 (4)	A—O4^viii	2.873 (5)
M3—O2^vi	2.035 (4)	A—O5	3.221 (5)
M3—O6^ix	2.203 (4)	A—O5^vii	3.180 (4)
M3—O6^iii	2.203 (4)	A—O5^viii	3.221 (5)
M3—O8	1.965 (4)	A—O5^xiv	3.180 (4)
M3—O8^x	1.965 (4)	A—O7	3.319 (5)
M4—O6	2.102 (4)	A—O7^viii	3.319 (5)
M4—O6^xi	2.184 (4)	A—F	3.210 (2)
M4—O6^xii	2.184 (4)	BNA—O3	2.471 (5)
M4—O6^ix	2.102 (4)	BNA—O3^v	2.471 (5)
M4—O8	1.948 (5)	BNA—O3^xv	2.471 (5)
M4—O8^ix	1.948 (5)	BNA—O3^vii	2.471 (5)
D—A^xiii	3.867 (2)	BNA—O4^v	2.548 (5)
D—A	3.867 (2)	BNA—O4^vii	2.548 (5)
D—BNA^xiv	3.3901 (14)	BNA—O4	2.548 (5)
D—BNA	3.4416 (15)	BNA—O4^xv	2.548 (5)
D—O1	1.770 (7)	BNA—F^iii	2.6502 (3)
D—O3^xiii	1.937 (4)	BNA—F	2.6502 (3)
M2—M1—M2^iii	111.80 (5)	O3—T2—A^iii	117.05 (17)
M2^iii—M1—M2^i	180.00 (5)	O3—T2—BNA	54.29 (17)
M2—M1—M2^i	68.20 (5)	O3—T2—O2	111.4 (2)
M2^iii—M1—M2^ii	68.20 (5)	O3—T2—O5	105.4 (2)
M2—M1—M2^ii	180.0	O4^vii—T2—M1^xvii	81.54 (18)
M2^i—M1—M2^ii	111.80 (5)	O4^vii—T2—A	120.57 (19)
M2^ii—M1—M3	124.10 (3)	O4^vii—T2—A^iii	46.87 (17)
M2^i—M1—M3^ii	55.90 (3)	O4^vii—T2—BNA	57.04 (18)
M2^iii—M1—M3	55.90 (3)	O4^vii—T2—O2	112.8 (2)
M2^iii—M1—M3^ii	124.10 (3)	O4^vii—T2—O3	110.9 (3)
M2^i—M1—M3	124.10 (3)	O4^vii—T2—O5	105.0 (2)
M2—M1—M3^ii	124.10 (3)	O5—T2—M1^xvii	141.90 (17)
M2^ii—M1—M3^ii	55.90 (3)	O5—T2—A^iii	58.30 (17)
M2—M1—M3	55.90 (3)	O5—T2—A	59.90 (17)
M3—M1—M3^ii	180.0	O5—T2—BNA	111.77 (16)
O1—M1—M2^ii	135.57 (11)	O3—A—T2	23.89 (9)
O1^ii—M1—M2^iii	44.43 (11)	O3^viii—A—T2	118.29 (11)
O1^ii—M1—M2^i	135.57 (11)	O3^viii—A—O3	96.41 (19)
O1—M1—M2^iii	135.57 (11)	O3—A—O4	71.88 (14)
O1—M1—M2	44.43 (11)	O3^viii—A—O4	55.58 (13)
O1—M1—M2^i	44.43 (11)	O3^viii—A—O4^viii	71.88 (14)
O1^ii—M1—M2	135.57 (11)	O3—A—O4^viii	55.57 (13)
O1^ii—M1—M2^ii	44.43 (11)	O3—A—O5^xiv	98.10 (12)
O1^ii—M1—M3	90.0	O3—A—O5^viii	140.92 (14)
O1—M1—M3^ii	90.0	O3—A—O5^vii	89.71 (12)
O1^ii—M1—M3^ii	90.0	O3^viii—A—O5^xiv	89.71 (12)
O1—M1—M3	90.0	O3^viii—A—O5^viii	50.05 (11)
O1—M1—O1^ii	180.00 (17)	O3^viii—A—O5	140.93 (14)
O1—M1—O2^vii	94.97 (14)	O3—A—O5	50.05 (12)
O1—M1—O2^vi	85.03 (14)	O3^viii—A—O5^vii	98.10 (12)
O1^ii—M1—O2^iv	94.97 (14)	O3^viii—A—O7^viii	172.36 (13)
O1^ii—M1—O2^vii	85.03 (14)	O3^viii—A—O7	90.78 (11)
O1—M1—O2^iv	85.03 (14)	O3—A—O7	172.36 (13)
O1—M1—O2^v	94.97 (14)	O3—A—O7^viii	90.78 (11)
O1^ii—M1—O2^vi	94.97 (14)	O3—A—F	48.20 (10)
O1^ii—M1—O2^v	85.03 (14)	O3^viii—A—F	48.20 (10)
O2^vii—M1—M2^ii	97.64 (10)	O4—A—T2	80.08 (10)
O2^vi—M1—M2	40.60 (10)	O4^viii—A—T2	74.80 (10)
O2^iv—M1—M2^ii	82.36 (10)	O4—A—O4^viii	97.79 (19)
O2^vi—M1—M2^i	97.64 (10)	O4—A—O5^xiv	140.98 (14)
O2^iv—M1—M2	97.64 (10)	O4^viii—A—O5^vii	140.98 (13)
O2^iv—M1—M2^i	40.60 (10)	O4—A—O5^vii	49.99 (11)
O2^vii—M1—M2^iii	40.60 (10)	O4—A—O5^viii	96.76 (12)
O2^v—M1—M2^ii	40.60 (10)	O4^viii—A—O5	96.76 (12)
O2^v—M1—M2	139.40 (10)	O4^viii—A—O5^xiv	49.99 (11)
O2^v—M1—M2^iii	97.64 (10)	O4—A—O5	90.84 (12)
O2^v—M1—M2^i	82.36 (10)	O4^viii—A—O5^viii	90.84 (12)
O2^vi—M1—M2^iii	82.36 (10)	O4—A—O7	110.52 (12)
O2^vii—M1—M2	82.36 (10)	O4—A—O7^viii	129.84 (12)
O2^vi—M1—M2^ii	139.40 (10)	O4^viii—A—O7^viii	110.52 (12)
O2^iv—M1—M2^iii	139.40 (10)	O4^viii—A—O7	129.84 (12)
O2^vii—M1—M2^i	139.40 (10)	O4^viii—A—F	48.89 (9)
O2^v—M1—M3	142.73 (10)	O4—A—F	48.89 (9)
O2^iv—M1—M3	142.73 (10)	O5^vii—A—T2	77.82 (8)
O2^iv—M1—M3^ii	37.27 (10)	O5^viii—A—T2	164.61 (11)
O2^vii—M1—M3^ii	142.73 (10)	O5^xiv—A—T2	106.16 (8)
O2^v—M1—M3^ii	37.27 (10)	O5—A—T2	26.15 (8)
O2^vii—M1—M3	37.27 (10)	O5^vii—A—O5^xiv	168.30 (18)
O2^vi—M1—M3	37.27 (10)	O5^xiv—A—O5^viii	66.94 (13)
O2^vi—M1—M3^ii	142.73 (10)	O5^vii—A—O5^viii	111.78 (12)
O2^vi—M1—O2^vii	74.5 (2)	O5^xiv—A—O5	111.78 (12)
O2^iv—M1—O2^vii	180.0	O5^vii—A—O5	66.94 (13)
O2^v—M1—O2^iv	74.5 (2)	O5^viii—A—O5	168.45 (17)
O2^v—M1—O2^vi	180.00 (17)	O5—A—O7	122.32 (12)
O2^v—M1—O2^vii	105.5 (2)	O5^vii—A—O7	86.70 (11)
O2^vi—M1—O2^iv	105.5 (2)	O5^viii—A—O7	46.66 (11)
M1^xiv—M2—M1	111.80 (5)	O5^viii—A—O7^viii	122.32 (12)
O1^i—M2—M1^xiv	45.35 (17)	O5^xiv—A—O7	84.48 (11)
O1^i—M2—M1	78.75 (17)	O5^vii—A—O7^viii	84.48 (11)
O1—M2—M1	45.35 (17)	O5^xiv—A—O7^viii	86.70 (11)
O1—M2—M1^xiv	78.75 (17)	O5—A—O7^viii	46.66 (11)
O1^i—M2—O1	73.6 (3)	O5^xiv—A—F	95.85 (9)
O2^viii—M2—M1^xiv	49.29 (12)	O5^vii—A—F	95.85 (9)
O2^vi—M2—M1	49.29 (12)	O7—A—T2	148.47 (10)
O2^vi—M2—M1^xiv	136.53 (13)	O7^viii—A—T2	69.25 (8)
O2^viii—M2—M1	136.53 (13)	O7^viii—A—O7	82.16 (16)
O2^viii—M2—O1^i	94.6 (2)	F—A—T2	70.71 (4)
O2^vi—M2—O1^i	91.4 (2)	F—A—O5^viii	95.78 (9)
O2^viii—M2—O1	91.4 (2)	F—A—O5	95.78 (9)
O2^vi—M2—O1	94.6 (2)	F—A—O7	138.92 (8)
O2^vi—M2—O2^viii	172.5 (3)	F—A—O7^viii	138.92 (8)
O2^viii—M2—O8	93.89 (17)	T2^xv—BNA—T2^vii	180.0
O2^vi—M2—O8	80.30 (17)	O3^xv—BNA—T2^vii	148.11 (11)
O2^viii—M2—O8^ix	80.30 (17)	O3^v—BNA—T2^xv	98.58 (11)
O2^vi—M2—O8^ix	93.89 (17)	O3^v—BNA—T2^vii	81.42 (11)
O8—M2—M1	93.48 (12)	O3^vii—BNA—T2^xv	148.11 (10)
O8^ix—M2—M1^xiv	93.48 (12)	O3^vii—BNA—T2^vii	31.89 (10)
O8—M2—M1^xiv	143.14 (12)	O3^xv—BNA—T2^xv	31.89 (11)
O8^ix—M2—M1	143.14 (12)	O3—BNA—T2^xv	81.42 (11)
O8^ix—M2—O1	171.2 (2)	O3—BNA—T2^vii	98.58 (11)
O8^ix—M2—O1^i	103.97 (19)	O3^vii—BNA—O3^v	64.8 (2)
O8—M2—O1	103.97 (19)	O3—BNA—O3^v	180.0
O8—M2—O1^i	171.2 (2)	O3^xv—BNA—O3^vii	180.00 (17)
O8—M2—O8^ix	79.7 (2)	O3^xv—BNA—O3^v	115.2 (2)
O2^vi—M3—M1	46.21 (12)	O3—BNA—O3^vii	115.2 (2)
O2^vii—M3—M1	46.21 (12)	O3—BNA—O3^xv	64.8 (2)
O2^vii—M3—O2^vi	92.4 (2)	O3^xv—BNA—O4	116.42 (14)
O2^vi—M3—O6^ix	94.35 (16)	O3^vii—BNA—O4^vii	83.64 (15)
O2^vii—M3—O6^iii	94.35 (16)	O3^xv—BNA—O4^v	63.58 (14)
O2^vi—M3—O6^iii	173.23 (17)	O3^vii—BNA—O4	63.58 (14)
O2^vii—M3—O6^ix	173.23 (17)	O3—BNA—O4	83.64 (15)
O6^ix—M3—M1	140.56 (11)	O3^v—BNA—O4	96.37 (15)
O6^iii—M3—M1	140.56 (11)	O3—BNA—O4^xv	116.42 (14)
O6^ix—M3—O6^iii	78.9 (2)	O3—BNA—O4^v	96.36 (15)
O8^x—M3—M1	92.32 (15)	O3^vii—BNA—O4^xv	96.36 (15)
O8—M3—M1	92.32 (15)	O3^v—BNA—O4^v	83.64 (15)
O8—M3—O2^vii	98.06 (18)	O3—BNA—O4^vii	63.58 (14)
O8—M3—O2^vi	85.17 (18)	O3^v—BNA—O4^xv	63.58 (14)
O8^x—M3—O2^vi	98.06 (18)	O3^vii—BNA—O4^v	116.42 (14)
O8^x—M3—O2^vii	85.17 (18)	O3^v—BNA—O4^vii	116.42 (14)
O8^x—M3—O6^iii	82.64 (17)	O3^xv—BNA—O4^xv	83.64 (15)
O8—M3—O6^iii	93.76 (18)	O3^xv—BNA—O4^vii	96.36 (15)
O8—M3—O6^ix	82.64 (17)	O3^v—BNA—F^iii	58.08 (10)
O8^x—M3—O6^ix	93.76 (17)	O3^vii—BNA—F^iii	58.08 (10)
O8^x—M3—O8	175.4 (3)	O3^vii—BNA—F	121.92 (10)
O6—M4—O6^xii	89.69 (14)	O3^v—BNA—F	121.92 (10)
O6^ix—M4—O6^xi	89.69 (14)	O3^xv—BNA—F	58.08 (10)
O6^xi—M4—O6^xii	79.7 (2)	O3—BNA—F^iii	121.92 (10)
O6—M4—O6^ix	167.8 (2)	O3—BNA—F	58.08 (10)
O6^ix—M4—O6^xii	80.94 (16)	O3^xv—BNA—F^iii	121.92 (10)
O6—M4—O6^xi	80.94 (16)	O4—BNA—T2^vii	31.85 (10)
O8^ix—M4—O6	85.75 (17)	O4^xv—BNA—T2^vii	80.10 (11)
O8—M4—O6^xi	174.29 (18)	O4—BNA—T2^xv	148.15 (10)
O8^ix—M4—O6^ix	103.09 (17)	O4^v—BNA—T2^xv	31.85 (10)
O8—M4—O6	103.09 (17)	O4^xv—BNA—T2^xv	99.90 (11)
O8—M4—O6^xii	96.17 (17)	O4^vii—BNA—T2^vii	99.90 (11)
O8^ix—M4—O6^xi	96.17 (17)	O4^v—BNA—T2^vii	148.15 (10)
O8—M4—O6^ix	85.75 (17)	O4^vii—BNA—T2^xv	80.10 (11)
O8^ix—M4—O6^xii	174.29 (18)	O4^xv—BNA—O4^vii	180.00 (17)
O8—M4—O8^ix	88.2 (3)	O4^xv—BNA—O4	62.5 (2)
M1—D—A^xiii	117.79 (3)	O4^v—BNA—O4	180.00 (17)
M1—D—A	117.79 (3)	O4^v—BNA—O4^vii	62.5 (2)
A—D—A^xiii	112.25 (5)	O4^v—BNA—O4^xv	117.5 (2)
BNA—D—M1	96.42 (4)	O4^vii—BNA—O4	117.5 (2)
BNA^xiv—D—M1	161.82 (5)	O4^xv—BNA—F	58.36 (10)
BNA—D—A^xiii	69.17 (3)	O4^v—BNA—F	121.64 (10)
BNA^xiv—D—A	69.65 (2)	O4—BNA—F	58.36 (10)
BNA—D—A	69.16 (2)	O4^xv—BNA—F^iii	121.64 (10)
BNA^xiv—D—A^xiii	69.66 (2)	O4^v—BNA—F^iii	58.36 (10)
BNA^xiv—D—BNA	101.76 (4)	O4—BNA—F^iii	121.64 (10)
O1—D—M1	36.1 (2)	O4^vii—BNA—F	121.64 (10)
O1—D—A	123.83 (3)	O4^vii—BNA—F^iii	58.36 (10)
O1—D—A^xiii	123.83 (3)	F^iii—BNA—T2^xv	90.07 (3)
O1—D—BNA^xiv	125.8 (2)	F^iii—BNA—T2^vii	89.93 (3)
O1—D—BNA	132.5 (2)	F—BNA—T2^vii	90.07 (3)
O1—D—O3^xiii	103.2 (2)	F—BNA—T2^xv	89.93 (3)
O1—D—O3^viii	103.2 (2)	F^iii—BNA—F	180.0
O1—D—O4	105.6 (2)	M2—O1—M1	90.2 (2)
O1—D—O4^xv	105.6 (2)	M2^i—O1—M1	90.2 (2)
O1—D—F	177.2 (2)	M2—O1—M2^i	106.4 (3)
O3^xiii—D—M1	126.35 (14)	D—O1—M1	116.7 (3)
O3^viii—D—M1	126.35 (14)	D—O1—M2^i	122.23 (18)
O3^viii—D—A	44.44 (14)	D—O1—M2	122.23 (18)
O3^xiii—D—A	114.92 (14)	M2^xvii—O2—M1^xvii	90.11 (16)
O3^xiii—D—A^xiii	44.44 (14)	M3^xvii—O2—M1^xvii	96.52 (17)
O3^viii—D—A^xiii	114.92 (14)	M3^xvii—O2—M2^xvii	96.30 (17)
O3^viii—D—BNA	110.90 (14)	T2—O2—M1^xvii	118.6 (2)
O3^xiii—D—BNA^xiv	45.90 (14)	T2—O2—M2^xvii	126.3 (2)
O3^viii—D—BNA^xiv	45.90 (14)	T2—O2—M3^xvii	121.2 (2)
O3^xiii—D—BNA	110.90 (14)	D^xiii—O3—A	106.94 (19)
O3^xiii—D—O3^viii	86.3 (3)	D^xiii—O3—BNA	99.85 (18)
O3^xiii—D—F	74.78 (14)	T2—O3—D^xiii	135.6 (3)
O3^viii—D—F	74.78 (14)	T2—O3—A	110.6 (2)
O4^xv—D—M1	79.48 (14)	T2—O3—BNA	93.8 (2)
O4—D—M1	79.48 (14)	BNA—O3—A	103.29 (16)
O4—D—A	45.75 (14)	D—O4—A	105.38 (18)
O4^xv—D—A	115.82 (15)	D—O4—BNA	99.35 (18)
O4—D—A^xiii	115.82 (15)	T2^vii—O4—D	141.5 (3)
O4^xv—D—A^xiii	45.75 (14)	T2^vii—O4—A	109.1 (2)
O4^xv—D—BNA	46.93 (14)	T2^vii—O4—BNA	91.1 (2)
O4^xv—D—BNA^xiv	113.22 (14)	BNA—O4—A	100.16 (16)
O4—D—BNA^xiv	113.22 (14)	T1^viii—O5—T2	139.1 (3)
O4—D—BNA	46.93 (14)	T1^viii—O5—A	105.6 (2)
O4^xv—D—O3^xiii	86.7 (2)	T1^viii—O5—A^iii	109.2 (2)
O4^xv—D—O3^viii	151.2 (2)	T2—O5—A^iii	95.66 (19)
O4—D—O3^viii	86.7 (2)	T2—O5—A	93.95 (19)
O4—D—O3^xiii	151.2 (2)	A^iii—O5—A	111.78 (12)
O4^xv—D—O4	86.1 (3)	M4—O6—M3^xiv	89.62 (15)
O4^xv—D—F	76.40 (15)	M4^xi—O6—M3^xiv	100.70 (17)
O4—D—F	76.40 (15)	M4—O6—M4^xi	99.06 (16)
F—D—M1	146.77 (6)	T1—O6—M3^xiv	119.3 (2)
F—D—A^xiii	56.12 (3)	T1—O6—M4	121.6 (2)
F—D—A	56.12 (3)	T1—O6—M4^xi	120.4 (2)
F—D—BNA^xiv	51.41 (3)	T1—O7—T1^xii	137.3 (3)
F—D—BNA	50.35 (3)	T1^xii—O7—A	104.7 (2)
O5^viii—T1—O6	112.2 (2)	T1—O7—A	101.20 (19)
O5^viii—T1—O7^xvi	106.8 (2)	M3—O8—M2	97.41 (19)
O5^viii—T1—O7	106.5 (2)	M4—O8—M2	96.04 (19)
O6—T1—O7^xvi	111.1 (2)	M4—O8—M3	101.7 (2)
O6—T1—O7	110.9 (2)	D—F—D^xiii	180.0
O7—T1—O7^xvi	109.04 (18)	D^xiii—F—A^xiii	90.0
M1^xvii—T2—A	147.74 (5)	D—F—A	90.0
M1^xvii—T2—A^iii	120.30 (5)	D^xiii—F—A	90.0
A—T2—A^iii	90.95 (4)	D—F—A^xiii	90.0
BNA—T2—M1^xvii	103.25 (4)	D^xiii—F—BNA	89.12 (4)
BNA—T2—A^iii	75.32 (4)	D—F—BNA	90.88 (4)
BNA—T2—A	75.39 (4)	D^xiii—F—BNA^xiv	90.88 (4)
O2—T2—M1^xvii	37.32 (15)	D—F—BNA^xiv	89.12 (4)
O2—T2—A	126.43 (17)	A—F—A^xiii	180.0
O2—T2—A^iii	131.49 (17)	BNA^xiv—F—A^xiii	90.0
O2—T2—BNA	137.32 (17)	BNA^xiv—F—A	90.0
O2—T2—O5	110.9 (2)	BNA—F—A	90.0
O3—T2—M1^xvii	107.02 (17)	BNA—F—A^xiii	90.0
O3—T2—A	45.48 (17)	BNA^xiv—F—BNA	180.0

Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, −y+1, −z; (iii) x−1, y, z; (iv) x, −y+1, z−1; (v) −x+1, −y+1, −z+1; (vi) x, y, z−1; (vii) −x+1, y, −z+1; (viii) −x+2, y, −z+1; (ix) −x+2, y, −z; (x) −x+1, y, −z; (xi) −x+5/2, −y+1/2, −z; (xii) x−1/2, −y+1/2, z; (xiii) −x+2, −y+1, −z+1; (xiv) x+1, y, z; (xv) x, −y+1, z; (xvi) x+1/2, −y+1/2, z; (xvii) x, y, z+1.

(lb590-2)

Crystal data

0.5(Ca0.16F0.24Fe8.8K3.87Na3.79O60Si15.04Ti3.94)	F(000) = 1127
Mr = 1156.05	Dx = 3.084 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 5.3048 (3) Å	Cell parameters from 3378 reflections
b = 23.0985 (13) Å	θ = 1.7–36.2°
c = 10.2982 (6) Å	µ = 3.97 mm^−1
β = 99.353 (5)°	T = 293 K
V = 1245.09 (12) Å^3	Prism, brown
Z = 2	0.22 × 0.18 × 0.11 mm

Data collection

Saxi-CrysAlisPro-abstract goniometer imported SAXI images diffractometer	3013 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2206 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.071
ω scans	θmax = 36.5°, θmin = 1.8°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→8
Tmin = 0.795, Tmax = 1.000	k = −37→38
11593 measured reflections	l = −16→16

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: dual
R[F^2 > 2σ(F^2)] = 0.076	w = 1/[σ^2(Fo^2) + (0.0426P)^2 + 8.065P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.140	(Δ/σ)max < 0.001
S = 1.14	Δρmax = 1.59 e Å^−3
3013 reflections	Δρmin = −1.05 e Å^−3
133 parameters

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
M1	0.500000	0.500000	0.000000	0.0156 (10)	0.972 (15)
M2	1.000000	0.42178 (5)	0.000000	0.0205 (4)	0.764 (5)
M3	0.500000	0.35555 (4)	0.000000	0.0094 (3)	0.768 (5)
M4	1.000000	0.29138 (5)	0.000000	0.0104 (3)	0.669 (5)
D	0.93872 (17)	0.500000	0.28692 (9)	0.0097 (2)	0.985 (7)
T1	1.42122 (19)	0.28203 (4)	0.26774 (10)	0.0072 (3)	0.938 (7)
T2	0.57216 (19)	0.41413 (4)	0.72626 (10)	0.0078 (3)	0.942 (7)
A	1.000000	0.36073 (7)	0.500000	0.0274 (5)	0.968 (8)
BNA	0.500000	0.500000	0.500000	0.0128 (11)	0.92 (2)
BCA	0.500000	0.500000	0.500000	0.0128 (11)	0.08 (2)
O1	0.9053 (8)	0.500000	0.1129 (4)	0.0269 (11)
O2	0.6372 (5)	0.41619 (12)	0.8866 (3)	0.0143 (5)
O3	0.7962 (6)	0.44283 (13)	0.6598 (3)	0.0196 (6)
O4	0.6993 (6)	0.44304 (13)	0.3306 (3)	0.0204 (7)
O5	0.5513 (6)	0.34652 (12)	0.6736 (3)	0.0182 (6)
O6	1.3703 (5)	0.28156 (11)	0.1081 (3)	0.0124 (5)
O7	1.1846 (5)	0.25239 (12)	0.3260 (3)	0.0156 (6)
O8	0.8514 (6)	0.35215 (13)	0.0954 (3)	0.0192 (6)
F	1.000000	0.500000	0.500000	0.012 (10)*	0.121 (18)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
M1	0.0136 (17)	0.0122 (16)	0.0191 (18)	0.000	−0.0030 (12)	0.000
M2	0.0077 (5)	0.0306 (7)	0.0209 (6)	0.000	−0.0047 (4)	0.000
M3	0.0078 (4)	0.0095 (4)	0.0108 (5)	0.000	0.0012 (3)	0.000
M4	0.0060 (5)	0.0136 (6)	0.0110 (5)	0.000	0.0000 (3)	0.000
D	0.0044 (4)	0.0134 (4)	0.0110 (4)	0.000	0.0002 (3)	0.000
T1	0.0062 (5)	0.0072 (5)	0.0078 (5)	0.0004 (3)	−0.0005 (3)	−0.0008 (3)
T2	0.0064 (5)	0.0076 (4)	0.0089 (5)	0.0007 (3)	−0.0005 (3)	0.0009 (3)
A	0.0233 (7)	0.0249 (8)	0.0340 (9)	0.000	0.0043 (6)	0.000
BNA	0.0152 (16)	0.0136 (16)	0.0082 (15)	0.000	−0.0024 (10)	0.000
BCA	0.0152 (16)	0.0136 (16)	0.0082 (15)	0.000	−0.0024 (10)	0.000
O1	0.0115 (19)	0.052 (3)	0.017 (2)	0.000	0.0010 (16)	0.000
O2	0.0125 (12)	0.0182 (13)	0.0115 (12)	−0.0008 (10)	−0.0006 (9)	−0.0008 (10)
O3	0.0129 (13)	0.0247 (15)	0.0211 (15)	−0.0061 (11)	0.0027 (11)	0.0001 (11)
O4	0.0138 (13)	0.0246 (15)	0.0215 (15)	−0.0065 (11)	−0.0012 (11)	0.0011 (12)
O5	0.0286 (16)	0.0106 (12)	0.0140 (13)	0.0009 (10)	−0.0008 (11)	0.0018 (9)
O6	0.0095 (11)	0.0166 (12)	0.0106 (11)	−0.0004 (9)	−0.0005 (9)	−0.0021 (9)
O7	0.0117 (12)	0.0222 (14)	0.0129 (12)	−0.0066 (10)	0.0022 (10)	−0.0017 (10)
O8	0.0137 (13)	0.0291 (16)	0.0147 (13)	0.0035 (11)	0.0020 (10)	−0.0017 (11)

Geometric parameters (Å, º)

M1—M2^i	3.2093 (7)	D—O3^viii	1.942 (3)
M1—M2^ii	3.2093 (7)	D—O4	1.932 (3)
M1—M2	3.2093 (7)	D—O4^xv	1.932 (3)
M1—M2^iii	3.2093 (7)	D—F	2.1654 (9)
M1—M3^ii	3.3366 (10)	T1—O5^viii	1.605 (3)
M1—M3	3.3367 (10)	T1—O6	1.622 (3)
M1—O1	2.272 (4)	T1—O7	1.627 (3)
M1—O1^ii	2.272 (4)	T1—O7^xvi	1.635 (3)
M1—O2^iv	2.433 (3)	T2—A	3.7177 (12)
M1—O2^v	2.433 (3)	T2—A^i	3.7235 (11)
M1—O2^vi	2.433 (3)	T2—BNA	3.0364 (10)
M1—O2^vii	2.433 (3)	T2—O2	1.631 (3)
M2—O1^iii	2.249 (3)	T2—O3	1.608 (3)
M2—O1	2.249 (3)	T2—O4^vii	1.609 (3)
M2—O2^vi	2.087 (3)	T2—O5	1.651 (3)
M2—O2^viii	2.087 (3)	A—O3^viii	2.838 (3)
M2—O8^ix	2.104 (3)	A—O3	2.838 (3)
M2—O8	2.104 (3)	A—O4^viii	2.880 (3)
M3—O2^vii	2.033 (3)	A—O4	2.880 (3)
M3—O2^vi	2.033 (3)	A—O5	3.218 (3)
M3—O6^ix	2.209 (3)	A—O5^vii	3.187 (3)
M3—O6^i	2.209 (3)	A—O5^viii	3.218 (3)
M3—O8^x	1.962 (3)	A—O5^xiv	3.187 (3)
M3—O8	1.962 (3)	A—O7^viii	3.317 (3)
M4—O6^ix	2.107 (3)	A—O7	3.317 (3)
M4—O6^xi	2.191 (3)	A—F	3.2169 (15)
M4—O6^xii	2.191 (3)	BNA—O3^xv	2.466 (3)
M4—O6	2.107 (3)	BNA—O3	2.466 (3)
M4—O8	1.952 (3)	BNA—O3^vii	2.466 (3)
M4—O8^ix	1.952 (3)	BNA—O3^v	2.466 (3)
D—A	3.8778 (14)	BNA—O4	2.548 (3)
D—A^xiii	3.8777 (14)	BNA—O4^xv	2.548 (3)
D—BNA^xiv	3.3995 (9)	BNA—O4^vii	2.548 (3)
D—BNA	3.4484 (10)	BNA—O4^v	2.548 (3)
D—O1	1.772 (5)	BNA—F^i	2.6524 (1)
D—O3^xiii	1.942 (3)	BNA—F	2.6524 (1)
M2^i—M1—M2^iii	180.00 (4)	O3—T2—A^i	117.00 (12)
M2^iii—M1—M2^ii	111.48 (4)	O3—T2—BNA	54.11 (11)
M2^i—M1—M2^ii	68.52 (4)	O3—T2—O2	111.67 (16)
M2^iii—M1—M2	68.52 (4)	O3—T2—O4^vii	110.72 (17)
M2^i—M1—M2	111.48 (4)	O3—T2—O5	105.37 (17)
M2^ii—M1—M2	180.0	O4^vii—T2—M1^xvii	81.39 (12)
M2—M1—M3^ii	124.262 (18)	O4^vii—T2—A	120.73 (12)
M2^ii—M1—M3	124.261 (18)	O4^vii—T2—A^i	47.09 (12)
M2^iii—M1—M3^ii	55.739 (19)	O4^vii—T2—BNA	57.03 (12)
M2^iii—M1—M3	124.261 (19)	O4^vii—T2—O2	112.71 (16)
M2^ii—M1—M3^ii	55.739 (18)	O4^vii—T2—O5	105.36 (16)
M2^i—M1—M3	55.739 (18)	O5—T2—M1^xvii	141.83 (12)
M2—M1—M3	55.738 (19)	O5—T2—A^i	58.47 (11)
M2^i—M1—M3^ii	124.261 (18)	O5—T2—A	59.70 (12)
M3^ii—M1—M3	180.0	O5—T2—BNA	111.88 (11)
O1—M1—M2	44.48 (7)	O3^viii—A—T2^viii	23.91 (6)
O1^ii—M1—M2^iii	135.52 (7)	O3—A—T2^viii	118.08 (8)
O1^ii—M1—M2^ii	44.48 (7)	O3—A—O3^viii	96.13 (13)
O1—M1—M2^iii	44.48 (7)	O3—A—O4	71.61 (9)
O1—M1—M2^i	135.52 (7)	O3—A—O4^viii	55.48 (9)
O1—M1—M2^ii	135.52 (7)	O3^viii—A—O4	55.48 (9)
O1^ii—M1—M2^i	44.48 (7)	O3^viii—A—O4^viii	71.61 (9)
O1^ii—M1—M2	135.52 (7)	O3^viii—A—O5^xiv	89.59 (8)
O1^ii—M1—M3^ii	90.0	O3—A—O5^vii	89.59 (8)
O1—M1—M3	90.0	O3^viii—A—O5^vii	98.33 (8)
O1^ii—M1—M3	90.0	O3^viii—A—O5	140.94 (9)
O1—M1—M3^ii	90.0	O3^viii—A—O5^viii	50.20 (8)
O1—M1—O1^ii	180.0	O3—A—O5^xiv	98.33 (8)
O1—M1—O2^vii	94.96 (9)	O3—A—O5^viii	140.94 (9)
O1—M1—O2^vi	85.04 (9)	O3—A—O5	50.20 (8)
O1^ii—M1—O2^iv	94.96 (9)	O3—A—O7	172.43 (8)
O1^ii—M1—O2^vii	85.04 (9)	O3—A—O7^viii	90.98 (8)
O1—M1—O2^iv	85.04 (9)	O3^viii—A—O7^viii	172.43 (8)
O1—M1—O2^v	94.96 (9)	O3^viii—A—O7	90.98 (8)
O1^ii—M1—O2^vi	94.96 (9)	O3^viii—A—F	48.06 (6)
O1^ii—M1—O2^v	85.04 (9)	O3—A—F	48.06 (6)
O2^vii—M1—M2	82.17 (7)	O4^viii—A—T2^viii	79.99 (7)
O2^vi—M1—M2^i	82.17 (7)	O4—A—T2^viii	74.68 (7)
O2^iv—M1—M2	97.83 (7)	O4^viii—A—O4	97.40 (13)
O2^vi—M1—M2^ii	139.44 (6)	O4^viii—A—O5^xiv	50.28 (7)
O2^iv—M1—M2^i	139.44 (6)	O4—A—O5^vii	50.28 (7)
O2^iv—M1—M2^ii	82.17 (7)	O4^viii—A—O5^vii	140.81 (9)
O2^vii—M1—M2^iii	139.44 (6)	O4^viii—A—O5^viii	90.98 (8)
O2^v—M1—M2	139.44 (6)	O4—A—O5	90.98 (8)
O2^v—M1—M2^i	97.83 (7)	O4—A—O5^xiv	140.81 (9)
O2^v—M1—M2^iii	82.17 (7)	O4^viii—A—O5	96.75 (8)
O2^v—M1—M2^ii	40.56 (6)	O4—A—O5^viii	96.76 (8)
O2^vi—M1—M2^iii	97.83 (7)	O4^viii—A—O7^viii	110.72 (8)
O2^vii—M1—M2^i	40.56 (6)	O4^viii—A—O7	129.94 (8)
O2^vi—M1—M2	40.56 (6)	O4—A—O7	110.72 (8)
O2^iv—M1—M2^iii	40.56 (6)	O4—A—O7^viii	129.94 (8)
O2^vii—M1—M2^ii	97.83 (7)	O4—A—F	48.70 (6)
O2^v—M1—M3^ii	37.28 (7)	O4^viii—A—F	48.70 (6)
O2^iv—M1—M3^ii	37.28 (7)	O5^vii—A—T2^viii	106.29 (6)
O2^iv—M1—M3	142.72 (7)	O5^viii—A—T2^viii	26.30 (5)
O2^vii—M1—M3	37.28 (7)	O5^xiv—A—T2^viii	77.75 (6)
O2^v—M1—M3	142.72 (7)	O5—A—T2^viii	164.63 (7)
O2^vii—M1—M3^ii	142.72 (7)	O5^vii—A—O5^xiv	168.18 (11)
O2^vi—M1—M3^ii	142.72 (7)	O5^xiv—A—O5^viii	66.86 (9)
O2^vi—M1—M3	37.28 (7)	O5^vii—A—O5^viii	111.83 (9)
O2^vi—M1—O2^vii	74.55 (13)	O5^xiv—A—O5	111.83 (9)
O2^iv—M1—O2^vii	180.00 (11)	O5^vii—A—O5	66.86 (9)
O2^v—M1—O2^iv	74.55 (13)	O5^viii—A—O5	168.29 (11)
O2^v—M1—O2^vi	180.00 (11)	O5—A—O7^viii	46.59 (7)
O2^v—M1—O2^vii	105.45 (14)	O5^vii—A—O7^viii	84.31 (7)
O2^vi—M1—O2^iv	105.45 (14)	O5^viii—A—O7^viii	122.23 (8)
M1^xiv—M2—M1	111.48 (4)	O5^viii—A—O7	46.59 (7)
O1—M2—M1^xiv	78.57 (11)	O5^xiv—A—O7^viii	86.78 (7)
O1—M2—M1	45.06 (11)	O5^vii—A—O7	86.78 (7)
O1^iii—M2—M1	78.57 (11)	O5^xiv—A—O7	84.31 (7)
O1^iii—M2—M1^xiv	45.06 (11)	O5—A—O7	122.23 (8)
O1—M2—O1^iii	73.09 (19)	O5^xiv—A—F	95.91 (6)
O2^viii—M2—M1^xiv	49.29 (8)	O5^vii—A—F	95.91 (6)
O2^vi—M2—M1	49.29 (8)	O7^viii—A—T2^viii	148.52 (6)
O2^vi—M2—M1^xiv	136.21 (9)	O7—A—T2^viii	69.37 (5)
O2^viii—M2—M1	136.21 (9)	O7—A—O7^viii	82.06 (10)
O2^viii—M2—O1	91.35 (14)	F—A—T2^viii	70.62 (3)
O2^vi—M2—O1	94.35 (14)	F—A—O5^viii	95.86 (5)
O2^viii—M2—O1^iii	94.35 (14)	F—A—O5	95.86 (5)
O2^vi—M2—O1^iii	91.35 (14)	F—A—O7^viii	138.97 (5)
O2^vi—M2—O2^viii	172.91 (17)	F—A—O7	138.97 (5)
O2^viii—M2—O8	94.17 (12)	T2^xv—BNA—T2^vii	180.0
O2^vi—M2—O8	80.37 (11)	O3^vii—BNA—T2^vii	31.88 (7)
O2^viii—M2—O8^ix	80.37 (11)	O3—BNA—T2^xv	81.40 (7)
O2^vi—M2—O8^ix	94.17 (12)	O3—BNA—T2^vii	98.60 (7)
O8—M2—M1	93.32 (8)	O3^v—BNA—T2^xv	98.61 (7)
O8^ix—M2—M1^xiv	93.32 (8)	O3^v—BNA—T2^vii	81.39 (7)
O8—M2—M1^xiv	143.40 (8)	O3^vii—BNA—T2^xv	148.12 (7)
O8^ix—M2—M1	143.40 (8)	O3^xv—BNA—T2^xv	31.88 (7)
O8^ix—M2—O1^iii	103.92 (13)	O3^xv—BNA—T2^vii	148.12 (7)
O8^ix—M2—O1	171.04 (14)	O3^v—BNA—O3	180.0
O8—M2—O1^iii	171.03 (13)	O3^xv—BNA—O3	64.75 (14)
O8—M2—O1	103.92 (13)	O3^vii—BNA—O3^v	64.75 (14)
O8—M2—O8^ix	80.29 (17)	O3^vii—BNA—O3	115.25 (14)
O2^vi—M3—M1	46.45 (8)	O3^xv—BNA—O3^v	115.25 (14)
O2^vii—M3—M1	46.45 (8)	O3^xv—BNA—O3^vii	180.00 (12)
O2^vii—M3—O2^vi	92.90 (16)	O3^vii—BNA—O4^vii	83.69 (10)
O2^vi—M3—O6^ix	94.22 (11)	O3^v—BNA—O4^xv	63.69 (9)
O2^vii—M3—O6^i	94.22 (11)	O3^vii—BNA—O4	63.69 (9)
O2^vi—M3—O6^i	172.88 (11)	O3^v—BNA—O4^vii	116.31 (10)
O2^vii—M3—O6^ix	172.88 (11)	O3^xv—BNA—O4^vii	96.31 (10)
O6^ix—M3—M1	140.67 (7)	O3—BNA—O4^vii	63.69 (9)
O6^i—M3—M1	140.67 (7)	O3^xv—BNA—O4^v	63.69 (9)
O6^ix—M3—O6^i	78.67 (14)	O3^xv—BNA—O4	116.31 (10)
O8—M3—M1	92.29 (10)	O3^v—BNA—O4^v	83.69 (10)
O8^x—M3—M1	92.29 (10)	O3—BNA—O4	83.69 (10)
O8^x—M3—O2^vii	85.17 (12)	O3^xv—BNA—O4^xv	83.69 (10)
O8^x—M3—O2^vi	98.01 (12)	O3—BNA—O4^v	96.31 (10)
O8—M3—O2^vi	85.17 (12)	O3^v—BNA—O4	96.31 (10)
O8—M3—O2^vii	98.01 (12)	O3—BNA—O4^xv	116.31 (10)
O8—M3—O6^i	93.72 (12)	O3^vii—BNA—O4^v	116.31 (9)
O8^x—M3—O6^i	82.72 (11)	O3^vii—BNA—O4^xv	96.31 (10)
O8^x—M3—O6^ix	93.72 (12)	O3—BNA—F^i	121.92 (7)
O8—M3—O6^ix	82.72 (11)	O3^v—BNA—F^i	58.08 (7)
O8—M3—O8^x	175.42 (19)	O3^v—BNA—F	121.92 (7)
O6^ix—M4—O6^xii	80.96 (10)	O3—BNA—F	58.08 (7)
O6—M4—O6^xi	80.96 (11)	O3^vii—BNA—F	121.92 (7)
O6^xi—M4—O6^xii	79.46 (15)	O3^xv—BNA—F^i	121.92 (7)
O6^ix—M4—O6	167.65 (16)	O3^xv—BNA—F	58.08 (7)
O6—M4—O6^xii	89.52 (9)	O3^vii—BNA—F^i	58.08 (7)
O6^ix—M4—O6^xi	89.52 (9)	O4^vii—BNA—T2^vii	99.99 (7)
O8^ix—M4—O6^ix	103.27 (12)	O4^v—BNA—T2^vii	148.01 (7)
O8—M4—O6^xi	174.13 (12)	O4^vii—BNA—T2^xv	80.01 (7)
O8^ix—M4—O6	85.71 (11)	O4—BNA—T2^xv	148.01 (7)
O8—M4—O6^ix	85.71 (11)	O4^v—BNA—T2^xv	31.99 (7)
O8—M4—O6^xii	96.39 (12)	O4^xv—BNA—T2^vii	80.01 (7)
O8^ix—M4—O6^xi	96.39 (12)	O4—BNA—T2^vii	31.99 (7)
O8—M4—O6	103.27 (12)	O4^xv—BNA—T2^xv	99.99 (7)
O8^ix—M4—O6^xii	174.13 (12)	O4^v—BNA—O4^xv	117.81 (14)
O8—M4—O8^ix	88.03 (19)	O4^v—BNA—O4^vii	62.19 (14)
M1—D—A	117.859 (17)	O4—BNA—O4^vii	117.81 (14)
M1—D—A^xiii	117.860 (17)	O4—BNA—O4^xv	62.19 (14)
A^xiii—D—A	112.11 (3)	O4—BNA—O4^v	180.0
BNA—D—M1	96.54 (2)	O4^xv—BNA—O4^vii	180.00 (12)
BNA^xiv—D—M1	161.92 (3)	O4^v—BNA—F	121.76 (6)
BNA—D—A	69.089 (16)	O4—BNA—F	58.24 (6)
BNA^xiv—D—A^xiii	69.552 (15)	O4^vii—BNA—F	121.76 (6)
BNA—D—A^xiii	69.089 (16)	O4^v—BNA—F^i	58.24 (6)
BNA^xiv—D—A	69.553 (15)	O4—BNA—F^i	121.76 (6)
BNA^xiv—D—BNA	101.55 (2)	O4^vii—BNA—F^i	58.24 (6)
O1—D—M1	36.04 (14)	O4^xv—BNA—F	58.24 (6)
O1—D—A^xiii	123.899 (18)	O4^xv—BNA—F^i	121.76 (6)
O1—D—A	123.898 (18)	F^i—BNA—T2^xv	90.08 (2)
O1—D—BNA^xiv	125.88 (15)	F^i—BNA—T2^vii	89.92 (2)
O1—D—BNA	132.58 (15)	F—BNA—T2^vii	90.08 (2)
O1—D—O3^xiii	103.56 (14)	F—BNA—T2^xv	89.92 (2)
O1—D—O3^viii	103.56 (14)	F^i—BNA—F	180.0
O1—D—O4	105.91 (14)	M2^iii—O1—M1	90.46 (13)
O1—D—O4^xv	105.91 (14)	M2—O1—M1	90.46 (13)
O1—D—F	177.15 (15)	M2^iii—O1—M2	106.91 (19)
O3^xiii—D—M1	126.76 (10)	D—O1—M1	116.6 (2)
O3^viii—D—M1	126.76 (10)	D—O1—M2	121.91 (12)
O3^viii—D—A^xiii	114.45 (10)	D—O1—M2^iii	121.91 (12)
O3^xiii—D—A^xiii	44.43 (9)	M2^xvii—O2—M1^xvii	90.15 (10)
O3^xiii—D—A	114.45 (10)	M3^xvii—O2—M1^xvii	96.27 (11)
O3^viii—D—A	44.43 (9)	M3^xvii—O2—M2^xvii	96.01 (11)
O3^viii—D—BNA	110.67 (10)	T2—O2—M1^xvii	118.59 (14)
O3^xiii—D—BNA^xiv	45.54 (9)	T2—O2—M2^xvii	126.34 (16)
O3^viii—D—BNA^xiv	45.54 (9)	T2—O2—M3^xvii	121.66 (15)
O3^xiii—D—BNA	110.67 (10)	D^xiii—O3—A	106.95 (13)
O3^xiii—D—O3^viii	85.68 (19)	D^xiii—O3—BNA	100.25 (13)
O3^xiii—D—F	74.41 (10)	T2—O3—D^xiii	135.37 (19)
O3^viii—D—F	74.41 (10)	T2—O3—A	110.42 (15)
O4^xv—D—M1	79.76 (9)	T2—O3—BNA	94.01 (14)
O4—D—M1	79.76 (9)	BNA—O3—A	103.43 (11)
O4—D—A^xiii	115.53 (10)	D—O4—A	105.68 (12)
O4^xv—D—A^xiii	45.65 (9)	D—O4—BNA	99.76 (13)
O4—D—A	45.65 (9)	T2^vii—O4—D	141.4 (2)
O4^xv—D—A	115.53 (10)	T2^vii—O4—A	108.75 (15)
O4^xv—D—BNA	46.73 (10)	T2^vii—O4—BNA	90.98 (14)
O4^xv—D—BNA^xiv	112.93 (9)	BNA—O4—A	100.19 (10)
O4—D—BNA^xiv	112.93 (9)	T1^viii—O5—T2	139.23 (19)
O4—D—BNA	46.73 (10)	T1^viii—O5—A	105.88 (14)
O4^xv—D—O3^xiii	86.81 (13)	T1^viii—O5—A^i	109.00 (14)
O4^xv—D—O3^viii	150.52 (14)	T2—O5—A^i	95.34 (13)
O4—D—O3^viii	86.81 (13)	T2—O5—A	94.01 (13)
O4—D—O3^xiii	150.52 (14)	A^i—O5—A	111.83 (8)
O4^xv—D—O4	85.9 (2)	M4—O6—M3^xiv	89.46 (10)
O4^xv—D—F	76.11 (10)	M4^xi—O6—M3^xiv	100.94 (11)
O4—D—F	76.11 (10)	M4—O6—M4^xi	99.04 (10)
F—D—M1	146.81 (4)	T1—O6—M3^xiv	119.42 (14)
F—D—A	56.054 (17)	T1—O6—M4	121.46 (15)
F—D—A^xiii	56.053 (17)	T1—O6—M4^xi	120.39 (14)
F—D—BNA^xiv	51.274 (19)	T1—O7—T1^xii	137.22 (19)
F—D—BNA	50.27 (2)	T1^xii—O7—A	104.79 (13)
O5^viii—T1—O6	112.18 (15)	T1—O7—A	101.23 (12)
O5^viii—T1—O7^xvi	107.07 (16)	M3—O8—M2	97.64 (13)
O5^viii—T1—O7	106.27 (16)	M4—O8—M2	95.84 (13)
O6—T1—O7^xvi	111.10 (15)	M4—O8—M3	101.83 (14)
O6—T1—O7	111.06 (14)	D—F—D^xiii	180.0
O7—T1—O7^xvi	108.94 (11)	D^xiii—F—A	90.0
M1^xvii—T2—A	147.81 (3)	D—F—A^xiii	90.0
M1^xvii—T2—A^i	120.29 (3)	D^xiii—F—A^xiii	90.0
A—T2—A^i	90.94 (3)	D—F—A	90.0
BNA—T2—M1^xvii	103.30 (3)	D^xiii—F—BNA	89.16 (2)
BNA—T2—A^i	75.40 (3)	D—F—BNA	90.83 (2)
BNA—T2—A	75.49 (3)	D^xiii—F—BNA^xiv	90.84 (2)
O2—T2—M1^xvii	37.39 (10)	D—F—BNA^xiv	89.17 (2)
O2—T2—A	126.41 (11)	A^xiii—F—A	180.0
O2—T2—A^i	131.28 (11)	BNA^xiv—F—A	90.0
O2—T2—BNA	137.48 (11)	BNA^xiv—F—A^xiii	90.0
O2—T2—O5	110.58 (15)	BNA—F—A^xiii	90.0
O3—T2—M1^xvii	107.02 (12)	BNA—F—A	90.0
O3—T2—A	45.67 (12)	BNA^xiv—F—BNA	180.0

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z; (iii) −x+2, −y+1, −z; (iv) x, −y+1, z−1; (v) −x+1, −y+1, −z+1; (vi) x, y, z−1; (vii) −x+1, y, −z+1; (viii) −x+2, y, −z+1; (ix) −x+2, y, −z; (x) −x+1, y, −z; (xi) −x+5/2, −y+1/2, −z; (xii) x−1/2, −y+1/2, z; (xiii) −x+2, −y+1, −z+1; (xiv) x+1, y, z; (xv) x, −y+1, z; (xvi) x+1/2, −y+1/2, z; (xvii) x, y, z+1.

(lb590-3)

Crystal data

0.5(Ca0.2F0.25Fe8.9K3.91Na3.8O60Si15Ti3.96)	F(000) = 1131
Mr = 1160.55	Dx = 3.124 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 5.2867 (4) Å	Cell parameters from 2578 reflections
b = 23.0307 (18) Å	θ = 1.8–36.2°
c = 10.2716 (9) Å	µ = 4.04 mm^−1
β = 99.401 (8)°	T = 293 K
V = 1233.83 (18) Å^3	Prism, brown
Z = 2	0.22 × 0.18 × 0.11 mm

Data collection

Saxi-CrysAlisPro-abstract goniometer imported SAXI images diffractometer	2976 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2050 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.092
ω scans	θmax = 36.6°, θmin = 1.8°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −7→8
Tmin = 0.792, Tmax = 1.000	k = −37→37
11474 measured reflections	l = −16→16

Refinement

Refinement on F^2	133 parameters
Least-squares matrix: full	0 restraints
R[F^2 > 2σ(F^2)] = 0.084	w = 1/[σ^2(Fo^2) + (0.0043P)^2 + 19.4916P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.114	(Δ/σ)max < 0.001
S = 1.13	Δρmax = 1.15 e Å^−3
2976 reflections	Δρmin = −1.10 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
M1	0.500000	0.500000	0.000000	0.0140 (11)	1.000 (17)
M2	1.000000	0.42205 (6)	0.000000	0.0196 (4)	0.775 (6)
M3	0.500000	0.35539 (5)	0.000000	0.0084 (3)	0.770 (5)
M4	1.000000	0.29132 (6)	0.000000	0.0097 (4)	0.680 (5)
D	0.9393 (2)	0.500000	0.28752 (12)	0.0092 (3)	0.989 (7)
T1	1.4210 (2)	0.28201 (5)	0.26758 (12)	0.0065 (3)	0.936 (7)
T2	0.5718 (2)	0.41400 (5)	0.72650 (12)	0.0070 (3)	0.939 (7)
A	1.000000	0.36085 (8)	0.500000	0.0278 (5)	0.977 (8)
BNA	0.500000	0.500000	0.500000	0.0124 (13)	0.90 (2)
BCA	0.500000	0.500000	0.500000	0.0124 (13)	0.10 (2)
O1	0.9062 (10)	0.500000	0.1125 (5)	0.0254 (12)
O2	0.6369 (6)	0.41616 (14)	0.8869 (3)	0.0144 (7)
O3	0.7966 (7)	0.44250 (16)	0.6604 (4)	0.0192 (8)
O4	0.6983 (7)	0.44287 (15)	0.3303 (4)	0.0196 (8)
O5	0.5502 (7)	0.34652 (14)	0.6742 (3)	0.0180 (7)
O6	1.3701 (6)	0.28158 (14)	0.1080 (3)	0.0121 (6)
O7	1.1844 (7)	0.25244 (16)	0.3259 (3)	0.0166 (7)
O8	0.8514 (6)	0.35194 (16)	0.0958 (3)	0.0186 (7)
F	1.000000	0.500000	0.500000	0.004 (9)*	0.126 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
M1	0.012 (2)	0.0092 (18)	0.019 (2)	0.000	−0.0031 (15)	0.000
M2	0.0087 (6)	0.0269 (8)	0.0214 (7)	0.000	−0.0033 (5)	0.000
M3	0.0072 (5)	0.0067 (5)	0.0115 (5)	0.000	0.0024 (4)	0.000
M4	0.0063 (6)	0.0108 (6)	0.0116 (6)	0.000	0.0004 (4)	0.000
D	0.0045 (5)	0.0102 (5)	0.0128 (5)	0.000	0.0006 (4)	0.000
T1	0.0058 (6)	0.0055 (6)	0.0076 (6)	−0.0001 (4)	−0.0003 (4)	−0.0012 (4)
T2	0.0063 (6)	0.0051 (5)	0.0095 (6)	0.0008 (4)	0.0009 (4)	0.0006 (4)
A	0.0249 (9)	0.0245 (9)	0.0343 (10)	0.000	0.0060 (7)	0.000
BNA	0.015 (2)	0.0109 (18)	0.0099 (18)	0.000	−0.0020 (12)	0.000
BCA	0.015 (2)	0.0109 (18)	0.0099 (18)	0.000	−0.0020 (12)	0.000
O1	0.015 (3)	0.048 (4)	0.015 (2)	0.000	0.005 (2)	0.000
O2	0.0141 (15)	0.0143 (15)	0.0143 (15)	−0.0008 (12)	0.0012 (12)	−0.0002 (12)
O3	0.0167 (17)	0.0236 (18)	0.0179 (16)	−0.0067 (14)	0.0050 (13)	0.0004 (14)
O4	0.0132 (16)	0.0202 (18)	0.0242 (18)	−0.0072 (13)	0.0000 (14)	0.0017 (14)
O5	0.0275 (18)	0.0098 (15)	0.0159 (15)	0.0010 (13)	0.0009 (13)	−0.0003 (12)
O6	0.0137 (15)	0.0131 (14)	0.0091 (13)	0.0008 (12)	0.0004 (11)	0.0005 (11)
O7	0.0145 (16)	0.0223 (17)	0.0123 (15)	−0.0058 (13)	−0.0001 (12)	−0.0009 (13)
O8	0.0143 (15)	0.0256 (19)	0.0161 (16)	0.0014 (14)	0.0034 (12)	−0.0002 (14)

Geometric parameters (Å, º)

M1—M2^i	3.1953 (8)	D—O3^viii	1.936 (4)
M1—M2^ii	3.1953 (8)	D—O4^xv	1.931 (3)
M1—M2	3.1953 (8)	D—O4	1.931 (4)
M1—M2^iii	3.1953 (8)	D—F	2.1535 (12)
M1—M3^ii	3.3305 (12)	T1—O5^viii	1.599 (3)
M1—M3	3.3306 (12)	T1—O6	1.617 (3)
M1—O1^ii	2.266 (5)	T1—O7	1.622 (4)
M1—O1	2.266 (5)	T1—O7^xvi	1.629 (4)
M1—O2^iv	2.424 (3)	T2—A^i	3.7083 (14)
M1—O2^v	2.424 (3)	T2—A	3.7089 (15)
M1—O2^vi	2.424 (3)	T2—BNA	3.0316 (12)
M1—O2^vii	2.424 (3)	T2—O2	1.628 (4)
M2—O1^iii	2.234 (3)	T2—O3	1.602 (4)
M2—O1	2.234 (3)	T2—O4^vii	1.596 (4)
M2—O2^vi	2.080 (3)	T2—O5	1.642 (3)
M2—O2^viii	2.080 (3)	A—O3	2.826 (4)
M2—O8	2.108 (4)	A—O3^viii	2.826 (4)
M2—O8^ix	2.108 (4)	A—O4	2.871 (4)
M3—O2^vii	2.027 (3)	A—O4^viii	2.871 (4)
M3—O2^vi	2.027 (3)	A—O5^viii	3.218 (4)
M3—O6^ix	2.200 (3)	A—O5^vii	3.174 (4)
M3—O6^i	2.200 (3)	A—O5	3.218 (4)
M3—O8	1.957 (3)	A—O5^xiv	3.174 (4)
M3—O8^x	1.957 (3)	A—O7^viii	3.310 (4)
M4—O6	2.098 (3)	A—O7	3.310 (4)
M4—O6^xi	2.184 (3)	A—F	3.2046 (19)
M4—O6^xii	2.184 (3)	BNA—O3	2.466 (4)
M4—O6^ix	2.098 (3)	BNA—O3^v	2.466 (4)
M4—O8	1.946 (4)	BNA—O3^xv	2.466 (4)
M4—O8^ix	1.946 (4)	BNA—O3^vii	2.466 (4)
D—A^xiii	3.8610 (17)	BNA—O4^v	2.543 (4)
D—A	3.8610 (17)	BNA—O4^vii	2.543 (4)
D—BNA^xiv	3.3820 (12)	BNA—O4	2.543 (4)
D—BNA	3.4368 (12)	BNA—O4^xv	2.543 (4)
D—O1	1.778 (5)	BNA—F^i	2.6433 (2)
D—O3^xiii	1.936 (4)	BNA—F	2.6433 (2)
M2^i—M1—M2^iii	180.00 (4)	O3—T2—A	45.44 (14)
M2^iii—M1—M2^ii	111.64 (4)	O3—T2—BNA	54.25 (14)
M2^i—M1—M2^ii	68.36 (4)	O3—T2—O2	111.57 (19)
M2^iii—M1—M2	68.36 (4)	O3—T2—O5	105.4 (2)
M2^i—M1—M2	111.64 (4)	O4^vii—T2—M1^xvii	81.38 (14)
M2^ii—M1—M2	180.00 (4)	O4^vii—T2—A^i	47.12 (14)
M2—M1—M3^ii	124.18 (2)	O4^vii—T2—A	120.63 (15)
M2^ii—M1—M3	124.18 (2)	O4^vii—T2—BNA	56.99 (14)
M2^iii—M1—M3^ii	55.82 (2)	O4^vii—T2—O2	112.68 (19)
M2^iii—M1—M3	124.18 (2)	O4^vii—T2—O3	110.8 (2)
M2^ii—M1—M3^ii	55.82 (2)	O4^vii—T2—O5	105.33 (19)
M2^i—M1—M3	55.82 (2)	O5—T2—M1^xvii	141.74 (14)
M2—M1—M3	55.82 (2)	O5—T2—A	59.97 (14)
M2^i—M1—M3^ii	124.18 (2)	O5—T2—A^i	58.43 (13)
M3^ii—M1—M3	180.0	O5—T2—BNA	111.97 (13)
O1^ii—M1—M2	135.64 (8)	O3—A—T2^xiv	76.32 (8)
O1—M1—M2^iii	44.36 (8)	O3^viii—A—T2^xiv	78.30 (8)
O1—M1—M2^ii	135.64 (8)	O3^viii—A—O3	96.57 (15)
O1^ii—M1—M2^iii	135.64 (8)	O3—A—O4	71.92 (11)
O1^ii—M1—M2^i	44.36 (8)	O3^viii—A—O4	55.59 (10)
O1^ii—M1—M2^ii	44.36 (8)	O3^viii—A—O4^viii	71.92 (11)
O1—M1—M2^i	135.64 (8)	O3—A—O4^viii	55.59 (10)
O1—M1—M2	44.36 (8)	O3—A—O5^xiv	98.14 (10)
O1—M1—M3^ii	90.0	O3—A—O5	50.05 (9)
O1^ii—M1—M3	90.0	O3—A—O5^vii	89.82 (10)
O1—M1—M3	90.0	O3^viii—A—O5^xiv	89.82 (10)
O1^ii—M1—M3^ii	90.0	O3^viii—A—O5	141.14 (11)
O1^ii—M1—O1	180.0	O3^viii—A—O5^viii	50.05 (9)
O1^ii—M1—O2^vii	84.96 (11)	O3—A—O5^viii	141.13 (11)
O1^ii—M1—O2^vi	95.04 (11)	O3^viii—A—O5^vii	98.14 (10)
O1—M1—O2^iv	84.96 (11)	O3^viii—A—O7	90.76 (9)
O1—M1—O2^vii	95.04 (11)	O3^viii—A—O7^viii	172.24 (11)
O1^ii—M1—O2^iv	95.04 (11)	O3—A—O7^viii	90.76 (9)
O1^ii—M1—O2^v	84.96 (11)	O3—A—O7	172.24 (11)
O1—M1—O2^vi	84.96 (11)	O3—A—F	48.28 (8)
O1—M1—O2^v	95.04 (11)	O3^viii—A—F	48.29 (8)
O2^vii—M1—M2	82.20 (8)	O4—A—T2^xiv	118.62 (9)
O2^vi—M1—M2^i	82.20 (8)	O4^viii—A—T2^xiv	24.04 (7)
O2^iv—M1—M2	97.80 (8)	O4—A—O4^viii	97.72 (15)
O2^vi—M1—M2^ii	139.39 (8)	O4—A—O5^xiv	141.08 (11)
O2^iv—M1—M2^i	139.39 (8)	O4^viii—A—O5^vii	141.08 (11)
O2^iv—M1—M2^ii	82.20 (8)	O4—A—O5^vii	50.12 (9)
O2^vii—M1—M2^iii	139.39 (8)	O4—A—O5	91.00 (10)
O2^v—M1—M2	139.39 (8)	O4^viii—A—O5^viii	91.00 (10)
O2^v—M1—M2^i	97.80 (8)	O4^viii—A—O5^xiv	50.12 (9)
O2^v—M1—M2^iii	82.20 (8)	O4—A—O5^viii	96.75 (10)
O2^v—M1—M2^ii	40.61 (8)	O4^viii—A—O5	96.75 (10)
O2^vi—M1—M2^iii	97.80 (8)	O4—A—O7^viii	129.86 (10)
O2^vii—M1—M2^i	40.61 (8)	O4—A—O7	110.59 (9)
O2^vi—M1—M2	40.61 (8)	O4^viii—A—O7	129.86 (10)
O2^iv—M1—M2^iii	40.61 (8)	O4^viii—A—O7^viii	110.59 (9)
O2^vii—M1—M2^ii	97.80 (8)	O4^viii—A—F	48.86 (8)
O2^v—M1—M3^ii	37.20 (8)	O4—A—F	48.86 (8)
O2^iv—M1—M3^ii	37.20 (8)	O5^vii—A—T2^xiv	165.07 (8)
O2^iv—M1—M3	142.80 (8)	O5—A—T2^xiv	106.60 (6)
O2^vii—M1—M3	37.20 (8)	O5^xiv—A—T2^xiv	26.16 (6)
O2^v—M1—M3	142.80 (8)	O5^viii—A—T2^xiv	77.41 (6)
O2^vii—M1—M3^ii	142.80 (8)	O5^vii—A—O5^xiv	168.06 (13)
O2^vi—M1—M3^ii	142.80 (8)	O5^xiv—A—O5	111.60 (10)
O2^vi—M1—M3	37.20 (8)	O5^vii—A—O5	67.08 (10)
O2^vi—M1—O2^vii	74.41 (16)	O5^xiv—A—O5^viii	67.08 (10)
O2^iv—M1—O2^vii	180.0	O5^vii—A—O5^viii	111.60 (10)
O2^v—M1—O2^iv	74.41 (16)	O5—A—O5^viii	168.22 (13)
O2^v—M1—O2^vi	180.00 (14)	O5^viii—A—O7^viii	122.20 (10)
O2^v—M1—O2^vii	105.59 (16)	O5^vii—A—O7^viii	84.41 (9)
O2^vi—M1—O2^iv	105.59 (16)	O5—A—O7^viii	46.56 (8)
M1^xiv—M2—M1	111.63 (4)	O5—A—O7	122.20 (10)
O1—M2—M1^xiv	78.58 (13)	O5^xiv—A—O7^viii	86.59 (9)
O1—M2—M1	45.17 (14)	O5^vii—A—O7	86.59 (9)
O1^iii—M2—M1	78.58 (13)	O5^xiv—A—O7	84.40 (9)
O1^iii—M2—M1^xiv	45.17 (14)	O5^viii—A—O7	46.56 (8)
O1—M2—O1^iii	73.0 (2)	O5^xiv—A—F	95.97 (7)
O2^viii—M2—M1^xiv	49.35 (9)	O5^vii—A—F	95.97 (7)
O2^vi—M2—M1	49.35 (9)	O7^viii—A—T2^xiv	101.06 (6)
O2^vi—M2—M1^xiv	136.45 (10)	O7—A—T2^xiv	107.83 (6)
O2^viii—M2—M1	136.45 (10)	O7—A—O7^viii	82.05 (13)
O2^viii—M2—O1	91.49 (17)	F—A—T2^xiv	70.73 (3)
O2^vi—M2—O1	94.52 (17)	F—A—O5	95.89 (7)
O2^viii—M2—O1^iii	94.52 (17)	F—A—O5^viii	95.89 (7)
O2^vi—M2—O1^iii	91.49 (17)	F—A—O7^viii	138.97 (6)
O2^vi—M2—O2^viii	172.5 (2)	F—A—O7	138.98 (6)
O2^viii—M2—O8^ix	80.24 (13)	T2^xv—BNA—T2^vii	180.0
O2^vi—M2—O8^ix	93.99 (14)	O3^xv—BNA—T2^vii	148.18 (8)
O2^viii—M2—O8	93.99 (14)	O3^v—BNA—T2^xv	98.51 (9)
O2^vi—M2—O8	80.24 (13)	O3^v—BNA—T2^vii	81.49 (9)
O8^ix—M2—M1	143.28 (9)	O3^vii—BNA—T2^xv	148.18 (8)
O8—M2—M1^xiv	143.28 (9)	O3^vii—BNA—T2^vii	31.82 (8)
O8^ix—M2—M1^xiv	93.37 (9)	O3^xv—BNA—T2^xv	31.82 (8)
O8—M2—M1	93.38 (9)	O3—BNA—T2^xv	81.49 (9)
O8—M2—O1^iii	171.08 (17)	O3—BNA—T2^vii	98.51 (9)
O8—M2—O1	104.05 (15)	O3^vii—BNA—O3^v	64.96 (16)
O8^ix—M2—O1^iii	104.05 (15)	O3—BNA—O3^v	180.0
O8^ix—M2—O1	171.08 (17)	O3^xv—BNA—O3^vii	180.00 (14)
O8^ix—M2—O8	80.0 (2)	O3^xv—BNA—O3^v	115.04 (16)
O2^vi—M3—M1	46.32 (10)	O3—BNA—O3^vii	115.04 (16)
O2^vii—M3—M1	46.32 (10)	O3—BNA—O3^xv	64.96 (16)
O2^vii—M3—O2^vi	92.6 (2)	O3^xv—BNA—O4	116.59 (11)
O2^vi—M3—O6^ix	94.27 (13)	O3^vii—BNA—O4^vii	83.79 (12)
O2^vii—M3—O6^i	94.27 (13)	O3^xv—BNA—O4^v	63.41 (11)
O2^vi—M3—O6^i	173.09 (14)	O3^vii—BNA—O4	63.41 (11)
O2^vii—M3—O6^ix	173.09 (13)	O3—BNA—O4	83.79 (11)
O6^ix—M3—M1	140.59 (9)	O3^v—BNA—O4	96.21 (11)
O6^i—M3—M1	140.59 (9)	O3—BNA—O4^xv	116.59 (11)
O6^ix—M3—O6^i	78.82 (17)	O3—BNA—O4^v	96.21 (11)
O8^x—M3—M1	92.32 (12)	O3^vii—BNA—O4^xv	96.21 (11)
O8—M3—M1	92.32 (12)	O3^v—BNA—O4^v	83.79 (11)
O8—M3—O2^vii	97.94 (14)	O3—BNA—O4^vii	63.41 (11)
O8—M3—O2^vi	85.28 (14)	O3^v—BNA—O4^xv	63.41 (11)
O8^x—M3—O2^vi	97.94 (14)	O3^vii—BNA—O4^v	116.59 (11)
O8^x—M3—O2^vii	85.28 (14)	O3^v—BNA—O4^vii	116.59 (11)
O8^x—M3—O6^i	82.73 (13)	O3^xv—BNA—O4^xv	83.79 (12)
O8—M3—O6^i	93.67 (14)	O3^xv—BNA—O4^vii	96.21 (11)
O8—M3—O6^ix	82.73 (13)	O3^v—BNA—F^i	58.22 (8)
O8^x—M3—O6^ix	93.67 (14)	O3^vii—BNA—F^i	58.22 (8)
O8^x—M3—O8	175.4 (2)	O3^vii—BNA—F	121.78 (8)
O6—M4—O6^xii	89.58 (11)	O3^v—BNA—F	121.78 (8)
O6^ix—M4—O6^xi	89.58 (11)	O3^xv—BNA—F	58.22 (8)
O6^xi—M4—O6^xii	79.53 (17)	O3—BNA—F^i	121.78 (8)
O6—M4—O6^ix	167.72 (19)	O3—BNA—F	58.22 (8)
O6^ix—M4—O6^xii	80.96 (13)	O3^xv—BNA—F^i	121.78 (8)
O6—M4—O6^xi	80.96 (13)	O4—BNA—T2^vii	31.76 (8)
O8^ix—M4—O6	85.72 (13)	O4^xv—BNA—T2^vii	79.97 (8)
O8—M4—O6^xi	174.12 (14)	O4—BNA—T2^xv	148.24 (8)
O8^ix—M4—O6^ix	103.18 (13)	O4^v—BNA—T2^xv	31.76 (8)
O8—M4—O6	103.18 (13)	O4^xv—BNA—T2^xv	100.03 (8)
O8—M4—O6^xii	96.21 (13)	O4^vii—BNA—T2^vii	100.03 (8)
O8^ix—M4—O6^xi	96.21 (13)	O4^v—BNA—T2^vii	148.24 (8)
O8—M4—O6^ix	85.72 (13)	O4^vii—BNA—T2^xv	79.97 (8)
O8^ix—M4—O6^xii	174.12 (14)	O4^xv—BNA—O4^vii	180.00 (14)
O8—M4—O8^ix	88.3 (2)	O4^xv—BNA—O4	62.32 (16)
M1—D—A^xiii	117.82 (2)	O4^v—BNA—O4	180.00 (14)
M1—D—A	117.82 (2)	O4^v—BNA—O4^vii	62.32 (16)
A—D—A^xiii	112.20 (4)	O4^v—BNA—O4^xv	117.68 (16)
BNA—D—M1	96.52 (3)	O4^vii—BNA—O4	117.68 (16)
BNA^xiv—D—M1	161.81 (4)	O4^xv—BNA—F	58.39 (8)
BNA—D—A^xiii	69.11 (2)	O4^v—BNA—F	121.61 (8)
BNA^xiv—D—A	69.64 (2)	O4—BNA—F	58.39 (8)
BNA—D—A	69.11 (2)	O4^xv—BNA—F^i	121.61 (8)
BNA^xiv—D—A^xiii	69.64 (2)	O4^v—BNA—F^i	58.39 (8)
BNA^xiv—D—BNA	101.66 (3)	O4—BNA—F^i	121.61 (8)
O1—D—M1	36.11 (18)	O4^vii—BNA—F	121.61 (8)
O1—D—A	123.85 (2)	O4^vii—BNA—F^i	58.39 (8)
O1—D—A^xiii	123.85 (2)	F^i—BNA—T2^xv	89.99 (3)
O1—D—BNA^xiv	125.71 (18)	F^i—BNA—T2^vii	90.01 (3)
O1—D—BNA	132.63 (18)	F—BNA—T2^vii	89.99 (3)
O1—D—O3^xiii	103.12 (17)	F—BNA—T2^xv	90.01 (3)
O1—D—O3^viii	103.12 (17)	F^i—BNA—F	180.0
O1—D—O4^xv	105.69 (17)	M2^iii—O1—M1	90.47 (16)
O1—D—O4	105.69 (17)	M2—O1—M1	90.47 (16)
O1—D—F	177.10 (19)	M2^iii—O1—M2	107.0 (2)
O3^xiii—D—M1	126.28 (11)	D—O1—M1	116.4 (3)
O3^viii—D—M1	126.28 (11)	D—O1—M2	121.98 (14)
O3^viii—D—A	44.45 (11)	D—O1—M2^iii	121.98 (14)
O3^xiii—D—A	114.96 (12)	M2^xvii—O2—M1^xvii	90.05 (12)
O3^xiii—D—A^xiii	44.45 (11)	M3^xvii—O2—M1^xvii	96.47 (14)
O3^viii—D—A^xiii	114.96 (12)	M3^xvii—O2—M2^xvii	96.21 (14)
O3^viii—D—BNA	110.87 (12)	T2—O2—M1^xvii	118.63 (17)
O3^xiii—D—BNA^xiv	45.95 (11)	T2—O2—M2^xvii	126.2 (2)
O3^viii—D—BNA^xiv	45.95 (11)	T2—O2—M3^xvii	121.53 (19)
O3^xiii—D—BNA	110.87 (12)	D^xiii—O3—A	106.88 (15)
O3^xiii—D—O3^viii	86.3 (2)	D^xiii—O3—BNA	99.71 (15)
O3^xiii—D—F	74.83 (11)	T2—O3—D^xiii	135.6 (2)
O3^viii—D—F	74.83 (11)	T2—O3—A	110.72 (17)
O4—D—M1	79.49 (11)	T2—O3—BNA	93.93 (17)
O4^xv—D—M1	79.49 (11)	BNA—O3—A	103.24 (12)
O4^xv—D—A	115.72 (12)	D—O4—A	105.34 (14)
O4—D—A	45.82 (11)	D—O4—BNA	99.46 (15)
O4^xv—D—A^xiii	45.82 (11)	T2^vii—O4—D	141.7 (2)
O4—D—A^xiii	115.72 (12)	T2^vii—O4—A	108.84 (17)
O4—D—BNA	46.87 (12)	T2^vii—O4—BNA	91.24 (17)
O4—D—BNA^xiv	113.24 (11)	BNA—O4—A	100.04 (12)
O4^xv—D—BNA^xiv	113.24 (11)	T1^viii—O5—T2	139.4 (2)
O4^xv—D—BNA	46.87 (12)	T1^viii—O5—A	105.61 (16)
O4—D—O3^xiii	151.19 (16)	T1^viii—O5—A^i	109.26 (17)
O4—D—O3^viii	86.79 (16)	T2—O5—A^i	95.41 (15)
O4^xv—D—O3^viii	151.19 (16)	T2—O5—A	93.81 (15)
O4^xv—D—O3^xiii	86.79 (16)	A^i—O5—A	111.60 (10)
O4—D—O4^xv	85.9 (2)	M4—O6—M3^xiv	89.53 (12)
O4—D—F	76.37 (12)	M4^xi—O6—M3^xiv	100.83 (13)
O4^xv—D—F	76.37 (12)	M4—O6—M4^xi	99.04 (13)
F—D—M1	146.79 (5)	T1—O6—M3^xiv	119.50 (18)
F—D—A^xiii	56.10 (2)	T1—O6—M4	121.45 (19)
F—D—A	56.10 (2)	T1—O6—M4^xi	120.37 (18)
F—D—BNA^xiv	51.40 (2)	T1—O7—T1^xii	137.1 (2)
F—D—BNA	50.27 (3)	T1^xii—O7—A	104.85 (16)
O5^viii—T1—O6	111.98 (18)	T1—O7—A	101.29 (15)
O5^viii—T1—O7^xvi	106.95 (19)	M3—O8—M2	97.45 (15)
O5^viii—T1—O7	106.51 (19)	M4—O8—M2	95.82 (15)
O6—T1—O7^xvi	111.11 (18)	M4—O8—M3	101.72 (16)
O6—T1—O7	111.16 (18)	D^xiii—F—D	180.0
O7—T1—O7^xvi	108.92 (14)	D—F—A^xiii	90.0
M1^xvii—T2—A^i	120.33 (4)	D^xiii—F—A	90.0
M1^xvii—T2—A	147.74 (4)	D—F—A	90.0
A^i—T2—A	90.92 (3)	D^xiii—F—A^xiii	90.0
BNA—T2—M1^xvii	103.26 (3)	D—F—BNA	90.94 (3)
BNA—T2—A	75.34 (4)	D^xiii—F—BNA	89.06 (3)
BNA—T2—A^i	75.35 (3)	D—F—BNA^xiv	89.06 (3)
O2—T2—M1^xvii	37.34 (12)	D^xiii—F—BNA^xiv	90.94 (3)
O2—T2—A^i	131.37 (13)	A—F—A^xiii	180.0
O2—T2—A	126.52 (13)	BNA^xiv—F—A^xiii	90.0
O2—T2—BNA	137.39 (13)	BNA^xiv—F—A	90.0
O2—T2—O5	110.59 (18)	BNA—F—A	90.0
O3—T2—M1^xvii	107.04 (14)	BNA—F—A^xiii	90.0
O3—T2—A^i	117.01 (14)	BNA^xiv—F—BNA	180.0

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z; (iii) −x+2, −y+1, −z; (iv) x, −y+1, z−1; (v) −x+1, −y+1, −z+1; (vi) x, y, z−1; (vii) −x+1, y, −z+1; (viii) −x+2, y, −z+1; (ix) −x+2, y, −z; (x) −x+1, y, −z; (xi) −x+5/2, −y+1/2, −z; (xii) x−1/2, −y+1/2, z; (xiii) −x+2, −y+1, −z+1; (xiv) x+1, y, z; (xv) x, −y+1, z; (xvi) x+1/2, −y+1/2, z; (xvii) x, y, z+1.

(lb610)

Crystal data

0.5(Ca0.25F0.44Fe8.98K4Na3.66O60Si15.08Ti4)	F(000) = 1138
Mr = 1167.71	Dx = 3.109 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 5.3072 (2) Å	Cell parameters from 4353 reflections
b = 23.1144 (11) Å	θ = 1.8–36.2°
c = 10.3073 (5) Å	µ = 4.04 mm^−1
β = 99.399 (4)°	T = 293 K
V = 1247.45 (10) Å^3	Prism, brown
Z = 2	0.22 × 0.18 × 0.11 mm

Data collection

Saxi-CrysAlisPro-abstract goniometer imported SAXI images diffractometer	2996 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2437 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
ω scans	θmax = 36.5°, θmin = 1.8°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→8
Tmin = 0.829, Tmax = 1.000	k = −33→38
11470 measured reflections	l = −16→17

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: dual
R[F^2 > 2σ(F^2)] = 0.062	w = 1/[σ^2(Fo^2) + (0.0296P)^2 + 11.2187P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.117	(Δ/σ)max < 0.001
S = 1.15	Δρmax = 2.64 e Å^−3
2996 reflections	Δρmin = −0.93 e Å^−3
131 parameters

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
M1	0.500000	0.500000	0.000000	0.0139 (8)	0.952 (13)
M2	1.000000	0.42170 (5)	0.000000	0.0220 (3)	0.766 (4)
M3	0.500000	0.35535 (3)	0.000000	0.0098 (2)	0.791 (4)
M4	1.000000	0.29156 (4)	0.000000	0.0111 (3)	0.689 (4)
D	0.94007 (14)	0.500000	0.28875 (8)	0.01080 (17)
T1	1.42206 (15)	0.28194 (4)	0.26763 (8)	0.0073 (2)	0.943 (5)
T2	0.57154 (16)	0.41384 (4)	0.72683 (8)	0.0082 (2)	0.942 (5)
A	1.000000	0.36097 (6)	0.500000	0.0285 (3)
BNA	0.500000	0.500000	0.500000	0.0130 (9)	0.88 (2)
BCA	0.500000	0.500000	0.500000	0.0130 (9)	0.12 (2)
O1	0.9063 (7)	0.500000	0.1130 (4)	0.0291 (10)
O2	0.6373 (4)	0.41586 (10)	0.8871 (2)	0.0150 (4)
O3	0.7949 (5)	0.44250 (11)	0.6605 (3)	0.0193 (5)
O4	0.6990 (5)	0.44290 (12)	0.3298 (3)	0.0219 (5)
O5	0.5489 (5)	0.34660 (10)	0.6744 (2)	0.0185 (5)
O6	1.3705 (4)	0.28126 (10)	0.1080 (2)	0.0117 (4)
O7	1.1850 (4)	0.25229 (11)	0.3259 (2)	0.0164 (5)
O8	0.8493 (5)	0.35197 (12)	0.0951 (3)	0.0186 (5)
F	1.000000	0.500000	0.500000	0.012 (5)*	0.219 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
M1	0.0108 (13)	0.0093 (13)	0.0197 (15)	0.000	−0.0034 (10)	0.000
M2	0.0085 (4)	0.0316 (6)	0.0233 (5)	0.000	−0.0047 (3)	0.000
M3	0.0074 (3)	0.0101 (4)	0.0119 (4)	0.000	0.0016 (2)	0.000
M4	0.0065 (4)	0.0143 (5)	0.0122 (4)	0.000	0.0005 (3)	0.000
D	0.0035 (3)	0.0129 (3)	0.0158 (3)	0.000	0.0012 (2)	0.000
T1	0.0061 (4)	0.0069 (4)	0.0082 (4)	0.0001 (3)	−0.0004 (3)	−0.0001 (3)
T2	0.0071 (4)	0.0073 (4)	0.0098 (4)	0.0009 (3)	0.0002 (3)	0.0009 (3)
A	0.0244 (5)	0.0265 (6)	0.0347 (7)	0.000	0.0047 (5)	0.000
BNA	0.0164 (13)	0.0136 (13)	0.0078 (12)	0.000	−0.0017 (8)	0.000
BCA	0.0164 (13)	0.0136 (13)	0.0078 (12)	0.000	−0.0017 (8)	0.000
O1	0.0109 (15)	0.063 (3)	0.0132 (16)	0.000	0.0026 (12)	0.000
O2	0.0145 (10)	0.0156 (10)	0.0141 (10)	−0.0019 (8)	−0.0002 (8)	0.0005 (8)
O3	0.0139 (10)	0.0236 (12)	0.0204 (12)	−0.0070 (9)	0.0031 (9)	−0.0005 (9)
O4	0.0153 (11)	0.0232 (13)	0.0259 (13)	−0.0093 (9)	−0.0002 (9)	0.0000 (10)
O5	0.0278 (13)	0.0103 (10)	0.0161 (11)	0.0015 (9)	−0.0004 (9)	0.0001 (8)
O6	0.0101 (9)	0.0141 (10)	0.0107 (9)	0.0012 (7)	0.0006 (7)	−0.0013 (8)
O7	0.0117 (9)	0.0246 (12)	0.0125 (10)	−0.0082 (9)	0.0013 (8)	−0.0012 (9)
O8	0.0122 (10)	0.0258 (13)	0.0173 (11)	0.0029 (9)	0.0007 (8)	−0.0020 (9)

Geometric parameters (Å, º)

M1—M2	3.2121 (6)	D—O3^viii	1.944 (2)
M1—M2^i	3.2121 (6)	D—O4	1.933 (3)
M1—M2^ii	3.2121 (6)	D—O4^xv	1.933 (3)
M1—M2^iii	3.2121 (6)	D—F	2.1485 (8)
M1—M3	3.3434 (8)	T1—O5^viii	1.608 (3)
M1—M3^ii	3.3435 (8)	T1—O6	1.623 (2)
M1—O1^ii	2.277 (4)	T1—O7	1.631 (2)
M1—O1	2.277 (4)	T1—O7^xvi	1.631 (2)
M1—O2^iv	2.438 (2)	T2—A^iii	3.7208 (10)
M1—O2^v	2.438 (2)	T2—A	3.7238 (10)
M1—O2^vi	2.438 (2)	T2—BNA	3.0475 (9)
M1—O2^vii	2.438 (2)	T2—O2	1.632 (3)
M2—O1^i	2.251 (2)	T2—O3	1.605 (3)
M2—O1	2.251 (2)	T2—O4^vii	1.606 (3)
M2—O2^vi	2.085 (2)	T2—O5	1.643 (3)
M2—O2^viii	2.085 (2)	A—O3	2.839 (3)
M2—O8^ix	2.110 (3)	A—O3^viii	2.839 (3)
M2—O8	2.110 (3)	A—O4	2.881 (3)
M3—O2^vii	2.030 (2)	A—O4^viii	2.881 (3)
M3—O2^vi	2.030 (2)	A—O5^viii	3.237 (3)
M3—O6^ix	2.212 (2)	A—O5^vii	3.181 (3)
M3—O6^iii	2.212 (2)	A—O5	3.237 (3)
M3—O8^x	1.952 (2)	A—O5^xiv	3.181 (3)
M3—O8	1.952 (2)	A—O7^viii	3.328 (3)
M4—O6	2.109 (2)	A—O7	3.328 (3)
M4—O6^xi	2.190 (2)	A—F	3.2137 (13)
M4—O6^xii	2.190 (2)	BNA—O3	2.471 (3)
M4—O6^ix	2.109 (2)	BNA—O3^v	2.471 (3)
M4—O8^ix	1.951 (3)	BNA—O3^xv	2.471 (3)
M4—O8	1.951 (3)	BNA—O3^vii	2.471 (3)
D—A^xiii	3.8657 (12)	BNA—O4^v	2.557 (3)
D—A	3.8657 (12)	BNA—O4^vii	2.557 (3)
D—BNA^xiv	3.3850 (7)	BNA—O4	2.557 (3)
D—BNA	3.4433 (8)	BNA—O4^xv	2.557 (3)
D—O1	1.791 (4)	BNA—F^iii	2.6536 (1)
D—O3^xiii	1.944 (2)	BNA—F	2.6536 (1)
M2—M1—M2^iii	111.41 (3)	O3—T2—A	45.47 (10)
M2^iii—M1—M2^i	180.00 (3)	O3—T2—BNA	53.96 (10)
M2—M1—M2^i	68.59 (3)	O3—T2—O2	111.62 (13)
M2^iii—M1—M2^ii	68.59 (3)	O3—T2—O4^vii	110.56 (15)
M2—M1—M2^ii	180.0	O3—T2—O5	105.64 (15)
M2^i—M1—M2^ii	111.41 (3)	O4^vii—T2—M1^xvii	81.21 (11)
M2^ii—M1—M3	124.297 (17)	O4^vii—T2—A^iii	47.19 (10)
M2^i—M1—M3^ii	55.703 (17)	O4^vii—T2—A	120.69 (11)
M2^iii—M1—M3	55.703 (17)	O4^vii—T2—BNA	57.04 (11)
M2^iii—M1—M3^ii	124.297 (17)	O4^vii—T2—O2	112.74 (14)
M2^i—M1—M3	124.297 (17)	O4^vii—T2—O5	105.25 (14)
M2—M1—M3^ii	124.297 (17)	O5—T2—M1^xvii	141.87 (10)
M2^ii—M1—M3^ii	55.703 (17)	O5—T2—A	60.16 (10)
M2—M1—M3	55.703 (17)	O5—T2—A^iii	58.30 (10)
M3—M1—M3^ii	180.0	O5—T2—BNA	111.87 (9)
O1^ii—M1—M2^ii	44.49 (6)	O3—A—T2^xiv	76.50 (5)
O1—M1—M2^iii	135.51 (6)	O3^viii—A—T2^xiv	78.31 (6)
O1—M1—M2^i	44.49 (6)	O3^viii—A—O3	96.82 (11)
O1^ii—M1—M2^iii	44.49 (6)	O3^viii—A—O4^viii	72.02 (8)
O1^ii—M1—M2	135.51 (6)	O3^viii—A—O4	55.68 (7)
O1^ii—M1—M2^i	135.51 (6)	O3—A—O4^viii	55.68 (7)
O1—M1—M2	44.49 (6)	O3—A—O4	72.02 (8)
O1—M1—M2^ii	135.51 (6)	O3—A—O5^xiv	98.22 (7)
O1—M1—M3	90.0	O3^viii—A—O5^vii	98.22 (7)
O1^ii—M1—M3^ii	90.0	O3—A—O5^vii	89.75 (7)
O1—M1—M3^ii	90.0	O3—A—O5^viii	141.29 (8)
O1^ii—M1—M3	90.0	O3—A—O5	49.90 (7)
O1^ii—M1—O1	180.0	O3^viii—A—O5^xiv	89.75 (7)
O1^ii—M1—O2^vii	84.96 (8)	O3^viii—A—O5	141.29 (8)
O1^ii—M1—O2^vi	95.04 (8)	O3^viii—A—O5^viii	49.90 (7)
O1—M1—O2^iv	84.96 (8)	O3^viii—A—O7	90.68 (7)
O1—M1—O2^vii	95.04 (8)	O3^viii—A—O7^viii	172.05 (7)
O1^ii—M1—O2^iv	95.04 (8)	O3—A—O7^viii	90.68 (7)
O1^ii—M1—O2^v	84.96 (8)	O3—A—O7	172.06 (7)
O1—M1—O2^vi	84.96 (8)	O3—A—F	48.41 (6)
O1—M1—O2^v	95.04 (8)	O3^viii—A—F	48.41 (6)
O2^vii—M1—M2^ii	97.94 (6)	O4—A—T2^xiv	118.74 (6)
O2^vi—M1—M2	40.47 (5)	O4^viii—A—T2^xiv	24.13 (5)
O2^iv—M1—M2^ii	82.06 (6)	O4—A—O4^viii	97.82 (11)
O2^vi—M1—M2^i	97.94 (6)	O4—A—O5^xiv	141.11 (8)
O2^iv—M1—M2	97.94 (6)	O4^viii—A—O5^vii	141.11 (8)
O2^iv—M1—M2^i	40.47 (5)	O4—A—O5^vii	50.12 (6)
O2^vii—M1—M2^iii	40.47 (6)	O4—A—O5	91.07 (7)
O2^v—M1—M2^ii	40.47 (6)	O4^viii—A—O5^viii	91.07 (7)
O2^v—M1—M2	139.53 (6)	O4^viii—A—O5^xiv	50.13 (6)
O2^v—M1—M2^iii	97.94 (6)	O4—A—O5^viii	96.67 (7)
O2^v—M1—M2^i	82.06 (6)	O4^viii—A—O5	96.67 (7)
O2^vi—M1—M2^iii	82.06 (6)	O4—A—O7^viii	129.90 (6)
O2^vii—M1—M2	82.06 (6)	O4—A—O7	110.54 (7)
O2^vi—M1—M2^ii	139.53 (6)	O4^viii—A—O7	129.90 (6)
O2^iv—M1—M2^iii	139.53 (5)	O4^viii—A—O7^viii	110.54 (7)
O2^vii—M1—M2^i	139.53 (6)	O4^viii—A—F	48.91 (5)
O2^v—M1—M3	142.90 (6)	O4—A—F	48.91 (6)
O2^iv—M1—M3	142.90 (6)	O5^vii—A—T2^xiv	165.19 (6)
O2^iv—M1—M3^ii	37.10 (6)	O5—A—T2^xiv	106.60 (5)
O2^vii—M1—M3^ii	142.90 (6)	O5^xiv—A—T2^xiv	26.07 (5)
O2^v—M1—M3^ii	37.10 (6)	O5^viii—A—T2^xiv	77.39 (5)
O2^vii—M1—M3	37.10 (6)	O5^vii—A—O5^xiv	168.02 (10)
O2^vi—M1—M3	37.10 (6)	O5^xiv—A—O5	111.57 (7)
O2^vi—M1—M3^ii	142.90 (6)	O5^vii—A—O5	67.11 (8)
O2^vi—M1—O2^vii	74.20 (11)	O5^xiv—A—O5^viii	67.11 (8)
O2^iv—M1—O2^vii	180.0	O5^vii—A—O5^viii	111.57 (7)
O2^v—M1—O2^iv	74.20 (11)	O5—A—O5^viii	168.22 (10)
O2^v—M1—O2^vi	180.0	O5^viii—A—O7^viii	122.16 (7)
O2^v—M1—O2^vii	105.80 (11)	O5^vii—A—O7^viii	84.39 (6)
O2^vi—M1—O2^iv	105.80 (11)	O5—A—O7^viii	46.59 (6)
M1^xiv—M2—M1	111.41 (3)	O5—A—O7	122.16 (7)
O1—M2—M1^xiv	78.42 (9)	O5^xiv—A—O7^viii	86.57 (6)
O1—M2—M1	45.14 (10)	O5^vii—A—O7	86.57 (6)
O1^i—M2—M1	78.42 (9)	O5^xiv—A—O7	84.39 (6)
O1^i—M2—M1^xiv	45.14 (10)	O5^viii—A—O7	46.59 (6)
O1—M2—O1^i	72.98 (16)	O5^xiv—A—F	95.99 (5)
O2^viii—M2—M1^xiv	49.38 (7)	O5^vii—A—F	95.99 (5)
O2^vi—M2—M1	49.38 (7)	O7^viii—A—T2^xiv	101.02 (4)
O2^vi—M2—M1^xiv	136.37 (7)	O7—A—T2^xiv	107.75 (4)
O2^viii—M2—M1	136.37 (7)	O7—A—O7^viii	81.96 (9)
O2^viii—M2—O1	91.43 (12)	F—A—T2^xiv	70.82 (2)
O2^vi—M2—O1	94.53 (12)	F—A—O5	95.89 (5)
O2^viii—M2—O1^i	94.53 (12)	F—A—O5^viii	95.89 (5)
O2^vi—M2—O1^i	91.43 (12)	F—A—O7^viii	139.02 (4)
O2^vi—M2—O2^viii	172.59 (15)	F—A—O7	139.02 (4)
O2^viii—M2—O8	94.40 (10)	T2^xv—BNA—T2^vii	180.0
O2^vi—M2—O8	79.90 (10)	O3^xv—BNA—T2^vii	148.32 (6)
O2^viii—M2—O8^ix	79.90 (10)	O3^v—BNA—T2^xv	98.51 (6)
O2^vi—M2—O8^ix	94.40 (10)	O3^v—BNA—T2^vii	81.49 (6)
O8—M2—M1	93.13 (7)	O3^vii—BNA—T2^xv	148.32 (6)
O8^ix—M2—M1^xiv	93.13 (7)	O3^vii—BNA—T2^vii	31.68 (6)
O8—M2—M1^xiv	143.71 (7)	O3^xv—BNA—T2^xv	31.68 (6)
O8^ix—M2—M1	143.71 (7)	O3—BNA—T2^xv	81.49 (6)
O8^ix—M2—O1^i	103.96 (11)	O3—BNA—T2^vii	98.51 (6)
O8^ix—M2—O1	170.64 (11)	O3^vii—BNA—O3^v	65.08 (12)
O8—M2—O1^i	170.64 (11)	O3—BNA—O3^v	180.0
O8—M2—O1	103.96 (11)	O3^xv—BNA—O3^vii	180.00 (10)
O8—M2—O8^ix	80.42 (14)	O3^xv—BNA—O3^v	114.92 (12)
O2^vi—M3—M1	46.44 (7)	O3—BNA—O3^vii	114.93 (12)
O2^vii—M3—M1	46.44 (7)	O3—BNA—O3^xv	65.07 (12)
O2^vii—M3—O2^vi	92.87 (14)	O3^xv—BNA—O4	116.71 (8)
O2^vi—M3—O6^ix	94.29 (9)	O3^vii—BNA—O4^vii	83.93 (9)
O2^vii—M3—O6^iii	94.29 (9)	O3^xv—BNA—O4^v	63.29 (8)
O2^vi—M3—O6^iii	172.83 (9)	O3^vii—BNA—O4	63.29 (8)
O2^vii—M3—O6^ix	172.83 (9)	O3—BNA—O4	83.93 (9)
O6^ix—M3—M1	140.73 (6)	O3^v—BNA—O4	96.07 (9)
O6^iii—M3—M1	140.73 (6)	O3—BNA—O4^xv	116.71 (8)
O6^ix—M3—O6^iii	78.54 (12)	O3—BNA—O4^v	96.07 (9)
O8—M3—M1	92.29 (8)	O3^vii—BNA—O4^xv	96.07 (9)
O8^x—M3—M1	92.29 (8)	O3^v—BNA—O4^v	83.93 (9)
O8^x—M3—O2^vii	85.13 (10)	O3—BNA—O4^vii	63.29 (8)
O8^x—M3—O2^vi	98.06 (10)	O3^v—BNA—O4^xv	63.29 (8)
O8—M3—O2^vi	85.12 (10)	O3^vii—BNA—O4^v	116.71 (8)
O8—M3—O2^vii	98.06 (10)	O3^v—BNA—O4^vii	116.71 (8)
O8—M3—O6^iii	93.67 (10)	O3^xv—BNA—O4^xv	83.93 (9)
O8^x—M3—O6^iii	82.77 (10)	O3^xv—BNA—O4^vii	96.07 (9)
O8^x—M3—O6^ix	93.67 (10)	O3^v—BNA—F^iii	58.39 (6)
O8—M3—O6^ix	82.77 (10)	O3^vii—BNA—F^iii	58.39 (6)
O8—M3—O8^x	175.41 (16)	O3^vii—BNA—F	121.61 (6)
O6—M4—O6^xii	89.30 (8)	O3^v—BNA—F	121.61 (6)
O6^ix—M4—O6^xi	89.30 (8)	O3^xv—BNA—F	58.39 (6)
O6^xi—M4—O6^xii	79.53 (12)	O3—BNA—F^iii	121.61 (6)
O6—M4—O6^ix	167.03 (13)	O3—BNA—F	58.39 (6)
O6^ix—M4—O6^xii	80.71 (9)	O3^xv—BNA—F^iii	121.61 (6)
O6—M4—O6^xi	80.71 (9)	O4—BNA—T2^vii	31.79 (6)
O8—M4—O6	103.83 (10)	O4^xv—BNA—T2^vii	79.90 (6)
O8^ix—M4—O6^xi	96.10 (10)	O4—BNA—T2^xv	148.21 (6)
O8—M4—O6^ix	85.57 (10)	O4^v—BNA—T2^xv	31.79 (6)
O8^ix—M4—O6	85.56 (10)	O4^xv—BNA—T2^xv	100.10 (6)
O8^ix—M4—O6^xii	173.75 (10)	O4^vii—BNA—T2^vii	100.10 (6)
O8—M4—O6^xi	173.76 (10)	O4^v—BNA—T2^vii	148.21 (6)
O8^ix—M4—O6^ix	103.83 (10)	O4^vii—BNA—T2^xv	79.90 (6)
O8—M4—O6^xii	96.10 (10)	O4^xv—BNA—O4^vii	180.00 (10)
O8^ix—M4—O8	88.59 (16)	O4^xv—BNA—O4	62.14 (12)
M1—D—A^xiii	117.712 (14)	O4^v—BNA—O4	180.00 (10)
M1—D—A	117.712 (14)	O4^v—BNA—O4^vii	62.14 (12)
A—D—A^xiii	112.47 (3)	O4^v—BNA—O4^xv	117.86 (12)
BNA—D—M1	96.393 (18)	O4^vii—BNA—O4	117.86 (12)
BNA^xiv—D—M1	161.60 (3)	O4^xv—BNA—F	58.34 (6)
BNA—D—A^xiii	69.252 (14)	O4^v—BNA—F	121.66 (6)
BNA^xiv—D—A	69.809 (13)	O4—BNA—F	58.34 (6)
BNA—D—A	69.252 (14)	O4^xv—BNA—F^iii	121.66 (6)
BNA^xiv—D—A^xiii	69.809 (13)	O4^v—BNA—F^iii	58.34 (6)
BNA^xiv—D—BNA	102.01 (2)	O4—BNA—F^iii	121.66 (6)
O1—D—M1	35.94 (12)	O4^vii—BNA—F	121.66 (6)
O1—D—A	123.721 (16)	O4^vii—BNA—F^iii	58.34 (6)
O1—D—A^xiii	123.721 (16)	F^iii—BNA—T2^xv	89.960 (16)
O1—D—BNA^xiv	125.66 (12)	F^iii—BNA—T2^vii	90.040 (16)
O1—D—BNA	132.33 (12)	F—BNA—T2^vii	89.960 (16)
O1—D—O3^xiii	102.75 (12)	F—BNA—T2^xv	90.040 (16)
O1—D—O3^viii	102.75 (12)	F^iii—BNA—F	180.0
O1—D—O4	105.12 (12)	M2—O1—M1	90.36 (11)
O1—D—O4^xv	105.12 (12)	M2^i—O1—M1	90.36 (11)
O1—D—F	177.27 (13)	M2—O1—M2^i	107.03 (16)
O3^xiii—D—M1	125.94 (8)	D—O1—M1	116.56 (19)
O3^viii—D—M1	125.94 (8)	D—O1—M2^i	121.94 (10)
O3^viii—D—A	44.81 (8)	D—O1—M2	121.94 (10)
O3^xiii—D—A	115.31 (8)	M2^xvii—O2—M1^xvii	90.15 (9)
O3^xiii—D—A^xiii	44.81 (8)	M3^xvii—O2—M1^xvii	96.47 (10)
O3^viii—D—A^xiii	115.31 (8)	M3^xvii—O2—M2^xvii	96.29 (10)
O3^viii—D—BNA	111.44 (8)	T2—O2—M1^xvii	118.34 (13)
O3^xiii—D—BNA^xiv	46.07 (8)	T2—O2—M2^xvii	126.32 (14)
O3^viii—D—BNA^xiv	46.07 (8)	T2—O2—M3^xvii	121.54 (13)
O3^xiii—D—BNA	111.44 (8)	D^xiii—O3—A	106.34 (11)
O3^xiii—D—O3^viii	86.28 (16)	D^xiii—O3—BNA	99.43 (11)
O3^xiii—D—F	75.30 (8)	T2—O3—D^xiii	136.04 (17)
O3^viii—D—F	75.30 (8)	T2—O3—A	110.75 (13)
O4^xv—D—M1	79.09 (8)	T2—O3—BNA	94.36 (12)
O4—D—M1	79.09 (8)	BNA—O3—A	103.19 (9)
O4—D—A	46.01 (8)	D—O4—A	105.13 (11)
O4^xv—D—A	116.17 (9)	D—O4—BNA	99.20 (11)
O4—D—A^xiii	116.17 (9)	T2^vii—O4—D	142.25 (18)
O4^xv—D—A^xiii	46.01 (8)	T2^vii—O4—A	108.68 (13)
O4^xv—D—BNA	47.15 (9)	T2^vii—O4—BNA	91.17 (12)
O4^xv—D—BNA^xiv	113.72 (9)	BNA—O4—A	99.87 (9)
O4—D—BNA^xiv	113.72 (9)	T1^viii—O5—T2	139.42 (17)
O4—D—BNA	47.15 (9)	T1^viii—O5—A	105.49 (12)
O4^xv—D—O3^xiii	87.13 (12)	T1^viii—O5—A^iii	109.29 (12)
O4^xv—D—O3^viii	152.12 (12)	T2—O5—A^iii	95.63 (11)
O4—D—O3^viii	87.13 (12)	T2—O5—A	93.71 (11)
O4—D—O3^xiii	152.12 (12)	A^iii—O5—A	111.57 (7)
O4^xv—D—O4	86.15 (18)	M4—O6—M3^xiv	89.23 (8)
O4^xv—D—F	76.82 (9)	M4^xi—O6—M3^xiv	100.96 (9)
O4—D—F	76.82 (9)	M4—O6—M4^xi	99.29 (9)
F—D—M1	146.79 (3)	T1—O6—M3^xiv	119.19 (12)
F—D—A^xiii	56.236 (15)	T1—O6—M4	121.48 (13)
F—D—A	56.236 (15)	T1—O6—M4^xi	120.52 (12)
F—D—BNA^xiv	51.610 (16)	T1—O7—T1^xii	137.20 (16)
F—D—BNA	50.402 (17)	T1^xii—O7—A	104.74 (11)
O5^viii—T1—O6	112.08 (13)	T1—O7—A	101.22 (11)
O5^viii—T1—O7^xvi	106.85 (14)	M3—O8—M2	97.88 (11)
O5^viii—T1—O7	106.67 (14)	M4—O8—M2	95.50 (11)
O6—T1—O7^xvi	111.14 (12)	M4—O8—M3	102.12 (12)
O6—T1—O7	110.88 (12)	D—F—D^xiii	180.0
O7—T1—O7^xvi	109.02 (10)	D^xiii—F—A^xiii	90.0
M1^xvii—T2—A^iii	120.34 (3)	D—F—A	90.0
M1^xvii—T2—A	147.64 (3)	D^xiii—F—A	90.0
A^iii—T2—A	90.94 (2)	D—F—A^xiii	90.0
BNA—T2—M1^xvii	103.16 (2)	D^xiii—F—BNA	89.00 (2)
BNA—T2—A	75.23 (2)	D—F—BNA	91.00 (2)
BNA—T2—A^iii	75.28 (2)	D^xiii—F—BNA^xiv	91.00 (2)
O2—T2—M1^xvii	37.57 (9)	D—F—BNA^xiv	89.00 (2)
O2—T2—A^iii	131.53 (9)	A—F—A^xiii	180.0
O2—T2—A	126.38 (9)	BNA^xiv—F—A^xiii	90.0
O2—T2—BNA	137.47 (10)	BNA^xiv—F—A	90.0
O2—T2—O5	110.61 (13)	BNA—F—A	90.0
O3—T2—M1^xvii	106.92 (10)	BNA—F—A^xiii	90.0
O3—T2—A^iii	116.80 (10)	BNA^xiv—F—BNA	180.0

Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, −y+1, −z; (iii) x−1, y, z; (iv) x, −y+1, z−1; (v) −x+1, −y+1, −z+1; (vi) x, y, z−1; (vii) −x+1, y, −z+1; (viii) −x+2, y, −z+1; (ix) −x+2, y, −z; (x) −x+1, y, −z; (xi) −x+5/2, −y+1/2, −z; (xii) x−1/2, −y+1/2, z; (xiii) −x+2, −y+1, −z+1; (xiv) x+1, y, z; (xv) x, −y+1, z; (xvi) x+1/2, −y+1/2, z; (xvii) x, y, z+1.

(lb630)

Crystal data

0.5(Ca0.34F0.4Fe8.96K3.87Na3.46O60Si15.14Ti4)	F(000) = 1135
Mr = 1164.69	Dx = 3.071 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 5.3221 (5) Å	Cell parameters from 3088 reflections
b = 23.192 (2) Å	θ = 1.9–35.8°
c = 10.3452 (9) Å	µ = 3.99 mm^−1
β = 99.454 (9)°	T = 293 K
V = 1259.6 (2) Å^3	Prism, brown
Z = 2	0.22 × 0.18 × 0.11 mm

Data collection

Saxi-CrysAlisPro-abstract goniometer imported SAXI images diffractometer	3000 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2296 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.062
ω scans	θmax = 36.3°, θmin = 1.8°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→8
Tmin = 0.822, Tmax = 1.000	k = −38→33
11372 measured reflections	l = −17→16

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: dual
R[F^2 > 2σ(F^2)] = 0.077	w = 1/[σ^2(Fo^2) + (0.0297P)^2 + 12.3572P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.129	(Δ/σ)max < 0.001
S = 1.17	Δρmax = 1.86 e Å^−3
3000 reflections	Δρmin = −1.35 e Å^−3
132 parameters

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
M1	0.500000	0.500000	0.000000	0.0179 (11)	0.900 (15)
M2	1.000000	0.42059 (6)	0.000000	0.0242 (4)	0.746 (5)
M3	0.500000	0.35551 (4)	0.000000	0.0101 (3)	0.805 (5)
M4	1.000000	0.29183 (5)	0.000000	0.0117 (3)	0.688 (4)
D	0.93991 (17)	0.500000	0.28815 (9)	0.0107 (2)
T1	1.42264 (19)	0.28198 (4)	0.26818 (10)	0.0079 (3)	0.947 (6)
T2	0.5716 (2)	0.41384 (5)	0.72624 (10)	0.0086 (3)	0.946 (6)
A	1.000000	0.36081 (7)	0.500000	0.0271 (4)	0.967 (7)
BNA	0.500000	0.500000	0.500000	0.0128 (10)	0.83 (2)
BCA	0.500000	0.500000	0.500000	0.0128 (10)	0.17 (2)
O1	0.9097 (9)	0.500000	0.1128 (4)	0.0294 (11)
O2	0.6384 (5)	0.41574 (12)	0.8870 (3)	0.0151 (5)
O3	0.7945 (6)	0.44248 (13)	0.6593 (3)	0.0204 (6)
O4	0.6982 (6)	0.44298 (14)	0.3306 (3)	0.0219 (6)
O5	0.5492 (6)	0.34657 (12)	0.6740 (3)	0.0191 (6)
O6	1.3710 (5)	0.28123 (11)	0.1086 (3)	0.0117 (5)
O7	1.1851 (5)	0.25239 (13)	0.3261 (3)	0.0178 (6)
O8	0.8493 (6)	0.35222 (14)	0.0945 (3)	0.0192 (6)
F	1.000000	0.500000	0.500000	0.016 (7)*	0.198 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
M1	0.016 (2)	0.0112 (18)	0.025 (2)	0.000	−0.0010 (15)	0.000
M2	0.0089 (6)	0.0357 (8)	0.0261 (7)	0.000	−0.0031 (4)	0.000
M3	0.0085 (4)	0.0115 (4)	0.0113 (4)	0.000	0.0041 (3)	0.000
M4	0.0085 (5)	0.0155 (6)	0.0116 (5)	0.000	0.0032 (4)	0.000
D	0.0048 (4)	0.0147 (4)	0.0134 (4)	0.000	0.0037 (3)	0.000
T1	0.0081 (5)	0.0086 (5)	0.0074 (5)	−0.0002 (3)	0.0023 (3)	−0.0010 (3)
T2	0.0075 (5)	0.0085 (5)	0.0105 (5)	0.0005 (3)	0.0029 (3)	0.0011 (3)
A	0.0237 (7)	0.0261 (8)	0.0324 (8)	0.000	0.0074 (6)	0.000
BNA	0.0152 (15)	0.0145 (15)	0.0083 (13)	0.000	0.0008 (9)	0.000
BCA	0.0152 (15)	0.0145 (15)	0.0083 (13)	0.000	0.0008 (9)	0.000
O1	0.013 (2)	0.062 (4)	0.0142 (19)	0.000	0.0066 (16)	0.000
O2	0.0139 (12)	0.0178 (13)	0.0143 (12)	−0.0015 (10)	0.0044 (10)	0.0013 (10)
O3	0.0171 (14)	0.0243 (15)	0.0210 (14)	−0.0063 (11)	0.0067 (11)	0.0010 (11)
O4	0.0162 (14)	0.0271 (16)	0.0221 (14)	−0.0094 (12)	0.0024 (11)	0.0013 (12)
O5	0.0285 (16)	0.0139 (13)	0.0148 (12)	−0.0017 (11)	0.0031 (11)	−0.0009 (10)
O6	0.0103 (11)	0.0143 (12)	0.0107 (11)	−0.0001 (9)	0.0027 (9)	−0.0011 (9)
O7	0.0129 (13)	0.0276 (15)	0.0136 (12)	−0.0088 (11)	0.0040 (10)	−0.0018 (11)
O8	0.0142 (13)	0.0289 (16)	0.0148 (12)	0.0018 (12)	0.0033 (10)	−0.0012 (11)

Geometric parameters (Å, º)

M1—M2^i	3.2362 (8)	D—O3^viii	1.955 (3)
M1—M2^ii	3.2362 (8)	D—O4^xv	1.945 (3)
M1—M2	3.2362 (8)	D—O4	1.945 (3)
M1—M2^iii	3.2362 (8)	D—F	2.1623 (10)
M1—M3	3.3511 (10)	T1—O5^viii	1.611 (3)
M1—M3^ii	3.3512 (10)	T1—O6	1.629 (3)
M1—O1	2.298 (5)	T1—O7^xvi	1.634 (3)
M1—O1^ii	2.298 (5)	T1—O7	1.636 (3)
M1—O2^iv	2.452 (3)	T2—A^i	3.7291 (12)
M1—O2^v	2.452 (3)	T2—A	3.7338 (12)
M1—O2^vi	2.452 (3)	T2—BNA	3.0534 (11)
M1—O2^vii	2.452 (3)	T2—O2	1.643 (3)
M2—O1^iii	2.273 (3)	T2—O3	1.612 (3)
M2—O1	2.273 (3)	T2—O4^vii	1.609 (3)
M2—O2^vi	2.084 (3)	T2—O5	1.649 (3)
M2—O2^viii	2.084 (3)	A—O3^viii	2.845 (3)
M2—O8^ix	2.091 (3)	A—O3	2.845 (3)
M2—O8	2.091 (3)	A—O4^viii	2.891 (3)
M3—O2^vii	2.036 (3)	A—O4	2.891 (3)
M3—O2^vi	2.036 (3)	A—O5	3.244 (3)
M3—O6^ix	2.226 (3)	A—O5^vii	3.188 (3)
M3—O6^i	2.226 (3)	A—O5^viii	3.244 (3)
M3—O8	1.954 (3)	A—O5^xiv	3.188 (3)
M3—O8^x	1.954 (3)	A—O7^viii	3.334 (3)
M4—O6^ix	2.120 (3)	A—O7	3.334 (3)
M4—O6^xi	2.204 (3)	A—F	3.2280 (16)
M4—O6^xii	2.204 (3)	BNA—O3^xv	2.471 (3)
M4—O6	2.120 (3)	BNA—O3	2.471 (3)
M4—O8^ix	1.954 (3)	BNA—O3^vii	2.471 (3)
M4—O8	1.954 (3)	BNA—O3^v	2.471 (3)
D—A^xiii	3.8853 (14)	BNA—O4	2.557 (3)
D—A	3.8853 (14)	BNA—O4^xv	2.557 (3)
D—BNA^xiv	3.3974 (10)	BNA—O4^vii	2.557 (3)
D—BNA	3.4599 (10)	BNA—O4^v	2.557 (3)
D—O1	1.795 (5)	BNA—F^i	2.6611 (3)
D—O3^xiii	1.955 (3)	BNA—F	2.6610 (3)
M2^i—M1—M2^iii	180.00 (4)	O3—T2—O2	111.81 (16)
M2^iii—M1—M2^ii	110.63 (4)	O3—T2—O5	105.54 (17)
M2^i—M1—M2^ii	69.37 (4)	O4^vii—T2—A^i	47.30 (12)
M2^ii—M1—M2	180.0	O4^vii—T2—A	120.63 (12)
M2^i—M1—M2	110.63 (4)	O4^vii—T2—BNA	56.85 (12)
M2^iii—M1—M2	69.37 (4)	O4^vii—T2—O2	112.99 (16)
M2^ii—M1—M3^ii	55.31 (2)	O4^vii—T2—O3	110.22 (18)
M2—M1—M3	55.31 (2)	O4^vii—T2—O5	105.38 (17)
M2—M1—M3^ii	124.69 (2)	O5—T2—A	60.11 (11)
M2^ii—M1—M3	124.69 (2)	O5—T2—A^i	58.29 (12)
M2^i—M1—M3	55.31 (2)	O5—T2—BNA	111.99 (11)
M2^i—M1—M3^ii	124.69 (2)	O3—A—T2^xiv	76.61 (7)
M2^iii—M1—M3^ii	55.31 (2)	O3^viii—A—T2^xiv	78.02 (7)
M2^iii—M1—M3	124.69 (2)	O3—A—O3^viii	96.52 (13)
M3—M1—M3^ii	180.0	O3—A—O4^viii	55.81 (9)
O1—M1—M2^iii	44.62 (7)	O3^viii—A—O4	55.81 (9)
O1—M1—M2^i	135.38 (7)	O3^viii—A—O4^viii	71.59 (10)
O1^ii—M1—M2^i	44.62 (7)	O3—A—O4	71.59 (10)
O1^ii—M1—M2	135.38 (7)	O3—A—O5^xiv	98.39 (9)
O1^ii—M1—M2^ii	44.62 (7)	O3—A—O5^vii	89.54 (8)
O1—M1—M2^ii	135.38 (7)	O3—A—O5^viii	141.17 (9)
O1^ii—M1—M2^iii	135.38 (7)	O3—A—O5	49.95 (8)
O1—M1—M2	44.62 (7)	O3^viii—A—O5^vii	98.39 (9)
O1—M1—M3	90.0	O3^viii—A—O5^xiv	89.54 (8)
O1^ii—M1—M3^ii	90.0	O3^viii—A—O5	141.17 (9)
O1—M1—M3^ii	90.0	O3^viii—A—O5^viii	49.95 (8)
O1^ii—M1—M3	90.0	O3—A—O7	172.20 (9)
O1—M1—O1^ii	180.0	O3—A—O7^viii	90.78 (8)
O1^ii—M1—O2^vii	84.70 (9)	O3^viii—A—O7^viii	172.20 (8)
O1—M1—O2^v	95.30 (9)	O3^viii—A—O7	90.78 (8)
O1^ii—M1—O2^v	84.70 (9)	O3—A—F	48.26 (6)
O1^ii—M1—O2^iv	95.30 (9)	O3^viii—A—F	48.26 (6)
O1^ii—M1—O2^vi	95.30 (9)	O4^viii—A—T2^xiv	24.13 (6)
O1—M1—O2^vii	95.30 (9)	O4—A—T2^xiv	118.54 (8)
O1—M1—O2^iv	84.70 (9)	O4^viii—A—O4	97.53 (13)
O1—M1—O2^vi	84.70 (9)	O4—A—O5	90.88 (8)
O2^v—M1—M2^ii	40.09 (7)	O4^viii—A—O5^viii	90.88 (8)
O2^v—M1—M2	139.91 (7)	O4—A—O5^vii	50.17 (8)
O2^vi—M1—M2^i	81.83 (7)	O4—A—O5^viii	96.82 (8)
O2^vi—M1—M2^iii	98.17 (7)	O4^viii—A—O5^vii	141.00 (9)
O2^iv—M1—M2^iii	40.09 (7)	O4^viii—A—O5^xiv	50.17 (8)
O2^vii—M1—M2	81.83 (7)	O4—A—O5^xiv	141.00 (9)
O2^vii—M1—M2^ii	98.17 (7)	O4^viii—A—O5	96.82 (8)
O2^v—M1—M2^iii	81.83 (7)	O4—A—O7^viii	129.82 (8)
O2^vi—M1—M2^ii	139.91 (7)	O4^viii—A—O7^viii	110.74 (8)
O2^vi—M1—M2	40.09 (7)	O4—A—O7	110.74 (8)
O2^iv—M1—M2^ii	81.83 (7)	O4^viii—A—O7	129.82 (8)
O2^iv—M1—M2	98.17 (7)	O4—A—F	48.76 (7)
O2^iv—M1—M2^i	139.91 (7)	O4^viii—A—F	48.76 (7)
O2^vii—M1—M2^i	40.09 (7)	O5^vii—A—T2^xiv	165.08 (7)
O2^v—M1—M2^i	98.17 (7)	O5^viii—A—T2^xiv	77.31 (6)
O2^vii—M1—M2^iii	139.91 (7)	O5—A—T2^xiv	106.67 (6)
O2^v—M1—M3^ii	37.15 (6)	O5^xiv—A—T2^xiv	26.11 (5)
O2^vi—M1—M3	37.15 (6)	O5^vii—A—O5^viii	111.68 (9)
O2^vii—M1—M3^ii	142.85 (6)	O5^vii—A—O5	67.02 (9)
O2^v—M1—M3	142.85 (6)	O5^viii—A—O5	168.31 (12)
O2^iv—M1—M3^ii	37.15 (6)	O5^vii—A—O5^xiv	168.11 (12)
O2^iv—M1—M3	142.85 (6)	O5^xiv—A—O5	111.68 (9)
O2^vi—M1—M3^ii	142.85 (6)	O5^xiv—A—O5^viii	67.02 (9)
O2^vii—M1—M3	37.15 (6)	O5^vii—A—O7^viii	84.36 (8)
O2^v—M1—O2^vi	180.0	O5^viii—A—O7	46.58 (7)
O2^v—M1—O2^iv	74.30 (13)	O5^xiv—A—O7	84.36 (8)
O2^vi—M1—O2^vii	74.30 (13)	O5^vii—A—O7	86.67 (8)
O2^iv—M1—O2^vii	180.0	O5—A—O7^viii	46.58 (7)
O2^vi—M1—O2^iv	105.70 (13)	O5—A—O7	122.25 (8)
O2^v—M1—O2^vii	105.70 (13)	O5^xiv—A—O7^viii	86.67 (8)
M1^xiv—M2—M1	110.62 (4)	O5^viii—A—O7^viii	122.25 (8)
O1^iii—M2—M1	77.41 (11)	O5^vii—A—F	95.95 (6)
O1—M2—M1	45.24 (12)	O5^xiv—A—F	95.95 (6)
O1^iii—M2—M1^xiv	45.24 (12)	O7—A—T2^xiv	107.73 (5)
O1—M2—M1^xiv	77.41 (11)	O7^viii—A—T2^xiv	101.12 (5)
O1—M2—O1^iii	71.78 (18)	O7—A—O7^viii	82.07 (10)
O2^viii—M2—M1^xiv	49.24 (8)	F—A—T2^xiv	70.74 (3)
O2^vi—M2—M1	49.24 (8)	F—A—O5	95.85 (6)
O2^viii—M2—M1	135.58 (9)	F—A—O5^viii	95.84 (6)
O2^vi—M2—M1^xiv	135.58 (9)	F—A—O7	138.96 (5)
O2^vi—M2—O1^iii	90.54 (14)	F—A—O7^viii	138.97 (5)
O2^viii—M2—O1^iii	94.47 (15)	T2^xv—BNA—T2^vii	180.0
O2^vi—M2—O1	94.47 (15)	O3^vii—BNA—T2^vii	31.75 (7)
O2^viii—M2—O1	90.54 (14)	O3—BNA—T2^xv	81.74 (8)
O2^vi—M2—O2^viii	173.82 (18)	O3—BNA—T2^vii	98.26 (8)
O2^viii—M2—O8	94.98 (12)	O3^vii—BNA—T2^xv	148.25 (7)
O2^vi—M2—O8^ix	94.98 (12)	O3^xv—BNA—T2^xv	31.75 (7)
O2^vi—M2—O8	80.30 (12)	O3^v—BNA—T2^vii	81.74 (8)
O2^viii—M2—O8^ix	80.30 (12)	O3^xv—BNA—T2^vii	148.25 (7)
O8—M2—M1	93.04 (8)	O3^v—BNA—T2^xv	98.26 (8)
O8^ix—M2—M1	144.13 (8)	O3^xv—BNA—O3^v	114.65 (14)
O8^ix—M2—M1^xiv	93.04 (8)	O3^v—BNA—O3	180.00 (12)
O8—M2—M1^xiv	144.13 (8)	O3^vii—BNA—O3^v	65.35 (14)
O8^ix—M2—O1	169.75 (14)	O3^xv—BNA—O3	65.35 (14)
O8—M2—O1^iii	169.75 (14)	O3^xv—BNA—O3^vii	180.00 (12)
O8^ix—M2—O1^iii	104.18 (12)	O3^vii—BNA—O3	114.65 (14)
O8—M2—O1	104.18 (12)	O3—BNA—O4	83.69 (10)
O8—M2—O8^ix	81.34 (17)	O3^xv—BNA—O4^vii	96.31 (10)
O2^vii—M3—M1	46.66 (8)	O3^vii—BNA—O4	63.35 (10)
O2^vi—M3—M1	46.66 (8)	O3^v—BNA—O4^xv	63.35 (10)
O2^vii—M3—O2^vi	93.32 (16)	O3^v—BNA—O4^v	83.69 (10)
O2^vi—M3—O6^i	172.61 (11)	O3—BNA—O4^xv	116.65 (10)
O2^vii—M3—O6^i	94.06 (11)	O3^xv—BNA—O4	116.65 (10)
O2^vii—M3—O6^ix	172.61 (11)	O3—BNA—O4^vii	63.35 (10)
O2^vi—M3—O6^ix	94.06 (11)	O3^v—BNA—O4	96.31 (10)
O6^i—M3—M1	140.72 (7)	O3^vii—BNA—O4^vii	83.69 (10)
O6^ix—M3—M1	140.72 (7)	O3—BNA—O4^v	96.31 (10)
O6^ix—M3—O6^i	78.57 (14)	O3^xv—BNA—O4^v	63.35 (10)
O8—M3—M1	92.24 (10)	O3^xv—BNA—O4^xv	83.69 (10)
O8^x—M3—M1	92.24 (10)	O3^vii—BNA—O4^v	116.65 (10)
O8^x—M3—O2^vi	98.27 (12)	O3^v—BNA—O4^vii	116.65 (10)
O8^x—M3—O2^vii	84.82 (12)	O3^vii—BNA—O4^xv	96.31 (10)
O8—M3—O2^vii	98.27 (12)	O3—BNA—F^i	121.65 (7)
O8—M3—O2^vi	84.82 (12)	O3^vii—BNA—F^i	58.35 (7)
O8—M3—O6^ix	82.84 (11)	O3^v—BNA—F	121.65 (7)
O8^x—M3—O6^i	82.84 (11)	O3—BNA—F	58.35 (7)
O8—M3—O6^i	93.69 (12)	O3^vii—BNA—F	121.65 (7)
O8^x—M3—O6^ix	93.69 (12)	O3^v—BNA—F^i	58.35 (7)
O8^x—M3—O8	175.5 (2)	O3^xv—BNA—F	58.35 (7)
O6^ix—M4—O6^xii	80.78 (11)	O3^xv—BNA—F^i	121.65 (7)
O6^ix—M4—O6^xi	88.95 (9)	O4—BNA—T2^xv	148.22 (7)
O6—M4—O6^xii	88.96 (9)	O4^xv—BNA—T2^vii	80.02 (7)
O6—M4—O6^xi	80.78 (11)	O4—BNA—T2^vii	31.78 (7)
O6^ix—M4—O6	166.67 (16)	O4^v—BNA—T2^vii	148.22 (7)
O6^xi—M4—O6^xii	79.51 (14)	O4^xv—BNA—T2^xv	99.98 (7)
O8—M4—O6^ix	85.70 (11)	O4^vii—BNA—T2^vii	99.98 (8)
O8^ix—M4—O6^ix	103.97 (12)	O4^v—BNA—T2^xv	31.78 (7)
O8—M4—O6^xi	173.64 (12)	O4^vii—BNA—T2^xv	80.02 (7)
O8^ix—M4—O6^xii	173.64 (12)	O4^v—BNA—O4^vii	62.28 (14)
O8—M4—O6	103.97 (12)	O4—BNA—O4^xv	62.28 (14)
O8^ix—M4—O6	85.69 (11)	O4—BNA—O4^vii	117.72 (14)
O8^ix—M4—O6^xi	96.22 (11)	O4—BNA—O4^v	180.0
O8—M4—O6^xii	96.22 (11)	O4^v—BNA—O4^xv	117.72 (14)
O8^ix—M4—O8	88.42 (19)	O4^xv—BNA—O4^vii	180.00 (12)
M1—D—A^xiii	117.732 (18)	O4^xv—BNA—F^i	121.67 (7)
M1—D—A	117.732 (18)	O4—BNA—F	58.33 (7)
A—D—A^xiii	112.37 (4)	O4^vii—BNA—F	121.67 (7)
BNA—D—M1	96.47 (2)	O4^v—BNA—F^i	58.33 (7)
BNA^xiv—D—M1	161.72 (3)	O4^v—BNA—F	121.67 (7)
BNA—D—A^xiii	69.160 (16)	O4^vii—BNA—F^i	58.33 (7)
BNA^xiv—D—A	69.752 (17)	O4^xv—BNA—F	58.33 (7)
BNA—D—A	69.160 (16)	O4—BNA—F^i	121.67 (7)
BNA^xiv—D—A^xiii	69.752 (17)	F—BNA—T2^vii	89.94 (2)
BNA^xiv—D—BNA	101.81 (3)	F—BNA—T2^xv	90.06 (2)
O1—D—M1	36.59 (15)	F^i—BNA—T2^xv	89.94 (2)
O1—D—A	123.751 (19)	F^i—BNA—T2^vii	90.06 (2)
O1—D—A^xiii	123.751 (19)	F^i—BNA—F	180.0
O1—D—BNA^xiv	125.13 (15)	M2—O1—M1	90.14 (14)
O1—D—BNA	133.06 (15)	M2^iii—O1—M1	90.14 (14)
O1—D—O3^xiii	102.80 (14)	M2^iii—O1—M2	108.22 (18)
O1—D—O3^viii	102.80 (14)	D—O1—M1	115.7 (2)
O1—D—O4	106.00 (14)	D—O1—M2	121.82 (12)
O1—D—O4^xv	106.00 (14)	D—O1—M2^iii	121.82 (12)
O1—D—F	176.68 (16)	M2^xvii—O2—M1^xvii	90.67 (11)
O3^viii—D—M1	126.37 (10)	M3^xvii—O2—M1^xvii	96.19 (11)
O3^xiii—D—M1	126.37 (10)	M3^xvii—O2—M2^xvii	95.90 (12)
O3^viii—D—A	44.55 (9)	T2—O2—M1^xvii	118.17 (15)
O3^xiii—D—A^xiii	44.55 (9)	T2—O2—M2^xvii	126.54 (16)
O3^viii—D—A^xiii	114.93 (10)	T2—O2—M3^xvii	121.62 (16)
O3^xiii—D—A	114.93 (10)	D^xiii—O3—A	106.63 (13)
O3^viii—D—BNA^xiv	45.81 (10)	D^xiii—O3—BNA	99.64 (13)
O3^viii—D—BNA	110.96 (10)	T2—O3—D^xiii	135.37 (19)
O3^xiii—D—BNA^xiv	45.81 (10)	T2—O3—A	110.77 (15)
O3^xiii—D—BNA	110.96 (10)	T2—O3—BNA	94.48 (14)
O3^xiii—D—O3^viii	86.1 (2)	BNA—O3—A	103.59 (11)
O3^xiii—D—F	74.84 (9)	D—O4—A	105.24 (13)
O3^viii—D—F	74.84 (9)	D—O4—BNA	99.54 (13)
O4^xv—D—M1	79.42 (10)	T2^vii—O4—D	141.9 (2)
O4—D—M1	79.42 (10)	T2^vii—O4—A	108.57 (15)
O4^xv—D—A	115.70 (10)	T2^vii—O4—BNA	91.37 (14)
O4—D—A^xiii	115.70 (10)	BNA—O4—A	100.15 (10)
O4—D—A	45.88 (10)	T1^viii—O5—T2	139.5 (2)
O4^xv—D—A^xiii	45.88 (10)	T1^viii—O5—A	105.58 (14)
O4—D—BNA^xiv	113.40 (10)	T1^viii—O5—A^i	109.08 (14)
O4^xv—D—BNA^xiv	113.40 (10)	T2—O5—A	93.74 (13)
O4—D—BNA	46.79 (10)	T2—O5—A^i	95.60 (13)
O4^xv—D—BNA	46.79 (10)	A^i—O5—A	111.68 (9)
O4—D—O3^xiii	151.20 (14)	M4^xi—O6—M3^xiv	100.96 (10)
O4^xv—D—O3^xiii	87.03 (14)	M4—O6—M3^xiv	88.88 (10)
O4—D—O3^viii	87.03 (14)	M4—O6—M4^xi	99.22 (11)
O4^xv—D—O3^viii	151.20 (14)	T1—O6—M3^xiv	119.25 (14)
O4—D—O4^xv	85.7 (2)	T1—O6—M4	121.55 (14)
O4—D—F	76.36 (10)	T1—O6—M4^xi	120.67 (15)
O4^xv—D—F	76.36 (10)	T1^xii—O7—T1	137.37 (19)
F—D—M1	146.74 (4)	T1—O7—A	101.30 (13)
F—D—A	56.184 (18)	T1^xii—O7—A	104.79 (13)
F—D—A^xiii	56.185 (18)	M3—O8—M2	98.23 (13)
F—D—BNA	50.263 (19)	M4—O8—M2	95.12 (12)
F—D—BNA^xiv	51.55 (2)	M4—O8—M3	102.28 (14)
O5^viii—T1—O6	112.12 (15)	D—F—D^xiii	180.0
O5^viii—T1—O7	106.52 (16)	D—F—A^xiii	90.0
O5^viii—T1—O7^xvi	107.19 (17)	D^xiii—F—A^xiii	90.0
O6—T1—O7^xvi	110.98 (15)	D—F—A	90.0
O6—T1—O7	110.78 (15)	D^xiii—F—A	90.0
O7^xvi—T1—O7	109.06 (11)	D^xiii—F—BNA	88.93 (3)
A^i—T2—A	90.98 (3)	D—F—BNA	91.07 (3)
BNA—T2—A^i	75.43 (3)	D^xiii—F—BNA^xiv	91.07 (3)
BNA—T2—A	75.36 (3)	D—F—BNA^xiv	88.93 (3)
O2—T2—A	126.19 (11)	A—F—A^xiii	180.0
O2—T2—A^i	131.50 (11)	BNA^xiv—F—A^xiii	90.0
O2—T2—BNA	137.50 (11)	BNA^xiv—F—A	90.0
O2—T2—O5	110.45 (15)	BNA—F—A	90.0
O3—T2—A	45.43 (12)	BNA—F—A^xiii	90.0
O3—T2—A^i	116.65 (12)	BNA^xiv—F—BNA	180.0
O3—T2—BNA	53.78 (12)

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z; (iii) −x+2, −y+1, −z; (iv) x, −y+1, z−1; (v) −x+1, −y+1, −z+1; (vi) x, y, z−1; (vii) −x+1, y, −z+1; (viii) −x+2, y, −z+1; (ix) −x+2, y, −z; (x) −x+1, y, −z; (xi) −x+5/2, −y+1/2, −z; (xii) x−1/2, −y+1/2, z; (xiii) −x+2, −y+1, −z+1; (xiv) x+1, y, z; (xv) x, −y+1, z; (xvi) x+1/2, −y+1/2, z; (xvii) x, y, z+1.

(lb630-2)

Crystal data

0.5(Ca0.32F0.32Fe8.96K3.9Na3.5O60Si15.18Ti4)	F(000) = 1136
Mr = 1165.42	Dx = 3.123 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 5.2961 (2) Å	Cell parameters from 4103 reflections
b = 23.0805 (10) Å	θ = 1.8–36.4°
c = 10.2752 (5) Å	µ = 4.06 mm^−1
β = 99.388 (4)°	T = 293 K
V = 1239.18 (9) Å^3	Prism, brown
Z = 2	0.22 × 0.18 × 0.11 mm

Data collection

Saxi-CrysAlisPro-abstract goniometer imported SAXI images diffractometer	2995 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2427 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
ω scans	θmax = 36.4°, θmin = 1.8°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→8
Tmin = 0.739, Tmax = 1.000	k = −36→38
11459 measured reflections	l = −15→16

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: dual
R[F^2 > 2σ(F^2)] = 0.059	w = 1/[σ^2(Fo^2) + (0.0175P)^2 + 10.1712P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.097	(Δ/σ)max < 0.001
S = 1.12	Δρmax = 1.64 e Å^−3
2995 reflections	Δρmin = −1.07 e Å^−3
132 parameters

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
M1	0.500000	0.500000	0.000000	0.0149 (8)	0.910 (11)
M2	1.000000	0.42093 (4)	0.000000	0.0232 (3)	0.753 (4)
M3	0.500000	0.35548 (3)	0.000000	0.01078 (19)	0.805 (4)
M4	1.000000	0.29170 (4)	0.000000	0.0114 (2)	0.683 (3)
D	0.93960 (12)	0.500000	0.28770 (7)	0.01123 (15)
T1	1.42213 (14)	0.28196 (3)	0.26841 (8)	0.0078 (2)	0.948 (5)
T2	0.57133 (14)	0.41388 (3)	0.72589 (8)	0.0090 (2)	0.949 (5)
A	1.000000	0.36055 (5)	0.500000	0.0277 (3)	0.974 (6)
BNA	0.500000	0.500000	0.500000	0.0135 (8)	0.839 (17)
BCA	0.500000	0.500000	0.500000	0.0135 (8)	0.161 (17)
O1	0.9070 (6)	0.500000	0.1126 (3)	0.0299 (9)
O2	0.6384 (4)	0.41582 (9)	0.8862 (2)	0.0152 (4)
O3	0.7953 (4)	0.44265 (10)	0.6590 (2)	0.0196 (5)
O4	0.6988 (4)	0.44307 (10)	0.3307 (2)	0.0215 (5)
O5	0.5487 (5)	0.34650 (9)	0.6736 (2)	0.0192 (4)
O6	1.3705 (4)	0.28129 (9)	0.1080 (2)	0.0121 (4)
O7	1.1852 (4)	0.25242 (10)	0.3266 (2)	0.0173 (4)
O8	0.8500 (4)	0.35238 (11)	0.0946 (2)	0.0196 (4)
F	1.000000	0.500000	0.500000	0.008 (5)*	0.158 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
M1	0.0114 (12)	0.0110 (13)	0.0204 (15)	0.000	−0.0030 (9)	0.000
M2	0.0091 (4)	0.0336 (6)	0.0245 (5)	0.000	−0.0045 (3)	0.000
M3	0.0083 (3)	0.0114 (3)	0.0128 (3)	0.000	0.0019 (2)	0.000
M4	0.0069 (3)	0.0143 (4)	0.0126 (4)	0.000	0.0002 (3)	0.000
D	0.0047 (2)	0.0147 (3)	0.0140 (3)	0.000	0.0009 (2)	0.000
T1	0.0061 (3)	0.0082 (3)	0.0087 (4)	0.0003 (2)	−0.0003 (2)	−0.0005 (3)
T2	0.0074 (3)	0.0079 (3)	0.0112 (4)	0.0007 (2)	0.0006 (2)	0.0006 (3)
A	0.0238 (5)	0.0255 (6)	0.0337 (7)	0.000	0.0045 (4)	0.000
BNA	0.0167 (11)	0.0131 (11)	0.0094 (11)	0.000	−0.0022 (7)	0.000
BCA	0.0167 (11)	0.0131 (11)	0.0094 (11)	0.000	−0.0022 (7)	0.000
O1	0.0119 (13)	0.063 (3)	0.0146 (15)	0.000	0.0020 (11)	0.000
O2	0.0143 (9)	0.0168 (10)	0.0141 (9)	−0.0005 (7)	0.0010 (7)	0.0007 (8)
O3	0.0144 (9)	0.0231 (11)	0.0212 (11)	−0.0059 (8)	0.0029 (8)	0.0010 (9)
O4	0.0137 (9)	0.0243 (12)	0.0255 (12)	−0.0070 (8)	0.0004 (8)	0.0011 (9)
O5	0.0275 (11)	0.0117 (9)	0.0170 (10)	0.0012 (8)	−0.0007 (9)	0.0002 (8)
O6	0.0097 (8)	0.0153 (9)	0.0110 (9)	−0.0006 (7)	0.0006 (6)	−0.0006 (7)
O7	0.0126 (8)	0.0247 (11)	0.0143 (10)	−0.0072 (8)	0.0013 (7)	−0.0020 (8)
O8	0.0118 (8)	0.0294 (12)	0.0172 (10)	0.0038 (8)	0.0016 (7)	−0.0017 (9)

Geometric parameters (Å, º)

M1—M2	3.2160 (6)	D—O3^viii	1.942 (2)
M1—M2^i	3.2160 (6)	D—O4^xv	1.932 (2)
M1—M2^ii	3.2160 (6)	D—O4	1.932 (2)
M1—M2^iii	3.2160 (6)	D—F	2.1525 (7)
M1—M3^ii	3.3355 (7)	T1—O5^viii	1.602 (2)
M1—M3	3.3356 (7)	T1—O6	1.626 (2)
M1—O1	2.274 (3)	T1—O7^xvi	1.630 (2)
M1—O1^ii	2.274 (3)	T1—O7	1.625 (2)
M1—O2^iv	2.441 (2)	T2—A^iii	3.7104 (9)
M1—O2^v	2.441 (2)	T2—A	3.7116 (9)
M1—O2^vi	2.441 (2)	T2—BNA	3.0324 (8)
M1—O2^vii	2.441 (2)	T2—O2	1.628 (2)
M2—O1^i	2.258 (2)	T2—O3	1.608 (2)
M2—O1	2.258 (2)	T2—O4^vii	1.603 (2)
M2—O2^vi	2.078 (2)	T2—O5	1.643 (2)
M2—O2^viii	2.078 (2)	A—O3^viii	2.831 (3)
M2—O8^ix	2.081 (3)	A—O3	2.831 (3)
M2—O8	2.081 (3)	A—O4^viii	2.880 (3)
M3—O2^vii	2.030 (2)	A—O4	2.880 (3)
M3—O2^vi	2.030 (2)	A—O5^viii	3.223 (2)
M3—O6^ix	2.210 (2)	A—O5^vii	3.169 (2)
M3—O6^iii	2.210 (2)	A—O5	3.223 (2)
M3—O8	1.949 (2)	A—O5^xiv	3.169 (2)
M3—O8^x	1.949 (2)	A—O7^viii	3.307 (2)
M4—O6	2.1047 (19)	A—O7	3.307 (2)
M4—O6^xi	2.188 (2)	A—F	3.2186 (12)
M4—O6^xii	2.188 (2)	BNA—O3	2.456 (2)
M4—O6^ix	2.1047 (19)	BNA—O3^v	2.456 (2)
M4—O8^ix	1.946 (2)	BNA—O3^xv	2.456 (2)
M4—O8	1.946 (2)	BNA—O3^vii	2.456 (2)
D—A	3.8720 (11)	BNA—O4^v	2.542 (3)
D—A^xiii	3.8720 (11)	BNA—O4^vii	2.542 (3)
D—BNA^xiv	3.3845 (7)	BNA—O4	2.542 (3)
D—BNA	3.4403 (7)	BNA—O4^xv	2.542 (3)
D—O1	1.779 (4)	BNA—F^iii	2.6481 (1)
D—O3^xiii	1.942 (2)	BNA—F	2.6481 (1)
M2—M1—M2^iii	110.85 (3)	O3—T2—A	45.62 (9)
M2^iii—M1—M2^i	180.00 (3)	O3—T2—BNA	53.89 (9)
M2—M1—M2^i	69.15 (3)	O3—T2—O2	111.51 (12)
M2^iii—M1—M2^ii	69.15 (3)	O3—T2—O5	105.69 (13)
M2—M1—M2^ii	180.0	O4^vii—T2—M1^xvii	81.18 (9)
M2^i—M1—M2^ii	110.85 (3)	O4^vii—T2—A^iii	47.45 (9)
M2^ii—M1—M3^ii	55.427 (15)	O4^vii—T2—A	120.91 (10)
M2^i—M1—M3	124.573 (15)	O4^vii—T2—BNA	56.93 (10)
M2^iii—M1—M3^ii	124.573 (15)	O4^vii—T2—O2	112.95 (13)
M2^iii—M1—M3	55.427 (15)	O4^vii—T2—O3	110.40 (13)
M2^i—M1—M3^ii	55.427 (15)	O4^vii—T2—O5	105.44 (13)
M2—M1—M3	55.427 (15)	O5—T2—M1^xvii	141.72 (9)
M2^ii—M1—M3	124.573 (15)	O5—T2—A	60.07 (9)
M2—M1—M3^ii	124.573 (15)	O5—T2—A^iii	58.20 (9)
M3^ii—M1—M3	180.0	O5—T2—BNA	112.13 (9)
O1—M1—M2^ii	135.41 (5)	O3^viii—A—T2^xiv	77.82 (5)
O1^ii—M1—M2^iii	44.59 (5)	O3—A—T2^xiv	76.52 (5)
O1^ii—M1—M2^i	135.41 (5)	O3—A—O3^viii	95.96 (10)
O1—M1—M2^iii	135.41 (5)	O3^viii—A—O4^viii	71.31 (7)
O1—M1—M2	44.59 (5)	O3—A—O4^viii	55.60 (7)
O1—M1—M2^i	44.59 (5)	O3—A—O4	71.31 (7)
O1^ii—M1—M2	135.41 (5)	O3^viii—A—O4	55.60 (7)
O1^ii—M1—M2^ii	44.59 (5)	O3^viii—A—O5^xiv	89.48 (6)
O1^ii—M1—M3^ii	90.0	O3^viii—A—O5	140.81 (7)
O1—M1—M3	90.0	O3^viii—A—O5^vii	98.40 (6)
O1^ii—M1—M3	90.0	O3—A—O5^xiv	98.40 (6)
O1—M1—M3^ii	90.0	O3—A—O5	50.18 (6)
O1—M1—O1^ii	180.0	O3—A—O5^viii	140.81 (7)
O1—M1—O2^vii	95.17 (7)	O3^viii—A—O5^viii	50.18 (6)
O1—M1—O2^vi	84.83 (7)	O3—A—O5^vii	89.48 (6)
O1^ii—M1—O2^iv	95.17 (7)	O3—A—O7	172.46 (7)
O1^ii—M1—O2^vii	84.83 (7)	O3—A—O7^viii	91.09 (6)
O1—M1—O2^iv	84.83 (7)	O3^viii—A—O7^viii	172.46 (7)
O1—M1—O2^v	95.17 (7)	O3^viii—A—O7	91.09 (6)
O1^ii—M1—O2^vi	95.17 (7)	O3^viii—A—F	47.98 (5)
O1^ii—M1—O2^v	84.83 (7)	O3—A—F	47.98 (5)
O2^vii—M1—M2^ii	98.05 (5)	O4^viii—A—T2^xiv	24.20 (5)
O2^vi—M1—M2	40.25 (5)	O4—A—T2^xiv	118.25 (6)
O2^iv—M1—M2^ii	81.95 (5)	O4^viii—A—O4	97.19 (10)
O2^vi—M1—M2^i	98.05 (5)	O4^viii—A—O5^xiv	50.28 (6)
O2^iv—M1—M2	98.05 (5)	O4—A—O5^vii	50.28 (6)
O2^iv—M1—M2^i	40.25 (5)	O4^viii—A—O5^vii	140.75 (7)
O2^vii—M1—M2^iii	40.25 (5)	O4^viii—A—O5	96.88 (6)
O2^v—M1—M2^ii	40.25 (5)	O4—A—O5^viii	96.88 (6)
O2^v—M1—M2	139.75 (5)	O4—A—O5^xiv	140.75 (7)
O2^v—M1—M2^iii	98.05 (5)	O4^viii—A—O5^viii	90.76 (6)
O2^v—M1—M2^i	81.95 (5)	O4—A—O5	90.76 (6)
O2^vi—M1—M2^iii	81.95 (5)	O4^viii—A—O7^viii	110.94 (6)
O2^vii—M1—M2	81.95 (5)	O4^viii—A—O7	129.86 (6)
O2^vi—M1—M2^ii	139.75 (5)	O4—A—O7	110.94 (6)
O2^iv—M1—M2^iii	139.75 (5)	O4—A—O7^viii	129.86 (6)
O2^vii—M1—M2^i	139.75 (5)	O4—A—F	48.59 (5)
O2^v—M1—M3^ii	37.25 (5)	O4^viii—A—F	48.59 (5)
O2^iv—M1—M3^ii	37.25 (5)	O5^vii—A—T2^xiv	164.91 (5)
O2^iv—M1—M3	142.75 (5)	O5—A—T2^xiv	106.85 (4)
O2^vii—M1—M3	37.25 (5)	O5^xiv—A—T2^xiv	26.15 (4)
O2^v—M1—M3	142.75 (5)	O5^viii—A—T2^xiv	77.11 (4)
O2^vii—M1—M3^ii	142.75 (5)	O5^vii—A—O5^xiv	168.25 (9)
O2^vi—M1—M3^ii	142.75 (5)	O5^xiv—A—O5	111.90 (7)
O2^vi—M1—M3	37.25 (5)	O5^vii—A—O5	66.83 (7)
O2^vi—M1—O2^vii	74.51 (10)	O5^xiv—A—O5^viii	66.83 (7)
O2^iv—M1—O2^vii	180.00 (9)	O5^vii—A—O5^viii	111.90 (7)
O2^v—M1—O2^iv	74.51 (10)	O5—A—O5^viii	168.45 (9)
O2^v—M1—O2^vi	180.00 (9)	O5^viii—A—O7^viii	122.28 (6)
O2^v—M1—O2^vii	105.49 (10)	O5^vii—A—O7^viii	84.30 (6)
O2^vi—M1—O2^iv	105.49 (10)	O5—A—O7^viii	46.69 (5)
M1^xiv—M2—M1	110.85 (3)	O5—A—O7	122.28 (6)
O1—M2—M1^xiv	77.86 (8)	O5^xiv—A—O7^viii	86.84 (6)
O1—M2—M1	45.00 (9)	O5^vii—A—O7	86.84 (6)
O1^i—M2—M1	77.86 (8)	O5^xiv—A—O7	84.30 (6)
O1^i—M2—M1^xiv	45.00 (9)	O5^viii—A—O7	46.69 (5)
O1—M2—O1^i	72.14 (15)	O5^xiv—A—F	95.87 (4)
O2^viii—M2—M1^xiv	49.38 (6)	O5^vii—A—F	95.87 (4)
O2^vi—M2—M1	49.38 (6)	O7^viii—A—T2^xiv	101.34 (4)
O2^vi—M2—M1^xiv	135.69 (7)	O7—A—T2^xiv	107.70 (4)
O2^viii—M2—M1	135.69 (7)	O7—A—O7^viii	82.00 (8)
O2^viii—M2—O1	90.90 (11)	F—A—T2^xiv	70.63 (2)
O2^vi—M2—O1	94.37 (11)	F—A—O5	95.77 (4)
O2^viii—M2—O1^i	94.37 (11)	F—A—O5^viii	95.77 (4)
O2^vi—M2—O1^i	90.90 (11)	F—A—O7^viii	139.00 (4)
O2^vi—M2—O2^viii	173.49 (13)	F—A—O7	139.00 (4)
O2^viii—M2—O8	94.66 (9)	T2—BNA—T2^vii	98.08 (3)
O2^vi—M2—O8	80.35 (9)	O3^xv—BNA—T2^vii	148.07 (5)
O2^viii—M2—O8^ix	80.35 (9)	O3^v—BNA—T2	148.07 (5)
O2^vi—M2—O8^ix	94.66 (9)	O3^v—BNA—T2^vii	81.83 (6)
O8—M2—M1	93.12 (6)	O3^vii—BNA—T2	98.17 (6)
O8^ix—M2—M1^xiv	93.12 (6)	O3^vii—BNA—T2^vii	31.93 (5)
O8—M2—M1^xiv	143.95 (6)	O3^xv—BNA—T2	81.83 (6)
O8^ix—M2—M1	143.95 (6)	O3—BNA—T2	31.93 (5)
O8^ix—M2—O1^i	104.09 (10)	O3—BNA—T2^vii	98.17 (6)
O8^ix—M2—O1	170.28 (10)	O3^vii—BNA—O3^v	65.22 (11)
O8—M2—O1^i	170.28 (10)	O3—BNA—O3^v	180.0
O8—M2—O1	104.09 (10)	O3^xv—BNA—O3^vii	180.00 (9)
O8—M2—O8^ix	81.02 (13)	O3^xv—BNA—O3^v	114.78 (11)
O2^vi—M3—M1	46.70 (6)	O3—BNA—O3^vii	114.78 (11)
O2^vii—M3—M1	46.70 (6)	O3—BNA—O3^xv	65.22 (11)
O2^vii—M3—O2^vi	93.40 (13)	O3^xv—BNA—O4	116.36 (7)
O2^vi—M3—O6^ix	94.10 (8)	O3^vii—BNA—O4^vii	83.50 (8)
O2^vii—M3—O6^iii	94.10 (8)	O3^xv—BNA—O4^v	63.64 (7)
O2^vi—M3—O6^iii	172.50 (8)	O3^vii—BNA—O4	63.64 (7)
O2^vii—M3—O6^ix	172.50 (8)	O3—BNA—O4	83.50 (8)
O6^ix—M3—M1	140.80 (5)	O3^v—BNA—O4	96.50 (8)
O6^iii—M3—M1	140.80 (5)	O3—BNA—O4^xv	116.36 (7)
O6^ix—M3—O6^iii	78.40 (11)	O3—BNA—O4^v	96.50 (8)
O8^x—M3—M1	92.11 (8)	O3^vii—BNA—O4^xv	96.50 (8)
O8—M3—M1	92.11 (8)	O3^v—BNA—O4^v	83.50 (8)
O8—M3—O2^vii	98.13 (9)	O3—BNA—O4^vii	63.64 (7)
O8—M3—O2^vi	84.78 (9)	O3^v—BNA—O4^xv	63.64 (7)
O8^x—M3—O2^vi	98.13 (9)	O3^vii—BNA—O4^v	116.36 (7)
O8^x—M3—O2^vii	84.78 (9)	O3^v—BNA—O4^vii	116.36 (7)
O8^x—M3—O6^iii	82.77 (9)	O3^xv—BNA—O4^xv	83.50 (8)
O8—M3—O6^iii	93.95 (9)	O3^xv—BNA—O4^vii	96.50 (8)
O8—M3—O6^ix	82.77 (9)	O3^v—BNA—F^iii	58.12 (5)
O8^x—M3—O6^ix	93.95 (9)	O3^vii—BNA—F^iii	58.12 (5)
O8^x—M3—O8	175.79 (15)	O3^vii—BNA—F	121.88 (5)
O6—M4—O6^xii	89.25 (7)	O3^v—BNA—F	121.88 (5)
O6^ix—M4—O6^xi	89.25 (7)	O3^xv—BNA—F	58.12 (5)
O6^xi—M4—O6^xii	79.32 (11)	O3—BNA—F^iii	121.88 (5)
O6—M4—O6^ix	166.88 (12)	O3—BNA—F	58.12 (5)
O6^ix—M4—O6^xii	80.63 (8)	O3^xv—BNA—F^iii	121.88 (5)
O6—M4—O6^xi	80.63 (8)	O4—BNA—T2^vii	31.89 (5)
O8—M4—O6	103.91 (9)	O4^xv—BNA—T2^vii	80.14 (6)
O8^ix—M4—O6^xi	96.52 (9)	O4—BNA—T2	99.86 (6)
O8—M4—O6^ix	85.64 (9)	O4^v—BNA—T2	80.14 (6)
O8^ix—M4—O6	85.64 (9)	O4^xv—BNA—T2	148.11 (5)
O8^ix—M4—O6^xii	173.89 (9)	O4^vii—BNA—T2^vii	99.86 (6)
O8—M4—O6^xi	173.89 (9)	O4^v—BNA—T2^vii	148.11 (5)
O8^ix—M4—O6^ix	103.91 (9)	O4^vii—BNA—T2	31.89 (5)
O8—M4—O6^xii	96.52 (9)	O4^xv—BNA—O4^vii	180.00 (9)
O8^ix—M4—O8	87.98 (15)	O4^xv—BNA—O4	62.25 (11)
M1—D—A	117.691 (13)	O4^v—BNA—O4	180.0
M1—D—A^xiii	117.691 (13)	O4^v—BNA—O4^vii	62.26 (11)
A^xiii—D—A	112.45 (3)	O4^v—BNA—O4^xv	117.74 (11)
BNA—D—M1	96.395 (16)	O4^vii—BNA—O4	117.75 (11)
BNA^xiv—D—M1	161.82 (2)	O4^xv—BNA—F	58.26 (5)
BNA—D—A	69.208 (12)	O4^v—BNA—F	121.74 (5)
BNA^xiv—D—A^xiii	69.739 (12)	O4—BNA—F	58.27 (5)
BNA—D—A^xiii	69.208 (13)	O4^xv—BNA—F^iii	121.74 (5)
BNA^xiv—D—A	69.739 (12)	O4^v—BNA—F^iii	58.26 (5)
BNA^xiv—D—BNA	101.79 (2)	O4—BNA—F^iii	121.73 (5)
O1—D—M1	36.23 (11)	O4^vii—BNA—F	121.74 (5)
O1—D—A^xiii	123.724 (14)	O4^vii—BNA—F^iii	58.26 (5)
O1—D—A	123.723 (14)	F^iii—BNA—T2	89.984 (15)
O1—D—BNA^xiv	125.59 (11)	F^iii—BNA—T2^vii	90.016 (15)
O1—D—BNA	132.62 (11)	F—BNA—T2^vii	89.984 (15)
O1—D—O3^xiii	103.39 (11)	F—BNA—T2	90.016 (14)
O1—D—O3^viii	103.39 (11)	F^iii—BNA—F	180.0
O1—D—O4^xv	105.81 (11)	M2—O1—M1	90.41 (10)
O1—D—O4	105.81 (11)	M2^i—O1—M1	90.41 (10)
O1—D—F	177.06 (11)	M2—O1—M2^i	107.86 (15)
O3^xiii—D—M1	126.66 (7)	D—O1—M1	116.23 (17)
O3^viii—D—M1	126.66 (7)	D—O1—M2^i	121.66 (9)
O3^viii—D—A^xiii	114.72 (8)	D—O1—M2	121.66 (9)
O3^xiii—D—A^xiii	44.37 (7)	M2^xvii—O2—M1^xvii	90.37 (8)
O3^xiii—D—A	114.72 (7)	M3^xvii—O2—M1^xvii	96.05 (9)
O3^viii—D—A	44.37 (7)	M3^xvii—O2—M2^xvii	95.80 (9)
O3^viii—D—BNA	110.74 (8)	T2—O2—M1^xvii	118.26 (11)
O3^xiii—D—BNA^xiv	45.63 (7)	T2—O2—M2^xvii	126.85 (12)
O3^viii—D—BNA^xiv	45.63 (7)	T2—O2—M3^xvii	121.60 (12)
O3^xiii—D—BNA	110.74 (8)	D^xiii—O3—A	106.96 (9)
O3^xiii—D—O3^viii	85.93 (14)	D^xiii—O3—BNA	99.95 (10)
O3^xiii—D—F	74.53 (7)	T2—O3—D^xiii	135.28 (15)
O3^viii—D—F	74.53 (7)	T2—O3—A	110.42 (11)
O4—D—M1	79.49 (7)	T2—O3—BNA	94.18 (10)
O4^xv—D—M1	79.49 (7)	BNA—O3—A	103.83 (8)
O4^xv—D—A^xiii	45.79 (7)	D—O4—A	105.48 (9)
O4—D—A^xiii	115.70 (8)	D—O4—BNA	99.64 (10)
O4^xv—D—A	115.70 (8)	T2^vii—O4—D	141.89 (16)
O4—D—A	45.79 (7)	T2^vii—O4—A	108.35 (11)
O4—D—BNA	46.75 (8)	T2^vii—O4—BNA	91.18 (11)
O4—D—BNA^xiv	113.25 (7)	BNA—O4—A	100.30 (8)
O4^xv—D—BNA^xiv	113.25 (7)	T1^viii—O5—T2	139.51 (15)
O4^xv—D—BNA	46.75 (8)	T1^viii—O5—A	105.32 (11)
O4—D—O3^xiii	150.80 (11)	T1^viii—O5—A^iii	109.16 (11)
O4—D—O3^viii	86.89 (10)	T2—O5—A^iii	95.65 (10)
O4^xv—D—O3^viii	150.80 (11)	T2—O5—A	93.72 (10)
O4^xv—D—O3^xiii	86.89 (10)	A^iii—O5—A	111.90 (7)
O4—D—O4^xv	85.73 (15)	M4—O6—M3^xiv	89.18 (8)
O4—D—F	76.28 (8)	M4^xi—O6—M3^xiv	101.14 (8)
O4^xv—D—F	76.28 (8)	M4—O6—M4^xi	99.37 (8)
F—D—M1	146.71 (3)	T1—O6—M3^xiv	119.15 (11)
F—D—A	56.226 (14)	T1—O6—M4	121.44 (11)
F—D—A^xiii	56.226 (14)	T1—O6—M4^xi	120.44 (11)
F—D—BNA^xiv	51.470 (14)	T1—O7—T1^xii	137.24 (15)
F—D—BNA	50.318 (15)	T1^xii—O7—A	104.73 (10)
O5^viii—T1—O6	112.08 (12)	T1—O7—A	101.32 (10)
O5^viii—T1—O7	106.64 (13)	M3—O8—M2	98.27 (10)
O5^viii—T1—O7^xvi	106.94 (12)	M4—O8—M2	95.50 (10)
O6—T1—O7^xvi	111.07 (11)	M4—O8—M3	102.13 (11)
O7—T1—O6	110.89 (11)	D—F—D^xiii	180.0
O7—T1—O7^xvi	109.01 (9)	D^xiii—F—A^xiii	90.0
M1^xvii—T2—A^iii	120.34 (2)	D—F—A	90.0
M1^xvii—T2—A	147.63 (3)	D^xiii—F—A	90.0
A^iii—T2—A	91.05 (2)	D—F—A^xiii	90.0
BNA—T2—M1^xvii	103.07 (2)	D^xiii—F—BNA	89.043 (18)
BNA—T2—A	75.60 (2)	D—F—BNA	90.957 (18)
BNA—T2—A^iii	75.61 (2)	D^xiii—F—BNA^xiv	90.957 (18)
O2—T2—M1^xvii	37.68 (8)	D—F—BNA^xiv	89.043 (18)
O2—T2—A^iii	131.54 (8)	A—F—A^xiii	180.0
O2—T2—A	125.95 (8)	BNA^xiv—F—A^xiii	90.0
O2—T2—BNA	137.37 (9)	BNA^xiv—F—A	90.0
O2—T2—O5	110.44 (12)	BNA—F—A	90.0
O3—T2—M1^xvii	106.97 (9)	BNA—F—A^xiii	90.0
O3—T2—A^iii	116.92 (9)	BNA^xiv—F—BNA	180.0

Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, −y+1, −z; (iii) x−1, y, z; (iv) x, −y+1, z−1; (v) −x+1, −y+1, −z+1; (vi) x, y, z−1; (vii) −x+1, y, −z+1; (viii) −x+2, y, −z+1; (ix) −x+2, y, −z; (x) −x+1, y, −z; (xi) −x+5/2, −y+1/2, −z; (xii) x−1/2, −y+1/2, z; (xiii) −x+2, −y+1, −z+1; (xiv) x+1, y, z; (xv) x, −y+1, z; (xvi) x+1/2, −y+1/2, z; (xvii) x, y, z+1.

(lb650)

Crystal data

0.5(Ca0.28F0.26Fe8.91K3.89Na3.56O60Si15.21Ti4)	F(000) = 1134
Mr = 1163.57	Dx = 3.101 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 5.3073 (4) Å	Cell parameters from 3673 reflections
b = 23.1299 (15) Å	θ = 1.8–36.2°
c = 10.2879 (5) Å	µ = 4.02 mm^−1
β = 99.336 (6)°	T = 293 K
V = 1246.19 (14) Å^3	Prism, brown
Z = 2	0.22 × 0.18 × 0.11 mm

Data collection

Saxi-CrysAlisPro-abstract goniometer imported SAXI images diffractometer	2984 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2374 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
ω scans	θmax = 36.3°, θmin = 1.8°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→8
Tmin = 0.694, Tmax = 1.000	k = −36→37
11317 measured reflections	l = −16→16

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: dual
R[F^2 > 2σ(F^2)] = 0.058	w = 1/[σ^2(Fo^2) + (0.0231P)^2 + 7.7951P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.100	(Δ/σ)max < 0.001
S = 1.14	Δρmax = 1.33 e Å^−3
2984 reflections	Δρmin = −0.94 e Å^−3
132 parameters

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
M1	0.500000	0.500000	0.000000	0.0162 (8)	0.916 (11)
M2	1.000000	0.42050 (4)	0.000000	0.0225 (3)	0.744 (4)
M3	0.500000	0.35557 (3)	0.000000	0.00985 (19)	0.805 (3)
M4	1.000000	0.29171 (4)	0.000000	0.0110 (2)	0.680 (3)
D	0.93946 (13)	0.500000	0.28740 (7)	0.01005 (15)
T1	1.42226 (14)	0.28198 (3)	0.26850 (7)	0.0072 (2)	0.952 (5)
T2	0.57156 (15)	0.41398 (3)	0.72566 (7)	0.0079 (2)	0.949 (5)
A	1.000000	0.36048 (5)	0.500000	0.0266 (3)	0.973 (5)
BNA	0.500000	0.500000	0.500000	0.0127 (8)	0.862 (17)
BCA	0.500000	0.500000	0.500000	0.0127 (8)	0.138 (17)
O1	0.9073 (7)	0.500000	0.1124 (3)	0.0300 (9)
O2	0.6382 (4)	0.41594 (9)	0.8866 (2)	0.0141 (4)
O3	0.7959 (4)	0.44261 (10)	0.6587 (2)	0.0191 (4)
O4	0.6990 (5)	0.44304 (10)	0.3310 (2)	0.0207 (5)
O5	0.5495 (5)	0.34650 (9)	0.6733 (2)	0.0181 (4)
O6	1.3707 (4)	0.28129 (8)	0.10822 (18)	0.0109 (4)
O7	1.1848 (4)	0.25233 (10)	0.3266 (2)	0.0170 (4)
O8	0.8491 (4)	0.35248 (10)	0.0942 (2)	0.0184 (4)
F	1.000000	0.500000	0.500000	0.014 (7)*	0.130 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
M1	0.0147 (14)	0.0123 (13)	0.0208 (14)	0.000	0.0002 (10)	0.000
M2	0.0103 (4)	0.0320 (6)	0.0230 (5)	0.000	−0.0032 (3)	0.000
M3	0.0095 (3)	0.0108 (3)	0.0099 (3)	0.000	0.0035 (2)	0.000
M4	0.0094 (4)	0.0139 (4)	0.0100 (4)	0.000	0.0022 (3)	0.000
D	0.0064 (3)	0.0140 (3)	0.0102 (3)	0.000	0.0028 (2)	0.000
T1	0.0079 (4)	0.0079 (3)	0.0061 (3)	−0.0003 (3)	0.0017 (2)	−0.0006 (2)
T2	0.0091 (4)	0.0074 (3)	0.0077 (3)	0.0004 (3)	0.0024 (2)	0.0008 (2)
A	0.0254 (6)	0.0245 (6)	0.0306 (6)	0.000	0.0067 (4)	0.000
BNA	0.0197 (13)	0.0119 (11)	0.0057 (10)	0.000	0.0001 (7)	0.000
BCA	0.0197 (13)	0.0119 (11)	0.0057 (10)	0.000	0.0001 (7)	0.000
O1	0.0152 (16)	0.064 (3)	0.0111 (13)	0.000	0.0028 (12)	0.000
O2	0.0164 (10)	0.0148 (9)	0.0116 (8)	−0.0016 (7)	0.0033 (7)	0.0013 (7)
O3	0.0162 (11)	0.0240 (11)	0.0183 (10)	−0.0063 (9)	0.0061 (8)	0.0002 (8)
O4	0.0169 (11)	0.0241 (11)	0.0210 (10)	−0.0074 (9)	0.0024 (8)	0.0004 (9)
O5	0.0304 (12)	0.0108 (9)	0.0126 (8)	−0.0002 (8)	0.0022 (8)	0.0003 (7)
O6	0.0118 (9)	0.0131 (8)	0.0080 (7)	−0.0001 (7)	0.0024 (6)	−0.0006 (6)
O7	0.0138 (10)	0.0256 (11)	0.0122 (8)	−0.0072 (8)	0.0040 (7)	−0.0008 (8)
O8	0.0151 (10)	0.0268 (11)	0.0144 (9)	0.0025 (9)	0.0054 (8)	−0.0016 (8)

Geometric parameters (Å, º)

M1—M2^i	3.2284 (6)	D—O3^viii	1.947 (2)
M1—M2^ii	3.2284 (6)	D—O4^xv	1.937 (2)
M1—M2	3.2285 (6)	D—O4	1.937 (2)
M1—M2^iii	3.2284 (6)	D—F	2.1585 (7)
M1—M3	3.3407 (7)	T1—O5^viii	1.606 (2)
M1—M3^ii	3.3407 (7)	T1—O6	1.627 (2)
M1—O1	2.280 (4)	T1—O7^xvi	1.630 (2)
M1—O1^ii	2.280 (4)	T1—O7	1.631 (2)
M1—O2^iv	2.441 (2)	T2—A	3.7154 (9)
M1—O2^v	2.441 (2)	T2—A^i	3.7199 (9)
M1—O2^vi	2.441 (2)	T2—BNA	3.0343 (8)
M1—O2^vii	2.441 (2)	T2—O2	1.636 (2)
M2—M4	2.9789 (14)	T2—O3	1.612 (2)
M2—O1^iii	2.268 (2)	T2—O4^vii	1.607 (2)
M2—O1	2.268 (2)	T2—O5	1.649 (2)
M2—O2^viii	2.081 (2)	A—O3^viii	2.832 (2)
M2—O2^vi	2.081 (2)	A—O3	2.832 (2)
M2—O8	2.075 (2)	A—O4^viii	2.885 (3)
M2—O8^ix	2.075 (2)	A—O4	2.885 (3)
M3—O2^vi	2.032 (2)	A—O5	3.222 (2)
M3—O2^vii	2.032 (2)	A—O5^vii	3.178 (2)
M3—O6^ix	2.216 (2)	A—O5^viii	3.222 (2)
M3—O6^i	2.216 (2)	A—O5^xiv	3.178 (2)
M3—O8^x	1.948 (2)	A—O7^viii	3.312 (2)
M3—O8	1.948 (2)	A—O7	3.312 (2)
M4—O6	2.111 (2)	A—F	3.2272 (12)
M4—O6^xi	2.193 (2)	BNA—O3^xv	2.462 (2)
M4—O6^xii	2.193 (2)	BNA—O3	2.462 (2)
M4—O6^ix	2.111 (2)	BNA—O3^vii	2.462 (2)
M4—O8^ix	1.951 (2)	BNA—O3^v	2.462 (2)
M4—O8	1.951 (2)	BNA—O4	2.544 (2)
D—A	3.8825 (11)	BNA—O4^xv	2.544 (2)
D—A^xiii	3.8825 (11)	BNA—O4^vii	2.544 (2)
D—BNA^xiv	3.3946 (7)	BNA—O4^v	2.544 (2)
D—BNA	3.4466 (7)	BNA—F^i	2.6537 (2)
D—O1	1.780 (3)	BNA—F	2.6536 (2)
D—O3^xiii	1.947 (2)
M2^i—M1—M2^iii	180.00 (3)	O2—T2—M1^xvii	37.61 (8)
M2^iii—M1—M2^ii	110.56 (3)	O2—T2—A	125.98 (8)
M2^i—M1—M2^ii	69.44 (3)	O2—T2—A^i	131.39 (8)
M2^iii—M1—M2	69.44 (3)	O2—T2—BNA	137.35 (8)
M2^i—M1—M2	110.56 (3)	O2—T2—O5	110.42 (11)
M2^ii—M1—M2	180.0	O3—T2—M1^xvii	107.08 (9)
M2^i—M1—M3	55.282 (15)	O3—T2—A^i	117.00 (9)
M2^ii—M1—M3^ii	55.282 (15)	O3—T2—A	45.59 (9)
M2^ii—M1—M3	124.718 (15)	O3—T2—BNA	54.04 (9)
M2^iii—M1—M3^ii	55.282 (15)	O3—T2—O2	111.58 (12)
M2—M1—M3	55.281 (15)	O3—T2—O5	105.51 (13)
M2^i—M1—M3^ii	124.718 (15)	O4^vii—T2—M1^xvii	81.26 (9)
M2—M1—M3^ii	124.719 (15)	O4^vii—T2—A	120.95 (9)
M2^iii—M1—M3	124.718 (15)	O4^vii—T2—A^i	47.35 (9)
M3—M1—M3^ii	180.0	O4^vii—T2—BNA	56.96 (9)
O1^ii—M1—M2^ii	44.64 (5)	O4^vii—T2—O2	112.90 (12)
O1^ii—M1—M2^iii	135.36 (5)	O4^vii—T2—O3	110.60 (13)
O1—M1—M2^ii	135.36 (5)	O4^vii—T2—O5	105.41 (13)
O1—M1—M2^iii	44.64 (5)	O5—T2—M1^xvii	141.71 (8)
O1—M1—M2^i	135.36 (5)	O5—T2—A^i	58.26 (9)
O1^ii—M1—M2	135.36 (5)	O5—T2—A	59.92 (9)
O1^ii—M1—M2^i	44.64 (5)	O5—T2—BNA	112.17 (8)
O1—M1—M2	44.64 (5)	O3^viii—A—T2^viii	23.98 (5)
O1—M1—M3^ii	90.0	O3—A—T2^viii	117.83 (6)
O1^ii—M1—M3^ii	90.0	O3—A—O3^viii	95.74 (10)
O1^ii—M1—M3	90.0	O3—A—O4^viii	55.57 (7)
O1—M1—M3	90.0	O3—A—O4	71.17 (7)
O1—M1—O1^ii	180.0	O3^viii—A—O4	55.57 (7)
O1^ii—M1—O2^iv	95.23 (7)	O3^viii—A—O4^viii	71.17 (7)
O1^ii—M1—O2^v	84.77 (7)	O3—A—O5^vii	89.40 (6)
O1—M1—O2^vii	95.23 (7)	O3^viii—A—O5^xiv	89.40 (6)
O1—M1—O2^v	95.23 (7)	O3—A—O5^viii	140.69 (7)
O1—M1—O2^vi	84.77 (7)	O3—A—O5	50.27 (6)
O1^ii—M1—O2^vi	95.23 (7)	O3—A—O5^xiv	98.44 (6)
O1—M1—O2^iv	84.77 (7)	O3^viii—A—O5^viii	50.27 (6)
O1^ii—M1—O2^vii	84.77 (7)	O3^viii—A—O5^vii	98.44 (6)
O2^v—M1—M2^iii	81.79 (5)	O3^viii—A—O5	140.69 (7)
O2^iv—M1—M2^ii	81.79 (5)	O3^viii—A—O7^viii	172.51 (6)
O2^v—M1—M2^ii	40.14 (5)	O3^viii—A—O7	91.25 (6)
O2^iv—M1—M2^i	139.86 (5)	O3—A—O7^viii	91.25 (6)
O2^vi—M1—M2	40.14 (5)	O3—A—O7	172.51 (6)
O2^vii—M1—M2^i	40.14 (5)	O3^viii—A—F	47.87 (5)
O2^iv—M1—M2	98.21 (5)	O3—A—F	47.87 (5)
O2^v—M1—M2	139.86 (5)	O4^viii—A—T2^viii	79.69 (5)
O2^vii—M1—M2^ii	98.21 (5)	O4—A—T2^viii	74.81 (5)
O2^iv—M1—M2^iii	40.14 (5)	O4^viii—A—O4	97.10 (10)
O2^vi—M1—M2^iii	98.21 (5)	O4^viii—A—O5^xiv	50.29 (6)
O2^v—M1—M2^i	98.21 (5)	O4^viii—A—O5^vii	140.67 (7)
O2^vi—M1—M2^ii	139.86 (5)	O4^viii—A—O5^viii	90.68 (6)
O2^vi—M1—M2^i	81.79 (5)	O4—A—O5^xiv	140.67 (7)
O2^vii—M1—M2^iii	139.86 (5)	O4^viii—A—O5	96.94 (6)
O2^vii—M1—M2	81.79 (5)	O4—A—O5	90.68 (6)
O2^vii—M1—M3	37.20 (5)	O4—A—O5^viii	96.94 (6)
O2^vi—M1—M3	37.20 (5)	O4—A—O5^vii	50.29 (6)
O2^vi—M1—M3^ii	142.80 (5)	O4^viii—A—O7^viii	111.01 (6)
O2^v—M1—M3	142.80 (5)	O4—A—O7	111.01 (6)
O2^iv—M1—M3^ii	37.20 (5)	O4^viii—A—O7	129.89 (6)
O2^iv—M1—M3	142.80 (5)	O4—A—O7^viii	129.89 (6)
O2^v—M1—M3^ii	37.20 (5)	O4—A—F	48.55 (5)
O2^vii—M1—M3^ii	142.80 (5)	O4^viii—A—F	48.55 (5)
O2^vi—M1—O2^iv	105.60 (10)	O5^viii—A—T2^viii	26.28 (4)
O2^v—M1—O2^iv	74.40 (10)	O5^xiv—A—T2^viii	77.61 (4)
O2^iv—M1—O2^vii	180.0	O5^vii—A—T2^viii	106.39 (4)
O2^vi—M1—O2^vii	74.40 (10)	O5—A—T2^viii	164.45 (5)
O2^v—M1—O2^vii	105.60 (10)	O5^vii—A—O5^viii	112.03 (6)
O2^v—M1—O2^vi	180.00 (8)	O5^vii—A—O5	66.71 (6)
M1^xiv—M2—M1	110.56 (3)	O5^vii—A—O5^xiv	168.33 (9)
M4—M2—M1	124.719 (15)	O5^xiv—A—O5	112.03 (6)
M4—M2—M1^xiv	124.719 (15)	O5^xiv—A—O5^viii	66.71 (6)
O1^iii—M2—M1^xiv	44.93 (9)	O5^viii—A—O5	168.49 (8)
O1—M2—M1^xiv	77.56 (9)	O5^viii—A—O7	46.77 (5)
O1^iii—M2—M1	77.56 (9)	O5^vii—A—O7^viii	84.29 (6)
O1—M2—M1	44.93 (9)	O5^viii—A—O7^viii	122.24 (6)
O1^iii—M2—M4	144.15 (7)	O5—A—O7^viii	46.77 (5)
O1—M2—M4	144.15 (7)	O5^xiv—A—O7^viii	86.90 (6)
O1—M2—O1^iii	71.69 (14)	O5^xiv—A—O7	84.29 (6)
O2^vi—M2—M1^xiv	135.42 (6)	O5^vii—A—O7	86.90 (6)
O2^vi—M2—M1	49.12 (6)	O5—A—O7	122.24 (6)
O2^viii—M2—M1^xiv	49.12 (6)	O5^vii—A—F	95.83 (4)
O2^viii—M2—M1	135.42 (6)	O5—A—F	95.76 (4)
O2^viii—M2—M4	87.09 (6)	O5^viii—A—F	95.75 (4)
O2^vi—M2—M4	87.09 (6)	O5^xiv—A—F	95.83 (4)
O2^viii—M2—O1	90.68 (11)	O7—A—T2^viii	69.53 (4)
O2^vi—M2—O1^iii	90.68 (11)	O7^viii—A—T2^viii	148.52 (5)
O2^vi—M2—O1	94.04 (11)	O7—A—O7^viii	81.91 (8)
O2^viii—M2—O1^iii	94.04 (11)	F—A—T2^viii	70.55 (2)
O2^vi—M2—O2^viii	174.19 (13)	F—A—O7	139.04 (4)
O8—M2—M1	93.00 (6)	F—A—O7^viii	139.05 (4)
O8^ix—M2—M1	144.21 (6)	T2—BNA—T2^vii	98.05 (3)
O8—M2—M1^xiv	144.21 (6)	O3^vii—BNA—T2^vii	32.00 (5)
O8^ix—M2—M1^xiv	93.00 (6)	O3—BNA—T2	32.00 (5)
O8—M2—M4	40.71 (6)	O3—BNA—T2^vii	98.10 (6)
O8^ix—M2—M4	40.71 (6)	O3^v—BNA—T2	148.00 (5)
O8^ix—M2—O1	169.93 (11)	O3^xv—BNA—T2	81.90 (6)
O8—M2—O1^iii	169.93 (11)	O3^xv—BNA—T2^vii	148.00 (5)
O8—M2—O1	104.14 (9)	O3^v—BNA—T2^vii	81.90 (6)
O8^ix—M2—O1^iii	104.14 (9)	O3^vii—BNA—T2	98.10 (6)
O8—M2—O2^vi	80.36 (9)	O3^xv—BNA—O3^vii	180.00 (9)
O8^ix—M2—O2^vi	95.19 (9)	O3^xv—BNA—O3	65.26 (11)
O8—M2—O2^viii	95.19 (9)	O3^xv—BNA—O3^v	114.74 (11)
O8^ix—M2—O2^viii	80.36 (9)	O3^v—BNA—O3	180.0
O8—M2—O8^ix	81.41 (13)	O3^vii—BNA—O3	114.74 (11)
O2^vii—M3—M1	46.58 (6)	O3^vii—BNA—O3^v	65.26 (11)
O2^vi—M3—M1	46.58 (6)	O3^xv—BNA—O4^vii	96.72 (8)
O2^vii—M3—O2^vi	93.17 (12)	O3^xv—BNA—O4^v	63.80 (7)
O2^vii—M3—O6^ix	172.57 (8)	O3^vii—BNA—O4^vii	83.28 (8)
O2^vi—M3—O6^ix	94.25 (8)	O3^xv—BNA—O4^xv	83.28 (8)
O2^vi—M3—O6^i	172.57 (8)	O3^v—BNA—O4^vii	116.20 (7)
O2^vii—M3—O6^i	94.25 (8)	O3—BNA—O4^xv	116.20 (7)
O6^i—M3—M1	140.84 (5)	O3^xv—BNA—O4	116.20 (7)
O6^ix—M3—M1	140.84 (5)	O3^vii—BNA—O4	63.80 (7)
O6^ix—M3—O6^i	78.33 (10)	O3^v—BNA—O4	96.72 (8)
O8^x—M3—M1	92.10 (7)	O3^vii—BNA—O4^v	116.20 (7)
O8—M3—M1	92.10 (7)	O3—BNA—O4^vii	63.80 (7)
O8—M3—O2^vi	84.72 (9)	O3—BNA—O4^v	96.72 (8)
O8—M3—O2^vii	98.19 (9)	O3^v—BNA—O4^v	83.28 (8)
O8^x—M3—O2^vii	84.72 (9)	O3—BNA—O4	83.28 (8)
O8^x—M3—O2^vi	98.19 (9)	O3^v—BNA—O4^xv	63.80 (7)
O8^x—M3—O6^ix	93.94 (9)	O3^vii—BNA—O4^xv	96.72 (8)
O8—M3—O6^i	93.94 (9)	O3^xv—BNA—F	57.97 (5)
O8^x—M3—O6^i	82.79 (8)	O3^vii—BNA—F^i	57.97 (5)
O8—M3—O6^ix	82.79 (8)	O3—BNA—F	57.97 (5)
O8^x—M3—O8	175.80 (15)	O3^xv—BNA—F^i	122.03 (5)
O6^xii—M4—M2	140.35 (5)	O3^v—BNA—F	122.03 (5)
O6^xi—M4—M2	140.35 (5)	O3^v—BNA—F^i	57.97 (5)
O6^ix—M4—M2	96.56 (6)	O3^vii—BNA—F	122.03 (5)
O6—M4—M2	96.56 (6)	O3—BNA—F^i	122.03 (5)
O6—M4—O6^ix	166.89 (12)	O4—BNA—T2	99.73 (6)
O6^ix—M4—O6^xi	89.19 (7)	O4^vii—BNA—T2^vii	99.73 (6)
O6—M4—O6^xi	80.69 (8)	O4^xv—BNA—T2	148.03 (5)
O6^xi—M4—O6^xii	79.31 (10)	O4^v—BNA—T2^vii	148.03 (5)
O6^ix—M4—O6^xii	80.69 (8)	O4^xv—BNA—T2^vii	80.27 (6)
O6—M4—O6^xii	89.19 (7)	O4—BNA—T2^vii	31.97 (5)
O8—M4—M2	43.92 (7)	O4^v—BNA—T2	80.27 (6)
O8^ix—M4—M2	43.92 (7)	O4^vii—BNA—T2	31.97 (5)
O8^ix—M4—O6	85.51 (9)	O4^v—BNA—O4^vii	62.39 (10)
O8^ix—M4—O6^xii	173.79 (9)	O4—BNA—O4^v	180.0
O8—M4—O6^xi	173.79 (9)	O4^xv—BNA—O4^vii	180.00 (9)
O8^ix—M4—O6^ix	104.05 (9)	O4—BNA—O4^vii	117.61 (10)
O8—M4—O6^xii	96.61 (8)	O4^v—BNA—O4^xv	117.61 (10)
O8^ix—M4—O6^xi	96.61 (8)	O4—BNA—O4^xv	62.39 (10)
O8—M4—O6	104.05 (9)	O4^v—BNA—F^i	58.26 (5)
O8—M4—O6^ix	85.51 (9)	O4—BNA—F^i	121.74 (5)
O8^ix—M4—O8	87.84 (14)	O4—BNA—F	58.26 (5)
M1—D—A^xiii	117.688 (13)	O4^v—BNA—F	121.74 (5)
M1—D—A	117.687 (13)	O4^xv—BNA—F	58.26 (5)
A^xiii—D—A	112.45 (3)	O4^vii—BNA—F^i	58.26 (5)
BNA—D—M1	96.355 (18)	O4^xv—BNA—F^i	121.74 (5)
BNA^xiv—D—M1	161.89 (2)	O4^vii—BNA—F	121.74 (5)
BNA—D—A	69.217 (12)	F^i—BNA—T2	90.060 (16)
BNA^xiv—D—A^xiii	69.710 (12)	F^i—BNA—T2^vii	89.939 (16)
BNA^xiv—D—A	69.710 (12)	F—BNA—T2	89.940 (16)
BNA—D—A^xiii	69.217 (12)	F—BNA—T2^vii	90.061 (16)
BNA^xiv—D—BNA	101.750 (18)	F^i—BNA—F	180.0
O1—D—M1	36.33 (12)	M2^iii—O1—M1	90.43 (10)
O1—D—A^xiii	123.724 (14)	M2—O1—M1	90.43 (10)
O1—D—A	123.724 (13)	M2^iii—O1—M2	108.31 (14)
O1—D—BNA^xiv	125.57 (12)	D—O1—M1	116.13 (17)
O1—D—BNA	132.68 (12)	D—O1—M2	121.50 (9)
O1—D—O3^xiii	103.57 (11)	D—O1—M2^iii	121.50 (9)
O1—D—O3^viii	103.57 (11)	M2^xvii—O2—M1^xvii	90.74 (8)
O1—D—O4^xv	105.98 (11)	M3^xvii—O2—M1^xvii	96.22 (8)
O1—D—O4	105.98 (11)	M3^xvii—O2—M2^xvii	95.68 (9)
O1—D—F	176.98 (12)	T2—O2—M1^xvii	118.25 (11)
O3^viii—D—M1	126.83 (7)	T2—O2—M2^xvii	126.66 (12)
O3^xiii—D—M1	126.83 (7)	T2—O2—M3^xvii	121.54 (12)
O3^viii—D—A	44.17 (7)	D^xiii—O3—A	107.22 (10)
O3^viii—D—A^xiii	114.60 (7)	D^xiii—O3—BNA	100.04 (10)
O3^xiii—D—A	114.60 (7)	T2—O3—D^xiii	135.00 (14)
O3^xiii—D—A^xiii	44.17 (7)	T2—O3—A	110.43 (11)
O3^viii—D—BNA^xiv	45.57 (7)	T2—O3—BNA	93.96 (11)
O3^viii—D—BNA	110.51 (7)	BNA—O3—A	104.01 (8)
O3^xiii—D—BNA^xiv	45.57 (7)	D—O4—A	105.58 (10)
O3^xiii—D—BNA	110.51 (7)	D—O4—BNA	99.68 (10)
O3^xiii—D—O3^viii	85.98 (15)	T2^vii—O4—D	141.66 (15)
O3^viii—D—F	74.29 (7)	T2^vii—O4—A	108.46 (11)
O3^xiii—D—F	74.29 (7)	T2^vii—O4—BNA	91.08 (11)
O4^xv—D—M1	79.60 (7)	BNA—O4—A	100.46 (8)
O4—D—M1	79.60 (7)	T1^viii—O5—T2	139.50 (14)
O4^xv—D—A^xiii	45.70 (7)	T1^viii—O5—A^i	108.98 (11)
O4—D—A^xiii	115.63 (8)	T1^viii—O5—A	105.47 (11)
O4—D—A	45.70 (7)	T2—O5—A^i	95.56 (10)
O4^xv—D—A	115.63 (8)	T2—O5—A	93.79 (10)
O4—D—BNA	46.69 (7)	A^i—O5—A	112.03 (6)
O4—D—BNA^xiv	113.10 (7)	M4—O6—M3^xiv	89.11 (7)
O4^xv—D—BNA	46.69 (7)	M4^xi—O6—M3^xiv	101.18 (8)
O4^xv—D—BNA^xiv	113.10 (7)	M4—O6—M4^xi	99.31 (8)
O4—D—O3^xiii	150.45 (10)	T1—O6—M3^xiv	119.12 (11)
O4—D—O3^viii	86.68 (10)	T1—O6—M4	121.49 (11)
O4^xv—D—O3^viii	150.45 (10)	T1—O6—M4^xi	120.47 (11)
O4^xv—D—O3^xiii	86.68 (10)	T1^xii—O7—T1	137.38 (14)
O4—D—O4^xv	85.73 (15)	T1^xii—O7—A	104.77 (10)
O4—D—F	76.16 (7)	T1—O7—A	101.16 (10)
O4^xv—D—F	76.16 (7)	M3—O8—M2	98.51 (10)
F—D—M1	146.69 (3)	M3—O8—M4	102.31 (10)
F—D—A^xiii	56.223 (13)	M4—O8—M2	95.37 (9)
F—D—A	56.223 (13)	D—F—D^xiii	180.0
F—D—BNA^xiv	51.410 (15)	D^xiii—F—A	90.0
F—D—BNA	50.340 (14)	D—F—A^xiii	90.0
O5^viii—T1—O6	112.16 (11)	D—F—A	90.0
O5^viii—T1—O7^xvi	107.06 (12)	D^xiii—F—A^xiii	90.0
O5^viii—T1—O7	106.57 (13)	D—F—BNA^xiv	89.11 (2)
O6—T1—O7	110.74 (11)	D^xiii—F—BNA^xiv	90.89 (2)
O6—T1—O7^xvi	111.08 (11)	D^xiii—F—BNA	89.11 (2)
O7^xvi—T1—O7	109.05 (8)	D—F—BNA	90.89 (2)
M1^xvii—T2—A	147.67 (3)	A^xiii—F—A	180.0
M1^xvii—T2—A^i	120.32 (2)	BNA^xiv—F—A	90.0
A—T2—A^i	91.09 (2)	BNA—F—A^xiii	90.0
BNA—T2—M1^xvii	103.07 (2)	BNA—F—A	90.0
BNA—T2—A^i	75.67 (2)	BNA^xiv—F—A^xiii	90.0
BNA—T2—A	75.74 (2)	BNA^xiv—F—BNA	180.0

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z; (iii) −x+2, −y+1, −z; (iv) x, −y+1, z−1; (v) −x+1, −y+1, −z+1; (vi) x, y, z−1; (vii) −x+1, y, −z+1; (viii) −x+2, y, −z+1; (ix) −x+2, y, −z; (x) −x+1, y, −z; (xi) −x+5/2, −y+1/2, −z; (xii) x−1/2, −y+1/2, z; (xiii) −x+2, −y+1, −z+1; (xiv) x+1, y, z; (xv) x, −y+1, z; (xvi) x+1/2, −y+1/2, z; (xvii) x, y, z+1.

(lb670)

Crystal data

0.5(Ca0.37F0.34Fe8.9K3.89Na3.41O60Si15.12Ti4)	F(000) = 1133
Mr = 1162.59	Dx = 3.138 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 5.2852 (4) Å	Cell parameters from 3197 reflections
b = 23.041 (2) Å	θ = 1.8–36.2°
c = 10.2428 (10) Å	µ = 4.07 mm^−1
β = 99.391 (8)°	T = 293 K
V = 1230.61 (19) Å^3	Prism, brown
Z = 2	0.22 × 0.18 × 0.11 mm

Data collection

Saxi-CrysAlisPro-abstract goniometer imported SAXI images diffractometer	2968 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2494 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
ω scans	θmax = 36.6°, θmin = 1.8°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→8
Tmin = 0.749, Tmax = 1.000	k = −36→38
11195 measured reflections	l = −16→17

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: dual
R[F^2 > 2σ(F^2)] = 0.073	w = 1/[σ^2(Fo^2) + (0.0206P)^2 + 13.8237P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.121	(Δ/σ)max < 0.001
S = 1.23	Δρmax = 2.28 e Å^−3
2968 reflections	Δρmin = −1.02 e Å^−3
132 parameters

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
M1	0.500000	0.500000	0.000000	0.0156 (10)	0.890 (14)
M2	1.000000	0.42118 (6)	0.000000	0.0235 (4)	0.748 (5)
M3	0.500000	0.35547 (4)	0.000000	0.0113 (2)	0.801 (4)
M4	1.000000	0.29176 (5)	0.000000	0.0115 (3)	0.676 (4)
D	0.93932 (16)	0.500000	0.28790 (9)	0.01158 (19)
T1	1.42207 (17)	0.28197 (4)	0.26860 (10)	0.0085 (3)	0.949 (6)
T2	0.57126 (18)	0.41387 (4)	0.72587 (10)	0.0088 (3)	0.941 (6)
A	1.000000	0.36017 (7)	0.500000	0.0279 (4)	0.972 (7)
BNA	0.500000	0.500000	0.500000	0.0145 (9)	0.81 (2)
BCA	0.500000	0.500000	0.500000	0.0145 (9)	0.19 (2)
O1	0.9076 (8)	0.500000	0.1131 (5)	0.0312 (11)
O2	0.6377 (5)	0.41587 (12)	0.8865 (3)	0.0157 (5)
O3	0.7951 (6)	0.44258 (13)	0.6595 (3)	0.0215 (6)
O4	0.6978 (5)	0.44299 (13)	0.3316 (3)	0.0227 (6)
O5	0.5489 (6)	0.34659 (11)	0.6726 (3)	0.0197 (6)
O6	1.3705 (5)	0.28141 (11)	0.1083 (2)	0.0125 (4)
O7	1.1850 (5)	0.25242 (13)	0.3268 (3)	0.0187 (5)
O8	0.8499 (5)	0.35218 (13)	0.0948 (3)	0.0202 (6)
F	1.000000	0.500000	0.500000	0.015 (7)*	0.172 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
M1	0.0124 (16)	0.0096 (15)	0.0230 (19)	0.000	−0.0025 (12)	0.000
M2	0.0083 (4)	0.0334 (7)	0.0265 (6)	0.000	−0.0039 (4)	0.000
M3	0.0078 (4)	0.0114 (4)	0.0149 (4)	0.000	0.0026 (3)	0.000
M4	0.0065 (4)	0.0142 (5)	0.0137 (5)	0.000	0.0010 (3)	0.000
D	0.0045 (3)	0.0145 (4)	0.0158 (4)	0.000	0.0018 (3)	0.000
T1	0.0064 (4)	0.0084 (4)	0.0106 (4)	−0.0002 (3)	0.0012 (3)	−0.0011 (3)
T2	0.0069 (4)	0.0075 (4)	0.0120 (5)	0.0006 (3)	0.0013 (3)	0.0008 (3)
A	0.0222 (6)	0.0255 (7)	0.0366 (8)	0.000	0.0067 (5)	0.000
BNA	0.0183 (14)	0.0132 (13)	0.0108 (13)	0.000	−0.0008 (8)	0.000
BCA	0.0183 (14)	0.0132 (13)	0.0108 (13)	0.000	−0.0008 (8)	0.000
O1	0.0131 (18)	0.061 (3)	0.020 (2)	0.000	0.0036 (15)	0.000
O2	0.0142 (11)	0.0161 (11)	0.0165 (12)	−0.0015 (9)	0.0019 (9)	0.0017 (9)
O3	0.0163 (12)	0.0254 (14)	0.0235 (14)	−0.0068 (10)	0.0054 (10)	0.0005 (11)
O4	0.0150 (12)	0.0243 (14)	0.0279 (15)	−0.0078 (10)	0.0010 (11)	0.0014 (12)
O5	0.0295 (14)	0.0108 (11)	0.0183 (12)	0.0020 (10)	0.0023 (11)	−0.0007 (9)
O6	0.0104 (10)	0.0137 (10)	0.0136 (10)	−0.0003 (8)	0.0021 (8)	−0.0005 (9)
O7	0.0129 (11)	0.0245 (14)	0.0187 (12)	−0.0077 (10)	0.0027 (9)	−0.0017 (10)
O8	0.0127 (11)	0.0293 (15)	0.0185 (13)	0.0011 (10)	0.0027 (9)	−0.0018 (11)

Geometric parameters (Å, º)

M1—M2^i	3.2064 (8)	D—O4^xv	1.935 (3)
M1—M2^ii	3.2064 (8)	D—O4	1.935 (3)
M1—M2	3.2065 (8)	D—F	2.1436 (9)
M1—M2^iii	3.2064 (8)	T1—O5^viii	1.604 (3)
M1—M3^iii	3.3302 (9)	T1—O6	1.620 (3)
M1—M3	3.3302 (9)	T1—O7	1.622 (3)
M1—O1	2.273 (4)	T1—O7^xvi	1.626 (3)
M1—O1^iii	2.273 (4)	T2—A	3.7052 (12)
M1—O2^iv	2.432 (3)	T2—A^ii	3.7039 (11)
M1—O2^v	2.432 (3)	T2—BNA	3.0246 (10)
M1—O2^vi	2.432 (3)	T2—O2	1.626 (3)
M1—O2^vii	2.432 (3)	T2—O3	1.601 (3)
M2—O1	2.250 (3)	T2—O4^iv	1.596 (3)
M2—O1^i	2.250 (3)	T2—O5	1.641 (3)
M2—O2^vii	2.075 (3)	A—O3^viii	2.833 (3)
M2—O2^viii	2.075 (3)	A—O3	2.833 (3)
M2—O8	2.086 (3)	A—O4^viii	2.875 (3)
M2—O8^ix	2.086 (3)	A—O4	2.875 (3)
M3—O2^vii	2.023 (3)	A—O5^iv	3.157 (3)
M3—O2^iv	2.023 (3)	A—O5	3.207 (3)
M3—O6^ii	2.204 (3)	A—O5^viii	3.207 (3)
M3—O6^ix	2.204 (3)	A—O5^xiv	3.157 (3)
M3—O8	1.945 (3)	A—O7^viii	3.292 (3)
M3—O8^x	1.945 (3)	A—O7	3.292 (3)
M4—O6^xi	2.188 (3)	A—O7^xi	3.418 (3)
M4—O6	2.100 (2)	A—F	3.2218 (15)
M4—O6^ix	2.100 (2)	BNA—O3^iv	2.454 (3)
M4—O6^xii	2.188 (3)	BNA—O3^xv	2.454 (3)
M4—O8	1.940 (3)	BNA—O3	2.454 (3)
M4—O8^ix	1.940 (3)	BNA—O3^v	2.454 (3)
D—A	3.8697 (14)	BNA—O4^v	2.526 (3)
D—A^xiii	3.8698 (14)	BNA—O4^iv	2.526 (3)
D—BNA	3.4288 (9)	BNA—O4	2.526 (3)
D—BNA^xiv	3.3764 (9)	BNA—O4^xv	2.526 (3)
D—O1	1.771 (5)	BNA—F^ii	2.6426 (2)
D—O3^xiii	1.940 (3)	BNA—F	2.6426 (2)
D—O3^viii	1.940 (3)
M2^ii—M1—M2^i	180.00 (4)	O3—T2—O2	111.43 (15)
M2^i—M1—M2^iii	111.01 (4)	O3—T2—O5	105.51 (17)
M2^ii—M1—M2^iii	68.99 (4)	O4^iv—T2—M1^xvii	81.49 (12)
M2^i—M1—M2	68.99 (4)	O4^iv—T2—A	120.59 (13)
M2^ii—M1—M2	111.01 (4)	O4^iv—T2—A^ii	47.42 (12)
M2^iii—M1—M2	180.0	O4^iv—T2—BNA	56.59 (12)
M2—M1—M3	55.50 (2)	O4^iv—T2—O2	113.19 (16)
M2^iii—M1—M3^iii	55.503 (19)	O4^iv—T2—O3	110.20 (17)
M2^i—M1—M3	124.50 (2)	O4^iv—T2—O5	105.25 (16)
M2^i—M1—M3^iii	55.50 (2)	O5—T2—M1^xvii	142.09 (11)
M2^iii—M1—M3	124.497 (19)	O5—T2—A^ii	57.98 (11)
M2^ii—M1—M3^iii	124.50 (2)	O5—T2—A	59.69 (11)
M2—M1—M3^iii	124.50 (2)	O5—T2—BNA	111.85 (11)
M2^ii—M1—M3	55.50 (2)	O3—A—O3^viii	95.82 (13)
M3—M1—M3^iii	180.0	O3^viii—A—O4	55.70 (9)
O1—M1—M2	44.56 (7)	O3—A—O4^viii	55.70 (9)
O1^iii—M1—M2^i	135.44 (7)	O3^viii—A—O4^viii	70.96 (9)
O1^iii—M1—M2^iii	44.56 (7)	O3—A—O4	70.96 (9)
O1—M1—M2^i	44.56 (7)	O3^viii—A—O5^viii	50.13 (7)
O1—M1—M2^ii	135.44 (7)	O3—A—O5^viii	140.53 (9)
O1—M1—M2^iii	135.44 (7)	O3^viii—A—O5^iv	98.41 (8)
O1^iii—M1—M2^ii	44.56 (7)	O3^viii—A—O5	140.53 (9)
O1^iii—M1—M2	135.44 (7)	O3^viii—A—O5^xiv	89.24 (8)
O1^iii—M1—M3	90.0	O3—A—O5^iv	89.24 (8)
O1—M1—M3^iii	90.0	O3—A—O5^xiv	98.41 (8)
O1^iii—M1—M3^iii	90.0	O3—A—O5	50.13 (7)
O1—M1—M3	90.0	O3—A—O7^viii	91.12 (8)
O1—M1—O1^iii	180.0	O3—A—O7	172.57 (8)
O1—M1—O2^iv	95.11 (9)	O3—A—O7^xi	127.48 (7)
O1—M1—O2^vii	84.89 (9)	O3^viii—A—O7^xi	114.14 (8)
O1^iii—M1—O2^vi	95.11 (9)	O3^viii—A—O7^viii	172.57 (8)
O1^iii—M1—O2^iv	84.89 (9)	O3^viii—A—O7	91.12 (8)
O1—M1—O2^vi	84.89 (9)	O3^viii—A—F	47.91 (6)
O1—M1—O2^v	95.11 (9)	O3—A—F	47.91 (6)
O1^iii—M1—O2^vii	95.11 (9)	O4—A—O4^viii	96.84 (13)
O1^iii—M1—O2^v	84.89 (9)	O4^viii—A—O5^iv	140.49 (9)
O2^iv—M1—M2	81.92 (6)	O4^viii—A—O5^viii	90.29 (8)
O2^vii—M1—M2^ii	81.92 (6)	O4—A—O5^iv	50.22 (7)
O2^vi—M1—M2	98.08 (6)	O4—A—O5^xiv	140.49 (9)
O2^vii—M1—M2^iii	139.67 (6)	O4^viii—A—O5^xiv	50.22 (7)
O2^vi—M1—M2^ii	139.67 (6)	O4^viii—A—O5	97.15 (8)
O2^vi—M1—M2^iii	81.92 (6)	O4—A—O5^viii	97.15 (8)
O2^iv—M1—M2^i	139.67 (6)	O4—A—O5	90.29 (8)
O2^v—M1—M2	139.67 (6)	O4—A—O7^xi	90.95 (7)
O2^v—M1—M2^ii	98.08 (6)	O4^viii—A—O7^xi	172.21 (8)
O2^v—M1—M2^i	81.92 (6)	O4—A—O7	111.23 (8)
O2^v—M1—M2^iii	40.33 (6)	O4—A—O7^viii	129.72 (8)
O2^vii—M1—M2^i	98.08 (6)	O4^viii—A—O7	129.72 (8)
O2^iv—M1—M2^ii	40.33 (6)	O4^viii—A—O7^viii	111.23 (8)
O2^vii—M1—M2	40.33 (6)	O4^viii—A—F	48.42 (6)
O2^vi—M1—M2^i	40.33 (6)	O4—A—F	48.42 (6)
O2^iv—M1—M2^iii	98.08 (6)	O5^xiv—A—O5^viii	66.49 (9)
O2^v—M1—M3	142.85 (6)	O5^iv—A—O5	66.49 (9)
O2^vi—M1—M3	142.85 (6)	O5^iv—A—O5^xiv	168.62 (11)
O2^vi—M1—M3^iii	37.15 (6)	O5^iv—A—O5^viii	112.31 (9)
O2^iv—M1—M3^iii	142.85 (6)	O5—A—O5^viii	168.80 (11)
O2^v—M1—M3^iii	37.15 (6)	O5^xiv—A—O5	112.31 (9)
O2^iv—M1—M3	37.15 (6)	O5^iv—A—O7	87.14 (7)
O2^vii—M1—M3	37.15 (6)	O5^iv—A—O7^viii	84.28 (7)
O2^vii—M1—M3^iii	142.85 (6)	O5^viii—A—O7^xi	89.01 (7)
O2^vii—M1—O2^iv	74.30 (13)	O5^iv—A—O7^xi	46.28 (7)
O2^vi—M1—O2^iv	180.00 (11)	O5^viii—A—O7^viii	122.45 (8)
O2^v—M1—O2^vi	74.30 (13)	O5—A—O7^viii	46.86 (7)
O2^v—M1—O2^vii	180.00 (8)	O5^xiv—A—O7^xi	122.73 (8)
O2^v—M1—O2^iv	105.70 (13)	O5^xiv—A—O7	84.28 (7)
O2^vii—M1—O2^vi	105.70 (13)	O5^xiv—A—O7^viii	87.14 (7)
M1^xiv—M2—M1	111.00 (4)	O5—A—O7^xi	82.48 (7)
O1^i—M2—M1^xiv	45.15 (11)	O5—A—O7	122.45 (8)
O1^i—M2—M1	77.94 (11)	O5^viii—A—O7	46.86 (7)
O1—M2—M1	45.15 (11)	O5^xiv—A—F	95.69 (6)
O1—M2—M1^xiv	77.94 (11)	O5^iv—A—F	95.69 (6)
O1^i—M2—O1	72.37 (19)	O5^viii—A—F	95.60 (5)
O2^viii—M2—M1^xiv	49.32 (8)	O5—A—F	95.60 (5)
O2^vii—M2—M1	49.32 (8)	O7—A—O7^viii	82.07 (10)
O2^vii—M2—M1^xiv	135.93 (8)	O7^viii—A—O7^xi	62.93 (9)
O2^viii—M2—M1	135.93 (8)	O7—A—O7^xi	46.38 (3)
O2^viii—M2—O1^i	94.47 (14)	F—A—O7^xi	139.37 (5)
O2^vii—M2—O1^i	90.99 (14)	F—A—O7	138.96 (5)
O2^viii—M2—O1	90.99 (14)	F—A—O7^viii	138.96 (5)
O2^vii—M2—O1	94.47 (14)	T2^xv—BNA—T2^iv	180.0
O2^vii—M2—O2^viii	173.24 (17)	O3^v—BNA—T2^iv	81.84 (7)
O2^viii—M2—O8^ix	80.19 (11)	O3^iv—BNA—T2^iv	31.86 (7)
O2^vii—M2—O8^ix	94.62 (11)	O3^xv—BNA—T2^xv	31.86 (7)
O2^viii—M2—O8	94.62 (11)	O3^xv—BNA—T2^iv	148.14 (7)
O2^vii—M2—O8	80.19 (11)	O3^iv—BNA—T2^xv	148.14 (7)
O8^ix—M2—M1	143.87 (8)	O3—BNA—T2^xv	81.84 (7)
O8—M2—M1^xiv	143.87 (8)	O3—BNA—T2^iv	98.16 (7)
O8^ix—M2—M1^xiv	93.19 (8)	O3^v—BNA—T2^xv	98.16 (7)
O8—M2—M1	93.19 (8)	O3^iv—BNA—O3^v	65.25 (14)
O8—M2—O1	104.15 (13)	O3^iv—BNA—O3	114.75 (14)
O8—M2—O1^i	170.33 (13)	O3^xv—BNA—O3	65.25 (14)
O8^ix—M2—O1	170.33 (13)	O3^xv—BNA—O3^v	114.75 (14)
O8^ix—M2—O1^i	104.15 (13)	O3^v—BNA—O3	180.00 (12)
O8^ix—M2—O8	80.70 (17)	O3^xv—BNA—O3^iv	180.00 (12)
O2^vii—M3—M1	46.54 (8)	O3^iv—BNA—O4^iv	83.42 (10)
O2^iv—M3—M1	46.54 (8)	O3^v—BNA—O4^iv	116.49 (9)
O2^iv—M3—O2^vii	93.07 (16)	O3^iv—BNA—O4^v	116.49 (9)
O2^vii—M3—O6^ix	94.19 (10)	O3^v—BNA—O4	96.58 (10)
O2^iv—M3—O6^ii	94.19 (10)	O3^xv—BNA—O4	116.49 (9)
O2^vii—M3—O6^ii	172.73 (11)	O3—BNA—O4	83.42 (10)
O2^iv—M3—O6^ix	172.73 (11)	O3^iv—BNA—O4	63.51 (9)
O6^ii—M3—M1	140.73 (7)	O3^xv—BNA—O4^v	63.51 (9)
O6^ix—M3—M1	140.73 (7)	O3^v—BNA—O4^xv	63.51 (9)
O6^ix—M3—O6^ii	78.54 (13)	O3—BNA—O4^v	96.58 (10)
O8—M3—M1	92.23 (10)	O3^xv—BNA—O4^iv	96.58 (10)
O8^x—M3—M1	92.23 (10)	O3—BNA—O4^xv	116.49 (9)
O8—M3—O2^vii	84.94 (12)	O3^v—BNA—O4^v	83.42 (10)
O8^x—M3—O2^iv	84.94 (12)	O3—BNA—O4^iv	63.51 (9)
O8^x—M3—O2^vii	98.14 (12)	O3^iv—BNA—O4^xv	96.58 (10)
O8—M3—O2^iv	98.14 (12)	O3^xv—BNA—O4^xv	83.42 (10)
O8—M3—O6^ii	93.83 (11)	O3—BNA—F^ii	121.80 (7)
O8^x—M3—O6^ii	82.71 (11)	O3^iv—BNA—F^ii	58.19 (7)
O8^x—M3—O6^ix	93.83 (11)	O3^v—BNA—F	121.81 (7)
O8—M3—O6^ix	82.71 (11)	O3—BNA—F	58.20 (7)
O8—M3—O8^x	175.54 (19)	O3^iv—BNA—F	121.81 (7)
O6^ix—M4—O6	166.96 (15)	O3^xv—BNA—F^ii	121.81 (7)
O6—M4—O6^xii	80.70 (10)	O3^xv—BNA—F	58.19 (7)
O6—M4—O6^xi	89.24 (9)	O3^v—BNA—F^ii	58.19 (7)
O6^ix—M4—O6^xi	80.70 (10)	O4—BNA—T2^xv	148.18 (7)
O6^xii—M4—O6^xi	79.22 (14)	O4—BNA—T2^iv	31.82 (7)
O6^ix—M4—O6^xii	89.24 (9)	O4^iv—BNA—T2^xv	80.37 (7)
O8—M4—O6^xii	173.76 (11)	O4^iv—BNA—T2^iv	99.63 (7)
O8^ix—M4—O6	85.63 (11)	O4^v—BNA—T2^iv	148.18 (7)
O8^ix—M4—O6^xii	96.42 (11)	O4^v—BNA—T2^xv	31.82 (7)
O8—M4—O6^xi	96.42 (11)	O4^xv—BNA—T2^xv	99.63 (7)
O8—M4—O6^ix	85.63 (11)	O4^xv—BNA—T2^iv	80.37 (7)
O8—M4—O6	103.84 (11)	O4^v—BNA—O4^xv	117.33 (14)
O8^ix—M4—O6^ix	103.84 (11)	O4^iv—BNA—O4	117.33 (14)
O8^ix—M4—O6^xi	173.76 (11)	O4^v—BNA—O4	180.00 (11)
O8^ix—M4—O8	88.25 (18)	O4^xv—BNA—O4^iv	180.00 (12)
M1—D—A^xiii	117.606 (16)	O4^v—BNA—O4^iv	62.67 (14)
M1—D—A	117.607 (16)	O4^xv—BNA—O4	62.67 (14)
A—D—A^xiii	112.72 (3)	O4—BNA—F^ii	121.68 (6)
BNA—D—M1	96.37 (2)	O4^xv—BNA—F^ii	121.68 (6)
BNA^xiv—D—M1	161.73 (3)	O4^iv—BNA—F	121.68 (6)
BNA—D—A^xiii	69.327 (16)	O4^xv—BNA—F	58.32 (6)
BNA^xiv—D—A	69.827 (15)	O4^iv—BNA—F^ii	58.32 (6)
BNA^xiv—D—A^xiii	69.827 (15)	O4^v—BNA—F^ii	58.32 (6)
BNA—D—A	69.327 (16)	O4—BNA—F	58.32 (6)
BNA^xiv—D—BNA	101.90 (3)	O4^v—BNA—F	121.68 (6)
O1—D—M1	36.35 (14)	F—BNA—T2^iv	89.983 (19)
O1—D—A^xiii	123.581 (18)	F—BNA—T2^xv	90.017 (19)
O1—D—A	123.581 (18)	F^ii—BNA—T2^xv	89.983 (19)
O1—D—BNA^xiv	125.38 (15)	F^ii—BNA—T2^iv	90.017 (19)
O1—D—BNA	132.72 (15)	F^ii—BNA—F	180.0
O1—D—O3^xiii	103.04 (14)	M2—O1—M1	90.29 (13)
O1—D—O3^viii	103.04 (14)	M2^i—O1—M1	90.29 (13)
O1—D—O4^xv	106.08 (14)	M2^i—O1—M2	107.63 (19)
O1—D—O4	106.08 (14)	D—O1—M1	116.1 (2)
O1—D—F	176.88 (15)	D—O1—M2^i	121.85 (12)
O3^viii—D—M1	126.44 (10)	D—O1—M2	121.85 (12)
O3^xiii—D—M1	126.44 (10)	M2^xvii—O2—M1^xvii	90.34 (10)
O3^xiii—D—A^xiii	44.48 (9)	M3^xvii—O2—M1^xvii	96.32 (11)
O3^xiii—D—A	114.96 (10)	M3^xvii—O2—M2^xvii	95.98 (11)
O3^viii—D—A	44.48 (9)	T2—O2—M1^xvii	118.32 (14)
O3^viii—D—A^xiii	114.96 (10)	T2—O2—M2^xvii	126.55 (16)
O3^xiii—D—BNA^xiv	45.75 (9)	T2—O2—M3^xvii	121.55 (15)
O3^xiii—D—BNA	110.99 (10)	D^xiii—O3—A	106.86 (12)
O3^viii—D—BNA	110.99 (10)	D^xiii—O3—BNA	99.77 (13)
O3^viii—D—BNA^xiv	45.75 (9)	T2—O3—D^xiii	135.69 (19)
O3^xiii—D—O3^viii	86.00 (19)	T2—O3—A	110.27 (15)
O3^xiii—D—F	74.74 (9)	T2—O3—BNA	94.12 (13)
O3^viii—D—F	74.74 (9)	BNA—O3—A	103.80 (11)
O4—D—M1	79.63 (9)	D—O4—A	105.45 (12)
O4^xv—D—M1	79.63 (9)	D—O4—BNA	99.63 (13)
O4—D—A	45.74 (9)	T2^iv—O4—D	141.5 (2)
O4—D—A^xiii	115.63 (10)	T2^iv—O4—A	108.46 (15)
O4^xv—D—A	115.63 (10)	T2^iv—O4—BNA	91.59 (14)
O4^xv—D—A^xiii	45.74 (9)	BNA—O4—A	100.78 (11)
O4^xv—D—BNA^xiv	113.21 (10)	T1^viii—O5—T2	138.99 (19)
O4—D—BNA^xiv	113.21 (10)	T1^viii—O5—A^ii	108.97 (14)
O4—D—BNA	46.57 (10)	T1^viii—O5—A	105.27 (14)
O4^xv—D—BNA	46.57 (10)	T2—O5—A^ii	95.87 (12)
O4^xv—D—O3^xiii	87.00 (13)	T2—O5—A	94.09 (13)
O4—D—O3^viii	87.00 (13)	A^ii—O5—A	112.31 (9)
O4^xv—D—O3^viii	150.88 (14)	M4—O6—M3^xiv	89.18 (10)
O4—D—O3^xiii	150.88 (14)	M4^xii—O6—M3^xiv	101.12 (10)
O4^xv—D—O4	85.52 (19)	M4—O6—M4^xii	99.30 (10)
O4^xv—D—F	76.14 (10)	T1—O6—M3^xiv	119.28 (14)
O4—D—F	76.14 (10)	T1—O6—M4^xii	120.33 (14)
F—D—M1	146.78 (4)	T1—O6—M4	121.50 (14)
F—D—A^xiii	56.362 (17)	T1—O7—T1^xi	137.3 (2)
F—D—A	56.362 (17)	T1^xi—O7—A	104.70 (13)
F—D—BNA	50.408 (19)	T1—O7—A	101.34 (13)
F—D—BNA^xiv	51.497 (18)	T1^xi—O7—A^xviii	97.77 (13)
O5^viii—T1—O6	112.20 (15)	T1—O7—A^xviii	99.74 (12)
O5^viii—T1—O7^xvi	106.92 (16)	A—O7—A^xviii	117.07 (9)
O5^viii—T1—O7	106.49 (16)	M3—O8—M2	98.09 (13)
O6—T1—O7	110.89 (14)	M4—O8—M2	95.53 (12)
O6—T1—O7^xvi	111.10 (14)	M4—O8—M3	102.18 (13)
O7—T1—O7^xvi	109.03 (12)	D^xiii—F—D	180.0
M1^xvii—T2—A	147.67 (3)	D^xiii—F—A^xiii	90.0
M1^xvii—T2—A^ii	120.38 (3)	D—F—A^xiii	90.0
A^ii—T2—A	91.01 (3)	D—F—A	90.0
BNA—T2—M1^xvii	102.99 (3)	D^xiii—F—A	90.0
BNA—T2—A	75.76 (3)	D^xiii—F—BNA	89.10 (2)
BNA—T2—A^ii	75.78 (3)	D^xiii—F—BNA^xiv	90.90 (2)
O2—T2—M1^xvii	37.60 (10)	D—F—BNA	90.90 (2)
O2—T2—A^ii	131.37 (10)	D—F—BNA^xiv	89.10 (2)
O2—T2—A	126.04 (10)	A—F—A^xiii	180.0
O2—T2—BNA	137.28 (11)	BNA—F—A^xiii	90.0
O2—T2—O5	110.81 (15)	BNA^xiv—F—A	90.0
O3—T2—M1^xvii	106.81 (12)	BNA^xiv—F—A^xiii	90.0
O3—T2—A	45.83 (12)	BNA—F—A	90.0
O3—T2—A^ii	117.17 (12)	BNA^xiv—F—BNA	180.0
O3—T2—BNA	54.02 (11)

Symmetry codes: (i) −x+2, −y+1, −z; (ii) x−1, y, z; (iii) −x+1, −y+1, −z; (iv) −x+1, y, −z+1; (v) −x+1, −y+1, −z+1; (vi) x, −y+1, z−1; (vii) x, y, z−1; (viii) −x+2, y, −z+1; (ix) −x+2, y, −z; (x) −x+1, y, −z; (xi) x−1/2, −y+1/2, z; (xii) −x+5/2, −y+1/2, −z; (xiii) −x+2, −y+1, −z+1; (xiv) x+1, y, z; (xv) x, −y+1, z; (xvi) x+1/2, −y+1/2, z; (xvii) x, y, z+1; (xviii) −x+5/2, −y+1/2, −z+1.

(lb690)

Crystal data

0.5(Ca0.29F0.28Fe8.89K3.89Na3.38O60Si15.17Ti4)	F(000) = 1131
Mr = 1160.49	Dx = 3.093 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 5.3017 (5) Å	Cell parameters from 2218 reflections
b = 23.1074 (19) Å	θ = 1.8–35.6°
c = 10.3099 (10) Å	µ = 4.01 mm^−1
β = 99.442 (9)°	T = 293 K
V = 1245.9 (2) Å^3	Prism, brown
Z = 2	0.22 × 0.18 × 0.11 mm

Data collection

Saxi-CrysAlisPro-abstract goniometer imported SAXI images diffractometer	2968 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1869 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.088
ω scans	θmax = 36.4°, θmin = 1.8°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→8
Tmin = 0.562, Tmax = 1.000	k = −37→37
8950 measured reflections	l = −16→14

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: dual
R[F^2 > 2σ(F^2)] = 0.083	w = 1/[σ^2(Fo^2) + (0.0373P)^2 + 15.569P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.153	(Δ/σ)max < 0.001
S = 1.09	Δρmax = 1.33 e Å^−3
2968 reflections	Δρmin = −1.09 e Å^−3
132 parameters

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
M1	0.500000	0.500000	0.000000	0.0163 (15)	0.836 (17)
M2	1.000000	0.42033 (7)	0.000000	0.0248 (5)	0.742 (6)
M3	0.500000	0.35562 (5)	0.000000	0.0108 (3)	0.808 (5)
M4	1.000000	0.29184 (6)	0.000000	0.0123 (4)	0.673 (5)
D	0.9391 (2)	0.500000	0.28770 (12)	0.0117 (3)
T1	1.4235 (2)	0.28208 (5)	0.26869 (13)	0.0084 (4)	0.948 (7)
T2	0.5717 (2)	0.41388 (6)	0.72557 (13)	0.0099 (4)	0.948 (7)
A	1.000000	0.36029 (8)	0.500000	0.0277 (6)	0.971 (8)
BNA	0.500000	0.500000	0.500000	0.0141 (13)	0.85 (3)
BCA	0.500000	0.500000	0.500000	0.0141 (13)	0.15 (3)
O1	0.9098 (10)	0.500000	0.1123 (6)	0.0301 (14)
O2	0.6388 (7)	0.41593 (15)	0.8863 (3)	0.0163 (7)
O3	0.7951 (7)	0.44244 (17)	0.6590 (4)	0.0223 (8)
O4	0.6985 (7)	0.44310 (18)	0.3308 (4)	0.0242 (9)
O5	0.5495 (7)	0.34673 (15)	0.6735 (4)	0.0198 (8)
O6	1.3716 (6)	0.28140 (14)	0.1083 (3)	0.0126 (6)
O7	1.1859 (6)	0.25236 (16)	0.3270 (3)	0.0186 (7)
O8	0.8498 (7)	0.35266 (17)	0.0937 (4)	0.0203 (7)
F	1.000000	0.500000	0.500000	0.010 (10)*	0.14 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
M1	0.011 (2)	0.017 (3)	0.020 (3)	0.000	−0.0009 (18)	0.000
M2	0.0099 (7)	0.0361 (10)	0.0269 (9)	0.000	−0.0013 (6)	0.000
M3	0.0086 (5)	0.0123 (6)	0.0123 (6)	0.000	0.0046 (4)	0.000
M4	0.0082 (6)	0.0167 (8)	0.0121 (7)	0.000	0.0024 (5)	0.000
D	0.0047 (5)	0.0160 (6)	0.0149 (6)	0.000	0.0035 (4)	0.000
T1	0.0071 (6)	0.0091 (6)	0.0094 (6)	−0.0005 (4)	0.0029 (4)	−0.0008 (4)
T2	0.0089 (6)	0.0091 (6)	0.0125 (7)	0.0009 (4)	0.0037 (5)	0.0010 (5)
A	0.0241 (9)	0.0262 (10)	0.0335 (11)	0.000	0.0074 (7)	0.000
BNA	0.0156 (19)	0.0167 (19)	0.0095 (18)	0.000	0.0007 (12)	0.000
BCA	0.0156 (19)	0.0167 (19)	0.0095 (18)	0.000	0.0007 (12)	0.000
O1	0.012 (2)	0.063 (4)	0.017 (3)	0.000	0.005 (2)	0.000
O2	0.0151 (15)	0.0196 (17)	0.0146 (16)	0.0004 (13)	0.0035 (13)	0.0007 (13)
O3	0.0175 (17)	0.026 (2)	0.025 (2)	−0.0075 (14)	0.0097 (15)	−0.0013 (15)
O4	0.0148 (17)	0.032 (2)	0.025 (2)	−0.0077 (15)	0.0040 (15)	−0.0008 (16)
O5	0.0290 (19)	0.0136 (17)	0.0173 (17)	−0.0001 (13)	0.0053 (15)	−0.0001 (13)
O6	0.0091 (13)	0.0150 (15)	0.0133 (15)	0.0010 (11)	0.0009 (11)	0.0000 (12)
O7	0.0133 (15)	0.0265 (19)	0.0168 (17)	−0.0076 (13)	0.0048 (13)	0.0001 (15)
O8	0.0136 (15)	0.031 (2)	0.0175 (17)	0.0021 (14)	0.0052 (13)	−0.0025 (15)

Geometric parameters (Å, º)

M1—M2^i	3.2274 (10)	D—O3^viii	1.950 (4)
M1—M2^ii	3.2274 (10)	D—O4	1.934 (4)
M1—M2	3.2274 (10)	D—O4^xv	1.934 (4)
M1—M2^iii	3.2274 (10)	D—F	2.1594 (13)
M1—M3^ii	3.3363 (12)	T1—O5^viii	1.606 (4)
M1—M3	3.3363 (12)	T1—O6	1.631 (4)
M1—O1	2.288 (5)	T1—O7	1.634 (4)
M1—O1^ii	2.288 (5)	T1—O7^xvi	1.630 (4)
M1—O2^iv	2.444 (4)	T2—A^i	3.7170 (15)
M1—O2^v	2.444 (4)	T2—A	3.7190 (15)
M1—O2^vi	2.444 (4)	T2—BNA	3.0370 (14)
M1—O2^vii	2.444 (4)	T2—O2	1.638 (4)
M2—M4	2.969 (2)	T2—O3	1.605 (4)
M2—O1^iii	2.267 (4)	T2—O4^vii	1.604 (4)
M2—O1	2.267 (4)	T2—O5	1.640 (4)
M2—O2^viii	2.077 (3)	A—O3^viii	2.838 (4)
M2—O2^vi	2.077 (3)	A—O3	2.838 (4)
M2—O8^ix	2.065 (4)	A—O4^viii	2.889 (4)
M2—O8	2.065 (4)	A—O4	2.889 (4)
M3—O2^vi	2.035 (4)	A—O5^viii	3.226 (4)
M3—O2^vii	2.035 (4)	A—O5^xiv	3.174 (4)
M3—O6^ix	2.214 (3)	A—O5	3.225 (4)
M3—O6^i	2.214 (3)	A—O5^vii	3.174 (4)
M3—O8	1.947 (4)	A—O7	3.309 (4)
M3—O8^x	1.947 (4)	A—O7^xii	3.428 (4)
M4—O6^ix	2.113 (3)	A—O7^viii	3.309 (4)
M4—O6^xi	2.197 (3)	A—F	3.228 (2)
M4—O6^xii	2.197 (3)	BNA—O3^xv	2.462 (4)
M4—O6	2.113 (3)	BNA—O3^v	2.462 (4)
M4—O8	1.948 (4)	BNA—O3	2.462 (4)
M4—O8^ix	1.948 (4)	BNA—O3^vii	2.462 (4)
D—A	3.8840 (18)	BNA—O4	2.546 (4)
D—A^xiii	3.8840 (18)	BNA—O4^xv	2.546 (4)
D—BNA^xiv	3.3909 (12)	BNA—O4^vii	2.546 (4)
D—BNA	3.4470 (12)	BNA—O4^v	2.546 (4)
D—O1	1.790 (6)	BNA—F^i	2.6509 (3)
D—O3^xiii	1.950 (4)	BNA—F	2.6509 (3)
M2^i—M1—M2^iii	180.00 (5)	O2—T2—A	126.08 (13)
M2^iii—M1—M2^ii	110.44 (5)	O2—T2—BNA	137.31 (14)
M2^i—M1—M2^ii	69.56 (5)	O2—T2—O5	110.5 (2)
M2^iii—M1—M2	69.56 (5)	O3—T2—A^i	116.91 (16)
M2^i—M1—M2	110.44 (5)	O3—T2—A	45.60 (15)
M2^ii—M1—M2	180.0	O3—T2—BNA	53.95 (15)
M2^ii—M1—M3^ii	55.22 (3)	O3—T2—O2	111.6 (2)
M2^ii—M1—M3	124.78 (3)	O3—T2—O5	105.5 (2)
M2^iii—M1—M3^ii	55.22 (3)	O4^vii—T2—A	120.94 (16)
M2^iii—M1—M3	124.78 (3)	O4^vii—T2—A^i	47.58 (16)
M2—M1—M3^ii	124.78 (3)	O4^vii—T2—BNA	56.94 (16)
M2^i—M1—M3	55.22 (3)	O4^vii—T2—O2	112.8 (2)
M2—M1—M3	55.22 (3)	O4^vii—T2—O3	110.5 (2)
M2^i—M1—M3^ii	124.78 (3)	O4^vii—T2—O5	105.5 (2)
M3^ii—M1—M3	180.0	O5—T2—A	59.90 (14)
O1^ii—M1—M2^ii	44.62 (9)	O5—T2—A^i	58.17 (14)
O1^ii—M1—M2^iii	135.38 (9)	O5—T2—BNA	112.09 (14)
O1—M1—M2^ii	135.38 (9)	O3—A—O3^viii	96.04 (16)
O1—M1—M2^iii	44.62 (9)	O3—A—O4	71.30 (12)
O1—M1—M2^i	135.38 (9)	O3—A—O4^viii	55.56 (11)
O1^ii—M1—M2	135.38 (9)	O3^viii—A—O4^viii	71.30 (12)
O1^ii—M1—M2^i	44.62 (9)	O3^viii—A—O4	55.56 (11)
O1—M1—M2	44.62 (9)	O3^viii—A—O5^xiv	89.35 (10)
O1—M1—M3	90.0	O3^viii—A—O5	140.68 (11)
O1^ii—M1—M3	90.0	O3—A—O5^xiv	98.24 (11)
O1^ii—M1—M3^ii	90.0	O3—A—O5	49.93 (10)
O1—M1—M3^ii	90.0	O3—A—O5^vii	89.35 (10)
O1—M1—O1^ii	180.0	O3^viii—A—O5^vii	98.24 (11)
O1^ii—M1—O2^iv	95.34 (12)	O3—A—O5^viii	140.68 (11)
O1^ii—M1—O2^v	84.66 (12)	O3^viii—A—O5^viii	49.93 (10)
O1—M1—O2^vii	95.34 (12)	O3^viii—A—O7^viii	172.53 (11)
O1—M1—O2^v	95.34 (12)	O3^viii—A—O7^xii	114.00 (10)
O1—M1—O2^vi	84.66 (12)	O3^viii—A—O7	90.96 (10)
O1^ii—M1—O2^vi	95.34 (12)	O3—A—O7^viii	90.96 (10)
O1—M1—O2^iv	84.66 (12)	O3—A—O7	172.53 (11)
O1^ii—M1—O2^vii	84.66 (12)	O3—A—O7^xii	127.51 (10)
O2^v—M1—M2^iii	81.87 (9)	O3—A—F	48.02 (8)
O2^iv—M1—M2^ii	81.87 (9)	O3^viii—A—F	48.02 (8)
O2^v—M1—M2^ii	40.06 (8)	O4^viii—A—O4	97.03 (17)
O2^iv—M1—M2^i	139.94 (8)	O4^viii—A—O5^xiv	50.15 (10)
O2^vi—M1—M2	40.06 (8)	O4^viii—A—O5^vii	140.48 (11)
O2^vii—M1—M2^i	40.06 (8)	O4—A—O5^xiv	140.48 (11)
O2^iv—M1—M2	98.13 (9)	O4^viii—A—O5	96.67 (10)
O2^v—M1—M2	139.94 (8)	O4—A—O5^viii	96.67 (10)
O2^vii—M1—M2^ii	98.13 (9)	O4—A—O5^vii	50.15 (10)
O2^iv—M1—M2^iii	40.06 (8)	O4—A—O5	90.71 (10)
O2^vi—M1—M2^iii	98.13 (9)	O4^viii—A—O5^viii	90.71 (10)
O2^v—M1—M2^i	98.13 (9)	O4—A—O7^viii	129.83 (10)
O2^vi—M1—M2^ii	139.94 (8)	O4—A—O7^xii	90.88 (10)
O2^vi—M1—M2^i	81.87 (9)	O4^viii—A—O7^xii	172.07 (11)
O2^vii—M1—M2^iii	139.94 (8)	O4^viii—A—O7^viii	110.98 (10)
O2^vii—M1—M2	81.87 (9)	O4—A—O7	110.98 (10)
O2^vii—M1—M3^ii	142.65 (8)	O4^viii—A—O7	129.83 (10)
O2^vi—M1—M3^ii	142.65 (8)	O4^viii—A—F	48.52 (8)
O2^vii—M1—M3	37.35 (8)	O4—A—F	48.52 (8)
O2^v—M1—M3^ii	37.35 (8)	O5^xiv—A—O5	111.87 (11)
O2^vi—M1—M3	37.35 (8)	O5^xiv—A—O5^viii	66.94 (11)
O2^iv—M1—M3^ii	37.35 (8)	O5—A—O5^viii	168.86 (14)
O2^v—M1—M3	142.65 (8)	O5^vii—A—O5	66.94 (11)
O2^iv—M1—M3	142.65 (8)	O5^vii—A—O5^viii	111.87 (11)
O2^vi—M1—O2^vii	74.70 (17)	O5^vii—A—O5^xiv	168.68 (14)
O2^iv—M1—O2^vii	180.0	O5^xiv—A—O7^viii	87.08 (9)
O2^vi—M1—O2^iv	105.30 (17)	O5—A—O7	122.61 (10)
O2^v—M1—O2^iv	74.70 (17)	O5^xiv—A—O7^xii	122.74 (10)
O2^v—M1—O2^vii	105.30 (17)	O5—A—O7^xii	82.76 (9)
O2^v—M1—O2^vi	180.00 (14)	O5—A—O7^viii	46.75 (9)
M1^xiv—M2—M1	110.44 (5)	O5^vii—A—O7^xii	46.32 (8)
M4—M2—M1	124.78 (3)	O5^viii—A—O7^xii	88.77 (9)
M4—M2—M1^xiv	124.78 (3)	O5^viii—A—O7^viii	122.61 (10)
O1^iii—M2—M1	77.22 (13)	O5^viii—A—O7	46.75 (9)
O1—M2—M1	45.15 (14)	O5^vii—A—O7^viii	84.39 (9)
O1—M2—M1^xiv	77.22 (13)	O5^vii—A—O7	87.08 (9)
O1^iii—M2—M1^xiv	45.15 (14)	O5^xiv—A—O7	84.39 (9)
O1—M2—M4	144.30 (12)	O5^vii—A—F	95.66 (7)
O1^iii—M2—M4	144.30 (12)	O5^viii—A—F	95.57 (7)
O1—M2—O1^iii	71.4 (2)	O5—A—F	95.57 (7)
O2^viii—M2—M1^xiv	49.21 (10)	O5^xiv—A—F	95.66 (7)
O2^vi—M2—M1^xiv	135.16 (11)	O7—A—O7^xii	46.34 (3)
O2^viii—M2—M1	135.16 (11)	O7—A—O7^viii	82.17 (13)
O2^vi—M2—M1	49.21 (10)	O7^viii—A—O7^xii	62.99 (11)
O2^viii—M2—M4	87.20 (11)	F—A—O7	138.91 (6)
O2^vi—M2—M4	87.20 (11)	F—A—O7^viii	138.92 (6)
O2^viii—M2—O1	90.21 (17)	F—A—O7^xii	139.40 (6)
O2^vi—M2—O1^iii	90.21 (17)	T2—BNA—T2^vii	98.12 (5)
O2^viii—M2—O1^iii	94.35 (17)	O3^xv—BNA—T2	81.84 (10)
O2^vi—M2—O1	94.34 (17)	O3^vii—BNA—T2^vii	31.81 (9)
O2^vi—M2—O2^viii	174.4 (2)	O3^vii—BNA—T2	98.16 (10)
O8—M2—M1^xiv	144.26 (10)	O3^xv—BNA—T2^vii	148.19 (9)
O8^ix—M2—M1	144.26 (10)	O3—BNA—T2^vii	98.16 (10)
O8—M2—M1	92.99 (10)	O3—BNA—T2	31.81 (9)
O8^ix—M2—M1^xiv	92.99 (10)	O3^v—BNA—T2^vii	81.84 (10)
O8—M2—M4	40.79 (11)	O3^v—BNA—T2	148.19 (9)
O8^ix—M2—M4	40.79 (11)	O3^xv—BNA—O3	65.40 (18)
O8^ix—M2—O1^iii	104.25 (16)	O3^vii—BNA—O3^v	65.39 (18)
O8^ix—M2—O1	169.59 (17)	O3^vii—BNA—O3	114.60 (18)
O8—M2—O1	104.25 (16)	O3^xv—BNA—O3^v	114.61 (18)
O8—M2—O1^iii	169.59 (17)	O3^xv—BNA—O3^vii	180.00 (15)
O8^ix—M2—O2^vi	95.14 (15)	O3^v—BNA—O3	180.0
O8^ix—M2—O2^viii	80.58 (14)	O3—BNA—O4^v	96.42 (13)
O8—M2—O2^viii	95.14 (15)	O3^xv—BNA—O4^xv	83.58 (13)
O8—M2—O2^vi	80.58 (14)	O3^vii—BNA—O4^vii	83.58 (13)
O8^ix—M2—O8	81.6 (2)	O3^v—BNA—O4^xv	63.50 (12)
O2^vii—M3—M1	46.77 (10)	O3^xv—BNA—O4	116.50 (12)
O2^vi—M3—M1	46.77 (10)	O3^xv—BNA—O4^vii	96.42 (13)
O2^vii—M3—O2^vi	93.5 (2)	O3^vii—BNA—O4	63.50 (12)
O2^vi—M3—O6^i	172.45 (14)	O3^v—BNA—O4^v	83.58 (13)
O2^vii—M3—O6^i	94.00 (13)	O3^v—BNA—O4	96.42 (13)
O2^vi—M3—O6^ix	94.00 (13)	O3^v—BNA—O4^vii	116.50 (12)
O2^vii—M3—O6^ix	172.45 (14)	O3—BNA—O4	83.58 (13)
O6^ix—M3—M1	140.77 (9)	O3^vii—BNA—O4^v	116.50 (12)
O6^i—M3—M1	140.77 (9)	O3^xv—BNA—O4^v	63.50 (12)
O6^ix—M3—O6^i	78.46 (18)	O3—BNA—O4^xv	116.50 (12)
O8^x—M3—M1	92.01 (12)	O3—BNA—O4^vii	63.50 (12)
O8—M3—M1	92.01 (12)	O3^vii—BNA—O4^xv	96.42 (13)
O8—M3—O2^vi	84.53 (15)	O3—BNA—F^i	121.75 (9)
O8—M3—O2^vii	98.24 (15)	O3^vii—BNA—F^i	58.25 (9)
O8^x—M3—O2^vi	98.24 (15)	O3^v—BNA—F	121.75 (9)
O8^x—M3—O2^vii	84.53 (15)	O3—BNA—F	58.25 (9)
O8^x—M3—O6^i	82.90 (14)	O3^vii—BNA—F	121.75 (9)
O8—M3—O6^ix	82.90 (14)	O3^v—BNA—F^i	58.25 (9)
O8—M3—O6^i	93.98 (15)	O3^xv—BNA—F	58.25 (9)
O8^x—M3—O6^ix	93.98 (15)	O3^xv—BNA—F^i	121.75 (9)
O8—M3—O8^x	176.0 (2)	O4—BNA—T2	99.93 (10)
O6—M4—M2	96.56 (10)	O4^xv—BNA—T2^vii	80.07 (10)
O6^xii—M4—M2	140.40 (9)	O4—BNA—T2^vii	31.87 (9)
O6^ix—M4—M2	96.55 (10)	O4^v—BNA—T2^vii	148.13 (9)
O6^xi—M4—M2	140.40 (9)	O4^xv—BNA—T2	148.13 (9)
O6^ix—M4—O6^xi	89.04 (12)	O4^vii—BNA—T2^vii	99.93 (10)
O6—M4—O6^xii	89.04 (12)	O4^v—BNA—T2	80.07 (10)
O6^ix—M4—O6	166.89 (19)	O4^vii—BNA—T2	31.87 (9)
O6—M4—O6^xi	80.84 (13)	O4^v—BNA—O4^xv	117.81 (18)
O6^ix—M4—O6^xii	80.84 (13)	O4^xv—BNA—O4^vii	180.00 (16)
O6^xi—M4—O6^xii	79.19 (18)	O4—BNA—O4^vii	117.81 (18)
O8—M4—M2	43.83 (12)	O4—BNA—O4^xv	62.19 (18)
O8^ix—M4—M2	43.83 (12)	O4—BNA—O4^v	180.0
O8^ix—M4—O6^xii	173.74 (14)	O4^v—BNA—O4^vii	62.19 (18)
O8—M4—O6	103.99 (14)	O4^xv—BNA—F^i	121.72 (8)
O8^ix—M4—O6^xi	96.76 (15)	O4—BNA—F	58.28 (8)
O8^ix—M4—O6^ix	103.99 (14)	O4^vii—BNA—F	121.72 (8)
O8—M4—O6^xi	173.74 (14)	O4^v—BNA—F^i	58.28 (8)
O8—M4—O6^xii	96.76 (15)	O4^v—BNA—F	121.72 (8)
O8^ix—M4—O6	85.58 (14)	O4^vii—BNA—F^i	58.28 (8)
O8—M4—O6^ix	85.58 (14)	O4—BNA—F^i	121.72 (8)
O8—M4—O8^ix	87.7 (2)	O4^xv—BNA—F	58.28 (8)
M1—D—A^xiii	117.74 (2)	F—BNA—T2	90.03 (3)
M1—D—A	117.74 (2)	F—BNA—T2^vii	89.97 (3)
A^xiii—D—A	112.44 (4)	F^i—BNA—T2	89.97 (3)
BNA^xiv—D—M1	161.73 (4)	F^i—BNA—T2^vii	90.03 (3)
BNA—D—M1	96.60 (3)	F^i—BNA—F	180.0
BNA^xiv—D—A	69.71 (2)	M2^iii—O1—M1	90.23 (16)
BNA^xiv—D—A^xiii	69.71 (2)	M2—O1—M1	90.23 (16)
BNA—D—A^xiii	69.18 (2)	M2^iii—O1—M2	108.6 (2)
BNA—D—A	69.18 (2)	D—O1—M1	115.4 (3)
BNA^xiv—D—BNA	101.67 (3)	D—O1—M2	121.70 (15)
O1—D—M1	36.72 (17)	D—O1—M2^iii	121.70 (15)
O1—D—A	123.70 (2)	M2^xvii—O2—M1^xvii	90.73 (13)
O1—D—A^xiii	123.70 (2)	M3^xvii—O2—M1^xvii	95.88 (14)
O1—D—BNA^xiv	125.01 (18)	M3^xvii—O2—M2^xvii	95.49 (15)
O1—D—BNA	133.32 (18)	T2—O2—M1^xvii	118.41 (18)
O1—D—O3^xiii	102.92 (18)	T2—O2—M2^xvii	126.8 (2)
O1—D—O3^viii	102.92 (18)	T2—O2—M3^xvii	121.6 (2)
O1—D—O4^xv	106.33 (18)	D^xiii—O3—A	106.95 (15)
O1—D—O4	106.33 (18)	D^xiii—O3—BNA	99.79 (16)
O1—D—F	176.42 (18)	T2—O3—D^xiii	135.2 (2)
O3^xiii—D—M1	126.55 (13)	T2—O3—A	110.56 (19)
O3^viii—D—M1	126.55 (13)	T2—O3—BNA	94.24 (18)
O3^xiii—D—A	114.75 (13)	BNA—O3—A	103.79 (14)
O3^viii—D—A	44.35 (12)	D—O4—A	105.58 (15)
O3^viii—D—A^xiii	114.75 (13)	D—O4—BNA	99.71 (17)
O3^xiii—D—A^xiii	44.35 (12)	T2^vii—O4—D	141.9 (3)
O3^xiii—D—BNA	110.68 (12)	T2^vii—O4—A	108.23 (19)
O3^viii—D—BNA^xiv	45.69 (12)	T2^vii—O4—BNA	91.19 (18)
O3^viii—D—BNA	110.68 (12)	BNA—O4—A	100.27 (14)
O3^xiii—D—BNA^xiv	45.69 (12)	T1^viii—O5—T2	139.6 (3)
O3^xiii—D—O3^viii	86.0 (2)	T1^viii—O5—A	105.50 (17)
O3^xiii—D—F	74.54 (12)	T1^viii—O5—A^i	108.57 (17)
O3^viii—D—F	74.54 (12)	T2—O5—A^i	95.80 (16)
O4^xv—D—M1	79.66 (12)	T2—O5—A	94.00 (16)
O4—D—M1	79.66 (12)	A^i—O5—A	111.87 (11)
O4^xv—D—A^xiii	45.76 (12)	M4—O6—M3^xiv	88.98 (12)
O4—D—A^xiii	115.64 (13)	M4^xi—O6—M3^xiv	101.17 (14)
O4—D—A	45.76 (12)	M4—O6—M4^xi	99.16 (13)
O4^xv—D—A	115.64 (13)	T1—O6—M3^xiv	119.28 (18)
O4—D—BNA^xiv	113.16 (13)	T1—O6—M4^xi	120.52 (18)
O4^xv—D—BNA	46.72 (13)	T1—O6—M4	121.50 (18)
O4—D—BNA	46.72 (13)	T1^xii—O7—T1	137.1 (2)
O4^xv—D—BNA^xiv	113.16 (13)	T1^xii—O7—A	104.79 (16)
O4^xv—D—O3^viii	150.74 (18)	T1—O7—A^xviii	99.94 (16)
O4^xv—D—O3^xiii	86.84 (17)	T1^xii—O7—A^xviii	97.67 (16)
O4—D—O3^xiii	150.74 (18)	T1—O7—A	101.39 (16)
O4—D—O3^viii	86.84 (17)	A—O7—A^xviii	117.01 (11)
O4^xv—D—O4	85.7 (3)	M3—O8—M2	98.65 (17)
O4^xv—D—F	76.21 (13)	M3—O8—M4	102.29 (17)
O4—D—F	76.21 (13)	M4—O8—M2	95.38 (16)
F—D—M1	146.86 (5)	D—F—D^xiii	180.0
F—D—A	56.22 (2)	D—F—A^xiii	90.0
F—D—A^xiii	56.22 (2)	D^xiii—F—A	90.0
F—D—BNA	50.26 (3)	D^xiii—F—A^xiii	90.0
F—D—BNA^xiv	51.41 (2)	D—F—A	90.0
O5^viii—T1—O6	112.02 (19)	D—F—BNA^xiv	89.04 (3)
O5^viii—T1—O7^xvi	107.4 (2)	D^xiii—F—BNA	89.04 (3)
O5^viii—T1—O7	106.3 (2)	D—F—BNA	90.96 (3)
O6—T1—O7	110.91 (18)	D^xiii—F—BNA^xiv	90.96 (3)
O7^xvi—T1—O6	111.20 (18)	A^xiii—F—A	180.0
O7^xvi—T1—O7	108.78 (15)	BNA^xiv—F—A	90.0
A^i—T2—A	90.96 (4)	BNA^xiv—F—A^xiii	90.0
BNA—T2—A^i	75.66 (4)	BNA—F—A^xiii	90.0
BNA—T2—A	75.63 (4)	BNA—F—A	90.0
O2—T2—A^i	131.47 (14)	BNA^xiv—F—BNA	180.0

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z; (iii) −x+2, −y+1, −z; (iv) x, −y+1, z−1; (v) −x+1, −y+1, −z+1; (vi) x, y, z−1; (vii) −x+1, y, −z+1; (viii) −x+2, y, −z+1; (ix) −x+2, y, −z; (x) −x+1, y, −z; (xi) −x+5/2, −y+1/2, −z; (xii) x−1/2, −y+1/2, z; (xiii) −x+2, −y+1, −z+1; (xiv) x+1, y, z; (xv) x, −y+1, z; (xvi) x+1/2, −y+1/2, z; (xvii) x, y, z+1; (xviii) −x+5/2, −y+1/2, −z+1.

(lb710)

Crystal data

0.5(Ca0.3F0.25Fe8.86K3.9Na3.44O60Si15.38Ti4)	F(000) = 1134
Mr = 1163.40	Dx = 3.095 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 5.3110 (3) Å	Cell parameters from 4141 reflections
b = 23.1413 (11) Å	θ = 1.8–36.2°
c = 10.2979 (6) Å	µ = 4.00 mm^−1
β = 99.476 (5)°	T = 293 K
V = 1248.38 (12) Å^3	Prism, brown
Z = 2	0.22 × 0.18 × 0.11 mm

Data collection

Saxi-CrysAlisPro-abstract goniometer imported SAXI images diffractometer	2976 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2492 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
ω scans	θmax = 36.3°, θmin = 1.8°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→8
Tmin = 0.727, Tmax = 1.000	k = −37→37
11250 measured reflections	l = −16→16

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: dual
R[F^2 > 2σ(F^2)] = 0.052	w = 1/[σ^2(Fo^2) + (0.0254P)^2 + 7.6476P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.099	(Δ/σ)max < 0.001
S = 1.14	Δρmax = 1.37 e Å^−3
2976 reflections	Δρmin = −0.71 e Å^−3
132 parameters

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
M1	0.500000	0.500000	0.000000	0.0158 (7)	0.870 (11)
M2	1.000000	0.42008 (4)	0.000000	0.0238 (3)	0.736 (4)
M3	0.500000	0.35555 (3)	0.000000	0.01100 (17)	0.805 (3)
M4	1.000000	0.29183 (3)	0.000000	0.0122 (2)	0.674 (3)
D	0.93896 (11)	0.500000	0.28718 (6)	0.01138 (14)
T1	1.42298 (13)	0.28200 (3)	0.26892 (7)	0.00893 (19)	0.965 (4)
T2	0.57159 (13)	0.41398 (3)	0.72535 (7)	0.00977 (19)	0.957 (5)
A	1.000000	0.36000 (5)	0.500000	0.0275 (3)	0.976 (5)
BNA	0.500000	0.500000	0.500000	0.0142 (7)	0.851 (16)
BCA	0.500000	0.500000	0.500000	0.0142 (7)	0.149 (16)
O1	0.9074 (6)	0.500000	0.1119 (3)	0.0303 (8)
O2	0.6390 (4)	0.41602 (9)	0.88593 (19)	0.0155 (3)
O3	0.7958 (4)	0.44276 (9)	0.6585 (2)	0.0204 (4)
O4	0.6986 (4)	0.44320 (10)	0.3313 (2)	0.0224 (4)
O5	0.5491 (4)	0.34660 (8)	0.6730 (2)	0.0201 (4)
O6	1.3713 (3)	0.28143 (8)	0.10832 (18)	0.0124 (3)
O7	1.1858 (4)	0.25223 (9)	0.32710 (19)	0.0187 (4)
O8	0.8502 (4)	0.35282 (10)	0.0942 (2)	0.0198 (4)
F	1.000000	0.500000	0.500000	0.009 (6)*	0.125 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
M1	0.0107 (12)	0.0134 (12)	0.0218 (14)	0.000	−0.0019 (9)	0.000
M2	0.0087 (3)	0.0352 (5)	0.0254 (5)	0.000	−0.0032 (3)	0.000
M3	0.0085 (3)	0.0134 (3)	0.0117 (3)	0.000	0.0035 (2)	0.000
M4	0.0074 (3)	0.0169 (4)	0.0124 (4)	0.000	0.0020 (2)	0.000
D	0.0051 (2)	0.0166 (3)	0.0128 (3)	0.000	0.00264 (19)	0.000
T1	0.0071 (3)	0.0100 (3)	0.0100 (3)	0.0001 (2)	0.0020 (2)	−0.0005 (2)
T2	0.0081 (3)	0.0101 (3)	0.0114 (3)	0.0003 (2)	0.0026 (2)	0.0007 (2)
A	0.0236 (5)	0.0260 (5)	0.0338 (6)	0.000	0.0073 (4)	0.000
BNA	0.0172 (11)	0.0152 (10)	0.0096 (10)	0.000	0.0001 (6)	0.000
BCA	0.0172 (11)	0.0152 (10)	0.0096 (10)	0.000	0.0001 (6)	0.000
O1	0.0133 (13)	0.065 (2)	0.0132 (13)	0.000	0.0034 (10)	0.000
O2	0.0137 (8)	0.0186 (8)	0.0143 (8)	−0.0009 (6)	0.0024 (6)	0.0005 (7)
O3	0.0155 (9)	0.0256 (10)	0.0214 (10)	−0.0069 (7)	0.0067 (7)	0.0000 (8)
O4	0.0144 (9)	0.0279 (11)	0.0249 (11)	−0.0079 (8)	0.0030 (8)	−0.0004 (8)
O5	0.0308 (11)	0.0125 (8)	0.0164 (9)	0.0007 (7)	0.0018 (8)	0.0008 (7)
O6	0.0096 (7)	0.0163 (8)	0.0111 (7)	0.0004 (6)	0.0016 (6)	−0.0008 (6)
O7	0.0135 (8)	0.0281 (10)	0.0147 (9)	−0.0080 (7)	0.0030 (7)	−0.0007 (7)
O8	0.0130 (8)	0.0308 (11)	0.0157 (9)	0.0017 (7)	0.0030 (7)	−0.0025 (8)

Geometric parameters (Å, º)

M1—M2^i	3.2360 (6)	D—O3^viii	1.947 (2)
M1—M2^ii	3.2360 (6)	D—O4^xv	1.938 (2)
M1—M2	3.2360 (6)	D—O4	1.938 (2)
M1—M2^iii	3.2360 (6)	D—F	2.1620 (7)
M1—M3^ii	3.3426 (7)	T1—O5^viii	1.608 (2)
M1—M3	3.3427 (7)	T1—O6	1.6314 (19)
M1—O1	2.278 (3)	T1—O7	1.634 (2)
M1—O1^ii	2.278 (3)	T1—O7^xvi	1.631 (2)
M1—O2^iv	2.447 (2)	T2—A^i	3.7205 (8)
M1—O2^v	2.447 (2)	T2—A	3.7231 (8)
M1—O2^vi	2.447 (2)	T2—BNA	3.0334 (7)
M1—O2^vii	2.447 (2)	T2—O2	1.634 (2)
M2—M4	2.9680 (13)	T2—O3	1.614 (2)
M2—O1	2.275 (2)	T2—O4^vii	1.607 (2)
M2—O1^iii	2.275 (2)	T2—O5	1.648 (2)
M2—O2^viii	2.0793 (19)	A—O3	2.844 (2)
M2—O2^vi	2.0793 (19)	A—O3^viii	2.844 (2)
M2—O8^ix	2.062 (2)	A—O4^viii	2.893 (2)
M2—O8	2.062 (2)	A—O4	2.893 (2)
M3—O2^vi	2.042 (2)	A—O5	3.227 (2)
M3—O2^vii	2.042 (2)	A—O5^xiv	3.173 (2)
M3—O6^ix	2.2145 (19)	A—O5^viii	3.227 (2)
M3—O6^i	2.2145 (19)	A—O5^vii	3.173 (2)
M3—O8^x	1.952 (2)	A—O7	3.308 (2)
M3—O8	1.952 (2)	A—O7^xii	3.424 (2)
M4—O6^ix	2.1136 (18)	A—O7^viii	3.308 (2)
M4—O6^xi	2.1993 (19)	A—F	3.2398 (11)
M4—O6^xii	2.1993 (19)	BNA—O3	2.458 (2)
M4—O6	2.1136 (18)	BNA—O3^vii	2.458 (2)
M4—O8	1.954 (2)	BNA—O3^v	2.458 (2)
M4—O8^ix	1.954 (2)	BNA—O3^xv	2.458 (2)
D—A	3.8949 (10)	BNA—O4	2.542 (2)
D—A^xiii	3.8949 (10)	BNA—O4^xv	2.542 (2)
D—BNA^xiv	3.3958 (7)	BNA—O4^vii	2.542 (2)
D—BNA	3.4526 (6)	BNA—O4^v	2.542 (2)
D—O1	1.785 (3)	BNA—F^i	2.6555 (1)
D—O3^xiii	1.947 (2)	BNA—F	2.6555 (1)
M2^i—M1—M2^iii	180.00 (3)	O2—T2—A	125.87 (7)
M2^i—M1—M2	110.29 (3)	O2—T2—BNA	137.24 (8)
M2^i—M1—M2^ii	69.71 (3)	O2—T2—O5	110.50 (11)
M2^ii—M1—M2	180.0	O3—T2—M1^xvii	107.06 (8)
M2^iii—M1—M2	69.71 (3)	O3—T2—A	45.82 (8)
M2^iii—M1—M2^ii	110.29 (3)	O3—T2—A^i	117.13 (8)
M2—M1—M3	55.146 (14)	O3—T2—BNA	53.94 (8)
M2^i—M1—M3	55.146 (14)	O3—T2—O2	111.44 (11)
M2—M1—M3^ii	124.854 (14)	O3—T2—O5	105.66 (12)
M2^i—M1—M3^ii	124.854 (14)	O4^vii—T2—M1^xvii	81.15 (9)
M2^ii—M1—M3	124.854 (14)	O4^vii—T2—A	121.05 (9)
M2^ii—M1—M3^ii	55.146 (14)	O4^vii—T2—A^i	47.66 (9)
M2^iii—M1—M3	124.854 (14)	O4^vii—T2—BNA	56.91 (9)
M2^iii—M1—M3^ii	55.146 (14)	O4^vii—T2—O2	112.90 (11)
M3^ii—M1—M3	180.0	O4^vii—T2—O3	110.43 (12)
O1—M1—M2^iii	44.67 (5)	O4^vii—T2—O5	105.50 (12)
O1^ii—M1—M2^iii	135.33 (5)	O5—T2—M1^xvii	141.63 (8)
O1—M1—M2^i	135.33 (5)	O5—T2—A^i	58.03 (8)
O1^ii—M1—M2^i	44.67 (5)	O5—T2—A	59.84 (8)
O1^ii—M1—M2^ii	44.67 (5)	O5—T2—BNA	112.19 (8)
O1^ii—M1—M2	135.33 (5)	O3^viii—A—O3	95.35 (9)
O1—M1—M2^ii	135.33 (5)	O3—A—O4^viii	55.45 (6)
O1—M1—M2	44.67 (5)	O3^viii—A—O4	55.45 (6)
O1^ii—M1—M3^ii	90.0	O3^viii—A—O4^viii	70.79 (7)
O1—M1—M3^ii	90.0	O3—A—O4	70.79 (7)
O1—M1—M3	90.0	O3—A—O5^viii	140.29 (6)
O1^ii—M1—M3	90.0	O3—A—O5	50.21 (5)
O1—M1—O1^ii	180.00 (16)	O3^viii—A—O5	140.29 (6)
O1—M1—O2^iv	84.62 (7)	O3—A—O5^xiv	98.36 (6)
O1^ii—M1—O2^iv	95.38 (7)	O3—A—O5^vii	89.20 (6)
O1^ii—M1—O2^v	84.62 (7)	O3^viii—A—O5^viii	50.21 (5)
O1—M1—O2^vii	95.38 (7)	O3^viii—A—O5^vii	98.36 (6)
O1^ii—M1—O2^vi	95.38 (7)	O3^viii—A—O5^xiv	89.20 (6)
O1—M1—O2^v	95.38 (7)	O3—A—O7	172.84 (6)
O1—M1—O2^vi	84.62 (7)	O3^viii—A—O7	91.32 (5)
O1^ii—M1—O2^vii	84.62 (7)	O3—A—O7^viii	91.32 (5)
O2^iv—M1—M2^i	140.02 (5)	O3—A—O7^xii	127.59 (5)
O2^vi—M1—M2^iii	98.13 (5)	O3^viii—A—O7^xii	114.30 (6)
O2^vii—M1—M2^ii	98.13 (5)	O3^viii—A—O7^viii	172.84 (6)
O2^v—M1—M2^iii	81.87 (5)	O3^viii—A—F	47.68 (4)
O2^vii—M1—M2^iii	140.02 (5)	O3—A—F	47.68 (4)
O2^vi—M1—M2	39.98 (5)	O4^viii—A—O4	96.56 (9)
O2^v—M1—M2	140.02 (5)	O4—A—O5	90.46 (6)
O2^vii—M1—M2^i	39.98 (5)	O4—A—O5^vii	50.30 (5)
O2^vi—M1—M2^ii	140.02 (5)	O4^viii—A—O5^vii	140.24 (6)
O2^iv—M1—M2^iii	39.98 (5)	O4^viii—A—O5^viii	90.46 (6)
O2^iv—M1—M2	98.13 (5)	O4^viii—A—O5	96.89 (6)
O2^v—M1—M2^i	98.13 (5)	O4—A—O5^xiv	140.24 (6)
O2^vi—M1—M2^i	81.87 (5)	O4^viii—A—O5^xiv	50.30 (5)
O2^vii—M1—M2	81.87 (5)	O4—A—O5^viii	96.89 (6)
O2^v—M1—M2^ii	39.98 (5)	O4—A—O7^viii	129.82 (5)
O2^iv—M1—M2^ii	81.87 (5)	O4^viii—A—O7	129.82 (5)
O2^vi—M1—M3	37.42 (5)	O4—A—O7	111.29 (6)
O2^iv—M1—M3^ii	37.42 (5)	O4^viii—A—O7^viii	111.30 (6)
O2^vii—M1—M3	37.42 (5)	O4^viii—A—O7^xii	172.37 (6)
O2^v—M1—M3	142.58 (5)	O4—A—O7^xii	91.06 (5)
O2^vii—M1—M3^ii	142.58 (5)	O4^viii—A—F	48.28 (5)
O2^iv—M1—M3	142.58 (5)	O4—A—F	48.28 (5)
O2^vi—M1—M3^ii	142.58 (5)	O5^viii—A—O5	168.97 (8)
O2^v—M1—M3^ii	37.42 (5)	O5^xiv—A—O5	112.18 (6)
O2^v—M1—O2^vii	105.17 (9)	O5^vii—A—O5^xiv	168.79 (8)
O2^iv—M1—O2^vii	180.0	O5^vii—A—O5	66.65 (6)
O2^vi—M1—O2^vii	74.83 (9)	O5^xiv—A—O5^viii	66.65 (6)
O2^v—M1—O2^vi	180.0	O5^vii—A—O5^viii	112.18 (6)
O2^vi—M1—O2^iv	105.17 (9)	O5^vii—A—O7^xii	46.33 (5)
O2^v—M1—O2^iv	74.83 (9)	O5^vii—A—O7	87.25 (5)
M1^xiv—M2—M1	110.29 (3)	O5^xiv—A—O7^xii	122.84 (6)
M4—M2—M1	124.854 (14)	O5^viii—A—O7^xii	88.99 (5)
M4—M2—M1^xiv	124.854 (14)	O5^viii—A—O7	46.84 (5)
O1^iii—M2—M1^xiv	44.74 (8)	O5—A—O7^xii	82.63 (5)
O1—M2—M1^xiv	77.36 (8)	O5—A—O7	122.62 (6)
O1—M2—M1	44.74 (8)	O5^vii—A—O7^viii	84.29 (5)
O1^iii—M2—M1	77.36 (8)	O5—A—O7^viii	46.84 (5)
O1^iii—M2—M4	144.38 (7)	O5^xiv—A—O7	84.30 (5)
O1—M2—M4	144.38 (7)	O5^xiv—A—O7^viii	87.25 (5)
O1^iii—M2—O1	71.24 (13)	O5^viii—A—O7^viii	122.62 (6)
O2^viii—M2—M1	134.93 (6)	O5^viii—A—F	95.51 (4)
O2^viii—M2—M1^xiv	49.11 (6)	O5^vii—A—F	95.61 (4)
O2^vi—M2—M1^xiv	134.93 (6)	O5^xiv—A—F	95.61 (4)
O2^vi—M2—M1	49.11 (6)	O5—A—F	95.51 (4)
O2^vi—M2—M4	87.41 (6)	O7—A—O7^xii	46.466 (19)
O2^viii—M2—M4	87.41 (6)	O7—A—O7^viii	82.13 (7)
O2^viii—M2—O1	90.38 (10)	O7^viii—A—O7^xii	62.93 (6)
O2^vi—M2—O1	93.82 (10)	F—A—O7^viii	138.93 (4)
O2^viii—M2—O1^iii	93.83 (10)	F—A—O7^xii	139.34 (3)
O2^vi—M2—O1^iii	90.38 (10)	F—A—O7	138.93 (4)
O2^vi—M2—O2^viii	174.82 (12)	T2—BNA—T2^vii	97.98 (3)
O8—M2—M1^xiv	144.26 (6)	O3^vii—BNA—T2^vii	32.06 (5)
O8—M2—M1	92.94 (6)	O3^v—BNA—T2	147.94 (5)
O8^ix—M2—M1^xiv	92.94 (6)	O3^vii—BNA—T2	98.06 (5)
O8^ix—M2—M1	144.26 (6)	O3^v—BNA—T2^vii	81.94 (5)
O8—M2—M4	40.97 (6)	O3^xv—BNA—T2^vii	147.94 (5)
O8^ix—M2—M4	40.97 (6)	O3—BNA—T2	32.06 (5)
O8^ix—M2—O1^iii	104.08 (9)	O3^xv—BNA—T2	81.94 (5)
O8—M2—O1^iii	169.83 (10)	O3—BNA—T2^vii	98.06 (5)
O8^ix—M2—O1	169.83 (10)	O3—BNA—O3^v	180.0
O8—M2—O1	104.08 (9)	O3^vii—BNA—O3^v	65.21 (10)
O8^ix—M2—O2^vi	95.25 (8)	O3^xv—BNA—O3^vii	180.00 (9)
O8^ix—M2—O2^viii	80.81 (8)	O3—BNA—O3^vii	114.79 (10)
O8—M2—O2^vi	80.81 (8)	O3—BNA—O3^xv	65.21 (10)
O8—M2—O2^viii	95.25 (8)	O3^xv—BNA—O3^v	114.79 (10)
O8^ix—M2—O8	81.94 (12)	O3—BNA—O4	83.30 (7)
O2^vii—M3—M1	46.73 (6)	O3^vii—BNA—O4^vii	83.30 (7)
O2^vi—M3—M1	46.73 (6)	O3^xv—BNA—O4^vii	96.70 (7)
O2^vii—M3—O2^vi	93.46 (11)	O3^vii—BNA—O4^xv	96.70 (7)
O2^vi—M3—O6^ix	94.03 (7)	O3^xv—BNA—O4^xv	83.30 (7)
O2^vii—M3—O6^ix	172.50 (8)	O3—BNA—O4^vii	63.86 (7)
O2^vii—M3—O6^i	94.03 (7)	O3^xv—BNA—O4	116.14 (7)
O2^vi—M3—O6^i	172.50 (8)	O3^xv—BNA—O4^v	63.86 (7)
O6^ix—M3—M1	140.76 (5)	O3^vii—BNA—O4	63.86 (7)
O6^i—M3—M1	140.76 (5)	O3^v—BNA—O4^v	83.30 (7)
O6^ix—M3—O6^i	78.48 (10)	O3^v—BNA—O4	96.70 (7)
O8^x—M3—M1	91.86 (7)	O3—BNA—O4^xv	116.14 (7)
O8—M3—M1	91.86 (7)	O3—BNA—O4^v	96.70 (7)
O8—M3—O2^vii	98.14 (8)	O3^v—BNA—O4^xv	63.86 (7)
O8^x—M3—O2^vi	98.14 (8)	O3^v—BNA—O4^vii	116.14 (7)
O8—M3—O2^vi	84.43 (8)	O3^vii—BNA—O4^v	116.14 (7)
O8^x—M3—O2^vii	84.43 (8)	O3^v—BNA—F^i	58.01 (5)
O8^x—M3—O6^ix	94.16 (8)	O3^xv—BNA—F^i	121.99 (5)
O8^x—M3—O6^i	82.95 (8)	O3^vii—BNA—F	121.99 (5)
O8—M3—O6^i	94.15 (8)	O3^v—BNA—F	121.99 (5)
O8—M3—O6^ix	82.95 (8)	O3^xv—BNA—F	58.01 (5)
O8^x—M3—O8	176.28 (14)	O3—BNA—F^i	121.99 (5)
O6^xii—M4—M2	140.44 (5)	O3—BNA—F	58.01 (5)
O6—M4—M2	96.54 (5)	O3^vii—BNA—F^i	58.01 (5)
O6^xi—M4—M2	140.44 (5)	O4^vii—BNA—T2	31.98 (5)
O6^ix—M4—M2	96.53 (5)	O4^vii—BNA—T2^vii	99.77 (5)
O6^xi—M4—O6^xii	79.13 (10)	O4^xv—BNA—T2	148.02 (5)
O6—M4—O6^xii	89.16 (6)	O4^xv—BNA—T2^vii	80.23 (5)
O6—M4—O6^xi	80.74 (7)	O4—BNA—T2^vii	31.98 (5)
O6^ix—M4—O6^xii	80.74 (7)	O4—BNA—T2	99.77 (5)
O6^ix—M4—O6^xi	89.17 (6)	O4^v—BNA—T2	80.23 (5)
O6^ix—M4—O6	166.93 (11)	O4^v—BNA—T2^vii	148.02 (5)
O8—M4—M2	43.77 (7)	O4—BNA—O4^v	180.00 (8)
O8^ix—M4—M2	43.76 (7)	O4^xv—BNA—O4^vii	180.00 (9)
O8^ix—M4—O6^xi	96.85 (8)	O4—BNA—O4^vii	117.73 (10)
O8—M4—O6^ix	85.61 (8)	O4^v—BNA—O4^xv	117.73 (10)
O8—M4—O6^xi	173.87 (8)	O4—BNA—O4^xv	62.27 (10)
O8^ix—M4—O6^xii	173.87 (8)	O4^v—BNA—O4^vii	62.27 (10)
O8—M4—O6	103.94 (8)	O4^vii—BNA—F^i	58.16 (5)
O8^ix—M4—O6^ix	103.94 (8)	O4^v—BNA—F^i	58.16 (5)
O8^ix—M4—O6	85.61 (8)	O4^xv—BNA—F	58.16 (5)
O8—M4—O6^xii	96.84 (8)	O4^v—BNA—F	121.84 (5)
O8—M4—O8^ix	87.53 (13)	O4^xv—BNA—F^i	121.84 (5)
M1—D—A	117.650 (12)	O4—BNA—F^i	121.84 (5)
M1—D—A^xiii	117.650 (12)	O4^vii—BNA—F	121.84 (5)
M1—D—BNA	96.458 (15)	O4—BNA—F	58.16 (5)
A^xiii—D—A	112.57 (2)	F—BNA—T2^vii	89.965 (14)
BNA^xiv—D—M1	161.84 (2)	F—BNA—T2	90.035 (14)
BNA—D—A	69.218 (11)	F^i—BNA—T2	89.965 (14)
BNA^xiv—D—A	69.755 (11)	F^i—BNA—T2^vii	90.035 (14)
BNA^xiv—D—A^xiii	69.755 (11)	F^i—BNA—F	180.0
BNA—D—A^xiii	69.218 (11)	M2—O1—M1	90.60 (9)
BNA^xiv—D—BNA	101.701 (18)	M2^iii—O1—M1	90.60 (9)
O1—D—M1	36.47 (10)	M2^iii—O1—M2	108.76 (13)
O1—D—A	123.656 (13)	D—O1—M1	115.76 (15)
O1—D—A^xiii	123.656 (13)	D—O1—M2^iii	121.33 (8)
O1—D—BNA^xiv	125.37 (10)	D—O1—M2	121.33 (8)
O1—D—BNA	132.93 (10)	M2^xvii—O2—M1^xvii	90.91 (7)
O1—D—O3^xiii	103.50 (10)	M3^xvii—O2—M1^xvii	95.85 (8)
O1—D—O3^viii	103.50 (10)	M3^xvii—O2—M2^xvii	95.34 (8)
O1—D—O4	106.35 (10)	T2—O2—M1^xvii	118.40 (10)
O1—D—O4^xv	106.35 (10)	T2—O2—M2^xvii	126.94 (11)
O1—D—F	176.80 (11)	T2—O2—M3^xvii	121.52 (11)
O3^viii—D—M1	126.92 (7)	D^xiii—O3—A	107.26 (9)
O3^xiii—D—M1	126.92 (7)	D^xiii—O3—BNA	100.21 (9)
O3^xiii—D—A	114.52 (7)	T2—O3—D^xiii	135.05 (14)
O3^xiii—D—A^xiii	44.22 (6)	T2—O3—A	110.16 (10)
O3^viii—D—A^xiii	114.52 (7)	T2—O3—BNA	94.00 (10)
O3^viii—D—A	44.22 (6)	BNA—O3—A	104.13 (8)
O3^viii—D—BNA^xiv	45.44 (7)	D—O4—A	105.76 (9)
O3^xiii—D—BNA	110.47 (7)	D—O4—BNA	99.97 (9)
O3^viii—D—BNA	110.47 (7)	T2^vii—O4—D	141.61 (15)
O3^xiii—D—BNA^xiv	45.44 (7)	T2^vii—O4—A	108.10 (11)
O3^xiii—D—O3^viii	85.73 (14)	T2^vii—O4—BNA	91.12 (10)
O3^viii—D—F	74.23 (7)	BNA—O4—A	100.64 (8)
O3^xiii—D—F	74.23 (7)	T1^viii—O5—T2	139.57 (14)
O4^xv—D—M1	79.80 (7)	T1^viii—O5—A^i	108.64 (10)
O4—D—M1	79.80 (7)	T1^viii—O5—A	105.26 (10)
O4^xv—D—A	115.42 (7)	T2—O5—A^i	95.83 (9)
O4—D—A^xiii	115.42 (7)	T2—O5—A	93.97 (9)
O4^xv—D—A^xiii	45.64 (7)	A^i—O5—A	112.18 (6)
O4—D—A	45.64 (7)	M4—O6—M3^xiv	89.11 (7)
O4^xv—D—BNA^xiv	112.99 (7)	M4^xi—O6—M3^xiv	101.20 (7)
O4—D—BNA^xiv	112.99 (7)	M4—O6—M4^xi	99.26 (7)
O4—D—BNA	46.48 (7)	T1—O6—M3^xiv	119.35 (10)
O4^xv—D—BNA	46.48 (7)	T1—O6—M4^xi	120.39 (10)
O4^xv—D—O3^xiii	86.82 (10)	T1—O6—M4	121.38 (10)
O4^xv—D—O3^viii	150.15 (10)	T1^xii—O7—T1	137.32 (14)
O4—D—O3^viii	86.82 (10)	T1—O7—A	101.30 (9)
O4—D—O3^xiii	150.15 (10)	T1^xii—O7—A	104.53 (9)
O4—D—O4^xv	85.43 (14)	T1—O7—A^xviii	99.87 (9)
O4—D—F	75.93 (7)	T1^xii—O7—A^xviii	97.88 (9)
O4^xv—D—F	75.93 (7)	A—O7—A^xviii	117.07 (6)
F—D—M1	146.73 (2)	M3—O8—M2	98.73 (9)
F—D—A	56.284 (12)	M3—O8—M4	102.08 (10)
F—D—A^xiii	56.284 (12)	M4—O8—M2	95.26 (9)
F—D—BNA^xiv	51.434 (14)	D^xiii—F—D	180.0
F—D—BNA	50.267 (13)	D^xiii—F—A^xiii	90.0
O5^viii—T1—O6	111.97 (11)	D—F—A	90.0
O5^viii—T1—O7	106.57 (12)	D—F—A^xiii	90.0
O5^viii—T1—O7^xvi	107.11 (12)	D^xiii—F—A	90.0
O6—T1—O7	110.94 (10)	D^xiii—F—BNA	89.030 (17)
O7^xvi—T1—O6	111.07 (10)	D^xiii—F—BNA^xiv	90.970 (17)
O7^xvi—T1—O7	109.00 (8)	D—F—BNA	90.970 (17)
M1^xvii—T2—A	147.79 (2)	D—F—BNA^xiv	89.030 (17)
M1^xvii—T2—A^i	120.31 (2)	A^xiii—F—A	180.0
A^i—T2—A	91.04 (2)	BNA—F—A	90.0
BNA—T2—M1^xvii	103.09 (2)	BNA^xiv—F—A^xiii	90.0
BNA—T2—A	75.87 (2)	BNA^xiv—F—A	90.0
BNA—T2—A^i	75.91 (2)	BNA—F—A^xiii	90.0
O2—T2—M1^xvii	37.57 (7)	BNA^xiv—F—BNA	180.0
O2—T2—A^i	131.39 (7)

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z; (iii) −x+2, −y+1, −z; (iv) x, −y+1, z−1; (v) −x+1, −y+1, −z+1; (vi) x, y, z−1; (vii) −x+1, y, −z+1; (viii) −x+2, y, −z+1; (ix) −x+2, y, −z; (x) −x+1, y, −z; (xi) −x+5/2, −y+1/2, −z; (xii) x−1/2, −y+1/2, z; (xiii) −x+2, −y+1, −z+1; (xiv) x+1, y, z; (xv) x, −y+1, z; (xvi) x+1/2, −y+1/2, z; (xvii) x, y, z+1; (xviii) −x+5/2, −y+1/2, −z+1.