Crystal structure refinements of tetragonal (OH,F)-rich spessartine and henritermierite garnets

Antao, S.M.; Cruickshank, L.A.

doi:10.1107/S2052520617018248

Crystal structure refinements of tetragonal (OH,F)-rich spessartine and henritermierite garnets

Cubic garnet (space group $Ia\overline 3 d$ ) has the general formula X₃Y₂Z₃O₁₂, where X, Y and Z are cation sites. In the tetragonal garnet (space group I4₁/acd), the corresponding cation sites are X1 and X2, Y, and Z1 and Z2. In both space groups only the Y site is the same. The crystal chemistry of a tetragonal (OH,F)-rich spessartine sample from Tongbei, near Yunxiao, Fujian Province, China, with composition ^X(Mn_2.82Fe $^{2+}_{0.14}$ Ca_0.04)_Σ3^Y{Al_1.95Fe $^{3+}_{0.05}$ }_Σ2^Z[(SiO₄)_2.61(O₄H₄)_0.28(F₄)_0.11]_Σ3 (Sps₉₄Alm₅Grs₁) was studied with single-crystal X-ray diffraction and space group I4₁/acd. The deviation of the unit-cell parameters from cubic symmetry is small [a = 11.64463 (1), c = 11.65481 (2) Å, c/a = 1.0009]. Point analyses and back-scattered electron images, obtained by electron-probe microanalysis, indicate a homogeneous composition. The Z2 site is fully occupied, but the Z1 site contains vacancies. The occupied Z1 and Z2 sites with Si atoms are surrounded by four O atoms, as in anhydrous cubic garnets. Pairs of split sites are O1 with F11 and O2 with O22. When the Z1 site is vacant, a larger [(O₂H₂)F₂] tetrahedron is formed by two OH and two F anions in the O22 and F11 sites, respectively. This [(O₂H₂)F₂] tetrahedron is similar to the O₄H₄ tetrahedron in hydrogarnets. These results indicate $^{X}{{\rm Mn}^ {2+}_{3}}\,$ $^{Y}{\rm Al}_{2}$ $^{Z}[({\rm SiO}_{4})_{2}({\rm O}_{2}{\rm H}_{2})_{0.5}({\rm F}_{2})_{0.5}]_{\Sigma3}$ as a possible end member, which is yet unknown. The H atom that is bonded to the O22 site is not located because of the small number of OH groups. In contrast, tetragonal henritermierite, ideally $^{X}{\rm Ca}_{3}\,^{Y}{\rm Mn}^{3+}_{2}\,$ $^{Z}[({\rm SiO}_{4})_{2}({\rm O}_{4}{\rm H}_{4})_1]_{\Sigma3}$ , has a vacant Z2 site that contains the O₄H₄ tetrahedron. The H atom is bonded to an O3 atom [O3—H3 = 0.73 (2) Å]. Because of O2—Mn³⁺—O2 Jahn–Teller elongation of the Mn³⁺O₆ octahedron, a weak hydrogen bond is formed to the under-bonded O2 atom. This causes a large deviation from cubic symmetry (c/a = 0.9534).

Keywords: (OH,F)-spessartine; henritermierite; garnets; ordering of anions; structure; chemistry; hydrogen bonding.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520617018248/ps5068sup1.cif Contains datablocks global, spessartine, henritermierite
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520617018248/ps5068spessartinesup2.hkl Contains datablock spessartine
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520617018248/ps5068henritermieritesup3.hkl Contains datablock henritermierite

CCDC references: 1812782; 1812783

Computing details top

For both structures, program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: ORTEP for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012).

(spessartine) top

Crystal data top

Al₁₆F_4.77Mn₂₄O_91.23Si_20.61	D_x = 4.076 Mg m⁻³
M_r = 3879.48	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4₁/acd	Cell parameters from 9698 reflections
Hall symbol: I 41/a c d	θ = 3.5–62.9°
a = 11.6446 (2) Å	µ = 5.43 mm⁻¹
c = 11.6548 (2) Å	T = 293 K
V = 1580.35 (5) Å³	Not given, orange
Z = 1	0.09 × 0.08 × 0.07 mm
F(000) = 1869

Data collection top

Bruker Nonius FR591 Rotating Anode diffractometer	R_int = 0.036
Graphite monochromator	θ_max = 62.8°, θ_min = 4.3°
50335 measured reflections	h = −29→23
3235 independent reflections	k = −26→27
2665 reflections with I > 2σ(I)	l = −29→29

Refinement top

Refinement on F²	0 constraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F² > 2σ(F²)] = 0.029	Secondary atom site location: difference Fourier map
wR(F²) = 0.077	w = 1/[σ²(F_o²) + (0.P)² + 1.0851P] where P = (F_o² + 2F_c²)/3
S = 1.23	(Δ/σ)_max = 0.001
3235 reflections	Δρ_max = 0.68 e Å⁻³
67 parameters	Δρ_min = −1.64 e Å⁻³
0 restraints

Special details top

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Al1	0	0	0	0.00458 (4)
Mn1	0.375435 (13)	0	0.25	0.00804 (3)
Mn2	0	0.25	0.125	0.00797 (3)
Si1	0.12554 (3)	0	0.25	0.00437 (4)	0.82
O1	0.29786 (12)	0.71431 (10)	0.09773 (11)	0.00639 (10)	0.85
O2	0.1523 (3)	0.53558 (17)	0.0471 (2)	0.00577 (15)	0.77
O3	0.45260 (4)	0.34800 (4)	0.03536 (4)	0.00711 (5)
Si2	0.5	0.25	0.125	0.00468 (5)	0.97
O22	0.1470 (9)	0.5206 (6)	0.0537 (8)	0.0073 (6)	0.23
F11	0.3069 (7)	0.7319 (6)	0.1058 (6)	0.0098 (7)	0.15

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Al1	0.00463 (10)	0.00434 (9)	0.00478 (7)	0.00025 (6)	0.00043 (6)	−0.00010 (6)
Mn1	0.00516 (4)	0.00952 (5)	0.00945 (4)	0	0	−0.00181 (3)
Mn2	0.00943 (4)	0.00943 (4)	0.00506 (4)	−0.00168 (4)	0	0
Si1	0.00363 (8)	0.00477 (9)	0.00471 (8)	0	0	−0.00007 (6)
O1	0.0073 (3)	0.0064 (3)	0.00550 (19)	−0.00109 (19)	−0.00008 (16)	−0.00088 (18)
O2	0.0054 (3)	0.0045 (4)	0.0074 (3)	−0.0012 (3)	0.0002 (2)	0.0013 (3)
O3	0.00809 (14)	0.00591 (12)	0.00733 (10)	−0.00025 (10)	−0.00071 (9)	0.00088 (9)
Si2	0.00495 (7)	0.00495 (7)	0.00414 (8)	0	0	0
O22	0.0067 (13)	0.0062 (17)	0.0090 (13)	−0.0001 (12)	−0.0013 (9)	0.0008 (11)
F11	0.0094 (15)	0.011 (2)	0.0091 (13)	−0.0018 (13)	−0.0004 (10)	−0.0019 (12)

Geometric parameters (Å, º) top

Al1—F11ⁱ	1.818 (8)	Si1—O2^ix	1.6326 (19)
Al1—F11ⁱⁱ	1.818 (8)	Si1—O2ⁱⁱ	1.6326 (19)
Al1—O22ⁱⁱⁱ	1.838 (10)	Si1—O1ⁱⁱ	1.6440 (9)
Al1—O22^iv	1.838 (10)	Si1—O1^ix	1.6440 (9)
Al1—O3^v	1.8993 (5)	Si1—O22^ix	1.815 (6)
Al1—O3^vi	1.8993 (5)	Si1—O22ⁱⁱ	1.815 (6)
Al1—O2^iv	1.902 (3)	Si1—F11ⁱⁱ	1.878 (5)
Al1—O2ⁱⁱⁱ	1.902 (3)	Si1—F11^ix	1.878 (5)
Al1—O1ⁱⁱ	1.9060 (12)	Si1—Mn1^xvi	2.9124 (4)
Al1—O1ⁱ	1.9060 (12)	O1—Si1^xvii	1.6440 (9)
Mn1—F11^vii	2.173 (9)	O1—Al1^xviii	1.9060 (12)
Mn1—F11^viii	2.173 (9)	O1—Mn1^xix	2.2562 (14)
Mn1—O22ⁱⁱ	2.174 (10)	O1—Mn2^xvii	2.4113 (13)
Mn1—O22^ix	2.174 (10)	O2—Si1^xvii	1.6326 (19)
Mn1—O1^vii	2.2562 (14)	O2—Al1^iv	1.902 (3)
Mn1—O1^viii	2.2562 (14)	O2—Mn1^xvii	2.260 (3)
Mn1—O2ⁱⁱ	2.260 (3)	O2—Mn1^x	2.423 (3)
Mn1—O2^ix	2.260 (3)	O3—Si2	1.6427 (4)
Mn1—O22^vi	2.315 (9)	O3—Al1^xx	1.8993 (5)
Mn1—O22^x	2.315 (9)	O3—Mn2^xxi	2.2583 (5)
Mn1—O3ⁱⁱ	2.4148 (5)	O3—Mn1^xvii	2.4148 (5)
Mn1—O3^ix	2.4148 (5)	Si2—O3^xvii	1.6427 (4)
Mn2—O3^v	2.2583 (5)	Si2—O3^xxii	1.6427 (4)
Mn2—O3^xi	2.2583 (5)	Si2—O3ⁱⁱ	1.6427 (4)
Mn2—O3^xii	2.2583 (5)	Si2—Mn2^x	2.9137
Mn2—O3^xiii	2.2583 (5)	Si2—Mn2^xxi	2.9137
Mn2—F11^xiv	2.269 (8)	O22—Si1^xvii	1.815 (6)
Mn2—F11^vi	2.269 (8)	O22—Al1^iv	1.838 (10)
Mn2—F11ⁱⁱ	2.269 (8)	O22—Mn1^xvii	2.174 (10)
Mn2—F11^xv	2.269 (8)	O22—Mn1^x	2.315 (9)
Mn2—O1^xv	2.4113 (13)	F11—Al1^xviii	1.818 (8)
Mn2—O1^xiv	2.4113 (13)	F11—Si1^xvii	1.878 (5)
Mn2—O1^vi	2.4113 (13)	F11—Mn1^xix	2.173 (9)
Mn2—O1ⁱⁱ	2.4113 (13)	F11—Mn2^xvii	2.269 (8)

F11ⁱ—Al1—F11ⁱⁱ	180.0 (5)	O3^xii—Mn2—F11^xv	96.53 (16)
F11ⁱ—Al1—O22ⁱⁱⁱ	80.8 (3)	O3^xiii—Mn2—F11^xv	66.64 (17)
F11ⁱⁱ—Al1—O22ⁱⁱⁱ	99.2 (3)	F11^xiv—Mn2—F11^xv	80.0 (4)
F11ⁱ—Al1—O22^iv	99.2 (3)	F11^vi—Mn2—F11^xv	168.7 (4)
F11ⁱⁱ—Al1—O22^iv	80.8 (3)	F11ⁱⁱ—Mn2—F11^xv	101.2 (3)
O22ⁱⁱⁱ—Al1—O22^iv	180.0 (6)	O3^v—Mn2—O1^xv	74.90 (3)
F11ⁱ—Al1—O3^v	96.1 (2)	O3^xi—Mn2—O1^xv	124.07 (3)
F11ⁱⁱ—Al1—O3^v	83.9 (2)	O3^xii—Mn2—O1^xv	92.43 (3)
O22ⁱⁱⁱ—Al1—O3^v	94.3 (3)	O3^xiii—Mn2—O1^xv	70.00 (3)
O22^iv—Al1—O3^v	85.7 (3)	F11^xiv—Mn2—O1^xv	75.61 (17)
F11ⁱ—Al1—O3^vi	83.9 (2)	F11^vi—Mn2—O1^xv	165.99 (19)
F11ⁱⁱ—Al1—O3^vi	96.1 (2)	F11ⁱⁱ—Mn2—O1^xv	105.93 (15)
O22ⁱⁱⁱ—Al1—O3^vi	85.7 (3)	F11^xv—Mn2—O1^xv	5.01 (17)
O22^iv—Al1—O3^vi	94.3 (3)	O3^v—Mn2—O1^xiv	124.07 (3)
O3^v—Al1—O3^vi	180.00 (3)	O3^xi—Mn2—O1^xiv	74.90 (3)
F11ⁱ—Al1—O2^iv	94.5 (3)	O3^xii—Mn2—O1^xiv	70.00 (3)
F11ⁱⁱ—Al1—O2^iv	85.5 (3)	O3^xiii—Mn2—O1^xiv	92.43 (3)
O22ⁱⁱⁱ—Al1—O2^iv	174.2 (2)	F11^xiv—Mn2—O1^xiv	5.01 (18)
O22^iv—Al1—O2^iv	5.8 (2)	F11^vi—Mn2—O1^xiv	105.93 (15)
O3^v—Al1—O2^iv	89.69 (8)	F11ⁱⁱ—Mn2—O1^xiv	165.99 (19)
O3^vi—Al1—O2^iv	90.31 (8)	F11^xv—Mn2—O1^xiv	75.61 (17)
F11ⁱ—Al1—O2ⁱⁱⁱ	85.5 (3)	O1^xv—Mn2—O1^xiv	71.39 (6)
F11ⁱⁱ—Al1—O2ⁱⁱⁱ	94.5 (3)	O3^v—Mn2—O1^vi	92.43 (3)
O22ⁱⁱⁱ—Al1—O2ⁱⁱⁱ	5.8 (2)	O3^xi—Mn2—O1^vi	70.00 (3)
O22^iv—Al1—O2ⁱⁱⁱ	174.2 (2)	O3^xii—Mn2—O1^vi	74.90 (3)
O3^v—Al1—O2ⁱⁱⁱ	90.31 (8)	O3^xiii—Mn2—O1^vi	124.07 (3)
O3^vi—Al1—O2ⁱⁱⁱ	89.69 (8)	F11^xiv—Mn2—O1^vi	105.93 (15)
O2^iv—Al1—O2ⁱⁱⁱ	180.0 (2)	F11^vi—Mn2—O1^vi	5.01 (17)
F11ⁱ—Al1—O1ⁱⁱ	172.82 (17)	F11ⁱⁱ—Mn2—O1^vi	75.61 (17)
F11ⁱⁱ—Al1—O1ⁱⁱ	7.18 (17)	F11^xv—Mn2—O1^vi	165.99 (19)
O22ⁱⁱⁱ—Al1—O1ⁱⁱ	94.4 (3)	O1^xv—Mn2—O1^vi	164.85 (6)
O22^iv—Al1—O1ⁱⁱ	85.6 (3)	O1^xiv—Mn2—O1^vi	110.73 (6)
O3^v—Al1—O1ⁱⁱ	89.59 (4)	O3^v—Mn2—O1ⁱⁱ	70.00 (3)
O3^vi—Al1—O1ⁱⁱ	90.41 (4)	O3^xi—Mn2—O1ⁱⁱ	92.43 (3)
O2^iv—Al1—O1ⁱⁱ	89.92 (8)	O3^xii—Mn2—O1ⁱⁱ	124.07 (3)
O2ⁱⁱⁱ—Al1—O1ⁱⁱ	90.08 (8)	O3^xiii—Mn2—O1ⁱⁱ	74.90 (3)
F11ⁱ—Al1—O1ⁱ	7.18 (17)	F11^xiv—Mn2—O1ⁱⁱ	165.99 (19)
F11ⁱⁱ—Al1—O1ⁱ	172.82 (17)	F11^vi—Mn2—O1ⁱⁱ	75.61 (17)
O22ⁱⁱⁱ—Al1—O1ⁱ	85.6 (3)	F11ⁱⁱ—Mn2—O1ⁱⁱ	5.01 (17)
O22^iv—Al1—O1ⁱ	94.4 (3)	F11^xv—Mn2—O1ⁱⁱ	105.93 (15)
O3^v—Al1—O1ⁱ	90.41 (4)	O1^xv—Mn2—O1ⁱⁱ	110.73 (6)
O3^vi—Al1—O1ⁱ	89.59 (4)	O1^xiv—Mn2—O1ⁱⁱ	164.85 (6)
O2^iv—Al1—O1ⁱ	90.08 (8)	O1^vi—Mn2—O1ⁱⁱ	71.39 (6)
O2ⁱⁱⁱ—Al1—O1ⁱ	89.92 (8)	O2^ix—Si1—O2ⁱⁱ	101.3 (2)
O1ⁱⁱ—Al1—O1ⁱ	180.00 (3)	O2^ix—Si1—O1ⁱⁱ	113.58 (11)
F11^vii—Mn1—F11^viii	80.3 (3)	O2ⁱⁱ—Si1—O1ⁱⁱ	114.01 (11)
F11^vii—Mn1—O22ⁱⁱ	158.5 (3)	O2^ix—Si1—O1^ix	114.01 (11)
F11^viii—Mn1—O22ⁱⁱ	105.4 (2)	O2ⁱⁱ—Si1—O1^ix	113.58 (11)
F11^vii—Mn1—O22^ix	105.4 (2)	O1ⁱⁱ—Si1—O1^ix	100.95 (10)
F11^viii—Mn1—O22^ix	158.5 (3)	O2^ix—Si1—O22^ix	2.8 (4)
O22ⁱⁱ—Mn1—O22^ix	77.0 (3)	O2ⁱⁱ—Si1—O22^ix	98.9 (2)
F11^vii—Mn1—O1^vii	6.08 (13)	O1ⁱⁱ—Si1—O22^ix	116.0 (3)
F11^viii—Mn1—O1^vii	74.31 (13)	O1^ix—Si1—O22^ix	114.1 (3)
O22ⁱⁱ—Mn1—O1^vii	158.3 (3)	O2^ix—Si1—O22ⁱⁱ	98.9 (2)
O22^ix—Mn1—O1^vii	111.44 (17)	O2ⁱⁱ—Si1—O22ⁱⁱ	2.8 (4)
F11^vii—Mn1—O1^viii	74.31 (13)	O1ⁱⁱ—Si1—O22ⁱⁱ	114.1 (3)
F11^viii—Mn1—O1^viii	6.08 (13)	O1^ix—Si1—O22ⁱⁱ	116.0 (3)
O22ⁱⁱ—Mn1—O1^viii	111.44 (17)	O22^ix—Si1—O22ⁱⁱ	96.5 (7)
O22^ix—Mn1—O1^viii	158.3 (3)	O2^ix—Si1—F11ⁱⁱ	113.4 (3)
O1^vii—Mn1—O1^viii	68.39 (5)	O2ⁱⁱ—Si1—F11ⁱⁱ	116.6 (3)
F11^vii—Mn1—O2ⁱⁱ	157.7 (2)	O1ⁱⁱ—Si1—F11ⁱⁱ	2.8 (3)
F11^viii—Mn1—O2ⁱⁱ	110.06 (14)	O1^ix—Si1—F11ⁱⁱ	98.7 (2)
O22ⁱⁱ—Mn1—O2ⁱⁱ	4.7 (2)	O22^ix—Si1—F11ⁱⁱ	115.9 (4)
O22^ix—Mn1—O2ⁱⁱ	72.45 (13)	O22ⁱⁱ—Si1—F11ⁱⁱ	116.8 (4)
O1^vii—Mn1—O2ⁱⁱ	158.88 (8)	O2^ix—Si1—F11^ix	116.6 (3)
O1^viii—Mn1—O2ⁱⁱ	116.06 (5)	O2ⁱⁱ—Si1—F11^ix	113.4 (3)
F11^vii—Mn1—O2^ix	110.06 (14)	O1ⁱⁱ—Si1—F11^ix	98.7 (2)
F11^viii—Mn1—O2^ix	157.7 (2)	O1^ix—Si1—F11^ix	2.8 (3)
O22ⁱⁱ—Mn1—O2^ix	72.45 (13)	O22^ix—Si1—F11^ix	116.8 (4)
O22^ix—Mn1—O2^ix	4.7 (2)	O22ⁱⁱ—Si1—F11^ix	115.9 (4)
O1^vii—Mn1—O2^ix	116.06 (5)	F11ⁱⁱ—Si1—F11^ix	96.4 (5)
O1^viii—Mn1—O2^ix	158.88 (8)	O2^ix—Si1—Mn1	50.66 (11)
O2ⁱⁱ—Mn1—O2^ix	67.91 (10)	O2ⁱⁱ—Si1—Mn1	50.66 (11)
F11^vii—Mn1—O22^vi	128.0 (3)	O1ⁱⁱ—Si1—Mn1	129.53 (5)
F11^viii—Mn1—O22^vi	63.7 (3)	O1^ix—Si1—Mn1	129.53 (5)
O22ⁱⁱ—Mn1—O22^vi	71.6 (4)	O22^ix—Si1—Mn1	48.2 (3)
O22^ix—Mn1—O22^vi	98.0 (2)	O22ⁱⁱ—Si1—Mn1	48.2 (3)
O1^vii—Mn1—O22^vi	124.5 (3)	F11ⁱⁱ—Si1—Mn1	131.8 (3)
O1^viii—Mn1—O22^vi	67.7 (2)	F11^ix—Si1—Mn1	131.8 (3)
O2ⁱⁱ—Mn1—O22^vi	73.7 (3)	O2^ix—Si1—Mn1^xvi	129.34 (11)
O2^ix—Mn1—O22^vi	95.4 (3)	O2ⁱⁱ—Si1—Mn1^xvi	129.34 (11)
F11^vii—Mn1—O22^x	63.7 (3)	O1ⁱⁱ—Si1—Mn1^xvi	50.47 (5)
F11^viii—Mn1—O22^x	128.0 (3)	O1^ix—Si1—Mn1^xvi	50.47 (5)
O22ⁱⁱ—Mn1—O22^x	98.0 (2)	O22^ix—Si1—Mn1^xvi	131.8 (3)
O22^ix—Mn1—O22^x	71.6 (4)	O22ⁱⁱ—Si1—Mn1^xvi	131.8 (3)
O1^vii—Mn1—O22^x	67.7 (2)	F11ⁱⁱ—Si1—Mn1^xvi	48.2 (3)
O1^viii—Mn1—O22^x	124.5 (3)	F11^ix—Si1—Mn1^xvi	48.2 (3)
O2ⁱⁱ—Mn1—O22^x	95.4 (3)	Mn1—Si1—Mn1^xvi	180
O2^ix—Mn1—O22^x	73.7 (3)	Si1^xvii—O1—Al1^xviii	133.22 (7)
O22^vi—Mn1—O22^x	167.1 (5)	Si1^xvii—O1—Mn1^xix	95.33 (6)
F11^vii—Mn1—O3ⁱⁱ	72.6 (2)	Al1^xviii—O1—Mn1^xix	102.56 (6)
F11^viii—Mn1—O3ⁱⁱ	95.9 (2)	Si1^xvii—O1—Mn2^xvii	122.14 (7)
O22ⁱⁱ—Mn1—O3ⁱⁱ	126.2 (2)	Al1^xviii—O1—Mn2^xvii	97.19 (4)
O22^ix—Mn1—O3ⁱⁱ	67.1 (2)	Mn1^xix—O1—Mn2^xvii	99.50 (4)
O1^vii—Mn1—O3ⁱⁱ	74.86 (4)	Si1^xvii—O2—Al1^iv	133.69 (14)
O1^viii—Mn1—O3ⁱⁱ	92.82 (4)	Si1^xvii—O2—Mn1^xvii	95.38 (14)
O2ⁱⁱ—Mn1—O3ⁱⁱ	123.81 (7)	Al1^iv—O2—Mn1^xvii	102.62 (11)
O2^ix—Mn1—O3ⁱⁱ	69.89 (7)	Si1^xvii—O2—Mn1^x	121.96 (15)
O22^vi—Mn1—O3ⁱⁱ	75.2 (2)	Al1^iv—O2—Mn1^x	96.88 (10)
O22^x—Mn1—O3ⁱⁱ	106.53 (18)	Mn1^xvii—O2—Mn1^x	99.33 (8)
F11^vii—Mn1—O3^ix	95.9 (2)	Si2—O3—Al1^xx	133.45 (3)
F11^viii—Mn1—O3^ix	72.6 (2)	Si2—O3—Mn2^xxi	95.35 (2)
O22ⁱⁱ—Mn1—O3^ix	67.1 (2)	Al1^xx—O3—Mn2^xxi	102.728 (19)
O22^ix—Mn1—O3^ix	126.2 (2)	Si2—O3—Mn1^xvii	121.72 (2)
O1^vii—Mn1—O3^ix	92.82 (4)	Al1^xx—O3—Mn1^xvii	97.326 (19)
O1^viii—Mn1—O3^ix	74.86 (4)	Mn2^xxi—O3—Mn1^xvii	99.339 (17)
O2ⁱⁱ—Mn1—O3^ix	69.89 (7)	O3^xvii—Si2—O3^xxii	113.859 (17)
O2^ix—Mn1—O3^ix	123.81 (7)	O3^xvii—Si2—O3	113.859 (17)
O22^vi—Mn1—O3^ix	106.53 (18)	O3^xxii—Si2—O3	101.01 (3)
O22^x—Mn1—O3^ix	75.2 (2)	O3^xvii—Si2—O3ⁱⁱ	101.01 (3)
O3ⁱⁱ—Mn1—O3^ix	165.28 (2)	O3^xxii—Si2—O3ⁱⁱ	113.859 (17)
O3^v—Mn2—O3^xi	158.74 (2)	O3—Si2—O3ⁱⁱ	113.859 (17)
O3^v—Mn2—O3^xii	68.30 (2)	O3^xvii—Si2—Mn2^x	50.506 (16)
O3^xi—Mn2—O3^xii	115.97 (2)	O3^xxii—Si2—Mn2^x	129.494 (16)
O3^v—Mn2—O3^xiii	115.97 (2)	O3—Si2—Mn2^x	129.494 (16)
O3^xi—Mn2—O3^xiii	68.30 (2)	O3ⁱⁱ—Si2—Mn2^x	50.506 (16)
O3^xii—Mn2—O3^xiii	158.74 (2)	O3^xvii—Si2—Mn2^xxi	129.494 (16)
O3^v—Mn2—F11^xiv	124.0 (2)	O3^xxii—Si2—Mn2^xxi	50.506 (16)
O3^xi—Mn2—F11^xiv	73.9 (2)	O3—Si2—Mn2^xxi	50.506 (16)
O3^xii—Mn2—F11^xiv	66.64 (17)	O3ⁱⁱ—Si2—Mn2^xxi	129.494 (16)
O3^xiii—Mn2—F11^xiv	96.53 (16)	Mn2^x—Si2—Mn2^xxi	180
O3^v—Mn2—F11^vi	96.53 (16)	Si1^xvii—O22—Al1^iv	125.8 (4)
O3^xi—Mn2—F11^vi	66.64 (17)	Si1^xvii—O22—Mn1^xvii	93.3 (5)
O3^xii—Mn2—F11^vi	73.9 (2)	Al1^iv—O22—Mn1^xvii	108.3 (4)
O3^xiii—Mn2—F11^vi	124.0 (2)	Si1^xvii—O22—Mn1^x	119.0 (5)
F11^xiv—Mn2—F11^vi	101.2 (3)	Al1^iv—O22—Mn1^x	102.6 (4)
O3^v—Mn2—F11ⁱⁱ	66.64 (17)	Mn1^xvii—O22—Mn1^x	105.4 (3)
O3^xi—Mn2—F11ⁱⁱ	96.53 (16)	Al1^xviii—F11—Si1^xvii	123.7 (4)
O3^xii—Mn2—F11ⁱⁱ	124.0 (2)	Al1^xviii—F11—Mn1^xix	108.9 (4)
O3^xiii—Mn2—F11ⁱⁱ	73.9 (2)	Si1^xvii—F11—Mn1^xix	91.6 (3)
F11^xiv—Mn2—F11ⁱⁱ	168.7 (4)	Al1^xviii—F11—Mn2^xvii	105.0 (3)
F11^vi—Mn2—F11ⁱⁱ	80.0 (4)	Si1^xvii—F11—Mn2^xvii	118.4 (4)
O3^v—Mn2—F11^xv	73.9 (2)	Mn1^xix—F11—Mn2^xvii	106.7 (3)
O3^xi—Mn2—F11^xv	124.0 (2)

Symmetry codes: (i) y−3/4, −x+1/4, z−1/4; (ii) −y+3/4, x−1/4, −z+1/4; (iii) x, y−1/2, −z; (iv) −x, −y+1/2, z; (v) x−1/2, −y+1/2, −z; (vi) −x+1/2, y−1/2, z; (vii) −y+5/4, x−1/4, z+1/4; (viii) −y+5/4, −x+1/4, −z+1/4; (ix) −y+3/4, −x+1/4, z+1/4; (x) −x+1/2, −y+1/2, −z+1/2; (xi) y−1/4, −x+3/4, z+1/4; (xii) −x+1/2, y, −z; (xiii) −y+1/4, x−1/4, z+1/4; (xiv) y−3/4, −x+3/4, −z+1/4; (xv) x−1/2, −y+1, z; (xvi) x−1/2, y, −z+1/2; (xvii) y+1/4, −x+3/4, −z+1/4; (xviii) −y+1/4, x+3/4, z+1/4; (xix) y+1/4, −x+5/4, z−1/4; (xx) x+1/2, −y+1/2, −z; (xxi) −y+3/4, x+1/4, z−1/4; (xxii) −x+1, −y+1/2, z.

(henritermierite) top

Crystal data top

H₃₂Al_0.48Ca₂₄Mn_15.52O₉₆Si_16.19	D_x = 3.441 Mg m⁻³
M_r = 3850.57	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4₁/acd	Cell parameters from 8993 reflections
Hall symbol: I 41/a c d	θ = 3.3–65.3°
a = 12.4908 (2) Å	µ = 4.63 mm⁻¹
c = 11.9092 (2) Å	T = 293 K
V = 1858.07 (5) Å³	Not given, orange
Z = 1	0.06 × 0.05 × 0.05 mm
F(000) = 1901

Data collection top

Bruker Nonius FR591 Rotating Anode diffractometer	R_int = 0.029
Graphite monochromator	θ_max = 40.0°, θ_min = 4.1°
17620 measured reflections	h = −20→22
1401 independent reflections	k = −17→22
1340 reflections with I > 2σ(I)	l = −21→21

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.020	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.043	H atoms treated by a mixture of independent and constrained refinement
S = 1.21	w = 1/[σ²(F_o²) + (0.0183P)² + 1.145P] where P = (F_o² + 2F_c²)/3
1401 reflections	(Δ/σ)_max = 0.001
52 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −1.36 e Å⁻³
0 constraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Mn1	0	0	0	0.00551 (4)	0.97
Al1	0	0	0	0.00551 (4)	0.03
Ca1	0.361703 (16)	0	0.25	0.00729 (4)
Ca2	0	0.25	0.125	0.00877 (5)
Si1	0.11588 (2)	0	0.25	0.00520 (5)
O1	0.29477 (4)	0.71843 (4)	0.09656 (4)	0.00759 (8)
O2	0.15993 (4)	0.55486 (4)	0.05376 (4)	0.00789 (8)
O3	0.44285 (4)	0.35989 (4)	0.02160 (5)	0.00923 (8)
Si2	0.5	0.25	0.125	0.012 (3)*	0.02
H3	0.4292 (16)	0.3520 (17)	0.0806 (19)	0.042 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.00596 (6)	0.00563 (6)	0.00495 (6)	0.00092 (4)	−0.00054 (4)	−0.00064 (3)
Al1	0.00596 (6)	0.00563 (6)	0.00495 (6)	0.00092 (4)	−0.00054 (4)	−0.00064 (3)
Ca1	0.00642 (7)	0.00744 (7)	0.00802 (7)	0	0	−0.00092 (5)
Ca2	0.00949 (6)	0.00949 (6)	0.00732 (9)	−0.00300 (7)	0	0
Si1	0.00475 (9)	0.00602 (10)	0.00482 (10)	0	0	−0.00037 (7)
O1	0.00975 (18)	0.00728 (17)	0.00576 (16)	−0.00094 (14)	0.00013 (14)	−0.00110 (13)
O2	0.00758 (17)	0.00845 (17)	0.00764 (17)	−0.00178 (14)	0.00077 (14)	0.00114 (14)
O3	0.01033 (19)	0.00817 (18)	0.00919 (17)	−0.00162 (15)	0.00259 (15)	−0.00098 (15)

Geometric parameters (Å, º) top

Mn1—O3ⁱ	1.9075 (5)	Ca2—O1ⁱⁱⁱ	2.6157 (5)
Mn1—O3ⁱⁱ	1.9075 (5)	Ca2—Si2^xix	2.9773
Mn1—O1ⁱⁱⁱ	1.9513 (5)	Ca2—Si2^xiii	2.9773
Mn1—O1^iv	1.9513 (5)	Si1—O2^xii	1.6297 (5)
Mn1—O2^v	2.2068 (5)	Si1—O2ⁱⁱⁱ	1.6297 (5)
Mn1—O2^vi	2.2068 (5)	Si1—O1ⁱⁱⁱ	1.6566 (5)
Mn1—Ca1^vii	3.4202	Si1—O1^xii	1.6566 (5)
Mn1—Ca1^viii	3.4202	Si1—Ca1^x	3.1749 (3)
Mn1—Ca1^ix	3.4421 (1)	O1—Si1^xxii	1.6566 (5)
Mn1—Ca1^x	3.4421 (1)	O1—Mn1^xxiii	1.9513 (5)
Mn1—Ca2	3.4594	O1—Al1^xxiii	1.9513 (5)
Mn1—Ca2^xi	3.4594	O1—Ca1^xxiv	2.4773 (5)
Ca1—O3ⁱⁱⁱ	2.4484 (6)	O1—Ca2^xxii	2.6157 (5)
Ca1—O3^xii	2.4484 (6)	O2—Si1^xxii	1.6297 (5)
Ca1—O2ⁱ	2.4504 (5)	O2—Mn1^vi	2.2068 (5)
Ca1—O2^xiii	2.4504 (5)	O2—Al1^vi	2.2068 (5)
Ca1—O2ⁱⁱⁱ	2.4504 (5)	O2—Ca1^xiii	2.4504 (5)
Ca1—O2^xii	2.4504 (5)	O2—Ca1^xxii	2.4504 (5)
Ca1—O1^xiv	2.4773 (5)	O3—Al1^xxv	1.9075 (5)
Ca1—O1^xv	2.4773 (5)	O3—Mn1^xxv	1.9075 (5)
Ca1—Si1	3.0705 (3)	O3—Si2	1.9773 (6)
Ca1—Si1^xvi	3.1749 (3)	O3—Ca2^xxvi	2.3328 (5)
Ca1—Mn1^xvii	3.4202	O3—Ca1^xxii	2.4484 (5)
Ca1—Al1^xvii	3.4202	O3—H3	0.73 (2)
Ca2—O3ⁱⁱ	2.3328 (5)	Si2—O3^xxii	1.9773 (6)
Ca2—O3^xviii	2.3328 (5)	Si2—O3^xxvii	1.9773 (6)
Ca2—O3^xix	2.3328 (5)	Si2—O3ⁱⁱⁱ	1.9773 (6)
Ca2—O3^xvii	2.3328 (5)	Si2—Ca2^xxvi	2.9773
Ca2—O1^xx	2.6157 (5)	Si2—Ca2^xiii	2.9773
Ca2—O1^xxi	2.6157 (5)	Si2—H3	1.64 (2)
Ca2—O1ⁱ	2.6157 (5)

O3ⁱ—Mn1—O3ⁱⁱ	180.00 (4)	Si1—Ca1—Al1^xvii	65.924 (3)
O3ⁱ—Mn1—O1ⁱⁱⁱ	93.50 (2)	Si1^xvi—Ca1—Al1^xvii	114.076 (3)
O3ⁱⁱ—Mn1—O1ⁱⁱⁱ	86.50 (2)	Mn1^xvii—Ca1—Al1^xvii	0
O3ⁱ—Mn1—O1^iv	86.50 (2)	O3ⁱⁱ—Ca2—O3^xviii	156.96 (3)
O3ⁱⁱ—Mn1—O1^iv	93.50 (2)	O3ⁱⁱ—Ca2—O3^xix	83.09 (3)
O1ⁱⁱⁱ—Mn1—O1^iv	180.000 (10)	O3^xviii—Ca2—O3^xix	101.54 (3)
O3ⁱ—Mn1—O2^v	89.16 (2)	O3ⁱⁱ—Ca2—O3^xvii	101.54 (3)
O3ⁱⁱ—Mn1—O2^v	90.84 (2)	O3^xviii—Ca2—O3^xvii	83.09 (3)
O1ⁱⁱⁱ—Mn1—O2^v	89.99 (2)	O3^xix—Ca2—O3^xvii	156.96 (3)
O1^iv—Mn1—O2^v	90.01 (2)	O3ⁱⁱ—Ca2—O1^xx	72.053 (17)
O3ⁱ—Mn1—O2^vi	90.84 (2)	O3^xviii—Ca2—O1^xx	128.862 (17)
O3ⁱⁱ—Mn1—O2^vi	89.16 (2)	O3^xix—Ca2—O1^xx	96.563 (17)
O1ⁱⁱⁱ—Mn1—O2^vi	90.01 (2)	O3^xvii—Ca2—O1^xx	64.303 (17)
O1^iv—Mn1—O2^vi	89.99 (2)	O3ⁱⁱ—Ca2—O1^xxi	128.862 (17)
O2^v—Mn1—O2^vi	180.00 (4)	O3^xviii—Ca2—O1^xxi	72.053 (17)
O3ⁱ—Mn1—Ca1^vii	44.278 (17)	O3^xix—Ca2—O1^xxi	64.303 (17)
O3ⁱⁱ—Mn1—Ca1^vii	135.722 (17)	O3^xvii—Ca2—O1^xxi	96.563 (17)
O1ⁱⁱⁱ—Mn1—Ca1^vii	86.125 (15)	O1^xx—Ca2—O1^xxi	73.82 (2)
O1^iv—Mn1—Ca1^vii	93.875 (15)	O3ⁱⁱ—Ca2—O1ⁱ	96.563 (17)
O2^v—Mn1—Ca1^vii	45.590 (14)	O3^xviii—Ca2—O1ⁱ	64.303 (17)
O2^vi—Mn1—Ca1^vii	134.410 (14)	O3^xix—Ca2—O1ⁱ	72.053 (17)
O3ⁱ—Mn1—Ca1^viii	135.722 (17)	O3^xvii—Ca2—O1ⁱ	128.862 (17)
O3ⁱⁱ—Mn1—Ca1^viii	44.278 (17)	O1^xx—Ca2—O1ⁱ	165.12 (2)
O1ⁱⁱⁱ—Mn1—Ca1^viii	93.875 (15)	O1^xxi—Ca2—O1ⁱ	108.19 (2)
O1^iv—Mn1—Ca1^viii	86.125 (15)	O3ⁱⁱ—Ca2—O1ⁱⁱⁱ	64.303 (17)
O2^v—Mn1—Ca1^viii	134.410 (14)	O3^xviii—Ca2—O1ⁱⁱⁱ	96.563 (17)
O2^vi—Mn1—Ca1^viii	45.590 (14)	O3^xix—Ca2—O1ⁱⁱⁱ	128.862 (17)
Ca1^vii—Mn1—Ca1^viii	180	O3^xvii—Ca2—O1ⁱⁱⁱ	72.053 (17)
O3ⁱ—Mn1—Ca1^ix	85.920 (17)	O1^xx—Ca2—O1ⁱⁱⁱ	108.19 (2)
O3ⁱⁱ—Mn1—Ca1^ix	94.080 (17)	O1^xxi—Ca2—O1ⁱⁱⁱ	165.12 (2)
O1ⁱⁱⁱ—Mn1—Ca1^ix	135.123 (15)	O1ⁱ—Ca2—O1ⁱⁱⁱ	73.82 (2)
O1^iv—Mn1—Ca1^ix	44.877 (15)	O3ⁱⁱ—Ca2—Si2^xix	41.545 (14)
O2^v—Mn1—Ca1^ix	45.152 (13)	O3^xviii—Ca2—Si2^xix	138.455 (14)
O2^vi—Mn1—Ca1^ix	134.848 (13)	O3^xix—Ca2—Si2^xix	41.545 (14)
Ca1^vii—Mn1—Ca1^ix	62.729 (3)	O3^xvii—Ca2—Si2^xix	138.455 (14)
Ca1^viii—Mn1—Ca1^ix	117.271 (3)	O1^xx—Ca2—Si2^xix	82.560 (11)
O3ⁱ—Mn1—Ca1^x	94.080 (17)	O1^xxi—Ca2—Si2^xix	97.440 (11)
O3ⁱⁱ—Mn1—Ca1^x	85.920 (17)	O1ⁱ—Ca2—Si2^xix	82.560 (11)
O1ⁱⁱⁱ—Mn1—Ca1^x	44.877 (15)	O1ⁱⁱⁱ—Ca2—Si2^xix	97.440 (11)
O1^iv—Mn1—Ca1^x	135.123 (15)	O3ⁱⁱ—Ca2—Si2^xiii	138.455 (14)
O2^v—Mn1—Ca1^x	134.848 (13)	O3^xviii—Ca2—Si2^xiii	41.545 (14)
O2^vi—Mn1—Ca1^x	45.152 (13)	O3^xix—Ca2—Si2^xiii	138.455 (14)
Ca1^vii—Mn1—Ca1^x	117.271 (3)	O3^xvii—Ca2—Si2^xiii	41.545 (14)
Ca1^viii—Mn1—Ca1^x	62.729 (3)	O1^xx—Ca2—Si2^xiii	97.440 (11)
Ca1^ix—Mn1—Ca1^x	180	O1^xxi—Ca2—Si2^xiii	82.560 (11)
O3ⁱ—Mn1—Ca2	140.366 (16)	O1ⁱ—Ca2—Si2^xiii	97.440 (11)
O3ⁱⁱ—Mn1—Ca2	39.634 (16)	O1ⁱⁱⁱ—Ca2—Si2^xiii	82.560 (11)
O1ⁱⁱⁱ—Mn1—Ca2	48.571 (15)	Si2^xix—Ca2—Si2^xiii	180
O1^iv—Mn1—Ca2	131.429 (15)	O3ⁱⁱ—Ca2—Mn1	31.439 (13)
O2^v—Mn1—Ca2	81.057 (13)	O3^xviii—Ca2—Mn1	126.748 (13)
O2^vi—Mn1—Ca2	98.943 (13)	O3^xix—Ca2—Mn1	102.067 (13)
Ca1^vii—Mn1—Ca2	111.607 (3)	O3^xvii—Ca2—Mn1	92.627 (14)
Ca1^viii—Mn1—Ca2	68.393 (3)	O1^xx—Ca2—Mn1	94.609 (11)
Ca1^ix—Mn1—Ca2	111.8520 (10)	O1^xxi—Ca2—Mn1	160.118 (11)
Ca1^x—Mn1—Ca2	68.1480 (10)	O1ⁱ—Ca2—Mn1	78.942 (11)
O3ⁱ—Mn1—Ca2^xi	39.634 (16)	O1ⁱⁱⁱ—Ca2—Mn1	34.009 (11)
O3ⁱⁱ—Mn1—Ca2^xi	140.366 (16)	Si2^xix—Ca2—Mn1	64.5120 (10)
O1ⁱⁱⁱ—Mn1—Ca2^xi	131.429 (15)	Si2^xiii—Ca2—Mn1	115.4880 (10)
O1^iv—Mn1—Ca2^xi	48.571 (15)	O2^xii—Si1—O2ⁱⁱⁱ	105.18 (4)
O2^v—Mn1—Ca2^xi	98.943 (13)	O2^xii—Si1—O1ⁱⁱⁱ	115.21 (3)
O2^vi—Mn1—Ca2^xi	81.057 (13)	O2ⁱⁱⁱ—Si1—O1ⁱⁱⁱ	110.28 (2)
Ca1^vii—Mn1—Ca2^xi	68.393 (3)	O2^xii—Si1—O1^xii	110.28 (2)
Ca1^viii—Mn1—Ca2^xi	111.607 (3)	O2ⁱⁱⁱ—Si1—O1^xii	115.21 (3)
Ca1^ix—Mn1—Ca2^xi	68.1480 (10)	O1ⁱⁱⁱ—Si1—O1^xii	101.05 (4)
Ca1^x—Mn1—Ca2^xi	111.8520 (10)	O2^xii—Si1—Ca1	52.59 (2)
Ca2—Mn1—Ca2^xi	180	O2ⁱⁱⁱ—Si1—Ca1	52.59 (2)
O3ⁱⁱⁱ—Ca1—O3^xii	163.33 (3)	O1ⁱⁱⁱ—Si1—Ca1	129.475 (19)
O3ⁱⁱⁱ—Ca1—O2ⁱ	68.937 (17)	O1^xii—Si1—Ca1	129.475 (19)
O3^xii—Ca1—O2ⁱ	113.038 (17)	O2^xii—Si1—Ca1^x	127.41 (2)
O3ⁱⁱⁱ—Ca1—O2^xiii	113.038 (17)	O2ⁱⁱⁱ—Si1—Ca1^x	127.41 (2)
O3^xii—Ca1—O2^xiii	68.937 (17)	O1ⁱⁱⁱ—Si1—Ca1^x	50.525 (19)
O2ⁱ—Ca1—O2^xiii	167.34 (2)	O1^xii—Si1—Ca1^x	50.525 (19)
O3ⁱⁱⁱ—Ca1—O2ⁱⁱⁱ	123.184 (18)	Ca1—Si1—Ca1^x	180
O3^xii—Ca1—O2ⁱⁱⁱ	72.469 (17)	Si1^xxii—O1—Mn1^xxiii	132.99 (3)
O2ⁱ—Ca1—O2ⁱⁱⁱ	77.619 (19)	Si1^xxii—O1—Al1^xxiii	132.99 (3)
O2^xiii—Ca1—O2ⁱⁱⁱ	91.558 (13)	Mn1^xxiii—O1—Al1^xxiii	0
O3ⁱⁱⁱ—Ca1—O2^xii	72.469 (17)	Si1^xxii—O1—Ca1^xxiv	98.40 (2)
O3^xii—Ca1—O2^xii	123.184 (18)	Mn1^xxiii—O1—Ca1^xxiv	101.36 (2)
O2ⁱ—Ca1—O2^xii	91.558 (13)	Al1^xxiii—O1—Ca1^xxiv	101.36 (2)
O2^xiii—Ca1—O2^xii	77.619 (19)	Si1^xxii—O1—Ca2^xxii	121.10 (3)
O2ⁱⁱⁱ—Ca1—O2^xii	63.78 (2)	Mn1^xxiii—O1—Ca2^xxii	97.420 (19)
O3ⁱⁱⁱ—Ca1—O1^xiv	72.696 (17)	Al1^xxiii—O1—Ca2^xxii	97.420 (19)
O3^xii—Ca1—O1^xiv	92.819 (18)	Ca1^xxiv—O1—Ca2^xxii	98.757 (17)
O2ⁱ—Ca1—O1^xiv	118.296 (17)	Si1^xxii—O2—Mn1^vi	134.39 (3)
O2^xiii—Ca1—O1^xiv	73.431 (16)	Si1^xxii—O2—Al1^vi	134.39 (3)
O2ⁱⁱⁱ—Ca1—O1^xiv	162.203 (17)	Mn1^vi—O2—Al1^vi	0
O2^xii—Ca1—O1^xiv	120.150 (16)	Si1^xxii—O2—Ca1^xiii	128.37 (3)
O3ⁱⁱⁱ—Ca1—O1^xv	92.819 (18)	Mn1^vi—O2—Ca1^xiii	95.167 (18)
O3^xii—Ca1—O1^xv	72.696 (17)	Al1^vi—O2—Ca1^xiii	95.167 (18)
O2ⁱ—Ca1—O1^xv	73.431 (16)	Si1^xxii—O2—Ca1^xxii	95.52 (2)
O2^xiii—Ca1—O1^xv	118.296 (17)	Mn1^vi—O2—Ca1^xxii	94.368 (19)
O2ⁱⁱⁱ—Ca1—O1^xv	120.150 (16)	Al1^vi—O2—Ca1^xxii	94.368 (19)
O2^xii—Ca1—O1^xv	162.203 (17)	Ca1^xiii—O2—Ca1^xxii	93.576 (17)
O1^xiv—Ca1—O1^xv	62.15 (2)	Al1^xxv—O3—Mn1^xxv	0
O3ⁱⁱⁱ—Ca1—Si1	98.333 (13)	Al1^xxv—O3—Si2	125.86 (3)
O3^xii—Ca1—Si1	98.333 (13)	Mn1^xxv—O3—Si2	125.86 (3)
O2ⁱ—Ca1—Si1	83.670 (12)	Al1^xxv—O3—Ca2^xxvi	108.93 (2)
O2^xiii—Ca1—Si1	83.670 (12)	Mn1^xxv—O3—Ca2^xxvi	108.93 (2)
O2ⁱⁱⁱ—Ca1—Si1	31.890 (12)	Si2—O3—Ca2^xxvi	86.97 (2)
O2^xii—Ca1—Si1	31.890 (12)	Al1^xxv—O3—Ca1^xxii	102.77 (2)
O1^xiv—Ca1—Si1	148.924 (12)	Mn1^xxv—O3—Ca1^xxii	102.77 (2)
O1^xv—Ca1—Si1	148.924 (12)	Si2—O3—Ca1^xxii	121.42 (2)
O3ⁱⁱⁱ—Ca1—Si1^xvi	81.667 (13)	Ca2^xxvi—O3—Ca1^xxii	107.92 (2)
O3^xii—Ca1—Si1^xvi	81.667 (13)	Al1^xxv—O3—H3	110.0 (16)
O2ⁱ—Ca1—Si1^xvi	96.330 (12)	Mn1^xxv—O3—H3	110.0 (16)
O2^xiii—Ca1—Si1^xvi	96.330 (12)	Si2—O3—H3	52.4 (16)
O2ⁱⁱⁱ—Ca1—Si1^xvi	148.110 (12)	Ca2^xxvi—O3—H3	135.4 (16)
O2^xii—Ca1—Si1^xvi	148.110 (12)	Ca1^xxii—O3—H3	83.8 (16)
O1^xiv—Ca1—Si1^xvi	31.076 (12)	O3^xxii—Si2—O3^xxvii	112.817 (16)
O1^xv—Ca1—Si1^xvi	31.076 (12)	O3^xxii—Si2—O3ⁱⁱⁱ	102.97 (3)
Si1—Ca1—Si1^xvi	180	O3^xxvii—Si2—O3ⁱⁱⁱ	112.817 (16)
O3ⁱⁱⁱ—Ca1—Mn1^xvii	163.212 (14)	O3^xxii—Si2—O3	112.817 (16)
O3^xii—Ca1—Mn1^xvii	32.951 (13)	O3^xxvii—Si2—O3	102.97 (3)
O2ⁱ—Ca1—Mn1^xvii	102.143 (12)	O3ⁱⁱⁱ—Si2—O3	112.817 (16)
O2^xiii—Ca1—Mn1^xvii	72.524 (12)	O3^xxii—Si2—Ca2^xxvi	128.516 (16)
O2ⁱⁱⁱ—Ca1—Mn1^xvii	40.042 (12)	O3^xxvii—Si2—Ca2^xxvi	51.484 (15)
O2^xii—Ca1—Mn1^xvii	94.177 (13)	O3ⁱⁱⁱ—Si2—Ca2^xxvi	128.516 (15)
O1^xiv—Ca1—Mn1^xvii	123.745 (12)	O3—Si2—Ca2^xxvi	51.484 (15)
O1^xv—Ca1—Mn1^xvii	98.239 (12)	O3^xxii—Si2—Ca2^xiii	51.484 (16)
Si1—Ca1—Mn1^xvii	65.924 (3)	O3^xxvii—Si2—Ca2^xiii	128.516 (15)
Si1^xvi—Ca1—Mn1^xvii	114.076 (3)	O3ⁱⁱⁱ—Si2—Ca2^xiii	51.484 (15)
O3ⁱⁱⁱ—Ca1—Al1^xvii	163.212 (14)	O3—Si2—Ca2^xiii	128.516 (15)
O3^xii—Ca1—Al1^xvii	32.951 (13)	Ca2^xxvi—Si2—Ca2^xiii	180
O2ⁱ—Ca1—Al1^xvii	102.143 (12)	O3^xxii—Si2—H3	107.2 (7)
O2^xiii—Ca1—Al1^xvii	72.524 (12)	O3^xxvii—Si2—H3	122.2 (8)
O2ⁱⁱⁱ—Ca1—Al1^xvii	40.042 (12)	O3ⁱⁱⁱ—Si2—H3	96.2 (7)
O2^xii—Ca1—Al1^xvii	94.177 (13)	O3—Si2—H3	20.7 (8)
O1^xiv—Ca1—Al1^xvii	123.745 (12)	Ca2^xxvi—Si2—H3	71.2 (8)
O1^xv—Ca1—Al1^xvii	98.239 (12)	Ca2^xiii—Si2—H3	108.8 (8)

Symmetry codes: (i) −x+1/2, y−1/2, z; (ii) x−1/2, −y+1/2, −z; (iii) −y+3/4, x−1/4, −z+1/4; (iv) y−3/4, −x+1/4, z−1/4; (v) x, y−1/2, −z; (vi) −x, −y+1/2, z; (vii) y+1/4, −x+1/4, z−1/4; (viii) −y−1/4, x−1/4, −z+1/4; (ix) −x+1/2, −y, z−1/2; (x) x−1/2, y, −z+1/2; (xi) −x, −y, −z; (xii) −y+3/4, −x+1/4, z+1/4; (xiii) −x+1/2, −y+1/2, −z+1/2; (xiv) −y+5/4, x−1/4, z+1/4; (xv) −y+5/4, −x+1/4, −z+1/4; (xvi) x+1/2, y, −z+1/2; (xvii) −y+1/4, x−1/4, z+1/4; (xviii) y−1/4, −x+3/4, z+1/4; (xix) −x+1/2, y, −z; (xx) x−1/2, −y+1, z; (xxi) y−3/4, −x+3/4, −z+1/4; (xxii) y+1/4, −x+3/4, −z+1/4; (xxiii) −y+1/4, x+3/4, z+1/4; (xxiv) y+1/4, −x+5/4, z−1/4; (xxv) x+1/2, −y+1/2, −z; (xxvi) −y+3/4, x+1/4, z−1/4; (xxvii) −x+1, −y+1/2, z.

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