New data on the crystal chemistry of the natural two-layer aluminosilicates latiumite and tuscanite

The crystal chemistry of the natural microporous two-layer aluminosilicates (2D zeolites) latiumite and tuscanite is re-investigated based on new data on the chemical composition, crystal structures, and infrared and Raman spectra. The CO₃²⁻-depleted and P- and H-enriched samples from Sacrofano paleovolcano, Lazio, Italy, are studied. Both minerals are monoclinic; latiumite P2₁, a = 12.0206 (3), b = 5.09502 (10), c = 10.8527 (3) Å, β = 107.010 (3)°, V = 635.60 (3) ų and tuscanite P2₁/a, a = 23.9846 (9), b = 5.09694 (15), c = 10.8504 (4) Å, β = 107.032 (4)°, V = 1268.26 (8) ų. The obtained crystal chemical formulae (Z = 2 for both minerals) are [(H₃O)_0.48(H₂O)_0.24K_0.28](Ca_2.48K_0.21Na_0.21Sr_0.06Mg_0.04)(Si_2.86Al_2.14O₁₁)[(SO₄)_0.70(PO₄)_0.20](CO₃)_0.10 for latiumite and [(H₃O)_0.96(H₂O)_0.58K_0.46](Ca_4.94K_0.44Na_0.45Sr_0.09Mg_0.08)(Si_5.80Al_4.20O₂₂)[(SO₄)_1.53(PO₄)_0.33](CO₃)_0.14 for tuscanite. These minerals are dimorphous. Both latiumite and tuscanite show distinct affinity for the PO₄³⁻ anion. Hydrolytic alteration of these minerals results in partial leaching of potassium accompanied by protonation and hydration which is an important precondition for the existence of ion/proton conductivity of related materials.

Computing details

For both structures, program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2018).

(latiumite)

Crystal data

Al2.14Ca2.48K0.49S0.70Si2.86Sr0.06Mg0.04Na0.21O15.62P0.20C0.10H1.92	F(000) = 547
Mr = 549.38	Dx = 2.871 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 12.0206 (3) Å	Cell parameters from 3930 reflections
b = 5.09502 (10) Å	θ = 3.0–30.8°
c = 10.8527 (3) Å	µ = 2.16 mm^−1
β = 107.010 (3)°	T = 293 K
V = 635.60 (3) Å^3	Irregular, colorless
Z = 2	0.62 × 0.53 × 0.39 mm

Data collection

Xcalibur, Sapphire3 diffractometer	3100 independent reflections
Radiation source: fine-focus sealed X-ray tube	3067 reflections with I > 2σ(I)
Detector resolution: 16.0630 pixels mm^-1	Rint = 0.016
ω scans	θmax = 28.3°, θmin = 3.0°
Absorption correction: multi-scan	h = −12→16
Tmin = 0.839, Tmax = 1.000	k = −6→6
5280 measured reflections	l = −14→13

Refinement

Refinement on F^2	w = 1/[σ^2(Fo^2) + (0.0285P)^2 + 0.1524P] where P = (Fo^2 + 2Fc^2)/3
Least-squares matrix: full	(Δ/σ)max < 0.001
R[F^2 > 2σ(F^2)] = 0.019	Δρmax = 0.35 e Å^−3
wR(F^2) = 0.051	Δρmin = −0.28 e Å^−3
S = 1.06	Extinction correction: SHELXL-2018/3 (Sheldrick 2018), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
3100 reflections	Extinction coefficient: 0.064 (3)
233 parameters	Absolute structure: Refined as an inversion twin.
1 restraint	Absolute structure parameter: 0.10 (3)
H-atom parameters not defined

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.

Refinement. Refined as a 2-component inversion twin.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ca1	0.88319 (5)	0.25629 (14)	0.18942 (5)	0.0128 (2)	0.845 (8)
Sr1	0.88319 (5)	0.25629 (14)	0.18942 (5)	0.0128 (2)	0.06
Na1	0.88319 (5)	0.25629 (14)	0.18942 (5)	0.0128 (2)	0.095 (8)
Ca2	0.20735 (5)	0.25348 (16)	0.14632 (6)	0.0151 (2)	0.858 (8)
Na2	0.20735 (5)	0.25348 (16)	0.14632 (6)	0.0151 (2)	0.142 (8)
Ca3	0.11637 (5)	0.73936 (13)	0.45442 (5)	0.0106 (2)	0.990 (8)
Na3	0.11637 (5)	0.73936 (13)	0.45442 (5)	0.0106 (2)	0.010 (8)
S	0.03784 (6)	0.78031 (17)	0.13977 (7)	0.0101 (2)	0.897 (4)
Si1	0.37785 (6)	0.74005 (17)	0.07191 (6)	0.00635 (15)
Al1	0.38395 (6)	0.7512 (2)	0.35208 (7)	0.00635 (16)
Si2	0.34317 (6)	0.25169 (18)	0.47810 (6)	0.00787 (16)
Al2	0.65164 (6)	0.73990 (19)	0.08298 (7)	0.00665 (17)
Si6	0.82453 (7)	0.70703 (15)	0.35529 (7)	0.00749 (18)
K	0.57420 (11)	0.2526 (3)	0.27401 (12)	0.0175 (5)	0.281 (6)
OH3	0.57420 (11)	0.2526 (3)	0.27401 (12)	0.0175 (5)	0.719 (6)
O1	0.68992 (18)	0.0615 (4)	0.05198 (19)	0.0116 (4)
O2	0.51542 (17)	0.7197 (5)	0.1011 (2)	0.0161 (5)
O3	0.33617 (18)	0.0455 (4)	0.04667 (19)	0.0105 (4)
O4	0.34053 (18)	0.6273 (4)	0.19484 (19)	0.0109 (4)
O5	0.33846 (19)	0.0791 (4)	0.3480 (2)	0.0135 (4)
O6	0.53195 (18)	0.7235 (6)	0.4144 (2)	0.0183 (5)
O7	0.30773 (18)	0.5594 (4)	0.4360 (2)	0.0128 (4)
O8	0.24122 (18)	0.1241 (4)	0.5351 (2)	0.0122 (4)
O9	0.94012 (18)	0.5317 (4)	0.3956 (2)	0.0119 (4)
O10	0.8388 (2)	0.0168 (5)	0.3519 (2)	0.0188 (5)
O11	0.74747 (18)	0.5928 (4)	0.2169 (2)	0.0117 (4)
O12	0.9117 (2)	0.8138 (6)	0.0802 (2)	0.0250 (6)
O13	0.1048 (2)	0.8275 (5)	0.0478 (2)	0.0178 (6)	0.897 (4)
O14	0.0642 (2)	0.5178 (5)	0.1995 (2)	0.0187 (5)
O15	0.0728 (2)	0.9810 (5)	0.2448 (2)	0.0199 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca1	0.0114 (3)	0.0122 (3)	0.0151 (3)	−0.0002 (3)	0.0044 (2)	−0.0010 (3)
Sr1	0.0114 (3)	0.0122 (3)	0.0151 (3)	−0.0002 (3)	0.0044 (2)	−0.0010 (3)
Na1	0.0114 (3)	0.0122 (3)	0.0151 (3)	−0.0002 (3)	0.0044 (2)	−0.0010 (3)
Ca2	0.0128 (3)	0.0170 (4)	0.0161 (4)	0.0015 (3)	0.0051 (2)	−0.0023 (3)
Na2	0.0128 (3)	0.0170 (4)	0.0161 (4)	0.0015 (3)	0.0051 (2)	−0.0023 (3)
Ca3	0.0092 (3)	0.0096 (3)	0.0126 (3)	−0.0023 (3)	0.0026 (2)	−0.0003 (3)
Na3	0.0092 (3)	0.0096 (3)	0.0126 (3)	−0.0023 (3)	0.0026 (2)	−0.0003 (3)
S	0.0080 (4)	0.0103 (4)	0.0121 (4)	0.0010 (3)	0.0031 (3)	0.0018 (3)
Si1	0.0065 (3)	0.0063 (3)	0.0065 (3)	0.0001 (3)	0.0024 (2)	0.0000 (3)
Al1	0.0063 (3)	0.0060 (4)	0.0066 (3)	−0.0001 (4)	0.0017 (3)	−0.0002 (4)
Si2	0.0077 (3)	0.0076 (3)	0.0085 (3)	−0.0007 (3)	0.0026 (2)	0.0002 (4)
Al2	0.0065 (3)	0.0059 (4)	0.0074 (4)	−0.0002 (4)	0.0018 (3)	0.0002 (4)
Si6	0.0080 (3)	0.0073 (4)	0.0069 (3)	−0.0008 (3)	0.0017 (3)	0.0000 (3)
K	0.0236 (8)	0.0128 (7)	0.0180 (7)	−0.0023 (7)	0.0092 (5)	0.0013 (7)
OH3	0.0236 (8)	0.0128 (7)	0.0180 (7)	−0.0023 (7)	0.0092 (5)	0.0013 (7)
O1	0.0136 (10)	0.0084 (10)	0.0109 (10)	−0.0013 (8)	0.0008 (8)	0.0020 (8)
O2	0.0082 (9)	0.0221 (12)	0.0188 (10)	0.0025 (9)	0.0053 (8)	0.0024 (10)
O3	0.0145 (10)	0.0079 (9)	0.0103 (9)	0.0023 (8)	0.0057 (8)	0.0013 (8)
O4	0.0129 (10)	0.0110 (10)	0.0090 (9)	−0.0002 (8)	0.0033 (8)	0.0017 (8)
O5	0.0149 (10)	0.0114 (11)	0.0142 (10)	0.0032 (8)	0.0043 (8)	0.0012 (8)
O6	0.0128 (10)	0.0241 (12)	0.0162 (10)	0.0019 (10)	0.0014 (8)	−0.0022 (11)
O7	0.0133 (10)	0.0105 (10)	0.0160 (10)	0.0015 (8)	0.0063 (8)	0.0026 (8)
O8	0.0130 (10)	0.0137 (10)	0.0113 (10)	−0.0033 (9)	0.0059 (8)	−0.0033 (9)
O9	0.0070 (9)	0.0132 (10)	0.0151 (10)	−0.0012 (8)	0.0026 (8)	−0.0005 (9)
O10	0.0345 (14)	0.0082 (11)	0.0145 (11)	−0.0060 (10)	0.0083 (10)	−0.0013 (9)
O11	0.0119 (10)	0.0116 (11)	0.0085 (9)	0.0007 (8)	−0.0018 (8)	−0.0006 (8)
O12	0.0128 (11)	0.0350 (16)	0.0253 (12)	0.0041 (10)	0.0026 (9)	−0.0045 (11)
O13	0.0150 (12)	0.0221 (14)	0.0194 (12)	0.0005 (10)	0.0101 (10)	0.0062 (11)
O14	0.0206 (12)	0.0137 (11)	0.0257 (13)	0.0021 (9)	0.0130 (10)	0.0027 (10)
O15	0.0249 (13)	0.0143 (11)	0.0189 (12)	0.0003 (10)	0.0041 (10)	−0.0005 (10)

Geometric parameters (Å, º)

Ca1—O10	2.331 (2)	Si1—O1^ix	1.630 (2)
Ca1—O11	2.444 (2)	Si1—O4	1.631 (2)
Ca1—O14^i	2.526 (3)	Si1—O3^vii	1.633 (2)
Ca1—O9	2.559 (2)	Si1—K	3.6769 (17)
Ca1—O1	2.565 (2)	Si1—K^vii	3.7647 (16)
Ca1—O15^ii	2.592 (3)	Al1—O6	1.714 (2)
Ca1—O12^iii	2.616 (3)	Al1—O4	1.750 (2)
Ca1—O13^iv	2.645 (2)	Al1—O5^vii	1.754 (2)
Ca1—Si6	3.1232 (10)	Al1—O7	1.764 (2)
Ca1—S^ii	3.1959 (10)	Al1—K	3.6789 (17)
Ca1—S^i	3.3854 (10)	Al1—K^vii	3.6889 (17)
Ca1—Si6^iii	3.5088 (10)	Al1—K^vi	3.9403 (14)
Ca2—O3	2.381 (2)	Si2—O6^viii	1.615 (2)
Ca2—O14	2.385 (3)	Si2—O5	1.650 (2)
Ca2—O4	2.444 (2)	Si2—O7	1.654 (2)
Ca2—O5	2.459 (2)	Si2—O8	1.658 (2)
Ca2—O12^iv	2.475 (3)	Si2—K^viii	3.6230 (17)
Ca2—O13^iii	2.570 (3)	Si2—K^vi	3.6297 (17)
Ca2—O15^iii	2.589 (3)	Al2—O2	1.708 (2)
Ca2—S^iii	3.1439 (11)	Al2—O11	1.738 (2)
Ca2—S	3.3582 (11)	Al2—O1^vii	1.761 (2)
Ca2—Al2^iv	3.3968 (9)	Al2—O3^ix	1.762 (2)
Ca2—Si1	3.4593 (10)	Al2—K	3.5295 (17)
Ca2—Si2	3.4916 (9)	Al2—K^vii	3.6219 (17)
Ca3—O9^v	2.286 (2)	Si6—O10^vii	1.589 (2)
Ca3—O10^vi	2.309 (2)	Si6—O9	1.601 (2)
Ca3—O9^vi	2.445 (2)	Si6—O11	1.624 (2)
Ca3—O8^vii	2.468 (2)	Si6—O8^vi	1.664 (2)
Ca3—O15	2.503 (2)	Si6—K	3.6932 (16)
Ca3—O7	2.538 (2)	K—O11	2.912 (3)
Ca3—O14	2.882 (2)	K—O6	2.965 (3)
Ca3—Si6^vi	3.0966 (10)	K—O2	2.984 (3)
Ca3—S	3.2725 (9)	K—O8^vi	3.179 (3)
Ca3—Si6^viii	3.3567 (10)	K—O7^viii	3.205 (3)
Ca3—Si6^v	3.3591 (9)	K—O6^iii	3.209 (3)
Ca3—Al1	3.6976 (9)	K—O2^iii	3.259 (3)
S—O13	1.474 (2)	K—O1	3.264 (3)
S—O12^v	1.474 (2)	K—O10	3.272 (3)
S—O14	1.480 (3)	K—O5	3.284 (3)
S—O15	1.497 (3)	K—O4	3.295 (3)
Si1—O2	1.594 (2)	K—O3	3.355 (2)
O10—Ca1—O11	88.06 (8)	O6—Al1—Ca2^vii	130.64 (10)
O10—Ca1—O14^i	128.91 (8)	O4—Al1—Ca2^vii	72.64 (8)
O11—Ca1—O14^i	102.82 (8)	O5^vii—Al1—Ca2^vii	36.30 (7)
O10—Ca1—O9	71.78 (7)	O7—Al1—Ca2^vii	114.09 (8)
O11—Ca1—O9	61.70 (7)	Ca2—Al1—Ca2^vii	89.01 (2)
O14^i—Ca1—O9	70.50 (7)	O6—Al1—K	52.47 (9)
O10—Ca1—O1	82.46 (8)	O4—Al1—K	63.54 (8)
O11—Ca1—O1	79.58 (7)	O5^vii—Al1—K	149.53 (8)
O14^i—Ca1—O1	148.36 (7)	O7—Al1—K	100.84 (8)
O9—Ca1—O1	133.29 (7)	Ca2—Al1—K	70.53 (3)
O10—Ca1—O15^ii	85.49 (9)	Ca2^vii—Al1—K	129.35 (3)
O11—Ca1—O15^ii	157.52 (8)	O6—Al1—K^vii	60.41 (10)
O14^i—Ca1—O15^ii	65.66 (8)	O4—Al1—K^vii	93.10 (8)
O9—Ca1—O15^ii	95.84 (7)	O5^vii—Al1—K^vii	62.89 (8)
O1—Ca1—O15^ii	120.71 (8)	O7—Al1—K^vii	162.31 (8)
O10—Ca1—O12^iii	88.92 (9)	Ca2—Al1—K^vii	129.30 (3)
O11—Ca1—O12^iii	147.18 (7)	Ca2^vii—Al1—K^vii	70.24 (3)
O14^i—Ca1—O12^iii	104.41 (8)	K—Al1—K^vii	87.50 (3)
O9—Ca1—O12^iii	146.30 (8)	O6—Al1—Ca3	140.67 (8)
O1—Ca1—O12^iii	67.63 (7)	O4—Al1—Ca3	104.45 (7)
O15^ii—Ca1—O12^iii	54.27 (7)	O5^vii—Al1—Ca3	74.40 (8)
O10—Ca1—O13^iv	153.88 (9)	O7—Al1—Ca3	37.54 (7)
O11—Ca1—O13^iv	104.53 (8)	Ca2—Al1—Ca3	76.68 (2)
O14^i—Ca1—O13^iv	71.23 (8)	Ca2^vii—Al1—Ca3	78.08 (2)
O9—Ca1—O13^iv	134.34 (8)	K—Al1—Ca3	135.38 (4)
O1—Ca1—O13^iv	77.60 (7)	K^vii—Al1—Ca3	137.09 (4)
O15^ii—Ca1—O13^iv	90.32 (8)	O6—Al1—K^vi	77.78 (7)
O12^iii—Ca1—O13^iv	68.01 (8)	O4—Al1—K^vi	156.46 (8)
O10—Ca1—Si6	78.97 (6)	O5^vii—Al1—K^vi	88.24 (8)
O11—Ca1—Si6	30.97 (5)	O7—Al1—K^vi	53.02 (8)
O14^i—Ca1—Si6	85.64 (6)	Ca2—Al1—K^vi	120.72 (3)
O9—Ca1—Si6	30.74 (5)	Ca2^vii—Al1—K^vi	120.40 (3)
O1—Ca1—Si6	107.51 (5)	K—Al1—K^vi	109.74 (4)
O15^ii—Ca1—Si6	126.55 (6)	K^vii—Al1—K^vi	109.53 (4)
O12^iii—Ca1—Si6	167.56 (6)	Ca3—Al1—K^vi	63.32 (2)
O13^iv—Ca1—Si6	123.08 (6)	O6^viii—Si2—O5	111.25 (12)
O10—Ca1—S^ii	90.20 (7)	O6^viii—Si2—O7	113.17 (14)
O11—Ca1—S^ii	174.13 (6)	O5—Si2—O7	109.10 (11)
O14^i—Ca1—S^ii	82.61 (6)	O6^viii—Si2—O8	109.15 (12)
O9—Ca1—S^ii	122.93 (5)	O5—Si2—O8	105.42 (12)
O1—Ca1—S^ii	94.64 (5)	O7—Si2—O8	108.43 (11)
O15^ii—Ca1—S^ii	27.54 (6)	O6^viii—Si2—Ca2	143.14 (8)
O12^iii—Ca1—S^ii	27.11 (5)	O5—Si2—Ca2	39.68 (8)
O13^iv—Ca1—S^ii	74.93 (6)	O7—Si2—Ca2	73.00 (8)
Si6—Ca1—S^ii	153.60 (3)	O8—Si2—Ca2	102.23 (8)
O10—Ca1—S^i	142.28 (6)	O6^viii—Si2—K^viii	53.60 (10)
O11—Ca1—S^i	83.31 (6)	O5—Si2—K^viii	101.22 (9)
O14^i—Ca1—S^i	23.77 (6)	O7—Si2—K^viii	149.67 (9)
O9—Ca1—S^i	71.81 (5)	O8—Si2—K^viii	61.31 (8)
O1—Ca1—S^i	131.20 (5)	Ca2—Si2—K^viii	135.36 (4)
O15^ii—Ca1—S^i	88.70 (6)	O6^viii—Si2—K^vi	62.12 (10)
O12^iii—Ca1—S^i	117.18 (6)	O5—Si2—K^vi	160.44 (9)
O13^iv—Ca1—S^i	63.13 (6)	O7—Si2—K^vi	62.01 (8)
Si6—Ca1—S^i	74.87 (2)	O8—Si2—K^vi	94.09 (8)
S^ii—Ca1—S^i	101.42 (2)	Ca2—Si2—K^vi	134.95 (4)
O10—Ca1—Si6^iii	21.51 (6)	K^viii—Si2—K^vi	89.26 (3)
O11—Ca1—Si6^iii	104.80 (6)	O2—Al2—O11	107.50 (11)
O14^i—Ca1—Si6^iii	134.28 (6)	O2—Al2—O1^vii	113.02 (12)
O9—Ca1—Si6^iii	91.80 (5)	O11—Al2—O1^vii	114.50 (10)
O1—Ca1—Si6^iii	72.90 (5)	O2—Al2—O3^ix	111.38 (11)
O15^ii—Ca1—Si6^iii	75.19 (6)	O11—Al2—O3^ix	103.64 (11)
O12^iii—Ca1—Si6^iii	67.53 (6)	O1^vii—Al2—O3^ix	106.45 (10)
O13^iv—Ca1—Si6^iii	133.24 (6)	O2—Al2—Ca2^ix	141.82 (8)
Si6—Ca1—Si6^iii	100.23 (2)	O11—Al2—Ca2^ix	105.71 (8)
S^ii—Ca1—Si6^iii	72.27 (2)	O1^vii—Al2—Ca2^ix	68.08 (7)
S^i—Ca1—Si6^iii	155.89 (2)	O3^ix—Al2—Ca2^ix	41.44 (7)
O3—Ca2—O14	166.47 (8)	O2—Al2—K	57.56 (9)
O3—Ca2—O4	88.44 (8)	O11—Al2—K	55.23 (8)
O14—Ca2—O4	88.93 (8)	O1^vii—Al2—K	153.56 (8)
O3—Ca2—O5	84.88 (7)	O3^ix—Al2—K	99.88 (8)
O14—Ca2—O5	107.98 (8)	Ca2^ix—Al2—K	135.93 (4)
O4—Ca2—O5	83.17 (7)	O2—Al2—K^vii	64.03 (9)
O3—Ca2—O12^iv	82.42 (8)	O11—Al2—K^vii	92.91 (8)
O14—Ca2—O12^iv	85.51 (9)	O1^vii—Al2—K^vii	64.12 (8)
O4—Ca2—O12^iv	105.61 (8)	O3^ix—Al2—K^vii	163.37 (8)
O5—Ca2—O12^iv	164.30 (9)	Ca2^ix—Al2—K^vii	132.19 (4)
O3—Ca2—O13^iii	74.43 (8)	K—Al2—K^vii	90.86 (3)
O14—Ca2—O13^iii	106.58 (8)	O2—Al2—Ca1	126.28 (9)
O4—Ca2—O13^iii	162.19 (8)	O11—Al2—Ca1	35.44 (7)
O5—Ca2—O13^iii	99.78 (8)	O1^vii—Al2—Ca1	118.15 (8)
O12^iv—Ca2—O13^iii	67.91 (8)	O3^ix—Al2—Ca1	68.81 (8)
O3—Ca2—O15^iii	121.13 (8)	Ca2^ix—Al2—Ca1	75.37 (2)
O14—Ca2—O15^iii	67.69 (8)	K—Al2—Ca1	69.29 (3)
O4—Ca2—O15^iii	141.08 (8)	K^vii—Al2—Ca1	127.36 (3)
O5—Ca2—O15^iii	75.75 (8)	O10^vii—Si6—O9	117.99 (13)
O12^iv—Ca2—O15^iii	103.13 (8)	O10^vii—Si6—O11	111.77 (12)
O13^iii—Ca2—O15^iii	55.75 (8)	O9—Si6—O11	105.49 (11)
O3—Ca2—S^iii	98.72 (6)	O10^vii—Si6—O8^vi	110.24 (12)
O14—Ca2—S^iii	85.97 (6)	O9—Si6—O8^vi	102.64 (11)
O4—Ca2—S^iii	169.02 (5)	O11—Si6—O8^vi	107.97 (12)
O5—Ca2—S^iii	89.16 (6)	O10^vii—Si6—Ca3^viii	140.74 (9)
O12^iv—Ca2—S^iii	83.70 (6)	O9—Si6—Ca3^viii	51.48 (8)
O13^iii—Ca2—S^iii	27.63 (5)	O11—Si6—Ca3^viii	107.36 (8)
O15^iii—Ca2—S^iii	28.21 (6)	O8^vi—Si6—Ca3^viii	52.55 (8)
O3—Ca2—S	144.81 (6)	O10^vii—Si6—Ca1	132.29 (9)
O14—Ca2—S	22.72 (6)	O9—Si6—Ca1	54.75 (8)
O4—Ca2—S	74.74 (6)	O11—Si6—Ca1	50.76 (8)
O5—Ca2—S	122.32 (6)	O8^vi—Si6—Ca1	117.38 (9)
O12^iv—Ca2—S	73.07 (7)	Ca3^viii—Si6—Ca1	76.83 (2)
O13^iii—Ca2—S	116.87 (6)	O10^vii—Si6—Ca3^vi	37.52 (8)
O15^iii—Ca2—S	89.35 (6)	O9—Si6—Ca3^vi	105.80 (8)
S^iii—Ca2—S	103.13 (3)	O11—Si6—Ca3^vi	145.00 (8)
O3—Ca2—Al2^iv	29.32 (5)	O8^vi—Si6—Ca3^vi	79.90 (8)
O14—Ca2—Al2^iv	137.62 (7)	Ca3^viii—Si6—Ca3^vi	104.21 (3)
O4—Ca2—Al2^iv	74.81 (5)	Ca1—Si6—Ca3^vi	154.95 (3)
O5—Ca2—Al2^iv	108.51 (6)	O10^vii—Si6—Ca3^i	81.30 (10)
O12^iv—Ca2—Al2^iv	62.77 (6)	O9—Si6—Ca3^i	36.72 (8)
O13^iii—Ca2—Al2^iv	87.67 (6)	O11—Si6—Ca3^i	124.99 (8)
O15^iii—Ca2—Al2^iv	142.92 (6)	O8^vi—Si6—Ca3^i	116.96 (8)
S^iii—Ca2—Al2^iv	115.27 (3)	Ca3^viii—Si6—Ca3^i	79.03 (2)
S—Ca2—Al2^iv	115.50 (3)	Ca1—Si6—Ca3^i	80.21 (2)
O3—Ca2—Si1	72.82 (6)	Ca3^vi—Si6—Ca3^i	75.53 (2)
O14—Ca2—Si1	99.82 (7)	O10^vii—Si6—Ca1^vii	32.52 (8)
O4—Ca2—Si1	25.37 (5)	O9—Si6—Ca1^vii	107.24 (9)
O5—Ca2—Si1	101.40 (6)	O11—Si6—Ca1^vii	87.55 (8)
O12^iv—Ca2—Si1	83.63 (6)	O8^vi—Si6—Ca1^vii	141.09 (9)
O13^iii—Ca2—Si1	138.85 (6)	Ca3^viii—Si6—Ca1^vii	156.14 (3)
O15^iii—Ca2—Si1	164.88 (6)	Ca1—Si6—Ca1^vii	100.23 (2)
S^iii—Ca2—Si1	165.60 (3)	Ca3^vi—Si6—Ca1^vii	68.47 (2)
S—Ca2—Si1	79.60 (3)	Ca3^i—Si6—Ca1^vii	77.14 (2)
Al2^iv—Ca2—Si1	52.19 (2)	O10^vii—Si6—K	134.68 (11)
O3—Ca2—Si2	107.29 (5)	O9—Si6—K	107.26 (9)
O14—Ca2—Si2	84.53 (6)	O11—Si6—K	49.47 (8)
O4—Ca2—Si2	72.59 (5)	O8^vi—Si6—K	59.16 (8)
O5—Ca2—Si2	25.38 (5)	Ca3^viii—Si6—K	71.87 (3)
O12^iv—Ca2—Si2	169.91 (7)	Ca1—Si6—K	72.96 (3)
O13^iii—Ca2—Si2	116.73 (6)	Ca3^vi—Si6—K	131.64 (3)
O15^iii—Ca2—Si2	74.50 (6)	Ca3^i—Si6—K	143.98 (4)
S^iii—Ca2—Si2	97.22 (3)	Ca1^vii—Si6—K	130.50 (3)
S—Ca2—Si2	96.99 (3)	O11—K—O6	82.44 (7)
Al2^iv—Ca2—Si2	124.92 (2)	O11—K—O2	56.23 (6)
Si1—Ca2—Si2	96.45 (2)	O6—K—O2	68.49 (7)
O9^v—Ca3—O10^vi	88.70 (9)	O11—K—O8^vi	51.55 (6)
O9^v—Ca3—O9^vi	93.03 (5)	O6—K—O8^vi	51.33 (6)
O10^vi—Ca3—O9^vi	74.29 (7)	O2—K—O8^vi	85.81 (7)
O9^v—Ca3—O8^vii	152.19 (8)	O11—K—O7^viii	104.65 (7)
O10^vi—Ca3—O8^vii	96.40 (8)	O6—K—O7^viii	80.62 (7)
O9^vi—Ca3—O8^vii	62.52 (7)	O2—K—O7^viii	144.84 (8)
O9^v—Ca3—O15	92.47 (8)	O8^vi—K—O7^viii	61.23 (6)
O10^vi—Ca3—O15	178.66 (9)	O11—K—O6^iii	145.41 (7)
O9^vi—Ca3—O15	106.28 (8)	O6—K—O6^iii	111.16 (8)
O8^vii—Ca3—O15	82.85 (8)	O2—K—O6^iii	157.98 (7)
O9^v—Ca3—O7	126.74 (8)	O8^vi—K—O6^iii	111.57 (7)
O10^vi—Ca3—O7	85.35 (8)	O7^viii—K—O6^iii	50.35 (6)
O9^vi—Ca3—O7	135.01 (7)	O11—K—O2^iii	114.93 (7)
O8^vii—Ca3—O7	81.01 (7)	O6—K—O2^iii	158.36 (7)
O15—Ca3—O7	93.43 (8)	O2—K—O2^iii	109.32 (8)
O9^v—Ca3—O14	68.08 (7)	O8^vi—K—O2^iii	149.74 (7)
O10^vi—Ca3—O14	127.50 (8)	O7^viii—K—O2^iii	105.58 (7)
O9^vi—Ca3—O14	148.54 (7)	O6^iii—K—O2^iii	62.34 (6)
O8^vii—Ca3—O14	126.19 (7)	O11—K—O1	62.27 (6)
O15—Ca3—O14	52.52 (7)	O6—K—O1	142.67 (8)
O7—Ca3—O14	74.37 (7)	O2—K—O1	81.22 (6)
O9^v—Ca3—Si6^vi	123.75 (6)	O8^vi—K—O1	106.97 (6)
O10^vi—Ca3—Si6^vi	79.85 (6)	O7^viii—K—O1	118.12 (7)
O9^vi—Ca3—Si6^vi	30.83 (5)	O6^iii—K—O1	105.12 (7)
O8^vii—Ca3—Si6^vi	32.37 (5)	O2^iii—K—O1	52.67 (6)
O15—Ca3—Si6^vi	100.00 (6)	O11—K—O10	64.64 (6)
O7—Ca3—Si6^vi	107.10 (6)	O6—K—O10	117.65 (7)
O14—Ca3—Si6^vi	152.21 (6)	O2—K—O10	119.26 (7)
O9^v—Ca3—S	77.12 (6)	O8^vi—K—O10	67.03 (6)
O10^vi—Ca3—S	154.22 (7)	O7^viii—K—O10	61.03 (6)
O9^vi—Ca3—S	127.20 (6)	O6^iii—K—O10	81.13 (7)
O8^vii—Ca3—S	106.22 (5)	O2^iii—K—O10	82.73 (7)
O15—Ca3—S	25.94 (6)	O1—K—O10	59.27 (6)
O7—Ca3—S	86.12 (5)	O11—K—O5	159.09 (8)
O14—Ca3—S	26.87 (5)	O6—K—O5	78.61 (7)
Si6^vi—Ca3—S	125.93 (3)	O2—K—O5	107.81 (7)
O9^v—Ca3—Si6^viii	79.04 (6)	O8^vi—K—O5	119.24 (6)
O10^vi—Ca3—Si6^viii	24.79 (6)	O7^viii—K—O5	80.98 (6)
O9^vi—Ca3—Si6^viii	97.62 (5)	O6^iii—K—O5	52.42 (6)
O8^vii—Ca3—Si6^viii	115.23 (6)	O2^iii—K—O5	81.90 (6)
O15—Ca3—Si6^viii	155.07 (6)	O1—K—O5	133.21 (7)
O7—Ca3—Si6^viii	73.92 (5)	O10—K—O5	132.93 (7)
O14—Ca3—Si6^viii	102.80 (5)	O11—K—O4	102.00 (8)
Si6^vi—Ca3—Si6^viii	104.21 (3)	O6—K—O4	53.43 (6)
S—Ca3—Si6^viii	129.65 (3)	O2—K—O4	49.25 (6)
O9^v—Ca3—Si6^v	24.77 (6)	O8^vi—K—O4	101.79 (7)
O10^vi—Ca3—Si6^v	102.19 (7)	O7^viii—K—O4	122.19 (6)
O9^vi—Ca3—Si6^v	77.04 (5)	O6^iii—K—O4	111.66 (7)
O8^vii—Ca3—Si6^v	128.48 (6)	O2^iii—K—O4	107.93 (6)
O15—Ca3—Si6^v	79.14 (6)	O1—K—O4	119.68 (6)
O7—Ca3—Si6^v	147.44 (6)	O10—K—O4	165.99 (8)
O14—Ca3—Si6^v	76.10 (5)	O5—K—O4	59.28 (6)
Si6^vi—Ca3—Si6^v	105.41 (3)	O11—K—O3	122.68 (7)
S—Ca3—Si6^v	73.35 (2)	O6—K—O3	113.27 (7)
Si6^viii—Ca3—Si6^v	99.83 (2)	O2—K—O3	78.14 (6)
O9^v—Ca3—Al1	137.75 (6)	O8^vi—K—O3	161.61 (8)
O10^vi—Ca3—Al1	106.84 (7)	O7^viii—K—O3	131.51 (7)
O9^vi—Ca3—Al1	128.72 (6)	O6^iii—K—O3	82.28 (6)
O8^vii—Ca3—Al1	66.51 (5)	O2^iii—K—O3	47.14 (6)
O15—Ca3—Al1	71.85 (6)	O1—K—O3	79.58 (6)
O7—Ca3—Al1	25.06 (5)	O10—K—O3	129.05 (7)
O14—Ca3—Al1	71.47 (5)	O5—K—O3	58.93 (6)
Si6^vi—Ca3—Al1	97.92 (2)	O4—K—O3	60.79 (6)
S—Ca3—Al1	72.32 (2)	Si1^iv—O1—Al2^iii	125.55 (13)
Si6^viii—Ca3—Al1	98.74 (2)	Si1^iv—O1—Ca1	114.37 (11)
Si6^v—Ca3—Al1	145.42 (2)	Al2^iii—O1—Ca1	119.46 (10)
O13—S—O12^v	112.29 (14)	Si1^iv—O1—K	102.96 (10)
O13—S—O14	110.79 (15)	Al2^iii—O1—K	86.85 (8)
O12^v—S—O14	110.96 (16)	Ca1—O1—K	87.96 (6)
O13—S—O15	108.51 (16)	Si1—O2—Al2	161.26 (16)
O12^v—S—O15	106.15 (15)	Si1—O2—K	102.59 (11)
O14—S—O15	107.89 (14)	Al2—O2—K	93.55 (10)
O13—S—Ca2^vii	53.95 (11)	Si1—O2—K^vii	95.61 (11)
O12^v—S—Ca2^vii	119.86 (12)	Al2—O2—K^vii	87.85 (10)
O14—S—Ca2^vii	128.97 (11)	K—O2—K^vii	109.32 (7)
O15—S—Ca2^vii	54.81 (10)	Si1^iii—O3—Al2^iv	125.22 (13)
O13—S—Ca1^x	116.75 (11)	Si1^iii—O3—Ca2	123.80 (11)
O12^v—S—Ca1^x	53.96 (11)	Al2^iv—O3—Ca2	109.24 (11)
O14—S—Ca1^x	132.27 (10)	Si1^iii—O3—K	91.30 (9)
O15—S—Ca1^x	53.18 (10)	Al2^iv—O3—K	99.10 (9)
Ca2^vii—S—Ca1^x	79.60 (3)	Ca2—O3—K	93.09 (7)
O13—S—Ca3	132.01 (11)	Si1—O4—Al1	126.55 (14)
O12^v—S—Ca3	114.26 (10)	Si1—O4—Ca2	114.69 (11)
O14—S—Ca3	61.69 (10)	Al1—O4—Ca2	118.75 (10)
O15—S—Ca3	46.99 (9)	Si1—O4—K	90.00 (9)
Ca2^vii—S—Ca3	92.18 (3)	Al1—O4—K	88.08 (8)
Ca1^x—S—Ca3	82.93 (2)	Ca2—O4—K	93.40 (8)
O13—S—Ca2	72.34 (11)	Si2—O5—Al1^iii	123.60 (13)
O12^v—S—Ca2	129.92 (12)	Si2—O5—Ca2	114.94 (11)
O14—S—Ca2	38.50 (10)	Al1^iii—O5—Ca2	118.72 (11)
O15—S—Ca2	119.77 (10)	Si2—O5—K	104.45 (10)
Ca2^vii—S—Ca2	103.13 (3)	Al1^iii—O5—K	88.72 (9)
Ca1^x—S—Ca2	169.19 (3)	Ca2—O5—K	93.40 (7)
Ca3—S—Ca2	86.50 (2)	Si2^vi—O6—Al1	156.29 (15)
O13—S—Ca1^v	132.11 (12)	Si2^vi—O6—K	100.38 (12)
O12^v—S—Ca1^v	67.59 (11)	Al1—O6—K	100.23 (11)
O14—S—Ca1^v	43.49 (10)	Si2^vi—O6—K^vii	91.46 (11)
O15—S—Ca1^v	117.51 (10)	Al1—O6—K^vii	91.92 (11)
Ca2^vii—S—Ca1^v	169.61 (3)	K—O6—K^vii	111.16 (8)
Ca1^x—S—Ca1^v	101.42 (2)	Si2—O7—Al1	122.49 (13)
Ca3—S—Ca1^v	77.75 (2)	Si2—O7—Ca3	119.13 (11)
Ca2—S—Ca1^v	74.00 (2)	Al1—O7—Ca3	117.40 (11)
O2—Si1—O1^ix	111.51 (12)	Si2—O7—K^vi	90.89 (9)
O2—Si1—O4	109.39 (11)	Al1—O7—K^vi	100.90 (10)
O1^ix—Si1—O4	106.70 (11)	Ca3—O7—K^vi	87.88 (7)
O2—Si1—O3^vii	110.18 (13)	Si2—O8—Si6^viii	136.41 (14)
O1^ix—Si1—O3^vii	109.80 (11)	Si2—O8—Ca3^iii	128.18 (11)
O4—Si1—O3^vii	109.18 (11)	Si6^viii—O8—Ca3^iii	95.08 (10)
O2—Si1—Ca2	123.92 (10)	Si2—O8—K^viii	91.45 (9)
O1^ix—Si1—Ca2	66.76 (8)	Si6^viii—O8—K^viii	94.13 (9)
O4—Si1—Ca2	39.94 (8)	Ca3^iii—O8—K^viii	89.68 (8)
O3^vii—Si1—Ca2	123.25 (8)	Si6—O9—Ca3^i	118.51 (12)
O2—Si1—Ca2^vii	129.48 (10)	Si6—O9—Ca3^viii	97.69 (10)
O1^ix—Si1—Ca2^vii	114.54 (8)	Ca3^i—O9—Ca3^viii	120.74 (9)
O4—Si1—Ca2^vii	76.05 (8)	Si6—O9—Ca1	94.51 (9)
O3^vii—Si1—Ca2^vii	33.78 (7)	Ca3^i—O9—Ca1	119.16 (9)
Ca2—Si1—Ca2^vii	93.09 (2)	Ca3^viii—O9—Ca1	101.12 (8)
O2—Si1—Ca1^ix	141.35 (8)	Si6^iii—O10—Ca3^viii	117.70 (12)
O1^ix—Si1—Ca1^ix	40.99 (8)	Si6^iii—O10—Ca1	125.97 (13)
O4—Si1—Ca1^ix	105.69 (8)	Ca3^viii—O10—Ca1	112.81 (10)
O3^vii—Si1—Ca1^ix	71.87 (8)	Si6^iii—O10—K	105.49 (12)
Ca2—Si1—Ca1^ix	76.02 (2)	Ca3^viii—O10—K	90.30 (8)
Ca2^vii—Si1—Ca1^ix	74.45 (2)	Ca1—O10—K	91.87 (8)
O2—Si1—K	52.39 (9)	Si6—O11—Al2	132.68 (14)
O1^ix—Si1—K	101.17 (8)	Si6—O11—Ca1	98.26 (10)
O4—Si1—K	63.67 (8)	Al2—O11—Ca1	120.20 (11)
O3^vii—Si1—K	148.81 (8)	Si6—O11—K	105.45 (10)
Ca2—Si1—K	72.39 (3)	Al2—O11—K	95.41 (9)
Ca2^vii—Si1—K	132.29 (3)	Ca1—O11—K	98.80 (8)
Ca1^ix—Si1—K	138.83 (4)	S^i—O12—Ca2^ix	130.01 (14)
O2—Si1—K^vii	59.47 (10)	S^i—O12—Ca1^vii	98.93 (13)
O1^ix—Si1—K^vii	160.80 (9)	Ca2^ix—O12—Ca1^vii	116.28 (10)
O4—Si1—K^vii	92.49 (8)	S—O13—Ca2^vii	98.42 (13)
O3^vii—Si1—K^vii	63.00 (8)	S—O13—Ca1^ix	146.40 (16)
Ca2—Si1—K^vii	132.41 (3)	Ca2^vii—O13—Ca1^ix	111.40 (9)
Ca2^vii—Si1—K^vii	70.27 (3)	S—O14—Ca2	118.78 (13)
Ca1^ix—Si1—K^vii	134.73 (3)	S—O14—Ca1^v	112.74 (13)
K—Si1—K^vii	86.41 (3)	Ca2—O14—Ca1^v	111.41 (10)
O6—Al1—O4	109.53 (11)	S—O14—Ca3	91.44 (11)
O6—Al1—O5^vii	111.60 (13)	Ca2—O14—Ca3	118.92 (10)
O4—Al1—O5^vii	108.49 (11)	Ca1^v—O14—Ca3	101.01 (8)
O6—Al1—O7	112.73 (12)	S—O15—Ca3	107.08 (13)
O4—Al1—O7	104.59 (11)	S—O15—Ca2^vii	96.98 (12)
O5^vii—Al1—O7	109.60 (11)	Ca3—O15—Ca2^vii	130.47 (11)
O6—Al1—Ca2	122.58 (10)	S—O15—Ca1^x	99.28 (12)
O4—Al1—Ca2	36.22 (7)	Ca3—O15—Ca1^x	114.41 (10)
O5^vii—Al1—Ca2	121.90 (8)	Ca2^vii—O15—Ca1^x	103.13 (9)
O7—Al1—Ca2	68.39 (8)

Symmetry codes: (i) x+1, y, z; (ii) x+1, y−1, z; (iii) x, y−1, z; (iv) −x+1, y−1/2, −z; (v) x−1, y, z; (vi) −x+1, y+1/2, −z+1; (vii) x, y+1, z; (viii) −x+1, y−1/2, −z+1; (ix) −x+1, y+1/2, −z; (x) x−1, y+1, z.

(tuscanite)

Crystal data

Al4.20Ca4.94Si5.80Sr0.09K0.90Mg0.08Na0.45O31.40P0.33S1.53C0.14H4.04	F(000) = 1093
Mr = 1097.02	Dx = 2.873 Mg m^−3
Monoclinic, P21/a	Mo Kα radiation, λ = 0.71073 Å
a = 23.9846 (9) Å	Cell parameters from 4352 reflections
b = 5.09694 (15) Å	θ = 3.8–30.5°
c = 10.8504 (4) Å	µ = 2.10 mm^−1
β = 107.032 (4)°	T = 293 K
V = 1268.26 (8) Å^3	Irregular, colorless
Z = 2	0.22 × 0.17 × 0.12 mm

Data collection

Xcalibur, Sapphire3 diffractometer	3131 independent reflections
Radiation source: fine-focus sealed X-ray tube	2587 reflections with I > 2σ(I)
Detector resolution: 16.0630 pixels mm^-1	Rint = 0.037
ω scans	θmax = 28.3°, θmin = 3.0°
Absorption correction: multi-scan	h = −31→31
Tmin = 0.929, Tmax = 1.000	k = −6→6
10218 measured reflections	l = −10→14

Refinement

Refinement on F^2	H-atom parameters not defined
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0277P)^2 + 0.1441P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.031	(Δ/σ)max = 0.001
wR(F^2) = 0.069	Δρmax = 0.53 e Å^−3
S = 1.02	Δρmin = −0.39 e Å^−3
3131 reflections	Extinction correction: SHELXL-2018/3 (Sheldrick 2018), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
232 parameters	Extinction coefficient: 0.0023 (3)
0 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)
Ca1	0.19148 (2)	0.72350 (9)	0.18896 (5)	0.01243 (19)	0.876 (6)
Na1	0.19148 (2)	0.72350 (9)	0.18896 (5)	0.01243 (19)	0.079 (6)
Sr1	0.19148 (2)	0.72350 (9)	0.18896 (5)	0.01243 (19)	0.045
Ca2	0.35399 (3)	0.72594 (11)	0.14587 (6)	0.0152 (2)	0.835 (6)
Na2	0.35399 (3)	0.72594 (11)	0.14587 (6)	0.0152 (2)	0.165 (6)
Ca3	0.30801 (2)	0.24049 (9)	0.45473 (5)	0.01060 (19)	0.981 (6)
Na3	0.30801 (2)	0.24049 (9)	0.45473 (5)	0.01060 (19)	0.019 (6)
S	0.26906 (3)	0.19933 (13)	0.14020 (7)	0.0113 (2)	0.929 (2)
Si1	0.43865 (3)	0.24003 (12)	0.07234 (6)	0.00713 (16)
Al1	0.44175 (3)	0.22911 (13)	0.35250 (7)	0.00703 (16)
Si3	0.42174 (3)	0.72543 (12)	0.47864 (7)	0.00832 (16)
Si4	0.16167 (3)	0.27279 (12)	0.35433 (6)	0.00853 (16)
Al2	0.07546 (3)	0.23563 (13)	0.08261 (7)	0.00699 (17)
K	0.03728 (6)	0.7449 (2)	0.27281 (12)	0.0175 (5)	0.227 (4)
OW	0.03728 (6)	0.7449 (2)	0.27281 (12)	0.0175 (5)	0.773 (4)
O1	0.09658 (8)	0.9164 (3)	0.05158 (16)	0.0110 (4)
O2	0.00732 (8)	0.2301 (3)	0.10119 (18)	0.0167 (4)
O3	0.41981 (8)	0.9334 (3)	0.04746 (16)	0.0108 (4)
O4	0.41956 (8)	0.3486 (3)	0.19498 (16)	0.0116 (4)
O5	0.41978 (8)	0.8994 (3)	0.35014 (16)	0.0131 (4)
O6	0.01583 (9)	0.2414 (3)	0.41420 (18)	0.0184 (4)
O7	0.40299 (8)	0.4211 (3)	0.43522 (16)	0.0129 (4)
O8	0.37117 (8)	0.8548 (3)	0.53575 (16)	0.0131 (4)
O9	0.21970 (8)	0.4473 (3)	0.39544 (16)	0.0119 (4)
O10	0.16926 (9)	−0.0354 (3)	0.35147 (16)	0.0200 (5)
O11	0.12283 (8)	0.3866 (3)	0.21609 (16)	0.0123 (4)
O12	0.20596 (9)	0.1676 (4)	0.08147 (19)	0.0187 (5)	0.929 (2)
O13	0.30230 (9)	0.1514 (4)	0.04798 (19)	0.0244 (5)
O14	0.28248 (9)	0.4623 (3)	0.19931 (17)	0.0179 (4)
O15	0.28678 (9)	−0.0001 (3)	0.24569 (17)	0.0189 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca1	0.0111 (3)	0.0126 (3)	0.0138 (3)	0.0001 (2)	0.0039 (2)	0.00077 (19)
Na1	0.0111 (3)	0.0126 (3)	0.0138 (3)	0.0001 (2)	0.0039 (2)	0.00077 (19)
Sr1	0.0111 (3)	0.0126 (3)	0.0138 (3)	0.0001 (2)	0.0039 (2)	0.00077 (19)
Ca2	0.0130 (4)	0.0171 (4)	0.0158 (3)	−0.0012 (2)	0.0048 (3)	0.0023 (2)
Na2	0.0130 (4)	0.0171 (4)	0.0158 (3)	−0.0012 (2)	0.0048 (3)	0.0023 (2)
Ca3	0.0093 (3)	0.0098 (3)	0.0124 (3)	0.0018 (2)	0.0025 (2)	−0.00007 (19)
Na3	0.0093 (3)	0.0098 (3)	0.0124 (3)	0.0018 (2)	0.0025 (2)	−0.00007 (19)
S	0.0094 (4)	0.0114 (4)	0.0131 (4)	−0.0005 (3)	0.0033 (3)	−0.0012 (3)
Si1	0.0072 (4)	0.0071 (3)	0.0072 (3)	−0.0001 (3)	0.0023 (3)	0.0002 (2)
Al1	0.0074 (4)	0.0067 (4)	0.0072 (3)	0.0002 (3)	0.0025 (3)	−0.0001 (3)
Si3	0.0085 (4)	0.0082 (3)	0.0085 (3)	0.0003 (3)	0.0028 (3)	0.0000 (3)
Si4	0.0096 (4)	0.0082 (3)	0.0077 (3)	0.0007 (3)	0.0025 (3)	0.0007 (2)
Al2	0.0075 (4)	0.0063 (4)	0.0072 (3)	0.0001 (3)	0.0022 (3)	−0.0003 (3)
K	0.0233 (9)	0.0123 (7)	0.0182 (8)	−0.0012 (5)	0.0080 (6)	−0.0013 (5)
OW	0.0233 (9)	0.0123 (7)	0.0182 (8)	−0.0012 (5)	0.0080 (6)	−0.0013 (5)
O1	0.0103 (10)	0.0098 (9)	0.0112 (9)	0.0016 (7)	0.0005 (8)	−0.0017 (7)
O2	0.0089 (10)	0.0249 (11)	0.0168 (10)	−0.0003 (8)	0.0045 (9)	−0.0021 (8)
O3	0.0153 (10)	0.0080 (8)	0.0106 (8)	−0.0020 (7)	0.0062 (8)	−0.0012 (7)
O4	0.0114 (10)	0.0132 (9)	0.0105 (9)	0.0015 (8)	0.0038 (8)	−0.0009 (7)
O5	0.0156 (10)	0.0122 (9)	0.0122 (9)	−0.0022 (8)	0.0052 (8)	0.0000 (7)
O6	0.0116 (10)	0.0247 (11)	0.0168 (10)	0.0012 (8)	0.0007 (9)	0.0021 (8)
O7	0.0127 (10)	0.0120 (9)	0.0158 (9)	−0.0017 (7)	0.0069 (9)	−0.0022 (7)
O8	0.0152 (10)	0.0130 (9)	0.0140 (9)	0.0040 (8)	0.0091 (8)	0.0023 (7)
O9	0.0084 (9)	0.0128 (9)	0.0134 (9)	−0.0002 (7)	0.0017 (8)	−0.0008 (7)
O10	0.0376 (14)	0.0094 (9)	0.0137 (9)	0.0045 (9)	0.0085 (10)	0.0010 (7)
O11	0.0138 (10)	0.0113 (9)	0.0104 (8)	−0.0005 (8)	0.0014 (8)	−0.0001 (7)
O12	0.0067 (11)	0.0277 (12)	0.0210 (11)	−0.0026 (9)	0.0029 (10)	0.0040 (9)
O13	0.0214 (12)	0.0316 (11)	0.0238 (11)	−0.0028 (10)	0.0123 (10)	−0.0080 (9)
O14	0.0193 (11)	0.0121 (9)	0.0259 (10)	−0.0021 (8)	0.0121 (10)	−0.0031 (8)
O15	0.0225 (12)	0.0140 (9)	0.0188 (10)	0.0020 (8)	0.0039 (10)	0.0024 (8)

Geometric parameters (Å, º)

Ca1—O10^i	2.3355 (16)	Si1—O4	1.6259 (16)
Ca1—O11	2.4560 (17)	Si1—O3^v	1.6275 (17)
Ca1—O1	2.5264 (19)	Si1—O1^vii	1.6324 (18)
Ca1—O14	2.5307 (19)	Si1—K^vi	3.6635 (14)
Ca1—O9	2.5635 (18)	Si1—K^viii	3.7690 (14)
Ca1—O15^i	2.601 (2)	Al1—O6^vi	1.712 (2)
Ca1—O12^i	2.616 (2)	Al1—O4	1.7443 (18)
Ca1—O13^ii	2.6440 (19)	Al1—O5^v	1.7592 (17)
Ca1—O12	3.122 (2)	Al1—O7	1.7654 (17)
Ca1—Si4	3.1242 (8)	Al1—K^vi	3.6048 (14)
Ca1—S^i	3.1938 (8)	Al1—K^viii	3.7876 (14)
Ca1—S	3.3847 (8)	Al1—K^iv	3.9484 (14)
Ca2—O14	2.3802 (18)	Si3—O6^iii	1.606 (2)
Ca2—O3	2.3953 (16)	Si3—O5	1.6413 (17)
Ca2—O4	2.4425 (18)	Si3—O7	1.6450 (18)
Ca2—O5	2.4769 (19)	Si3—O8	1.6524 (17)
Ca2—O12^ii	2.483 (2)	Si3—K^iv	3.5616 (14)
Ca2—O13^i	2.568 (2)	Si3—K^iii	3.7008 (14)
Ca2—O15^i	2.5968 (18)	Si4—O10	1.5825 (18)
Ca2—S^i	3.1467 (9)	Si4—O9	1.6011 (19)
Ca2—S	3.3592 (9)	Si4—O11	1.6234 (19)
Ca2—Al2^ii	3.3865 (9)	Si4—O8^iv	1.6635 (16)
Ca2—Si1	3.4413 (8)	Al2—O2	1.705 (2)
Ca2—Si3	3.4987 (9)	Al2—O11	1.7367 (19)
Ca3—O9	2.2832 (19)	Al2—O3^vii	1.7648 (16)
Ca3—O10^iii	2.3136 (17)	Al2—O1^v	1.7654 (17)
Ca3—O9^iv	2.4394 (16)	Al2—K^v	3.5301 (13)
Ca3—O8^v	2.4804 (18)	Al2—K	3.5975 (13)
Ca3—O15	2.4963 (19)	Al2—K^ix	4.0106 (16)
Ca3—O7	2.5227 (17)	K—O11	2.944 (2)
Ca3—O14	2.8879 (18)	K—O2^i	3.052 (2)
Ca3—Si4^iv	3.1018 (8)	K—O6^i	3.080 (2)
Ca3—S	3.2705 (9)	K—O6	3.109 (2)
Ca3—Si4	3.3606 (9)	K—O2	3.176 (2)
Ca3—Si4^iii	3.3614 (8)	K—O7^iii	3.199 (2)
Ca3—Si3	3.6337 (9)	K—O8^iv	3.228 (2)
S—O12	1.469 (2)	K—O10^i	3.228 (3)
S—O13	1.4711 (18)	K—O1	3.2481 (19)
S—O14	1.4801 (18)	K—O5^x	3.252 (2)
S—O15	1.4965 (19)	K—O3^x	3.272 (2)
Si1—O2^vi	1.591 (2)	K—O4^x	3.403 (2)
O10^i—Ca1—O11	88.18 (6)	O7—Al1—Ca2^v	114.07 (7)
O10^i—Ca1—O1	82.83 (6)	K^vi—Al1—Ca2^v	70.96 (3)
O11—Ca1—O1	79.81 (6)	Ca2—Al1—Ca2^v	89.14 (2)
O10^i—Ca1—O14	128.90 (7)	O6^vi—Al1—Ca3	140.84 (7)
O11—Ca1—O14	103.10 (6)	O4—Al1—Ca3	104.27 (6)
O1—Ca1—O14	147.91 (6)	O5^v—Al1—Ca3	74.71 (6)
O10^i—Ca1—O9	71.90 (6)	O7—Al1—Ca3	37.31 (6)
O11—Ca1—O9	61.69 (6)	K^vi—Al1—Ca3	138.80 (3)
O1—Ca1—O9	133.71 (6)	Ca2—Al1—Ca3	77.065 (19)
O14—Ca1—O9	70.66 (6)	Ca2^v—Al1—Ca3	78.437 (19)
O10^i—Ca1—O15^i	85.15 (6)	O6^vi—Al1—K^viii	53.08 (7)
O11—Ca1—O15^i	157.52 (6)	O4—Al1—K^viii	63.93 (6)
O1—Ca1—O15^i	120.42 (6)	O5^v—Al1—K^viii	150.64 (6)
O14—Ca1—O15^i	65.65 (6)	O7—Al1—K^viii	99.64 (6)
O9—Ca1—O15^i	95.85 (6)	K^vi—Al1—K^viii	87.14 (3)
O10^i—Ca1—O12^i	88.32 (6)	Ca2—Al1—K^viii	69.17 (3)
O11—Ca1—O12^i	147.12 (7)	Ca2^v—Al1—K^viii	129.57 (3)
O1—Ca1—O12^i	67.32 (6)	Ca3—Al1—K^viii	134.03 (3)
O14—Ca1—O12^i	104.46 (6)	O6^vi—Al1—K^iv	77.93 (7)
O9—Ca1—O12^i	146.04 (6)	O4—Al1—K^iv	155.80 (6)
O15^i—Ca1—O12^i	54.17 (6)	O5^v—Al1—K^iv	88.95 (6)
O10^i—Ca1—O13^ii	153.84 (6)	O7—Al1—K^iv	52.59 (6)
O11—Ca1—O13^ii	104.48 (6)	K^vi—Al1—K^iv	111.25 (3)
O1—Ca1—O13^ii	77.18 (6)	Ca2—Al1—K^iv	119.94 (3)
O14—Ca1—O13^ii	71.13 (6)	Ca2^v—Al1—K^iv	121.63 (3)
O9—Ca1—O13^ii	134.25 (6)	Ca3—Al1—K^iv	63.25 (2)
O15^i—Ca1—O13^ii	90.54 (6)	K^viii—Al1—K^iv	108.51 (3)
O12^i—Ca1—O13^ii	68.54 (6)	O6^iii—Si3—O5	112.10 (10)
O10^i—Ca1—O12	146.58 (6)	O6^iii—Si3—O7	111.96 (10)
O11—Ca1—O12	64.02 (5)	O5—Si3—O7	109.19 (9)
O1—Ca1—O12	108.20 (6)	O6^iii—Si3—O8	109.84 (10)
O14—Ca1—O12	49.49 (6)	O5—Si3—O8	105.16 (9)
O9—Ca1—O12	78.36 (5)	O7—Si3—O8	108.32 (9)
O15^i—Ca1—O12	113.19 (6)	O6^iii—Si3—Ca2	143.10 (7)
O12^i—Ca1—O12	125.10 (7)	O5—Si3—Ca2	39.99 (7)
O13^ii—Ca1—O12	57.76 (6)	O7—Si3—Ca2	72.53 (7)
O10^i—Ca1—Si4	79.17 (5)	O8—Si3—Ca2	102.51 (7)
O11—Ca1—Si4	30.98 (4)	O6^iii—Si3—K^iv	59.66 (7)
O1—Ca1—Si4	107.87 (4)	O5—Si3—K^iv	161.37 (7)
O14—Ca1—Si4	85.83 (4)	O7—Si3—K^iv	63.90 (7)
O9—Ca1—Si4	30.73 (4)	O8—Si3—K^iv	93.47 (7)
O15^i—Ca1—Si4	126.55 (5)	Ca2—Si3—K^iv	136.36 (3)
O12^i—Ca1—Si4	167.17 (5)	O6^iii—Si3—Ca3	127.40 (7)
O13^ii—Ca1—Si4	122.95 (5)	O5—Si3—Ca3	118.21 (7)
O12—Ca1—Si4	67.44 (4)	O7—Si3—Ca3	37.02 (6)
O10^i—Ca1—S^i	89.90 (5)	O8—Si3—Ca3	71.33 (7)
O11—Ca1—S^i	173.97 (5)	Ca2—Si3—Ca3	79.32 (2)
O1—Ca1—S^i	94.28 (4)	K^iv—Si3—Ca3	67.74 (3)
O14—Ca1—S^i	82.54 (4)	O6^iii—Si3—K^iii	56.22 (7)
O9—Ca1—S^i	122.98 (5)	O5—Si3—K^iii	99.67 (7)
O15^i—Ca1—S^i	27.58 (4)	O7—Si3—K^iii	151.08 (7)
O12^i—Ca1—S^i	27.02 (5)	O8—Si3—K^iii	60.58 (7)
O13^ii—Ca1—S^i	75.11 (5)	Ca2—Si3—K^iii	134.06 (3)
O12—Ca1—S^i	119.57 (4)	K^iv—Si3—K^iii	89.13 (3)
Si4—Ca1—S^i	153.64 (3)	Ca3—Si3—K^iii	124.91 (3)
O10^i—Ca1—S	142.27 (5)	O10—Si4—O9	117.46 (11)
O11—Ca1—S	83.42 (4)	O10—Si4—O11	112.00 (10)
O1—Ca1—S	131.04 (4)	O9—Si4—O11	106.01 (9)
O14—Ca1—S	23.84 (4)	O10—Si4—O8^iv	110.17 (9)
O9—Ca1—S	71.74 (4)	O9—Si4—O8^iv	102.48 (9)
O15^i—Ca1—S	88.81 (4)	O11—Si4—O8^iv	107.98 (9)
O12^i—Ca1—S	117.55 (5)	O10—Si4—Ca3^iii	140.36 (8)
O13^ii—Ca1—S	63.14 (5)	O9—Si4—Ca3^iii	51.12 (6)
O12—Ca1—S	25.69 (4)	O11—Si4—Ca3^iii	107.55 (6)
Si4—Ca1—S	74.820 (19)	O8^iv—Si4—Ca3^iii	52.82 (6)
S^i—Ca1—S	101.53 (2)	O10—Si4—Ca1	132.18 (7)
O14—Ca2—O3	166.84 (6)	O9—Si4—Ca1	54.90 (6)
O14—Ca2—O4	88.06 (6)	O11—Si4—Ca1	51.14 (6)
O3—Ca2—O4	88.77 (6)	O8^iv—Si4—Ca1	117.59 (6)
O14—Ca2—O5	107.41 (6)	Ca3^iii—Si4—Ca1	76.71 (2)
O3—Ca2—O5	84.90 (6)	O10—Si4—Ca3	80.94 (8)
O4—Ca2—O5	83.40 (6)	O9—Si4—Ca3	36.56 (6)
O14—Ca2—O12^ii	85.73 (7)	O11—Si4—Ca3	125.39 (7)
O3—Ca2—O12^ii	82.84 (6)	O8^iv—Si4—Ca3	116.66 (7)
O4—Ca2—O12^ii	105.72 (6)	Ca3^iii—Si4—Ca3	78.63 (2)
O5—Ca2—O12^ii	164.50 (6)	Ca1—Si4—Ca3	80.16 (2)
O14—Ca2—O13^i	106.41 (7)	O10—Si4—Ca3^iv	37.41 (6)
O3—Ca2—O13^i	75.18 (6)	O9—Si4—Ca3^iv	105.25 (7)
O4—Ca2—O13^i	163.15 (6)	O11—Si4—Ca3^iv	145.06 (7)
O5—Ca2—O13^i	99.93 (6)	O8^iv—Si4—Ca3^iv	79.82 (6)
O12^ii—Ca2—O13^i	67.75 (6)	Ca3^iii—Si4—Ca3^iv	104.04 (2)
O14—Ca2—O15^i	67.81 (6)	Ca1—Si4—Ca3^iv	154.54 (3)
O3—Ca2—O15^i	121.28 (6)	Ca3—Si4—Ca3^iv	75.153 (19)
O4—Ca2—O15^i	140.45 (6)	O10—Si4—Ca1^v	32.49 (6)
O5—Ca2—O15^i	75.25 (6)	O9—Si4—Ca1^v	107.15 (6)
O12^ii—Ca2—O15^i	103.26 (7)	O11—Si4—Ca1^v	87.72 (6)
O13^i—Ca2—O15^i	55.61 (6)	O8^iv—Si4—Ca1^v	140.98 (7)
O14—Ca2—S^i	85.94 (5)	Ca3^iii—Si4—Ca1^v	155.70 (3)
O3—Ca2—S^i	99.22 (4)	Ca1—Si4—Ca1^v	100.24 (2)
O4—Ca2—S^i	168.48 (4)	Ca3—Si4—Ca1^v	77.103 (19)
O5—Ca2—S^i	89.02 (5)	Ca3^iv—Si4—Ca1^v	68.383 (17)
O12^ii—Ca2—S^i	83.64 (5)	O2—Al2—O11	108.93 (9)
O13^i—Ca2—S^i	27.52 (4)	O2—Al2—O3^vii	113.12 (10)
O15^i—Ca2—S^i	28.18 (4)	O11—Al2—O3^vii	103.55 (8)
O14—Ca2—S	22.64 (4)	O2—Al2—O1^v	110.23 (9)
O3—Ca2—S	145.07 (4)	O11—Al2—O1^v	114.40 (9)
O4—Ca2—S	73.92 (4)	O3^vii—Al2—O1^v	106.53 (8)
O5—Ca2—S	121.70 (4)	O2—Al2—Ca2^vii	142.03 (7)
O12^ii—Ca2—S	73.41 (5)	O11—Al2—Ca2^vii	105.78 (6)
O13^i—Ca2—S	116.77 (5)	O3^vii—Al2—Ca2^vii	42.26 (5)
O15^i—Ca2—S	89.43 (5)	O1^v—Al2—Ca2^vii	67.30 (5)
S^i—Ca2—S	103.10 (3)	O2—Al2—K^v	59.81 (7)
O14—Ca2—Al2^ii	137.45 (5)	O11—Al2—K^v	92.56 (6)
O3—Ca2—Al2^ii	29.70 (4)	O3^vii—Al2—K^v	163.88 (7)
O4—Ca2—Al2^ii	75.13 (4)	O1^v—Al2—K^v	66.21 (6)
O5—Ca2—Al2^ii	109.02 (4)	Ca2^vii—Al2—K^v	133.51 (3)
O12^ii—Ca2—Al2^ii	62.77 (5)	O2—Al2—K	61.98 (7)
O13^i—Ca2—Al2^ii	88.23 (4)	O11—Al2—K	54.29 (6)
O15^i—Ca2—Al2^ii	143.30 (5)	O3^vii—Al2—K	97.67 (6)
S^i—Ca2—Al2^ii	115.71 (2)	O1^v—Al2—K	155.48 (6)
S—Ca2—Al2^ii	115.38 (2)	Ca2^vii—Al2—K	134.12 (3)
O14—Ca2—Si1	99.58 (5)	K^v—Al2—K	91.30 (3)
O3—Ca2—Si1	72.76 (4)	O2—Al2—Ca1	129.88 (7)
O4—Ca2—Si1	25.56 (4)	O11—Al2—Ca1	35.35 (5)
O5—Ca2—Si1	101.53 (5)	O3^vii—Al2—Ca1	69.07 (6)
O12^ii—Ca2—Si1	83.84 (5)	O1^v—Al2—Ca1	116.90 (6)
O13^i—Ca2—Si1	139.28 (4)	Ca2^vii—Al2—Ca1	75.153 (19)
O15^i—Ca2—Si1	164.61 (4)	K^v—Al2—Ca1	126.94 (3)
S^i—Ca2—Si1	165.90 (3)	K—Al2—Ca1	68.07 (3)
S—Ca2—Si1	79.43 (2)	O2—Al2—K^ix	73.41 (7)
Al2^ii—Ca2—Si1	52.085 (17)	O11—Al2—K^ix	152.01 (6)
O14—Ca2—Si3	84.16 (5)	O3^vii—Al2—K^ix	53.13 (7)
O3—Ca2—Si3	107.03 (5)	O1^v—Al2—K^ix	89.41 (6)
O4—Ca2—Si3	72.51 (4)	Ca2^vii—Al2—K^ix	68.73 (2)
O5—Ca2—Si3	25.20 (4)	K^v—Al2—K^ix	111.25 (3)
O12^ii—Ca2—Si3	169.78 (5)	K—Al2—K^ix	108.70 (3)
O13^i—Ca2—Si3	116.71 (5)	Ca1—Al2—K^ix	121.53 (3)
O15^i—Ca2—Si3	74.18 (5)	O11—K—O2^i	115.41 (6)
S^i—Ca2—Si3	97.07 (2)	O11—K—O6^i	147.39 (7)
S—Ca2—Si3	96.56 (2)	O2^i—K—O6^i	66.06 (5)
Al2^ii—Ca2—Si3	125.09 (3)	O11—K—O6	79.47 (5)
Si1—Ca2—Si3	96.40 (2)	O2^i—K—O6	157.88 (7)
O9—Ca3—O10^iii	88.87 (7)	O6^i—K—O6	110.89 (6)
O9—Ca3—O9^iv	93.40 (4)	O11—K—O2	54.31 (5)
O10^iii—Ca3—O9^iv	74.60 (6)	O2^i—K—O2	109.83 (7)
O9—Ca3—O8^v	152.33 (6)	O6^i—K—O2	158.27 (7)
O10^iii—Ca3—O8^v	96.45 (7)	O6—K—O2	64.25 (5)
O9^iv—Ca3—O8^v	62.32 (6)	O11—K—O7^iii	104.11 (6)
O9—Ca3—O15	92.60 (6)	O2^i—K—O7^iii	109.50 (5)
O10^iii—Ca3—O15	178.18 (7)	O6^i—K—O7^iii	50.79 (5)
O9^iv—Ca3—O15	106.36 (6)	O6—K—O7^iii	80.44 (5)
O8^v—Ca3—O15	82.73 (6)	O2—K—O7^iii	140.48 (6)
O9—Ca3—O7	126.43 (6)	O11—K—O8^iv	50.79 (5)
O10^iii—Ca3—O7	85.29 (6)	O2^i—K—O8^iv	152.37 (7)
O9^iv—Ca3—O7	135.11 (6)	O6^i—K—O8^iv	111.54 (6)
O8^v—Ca3—O7	81.16 (6)	O6—K—O8^iv	49.74 (5)
O15—Ca3—O7	92.98 (6)	O2—K—O8^iv	82.11 (5)
O9—Ca3—O14	68.31 (6)	O7^iii—K—O8^iv	60.84 (5)
O10^iii—Ca3—O14	127.31 (6)	O11—K—O10^i	65.22 (5)
O9^iv—Ca3—O14	148.97 (6)	O2^i—K—O10^i	85.27 (6)
O8^v—Ca3—O14	125.89 (5)	O6^i—K—O10^i	82.94 (6)
O15—Ca3—O14	52.48 (5)	O6—K—O10^i	116.56 (6)
O7—Ca3—O14	73.71 (6)	O2—K—O10^i	118.53 (6)
O9—Ca3—Si4^iv	124.03 (5)	O7^iii—K—O10^i	61.36 (5)
O10^iii—Ca3—Si4^iv	79.96 (5)	O8^iv—K—O10^i	67.29 (5)
O9^iv—Ca3—Si4^iv	30.73 (4)	O11—K—O1	61.94 (5)
O8^v—Ca3—Si4^iv	32.30 (4)	O2^i—K—O1	53.61 (5)
O15—Ca3—Si4^iv	100.07 (4)	O6^i—K—O1	108.67 (5)
O7—Ca3—Si4^iv	107.20 (5)	O6—K—O1	139.33 (6)
O14—Ca3—Si4^iv	152.15 (4)	O2—K—O1	82.06 (5)
O9—Ca3—S	77.16 (4)	O7^iii—K—O1	119.35 (6)
O10^iii—Ca3—S	154.07 (5)	O8^iv—K—O1	106.19 (5)
O9^iv—Ca3—S	127.29 (5)	O10^i—K—O1	59.62 (5)
O8^v—Ca3—S	106.09 (4)	O11—K—O5^x	128.58 (6)
O15—Ca3—S	25.90 (4)	O2^i—K—O5^x	105.89 (6)
O7—Ca3—S	85.69 (4)	O6^i—K—O5^x	76.91 (5)
O14—Ca3—S	26.90 (4)	O6—K—O5^x	53.47 (5)
Si4^iv—Ca3—S	125.95 (2)	O2—K—O5^x	84.27 (5)
O9—Ca3—Si4	24.69 (4)	O7^iii—K—O5^x	88.77 (5)
O10^iii—Ca3—Si4	102.48 (6)	O8^iv—K—O5^x	99.92 (5)
O9^iv—Ca3—Si4	77.50 (5)	O10^i—K—O5^x	150.13 (6)
O8^v—Ca3—Si4	128.69 (5)	O1—K—O5^x	148.41 (6)
O15—Ca3—Si4	79.27 (5)	O11—K—O3^x	99.90 (6)
O7—Ca3—Si4	146.93 (5)	O2^i—K—O3^x	76.80 (5)
O14—Ca3—Si4	76.23 (4)	O6^i—K—O3^x	111.56 (6)
Si4^iv—Ca3—Si4	105.81 (2)	O6—K—O3^x	84.77 (5)
S—Ca3—Si4	73.32 (2)	O2—K—O3^x	48.32 (5)
O9—Ca3—Si4^iii	79.42 (5)	O7^iii—K—O3^x	148.84 (6)
O10^iii—Ca3—Si4^iii	24.55 (4)	O8^iv—K—O3^x	125.76 (5)
O9^iv—Ca3—Si4^iii	97.80 (4)	O10^i—K—O3^x	148.98 (5)
O8^v—Ca3—Si4^iii	114.95 (5)	O1—K—O3^x	89.43 (5)
O15—Ca3—Si4^iii	155.00 (5)	O5^x—K—O3^x	60.55 (5)
O7—Ca3—Si4^iii	73.71 (4)	O11—K—O4^x	154.74 (6)
O14—Ca3—Si4^iii	102.84 (4)	O2^i—K—O4^x	47.57 (5)
Si4^iv—Ca3—Si4^iii	104.04 (2)	O6^i—K—O4^x	51.38 (5)
S—Ca3—Si4^iii	129.72 (2)	O6—K—O4^x	112.32 (6)
Si4—Ca3—Si4^iii	100.20 (2)	O2—K—O4^x	109.19 (6)
O9—Ca3—Si3	108.74 (5)	O7^iii—K—O4^x	99.97 (5)
O10^iii—Ca3—Si3	68.10 (5)	O8^iv—K—O4^x	153.30 (5)
O9^iv—Ca3—Si3	135.60 (5)	O10^i—K—O4^x	122.17 (5)
O8^v—Ca3—Si3	98.40 (5)	O1—K—O4^x	99.42 (5)
O15—Ca3—Si3	110.38 (5)	O5^x—K—O4^x	58.86 (5)
O7—Ca3—Si3	23.11 (4)	O3^x—K—O4^x	60.88 (5)
O14—Ca3—Si3	75.28 (4)	Si1^ii—O1—Al2^i	123.81 (11)
Si4^iv—Ca3—Si3	116.80 (2)	Si1^ii—O1—Ca1	115.54 (8)
S—Ca3—Si3	95.58 (2)	Al2^i—O1—Ca1	120.36 (9)
Si4—Ca3—Si3	132.91 (2)	Si1^ii—O1—K	103.14 (8)
Si4^iii—Ca3—Si3	52.017 (17)	Al2^i—O1—K	83.97 (6)
O12—S—O13	112.43 (12)	Ca1—O1—K	88.45 (5)
O12—S—O14	110.70 (12)	Si1^xi—O2—Al2	161.48 (13)
O13—S—O14	110.65 (11)	Si1^xi—O2—K^v	104.05 (8)
O12—S—O15	106.42 (11)	Al2—O2—K^v	91.32 (8)
O13—S—O15	108.56 (11)	Si1^xi—O2—K	94.57 (8)
O14—S—O15	107.87 (11)	Al2—O2—K	89.74 (8)
O12—S—Ca2^v	120.19 (9)	K^v—O2—K	109.83 (7)
O13—S—Ca2^v	53.79 (8)	Si1^i—O3—Al2^ii	126.97 (10)
O14—S—Ca2^v	128.94 (9)	Si1^i—O3—Ca2	122.50 (8)
O15—S—Ca2^v	55.03 (7)	Al2^ii—O3—Ca2	108.03 (8)
O12—S—Ca1^v	53.99 (8)	Si1^i—O3—K^viii	90.36 (8)
O13—S—Ca1^v	116.41 (8)	Al2^ii—O3—K^viii	101.31 (8)
O14—S—Ca1^v	132.79 (7)	Ca2—O3—K^viii	94.59 (6)
O15—S—Ca1^v	53.57 (8)	Si1—O4—Al1	127.23 (11)
Ca2^v—S—Ca1^v	79.61 (2)	Si1—O4—Ca2	114.02 (9)
O12—S—Ca3	113.76 (8)	Al1—O4—Ca2	118.74 (8)
O13—S—Ca3	132.41 (9)	Si1—O4—K^viii	89.90 (7)
O14—S—Ca3	61.99 (7)	Al1—O4—K^viii	88.66 (7)
O15—S—Ca3	46.77 (7)	Ca2—O4—K^viii	90.52 (5)
Ca2^v—S—Ca3	92.48 (2)	Si3—O5—Al1^i	124.73 (11)
Ca1^v—S—Ca3	83.00 (2)	Si3—O5—Ca2	114.81 (9)
O12—S—Ca2	129.65 (9)	Al1^i—O5—Ca2	117.62 (9)
O13—S—Ca2	72.45 (8)	Si3—O5—K^viii	106.60 (9)
O14—S—Ca2	38.25 (7)	Al1^i—O5—K^viii	86.64 (7)
O15—S—Ca2	119.60 (9)	Ca2—O5—K^viii	93.53 (5)
Ca2^v—S—Ca2	103.10 (3)	Si3^iv—O6—Al1^xi	158.13 (12)
Ca1^v—S—Ca2	169.51 (3)	Si3^iv—O6—K^v	93.59 (8)
Ca3—S—Ca2	86.75 (2)	Al1^xi—O6—K^v	100.54 (8)
O2^vi—Si1—O4	109.26 (10)	Si3^iv—O6—K	98.35 (8)
O2^vi—Si1—O3^v	110.23 (10)	Al1^xi—O6—K	92.15 (8)
O4—Si1—O3^v	109.36 (9)	K^v—O6—K	110.89 (6)
O2^vi—Si1—O1^vii	111.44 (9)	Si3—O7—Al1	121.85 (10)
O4—Si1—O1^vii	106.54 (9)	Si3—O7—Ca3	119.87 (8)
O3^v—Si1—O1^vii	109.92 (9)	Al1—O7—Ca3	117.60 (8)
O2^vi—Si1—Ca2	122.18 (7)	Si3—O7—K^iv	88.60 (7)
O4—Si1—Ca2	40.41 (6)	Al1—O7—K^iv	101.42 (8)
O3^v—Si1—Ca2	125.14 (7)	Ca3—O7—K^iv	88.16 (5)
O1^vii—Si1—Ca2	66.19 (6)	Si3—O8—Si4^iii	136.25 (11)
O2^vi—Si1—Ca2^v	130.88 (7)	Si3—O8—Ca3^i	128.50 (9)
O4—Si1—Ca2^v	75.53 (6)	Si4^iii—O8—Ca3^i	94.87 (8)
O3^v—Si1—Ca2^v	34.73 (6)	Si3—O8—K^iii	92.94 (8)
O1^vii—Si1—Ca2^v	113.57 (7)	Si4^iii—O8—K^iii	93.96 (8)
Ca2—Si1—Ca2^v	93.67 (2)	Ca3^i—O8—K^iii	88.26 (5)
O2^vi—Si1—Ca1^vii	140.95 (7)	Si4—O9—Ca3	118.76 (9)
O4—Si1—Ca1^vii	105.61 (7)	Si4—O9—Ca3^iii	98.15 (8)
O3^v—Si1—Ca1^vii	73.04 (7)	Ca3—O9—Ca3^iii	120.42 (8)
O1^vii—Si1—Ca1^vii	39.95 (6)	Si4—O9—Ca1	94.37 (8)
Ca2—Si1—Ca1^vii	76.22 (2)	Ca3—O9—Ca1	119.04 (6)
Ca2^v—Si1—Ca1^vii	74.616 (19)	Ca3^iii—O9—Ca1	101.09 (6)
O2^vi—Si1—K^vi	59.78 (7)	Si4—O10—Ca3^iv	118.04 (9)
O4—Si1—K^vi	91.79 (7)	Si4—O10—Ca1^v	126.17 (9)
O3^v—Si1—K^vi	63.27 (7)	Ca3^iv—O10—Ca1^v	112.41 (7)
O1^vii—Si1—K^vi	161.64 (7)	Si4—O10—K^v	103.88 (10)
Ca2—Si1—K^vi	132.07 (3)	Ca3^iv—O10—K^v	91.19 (6)
Ca2^v—Si1—K^vi	71.37 (3)	Ca1^v—O10—K^v	92.34 (7)
Ca1^vii—Si1—K^vi	136.21 (3)	Si4—O11—Al2	132.11 (11)
O2^vi—Si1—K^viii	51.77 (7)	Si4—O11—Ca1	97.88 (9)
O4—Si1—K^viii	64.55 (7)	Al2—O11—Ca1	120.50 (8)
O3^v—Si1—K^viii	149.49 (8)	Si4—O11—K	105.96 (8)
O1^vii—Si1—K^viii	100.23 (7)	Al2—O11—K	97.09 (8)
Ca2—Si1—K^viii	71.22 (3)	Ca1—O11—K	97.13 (6)
Ca2^v—Si1—K^viii	133.54 (3)	S—O12—Ca2^vii	129.87 (11)
Ca1^vii—Si1—K^viii	137.21 (3)	S—O12—Ca1^v	98.99 (10)
K^vi—Si1—K^viii	86.58 (3)	Ca2^vii—O12—Ca1^v	115.65 (8)
O6^vi—Al1—O4	109.66 (9)	S—O12—Ca1	87.20 (9)
O6^vi—Al1—O5^v	111.20 (9)	Ca2^vii—O12—Ca1	99.62 (7)
O4—Al1—O5^v	108.37 (9)	Ca1^v—O12—Ca1	125.10 (7)
O6^vi—Al1—O7	113.16 (9)	S—O13—Ca2^v	98.68 (10)
O4—Al1—O7	104.46 (9)	S—O13—Ca1^vii	146.56 (13)
O5^v—Al1—O7	109.69 (8)	Ca2^v—O13—Ca1^vii	111.20 (7)
O6^vi—Al1—K^vi	59.52 (6)	S—O14—Ca2	119.11 (9)
O4—Al1—K^vi	91.83 (6)	S—O14—Ca1	112.45 (11)
O5^v—Al1—K^vi	64.21 (6)	Ca2—O14—Ca1	111.46 (7)
O7—Al1—K^vi	163.71 (7)	S—O14—Ca3	91.11 (8)
O6^vi—Al1—Ca2	121.97 (7)	Ca2—O14—Ca3	119.30 (8)
O4—Al1—Ca2	36.27 (5)	Ca1—O14—Ca3	100.73 (5)
O5^v—Al1—Ca2	122.81 (7)	S—O15—Ca3	107.32 (9)
O7—Al1—Ca2	68.27 (6)	S—O15—Ca2^v	96.79 (8)
K^vi—Al1—Ca2	127.98 (3)	Ca3—O15—Ca2^v	131.05 (9)
O6^vi—Al1—Ca2^v	130.45 (7)	S—O15—Ca1^v	98.85 (10)
O4—Al1—Ca2^v	71.77 (6)	Ca3—O15—Ca1^v	114.36 (7)
O5^v—Al1—Ca2^v	37.05 (6)	Ca2^v—O15—Ca1^v	102.71 (6)

Symmetry codes: (i) x, y+1, z; (ii) −x+1/2, y+1/2, −z; (iii) −x+1/2, y+1/2, −z+1; (iv) −x+1/2, y−1/2, −z+1; (v) x, y−1, z; (vi) x+1/2, −y+1/2, z; (vii) −x+1/2, y−1/2, −z; (viii) x+1/2, −y+3/2, z; (ix) −x, −y+1, −z; (x) x−1/2, −y+3/2, z; (xi) x−1/2, −y+1/2, z.