Structure and phase transition of the Se-rich variety of antimonpearceite, [(Ag,Cu)₆(Sb,As)₂(S,Se)₇][Ag₉Cu(S,Se)₂Se₂]

The crystal structure of a Se-rich antimonpearceite has been solved and refined by means of X-ray diffraction data collected at temperatures above (room temperature) and below (120 K) an ionic conductivity-induced phase transition. Both structure arrangements consist of the stacking of [(Ag,Cu)₆(Sb,As)₂(S,Se)₇]^2- A (A') and [Ag₉Cu(S,Se)₂Se₂]²⁺ B (B') module layers in which Sb forms isolated SbS₃ pyramids typically occurring in sulfosalts; copper links two S atoms in a linear coordination, and silver occupies sites with coordination ranging from quasi-linear to almost tetrahedral. In the ionic-conducting form, at room temperature, the silver d¹⁰ ions are found in the B (B') module layer along two-dimensional diffusion paths and their electron densities described by means of a combination of a Gram-Charlier development of the atomic displacement factors and a split-atom model. The structure resembles that of pearceite, except for the presence of both specific (Se) and mixed (S, Se) sites. In the low-temperature `ordered' phase at 120 K the silver d¹⁰ ions of the B (B') module layer are located in well defined sites with mixed S-Se coordination ranging from quasi-linear to almost tetrahedral. The structure is then similar to that of 222-pearceite but with major differences, specifically its cell metric, symmetry and local arrangement in the B (B') module layer.

Computing details

For both compounds, program(s) used to refine structure: (Jana2000; Petricek and Dusek, 2000); software used to prepare material for publication: (Jana2000; Petricek and Dusek, 2000).

Figures

(300K)

Crystal data

Ag14.585As0.337Cu1.415S8.341Sb1.663Se2.659	Z = 1
Mr = 2368.3	F(000) = 1046
Trigonal, P3m1	Dx = 6.518 Mg m^−3
Hall symbol: -P 3 2"	Mo Kα radiation, λ = 0.71069 Å
a = 7.5950 (4) Å	µ = 19.67 mm^−1
c = 12.0731 (6) Å	T = 300 K
V = 603.12 (5) Å^3	0.10 × 0.07 × 0.04 mm

Data collection

KappaCCD diffractometer	1253 independent reflections
Horizonally mounted graphite crystal monochromator	975 reflections with I > 2σ(I)
Detector resolution: 9 pixels mm^-1	Rint = 0.046
CCD, phi and ω frames scans	θmax = 38.0°, θmin = 6.4°
Absorption correction: gaussian (Jana2000; Petricek, Dusek & Palatinus, 2000)	h = −8→13
Tmin = 0.157, Tmax = 0.523	k = −13→11
13591 measured reflections	l = −20→14

Refinement

Refinement on F	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.0004F^2)
R[F^2 > 2σ(F^2)] = 0.049	(Δ/σ)max = 0.0004
wR(F^2) = 0.060	Δρmax = 0.79 e Å^−3
S = 1.80	Δρmin = −0.64 e Å^−3
1253 reflections	Extinction correction: B-C type 2 (Becker & Coppens, 1974)
95 parameters	Extinction coefficient: 0.332272

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Sb	0.333333	0.666667	0.40561 (5)	0.02348 (19)	0.83 (2)
As'	0.333333	0.666667	0.405612	0.02348 (19)	0.17 (2)
Ag1a	0.2851 (8)	0.1426 (4)	0.3899 (5)	0.0526 (8)	0.68 (2)
Ag1b	0.351 (3)	0.1753 (13)	0.3629 (9)	0.073 (2)	0.25 (3)
Cu1b'	0.350518	0.175259	0.362861	0.073 (2)	0.07 (3)
Ag2	0.2458 (19)	0.3649 (4)	0.1190 (4)	0.163 (8)	0.296 (6)
Ag3	0.3528 (8)	0.3128 (11)	0.1187 (4)	0.157 (3)	0.454 (6)
Cu	0	0	0	0.0313 (4)
S1	0	0	0.18217 (15)	0.0312 (6)	0.830 (11)
Se1'	0	0	0.182166	0.0312 (6)	0.170 (11)
S2	0.0146 (2)	0.50730 (10)	0.30757 (15)	0.0381 (5)
S3	0	0	0.5	0.117 (3)	0.68 (4)
Se3'	0	0	0.5	0.117 (3)	0.32 (4)
Se	0.666667	0.333333	0.0178 (2)	0.0466 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sb	0.0243 (2)	0.0243 (2)	0.0219 (3)	0.01213 (12)	0	0
As'	0.0243 (2)	0.0243 (2)	0.0219 (3)	0.01213 (12)	0	0
Ag1a	0.0588 (12)	0.0501 (6)	0.0518 (15)	0.0294 (6)	0.0033 (9)	0.0017 (5)
Ag1b	0.105 (4)	0.0514 (14)	0.080 (4)	0.0527 (19)	0.050 (5)	0.025 (2)
Cu1b'	0.105 (4)	0.0514 (14)	0.080 (4)	0.0527 (19)	0.050 (5)	0.025 (2)
Ag2	0.267 (19)	0.0379 (10)	0.0549 (15)	−0.019 (3)	−0.050 (5)	0.0044 (8)
Ag3	0.079 (2)	0.289 (6)	0.069 (2)	0.066 (3)	0.0046 (18)	−0.021 (3)
Cu	0.0387 (6)	0.0387 (6)	0.0166 (6)	0.0193 (3)	0	0
S1	0.0366 (8)	0.0366 (8)	0.0205 (8)	0.0183 (4)	0	0
Se1'	0.0366 (8)	0.0366 (8)	0.0205 (8)	0.0183 (4)	0	0
S2	0.0214 (6)	0.0387 (6)	0.0485 (9)	0.0107 (3)	−0.0036 (5)	−0.0018 (3)
S3	0.152 (4)	0.152 (4)	0.047 (6)	0.076 (2)	0	0
Se3'	0.152 (4)	0.152 (4)	0.047 (6)	0.076 (2)	0	0
Se	0.0455 (5)	0.0455 (5)	0.0487 (7)	0.0227 (2)	0	0

Geometric parameters (Å, º)

Sb—S2	2.4076 (15)	Ag2—Ag2^iv	0.96 (2)
Sb—S2^i	2.4076 (17)	Ag2—Ag3	1.067 (17)
Sb—S2^ii	2.4076 (15)	Ag2—Ag3^iv	2.001 (18)
Ag1a—Ag1b	0.540 (16)	Ag3—Ag3^v	2.073 (14)
Ag1a—S3	2.299 (6)	Cu—S1	2.1993 (18)
Ag1b—S2^i	2.291 (10)	Cu—S1^vi	2.1993 (18)
Ag1b—S2^iii	2.291 (18)
S2—Sb—S2^i	97.90 (5)	Ag1a—S3—Ag1a^xi	89.91 (15)
S2—Sb—S2^ii	97.90 (4)	Ag1a—S3—Ag1a^xii	90.09 (15)
S2^i—Sb—S2	97.90 (5)	Ag1a^ix—S3—Ag1a	180
S2^i—Sb—S2^ii	97.90 (5)	Ag1a^ix—S3—Ag1a^vii	90.09 (18)
S2^ii—Sb—S2	97.90 (4)	Ag1a^ix—S3—Ag1a^x	89.91 (18)
S2^ii—Sb—S2^i	97.90 (5)	Ag1a^ix—S3—Ag1a^xi	90.09 (15)
Ag1b—Ag1a—S3	178.1 (16)	Ag1a^ix—S3—Ag1a^xii	89.91 (15)
Ag1a—Ag1b—S2^i	120 (2)	Ag1a^vii—S3—Ag1a	89.91 (18)
Ag1a—Ag1b—S2^iii	120.1 (16)	Ag1a^vii—S3—Ag1a^ix	90.09 (18)
S2^i—Ag1b—S2^iii	119.8 (7)	Ag1a^vii—S3—Ag1a^x	180
S2^iii—Ag1b—S2^i	119.8 (7)	Ag1a^vii—S3—Ag1a^xi	89.9 (2)
Ag2^iv—Ag2—Ag3	161.3 (5)	Ag1a^vii—S3—Ag1a^xii	90.1 (2)
Ag2^iv—Ag2—Ag3^iv	9.9 (3)	Ag1a^x—S3—Ag1a	90.09 (18)
Ag3—Ag2—Ag3^iv	151.4 (5)	Ag1a^x—S3—Ag1a^ix	89.91 (18)
Ag3^iv—Ag2—Ag3	151.4 (5)	Ag1a^x—S3—Ag1a^vii	180
Ag2—Ag3—Ag2^iv	8.9 (3)	Ag1a^x—S3—Ag1a^xi	90.1 (2)
Ag2—Ag3—Ag3^v	138.7 (5)	Ag1a^x—S3—Ag1a^xii	89.9 (2)
Ag2^iv—Ag3—Ag2	8.9 (3)	Ag1a^xi—S3—Ag1a	89.91 (15)
Ag2^iv—Ag3—Ag3^v	129.9 (3)	Ag1a^xi—S3—Ag1a^ix	90.09 (15)
S1—Cu—S1^vi	180	Ag1a^xi—S3—Ag1a^vii	89.9 (2)
S1^vi—Cu—S1	180	Ag1a^xi—S3—Ag1a^x	90.1 (2)
Sb—S2—Ag1b^vii	109.4 (3)	Ag1a^xi—S3—Ag1a^xii	180
Sb—S2—Ag1b^viii	109.4 (3)	Ag1a^xii—S3—Ag1a	90.09 (15)
Ag1b^vii—S2—Ag1b^viii	103.6 (5)	Ag1a^xii—S3—Ag1a^ix	89.91 (15)
Ag1b^viii—S2—Ag1b^vii	103.6 (5)	Ag1a^xii—S3—Ag1a^vii	90.1 (2)
Ag1a—S3—Ag1a^ix	180	Ag1a^xii—S3—Ag1a^x	89.9 (2)
Ag1a—S3—Ag1a^vii	89.91 (18)	Ag1a^xii—S3—Ag1a^xi	180
Ag1a—S3—Ag1a^x	90.09 (18)

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

(120K)

Crystal data

Ag14.691Cu1.309S8.369Sb2Se2.631	V = 2366.4 (5) Å^3
Mr = 2387.5	Z = 4
Monoclinic, P21/c	F(000) = 4222
Hall symbol: -P 2ybc	Dx = 6.699 Mg m^−3
a = 13.1426 (14) Å	Mo Kα radiation, λ = 0.71069 Å
b = 7.5879 (7) Å	µ = 20.02 mm^−1
c = 23.729 (4) Å	T = 120 K
β = 90°	0.10 × 0.07 × 0.04 mm

Data collection

KappaCCD diffractometer	27670 independent reflections
Horizonally mounted graphite crystal monochromator	21308 reflections with I > 2σ(I)
Detector resolution: 9 pixels mm^-1	Rint = 0.085
CCD, phi and ω frames scans	θmax = 36.0°, θmin = 6.4°
Absorption correction: gaussian (Jana2000; Petricek, Dusek & Palatinus, 2000)	h = −21→21
Tmin = 0.137, Tmax = 0.363	k = −12→12
151079 measured reflections	l = −39→38

Refinement

Refinement on F	269 parameters
R[F^2 > 2σ(F^2)] = 0.069	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.000484F^2)
wR(F^2) = 0.076	(Δ/σ)max = 0.001
S = 1.80	Δρmax = 5.51 e Å^−3
27670 reflections	Δρmin = −2.74 e Å^−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Sb1	0.41934 (4)	0.74224 (6)	0.049318 (17)	0.01186 (10)
Sb2	0.08565 (4)	0.76029 (6)	0.454154 (17)	0.01168 (10)
Ag1	0.40458 (6)	0.23826 (8)	0.05653 (3)	0.02470 (17)
Ag2	0.10006 (6)	0.27073 (8)	0.44361 (3)	0.02431 (16)
Ag3	0.31297 (4)	0.44364 (8)	0.45025 (3)	0.02174 (15)
Ag4	0.34464 (5)	0.99558 (11)	0.43481 (3)	0.0301 (2)	0.787 (10)
Cu4'	0.344644	0.995578	0.434812	0.0301 (2)	0.213 (10)
Ag5	0.15689 (5)	0.51196 (12)	0.07541 (5)	0.0438 (3)	0.904 (11)
Cu5'	0.156889	0.511958	0.075407	0.0438 (3)	0.096 (11)
Ag6	0.18494 (4)	0.04946 (8)	0.05407 (3)	0.02094 (15)
Ag7	0.12076 (5)	0.00255 (8)	0.29899 (3)	0.02549 (16)
Ag8	0.06548 (5)	0.41819 (9)	0.30819 (3)	0.02599 (17)
Ag9	0.05475 (4)	0.25450 (10)	0.19192 (3)	0.02861 (19)
Ag10	0.24196 (7)	0.92516 (9)	0.19837 (3)	0.0356 (2)
Ag11	0.33018 (6)	0.54218 (8)	0.18872 (3)	0.02807 (18)
Ag12	0.24120 (5)	0.65338 (9)	0.30401 (3)	0.02619 (16)
Ag13	0.41747 (4)	0.14844 (10)	0.18436 (3)	0.02990 (18)
Ag14	0.41476 (4)	0.40030 (8)	0.30465 (3)	0.02381 (16)
Ag15	0.35615 (5)	0.01474 (7)	0.31001 (3)	0.02283 (15)
Cu1	0.23980 (5)	0.26900 (12)	0.24997 (3)	0.01036 (19)
S1	0.23947 (11)	0.26011 (17)	0.15720 (5)	0.0126 (3)	0.820 (7)
Se1'	0.239466	0.260111	0.157195	0.0126 (3)	0.180 (7)
S2	0.24226 (11)	0.26472 (17)	0.34245 (5)	0.0124 (3)	0.813 (7)
Se2'	0.242257	0.264725	0.342454	0.0124 (3)	0.187 (7)
S3	0.26031 (13)	0.7756 (3)	0.09869 (8)	0.0151 (4)
S4	0.24809 (13)	0.7270 (2)	0.40769 (8)	0.0147 (4)
S5	0.48649 (13)	0.5068 (2)	0.10716 (8)	0.0159 (4)
S6	0.49279 (12)	0.4862 (2)	0.40685 (7)	0.0129 (4)
S7	0.00299 (12)	0.0217 (2)	0.09274 (7)	0.0140 (4)
S8	0.02061 (13)	−0.0054 (2)	0.39546 (7)	0.0152 (4)
S9	0.24653 (16)	0.3317 (2)	0.00287 (7)	0.0365 (6)	0.737 (9)
Se9'	0.246528	0.331668	0.002866	0.0365 (6)	0.263 (9)
Se1	0.42892 (5)	0.75709 (8)	0.25433 (3)	0.01342 (16)
Se2	0.08817 (5)	0.71500 (9)	0.23224 (3)	0.01485 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sb1	0.01258 (19)	0.0116 (2)	0.01137 (16)	−0.00013 (14)	0.00045 (17)	−0.00031 (14)
Sb2	0.01123 (19)	0.01222 (19)	0.01160 (16)	0.00015 (14)	0.00046 (17)	−0.00029 (14)
Ag1	0.0347 (3)	0.0156 (3)	0.0237 (3)	0.0030 (2)	0.0024 (3)	−0.0003 (2)
Ag2	0.0303 (3)	0.0155 (2)	0.0271 (3)	−0.0015 (2)	0.0067 (2)	−0.0015 (2)
Ag3	0.0174 (2)	0.0275 (3)	0.0203 (2)	−0.0008 (2)	0.0019 (2)	0.0011 (2)
Ag4	0.0206 (3)	0.0418 (5)	0.0279 (4)	−0.0093 (3)	0.0058 (3)	0.0018 (3)
Cu4'	0.0206 (3)	0.0418 (5)	0.0279 (4)	−0.0093 (3)	0.0058 (3)	0.0018 (3)
Ag5	0.0181 (3)	0.0400 (5)	0.0734 (7)	−0.0085 (3)	0.0008 (3)	0.0160 (4)
Cu5'	0.0181 (3)	0.0400 (5)	0.0734 (7)	−0.0085 (3)	0.0008 (3)	0.0160 (4)
Ag6	0.0184 (2)	0.0252 (3)	0.0192 (2)	−0.0017 (2)	0.0024 (2)	0.0011 (2)
Ag7	0.0347 (3)	0.0175 (2)	0.0242 (3)	−0.0096 (2)	0.0118 (2)	−0.0063 (2)
Ag8	0.0190 (3)	0.0333 (3)	0.0256 (3)	−0.0049 (2)	0.0022 (2)	−0.0083 (2)
Ag9	0.0132 (2)	0.0549 (4)	0.0178 (3)	0.0015 (2)	0.00045 (19)	−0.0019 (3)
Ag10	0.0616 (5)	0.0205 (3)	0.0248 (3)	−0.0165 (3)	0.0193 (3)	−0.0060 (2)
Ag11	0.0494 (4)	0.0185 (3)	0.0162 (2)	−0.0152 (2)	0.0062 (2)	−0.0015 (2)
Ag12	0.0244 (3)	0.0337 (3)	0.0205 (3)	−0.0052 (2)	−0.0049 (2)	0.0024 (2)
Ag13	0.0134 (2)	0.0470 (4)	0.0294 (3)	0.0080 (2)	−0.0021 (2)	−0.0017 (3)
Ag14	0.0179 (2)	0.0277 (3)	0.0258 (3)	−0.0072 (2)	0.0020 (2)	−0.0061 (2)
Ag15	0.0314 (3)	0.0161 (2)	0.0210 (3)	0.0094 (2)	−0.0001 (2)	−0.0015 (2)
Cu1	0.0090 (3)	0.0145 (4)	0.0076 (3)	−0.0010 (2)	−0.0005 (3)	0.0002 (2)
S1	0.0117 (6)	0.0153 (7)	0.0107 (5)	−0.0002 (4)	0.0010 (4)	−0.0013 (4)
Se1'	0.0117 (6)	0.0153 (7)	0.0107 (5)	−0.0002 (4)	0.0010 (4)	−0.0013 (4)
S2	0.0130 (6)	0.0125 (6)	0.0118 (5)	0.0005 (4)	0.0002 (4)	0.0013 (4)
Se2'	0.0130 (6)	0.0125 (6)	0.0118 (5)	0.0005 (4)	0.0002 (4)	0.0013 (4)
S3	0.0105 (6)	0.0218 (8)	0.0131 (7)	0.0003 (6)	−0.0002 (5)	0.0024 (6)
S4	0.0102 (6)	0.0186 (7)	0.0151 (7)	0.0004 (6)	0.0014 (5)	−0.0008 (6)
S5	0.0164 (7)	0.0115 (7)	0.0199 (8)	−0.0003 (6)	−0.0009 (6)	0.0035 (6)
S6	0.0122 (6)	0.0112 (6)	0.0153 (7)	0.0002 (5)	0.0008 (5)	−0.0004 (6)
S7	0.0129 (7)	0.0134 (7)	0.0158 (7)	0.0044 (5)	0.0031 (6)	0.0020 (6)
S8	0.0171 (7)	0.0126 (7)	0.0158 (7)	0.0030 (6)	−0.0006 (6)	0.0027 (6)
S9	0.0717 (15)	0.0198 (8)	0.0180 (8)	−0.0005 (7)	−0.0179 (7)	−0.0002 (5)
Se9'	0.0717 (15)	0.0198 (8)	0.0180 (8)	−0.0005 (7)	−0.0179 (7)	−0.0002 (5)
Se1	0.0148 (3)	0.0102 (3)	0.0153 (3)	−0.0002 (2)	0.0016 (2)	−0.0007 (2)
Se2	0.0109 (3)	0.0188 (3)	0.0150 (3)	−0.0018 (2)	−0.0013 (2)	0.0028 (2)

Geometric parameters (Å, º)

Sb1—S3	2.4093 (18)	Ag8—Se2	2.8998 (10)
Sb1—S5	2.4197 (18)	Ag8—Se2^viii	2.7157 (9)
Sb1—S6^i	2.4173 (17)	Ag9—Cu1	2.7971 (9)
Sb2—S4	2.4160 (18)	Ag9—S1	2.5641 (15)
Sb2—S7^ii	2.4231 (17)	Ag9—S8^ii	2.9328 (18)
Sb2—S8^iii	2.4150 (18)	Ag9—Se2^viii	2.6184 (9)
Ag1—S5	2.5986 (19)	Ag10—Ag13^iii	2.8812 (10)
Ag1—S6^iv	2.4962 (18)	Ag10—Cu1^iii	2.8822 (11)
Ag1—S9	2.537 (2)	Ag10—S1^iii	2.7231 (15)
Ag2—S7^ii	2.4912 (18)	Ag10—S3	2.635 (2)
Ag2—S8	2.6046 (18)	Ag10—Se2	2.6971 (10)
Ag2—S9^v	2.507 (2)	Ag11—Cu1	2.7964 (10)
Ag3—Ag6^v	2.9837 (8)	Ag11—S1	2.5617 (15)
Ag3—S4	2.5241 (19)	Ag11—S3	2.923 (2)
Ag3—S6	2.5982 (17)	Ag11—S5	2.8353 (19)
Ag3—S9^v	2.5856 (18)	Ag11—Se1	2.6012 (9)
Ag4—Ag15^iii	2.9689 (10)	Ag12—Ag14	2.9817 (9)
Ag4—S4	2.485 (2)	Ag12—S4	2.524 (2)
Ag4—S5^i	2.4340 (19)	Ag12—Se1	2.8454 (9)
Ag4—S9^vi	2.4472 (19)	Ag12—Se2	2.6767 (9)
Ag5—S1	2.9319 (16)	Ag13—Ag14^iv	2.9112 (9)
Ag5—S3	2.481 (2)	Ag13—Cu1	2.9518 (10)
Ag5—S8^ii	2.4366 (18)	Ag13—S1	2.5702 (15)
Ag5—S9	2.4945 (19)	Ag13—S6^iv	2.7549 (18)
Ag6—S3^vii	2.534 (2)	Ag13—Se1^iv	2.6216 (9)
Ag6—S7	2.5700 (17)	Ag14—Cu1	2.8221 (9)
Ag6—S9	2.5917 (18)	Ag14—S2	2.6463 (15)
Ag7—Ag9^viii	2.9849 (9)	Ag14—S6	2.7125 (18)
Ag7—Ag10^vii	2.9297 (10)	Ag14—Se1	2.9648 (9)
Ag7—Cu1	2.8086 (10)	Ag14—Se1^iv	2.7130 (9)
Ag7—S2	2.7516 (15)	Ag15—Cu1	2.8444 (10)
Ag7—S8	2.6414 (18)	Ag15—S2	2.5360 (15)
Ag7—Se2^vii	2.7299 (9)	Ag15—S5^iv	2.8539 (18)
Ag8—Ag12	2.9203 (9)	Ag15—Se1^vii	2.5461 (9)
Ag8—Cu1	2.9049 (10)	Cu1—S1	2.2024 (15)
Ag8—S2	2.7230 (15)	Cu1—S2	2.1951 (14)
Ag8—S7^ii	2.6370 (18)
S3—Sb1—S5	96.78 (6)	Ag7—Cu1—Ag14	121.17 (3)
S3—Sb1—S6^i	97.17 (6)	Ag7—Cu1—Ag15	66.66 (3)
S5—Sb1—S6^i	98.47 (6)	Ag7—Cu1—S1	113.00 (5)
S4—Sb2—S7^ii	97.89 (6)	Ag7—Cu1—S2	65.39 (4)
S4—Sb2—S8^iii	97.27 (6)	Ag8—Cu1—Ag9	64.14 (2)
S7^ii—Sb2—S8^iii	96.61 (6)	Ag8—Cu1—Ag10^vii	124.23 (3)
S5—Ag1—S6^iv	102.46 (6)	Ag8—Cu1—Ag11	107.05 (3)
S5—Ag1—S9	110.62 (6)	Ag8—Cu1—Ag13	174.54 (4)
S6^iv—Ag1—S9	146.20 (6)	Ag8—Cu1—Ag14	106.64 (3)
S7^ii—Ag2—S8	104.19 (6)	Ag8—Cu1—Ag15	116.75 (3)
S7^ii—Ag2—S9^v	148.05 (6)	Ag8—Cu1—S1	119.06 (5)
S8—Ag2—S9^v	107.73 (6)	Ag8—Cu1—S2	62.74 (4)
Ag6^v—Ag3—S4	97.17 (5)	Ag9—Cu1—Ag10^vii	76.34 (3)
Ag6^v—Ag3—S6	146.94 (4)	Ag9—Cu1—Ag11	98.20 (3)
Ag6^v—Ag3—S9^v	54.90 (4)	Ag9—Cu1—Ag13	114.57 (3)
S4—Ag3—S6	92.45 (6)	Ag9—Cu1—Ag14	161.58 (4)
S4—Ag3—S9^v	140.12 (6)	Ag9—Cu1—Ag15	133.42 (4)
S6—Ag3—S9^v	126.81 (6)	Ag9—Cu1—S1	60.32 (4)
Ag15^iii—Ag4—S4	78.92 (5)	Ag9—Cu1—S2	120.30 (5)
Ag15^iii—Ag4—S5^i	62.85 (5)	Ag10^vii—Cu1—Ag11	116.49 (3)
Ag15^iii—Ag4—S9^vi	131.21 (5)	Ag10^vii—Cu1—Ag13	59.17 (3)
S4—Ag4—S5^i	112.84 (7)	Ag10^vii—Cu1—Ag14	120.46 (3)
S4—Ag4—S9^vi	109.94 (7)	Ag10^vii—Cu1—Ag15	66.01 (3)
S5^i—Ag4—S9^vi	137.03 (7)	Ag10^vii—Cu1—S1	63.11 (4)
S1—Ag5—S3	100.10 (6)	Ag10^vii—Cu1—S2	114.28 (5)
S1—Ag5—S8^ii	97.55 (6)	Ag11—Cu1—Ag13	67.64 (3)
S1—Ag5—S9	85.67 (5)	Ag11—Cu1—Ag14	68.36 (3)
S3—Ag5—S8^ii	120.32 (7)	Ag11—Cu1—Ag15	122.33 (3)
S3—Ag5—S9	109.70 (7)	Ag11—Cu1—S1	60.27 (4)
S8^ii—Ag5—S9	128.20 (7)	Ag11—Cu1—S2	121.62 (5)
Ag3^ix—Ag6—S3^vii	97.99 (5)	Ag13—Cu1—Ag14	72.99 (2)
Ag3^ix—Ag6—S7	145.19 (5)	Ag13—Cu1—Ag15	68.20 (3)
Ag3^ix—Ag6—S9	54.71 (4)	Ag13—Cu1—S1	57.65 (4)
S3^vii—Ag6—S7	98.48 (6)	Ag13—Cu1—S2	120.74 (5)
S3^vii—Ag6—S9	138.71 (6)	Ag14—Cu1—Ag15	64.60 (2)
S7—Ag6—S9	121.71 (6)	Ag14—Cu1—S1	118.17 (5)
Ag9^viii—Ag7—Ag10^vii	110.65 (3)	Ag14—Cu1—S2	62.19 (4)
Ag9^viii—Ag7—Cu1	156.11 (3)	Ag15—Cu1—S1	118.75 (5)
Ag9^viii—Ag7—S2	151.31 (4)	Ag15—Cu1—S2	58.75 (4)
Ag9^viii—Ag7—S8	62.48 (4)	S1—Cu1—S2	177.30 (7)
Ag9^viii—Ag7—Se2^vii	54.32 (2)	Ag5—S1—Ag9	82.71 (4)
Ag10^vii—Ag7—Cu1	60.26 (2)	Ag5—S1—Ag10^vii	148.24 (6)
Ag10^vii—Ag7—S2	97.75 (4)	Ag5—S1—Ag11	79.69 (4)
Ag10^vii—Ag7—S8	166.59 (5)	Ag5—S1—Ag13	135.87 (6)
Ag10^vii—Ag7—Se2^vii	56.79 (2)	Ag5—S1—Cu1	129.97 (6)
Cu1—Ag7—S2	46.49 (3)	Ag9—S1—Ag10^vii	83.14 (5)
Cu1—Ag7—S8	130.76 (5)	Ag9—S1—Ag11	111.14 (5)
Cu1—Ag7—Se2^vii	114.99 (3)	Ag9—S1—Ag13	140.87 (6)
S2—Ag7—S8	88.89 (5)	Ag9—S1—Cu1	71.41 (4)
S2—Ag7—Se2^vii	152.42 (4)	Ag10^vii—S1—Ag11	132.03 (6)
S8—Ag7—Se2^vii	113.99 (5)	Ag10^vii—S1—Ag13	65.88 (4)
Ag12—Ag8—Cu1	66.32 (2)	Ag10^vii—S1—Cu1	70.73 (4)
Ag12—Ag8—S2	66.22 (3)	Ag11—S1—Ag13	77.21 (5)
Ag12—Ag8—S7^ii	96.78 (4)	Ag11—S1—Cu1	71.43 (4)
Ag12—Ag8—Se2	54.76 (2)	Ag13—S1—Cu1	75.98 (5)
Ag12—Ag8—Se2^viii	157.37 (3)	Ag7—S2—Ag8	72.67 (4)
Cu1—Ag8—S2	45.77 (3)	Ag7—S2—Ag14	130.63 (5)
Cu1—Ag8—S7^ii	144.02 (5)	Ag7—S2—Ag15	71.82 (4)
Cu1—Ag8—Se2	85.76 (3)	Ag7—S2—Cu1	68.12 (4)
Cu1—Ag8—Se2^viii	101.37 (3)	Ag8—S2—Ag14	117.61 (5)
S2—Ag8—S7^ii	98.77 (5)	Ag8—S2—Ag15	137.12 (6)
S2—Ag8—Se2	115.47 (4)	Ag8—S2—Cu1	71.49 (4)
S2—Ag8—Se2^viii	119.81 (4)	Ag14—S2—Ag15	71.47 (4)
S7^ii—Ag8—Se2	110.96 (5)	Ag14—S2—Cu1	70.61 (4)
S7^ii—Ag8—Se2^viii	103.32 (4)	Ag15—S2—Cu1	73.51 (5)
Se2—Ag8—Se2^viii	107.33 (3)	Sb1—S3—Ag5	106.40 (7)
Se2^viii—Ag8—Se2	107.33 (3)	Sb1—S3—Ag6^iii	102.83 (7)
Ag7^ii—Ag9—Cu1	127.70 (3)	Sb1—S3—Ag10	124.14 (7)
Ag7^ii—Ag9—S1	138.11 (4)	Sb1—S3—Ag11	91.11 (6)
Ag7^ii—Ag9—S8^ii	53.01 (4)	Ag5—S3—Ag6^iii	110.74 (7)
Ag7^ii—Ag9—Se2^viii	57.87 (2)	Ag5—S3—Ag10	119.81 (8)
Cu1—Ag9—S1	48.27 (3)	Ag5—S3—Ag11	81.16 (6)
Cu1—Ag9—S8^ii	128.12 (4)	Ag6^iii—S3—Ag10	89.20 (6)
Cu1—Ag9—Se2^viii	106.85 (3)	Ag6^iii—S3—Ag11	157.68 (8)
S1—Ag9—S8^ii	94.71 (5)	Ag10—S3—Ag11	68.51 (5)
S1—Ag9—Se2^viii	154.42 (4)	Sb2—S4—Ag3	101.82 (7)
S8^ii—Ag9—Se2^viii	108.35 (4)	Sb2—S4—Ag4	104.32 (7)
Ag7^iii—Ag10—Ag13^iii	114.30 (3)	Sb2—S4—Ag12	115.86 (7)
Ag7^iii—Ag10—Cu1^iii	57.79 (2)	Ag3—S4—Ag4	114.98 (7)
Ag7^iii—Ag10—S1^iii	95.67 (4)	Ag3—S4—Ag12	102.33 (7)
Ag7^iii—Ag10—S3	150.21 (5)	Ag4—S4—Ag12	116.88 (7)
Ag7^iii—Ag10—Se2	57.87 (2)	Sb1—S5—Ag1	99.54 (6)
Ag13^iii—Ag10—Cu1^iii	61.62 (2)	Sb1—S5—Ag4^iv	97.25 (7)
Ag13^iii—Ag10—S1^iii	54.51 (4)	Sb1—S5—Ag11	93.03 (6)
Ag13^iii—Ag10—S3	94.38 (5)	Sb1—S5—Ag15^i	129.74 (7)
Ag13^iii—Ag10—Se2	169.11 (4)	Ag1—S5—Ag4^iv	99.28 (7)
Cu1^iii—Ag10—S1^iii	46.16 (3)	Ag1—S5—Ag11	95.15 (6)
Cu1^iii—Ag10—S3	140.56 (5)	Ag1—S5—Ag15^i	129.44 (7)
Cu1^iii—Ag10—Se2	113.65 (3)	Ag4^iv—S5—Ag11	160.61 (8)
S1^iii—Ag10—S3	94.65 (5)	Ag4^iv—S5—Ag15^i	67.78 (5)
S1^iii—Ag10—Se2	130.52 (5)	Ag11—S5—Ag15^i	93.03 (6)
S3—Ag10—Se2	94.67 (5)	Sb1^iv—S6—Ag1^i	100.30 (6)
Cu1—Ag11—S1	48.30 (3)	Sb1^iv—S6—Ag3	99.71 (6)
Cu1—Ag11—S3	134.07 (5)	Sb1^iv—S6—Ag13^i	118.40 (6)
Cu1—Ag11—S5	126.32 (4)	Sb1^iv—S6—Ag14	112.40 (6)
Cu1—Ag11—Se1	111.44 (3)	Ag1^i—S6—Ag3	116.67 (7)
S1—Ag11—S3	98.43 (5)	Ag1^i—S6—Ag13^i	72.54 (5)
S1—Ag11—S5	93.36 (5)	Ag1^i—S6—Ag14	134.40 (7)
S1—Ag11—Se1	158.55 (4)	Ag3—S6—Ag13^i	139.15 (7)
S3—Ag11—S5	77.65 (5)	Ag3—S6—Ag14	88.89 (5)
S3—Ag11—Se1	102.38 (4)	Ag13^i—S6—Ag14	64.34 (4)
S5—Ag11—Se1	96.11 (4)	Sb2^viii—S7—Ag2^viii	98.67 (6)
Ag8—Ag12—Ag14	102.19 (3)	Sb2^viii—S7—Ag6	102.84 (6)
Ag8—Ag12—S4	97.50 (5)	Sb2^viii—S7—Ag8^viii	117.90 (7)
Ag8—Ag12—Se1	150.32 (3)	Ag2^viii—S7—Ag6	116.41 (7)
Ag8—Ag12—Se2	62.23 (2)	Ag2^viii—S7—Ag8^viii	83.99 (6)
Ag14—Ag12—S4	96.33 (5)	Ag6—S7—Ag8^viii	131.32 (7)
Ag14—Ag12—Se1	61.11 (2)	Sb2^vii—S8—Ag2	101.39 (6)
Ag14—Ag12—Se2	133.68 (3)	Sb2^vii—S8—Ag5^viii	102.41 (7)
S4—Ag12—Se1	108.15 (5)	Sb2^vii—S8—Ag7	109.89 (7)
S4—Ag12—Se2	127.47 (5)	Sb2^vii—S8—Ag9^viii	94.00 (6)
Se1—Ag12—Se2	109.85 (3)	Ag2—S8—Ag5^viii	102.47 (7)
Ag10^vii—Ag13—Ag14^iv	102.46 (3)	Ag2—S8—Ag7	99.33 (6)
Ag10^vii—Ag13—Cu1	59.21 (2)	Ag2—S8—Ag9^viii	160.95 (7)
Ag10^vii—Ag13—S1	59.61 (4)	Ag5^viii—S8—Ag7	136.19 (8)
Ag10^vii—Ag13—S6^iv	99.83 (4)	Ag5^viii—S8—Ag9^viii	84.88 (6)
Ag10^vii—Ag13—Se1^iv	137.51 (3)	Ag7—S8—Ag9^viii	64.51 (4)
Ag14^iv—Ag13—Cu1	138.79 (3)	Ag1—S9—Ag2^ix	145.43 (7)
Ag14^iv—Ag13—S1	157.68 (4)	Ag1—S9—Ag3^ix	74.94 (5)
Ag14^iv—Ag13—S6^iv	57.13 (4)	Ag1—S9—Ag4^x	92.83 (7)
Ag14^iv—Ag13—Se1^iv	64.56 (2)	Ag1—S9—Ag5	101.16 (6)
Cu1—Ag13—S1	46.38 (3)	Ag1—S9—Ag6	77.86 (5)
Cu1—Ag13—S6^iv	153.06 (4)	Ag2^ix—S9—Ag3^ix	74.82 (5)
Cu1—Ag13—Se1^iv	102.65 (3)	Ag2^ix—S9—Ag4^x	101.57 (6)
S1—Ag13—S6^iv	109.87 (5)	Ag2^ix—S9—Ag5	101.21 (8)
S1—Ag13—Se1^iv	137.43 (4)	Ag2^ix—S9—Ag6	76.53 (6)
S6^iv—Ag13—Se1^iv	104.29 (4)	Ag3^ix—S9—Ag4^x	86.34 (6)
Ag12—Ag14—Ag13^i	99.40 (3)	Ag3^ix—S9—Ag5	159.36 (8)
Ag12—Ag14—Cu1	66.53 (2)	Ag3^ix—S9—Ag6	70.38 (5)
Ag12—Ag14—S2	66.22 (3)	Ag4^x—S9—Ag5	114.23 (7)
Ag12—Ag14—S6	97.99 (4)	Ag4^x—S9—Ag6	156.42 (8)
Ag12—Ag14—Se1	57.17 (2)	Ag5—S9—Ag6	88.98 (6)
Ag12—Ag14—Se1^iv	146.58 (3)	Ag11—Se1—Ag12	69.02 (3)
Ag13^i—Ag14—Cu1	152.46 (3)	Ag11—Se1—Ag13^i	121.28 (3)
Ag13^i—Ag14—S2	150.45 (4)	Ag11—Se1—Ag14	68.73 (2)
Ag13^i—Ag14—S6	58.54 (4)	Ag11—Se1—Ag14^i	108.67 (3)
Ag13^i—Ag14—Se1	52.98 (2)	Ag11—Se1—Ag15^iii	127.19 (3)
Ag13^i—Ag14—Se1^iv	74.44 (2)	Ag12—Se1—Ag13^i	110.53 (3)
Cu1—Ag14—S2	47.20 (3)	Ag12—Se1—Ag14	61.71 (2)
Cu1—Ag14—S6	143.52 (4)	Ag12—Se1—Ag14^i	168.85 (3)
Cu1—Ag14—Se1	100.85 (3)	Ag12—Se1—Ag15^iii	70.83 (3)
Cu1—Ag14—Se1^iv	103.79 (3)	Ag13^i—Se1—Ag14	62.46 (2)
S2—Ag14—S6	96.57 (5)	Ag13^i—Se1—Ag14^i	80.16 (3)
S2—Ag14—Se1	123.04 (4)	Ag13^i—Se1—Ag15^iii	104.05 (3)
S2—Ag14—Se1^iv	131.90 (4)	Ag14—Se1—Ag14^i	128.40 (3)
S6—Ag14—Se1	96.71 (4)	Ag14—Se1—Ag15^iii	117.94 (3)
S6—Ag14—Se1^iv	105.74 (4)	Ag14^i—Se1—Ag14	128.40 (3)
Se1—Ag14—Se1^iv	96.34 (3)	Ag14^i—Se1—Ag15^iii	104.16 (3)
Se1^iv—Ag14—Se1	96.34 (3)	Ag7^iii—Se2—Ag8	106.04 (3)
Ag4^vii—Ag15—Cu1	120.36 (3)	Ag7^iii—Se2—Ag8^ii	82.41 (3)
Ag4^vii—Ag15—S2	72.77 (4)	Ag7^iii—Se2—Ag9^ii	67.81 (3)
Ag4^vii—Ag15—S5^iv	49.37 (4)	Ag7^iii—Se2—Ag10	65.34 (3)
Ag4^vii—Ag15—Se1^vii	119.95 (3)	Ag7^iii—Se2—Ag12	69.67 (3)
Cu1—Ag15—S2	47.73 (3)	Ag8—Se2—Ag8^ii	125.73 (3)
Cu1—Ag15—S5^iv	138.50 (4)	Ag8—Se2—Ag9^ii	65.67 (3)
Cu1—Ag15—Se1^vii	117.57 (3)	Ag8—Se2—Ag10	136.17 (3)
S2—Ag15—S5^iv	103.56 (5)	Ag8—Se2—Ag12	63.01 (2)
S2—Ag15—Se1^vii	162.48 (4)	Ag8^ii—Se2—Ag8	125.73 (3)
S5^iv—Ag15—Se1^vii	93.95 (4)	Ag8^ii—Se2—Ag9^ii	69.17 (3)
Ag7—Cu1—Ag8	69.16 (2)	Ag8^ii—Se2—Ag10	96.68 (3)
Ag7—Cu1—Ag9	72.02 (3)	Ag8^ii—Se2—Ag12	151.97 (4)
Ag7—Cu1—Ag10^vii	61.95 (3)	Ag9^ii—Se2—Ag10	132.43 (4)
Ag7—Cu1—Ag11	170.21 (4)	Ag9^ii—Se2—Ag12	96.99 (3)
Ag7—Cu1—Ag13	115.85 (4)	Ag10—Se2—Ag12	74.32 (3)

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