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

Evain, M.; Bindi, L.; Menchetti, S.

doi:10.1107/S0108768106022798

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.

Keywords: Se-rich antimonpearceite; X-ray crystal-structure determination; twin; phase transition; disorder.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768106022798/lc5047sup1.cif Contains datablocks global, 300K, 120K
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768106022798/lc5047300Ksup2.hkl Contains datablock 300K
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768106022798/lc5047120Ksup3.hkl Contains datablock 120K

Computing details top

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 top

(300K) top

Crystal data top

Ag_14.585As_0.337Cu_1.415S_8.341Sb_1.663Se_2.659	Z = 1
M_r = 2368.3	F(000) = 1046
Trigonal, P3m1	D_x = 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) Å³	0.10 × 0.07 × 0.04 mm

Data collection top

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

Refinement top

Refinement on F	Weighting scheme based on measured s.u.'s w = 1/(σ²(F) + 0.0004F²)
R[F² > 2σ(F²)] = 0.049	(Δ/σ)_max = 0.0004
wR(F²) = 0.060	Δρ_max = 0.79 e Å⁻³
S = 1.80	Δρ_min = −0.64 e Å⁻³
1253 reflections	Extinction correction: B-C type 2 (Becker & Coppens, 1974)
95 parameters	Extinction coefficient: 0.332272

Crystal data top

Ag_14.585As_0.337Cu_1.415S_8.341Sb_1.663Se_2.659	Z = 1
M_r = 2368.3	Mo Kα radiation
Trigonal, P3m1	µ = 19.67 mm⁻¹
a = 7.5950 (4) Å	T = 300 K
c = 12.0731 (6) Å	0.10 × 0.07 × 0.04 mm
V = 603.12 (5) Å³

Data collection top

KappaCCD diffractometer	1253 independent reflections
Absorption correction: gaussian (Jana2000; Petricek, Dusek & Palatinus, 2000)	975 reflections with I > 2σ(I)
T_min = 0.157, T_max = 0.523	R_int = 0.046
13591 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	95 parameters
wR(F²) = 0.060	Δρ_max = 0.79 e Å⁻³
S = 1.80	Δρ_min = −0.64 e Å⁻³
1253 reflections

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

	x	y	z	U_iso*/U_eq	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 (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
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) top

Sb—S2	2.4076 (15)	Ag2—Ag2^iv	0.96 (2)
Sb—S2ⁱ	2.4076 (17)	Ag2—Ag3	1.067 (17)
Sb—S2ⁱⁱ	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—S2ⁱ	2.291 (10)	Cu—S1^vi	2.1993 (18)
Ag1b—S2ⁱⁱⁱ	2.291 (18)

S2—Sb—S2ⁱ	97.90 (5)	Ag1a—S3—Ag1a^xi	89.91 (15)
S2—Sb—S2ⁱⁱ	97.90 (4)	Ag1a—S3—Ag1a^xii	90.09 (15)
S2ⁱ—Sb—S2	97.90 (5)	Ag1a^ix—S3—Ag1a	180
S2ⁱ—Sb—S2ⁱⁱ	97.90 (5)	Ag1a^ix—S3—Ag1a^vii	90.09 (18)
S2ⁱⁱ—Sb—S2	97.90 (4)	Ag1a^ix—S3—Ag1a^x	89.91 (18)
S2ⁱⁱ—Sb—S2ⁱ	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—S2ⁱ	120 (2)	Ag1a^vii—S3—Ag1a	89.91 (18)
Ag1a—Ag1b—S2ⁱⁱⁱ	120.1 (16)	Ag1a^vii—S3—Ag1a^ix	90.09 (18)
S2ⁱ—Ag1b—S2ⁱⁱⁱ	119.8 (7)	Ag1a^vii—S3—Ag1a^x	180
S2ⁱⁱⁱ—Ag1b—S2ⁱ	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) top

Crystal data top

Ag_14.691Cu_1.309S_8.369Sb₂Se_2.631	V = 2366.4 (5) Å³
M_r = 2387.5	Z = 4
Monoclinic, P2₁/c	F(000) = 4222
Hall symbol: -P 2ybc	D_x = 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 top

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

Refinement top

Refinement on F	269 parameters
R[F² > 2σ(F²)] = 0.069	Weighting scheme based on measured s.u.'s w = 1/(σ²(F) + 0.000484F²)
wR(F²) = 0.076	(Δ/σ)_max = 0.001
S = 1.80	Δρ_max = 5.51 e Å⁻³
27670 reflections	Δρ_min = −2.74 e Å⁻³

Crystal data top

Ag_14.691Cu_1.309S_8.369Sb₂Se_2.631	V = 2366.4 (5) Å³
M_r = 2387.5	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.1426 (14) Å	µ = 20.02 mm⁻¹
b = 7.5879 (7) Å	T = 120 K
c = 23.729 (4) Å	0.10 × 0.07 × 0.04 mm
β = 90°

Data collection top

KappaCCD diffractometer	27670 independent reflections
Absorption correction: gaussian (Jana2000; Petricek, Dusek & Palatinus, 2000)	21308 reflections with I > 2σ(I)
T_min = 0.137, T_max = 0.363	R_int = 0.085
151079 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.069	269 parameters
wR(F²) = 0.076	Δρ_max = 5.51 e Å⁻³
S = 1.80	Δρ_min = −2.74 e Å⁻³
27670 reflections

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

	x	y	z	U_iso*/U_eq	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 (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
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) top

Sb1—S3	2.4093 (18)	Ag8—Se2	2.8998 (10)
Sb1—S5	2.4197 (18)	Ag8—Se2^viii	2.7157 (9)
Sb1—S6ⁱ	2.4173 (17)	Ag9—Cu1	2.7971 (9)
Sb2—S4	2.4160 (18)	Ag9—S1	2.5641 (15)
Sb2—S7ⁱⁱ	2.4231 (17)	Ag9—S8ⁱⁱ	2.9328 (18)
Sb2—S8ⁱⁱⁱ	2.4150 (18)	Ag9—Se2^viii	2.6184 (9)
Ag1—S5	2.5986 (19)	Ag10—Ag13ⁱⁱⁱ	2.8812 (10)
Ag1—S6^iv	2.4962 (18)	Ag10—Cu1ⁱⁱⁱ	2.8822 (11)
Ag1—S9	2.537 (2)	Ag10—S1ⁱⁱⁱ	2.7231 (15)
Ag2—S7ⁱⁱ	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—Ag15ⁱⁱⁱ	2.9689 (10)	Ag12—Ag14	2.9817 (9)
Ag4—S4	2.485 (2)	Ag12—S4	2.524 (2)
Ag4—S5ⁱ	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—S8ⁱⁱ	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—S7ⁱⁱ	2.6370 (18)

S3—Sb1—S5	96.78 (6)	Ag7—Cu1—Ag14	121.17 (3)
S3—Sb1—S6ⁱ	97.17 (6)	Ag7—Cu1—Ag15	66.66 (3)
S5—Sb1—S6ⁱ	98.47 (6)	Ag7—Cu1—S1	113.00 (5)
S4—Sb2—S7ⁱⁱ	97.89 (6)	Ag7—Cu1—S2	65.39 (4)
S4—Sb2—S8ⁱⁱⁱ	97.27 (6)	Ag8—Cu1—Ag9	64.14 (2)
S7ⁱⁱ—Sb2—S8ⁱⁱⁱ	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)
S7ⁱⁱ—Ag2—S8	104.19 (6)	Ag8—Cu1—Ag15	116.75 (3)
S7ⁱⁱ—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)
Ag15ⁱⁱⁱ—Ag4—S4	78.92 (5)	Ag9—Cu1—S2	120.30 (5)
Ag15ⁱⁱⁱ—Ag4—S5ⁱ	62.85 (5)	Ag10^vii—Cu1—Ag11	116.49 (3)
Ag15ⁱⁱⁱ—Ag4—S9^vi	131.21 (5)	Ag10^vii—Cu1—Ag13	59.17 (3)
S4—Ag4—S5ⁱ	112.84 (7)	Ag10^vii—Cu1—Ag14	120.46 (3)
S4—Ag4—S9^vi	109.94 (7)	Ag10^vii—Cu1—Ag15	66.01 (3)
S5ⁱ—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—S8ⁱⁱ	97.55 (6)	Ag11—Cu1—Ag13	67.64 (3)
S1—Ag5—S9	85.67 (5)	Ag11—Cu1—Ag14	68.36 (3)
S3—Ag5—S8ⁱⁱ	120.32 (7)	Ag11—Cu1—Ag15	122.33 (3)
S3—Ag5—S9	109.70 (7)	Ag11—Cu1—S1	60.27 (4)
S8ⁱⁱ—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—S7ⁱⁱ	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—S7ⁱⁱ	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—S7ⁱⁱ	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)
S7ⁱⁱ—Ag8—Se2	110.96 (5)	Ag14—S2—Cu1	70.61 (4)
S7ⁱⁱ—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—Ag6ⁱⁱⁱ	102.83 (7)
Ag7ⁱⁱ—Ag9—Cu1	127.70 (3)	Sb1—S3—Ag10	124.14 (7)
Ag7ⁱⁱ—Ag9—S1	138.11 (4)	Sb1—S3—Ag11	91.11 (6)
Ag7ⁱⁱ—Ag9—S8ⁱⁱ	53.01 (4)	Ag5—S3—Ag6ⁱⁱⁱ	110.74 (7)
Ag7ⁱⁱ—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—S8ⁱⁱ	128.12 (4)	Ag6ⁱⁱⁱ—S3—Ag10	89.20 (6)
Cu1—Ag9—Se2^viii	106.85 (3)	Ag6ⁱⁱⁱ—S3—Ag11	157.68 (8)
S1—Ag9—S8ⁱⁱ	94.71 (5)	Ag10—S3—Ag11	68.51 (5)
S1—Ag9—Se2^viii	154.42 (4)	Sb2—S4—Ag3	101.82 (7)
S8ⁱⁱ—Ag9—Se2^viii	108.35 (4)	Sb2—S4—Ag4	104.32 (7)
Ag7ⁱⁱⁱ—Ag10—Ag13ⁱⁱⁱ	114.30 (3)	Sb2—S4—Ag12	115.86 (7)
Ag7ⁱⁱⁱ—Ag10—Cu1ⁱⁱⁱ	57.79 (2)	Ag3—S4—Ag4	114.98 (7)
Ag7ⁱⁱⁱ—Ag10—S1ⁱⁱⁱ	95.67 (4)	Ag3—S4—Ag12	102.33 (7)
Ag7ⁱⁱⁱ—Ag10—S3	150.21 (5)	Ag4—S4—Ag12	116.88 (7)
Ag7ⁱⁱⁱ—Ag10—Se2	57.87 (2)	Sb1—S5—Ag1	99.54 (6)
Ag13ⁱⁱⁱ—Ag10—Cu1ⁱⁱⁱ	61.62 (2)	Sb1—S5—Ag4^iv	97.25 (7)
Ag13ⁱⁱⁱ—Ag10—S1ⁱⁱⁱ	54.51 (4)	Sb1—S5—Ag11	93.03 (6)
Ag13ⁱⁱⁱ—Ag10—S3	94.38 (5)	Sb1—S5—Ag15ⁱ	129.74 (7)
Ag13ⁱⁱⁱ—Ag10—Se2	169.11 (4)	Ag1—S5—Ag4^iv	99.28 (7)
Cu1ⁱⁱⁱ—Ag10—S1ⁱⁱⁱ	46.16 (3)	Ag1—S5—Ag11	95.15 (6)
Cu1ⁱⁱⁱ—Ag10—S3	140.56 (5)	Ag1—S5—Ag15ⁱ	129.44 (7)
Cu1ⁱⁱⁱ—Ag10—Se2	113.65 (3)	Ag4^iv—S5—Ag11	160.61 (8)
S1ⁱⁱⁱ—Ag10—S3	94.65 (5)	Ag4^iv—S5—Ag15ⁱ	67.78 (5)
S1ⁱⁱⁱ—Ag10—Se2	130.52 (5)	Ag11—S5—Ag15ⁱ	93.03 (6)
S3—Ag10—Se2	94.67 (5)	Sb1^iv—S6—Ag1ⁱ	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—Ag13ⁱ	118.40 (6)
Cu1—Ag11—S5	126.32 (4)	Sb1^iv—S6—Ag14	112.40 (6)
Cu1—Ag11—Se1	111.44 (3)	Ag1ⁱ—S6—Ag3	116.67 (7)
S1—Ag11—S3	98.43 (5)	Ag1ⁱ—S6—Ag13ⁱ	72.54 (5)
S1—Ag11—S5	93.36 (5)	Ag1ⁱ—S6—Ag14	134.40 (7)
S1—Ag11—Se1	158.55 (4)	Ag3—S6—Ag13ⁱ	139.15 (7)
S3—Ag11—S5	77.65 (5)	Ag3—S6—Ag14	88.89 (5)
S3—Ag11—Se1	102.38 (4)	Ag13ⁱ—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—Ag13ⁱ	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)
Ag13ⁱ—Ag14—Cu1	152.46 (3)	Ag11—Se1—Ag13ⁱ	121.28 (3)
Ag13ⁱ—Ag14—S2	150.45 (4)	Ag11—Se1—Ag14	68.73 (2)
Ag13ⁱ—Ag14—S6	58.54 (4)	Ag11—Se1—Ag14ⁱ	108.67 (3)
Ag13ⁱ—Ag14—Se1	52.98 (2)	Ag11—Se1—Ag15ⁱⁱⁱ	127.19 (3)
Ag13ⁱ—Ag14—Se1^iv	74.44 (2)	Ag12—Se1—Ag13ⁱ	110.53 (3)
Cu1—Ag14—S2	47.20 (3)	Ag12—Se1—Ag14	61.71 (2)
Cu1—Ag14—S6	143.52 (4)	Ag12—Se1—Ag14ⁱ	168.85 (3)
Cu1—Ag14—Se1	100.85 (3)	Ag12—Se1—Ag15ⁱⁱⁱ	70.83 (3)
Cu1—Ag14—Se1^iv	103.79 (3)	Ag13ⁱ—Se1—Ag14	62.46 (2)
S2—Ag14—S6	96.57 (5)	Ag13ⁱ—Se1—Ag14ⁱ	80.16 (3)
S2—Ag14—Se1	123.04 (4)	Ag13ⁱ—Se1—Ag15ⁱⁱⁱ	104.05 (3)
S2—Ag14—Se1^iv	131.90 (4)	Ag14—Se1—Ag14ⁱ	128.40 (3)
S6—Ag14—Se1	96.71 (4)	Ag14—Se1—Ag15ⁱⁱⁱ	117.94 (3)
S6—Ag14—Se1^iv	105.74 (4)	Ag14ⁱ—Se1—Ag14	128.40 (3)
Se1—Ag14—Se1^iv	96.34 (3)	Ag14ⁱ—Se1—Ag15ⁱⁱⁱ	104.16 (3)
Se1^iv—Ag14—Se1	96.34 (3)	Ag7ⁱⁱⁱ—Se2—Ag8	106.04 (3)
Ag4^vii—Ag15—Cu1	120.36 (3)	Ag7ⁱⁱⁱ—Se2—Ag8ⁱⁱ	82.41 (3)
Ag4^vii—Ag15—S2	72.77 (4)	Ag7ⁱⁱⁱ—Se2—Ag9ⁱⁱ	67.81 (3)
Ag4^vii—Ag15—S5^iv	49.37 (4)	Ag7ⁱⁱⁱ—Se2—Ag10	65.34 (3)
Ag4^vii—Ag15—Se1^vii	119.95 (3)	Ag7ⁱⁱⁱ—Se2—Ag12	69.67 (3)
Cu1—Ag15—S2	47.73 (3)	Ag8—Se2—Ag8ⁱⁱ	125.73 (3)
Cu1—Ag15—S5^iv	138.50 (4)	Ag8—Se2—Ag9ⁱⁱ	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)	Ag8ⁱⁱ—Se2—Ag8	125.73 (3)
S5^iv—Ag15—Se1^vii	93.95 (4)	Ag8ⁱⁱ—Se2—Ag9ⁱⁱ	69.17 (3)
Ag7—Cu1—Ag8	69.16 (2)	Ag8ⁱⁱ—Se2—Ag10	96.68 (3)
Ag7—Cu1—Ag9	72.02 (3)	Ag8ⁱⁱ—Se2—Ag12	151.97 (4)
Ag7—Cu1—Ag10^vii	61.95 (3)	Ag9ⁱⁱ—Se2—Ag10	132.43 (4)
Ag7—Cu1—Ag11	170.21 (4)	Ag9ⁱⁱ—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.

Experimental details

	(300K)	(120K)
Crystal data
Chemical formula	Ag_14.585As_0.337Cu_1.415S_8.341Sb_1.663Se_2.659	Ag_14.691Cu_1.309S_8.369Sb₂Se_2.631
M_r	2368.3	2387.5
Crystal system, space group	Trigonal, P3m1	Monoclinic, P2₁/c
Temperature (K)	300	120
a, b, c (Å)	7.5950 (4), 7.5950 (4), 12.0731 (6)	13.1426 (14), 7.5879 (7), 23.729 (4)
α, β, γ (°)	90, 90, 120	90, 90, 90
V (Å³)	603.12 (5)	2366.4 (5)
Z	1	4
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	19.67	20.02
Crystal size (mm)	0.10 × 0.07 × 0.04	0.10 × 0.07 × 0.04

Data collection
Diffractometer	KappaCCD diffractometer	KappaCCD diffractometer
Absorption correction	Gaussian (Jana2000; Petricek, Dusek & Palatinus, 2000)	Gaussian (Jana2000; Petricek, Dusek & Palatinus, 2000)
T_min, T_max	0.157, 0.523	0.137, 0.363
No. of measured, independent and observed [I > 2σ(I)] reflections	13591, 1253, 975	151079, 27670, 21308
R_int	0.046	0.085
(sin θ/λ)_max (Å⁻¹)	0.866	0.827

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.060, 1.80	0.069, 0.076, 1.80
No. of reflections	1253	27670
No. of parameters	95	269
No. of restraints	?	?
Δρ_max, Δρ_min (e Å⁻³)	0.79, −0.64	5.51, −2.74

Computer programs: (Jana2000; Petricek and Dusek, 2000).

Selected geometric parameters (Å, º) for (300K) top

Sb—S2	2.4076 (15)	Ag2—Ag2^iv	0.96 (2)
Sb—S2ⁱ	2.4076 (17)	Ag2—Ag3	1.067 (17)
Sb—S2ⁱⁱ	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—S2ⁱ	2.291 (10)	Cu—S1^vi	2.1993 (18)
Ag1b—S2ⁱⁱⁱ	2.291 (18)

S2—Sb—S2ⁱ	97.90 (5)	Ag1a—S3—Ag1a^xi	89.91 (15)
S2—Sb—S2ⁱⁱ	97.90 (4)	Ag1a—S3—Ag1a^xii	90.09 (15)
S2ⁱ—Sb—S2	97.90 (5)	Ag1a^ix—S3—Ag1a	180
S2ⁱ—Sb—S2ⁱⁱ	97.90 (5)	Ag1a^ix—S3—Ag1a^vii	90.09 (18)
S2ⁱⁱ—Sb—S2	97.90 (4)	Ag1a^ix—S3—Ag1a^x	89.91 (18)
S2ⁱⁱ—Sb—S2ⁱ	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—S2ⁱ	120 (2)	Ag1a^vii—S3—Ag1a	89.91 (18)
Ag1a—Ag1b—S2ⁱⁱⁱ	120.1 (16)	Ag1a^vii—S3—Ag1a^ix	90.09 (18)
S2ⁱ—Ag1b—S2ⁱⁱⁱ	119.8 (7)	Ag1a^vii—S3—Ag1a^x	180
S2ⁱⁱⁱ—Ag1b—S2ⁱ	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)

Selected geometric parameters (Å, º) for (120K) top

Sb1—S3	2.4093 (18)	Ag8—Se2	2.8998 (10)
Sb1—S5	2.4197 (18)	Ag8—Se2^viii	2.7157 (9)
Sb1—S6ⁱ	2.4173 (17)	Ag9—Cu1	2.7971 (9)
Sb2—S4	2.4160 (18)	Ag9—S1	2.5641 (15)
Sb2—S7ⁱⁱ	2.4231 (17)	Ag9—S8ⁱⁱ	2.9328 (18)
Sb2—S8ⁱⁱⁱ	2.4150 (18)	Ag9—Se2^viii	2.6184 (9)
Ag1—S5	2.5986 (19)	Ag10—Ag13ⁱⁱⁱ	2.8812 (10)
Ag1—S6^iv	2.4962 (18)	Ag10—Cu1ⁱⁱⁱ	2.8822 (11)
Ag1—S9	2.537 (2)	Ag10—S1ⁱⁱⁱ	2.7231 (15)
Ag2—S7ⁱⁱ	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—Ag15ⁱⁱⁱ	2.9689 (10)	Ag12—Ag14	2.9817 (9)
Ag4—S4	2.485 (2)	Ag12—S4	2.524 (2)
Ag4—S5ⁱ	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—S8ⁱⁱ	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—S7ⁱⁱ	2.6370 (18)

S3—Sb1—S5	96.78 (6)	Ag7—Cu1—Ag14	121.17 (3)
S3—Sb1—S6ⁱ	97.17 (6)	Ag7—Cu1—Ag15	66.66 (3)
S5—Sb1—S6ⁱ	98.47 (6)	Ag7—Cu1—S1	113.00 (5)
S4—Sb2—S7ⁱⁱ	97.89 (6)	Ag7—Cu1—S2	65.39 (4)
S4—Sb2—S8ⁱⁱⁱ	97.27 (6)	Ag8—Cu1—Ag9	64.14 (2)
S7ⁱⁱ—Sb2—S8ⁱⁱⁱ	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)
S7ⁱⁱ—Ag2—S8	104.19 (6)	Ag8—Cu1—Ag15	116.75 (3)
S7ⁱⁱ—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)
Ag15ⁱⁱⁱ—Ag4—S4	78.92 (5)	Ag9—Cu1—S2	120.30 (5)
Ag15ⁱⁱⁱ—Ag4—S5ⁱ	62.85 (5)	Ag10^vii—Cu1—Ag11	116.49 (3)
Ag15ⁱⁱⁱ—Ag4—S9^vi	131.21 (5)	Ag10^vii—Cu1—Ag13	59.17 (3)
S4—Ag4—S5ⁱ	112.84 (7)	Ag10^vii—Cu1—Ag14	120.46 (3)
S4—Ag4—S9^vi	109.94 (7)	Ag10^vii—Cu1—Ag15	66.01 (3)
S5ⁱ—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—S8ⁱⁱ	97.55 (6)	Ag11—Cu1—Ag13	67.64 (3)
S1—Ag5—S9	85.67 (5)	Ag11—Cu1—Ag14	68.36 (3)
S3—Ag5—S8ⁱⁱ	120.32 (7)	Ag11—Cu1—Ag15	122.33 (3)
S3—Ag5—S9	109.70 (7)	Ag11—Cu1—S1	60.27 (4)
S8ⁱⁱ—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—S7ⁱⁱ	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—S7ⁱⁱ	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—S7ⁱⁱ	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)
S7ⁱⁱ—Ag8—Se2	110.96 (5)	Ag14—S2—Cu1	70.61 (4)
S7ⁱⁱ—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—Ag6ⁱⁱⁱ	102.83 (7)
Ag7ⁱⁱ—Ag9—Cu1	127.70 (3)	Sb1—S3—Ag10	124.14 (7)
Ag7ⁱⁱ—Ag9—S1	138.11 (4)	Sb1—S3—Ag11	91.11 (6)
Ag7ⁱⁱ—Ag9—S8ⁱⁱ	53.01 (4)	Ag5—S3—Ag6ⁱⁱⁱ	110.74 (7)
Ag7ⁱⁱ—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—S8ⁱⁱ	128.12 (4)	Ag6ⁱⁱⁱ—S3—Ag10	89.20 (6)
Cu1—Ag9—Se2^viii	106.85 (3)	Ag6ⁱⁱⁱ—S3—Ag11	157.68 (8)
S1—Ag9—S8ⁱⁱ	94.71 (5)	Ag10—S3—Ag11	68.51 (5)
S1—Ag9—Se2^viii	154.42 (4)	Sb2—S4—Ag3	101.82 (7)
S8ⁱⁱ—Ag9—Se2^viii	108.35 (4)	Sb2—S4—Ag4	104.32 (7)
Ag7ⁱⁱⁱ—Ag10—Ag13ⁱⁱⁱ	114.30 (3)	Sb2—S4—Ag12	115.86 (7)
Ag7ⁱⁱⁱ—Ag10—Cu1ⁱⁱⁱ	57.79 (2)	Ag3—S4—Ag4	114.98 (7)
Ag7ⁱⁱⁱ—Ag10—S1ⁱⁱⁱ	95.67 (4)	Ag3—S4—Ag12	102.33 (7)
Ag7ⁱⁱⁱ—Ag10—S3	150.21 (5)	Ag4—S4—Ag12	116.88 (7)
Ag7ⁱⁱⁱ—Ag10—Se2	57.87 (2)	Sb1—S5—Ag1	99.54 (6)
Ag13ⁱⁱⁱ—Ag10—Cu1ⁱⁱⁱ	61.62 (2)	Sb1—S5—Ag4^iv	97.25 (7)
Ag13ⁱⁱⁱ—Ag10—S1ⁱⁱⁱ	54.51 (4)	Sb1—S5—Ag11	93.03 (6)
Ag13ⁱⁱⁱ—Ag10—S3	94.38 (5)	Sb1—S5—Ag15ⁱ	129.74 (7)
Ag13ⁱⁱⁱ—Ag10—Se2	169.11 (4)	Ag1—S5—Ag4^iv	99.28 (7)
Cu1ⁱⁱⁱ—Ag10—S1ⁱⁱⁱ	46.16 (3)	Ag1—S5—Ag11	95.15 (6)
Cu1ⁱⁱⁱ—Ag10—S3	140.56 (5)	Ag1—S5—Ag15ⁱ	129.44 (7)
Cu1ⁱⁱⁱ—Ag10—Se2	113.65 (3)	Ag4^iv—S5—Ag11	160.61 (8)
S1ⁱⁱⁱ—Ag10—S3	94.65 (5)	Ag4^iv—S5—Ag15ⁱ	67.78 (5)
S1ⁱⁱⁱ—Ag10—Se2	130.52 (5)	Ag11—S5—Ag15ⁱ	93.03 (6)
S3—Ag10—Se2	94.67 (5)	Sb1^iv—S6—Ag1ⁱ	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—Ag13ⁱ	118.40 (6)
Cu1—Ag11—S5	126.32 (4)	Sb1^iv—S6—Ag14	112.40 (6)
Cu1—Ag11—Se1	111.44 (3)	Ag1ⁱ—S6—Ag3	116.67 (7)
S1—Ag11—S3	98.43 (5)	Ag1ⁱ—S6—Ag13ⁱ	72.54 (5)
S1—Ag11—S5	93.36 (5)	Ag1ⁱ—S6—Ag14	134.40 (7)
S1—Ag11—Se1	158.55 (4)	Ag3—S6—Ag13ⁱ	139.15 (7)
S3—Ag11—S5	77.65 (5)	Ag3—S6—Ag14	88.89 (5)
S3—Ag11—Se1	102.38 (4)	Ag13ⁱ—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—Ag13ⁱ	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)
Ag13ⁱ—Ag14—Cu1	152.46 (3)	Ag11—Se1—Ag13ⁱ	121.28 (3)
Ag13ⁱ—Ag14—S2	150.45 (4)	Ag11—Se1—Ag14	68.73 (2)
Ag13ⁱ—Ag14—S6	58.54 (4)	Ag11—Se1—Ag14ⁱ	108.67 (3)
Ag13ⁱ—Ag14—Se1	52.98 (2)	Ag11—Se1—Ag15ⁱⁱⁱ	127.19 (3)
Ag13ⁱ—Ag14—Se1^iv	74.44 (2)	Ag12—Se1—Ag13ⁱ	110.53 (3)
Cu1—Ag14—S2	47.20 (3)	Ag12—Se1—Ag14	61.71 (2)
Cu1—Ag14—S6	143.52 (4)	Ag12—Se1—Ag14ⁱ	168.85 (3)
Cu1—Ag14—Se1	100.85 (3)	Ag12—Se1—Ag15ⁱⁱⁱ	70.83 (3)
Cu1—Ag14—Se1^iv	103.79 (3)	Ag13ⁱ—Se1—Ag14	62.46 (2)
S2—Ag14—S6	96.57 (5)	Ag13ⁱ—Se1—Ag14ⁱ	80.16 (3)
S2—Ag14—Se1	123.04 (4)	Ag13ⁱ—Se1—Ag15ⁱⁱⁱ	104.05 (3)
S2—Ag14—Se1^iv	131.90 (4)	Ag14—Se1—Ag14ⁱ	128.40 (3)
S6—Ag14—Se1	96.71 (4)	Ag14—Se1—Ag15ⁱⁱⁱ	117.94 (3)
S6—Ag14—Se1^iv	105.74 (4)	Ag14ⁱ—Se1—Ag14	128.40 (3)
Se1—Ag14—Se1^iv	96.34 (3)	Ag14ⁱ—Se1—Ag15ⁱⁱⁱ	104.16 (3)
Se1^iv—Ag14—Se1	96.34 (3)	Ag7ⁱⁱⁱ—Se2—Ag8	106.04 (3)
Ag4^vii—Ag15—Cu1	120.36 (3)	Ag7ⁱⁱⁱ—Se2—Ag8ⁱⁱ	82.41 (3)
Ag4^vii—Ag15—S2	72.77 (4)	Ag7ⁱⁱⁱ—Se2—Ag9ⁱⁱ	67.81 (3)
Ag4^vii—Ag15—S5^iv	49.37 (4)	Ag7ⁱⁱⁱ—Se2—Ag10	65.34 (3)
Ag4^vii—Ag15—Se1^vii	119.95 (3)	Ag7ⁱⁱⁱ—Se2—Ag12	69.67 (3)
Cu1—Ag15—S2	47.73 (3)	Ag8—Se2—Ag8ⁱⁱ	125.73 (3)
Cu1—Ag15—S5^iv	138.50 (4)	Ag8—Se2—Ag9ⁱⁱ	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)	Ag8ⁱⁱ—Se2—Ag8	125.73 (3)
S5^iv—Ag15—Se1^vii	93.95 (4)	Ag8ⁱⁱ—Se2—Ag9ⁱⁱ	69.17 (3)
Ag7—Cu1—Ag8	69.16 (2)	Ag8ⁱⁱ—Se2—Ag10	96.68 (3)
Ag7—Cu1—Ag9	72.02 (3)	Ag8ⁱⁱ—Se2—Ag12	151.97 (4)
Ag7—Cu1—Ag10^vii	61.95 (3)	Ag9ⁱⁱ—Se2—Ag10	132.43 (4)
Ag7—Cu1—Ag11	170.21 (4)	Ag9ⁱⁱ—Se2—Ag12	96.99 (3)
Ag7—Cu1—Ag13	115.85 (4)	Ag10—Se2—Ag12	74.32 (3)

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