Tennantite: multi-temperature crystal structure, phase transition and electronic structure of synthetic Cu₁₂As₄S₁₃

The structure of synthetic tennantite Cu₁₂As₄S₁₃ was investigated at various temperatures in the 90–293 K range. It crystallizes in space group . No structural transformation was observed in this temperature range. The structures were refined in anharmonic approximation for atomic displacements and electron density maps were refined using the maximum entropy method. Both approaches indicate a noticeable static disorder of the copper atoms in the triangular sulfur coordination and neighbouring site at high temperatures, whereas these split copper sites are well defined at lower temperatures. One particle potential is used to describe the behaviour of atoms at these copper sites. Such behaviour may be the structural reason for changes in magnetic properties.

Computing details

For all structures, program(s) used to solve structure: SIR2002 (Burla, M.C., et al., 2003); program(s) used to refine structure: Jana2006 (Petricek, Dusek & Palatinus, 2006); molecular graphics: Diamond (Brandenburg, K. & Putz, H., 2005); software used to prepare material for publication: Jana2006 (Petricek, Dusek & Palatinus, 2006).

Copper Arsenic Sulfide (90K)

Crystal data

As4Cu12S13	Dx = 4.706 Mg m^−3
Mr = 1479	Mo Kα radiation, λ = 0.71069 Å
Cubic, I43m	Cell parameters from 5573 reflections
Hall symbol: I -4;2;3	θ = 4.9–42.0°
a = 10.1439 (2) Å	µ = 19.54 mm^−1
V = 1043.79 (4) Å^3	T = 90 K
Z = 2	Prism, black
F(000) = 1376	0.46 × 0.31 × 0.25 mm

Data collection

Xcalibur, EosS2 diffractometer	719 independent reflections
Radiation source: sealed tube	693 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
θ scans	θmax = 42.1°, θmin = 4.0°
Absorption correction: analytical	h = −19→19
Tmin = 0.015, Tmax = 0.104	k = −12→19
11028 measured reflections	l = −18→15

Refinement

Refinement on F	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.001936F^2)
R[F^2 > 2σ(F^2)] = 0.034	(Δ/σ)max = 0.005
wR(F^2) = 0.053	Δρmax = 2.93 e Å^−3
S = 1.06	Δρmin = −1.77 e Å^−3
719 reflections	Extinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
36 parameters	Extinction coefficient: 890 (110)
0 restraints	Absolute structure: 318 of Friedel pairs used in the refinement
0 constraints

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.5	0.25	0	0.00698 (12)
Cu2	0.2173 (3)	0	0	0.0196 (2)	0.758 (3)
Cu21	0.2123 (4)	0.0777 (3)	0.0777 (3)	0.0134 (8)	0.1211 (15)
S1	0.35734 (10)	−0.11822 (7)	0.11822 (7)	0.00764 (15)
S2	0	0	0	0.0175 (9)
As1	0.24271 (11)	0.24271 (11)	0.24271 (11)	0.00764 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.00350 (15)	0.0139 (3)	0.00350 (15)	0	0	0
Cu2	0.0106 (5)	0.0241 (3)	0.0241 (3)	0	0	−0.0041 (6)
Cu21	0.0056 (14)	0.0173 (13)	0.0173 (13)	−0.0056 (9)	−0.0056 (9)	0.0121 (13)
S1	0.0059 (3)	0.0085 (2)	0.0085 (2)	−0.00398 (18)	0.00398 (18)	−0.0038 (3)
S2	0.0175 (16)	0.0175 (16)	0.0175 (16)	0	0	0
As1	0.00764 (16)	0.00764 (16)	0.00764 (16)	0.00232 (13)	0.00232 (13)	0.00232 (13)

Geometric parameters (Å, º)

Cu1—S1^i	2.3064 (9)	Cu21—Cu21^ii	2.229 (5)
Cu1—S1^ii	2.3064 (9)	Cu21—Cu21^v	1.930 (5)
Cu1—S1^iii	2.3064 (9)	Cu21—Cu21^vi	1.930 (5)
Cu1—S1^iv	2.3064 (9)	Cu21—S1	2.507 (4)
Cu2—Cu21	1.116 (4)	Cu21—S1^ii	2.507 (4)
Cu2—Cu21^ii	1.116 (4)	Cu21—S2	2.425 (4)
Cu2—S1	2.212 (2)	Cu21—As1	2.387 (4)
Cu2—S1^ii	2.212 (2)	S1—As1^vii	2.2383 (14)
Cu2—S2	2.205 (3)
S1^i—Cu1—S1^ii	109.16 (3)	Cu2^x—S2—Cu21^x	27.37 (9)
S1^i—Cu1—S1^iii	109.63 (3)	Cu2^x—S2—Cu21^xiii	27.37 (9)
S1^i—Cu1—S1^iv	109.63 (3)	Cu2^x—S2—Cu21^xiv	152.63 (9)
S1^ii—Cu1—S1^iii	109.63 (3)	Cu2^x—S2—Cu21^vi	108.97 (8)
S1^ii—Cu1—S1^iv	109.63 (3)	Cu2^x—S2—Cu21^xi	108.97 (8)
S1^iii—Cu1—S1^iv	109.16 (3)	Cu2^x—S2—Cu21^xv	71.03 (8)
Cu21—Cu2—Cu21^ii	174.7 (4)	Cu2^x—S2—Cu21^xvi	71.03 (8)
Cu21—Cu2—S1	91.7 (2)	Cu2^vi—S2—Cu2^xi	180
Cu21—Cu2—S1^ii	91.7 (2)	Cu2^vi—S2—Cu21	71.03 (8)
Cu21—Cu2—S2	87.3 (3)	Cu2^vi—S2—Cu21^ix	71.03 (8)
Cu21^ii—Cu2—S1	91.7 (2)	Cu2^vi—S2—Cu21^xii	108.97 (8)
Cu21^ii—Cu2—S1^ii	91.7 (2)	Cu2^vi—S2—Cu21^ii	108.97 (8)
Cu21^ii—Cu2—S2	87.3 (3)	Cu2^vi—S2—Cu21^v	71.03 (8)
S1—Cu2—S1^ii	100.12 (12)	Cu2^vi—S2—Cu21^x	108.97 (8)
S1—Cu2—S2	129.94 (6)	Cu2^vi—S2—Cu21^xiii	71.03 (8)
S1^ii—Cu2—S2	129.94 (6)	Cu2^vi—S2—Cu21^xiv	108.97 (8)
Cu2—Cu21—Cu21^ii	2.7 (2)	Cu2^vi—S2—Cu21^vi	27.37 (9)
Cu2—Cu21—Cu21^v	122.2 (3)	Cu2^vi—S2—Cu21^xi	152.63 (9)
Cu2—Cu21—Cu21^vi	122.2 (3)	Cu2^vi—S2—Cu21^xv	152.63 (9)
Cu2—Cu21—S1	61.88 (19)	Cu2^vi—S2—Cu21^xvi	27.37 (9)
Cu2—Cu21—S1^ii	61.88 (19)	Cu2^xi—S2—Cu21	108.97 (8)
Cu2—Cu21—S2	65.3 (2)	Cu2^xi—S2—Cu21^ix	108.97 (8)
Cu2—Cu21—As1	169.9 (3)	Cu2^xi—S2—Cu21^xii	71.03 (8)
Cu21^ii—Cu21—Cu21^v	120.0 (2)	Cu2^xi—S2—Cu21^ii	71.03 (8)
Cu21^ii—Cu21—Cu21^vi	120.0 (2)	Cu2^xi—S2—Cu21^v	108.97 (8)
Cu21^ii—Cu21—S1	63.60 (13)	Cu2^xi—S2—Cu21^x	71.03 (8)
Cu21^ii—Cu21—S1^ii	63.60 (13)	Cu2^xi—S2—Cu21^xiii	108.97 (8)
Cu21^ii—Cu21—S2	62.63 (14)	Cu2^xi—S2—Cu21^xiv	71.03 (8)
Cu21^ii—Cu21—As1	172.6 (2)	Cu2^xi—S2—Cu21^vi	152.63 (9)
Cu21^v—Cu21—Cu21^vi	60.00 (19)	Cu2^xi—S2—Cu21^xi	27.37 (9)
Cu21^v—Cu21—S1	167.3 (2)	Cu2^xi—S2—Cu21^xv	27.37 (9)
Cu21^v—Cu21—S1^ii	107.41 (18)	Cu2^xi—S2—Cu21^xvi	152.63 (9)
Cu21^v—Cu21—S2	66.54 (16)	Cu21—S2—Cu21^ix	142.06 (12)
Cu21^v—Cu21—As1	66.15 (15)	Cu21—S2—Cu21^xii	142.06 (12)
Cu21^vi—Cu21—S1	107.41 (18)	Cu21—S2—Cu21^ii	54.74 (12)
Cu21^vi—Cu21—S1^ii	167.3 (2)	Cu21—S2—Cu21^v	46.91 (12)
Cu21^vi—Cu21—S2	66.54 (16)	Cu21—S2—Cu21^x	96.07 (12)
Cu21^vi—Cu21—As1	66.15 (15)	Cu21—S2—Cu21^xiii	118.15 (12)
S1—Cu21—S1^ii	85.14 (12)	Cu21—S2—Cu21^xiv	96.07 (12)
S1—Cu21—S2	108.47 (14)	Cu21—S2—Cu21^vi	46.91 (12)
S1—Cu21—As1	111.41 (15)	Cu21—S2—Cu21^xi	118.15 (12)
S1^ii—Cu21—S2	108.47 (14)	Cu21—S2—Cu21^xv	96.07 (12)
S1^ii—Cu21—As1	111.41 (15)	Cu21—S2—Cu21^xvi	96.07 (12)
S2—Cu21—As1	124.81 (16)	Cu21^ix—S2—Cu21^xii	54.74 (12)
Cu1^i—S1—Cu1^viii	102.06 (4)	Cu21^ix—S2—Cu21^ii	142.06 (12)
Cu1^i—S1—Cu2	115.79 (4)	Cu21^ix—S2—Cu21^v	118.15 (12)
Cu1^i—S1—Cu21	137.95 (9)	Cu21^ix—S2—Cu21^x	96.07 (12)
Cu1^i—S1—Cu21^ii	92.93 (9)	Cu21^ix—S2—Cu21^xiii	46.91 (12)
Cu1^i—S1—As1^vii	104.29 (4)	Cu21^ix—S2—Cu21^xiv	96.07 (12)
Cu1^viii—S1—Cu2	115.79 (4)	Cu21^ix—S2—Cu21^vi	96.07 (12)
Cu1^viii—S1—Cu21	92.93 (9)	Cu21^ix—S2—Cu21^xi	96.07 (12)
Cu1^viii—S1—Cu21^ii	137.95 (9)	Cu21^ix—S2—Cu21^xv	118.15 (12)
Cu1^viii—S1—As1^vii	104.29 (4)	Cu21^ix—S2—Cu21^xvi	46.91 (12)
Cu2—S1—Cu21	26.42 (8)	Cu21^xii—S2—Cu21^ii	142.06 (12)
Cu2—S1—Cu21^ii	26.42 (8)	Cu21^xii—S2—Cu21^v	96.07 (12)
Cu2—S1—As1^vii	113.10 (8)	Cu21^xii—S2—Cu21^x	118.15 (12)
Cu21—S1—Cu21^ii	52.80 (12)	Cu21^xii—S2—Cu21^xiii	96.07 (12)
Cu21—S1—As1^vii	109.69 (10)	Cu21^xii—S2—Cu21^xiv	46.91 (12)
Cu21^ii—S1—As1^vii	109.69 (10)	Cu21^xii—S2—Cu21^vi	118.15 (12)
Cu2—S2—Cu2^ix	180	Cu21^xii—S2—Cu21^xi	46.91 (12)
Cu2—S2—Cu2^v	90	Cu21^xii—S2—Cu21^xv	96.07 (12)
Cu2—S2—Cu2^x	90	Cu21^xii—S2—Cu21^xvi	96.07 (12)
Cu2—S2—Cu2^vi	90	Cu21^ii—S2—Cu21^v	96.07 (12)
Cu2—S2—Cu2^xi	90	Cu21^ii—S2—Cu21^x	46.91 (12)
Cu2—S2—Cu21	27.37 (9)	Cu21^ii—S2—Cu21^xiii	96.07 (12)
Cu2—S2—Cu21^ix	152.63 (9)	Cu21^ii—S2—Cu21^xiv	118.15 (12)
Cu2—S2—Cu21^xii	152.63 (9)	Cu21^ii—S2—Cu21^vi	96.07 (12)
Cu2—S2—Cu21^ii	27.37 (9)	Cu21^ii—S2—Cu21^xi	96.07 (12)
Cu2—S2—Cu21^v	71.03 (8)	Cu21^ii—S2—Cu21^xv	46.91 (12)
Cu2—S2—Cu21^x	71.03 (8)	Cu21^ii—S2—Cu21^xvi	118.15 (12)
Cu2—S2—Cu21^xiii	108.97 (8)	Cu21^v—S2—Cu21^x	142.06 (12)
Cu2—S2—Cu21^xiv	108.97 (8)	Cu21^v—S2—Cu21^xiii	142.06 (12)
Cu2—S2—Cu21^vi	71.03 (8)	Cu21^v—S2—Cu21^xiv	54.74 (12)
Cu2—S2—Cu21^xi	108.97 (8)	Cu21^v—S2—Cu21^vi	46.91 (12)
Cu2—S2—Cu21^xv	71.03 (8)	Cu21^v—S2—Cu21^xi	96.07 (12)
Cu2—S2—Cu21^xvi	108.97 (8)	Cu21^v—S2—Cu21^xv	118.15 (12)
Cu2^ix—S2—Cu2^v	90	Cu21^v—S2—Cu21^xvi	96.07 (12)
Cu2^ix—S2—Cu2^x	90	Cu21^x—S2—Cu21^xiii	54.74 (12)
Cu2^ix—S2—Cu2^vi	90	Cu21^x—S2—Cu21^xiv	142.06 (12)
Cu2^ix—S2—Cu2^xi	90	Cu21^x—S2—Cu21^vi	118.15 (12)
Cu2^ix—S2—Cu21	152.63 (9)	Cu21^x—S2—Cu21^xi	96.07 (12)
Cu2^ix—S2—Cu21^ix	27.37 (9)	Cu21^x—S2—Cu21^xv	46.91 (12)
Cu2^ix—S2—Cu21^xii	27.37 (9)	Cu21^x—S2—Cu21^xvi	96.07 (12)
Cu2^ix—S2—Cu21^ii	152.63 (9)	Cu21^xiii—S2—Cu21^xiv	142.06 (12)
Cu2^ix—S2—Cu21^v	108.97 (8)	Cu21^xiii—S2—Cu21^vi	96.07 (12)
Cu2^ix—S2—Cu21^x	108.97 (8)	Cu21^xiii—S2—Cu21^xi	118.15 (12)
Cu2^ix—S2—Cu21^xiii	71.03 (8)	Cu21^xiii—S2—Cu21^xv	96.07 (12)
Cu2^ix—S2—Cu21^xiv	71.03 (8)	Cu21^xiii—S2—Cu21^xvi	46.91 (12)
Cu2^ix—S2—Cu21^vi	108.97 (8)	Cu21^xiv—S2—Cu21^vi	96.07 (12)
Cu2^ix—S2—Cu21^xi	71.03 (8)	Cu21^xiv—S2—Cu21^xi	46.91 (12)
Cu2^ix—S2—Cu21^xv	108.97 (8)	Cu21^xiv—S2—Cu21^xv	96.07 (12)
Cu2^ix—S2—Cu21^xvi	71.03 (8)	Cu21^xiv—S2—Cu21^xvi	118.15 (12)
Cu2^v—S2—Cu2^x	180	Cu21^vi—S2—Cu21^xi	142.06 (12)
Cu2^v—S2—Cu2^vi	90	Cu21^vi—S2—Cu21^xv	142.06 (12)
Cu2^v—S2—Cu2^xi	90	Cu21^vi—S2—Cu21^xvi	54.74 (12)
Cu2^v—S2—Cu21	71.03 (8)	Cu21^xi—S2—Cu21^xv	54.74 (12)
Cu2^v—S2—Cu21^ix	108.97 (8)	Cu21^xi—S2—Cu21^xvi	142.06 (12)
Cu2^v—S2—Cu21^xii	71.03 (8)	Cu21^xv—S2—Cu21^xvi	142.06 (12)
Cu2^v—S2—Cu21^ii	108.97 (8)	Cu21—As1—Cu21^v	47.70 (13)
Cu2^v—S2—Cu21^v	27.37 (9)	Cu21—As1—Cu21^vi	47.70 (13)
Cu2^v—S2—Cu21^x	152.63 (9)	Cu21—As1—S1^xvii	145.61 (11)
Cu2^v—S2—Cu21^xiii	152.63 (9)	Cu21—As1—S1^xviii	101.86 (10)
Cu2^v—S2—Cu21^xiv	27.37 (9)	Cu21—As1—S1^iii	101.86 (10)
Cu2^v—S2—Cu21^vi	71.03 (8)	Cu21^v—As1—Cu21^vi	47.70 (13)
Cu2^v—S2—Cu21^xi	71.03 (8)	Cu21^v—As1—S1^xvii	101.86 (10)
Cu2^v—S2—Cu21^xv	108.97 (8)	Cu21^v—As1—S1^xviii	145.61 (11)
Cu2^v—S2—Cu21^xvi	108.97 (8)	Cu21^v—As1—S1^iii	101.86 (10)
Cu2^x—S2—Cu2^vi	90	Cu21^vi—As1—S1^xvii	101.86 (10)
Cu2^x—S2—Cu2^xi	90	Cu21^vi—As1—S1^xviii	101.86 (10)
Cu2^x—S2—Cu21	108.97 (8)	Cu21^vi—As1—S1^iii	145.61 (11)
Cu2^x—S2—Cu21^ix	71.03 (8)	S1^xvii—As1—S1^xviii	100.04 (5)
Cu2^x—S2—Cu21^xii	108.97 (8)	S1^xvii—As1—S1^iii	100.04 (5)
Cu2^x—S2—Cu21^ii	71.03 (8)	S1^xviii—As1—S1^iii	100.04 (5)
Cu2^x—S2—Cu21^v	152.63 (9)

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

Copper Arsenic Sulfide (119K)

Crystal data

As4Cu12S13	Dx = 4.705 Mg m^−3
Mr = 1479	Mo Kα radiation, λ = 0.71069 Å
Cubic, I43m	Cell parameters from 5485 reflections
Hall symbol: I -4;2;3	θ = 4.1–42.0°
a = 10.1446 (2) Å	µ = 19.53 mm^−1
V = 1044.01 (4) Å^3	T = 119 K
Z = 2	Prism, black
F(000) = 1376	0.46 × 0.31 × 0.25 mm

Data collection

Xcalibur, EosS2 diffractometer	720 independent reflections
Radiation source: X-ray tube	691 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
θ scans	θmax = 42.1°, θmin = 4.0°
Absorption correction: analytical	h = −19→19
Tmin = 0.015, Tmax = 0.104	k = −12→19
11029 measured reflections	l = −18→15

Refinement

Refinement on F	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.001936F^2)
R[F^2 > 2σ(F^2)] = 0.036	(Δ/σ)max = 0.005
wR(F^2) = 0.056	Δρmax = 3.46 e Å^−3
S = 1.13	Δρmin = −1.73 e Å^−3
720 reflections	Extinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
42 parameters	Extinction coefficient: 1000 (120)
0 restraints	Absolute structure: 318 of Friedel pairs used in the refinement
0 constraints

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.5	0.25	0	0.00831 (14)
Cu2	0.2176 (3)	0	0	0.0216 (3)	0.752 (3)
Cu21	0.2124 (4)	0.0776 (4)	0.0776 (4)	0.0174 (9)	0.1238 (17)
S1	0.3575 (2)	−0.11807 (14)	0.11807 (14)	0.00808 (16)
S2	0	0	0	0.0167 (9)
As1	0.24265 (12)	0.24265 (12)	0.24265 (12)	0.00846 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.00495 (16)	0.0150 (4)	0.00495 (16)	0	0	0
Cu2	0.0113 (6)	0.0267 (4)	0.0267 (4)	0	0	0.0012 (8)
Cu21	0.0072 (15)	0.0225 (15)	0.0225 (15)	−0.0074 (10)	−0.0074 (10)	0.0147 (16)
S1	0.0063 (3)	0.0089 (2)	0.0089 (2)	−0.00366 (19)	0.00366 (19)	−0.0035 (3)
S2	0.0167 (16)	0.0167 (16)	0.0167 (16)	0	0	0
As1	0.00846 (18)	0.00846 (18)	0.00846 (18)	0.00207 (14)	0.00207 (14)	0.00207 (14)

Geometric parameters (Å, º)

Cu1—S1^i	2.3055 (18)	Cu21—Cu21^ii	2.225 (6)
Cu1—S1^ii	2.3055 (18)	Cu21—Cu21^v	1.935 (6)
Cu1—S1^iii	2.3055 (18)	Cu21—Cu21^vi	1.935 (6)
Cu1—S1^iv	2.3055 (18)	Cu21—S1	2.505 (5)
Cu2—Cu21	1.114 (4)	Cu21—S1^ii	2.505 (5)
Cu2—Cu21^ii	1.114 (4)	Cu21—S2	2.425 (4)
Cu2—S1	2.210 (3)	Cu21—As1	2.388 (4)
Cu2—S1^ii	2.210 (3)	S1—As1^vii	2.242 (2)
Cu2—S2	2.208 (3)
S1^i—Cu1—S1^ii	109.02 (6)	Cu2^x—S2—Cu21^x	27.31 (10)
S1^i—Cu1—S1^iii	109.70 (6)	Cu2^x—S2—Cu21^xiii	27.31 (10)
S1^i—Cu1—S1^iv	109.70 (6)	Cu2^x—S2—Cu21^xiv	152.69 (10)
S1^ii—Cu1—S1^iii	109.70 (6)	Cu2^x—S2—Cu21^vi	108.93 (10)
S1^ii—Cu1—S1^iv	109.70 (6)	Cu2^x—S2—Cu21^xi	108.93 (10)
S1^iii—Cu1—S1^iv	109.02 (6)	Cu2^x—S2—Cu21^xv	71.07 (10)
Cu21—Cu2—Cu21^ii	174.6 (5)	Cu2^x—S2—Cu21^xvi	71.07 (10)
Cu21—Cu2—S1	91.7 (2)	Cu2^vi—S2—Cu2^xi	180
Cu21—Cu2—S1^ii	91.7 (2)	Cu2^vi—S2—Cu21	71.07 (10)
Cu21—Cu2—S2	87.3 (3)	Cu2^vi—S2—Cu21^ix	71.07 (10)
Cu21^ii—Cu2—S1	91.7 (2)	Cu2^vi—S2—Cu21^xii	108.93 (10)
Cu21^ii—Cu2—S1^ii	91.7 (2)	Cu2^vi—S2—Cu21^ii	108.93 (10)
Cu21^ii—Cu2—S2	87.3 (3)	Cu2^vi—S2—Cu21^v	71.07 (10)
S1—Cu2—S1^ii	100.08 (15)	Cu2^vi—S2—Cu21^x	108.93 (10)
S1—Cu2—S2	129.96 (8)	Cu2^vi—S2—Cu21^xiii	71.07 (10)
S1^ii—Cu2—S2	129.96 (8)	Cu2^vi—S2—Cu21^xiv	108.93 (10)
Cu2—Cu21—Cu21^ii	2.7 (2)	Cu2^vi—S2—Cu21^vi	27.31 (10)
Cu2—Cu21—Cu21^v	122.2 (4)	Cu2^vi—S2—Cu21^xi	152.69 (10)
Cu2—Cu21—Cu21^vi	122.2 (4)	Cu2^vi—S2—Cu21^xv	152.69 (10)
Cu2—Cu21—S1	61.9 (2)	Cu2^vi—S2—Cu21^xvi	27.31 (10)
Cu2—Cu21—S1^ii	61.9 (2)	Cu2^xi—S2—Cu21	108.93 (10)
Cu2—Cu21—S2	65.4 (3)	Cu2^xi—S2—Cu21^ix	108.93 (10)
Cu2—Cu21—As1	169.9 (4)	Cu2^xi—S2—Cu21^xii	71.07 (10)
Cu21^ii—Cu21—Cu21^v	120.0 (3)	Cu2^xi—S2—Cu21^ii	71.07 (10)
Cu21^ii—Cu21—Cu21^vi	120.0 (3)	Cu2^xi—S2—Cu21^v	108.93 (10)
Cu21^ii—Cu21—S1	63.63 (16)	Cu2^xi—S2—Cu21^x	71.07 (10)
Cu21^ii—Cu21—S1^ii	63.63 (16)	Cu2^xi—S2—Cu21^xiii	108.93 (10)
Cu21^ii—Cu21—S2	62.69 (16)	Cu2^xi—S2—Cu21^xiv	71.07 (10)
Cu21^ii—Cu21—As1	172.6 (2)	Cu2^xi—S2—Cu21^vi	152.69 (10)
Cu21^v—Cu21—Cu21^vi	60.0 (2)	Cu2^xi—S2—Cu21^xi	27.31 (10)
Cu21^v—Cu21—S1	167.4 (3)	Cu2^xi—S2—Cu21^xv	27.31 (10)
Cu21^v—Cu21—S1^ii	107.4 (2)	Cu2^xi—S2—Cu21^xvi	152.69 (10)
Cu21^v—Cu21—S2	66.49 (18)	Cu21—S2—Cu21^ix	142.14 (14)
Cu21^v—Cu21—As1	66.10 (17)	Cu21—S2—Cu21^xii	142.14 (14)
Cu21^vi—Cu21—S1	107.4 (2)	Cu21—S2—Cu21^ii	54.61 (14)
Cu21^vi—Cu21—S1^ii	167.4 (3)	Cu21—S2—Cu21^v	47.02 (14)
Cu21^vi—Cu21—S2	66.49 (18)	Cu21—S2—Cu21^x	96.04 (14)
Cu21^vi—Cu21—As1	66.10 (17)	Cu21—S2—Cu21^xiii	118.12 (14)
S1—Cu21—S1^ii	85.11 (14)	Cu21—S2—Cu21^xiv	96.04 (14)
S1—Cu21—S2	108.56 (16)	Cu21—S2—Cu21^vi	47.02 (14)
S1—Cu21—As1	111.41 (17)	Cu21—S2—Cu21^xi	118.12 (14)
S1^ii—Cu21—S2	108.56 (16)	Cu21—S2—Cu21^xv	96.04 (14)
S1^ii—Cu21—As1	111.41 (17)	Cu21—S2—Cu21^xvi	96.04 (14)
S2—Cu21—As1	124.68 (18)	Cu21^ix—S2—Cu21^xii	54.61 (14)
Cu1^i—S1—Cu1^viii	102.13 (9)	Cu21^ix—S2—Cu21^ii	142.14 (14)
Cu1^i—S1—Cu2	115.83 (7)	Cu21^ix—S2—Cu21^v	118.12 (14)
Cu1^i—S1—Cu21	138.00 (11)	Cu21^ix—S2—Cu21^x	96.04 (14)
Cu1^i—S1—Cu21^ii	92.99 (11)	Cu21^ix—S2—Cu21^xiii	47.02 (14)
Cu1^i—S1—As1^vii	104.22 (7)	Cu21^ix—S2—Cu21^xiv	96.04 (14)
Cu1^viii—S1—Cu2	115.83 (7)	Cu21^ix—S2—Cu21^vi	96.04 (14)
Cu1^viii—S1—Cu21	92.99 (11)	Cu21^ix—S2—Cu21^xi	96.04 (14)
Cu1^viii—S1—Cu21^ii	138.00 (11)	Cu21^ix—S2—Cu21^xv	118.12 (14)
Cu1^viii—S1—As1^vii	104.22 (7)	Cu21^ix—S2—Cu21^xvi	47.02 (14)
Cu2—S1—Cu21	26.39 (10)	Cu21^xii—S2—Cu21^ii	142.14 (14)
Cu2—S1—Cu21^ii	26.39 (10)	Cu21^xii—S2—Cu21^v	96.04 (14)
Cu2—S1—As1^vii	113.09 (12)	Cu21^xii—S2—Cu21^x	118.12 (14)
Cu21—S1—Cu21^ii	52.75 (14)	Cu21^xii—S2—Cu21^xiii	96.04 (14)
Cu21—S1—As1^vii	109.66 (13)	Cu21^xii—S2—Cu21^xiv	47.02 (14)
Cu21^ii—S1—As1^vii	109.66 (13)	Cu21^xii—S2—Cu21^vi	118.12 (14)
Cu2—S2—Cu2^ix	180	Cu21^xii—S2—Cu21^xi	47.02 (14)
Cu2—S2—Cu2^v	90	Cu21^xii—S2—Cu21^xv	96.04 (14)
Cu2—S2—Cu2^x	90	Cu21^xii—S2—Cu21^xvi	96.04 (14)
Cu2—S2—Cu2^vi	90	Cu21^ii—S2—Cu21^v	96.04 (14)
Cu2—S2—Cu2^xi	90	Cu21^ii—S2—Cu21^x	47.02 (14)
Cu2—S2—Cu21	27.31 (10)	Cu21^ii—S2—Cu21^xiii	96.04 (14)
Cu2—S2—Cu21^ix	152.69 (10)	Cu21^ii—S2—Cu21^xiv	118.12 (14)
Cu2—S2—Cu21^xii	152.69 (10)	Cu21^ii—S2—Cu21^vi	96.04 (14)
Cu2—S2—Cu21^ii	27.31 (10)	Cu21^ii—S2—Cu21^xi	96.04 (14)
Cu2—S2—Cu21^v	71.07 (10)	Cu21^ii—S2—Cu21^xv	47.02 (14)
Cu2—S2—Cu21^x	71.07 (10)	Cu21^ii—S2—Cu21^xvi	118.12 (14)
Cu2—S2—Cu21^xiii	108.93 (10)	Cu21^v—S2—Cu21^x	142.14 (14)
Cu2—S2—Cu21^xiv	108.93 (10)	Cu21^v—S2—Cu21^xiii	142.14 (14)
Cu2—S2—Cu21^vi	71.07 (10)	Cu21^v—S2—Cu21^xiv	54.61 (14)
Cu2—S2—Cu21^xi	108.93 (10)	Cu21^v—S2—Cu21^vi	47.02 (14)
Cu2—S2—Cu21^xv	71.07 (10)	Cu21^v—S2—Cu21^xi	96.04 (14)
Cu2—S2—Cu21^xvi	108.93 (10)	Cu21^v—S2—Cu21^xv	118.12 (14)
Cu2^ix—S2—Cu2^v	90	Cu21^v—S2—Cu21^xvi	96.04 (14)
Cu2^ix—S2—Cu2^x	90	Cu21^x—S2—Cu21^xiii	54.61 (14)
Cu2^ix—S2—Cu2^vi	90	Cu21^x—S2—Cu21^xiv	142.14 (14)
Cu2^ix—S2—Cu2^xi	90	Cu21^x—S2—Cu21^vi	118.12 (14)
Cu2^ix—S2—Cu21	152.69 (10)	Cu21^x—S2—Cu21^xi	96.04 (14)
Cu2^ix—S2—Cu21^ix	27.31 (10)	Cu21^x—S2—Cu21^xv	47.02 (14)
Cu2^ix—S2—Cu21^xii	27.31 (10)	Cu21^x—S2—Cu21^xvi	96.04 (14)
Cu2^ix—S2—Cu21^ii	152.69 (10)	Cu21^xiii—S2—Cu21^xiv	142.14 (14)
Cu2^ix—S2—Cu21^v	108.93 (10)	Cu21^xiii—S2—Cu21^vi	96.04 (14)
Cu2^ix—S2—Cu21^x	108.93 (10)	Cu21^xiii—S2—Cu21^xi	118.12 (14)
Cu2^ix—S2—Cu21^xiii	71.07 (10)	Cu21^xiii—S2—Cu21^xv	96.04 (14)
Cu2^ix—S2—Cu21^xiv	71.07 (10)	Cu21^xiii—S2—Cu21^xvi	47.02 (14)
Cu2^ix—S2—Cu21^vi	108.93 (10)	Cu21^xiv—S2—Cu21^vi	96.04 (14)
Cu2^ix—S2—Cu21^xi	71.07 (10)	Cu21^xiv—S2—Cu21^xi	47.02 (14)
Cu2^ix—S2—Cu21^xv	108.93 (10)	Cu21^xiv—S2—Cu21^xv	96.04 (14)
Cu2^ix—S2—Cu21^xvi	71.07 (10)	Cu21^xiv—S2—Cu21^xvi	118.12 (14)
Cu2^v—S2—Cu2^x	180	Cu21^vi—S2—Cu21^xi	142.14 (14)
Cu2^v—S2—Cu2^vi	90	Cu21^vi—S2—Cu21^xv	142.14 (14)
Cu2^v—S2—Cu2^xi	90	Cu21^vi—S2—Cu21^xvi	54.61 (14)
Cu2^v—S2—Cu21	71.07 (10)	Cu21^xi—S2—Cu21^xv	54.61 (14)
Cu2^v—S2—Cu21^ix	108.93 (10)	Cu21^xi—S2—Cu21^xvi	142.14 (14)
Cu2^v—S2—Cu21^xii	71.07 (10)	Cu21^xv—S2—Cu21^xvi	142.14 (14)
Cu2^v—S2—Cu21^ii	108.93 (10)	Cu21—As1—Cu21^v	47.79 (15)
Cu2^v—S2—Cu21^v	27.31 (10)	Cu21—As1—Cu21^vi	47.79 (15)
Cu2^v—S2—Cu21^x	152.69 (10)	Cu21—As1—S1^xvii	145.67 (13)
Cu2^v—S2—Cu21^xiii	152.69 (10)	Cu21—As1—S1^xviii	101.83 (12)
Cu2^v—S2—Cu21^xiv	27.31 (10)	Cu21—As1—S1^iii	101.83 (12)
Cu2^v—S2—Cu21^vi	71.07 (10)	Cu21^v—As1—Cu21^vi	47.79 (15)
Cu2^v—S2—Cu21^xi	71.07 (10)	Cu21^v—As1—S1^xvii	101.83 (12)
Cu2^v—S2—Cu21^xv	108.93 (10)	Cu21^v—As1—S1^xviii	145.67 (13)
Cu2^v—S2—Cu21^xvi	108.93 (10)	Cu21^v—As1—S1^iii	101.83 (12)
Cu2^x—S2—Cu2^vi	90	Cu21^vi—As1—S1^xvii	101.83 (12)
Cu2^x—S2—Cu2^xi	90	Cu21^vi—As1—S1^xviii	101.83 (12)
Cu2^x—S2—Cu21	108.93 (10)	Cu21^vi—As1—S1^iii	145.67 (13)
Cu2^x—S2—Cu21^ix	71.07 (10)	S1^xvii—As1—S1^xviii	100.03 (8)
Cu2^x—S2—Cu21^xii	108.93 (10)	S1^xvii—As1—S1^iii	100.03 (8)
Cu2^x—S2—Cu21^ii	71.07 (10)	S1^xviii—As1—S1^iii	100.03 (8)
Cu2^x—S2—Cu21^v	152.69 (10)

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

Copper Arsenic Sulfide (182K)

Crystal data

As4Cu12S13	Dx = 4.703 Mg m^−3
Mr = 1479	Mo Kα radiation, λ = 0.71069 Å
Cubic, I43m	Cell parameters from 5323 reflections
Hall symbol: I -4;2;3	θ = 4.0–41.9°
a = 10.1463 (2) Å	µ = 19.52 mm^−1
V = 1044.54 (4) Å^3	T = 182 K
Z = 2	Prism, black
F(000) = 1376	0.46 × 0.31 × 0.25 mm

Data collection

Xcalibur, EosS2 diffractometer	719 independent reflections
Radiation source: sealed tube	685 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
θ scans	θmax = 42.1°, θmin = 4.0°
Absorption correction: analytical	h = −19→19
Tmin = 0.015, Tmax = 0.104	k = −12→19
11036 measured reflections	l = −18→15

Refinement

Refinement on F	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.0013690001F^2)
R[F^2 > 2σ(F^2)] = 0.031	(Δ/σ)max = 0.005
wR(F^2) = 0.045	Δρmax = 2.27 e Å^−3
S = 1.03	Δρmin = −1.07 e Å^−3
719 reflections	Extinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
47 parameters	Extinction coefficient: 1150 (100)
0 restraints	Absolute structure: 318 of Friedel pairs used in the refinement
0 constraints

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.5	0.25	0	0.0111 (3)
Cu2	0.2177 (4)	0	0	0.0234 (3)	0.703 (10)
Cu21	0.2130 (10)	0.0694 (19)	0.0694 (19)	0.032 (3)	0.148 (5)
S1	0.35734 (8)	−0.11850 (6)	0.11850 (6)	0.00795 (13)
S2	0	0	0	0.0133 (7)
As1	0.24177 (10)	0.24177 (10)	0.24177 (10)	0.00883 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0089 (3)	0.0156 (7)	0.0089 (3)	0	0	0
Cu2	0.0090 (5)	0.0306 (6)	0.0306 (6)	0	0	0.0125 (10)
Cu21	0.0135 (16)	0.041 (6)	0.041 (6)	−0.014 (2)	−0.014 (2)	0.029 (6)
S1	0.0057 (3)	0.0091 (2)	0.0091 (2)	−0.00239 (15)	0.00239 (15)	−0.0019 (2)
S2	0.0133 (13)	0.0133 (13)	0.0133 (13)	0	0	0
As1	0.00883 (15)	0.00883 (15)	0.00883 (15)	0.00075 (11)	0.00075 (11)	0.00075 (11)

Geometric parameters (Å, º)

Cu1—S1^i	2.3067 (7)	Cu21—Cu21^ii	1.99 (3)
Cu1—S1^ii	2.3067 (7)	Cu21—Cu21^v	2.06 (2)
Cu1—S1^iii	2.3067 (7)	Cu21—Cu21^vi	2.06 (2)
Cu1—S1^iv	2.3067 (7)	Cu21—S1	2.455 (17)
Cu2—Cu21	0.997 (19)	Cu21—S1^ii	2.455 (17)
Cu2—Cu21^ii	0.997 (19)	Cu21—S2	2.380 (13)
Cu2—S1	2.213 (2)	Cu21—As1	2.491 (19)
Cu2—S1^ii	2.213 (2)	S1—As1^vii	2.2430 (12)
Cu2—S2	2.209 (4)
S1^i—Cu1—S1^ii	109.32 (2)	Cu2^x—S2—Cu21^x	24.7 (4)
S1^i—Cu1—S1^iii	109.55 (3)	Cu2^x—S2—Cu21^xiii	24.7 (4)
S1^i—Cu1—S1^iv	109.55 (3)	Cu2^x—S2—Cu21^xiv	155.3 (4)
S1^ii—Cu1—S1^iii	109.55 (3)	Cu2^x—S2—Cu21^vi	107.2 (5)
S1^ii—Cu1—S1^iv	109.55 (3)	Cu2^x—S2—Cu21^xi	107.2 (5)
S1^iii—Cu1—S1^iv	109.32 (2)	Cu2^x—S2—Cu21^xv	72.8 (5)
Cu21—Cu2—Cu21^ii	174.5 (10)	Cu2^x—S2—Cu21^xvi	72.8 (5)
Cu21—Cu2—S1	91.7 (10)	Cu2^vi—S2—Cu2^xi	180
Cu21—Cu2—S1^ii	91.7 (10)	Cu2^vi—S2—Cu21	72.8 (5)
Cu21—Cu2—S2	87.3 (6)	Cu2^vi—S2—Cu21^ix	72.8 (5)
Cu21^ii—Cu2—S1	91.7 (10)	Cu2^vi—S2—Cu21^xii	107.2 (5)
Cu21^ii—Cu2—S1^ii	91.7 (10)	Cu2^vi—S2—Cu21^ii	107.2 (5)
Cu21^ii—Cu2—S2	87.3 (6)	Cu2^vi—S2—Cu21^v	72.8 (5)
S1—Cu2—S1^ii	100.40 (15)	Cu2^vi—S2—Cu21^x	107.2 (5)
S1—Cu2—S2	129.80 (8)	Cu2^vi—S2—Cu21^xiii	72.8 (5)
S1^ii—Cu2—S2	129.80 (8)	Cu2^vi—S2—Cu21^xiv	107.2 (5)
Cu2—Cu21—Cu21^ii	2.7 (5)	Cu2^vi—S2—Cu21^vi	24.7 (4)
Cu2—Cu21—Cu21^v	122.2 (13)	Cu2^vi—S2—Cu21^xi	155.3 (4)
Cu2—Cu21—Cu21^vi	122.2 (13)	Cu2^vi—S2—Cu21^xv	155.3 (4)
Cu2—Cu21—S1	64.3 (9)	Cu2^vi—S2—Cu21^xvi	24.7 (4)
Cu2—Cu21—S1^ii	64.3 (9)	Cu2^xi—S2—Cu21	107.2 (5)
Cu2—Cu21—S2	68.0 (7)	Cu2^xi—S2—Cu21^ix	107.2 (5)
Cu2—Cu21—As1	170.5 (9)	Cu2^xi—S2—Cu21^xii	72.8 (5)
Cu21^ii—Cu21—Cu21^v	120.0 (10)	Cu2^xi—S2—Cu21^ii	72.8 (5)
Cu21^ii—Cu21—Cu21^vi	120.0 (10)	Cu2^xi—S2—Cu21^v	107.2 (5)
Cu21^ii—Cu21—S1	66.1 (7)	Cu2^xi—S2—Cu21^x	72.8 (5)
Cu21^ii—Cu21—S1^ii	66.1 (7)	Cu2^xi—S2—Cu21^xiii	107.2 (5)
Cu21^ii—Cu21—S2	65.3 (6)	Cu2^xi—S2—Cu21^xiv	72.8 (5)
Cu21^ii—Cu21—As1	173.3 (6)	Cu2^xi—S2—Cu21^vi	155.3 (4)
Cu21^v—Cu21—Cu21^vi	60.0 (8)	Cu2^xi—S2—Cu21^xi	24.7 (4)
Cu21^v—Cu21—S1	166.1 (11)	Cu2^xi—S2—Cu21^xv	24.7 (4)
Cu21^v—Cu21—S1^ii	106.2 (9)	Cu2^xi—S2—Cu21^xvi	155.3 (4)
Cu21^v—Cu21—S2	64.3 (5)	Cu21—S2—Cu21^ix	145.6 (6)
Cu21^v—Cu21—As1	65.6 (7)	Cu21—S2—Cu21^xii	145.6 (6)
Cu21^vi—Cu21—S1	106.2 (9)	Cu21—S2—Cu21^ii	49.5 (6)
Cu21^vi—Cu21—S1^ii	166.1 (11)	Cu21—S2—Cu21^v	51.3 (6)
Cu21^vi—Cu21—S2	64.3 (5)	Cu21—S2—Cu21^x	95.0 (6)
Cu21^vi—Cu21—As1	65.6 (7)	Cu21—S2—Cu21^xiii	116.7 (7)
S1—Cu21—S1^ii	87.7 (5)	Cu21—S2—Cu21^xiv	95.0 (6)
S1—Cu21—S2	111.8 (7)	Cu21—S2—Cu21^vi	51.3 (6)
S1—Cu21—As1	109.4 (6)	Cu21—S2—Cu21^xi	116.7 (7)
S1^ii—Cu21—S2	111.8 (7)	Cu21—S2—Cu21^xv	95.0 (6)
S1^ii—Cu21—As1	109.4 (6)	Cu21—S2—Cu21^xvi	95.0 (6)
S2—Cu21—As1	121.5 (6)	Cu21^ix—S2—Cu21^xii	49.5 (6)
Cu1^i—S1—Cu1^viii	102.08 (3)	Cu21^ix—S2—Cu21^ii	145.6 (6)
Cu1^i—S1—Cu2	115.64 (5)	Cu21^ix—S2—Cu21^v	116.7 (7)
Cu1^i—S1—Cu21	135.9 (4)	Cu21^ix—S2—Cu21^x	95.0 (6)
Cu1^i—S1—Cu21^ii	95.0 (4)	Cu21^ix—S2—Cu21^xiii	51.3 (6)
Cu1^i—S1—As1^vii	104.19 (4)	Cu21^ix—S2—Cu21^xiv	95.0 (6)
Cu1^viii—S1—Cu2	115.64 (5)	Cu21^ix—S2—Cu21^vi	95.0 (6)
Cu1^viii—S1—Cu21	95.0 (4)	Cu21^ix—S2—Cu21^xi	95.0 (6)
Cu1^viii—S1—Cu21^ii	135.9 (4)	Cu21^ix—S2—Cu21^xv	116.7 (7)
Cu1^viii—S1—As1^vii	104.19 (4)	Cu21^ix—S2—Cu21^xvi	51.3 (6)
Cu2—S1—Cu21	23.9 (4)	Cu21^xii—S2—Cu21^ii	145.6 (6)
Cu2—S1—Cu21^ii	23.9 (4)	Cu21^xii—S2—Cu21^v	95.0 (6)
Cu2—S1—As1^vii	113.56 (9)	Cu21^xii—S2—Cu21^x	116.7 (7)
Cu21—S1—Cu21^ii	47.8 (6)	Cu21^xii—S2—Cu21^xiii	95.0 (6)
Cu21—S1—As1^vii	110.6 (4)	Cu21^xii—S2—Cu21^xiv	51.3 (6)
Cu21^ii—S1—As1^vii	110.6 (4)	Cu21^xii—S2—Cu21^vi	116.7 (7)
Cu2—S2—Cu2^ix	180	Cu21^xii—S2—Cu21^xi	51.3 (6)
Cu2—S2—Cu2^v	90	Cu21^xii—S2—Cu21^xv	95.0 (6)
Cu2—S2—Cu2^x	90	Cu21^xii—S2—Cu21^xvi	95.0 (6)
Cu2—S2—Cu2^vi	90	Cu21^ii—S2—Cu21^v	95.0 (6)
Cu2—S2—Cu2^xi	90	Cu21^ii—S2—Cu21^x	51.3 (6)
Cu2—S2—Cu21	24.7 (4)	Cu21^ii—S2—Cu21^xiii	95.0 (6)
Cu2—S2—Cu21^ix	155.3 (4)	Cu21^ii—S2—Cu21^xiv	116.7 (7)
Cu2—S2—Cu21^xii	155.3 (4)	Cu21^ii—S2—Cu21^vi	95.0 (6)
Cu2—S2—Cu21^ii	24.7 (4)	Cu21^ii—S2—Cu21^xi	95.0 (6)
Cu2—S2—Cu21^v	72.8 (5)	Cu21^ii—S2—Cu21^xv	51.3 (6)
Cu2—S2—Cu21^x	72.8 (5)	Cu21^ii—S2—Cu21^xvi	116.7 (7)
Cu2—S2—Cu21^xiii	107.2 (5)	Cu21^v—S2—Cu21^x	145.6 (6)
Cu2—S2—Cu21^xiv	107.2 (5)	Cu21^v—S2—Cu21^xiii	145.6 (6)
Cu2—S2—Cu21^vi	72.8 (5)	Cu21^v—S2—Cu21^xiv	49.5 (6)
Cu2—S2—Cu21^xi	107.2 (5)	Cu21^v—S2—Cu21^vi	51.3 (6)
Cu2—S2—Cu21^xv	72.8 (5)	Cu21^v—S2—Cu21^xi	95.0 (6)
Cu2—S2—Cu21^xvi	107.2 (5)	Cu21^v—S2—Cu21^xv	116.7 (7)
Cu2^ix—S2—Cu2^v	90	Cu21^v—S2—Cu21^xvi	95.0 (6)
Cu2^ix—S2—Cu2^x	90	Cu21^x—S2—Cu21^xiii	49.5 (6)
Cu2^ix—S2—Cu2^vi	90	Cu21^x—S2—Cu21^xiv	145.6 (6)
Cu2^ix—S2—Cu2^xi	90	Cu21^x—S2—Cu21^vi	116.7 (7)
Cu2^ix—S2—Cu21	155.3 (4)	Cu21^x—S2—Cu21^xi	95.0 (6)
Cu2^ix—S2—Cu21^ix	24.7 (4)	Cu21^x—S2—Cu21^xv	51.3 (6)
Cu2^ix—S2—Cu21^xii	24.7 (4)	Cu21^x—S2—Cu21^xvi	95.0 (6)
Cu2^ix—S2—Cu21^ii	155.3 (4)	Cu21^xiii—S2—Cu21^xiv	145.6 (6)
Cu2^ix—S2—Cu21^v	107.2 (5)	Cu21^xiii—S2—Cu21^vi	95.0 (6)
Cu2^ix—S2—Cu21^x	107.2 (5)	Cu21^xiii—S2—Cu21^xi	116.7 (7)
Cu2^ix—S2—Cu21^xiii	72.8 (5)	Cu21^xiii—S2—Cu21^xv	95.0 (6)
Cu2^ix—S2—Cu21^xiv	72.8 (5)	Cu21^xiii—S2—Cu21^xvi	51.3 (6)
Cu2^ix—S2—Cu21^vi	107.2 (5)	Cu21^xiv—S2—Cu21^vi	95.0 (6)
Cu2^ix—S2—Cu21^xi	72.8 (5)	Cu21^xiv—S2—Cu21^xi	51.3 (6)
Cu2^ix—S2—Cu21^xv	107.2 (5)	Cu21^xiv—S2—Cu21^xv	95.0 (6)
Cu2^ix—S2—Cu21^xvi	72.8 (5)	Cu21^xiv—S2—Cu21^xvi	116.7 (7)
Cu2^v—S2—Cu2^x	180	Cu21^vi—S2—Cu21^xi	145.6 (6)
Cu2^v—S2—Cu2^vi	90	Cu21^vi—S2—Cu21^xv	145.6 (6)
Cu2^v—S2—Cu2^xi	90	Cu21^vi—S2—Cu21^xvi	49.5 (6)
Cu2^v—S2—Cu21	72.8 (5)	Cu21^xi—S2—Cu21^xv	49.5 (6)
Cu2^v—S2—Cu21^ix	107.2 (5)	Cu21^xi—S2—Cu21^xvi	145.6 (6)
Cu2^v—S2—Cu21^xii	72.8 (5)	Cu21^xv—S2—Cu21^xvi	145.6 (6)
Cu2^v—S2—Cu21^ii	107.2 (5)	Cu21—As1—Cu21^v	48.9 (5)
Cu2^v—S2—Cu21^v	24.7 (4)	Cu21—As1—Cu21^vi	48.9 (5)
Cu2^v—S2—Cu21^x	155.3 (4)	Cu21—As1—S1^xvii	146.6 (3)
Cu2^v—S2—Cu21^xiii	155.3 (4)	Cu21—As1—S1^xviii	101.7 (4)
Cu2^v—S2—Cu21^xiv	24.7 (4)	Cu21—As1—S1^iii	101.7 (4)
Cu2^v—S2—Cu21^vi	72.8 (5)	Cu21^v—As1—Cu21^vi	48.9 (5)
Cu2^v—S2—Cu21^xi	72.8 (5)	Cu21^v—As1—S1^xvii	101.7 (4)
Cu2^v—S2—Cu21^xv	107.2 (5)	Cu21^v—As1—S1^xviii	146.6 (3)
Cu2^v—S2—Cu21^xvi	107.2 (5)	Cu21^v—As1—S1^iii	101.7 (4)
Cu2^x—S2—Cu2^vi	90	Cu21^vi—As1—S1^xvii	101.7 (4)
Cu2^x—S2—Cu2^xi	90	Cu21^vi—As1—S1^xviii	101.7 (4)
Cu2^x—S2—Cu21	107.2 (5)	Cu21^vi—As1—S1^iii	146.6 (3)
Cu2^x—S2—Cu21^ix	72.8 (5)	S1^xvii—As1—S1^xviii	99.63 (5)
Cu2^x—S2—Cu21^xii	107.2 (5)	S1^xvii—As1—S1^iii	99.63 (5)
Cu2^x—S2—Cu21^ii	72.8 (5)	S1^xviii—As1—S1^iii	99.63 (5)
Cu2^x—S2—Cu21^v	155.3 (4)

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

Copper Arsenic Sulfide (251K)

Crystal data

As4Cu12S13	Dx = 4.694 Mg m^−3
Mr = 1479	Mo Kα radiation, λ = 0.71069 Å
Cubic, I43m	Cell parameters from 5323 reflections
Hall symbol: I -4;2;3	θ = 4.0–41.9°
a = 10.1523 (2) Å	µ = 19.49 mm^−1
V = 1046.39 (4) Å^3	T = 251 K
Z = 2	Prism, black
F(000) = 1376	0.46 × 0.31 × 0.25 mm

Data collection

Xcalibur, EosS2 diffractometer	719 independent reflections
Radiation source: sealed tube	677 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
θ scans	θmax = 42.0°, θmin = 4.0°
Absorption correction: analytical	h = −19→19
Tmin = 0.015, Tmax = 0.104	k = −12→19
11010 measured reflections	l = −18→15

Refinement

Refinement on F	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.001225F^2)
R[F^2 > 2σ(F^2)] = 0.032	(Δ/σ)max = 0.004
wR(F^2) = 0.044	Δρmax = 1.76 e Å^−3
S = 1.01	Δρmin = −1.11 e Å^−3
719 reflections	Extinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
47 parameters	Extinction coefficient: 1380 (100)
0 restraints	Absolute structure: 318 of Friedel pairs used in the refinement
0 constraints

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.5	0.25	0	0.0155 (3)
Cu2	0.2176 (4)	0	0	0.0295 (4)	0.686 (11)
Cu21	0.2137 (12)	0.0675 (19)	0.0675 (19)	0.039 (3)	0.157 (5)
S1	0.35730 (8)	−0.11853 (6)	0.11853 (6)	0.00972 (13)
S2	0	0	0	0.0139 (7)
As1	0.24169 (10)	0.24169 (10)	0.24169 (10)	0.01038 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0127 (4)	0.0211 (8)	0.0127 (4)	0	0	0
Cu2	0.0105 (6)	0.0389 (8)	0.0389 (8)	0	0	0.0191 (11)
Cu21	0.0199 (18)	0.048 (6)	0.048 (6)	−0.017 (2)	−0.017 (2)	0.031 (6)
S1	0.0074 (3)	0.0109 (2)	0.0109 (2)	−0.00223 (15)	0.00223 (15)	−0.0013 (2)
S2	0.0139 (12)	0.0139 (12)	0.0139 (12)	0	0	0
As1	0.01038 (14)	0.01038 (14)	0.01038 (14)	0.00014 (11)	0.00014 (11)	0.00014 (11)

Geometric parameters (Å, º)

Cu1—S1^i	2.3083 (7)	Cu21—Cu21^ii	1.94 (3)
Cu1—S1^ii	2.3083 (7)	Cu21—Cu21^v	2.10 (2)
Cu1—S1^iii	2.3083 (7)	Cu21—Cu21^vi	2.10 (2)
Cu1—S1^iv	2.3083 (7)	Cu21—S1	2.442 (17)
Cu2—Cu21	0.970 (19)	Cu21—S1^ii	2.442 (17)
Cu2—Cu21^ii	0.970 (19)	Cu21—S2	2.376 (14)
Cu2—S1	2.216 (3)	Cu21—As1	2.517 (19)
Cu2—S1^ii	2.216 (3)	S1—As1^vii	2.2445 (12)
Cu2—S2	2.209 (5)
S1^i—Cu1—S1^ii	109.35 (2)	Cu2^x—S2—Cu21^x	24.1 (4)
S1^i—Cu1—S1^iii	109.53 (2)	Cu2^x—S2—Cu21^xiii	24.1 (4)
S1^i—Cu1—S1^iv	109.53 (2)	Cu2^x—S2—Cu21^xiv	155.9 (4)
S1^ii—Cu1—S1^iii	109.53 (2)	Cu2^x—S2—Cu21^vi	106.8 (5)
S1^ii—Cu1—S1^iv	109.53 (2)	Cu2^x—S2—Cu21^xi	106.8 (5)
S1^iii—Cu1—S1^iv	109.35 (2)	Cu2^x—S2—Cu21^xv	73.2 (5)
Cu21—Cu2—Cu21^ii	175.4 (11)	Cu2^x—S2—Cu21^xvi	73.2 (5)
Cu21—Cu2—S1	91.5 (10)	Cu2^vi—S2—Cu2^xi	180
Cu21—Cu2—S1^ii	91.5 (10)	Cu2^vi—S2—Cu21	73.2 (5)
Cu21—Cu2—S2	87.7 (8)	Cu2^vi—S2—Cu21^ix	73.2 (5)
Cu21^ii—Cu2—S1	91.5 (10)	Cu2^vi—S2—Cu21^xii	106.8 (5)
Cu21^ii—Cu2—S1^ii	91.5 (10)	Cu2^vi—S2—Cu21^ii	106.8 (5)
Cu21^ii—Cu2—S2	87.7 (8)	Cu2^vi—S2—Cu21^v	73.2 (5)
S1—Cu2—S1^ii	100.37 (18)	Cu2^vi—S2—Cu21^x	106.8 (5)
S1—Cu2—S2	129.82 (9)	Cu2^vi—S2—Cu21^xiii	73.2 (5)
S1^ii—Cu2—S2	129.82 (9)	Cu2^vi—S2—Cu21^xiv	106.8 (5)
Cu2—Cu21—Cu21^ii	2.3 (6)	Cu2^vi—S2—Cu21^vi	24.1 (4)
Cu2—Cu21—Cu21^v	121.9 (13)	Cu2^vi—S2—Cu21^xi	155.9 (4)
Cu2—Cu21—Cu21^vi	121.9 (13)	Cu2^vi—S2—Cu21^xv	155.9 (4)
Cu2—Cu21—S1	65.1 (9)	Cu2^vi—S2—Cu21^xvi	24.1 (4)
Cu2—Cu21—S1^ii	65.1 (9)	Cu2^xi—S2—Cu21	106.8 (5)
Cu2—Cu21—S2	68.2 (8)	Cu2^xi—S2—Cu21^ix	106.8 (5)
Cu2—Cu21—As1	171.2 (10)	Cu2^xi—S2—Cu21^xii	73.2 (5)
Cu21^ii—Cu21—Cu21^v	120.0 (10)	Cu2^xi—S2—Cu21^ii	73.2 (5)
Cu21^ii—Cu21—Cu21^vi	120.0 (10)	Cu2^xi—S2—Cu21^v	106.8 (5)
Cu21^ii—Cu21—S1	66.6 (7)	Cu2^xi—S2—Cu21^x	73.2 (5)
Cu21^ii—Cu21—S1^ii	66.6 (7)	Cu2^xi—S2—Cu21^xiii	106.8 (5)
Cu21^ii—Cu21—S2	65.9 (6)	Cu2^xi—S2—Cu21^xiv	73.2 (5)
Cu21^ii—Cu21—As1	173.5 (7)	Cu2^xi—S2—Cu21^vi	155.9 (4)
Cu21^v—Cu21—Cu21^vi	60.0 (8)	Cu2^xi—S2—Cu21^xi	24.1 (4)
Cu21^v—Cu21—S1	165.8 (10)	Cu2^xi—S2—Cu21^xv	24.1 (4)
Cu21^v—Cu21—S1^ii	105.8 (9)	Cu2^xi—S2—Cu21^xvi	155.9 (4)
Cu21^v—Cu21—S2	63.8 (6)	Cu21—S2—Cu21^ix	146.5 (6)
Cu21^v—Cu21—As1	65.4 (7)	Cu21—S2—Cu21^xii	146.5 (6)
Cu21^vi—Cu21—S1	105.8 (9)	Cu21—S2—Cu21^ii	48.1 (6)
Cu21^vi—Cu21—S1^ii	165.8 (10)	Cu21—S2—Cu21^v	52.4 (6)
Cu21^vi—Cu21—S2	63.8 (6)	Cu21—S2—Cu21^x	94.8 (6)
Cu21^vi—Cu21—As1	65.4 (7)	Cu21—S2—Cu21^xiii	116.3 (7)
S1—Cu21—S1^ii	88.4 (5)	Cu21—S2—Cu21^xiv	94.8 (6)
S1—Cu21—S2	112.5 (7)	Cu21—S2—Cu21^vi	52.4 (6)
S1—Cu21—As1	109.1 (6)	Cu21—S2—Cu21^xi	116.3 (7)
S1^ii—Cu21—S2	112.5 (7)	Cu21—S2—Cu21^xv	94.8 (6)
S1^ii—Cu21—As1	109.1 (6)	Cu21—S2—Cu21^xvi	94.8 (6)
S2—Cu21—As1	120.6 (6)	Cu21^ix—S2—Cu21^xii	48.1 (6)
Cu1^i—S1—Cu1^viii	102.06 (3)	Cu21^ix—S2—Cu21^ii	146.5 (6)
Cu1^i—S1—Cu2	115.65 (5)	Cu21^ix—S2—Cu21^v	116.3 (7)
Cu1^i—S1—Cu21	135.4 (4)	Cu21^ix—S2—Cu21^x	94.8 (6)
Cu1^i—S1—Cu21^ii	95.4 (4)	Cu21^ix—S2—Cu21^xiii	52.4 (6)
Cu1^i—S1—As1^vii	104.18 (4)	Cu21^ix—S2—Cu21^xiv	94.8 (6)
Cu1^viii—S1—Cu2	115.65 (5)	Cu21^ix—S2—Cu21^vi	94.8 (6)
Cu1^viii—S1—Cu21	95.4 (4)	Cu21^ix—S2—Cu21^xi	94.8 (6)
Cu1^viii—S1—Cu21^ii	135.4 (4)	Cu21^ix—S2—Cu21^xv	116.3 (7)
Cu1^viii—S1—As1^vii	104.18 (4)	Cu21^ix—S2—Cu21^xvi	52.4 (6)
Cu2—S1—Cu21	23.4 (4)	Cu21^xii—S2—Cu21^ii	146.5 (6)
Cu2—S1—Cu21^ii	23.4 (4)	Cu21^xii—S2—Cu21^v	94.8 (6)
Cu2—S1—As1^vii	113.59 (10)	Cu21^xii—S2—Cu21^x	116.3 (7)
Cu21—S1—Cu21^ii	46.8 (6)	Cu21^xii—S2—Cu21^xiii	94.8 (6)
Cu21—S1—As1^vii	110.8 (4)	Cu21^xii—S2—Cu21^xiv	52.4 (6)
Cu21^ii—S1—As1^vii	110.8 (4)	Cu21^xii—S2—Cu21^vi	116.3 (7)
Cu2—S2—Cu2^ix	180	Cu21^xii—S2—Cu21^xi	52.4 (6)
Cu2—S2—Cu2^v	90	Cu21^xii—S2—Cu21^xv	94.8 (6)
Cu2—S2—Cu2^x	90	Cu21^xii—S2—Cu21^xvi	94.8 (6)
Cu2—S2—Cu2^vi	90	Cu21^ii—S2—Cu21^v	94.8 (6)
Cu2—S2—Cu2^xi	90	Cu21^ii—S2—Cu21^x	52.4 (6)
Cu2—S2—Cu21	24.1 (4)	Cu21^ii—S2—Cu21^xiii	94.8 (6)
Cu2—S2—Cu21^ix	155.9 (4)	Cu21^ii—S2—Cu21^xiv	116.3 (7)
Cu2—S2—Cu21^xii	155.9 (4)	Cu21^ii—S2—Cu21^vi	94.8 (6)
Cu2—S2—Cu21^ii	24.1 (4)	Cu21^ii—S2—Cu21^xi	94.8 (6)
Cu2—S2—Cu21^v	73.2 (5)	Cu21^ii—S2—Cu21^xv	52.4 (6)
Cu2—S2—Cu21^x	73.2 (5)	Cu21^ii—S2—Cu21^xvi	116.3 (7)
Cu2—S2—Cu21^xiii	106.8 (5)	Cu21^v—S2—Cu21^x	146.5 (6)
Cu2—S2—Cu21^xiv	106.8 (5)	Cu21^v—S2—Cu21^xiii	146.5 (6)
Cu2—S2—Cu21^vi	73.2 (5)	Cu21^v—S2—Cu21^xiv	48.1 (6)
Cu2—S2—Cu21^xi	106.8 (5)	Cu21^v—S2—Cu21^vi	52.4 (6)
Cu2—S2—Cu21^xv	73.2 (5)	Cu21^v—S2—Cu21^xi	94.8 (6)
Cu2—S2—Cu21^xvi	106.8 (5)	Cu21^v—S2—Cu21^xv	116.3 (7)
Cu2^ix—S2—Cu2^v	90	Cu21^v—S2—Cu21^xvi	94.8 (6)
Cu2^ix—S2—Cu2^x	90	Cu21^x—S2—Cu21^xiii	48.1 (6)
Cu2^ix—S2—Cu2^vi	90	Cu21^x—S2—Cu21^xiv	146.5 (6)
Cu2^ix—S2—Cu2^xi	90	Cu21^x—S2—Cu21^vi	116.3 (7)
Cu2^ix—S2—Cu21	155.9 (4)	Cu21^x—S2—Cu21^xi	94.8 (6)
Cu2^ix—S2—Cu21^ix	24.1 (4)	Cu21^x—S2—Cu21^xv	52.4 (6)
Cu2^ix—S2—Cu21^xii	24.1 (4)	Cu21^x—S2—Cu21^xvi	94.8 (6)
Cu2^ix—S2—Cu21^ii	155.9 (4)	Cu21^xiii—S2—Cu21^xiv	146.5 (6)
Cu2^ix—S2—Cu21^v	106.8 (5)	Cu21^xiii—S2—Cu21^vi	94.8 (6)
Cu2^ix—S2—Cu21^x	106.8 (5)	Cu21^xiii—S2—Cu21^xi	116.3 (7)
Cu2^ix—S2—Cu21^xiii	73.2 (5)	Cu21^xiii—S2—Cu21^xv	94.8 (6)
Cu2^ix—S2—Cu21^xiv	73.2 (5)	Cu21^xiii—S2—Cu21^xvi	52.4 (6)
Cu2^ix—S2—Cu21^vi	106.8 (5)	Cu21^xiv—S2—Cu21^vi	94.8 (6)
Cu2^ix—S2—Cu21^xi	73.2 (5)	Cu21^xiv—S2—Cu21^xi	52.4 (6)
Cu2^ix—S2—Cu21^xv	106.8 (5)	Cu21^xiv—S2—Cu21^xv	94.8 (6)
Cu2^ix—S2—Cu21^xvi	73.2 (5)	Cu21^xiv—S2—Cu21^xvi	116.3 (7)
Cu2^v—S2—Cu2^x	180	Cu21^vi—S2—Cu21^xi	146.5 (6)
Cu2^v—S2—Cu2^vi	90	Cu21^vi—S2—Cu21^xv	146.5 (6)
Cu2^v—S2—Cu2^xi	90	Cu21^vi—S2—Cu21^xvi	48.1 (6)
Cu2^v—S2—Cu21	73.2 (5)	Cu21^xi—S2—Cu21^xv	48.1 (6)
Cu2^v—S2—Cu21^ix	106.8 (5)	Cu21^xi—S2—Cu21^xvi	146.5 (6)
Cu2^v—S2—Cu21^xii	73.2 (5)	Cu21^xv—S2—Cu21^xvi	146.5 (6)
Cu2^v—S2—Cu21^ii	106.8 (5)	Cu21—As1—Cu21^v	49.3 (5)
Cu2^v—S2—Cu21^v	24.1 (4)	Cu21—As1—Cu21^vi	49.3 (5)
Cu2^v—S2—Cu21^x	155.9 (4)	Cu21—As1—S1^xvii	146.9 (3)
Cu2^v—S2—Cu21^xiii	155.9 (4)	Cu21—As1—S1^xviii	101.6 (4)
Cu2^v—S2—Cu21^xiv	24.1 (4)	Cu21—As1—S1^iii	101.6 (4)
Cu2^v—S2—Cu21^vi	73.2 (5)	Cu21^v—As1—Cu21^vi	49.3 (5)
Cu2^v—S2—Cu21^xi	73.2 (5)	Cu21^v—As1—S1^xvii	101.6 (4)
Cu2^v—S2—Cu21^xv	106.8 (5)	Cu21^v—As1—S1^xviii	146.9 (3)
Cu2^v—S2—Cu21^xvi	106.8 (5)	Cu21^v—As1—S1^iii	101.6 (4)
Cu2^x—S2—Cu2^vi	90	Cu21^vi—As1—S1^xvii	101.6 (4)
Cu2^x—S2—Cu2^xi	90	Cu21^vi—As1—S1^xviii	101.6 (4)
Cu2^x—S2—Cu21	106.8 (5)	Cu21^vi—As1—S1^iii	146.9 (3)
Cu2^x—S2—Cu21^ix	73.2 (5)	S1^xvii—As1—S1^xviii	99.58 (5)
Cu2^x—S2—Cu21^xii	106.8 (5)	S1^xvii—As1—S1^iii	99.58 (5)
Cu2^x—S2—Cu21^ii	73.2 (5)	S1^xviii—As1—S1^iii	99.58 (5)
Cu2^x—S2—Cu21^v	155.9 (4)

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

Copper Arsenic Sulfide (293K)

Crystal data

As4Cu12S13	Dx = 4.687 Mg m^−3
Mr = 1479	Mo Kα radiation, λ = 0.71069 Å
Cubic, I43m	Cell parameters from 4858 reflections
Hall symbol: I -4;2;3	θ = 4.0–41.8°
a = 10.1572 (2) Å	µ = 19.46 mm^−1
V = 1047.91 (4) Å^3	T = 293 K
Z = 2	Prism, black
F(000) = 1376	0.46 × 0.31 × 0.25 mm

Data collection

Xcalibur, EosS2 diffractometer	719 independent reflections
Radiation source: sealed tube	667 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
θ scans	θmax = 42.0°, θmin = 4.0°
Absorption correction: analytical	h = −19→19
Tmin = 0.015, Tmax = 0.104	k = −12→19
11026 measured reflections	l = −18→15

Refinement

Refinement on F	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.0009F^2)
R[F^2 > 2σ(F^2)] = 0.029	(Δ/σ)max = 0.005
wR(F^2) = 0.039	Δρmax = 1.72 e Å^−3
S = 1.00	Δρmin = −1.17 e Å^−3
719 reflections	Extinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
44 parameters	Extinction coefficient: 1540 (100)
0 restraints	Absolute structure: 318 of Friedel pairs used in the refinement
0 constraints

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.5	0.25	0	0.0184 (3)
Cu2	0.2172 (5)	0	0	0.0339 (5)	0.679 (11)
Cu21	0.2149 (12)	0.0662 (19)	0.0662 (19)	0.042 (3)	0.161 (6)
S1	0.35722 (7)	−0.11854 (6)	0.11854 (6)	0.01110 (13)
S2	0	0	0	0.0160 (7)
As1	0.24162 (4)	0.24162 (4)	0.24162 (4)	0.01140 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0148 (3)	0.0255 (7)	0.0148 (3)	0	0	0
Cu2	0.0116 (7)	0.0450 (8)	0.0450 (8)	0	0	0.0232 (12)
Cu21	0.0221 (18)	0.051 (6)	0.051 (6)	−0.018 (3)	−0.018 (3)	0.031 (6)
S1	0.0090 (3)	0.01213 (18)	0.01213 (18)	−0.00238 (15)	0.00238 (15)	−0.0009 (2)
S2	0.0160 (11)	0.0160 (11)	0.0160 (11)	0	0	0
As1	0.01140 (13)	0.01140 (13)	0.01140 (13)	−0.00019 (10)	−0.00019 (10)	−0.0002 (1)

Geometric parameters (Å, º)

Cu1—S1^i	2.3099 (6)	Cu21—Cu21^ii	1.90 (3)
Cu1—S1^ii	2.3099 (6)	Cu21—Cu21^v	2.14 (2)
Cu1—S1^iii	2.3099 (6)	Cu21—Cu21^vi	2.14 (2)
Cu1—S1^iv	2.3099 (6)	Cu21—S1	2.427 (17)
Cu2—Cu21	0.95 (2)	Cu21—S1^ii	2.427 (17)
Cu2—Cu21^ii	0.95 (2)	Cu21—S2	2.380 (14)
Cu2—S1	2.219 (3)	Cu21—As1	2.535 (19)
Cu2—S1^ii	2.219 (3)	S1—As1^vii	2.2457 (7)
Cu2—S2	2.206 (5)
S1^i—Cu1—S1^ii	109.37 (2)	Cu2^x—S2—Cu21^x	23.5 (4)
S1^i—Cu1—S1^iii	109.52 (2)	Cu2^x—S2—Cu21^xiii	23.5 (4)
S1^i—Cu1—S1^iv	109.52 (2)	Cu2^x—S2—Cu21^xiv	156.5 (4)
S1^ii—Cu1—S1^iii	109.52 (2)	Cu2^x—S2—Cu21^vi	106.4 (5)
S1^ii—Cu1—S1^iv	109.52 (2)	Cu2^x—S2—Cu21^xi	106.4 (5)
S1^iii—Cu1—S1^iv	109.37 (2)	Cu2^x—S2—Cu21^xv	73.6 (5)
Cu21—Cu2—Cu21^ii	177.2 (12)	Cu2^x—S2—Cu21^xvi	73.6 (5)
Cu21—Cu2—S1	90.9 (10)	Cu2^vi—S2—Cu2^xi	180
Cu21—Cu2—S1^ii	90.9 (10)	Cu2^vi—S2—Cu21	73.6 (5)
Cu21—Cu2—S2	88.6 (8)	Cu2^vi—S2—Cu21^ix	73.6 (5)
Cu21^ii—Cu2—S1	90.9 (10)	Cu2^vi—S2—Cu21^xii	106.4 (5)
Cu21^ii—Cu2—S1^ii	90.9 (10)	Cu2^vi—S2—Cu21^ii	106.4 (5)
Cu21^ii—Cu2—S2	88.6 (8)	Cu2^vi—S2—Cu21^v	73.6 (5)
S1—Cu2—S1^ii	100.2 (2)	Cu2^vi—S2—Cu21^x	106.4 (5)
S1—Cu2—S2	129.88 (10)	Cu2^vi—S2—Cu21^xiii	73.6 (5)
S1^ii—Cu2—S2	129.88 (10)	Cu2^vi—S2—Cu21^xiv	106.4 (5)
Cu2—Cu21—Cu21^ii	1.4 (6)	Cu2^vi—S2—Cu21^vi	23.5 (4)
Cu2—Cu21—Cu21^v	121.1 (13)	Cu2^vi—S2—Cu21^xi	156.5 (4)
Cu2—Cu21—Cu21^vi	121.1 (13)	Cu2^vi—S2—Cu21^xv	156.5 (4)
Cu2—Cu21—S1	66.0 (10)	Cu2^vi—S2—Cu21^xvi	23.5 (4)
Cu2—Cu21—S1^ii	66.0 (10)	Cu2^xi—S2—Cu21	106.4 (5)
Cu2—Cu21—S2	67.9 (8)	Cu2^xi—S2—Cu21^ix	106.4 (5)
Cu2—Cu21—As1	172.4 (11)	Cu2^xi—S2—Cu21^xii	73.6 (5)
Cu21^ii—Cu21—Cu21^v	120.0 (11)	Cu2^xi—S2—Cu21^ii	73.6 (5)
Cu21^ii—Cu21—Cu21^vi	120.0 (11)	Cu2^xi—S2—Cu21^v	106.4 (5)
Cu21^ii—Cu21—S1	67.0 (8)	Cu2^xi—S2—Cu21^x	73.6 (5)
Cu21^ii—Cu21—S1^ii	67.0 (8)	Cu2^xi—S2—Cu21^xiii	106.4 (5)
Cu21^ii—Cu21—S2	66.5 (6)	Cu2^xi—S2—Cu21^xiv	73.6 (5)
Cu21^ii—Cu21—As1	173.8 (8)	Cu2^xi—S2—Cu21^vi	156.5 (4)
Cu21^v—Cu21—Cu21^vi	60.0 (8)	Cu2^xi—S2—Cu21^xi	23.5 (4)
Cu21^v—Cu21—S1	165.4 (11)	Cu2^xi—S2—Cu21^xv	23.5 (4)
Cu21^v—Cu21—S1^ii	105.4 (9)	Cu2^xi—S2—Cu21^xvi	156.5 (4)
Cu21^v—Cu21—S2	63.3 (6)	Cu21—S2—Cu21^ix	147.2 (7)
Cu21^v—Cu21—As1	65.1 (7)	Cu21—S2—Cu21^xii	147.2 (7)
Cu21^vi—Cu21—S1	105.4 (9)	Cu21—S2—Cu21^ii	47.1 (6)
Cu21^vi—Cu21—S1^ii	165.4 (11)	Cu21—S2—Cu21^v	53.3 (6)
Cu21^vi—Cu21—S2	63.3 (6)	Cu21—S2—Cu21^x	94.6 (6)
Cu21^vi—Cu21—As1	65.1 (7)	Cu21—S2—Cu21^xiii	116.0 (7)
S1—Cu21—S1^ii	89.1 (5)	Cu21—S2—Cu21^xiv	94.6 (6)
S1—Cu21—S2	112.9 (8)	Cu21—S2—Cu21^vi	53.3 (6)
S1—Cu21—As1	109.0 (7)	Cu21—S2—Cu21^xi	116.0 (7)
S1^ii—Cu21—S2	112.9 (8)	Cu21—S2—Cu21^xv	94.6 (6)
S1^ii—Cu21—As1	109.0 (7)	Cu21—S2—Cu21^xvi	94.6 (6)
S2—Cu21—As1	119.7 (6)	Cu21^ix—S2—Cu21^xii	47.1 (6)
Cu1^i—S1—Cu1^viii	102.03 (3)	Cu21^ix—S2—Cu21^ii	147.2 (7)
Cu1^i—S1—Cu2	115.68 (6)	Cu21^ix—S2—Cu21^v	116.0 (7)
Cu1^i—S1—Cu21	134.9 (4)	Cu21^ix—S2—Cu21^x	94.6 (6)
Cu1^i—S1—Cu21^ii	95.6 (4)	Cu21^ix—S2—Cu21^xiii	53.3 (6)
Cu1^i—S1—As1^vii	104.17 (3)	Cu21^ix—S2—Cu21^xiv	94.6 (6)
Cu1^viii—S1—Cu2	115.68 (6)	Cu21^ix—S2—Cu21^vi	94.6 (6)
Cu1^viii—S1—Cu21	95.6 (4)	Cu21^ix—S2—Cu21^xi	94.6 (6)
Cu1^viii—S1—Cu21^ii	134.9 (4)	Cu21^ix—S2—Cu21^xv	116.0 (7)
Cu1^viii—S1—As1^vii	104.17 (3)	Cu21^ix—S2—Cu21^xvi	53.3 (6)
Cu2—S1—Cu21	23.0 (5)	Cu21^xii—S2—Cu21^ii	147.2 (7)
Cu2—S1—Cu21^ii	23.0 (5)	Cu21^xii—S2—Cu21^v	94.6 (6)
Cu2—S1—As1^vii	113.57 (11)	Cu21^xii—S2—Cu21^x	116.0 (7)
Cu21—S1—Cu21^ii	46.1 (6)	Cu21^xii—S2—Cu21^xiii	94.6 (6)
Cu21—S1—As1^vii	111.2 (4)	Cu21^xii—S2—Cu21^xiv	53.3 (6)
Cu21^ii—S1—As1^vii	111.2 (4)	Cu21^xii—S2—Cu21^vi	116.0 (7)
Cu2—S2—Cu2^ix	180	Cu21^xii—S2—Cu21^xi	53.3 (6)
Cu2—S2—Cu2^v	90	Cu21^xii—S2—Cu21^xv	94.6 (6)
Cu2—S2—Cu2^x	90	Cu21^xii—S2—Cu21^xvi	94.6 (6)
Cu2—S2—Cu2^vi	90	Cu21^ii—S2—Cu21^v	94.6 (6)
Cu2—S2—Cu2^xi	90	Cu21^ii—S2—Cu21^x	53.3 (6)
Cu2—S2—Cu21	23.5 (4)	Cu21^ii—S2—Cu21^xiii	94.6 (6)
Cu2—S2—Cu21^ix	156.5 (4)	Cu21^ii—S2—Cu21^xiv	116.0 (7)
Cu2—S2—Cu21^xii	156.5 (4)	Cu21^ii—S2—Cu21^vi	94.6 (6)
Cu2—S2—Cu21^ii	23.5 (4)	Cu21^ii—S2—Cu21^xi	94.6 (6)
Cu2—S2—Cu21^v	73.6 (5)	Cu21^ii—S2—Cu21^xv	53.3 (6)
Cu2—S2—Cu21^x	73.6 (5)	Cu21^ii—S2—Cu21^xvi	116.0 (7)
Cu2—S2—Cu21^xiii	106.4 (5)	Cu21^v—S2—Cu21^x	147.2 (7)
Cu2—S2—Cu21^xiv	106.4 (5)	Cu21^v—S2—Cu21^xiii	147.2 (7)
Cu2—S2—Cu21^vi	73.6 (5)	Cu21^v—S2—Cu21^xiv	47.1 (6)
Cu2—S2—Cu21^xi	106.4 (5)	Cu21^v—S2—Cu21^vi	53.3 (6)
Cu2—S2—Cu21^xv	73.6 (5)	Cu21^v—S2—Cu21^xi	94.6 (6)
Cu2—S2—Cu21^xvi	106.4 (5)	Cu21^v—S2—Cu21^xv	116.0 (7)
Cu2^ix—S2—Cu2^v	90	Cu21^v—S2—Cu21^xvi	94.6 (6)
Cu2^ix—S2—Cu2^x	90	Cu21^x—S2—Cu21^xiii	47.1 (6)
Cu2^ix—S2—Cu2^vi	90	Cu21^x—S2—Cu21^xiv	147.2 (7)
Cu2^ix—S2—Cu2^xi	90	Cu21^x—S2—Cu21^vi	116.0 (7)
Cu2^ix—S2—Cu21	156.5 (4)	Cu21^x—S2—Cu21^xi	94.6 (6)
Cu2^ix—S2—Cu21^ix	23.5 (4)	Cu21^x—S2—Cu21^xv	53.3 (6)
Cu2^ix—S2—Cu21^xii	23.5 (4)	Cu21^x—S2—Cu21^xvi	94.6 (6)
Cu2^ix—S2—Cu21^ii	156.5 (4)	Cu21^xiii—S2—Cu21^xiv	147.2 (7)
Cu2^ix—S2—Cu21^v	106.4 (5)	Cu21^xiii—S2—Cu21^vi	94.6 (6)
Cu2^ix—S2—Cu21^x	106.4 (5)	Cu21^xiii—S2—Cu21^xi	116.0 (7)
Cu2^ix—S2—Cu21^xiii	73.6 (5)	Cu21^xiii—S2—Cu21^xv	94.6 (6)
Cu2^ix—S2—Cu21^xiv	73.6 (5)	Cu21^xiii—S2—Cu21^xvi	53.3 (6)
Cu2^ix—S2—Cu21^vi	106.4 (5)	Cu21^xiv—S2—Cu21^vi	94.6 (6)
Cu2^ix—S2—Cu21^xi	73.6 (5)	Cu21^xiv—S2—Cu21^xi	53.3 (6)
Cu2^ix—S2—Cu21^xv	106.4 (5)	Cu21^xiv—S2—Cu21^xv	94.6 (6)
Cu2^ix—S2—Cu21^xvi	73.6 (5)	Cu21^xiv—S2—Cu21^xvi	116.0 (7)
Cu2^v—S2—Cu2^x	180	Cu21^vi—S2—Cu21^xi	147.2 (7)
Cu2^v—S2—Cu2^vi	90	Cu21^vi—S2—Cu21^xv	147.2 (7)
Cu2^v—S2—Cu2^xi	90	Cu21^vi—S2—Cu21^xvi	47.1 (6)
Cu2^v—S2—Cu21	73.6 (5)	Cu21^xi—S2—Cu21^xv	47.1 (6)
Cu2^v—S2—Cu21^ix	106.4 (5)	Cu21^xi—S2—Cu21^xvi	147.2 (7)
Cu2^v—S2—Cu21^xii	73.6 (5)	Cu21^xv—S2—Cu21^xvi	147.2 (7)
Cu2^v—S2—Cu21^ii	106.4 (5)	Cu21—As1—Cu21^v	49.8 (5)
Cu2^v—S2—Cu21^v	23.5 (4)	Cu21—As1—Cu21^vi	49.8 (5)
Cu2^v—S2—Cu21^x	156.5 (4)	Cu21—As1—S1^xvii	147.3 (3)
Cu2^v—S2—Cu21^xiii	156.5 (4)	Cu21—As1—S1^xviii	101.4 (4)
Cu2^v—S2—Cu21^xiv	23.5 (4)	Cu21—As1—S1^iii	101.4 (4)
Cu2^v—S2—Cu21^vi	73.6 (5)	Cu21^v—As1—Cu21^vi	49.8 (5)
Cu2^v—S2—Cu21^xi	73.6 (5)	Cu21^v—As1—S1^xvii	101.4 (4)
Cu2^v—S2—Cu21^xv	106.4 (5)	Cu21^v—As1—S1^xviii	147.3 (3)
Cu2^v—S2—Cu21^xvi	106.4 (5)	Cu21^v—As1—S1^iii	101.4 (4)
Cu2^x—S2—Cu2^vi	90	Cu21^vi—As1—S1^xvii	101.4 (4)
Cu2^x—S2—Cu2^xi	90	Cu21^vi—As1—S1^xviii	101.4 (4)
Cu2^x—S2—Cu21	106.4 (5)	Cu21^vi—As1—S1^iii	147.3 (3)
Cu2^x—S2—Cu21^ix	73.6 (5)	S1^xvii—As1—S1^xviii	99.52 (3)
Cu2^x—S2—Cu21^xii	106.4 (5)	S1^xvii—As1—S1^iii	99.52 (3)
Cu2^x—S2—Cu21^ii	73.6 (5)	S1^xviii—As1—S1^iii	99.52 (3)
Cu2^x—S2—Cu21^v	156.5 (4)

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