Structure of a synthetic halogen sulfosalt, Cu₃Bi₂S₃I₃

Cu₃Bi₂S₃I₃ was crystallized during an attempt to synthesize Cu-Pb-Bi sulfosalts with iodine as the transport medium. The crystal structure was solved from a black needle-like crystal on a four-circle diffractometer with a CCD detector. The solution was obtained by direct methods and subsequent difference-Fourier syntheses. S and I atoms are arranged in a systematically distorted cubic eutaxy (close packing). Bi atoms have monocapped trigonal prismatic coordinations, while Cu atoms occupy coordination sites which vary from trigonal planar to distorted tetrahedral. A prominent feature is the distribution of Cu atoms over many closely spaced sites in the structure, the majority of them being only partly occupied, which strengthens the case for mobile Cu atoms during crystal growth at elevated temperatures. In this respect, Cu₃Bi₂S₃I₃ represents an extreme example of a statistical distribution of Cu in the structure; a frequently observed property of this element in sulfosalts.

Computing details

Program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).

Figures

(j94am)

Crystal data

Bi2Cu3.26I2.62S3.38	F(000) = 1814
Mr = 1065.97	Dx = 6.221 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 28.056 (6) Å	Cell parameters from 1398 reflections
b = 4.1048 (9) Å	θ = 6.0–32.3°
c = 10.580 (2) Å	µ = 44.86 mm^−1
β = 110.572 (4)°	T = 299 K
V = 1140.7 (4) Å^3	Needle, black
Z = 4	1.0 × 0.04 × 0.02 mm

Data collection

SMART 1000CCD, P4 diffractometer	2276 independent reflections
Radiation source: fine-focus sealed tube	1471 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.071
\v and ο scans	θmax = 33.7°, θmin = 5.8°
Absorption correction: gaussian ?	h = −42→43
Tmin = 0.291, Tmax = 0.521	k = −4→6
5437 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	w = 1/[σ^2(Fo^2) + (0.0719P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.129	(Δ/σ)max = 0.001
S = 0.89	Δρmax = 3.94 e Å^−3
2276 reflections	Δρmin = −4.60 e Å^−3
94 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.00022 (6)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Bi1	0.48704 (2)	0.0000	0.78263 (5)	0.01894 (17)
Bi2A	0.24529 (13)	0.0000	0.1594 (3)	0.0344 (5)	0.674 (7)
Bi2B	0.26089 (19)	0.0000	0.1927 (5)	0.0344 (5)	0.326 (7)
I1	0.07651 (4)	0.0000	0.01201 (10)	0.0212 (2)
I2	0.31470 (4)	0.0000	0.65380 (12)	0.0276 (3)
I3	0.17145 (19)	0.0000	0.6766 (7)	0.0201 (7)	0.625 (5)
S4	0.1775 (16)	0.0000	0.668 (5)	0.0201 (7)	0.38
Cu1A	0.05644 (13)	0.0000	0.5831 (3)	0.0354 (10)	0.811 (10)
Cu1B	0.0921 (6)	0.0000	0.6855 (13)	0.0354 (10)	0.19
Cu2	0.38565 (11)	0.0000	0.1130 (3)	0.0684 (10)
Cu3A	0.1472 (3)	0.0000	0.4567 (10)	0.0373 (13)	0.368 (8)
Cu3B	0.1262 (3)	0.0000	0.2962 (10)	0.0373 (13)	0.322 (6)
Cu3C	0.1403 (3)	0.0000	0.3855 (14)	0.0373 (13)	0.319 (7)
Cu4	0.2177 (6)	0.0000	0.5086 (14)	0.043 (6)	0.170 (11)
Cu5	0.0000	0.154 (7)	0.5000	0.038 (9)*	0.091 (10)
S1	0.44430 (14)	0.0000	0.3231 (4)	0.0183 (7)
S2	0.05913 (14)	0.0000	0.3740 (4)	0.0198 (7)
S3	0.30279 (13)	0.0000	0.0110 (4)	0.0196 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.0244 (3)	0.0142 (3)	0.0206 (3)	0.000	0.0108 (2)	0.000
Bi2A	0.0329 (12)	0.0420 (5)	0.0337 (11)	0.000	0.0185 (9)	0.000
Bi2B	0.0329 (12)	0.0420 (5)	0.0337 (11)	0.000	0.0185 (9)	0.000
I1	0.0267 (5)	0.0136 (5)	0.0237 (5)	0.000	0.0093 (4)	0.000
I2	0.0337 (5)	0.0163 (5)	0.0366 (6)	0.000	0.0170 (5)	0.000
I3	0.0172 (17)	0.0169 (8)	0.0257 (12)	0.000	0.0070 (9)	0.000
S4	0.0172 (17)	0.0169 (8)	0.0257 (12)	0.000	0.0070 (9)	0.000
Cu1A	0.063 (2)	0.0159 (14)	0.0370 (16)	0.000	0.0294 (14)	0.000
Cu1B	0.063 (2)	0.0159 (14)	0.0370 (16)	0.000	0.0294 (14)	0.000
Cu2	0.0318 (13)	0.099 (3)	0.0574 (18)	0.000	−0.0048 (12)	0.000
Cu3A	0.033 (2)	0.030 (2)	0.055 (3)	0.000	0.023 (3)	0.000
Cu3B	0.033 (2)	0.030 (2)	0.055 (3)	0.000	0.023 (3)	0.000
Cu3C	0.033 (2)	0.030 (2)	0.055 (3)	0.000	0.023 (3)	0.000
Cu4	0.048 (9)	0.033 (10)	0.034 (8)	0.000	−0.003 (6)	0.000
S1	0.0201 (15)	0.0134 (17)	0.0236 (16)	0.000	0.0104 (13)	0.000
S2	0.0228 (16)	0.0115 (18)	0.0222 (16)	0.000	0.0042 (13)	0.000
S3	0.0179 (15)	0.0189 (19)	0.0227 (16)	0.000	0.0082 (13)	0.000

Geometric parameters (Å, º)

Bi1—S1^i	2.544 (3)	Cu1B—S1^iii	2.280 (6)
Bi1—S2^ii	2.670 (2)	Cu1B—Cu5^vi	2.714 (16)
Bi1—S2^iii	2.670 (2)	Cu1B—Cu5	2.714 (16)
Bi1—Cu2^i	3.347 (3)	Cu1B—Cu2^iii	2.865 (9)
Bi2A—S3	2.617 (4)	Cu1B—Cu2^ii	2.865 (9)
Bi2A—S3^iv	2.752 (3)	Cu2—S3	2.192 (4)
Bi2A—S3^v	2.752 (3)	Cu2—S1	2.253 (5)
Bi2A—S4^iii	3.07 (4)	Cu2—I1^iv	2.842 (3)
Bi2A—S4^ii	3.07 (4)	Cu2—I1^v	2.842 (3)
Bi2A—I3^iii	3.136 (6)	Cu2—Cu1B^iii	2.865 (9)
Bi2A—I3^ii	3.136 (6)	Cu2—Cu1B^ii	2.865 (9)
Bi2B—S3	2.582 (6)	Cu2—Bi1^i	3.347 (3)
Bi2B—S4^iii	2.75 (3)	Cu3A—Cu3C	0.708 (11)
Bi2B—S4^ii	2.75 (3)	Cu3A—Cu3B	1.590 (12)
Bi2B—I3^iii	2.808 (6)	Cu3A—Cu4	1.858 (17)
Bi2B—I3^ii	2.808 (6)	Cu3A—S2	2.313 (8)
Bi2B—S3^iv	3.056 (5)	Cu3A—I2^ii	2.757 (6)
Bi2B—S3^v	3.056 (5)	Cu3A—I2^iii	2.757 (6)
I1—Cu3B	2.835 (10)	Cu3B—Cu3C	0.887 (12)
I1—Cu2^iv	2.842 (3)	Cu3B—S2	2.303 (8)
I1—Cu2^v	2.842 (3)	Cu3B—I2^iii	2.574 (5)
I2—Cu3C^iii	2.520 (5)	Cu3B—I2^ii	2.574 (5)
I2—Cu3C^ii	2.520 (5)	Cu3B—Cu4	2.755 (17)
I2—Cu3B^iii	2.574 (5)	Cu3C—Cu4	2.104 (18)
I2—Cu3B^ii	2.574 (5)	Cu3C—S2	2.236 (9)
I2—Cu4	2.613 (15)	Cu3C—I2^iii	2.520 (5)
I2—Cu4^ii	2.625 (9)	Cu3C—I2^ii	2.520 (5)
I2—Cu4^iii	2.625 (9)	Cu4—I2^ii	2.625 (9)
I2—Cu3A^ii	2.757 (6)	Cu4—I2^iii	2.625 (9)
I2—Cu3A^iii	2.757 (6)	Cu4—Cu4^iii	2.79 (2)
I3—Cu3A	2.183 (12)	Cu4—Cu4^ii	2.79 (2)
I3—Cu1B	2.260 (14)	Cu5—Cu5^vi	1.26 (6)
I3—Cu4	2.543 (17)	Cu5—Cu1A^vi	1.643 (12)
I3—Bi2B^iii	2.808 (6)	Cu5—S1^iii	2.431 (18)
I3—Bi2B^ii	2.808 (6)	Cu5—S1^vii	2.431 (18)
I3—Cu3C	2.891 (15)	Cu5—S2^vi	2.546 (8)
I3—Cu1A	3.024 (6)	Cu5—S2	2.546 (8)
I3—Bi2A^iii	3.136 (6)	Cu5—Cu1B^vi	2.714 (16)
I3—Bi2A^ii	3.136 (6)	Cu5—Cu5^viii	2.84 (6)
S4—Cu3A	2.10 (5)	S1—Cu1B^ii	2.280 (6)
S4—Cu4	2.34 (4)	S1—Cu1B^iii	2.280 (6)
S4—Cu1B	2.47 (4)	S1—Cu1A^iii	2.283 (2)
S4—Bi2B^iii	2.75 (3)	S1—Cu1A^ii	2.283 (2)
S4—Bi2B^ii	2.75 (3)	S1—Cu5^iii	2.431 (18)
S4—Bi2A^iii	3.07 (4)	S1—Cu5^ix	2.431 (18)
S4—Bi2A^ii	3.07 (4)	S1—Bi1^i	2.544 (3)
Cu1A—Cu1B	1.189 (14)	S2—Cu5^vi	2.546 (8)
Cu1A—Cu5^vi	1.643 (12)	S2—Bi1^ii	2.670 (2)
Cu1A—Cu5	1.643 (12)	S2—Bi1^iii	2.670 (2)
Cu1A—S2	2.239 (5)	S3—Bi2A^iv	2.752 (3)
Cu1A—S1^iii	2.283 (2)	S3—Bi2A^v	2.752 (3)
Cu1A—S1^ii	2.283 (2)	S3—Bi2B^iv	3.056 (5)
Cu1A—Cu1A^vi	3.034 (7)	S3—Bi2B^v	3.056 (5)
Cu1B—S1^ii	2.280 (6)
S1^i—Bi1—S2^ii	90.24 (10)	Cu3B—Cu3A—S4	178.0 (11)
S1^i—Bi1—S2^iii	90.24 (10)	Cu4—Cu3A—S4	72.2 (11)
S2^ii—Bi1—S2^iii	100.48 (12)	Cu3C—Cu3A—I3	177.9 (11)
S1^i—Bi1—Cu2^i	42.28 (10)	Cu3B—Cu3A—I3	176.7 (5)
S2^ii—Bi1—Cu2^i	115.68 (8)	Cu4—Cu3A—I3	77.5 (6)
S2^iii—Bi1—Cu2^i	115.68 (8)	S4—Cu3A—I3	5.4 (10)
S3—Bi2A—S3^iv	82.56 (11)	Cu3C—Cu3A—S2	75.0 (10)
S3—Bi2A—S3^v	82.56 (11)	Cu3B—Cu3A—S2	69.5 (4)
S3^iv—Bi2A—S3^v	96.47 (16)	Cu4—Cu3A—S2	175.4 (7)
S3—Bi2A—S4^iii	84.3 (6)	S4—Cu3A—S2	112.5 (10)
S3^iv—Bi2A—S4^iii	165.3 (6)	I3—Cu3A—S2	107.1 (4)
S3^v—Bi2A—S4^iii	88.4 (7)	Cu3C—Cu3A—I2^ii	63.4 (5)
S3—Bi2A—S4^ii	84.3 (6)	Cu3B—Cu3A—I2^ii	66.5 (3)
S3^iv—Bi2A—S4^ii	88.4 (7)	Cu4—Cu3A—I2^ii	66.0 (3)
S3^v—Bi2A—S4^ii	165.3 (6)	S4—Cu3A—I2^ii	112.3 (6)
S4^iii—Bi2A—S4^ii	83.8 (12)	I3—Cu3A—I2^ii	115.5 (2)
S3—Bi2A—I3^iii	80.54 (11)	S2—Cu3A—I2^ii	111.2 (3)
S3^iv—Bi2A—I3^iii	161.64 (12)	Cu3C—Cu3A—I2^iii	63.4 (5)
S3^v—Bi2A—I3^iii	88.43 (11)	Cu3B—Cu3A—I2^iii	66.5 (3)
S4^iii—Bi2A—I3^iii	3.8 (7)	Cu4—Cu3A—I2^iii	66.0 (3)
S4^ii—Bi2A—I3^iii	82.9 (5)	S4—Cu3A—I2^iii	112.3 (6)
S3—Bi2A—I3^ii	80.53 (11)	I3—Cu3A—I2^iii	115.5 (2)
S3^iv—Bi2A—I3^ii	88.43 (11)	S2—Cu3A—I2^iii	111.2 (3)
S3^v—Bi2A—I3^ii	161.64 (12)	I2^ii—Cu3A—I2^iii	96.2 (3)
S4^iii—Bi2A—I3^ii	82.9 (5)	Cu3C—Cu3B—Cu3A	4.3 (6)
S4^ii—Bi2A—I3^ii	3.8 (7)	Cu3C—Cu3B—S2	74.5 (7)
I3^iii—Bi2A—I3^ii	81.77 (18)	Cu3A—Cu3B—S2	70.2 (4)
S3—Bi2B—S4^iii	91.9 (8)	Cu3C—Cu3B—I2^iii	76.5 (4)
S3—Bi2B—S4^ii	91.9 (8)	Cu3A—Cu3B—I2^iii	79.0 (3)
S4^iii—Bi2B—S4^ii	96.5 (16)	S2—Cu3B—I2^iii	118.3 (2)
S3—Bi2B—I3^iii	87.75 (15)	Cu3C—Cu3B—I2^ii	76.5 (4)
S4^iii—Bi2B—I3^iii	4.3 (7)	Cu3A—Cu3B—I2^ii	79.0 (3)
S4^ii—Bi2B—I3^iii	95.3 (7)	S2—Cu3B—I2^ii	118.3 (2)
S3—Bi2B—I3^ii	87.75 (15)	I2^iii—Cu3B—I2^ii	105.7 (3)
S4^iii—Bi2B—I3^ii	95.3 (7)	Cu3C—Cu3B—Cu4	36.1 (7)
S4^ii—Bi2B—I3^ii	4.3 (7)	Cu3A—Cu3B—Cu4	40.5 (5)
I3^iii—Bi2B—I3^ii	93.9 (2)	S2—Cu3B—Cu4	110.6 (5)
S3—Bi2B—S3^iv	77.37 (15)	I2^iii—Cu3B—Cu4	58.9 (2)
S4^iii—Bi2B—S3^iv	168.3 (8)	I2^ii—Cu3B—Cu4	58.9 (2)
S4^ii—Bi2B—S3^iv	88.7 (8)	Cu3C—Cu3B—I1	177.3 (8)
I3^iii—Bi2B—S3^iv	164.7 (2)	Cu3A—Cu3B—I1	172.9 (5)
I3^ii—Bi2B—S3^iv	89.02 (12)	S2—Cu3B—I1	102.7 (3)
S3—Bi2B—S3^v	77.37 (15)	I2^iii—Cu3B—I1	105.0 (2)
S4^iii—Bi2B—S3^v	88.7 (8)	I2^ii—Cu3B—I1	105.0 (2)
S4^ii—Bi2B—S3^v	168.3 (8)	Cu4—Cu3B—I1	146.6 (4)
I3^iii—Bi2B—S3^v	89.02 (12)	Cu3A—Cu3C—Cu3B	170.2 (15)
I3^ii—Bi2B—S3^v	164.7 (2)	Cu3A—Cu3C—Cu4	60.3 (11)
S3^iv—Bi2B—S3^v	84.37 (16)	Cu3B—Cu3C—Cu4	129.5 (9)
Cu3B—I1—Cu2^iv	111.65 (11)	Cu3A—Cu3C—S2	87.2 (10)
Cu3B—I1—Cu2^v	111.65 (11)	Cu3B—Cu3C—S2	83.0 (7)
Cu2^iv—I1—Cu2^v	92.47 (11)	Cu4—Cu3C—S2	147.5 (8)
Cu3C^iii—I2—Cu3C^ii	109.1 (3)	Cu3A—Cu3C—I2^iii	102.1 (7)
Cu3C^iii—I2—Cu3B^iii	20.0 (3)	Cu3B—Cu3C—I2^iii	83.4 (5)
Cu3C^ii—I2—Cu3B^iii	111.0 (2)	Cu4—Cu3C—I2^iii	68.5 (3)
Cu3C^iii—I2—Cu3B^ii	111.0 (2)	S2—Cu3C—I2^iii	123.4 (2)
Cu3C^ii—I2—Cu3B^ii	20.0 (3)	Cu3A—Cu3C—I2^ii	102.1 (7)
Cu3B^iii—I2—Cu3B^ii	105.7 (3)	Cu3B—Cu3C—I2^ii	83.4 (5)
Cu3C^iii—I2—Cu4	112.5 (3)	Cu4—Cu3C—I2^ii	68.5 (3)
Cu3C^ii—I2—Cu4	112.5 (3)	S2—Cu3C—I2^ii	123.4 (2)
Cu3B^iii—I2—Cu4	125.71 (17)	I2^iii—Cu3C—I2^ii	109.1 (3)
Cu3B^ii—I2—Cu4	125.71 (17)	Cu3A—Cu3C—I3	1.6 (8)
Cu3C^iii—I2—Cu4^ii	127.4 (4)	Cu3B—Cu3C—I3	171.8 (8)
Cu3C^ii—I2—Cu4^ii	48.2 (4)	Cu4—Cu3C—I3	58.7 (6)
Cu3B^iii—I2—Cu4^ii	143.9 (4)	S2—Cu3C—I3	88.8 (4)
Cu3B^ii—I2—Cu4^ii	64.0 (3)	I2^iii—Cu3C—I3	101.2 (3)
Cu4—I2—Cu4^ii	64.3 (4)	I2^ii—Cu3C—I3	101.2 (3)
Cu3C^iii—I2—Cu4^iii	48.2 (4)	Cu3A—Cu4—Cu3C	19.3 (3)
Cu3C^ii—I2—Cu4^iii	127.4 (4)	Cu3A—Cu4—S4	58.7 (13)
Cu3B^iii—I2—Cu4^iii	64.0 (3)	Cu3C—Cu4—S4	78.0 (14)
Cu3B^ii—I2—Cu4^iii	143.9 (4)	Cu3A—Cu4—I3	57.0 (6)
Cu4—I2—Cu4^iii	64.3 (4)	Cu3C—Cu4—I3	76.3 (6)
Cu4^ii—I2—Cu4^iii	102.8 (5)	S4—Cu4—I3	1.7 (14)
Cu3C^iii—I2—Cu3A^ii	104.2 (2)	Cu3A—Cu4—I2	162.7 (8)
Cu3C^ii—I2—Cu3A^ii	14.6 (2)	Cu3C—Cu4—I2	178.0 (9)
Cu3B^iii—I2—Cu3A^ii	111.28 (18)	S4—Cu4—I2	104.0 (13)
Cu3B^ii—I2—Cu3A^ii	34.5 (3)	I3—Cu4—I2	105.7 (5)
Cu4—I2—Cu3A^ii	103.3 (3)	Cu3A—Cu4—I2^ii	73.7 (4)
Cu4^ii—I2—Cu3A^ii	40.3 (4)	Cu3C—Cu4—I2^ii	63.3 (3)
Cu4^iii—I2—Cu3A^ii	113.7 (4)	S4—Cu4—I2^ii	109.2 (8)
Cu3C^iii—I2—Cu3A^iii	14.6 (2)	I3—Cu4—I2^ii	108.3 (5)
Cu3C^ii—I2—Cu3A^iii	104.2 (2)	I2—Cu4—I2^ii	115.7 (4)
Cu3B^iii—I2—Cu3A^iii	34.5 (3)	Cu3A—Cu4—I2^iii	73.7 (4)
Cu3B^ii—I2—Cu3A^iii	111.28 (18)	Cu3C—Cu4—I2^iii	63.3 (3)
Cu4—I2—Cu3A^iii	103.3 (3)	S4—Cu4—I2^iii	109.2 (8)
Cu4^ii—I2—Cu3A^iii	113.7 (4)	I3—Cu4—I2^iii	108.3 (5)
Cu4^iii—I2—Cu3A^iii	40.3 (4)	I2—Cu4—I2^iii	115.7 (4)
Cu3A^ii—I2—Cu3A^iii	96.2 (3)	I2^ii—Cu4—I2^iii	102.8 (5)
Cu3A—I3—Cu1B	95.8 (4)	Cu3A—Cu4—Cu3B	33.7 (4)
Cu3A—I3—Cu4	45.5 (4)	Cu3C—Cu4—Cu3B	14.4 (3)
Cu1B—I3—Cu4	141.3 (5)	S4—Cu4—Cu3B	92.4 (13)
Cu3A—I3—Bi2B^iii	115.38 (17)	I3—Cu4—Cu3B	90.7 (6)
Cu1B—I3—Bi2B^iii	119.0 (2)	I2—Cu4—Cu3B	163.6 (7)
Cu4—I3—Bi2B^iii	85.5 (3)	I2^ii—Cu4—Cu3B	57.1 (3)
Cu3A—I3—Bi2B^ii	115.38 (17)	I2^iii—Cu4—Cu3B	57.1 (3)
Cu1B—I3—Bi2B^ii	119.0 (2)	Cu3A—Cu4—Cu4^iii	129.1 (5)
Cu4—I3—Bi2B^ii	85.5 (3)	Cu3C—Cu4—Cu4^iii	120.9 (6)
Bi2B^iii—I3—Bi2B^ii	93.9 (2)	S4—Cu4—Cu4^iii	122.5 (9)
Cu3A—I3—Cu3C	0.5 (3)	I3—Cu4—Cu4^iii	123.3 (6)
Cu1B—I3—Cu3C	96.4 (4)	I2—Cu4—Cu4^iii	58.1 (5)
Cu4—I3—Cu3C	45.0 (4)	I2^ii—Cu4—Cu4^iii	128.1 (9)
Bi2B^iii—I3—Cu3C	115.08 (16)	I2^iii—Cu4—Cu4^iii	57.7 (3)
Bi2B^ii—I3—Cu3C	115.08 (16)	Cu3B—Cu4—Cu4^iii	112.8 (6)
Cu3A—I3—Cu1A	75.8 (3)	Cu3A—Cu4—Cu4^ii	129.1 (5)
Cu1B—I3—Cu1A	20.1 (3)	Cu3C—Cu4—Cu4^ii	120.9 (6)
Cu4—I3—Cu1A	121.3 (4)	S4—Cu4—Cu4^ii	122.5 (9)
Bi2B^iii—I3—Cu1A	128.33 (10)	I3—Cu4—Cu4^ii	123.3 (6)
Bi2B^ii—I3—Cu1A	128.33 (10)	I2—Cu4—Cu4^ii	58.1 (5)
Cu3C—I3—Cu1A	76.3 (2)	I2^ii—Cu4—Cu4^ii	57.7 (3)
Cu3A—I3—Bi2A^iii	118.85 (15)	I2^iii—Cu4—Cu4^ii	128.1 (9)
Cu1B—I3—Bi2A^iii	122.0 (2)	Cu3B—Cu4—Cu4^ii	112.8 (6)
Cu4—I3—Bi2A^iii	85.6 (3)	Cu4^iii—Cu4—Cu4^ii	94.9 (10)
Bi2B^iii—I3—Bi2A^iii	6.10 (6)	Cu5^vi—Cu5—Cu1A^vi	67.4 (10)
Bi2B^ii—I3—Bi2A^iii	87.9 (2)	Cu5^vi—Cu5—Cu1A	67.4 (9)
Cu3C—I3—Bi2A^iii	118.51 (14)	Cu1A^vi—Cu5—Cu1A	134.8 (19)
Cu1A—I3—Bi2A^iii	133.07 (8)	Cu5^vi—Cu5—S1^iii	125.8 (6)
Cu3A—I3—Bi2A^ii	118.85 (15)	Cu1A^vi—Cu5—S1^iii	151.0 (7)
Cu1B—I3—Bi2A^ii	122.0 (2)	Cu1A—Cu5—S1^iii	64.8 (4)
Cu4—I3—Bi2A^ii	85.6 (3)	Cu5^vi—Cu5—S1^vii	125.8 (6)
Bi2B^iii—I3—Bi2A^ii	87.9 (2)	Cu1A^vi—Cu5—S1^vii	64.8 (4)
Bi2B^ii—I3—Bi2A^ii	6.10 (6)	Cu1A—Cu5—S1^vii	151.0 (7)
Cu3C—I3—Bi2A^ii	118.51 (14)	S1^iii—Cu5—S1^vii	108.5 (11)
Cu1A—I3—Bi2A^ii	133.07 (8)	Cu5^vi—Cu5—S2^vi	75.6 (7)
Bi2A^iii—I3—Bi2A^ii	81.77 (18)	Cu1A^vi—Cu5—S2^vi	60.1 (3)
Cu3A—S4—Cu4	49.1 (10)	Cu1A—Cu5—S2^vi	107.9 (7)
Cu3A—S4—Cu1B	92.2 (18)	S1^iii—Cu5—S2^vi	95.9 (3)
Cu4—S4—Cu1B	141 (2)	S1^vii—Cu5—S2^vi	100.8 (3)
Cu3A—S4—Bi2B^iii	120.9 (10)	Cu5^vi—Cu5—S2	75.6 (6)
Cu4—S4—Bi2B^iii	90.8 (9)	Cu1A^vi—Cu5—S2	107.9 (7)
Cu1B—S4—Bi2B^iii	113.9 (10)	Cu1A—Cu5—S2	60.1 (3)
Cu3A—S4—Bi2B^ii	120.9 (10)	S1^iii—Cu5—S2	100.8 (3)
Cu4—S4—Bi2B^ii	90.8 (9)	S1^vii—Cu5—S2	95.9 (3)
Cu1B—S4—Bi2B^ii	113.9 (10)	S2^vi—Cu5—S2	151.3 (13)
Bi2B^iii—S4—Bi2B^ii	96.5 (16)	Cu5^vi—Cu5—Cu1B^vi	76.6 (6)
Cu3A—S4—Bi2A^iii	124.7 (9)	Cu1A^vi—Cu5—Cu1B^vi	14.1 (3)
Cu4—S4—Bi2A^iii	90.6 (10)	Cu1A—Cu5—Cu1B^vi	142.3 (15)
Cu1B—S4—Bi2A^iii	117.2 (11)	S1^iii—Cu5—Cu1B^vi	152.1 (9)
Bi2B^iii—S4—Bi2A^iii	6.34 (16)	S1^vii—Cu5—Cu1B^vi	52.26 (13)
Bi2B^ii—S4—Bi2A^iii	90.1 (14)	S2^vi—Cu5—Cu1B^vi	72.0 (3)
Cu3A—S4—Bi2A^ii	124.7 (9)	S2—Cu5—Cu1B^vi	101.2 (5)
Cu4—S4—Bi2A^ii	90.6 (10)	Cu5^vi—Cu5—Cu1B	76.6 (6)
Cu1B—S4—Bi2A^ii	117.2 (11)	Cu1A^vi—Cu5—Cu1B	142.3 (15)
Bi2B^iii—S4—Bi2A^ii	90.1 (14)	Cu1A—Cu5—Cu1B	14.1 (3)
Bi2B^ii—S4—Bi2A^ii	6.34 (16)	S1^iii—Cu5—Cu1B	52.26 (13)
Bi2A^iii—S4—Bi2A^ii	83.8 (12)	S1^vii—Cu5—Cu1B	152.1 (9)
Cu1B—Cu1A—Cu5^vi	146.3 (8)	S2^vi—Cu5—Cu1B	101.2 (5)
Cu1B—Cu1A—Cu5	146.3 (8)	S2—Cu5—Cu1B	72.0 (3)
Cu5^vi—Cu1A—Cu5	45.2 (19)	Cu1B^vi—Cu5—Cu1B	153.1 (12)
Cu1B—Cu1A—S2	126.2 (6)	Cu5^vi—Cu5—Cu5^viii	180.000 (18)
Cu5^vi—Cu1A—S2	80.34 (15)	Cu1A^vi—Cu5—Cu5^viii	112.6 (10)
Cu5—Cu1A—S2	80.34 (15)	Cu1A—Cu5—Cu5^viii	112.6 (10)
Cu1B—Cu1A—S1^iii	74.7 (2)	S1^iii—Cu5—Cu5^viii	54.2 (6)
Cu5^vi—Cu1A—S1^iii	115.1 (9)	S1^vii—Cu5—Cu5^viii	54.2 (6)
Cu5—Cu1A—S1^iii	74.5 (9)	S2^vi—Cu5—Cu5^viii	104.4 (6)
S2—Cu1A—S1^iii	115.99 (10)	S2—Cu5—Cu5^viii	104.4 (7)
Cu1B—Cu1A—S1^ii	74.7 (2)	Cu1B^vi—Cu5—Cu5^viii	103.4 (6)
Cu5^vi—Cu1A—S1^ii	74.5 (9)	Cu1B—Cu5—Cu5^viii	103.4 (6)
Cu5—Cu1A—S1^ii	115.1 (9)	Cu2—S1—Cu1B^ii	78.4 (4)
S2—Cu1A—S1^ii	115.99 (10)	Cu2—S1—Cu1B^iii	78.4 (3)
S1^iii—Cu1A—S1^ii	128.0 (2)	Cu1B^ii—S1—Cu1B^iii	128.3 (7)
Cu1B—Cu1A—I3	40.7 (6)	Cu2—S1—Cu1A^iii	108.29 (13)
Cu5^vi—Cu1A—I3	153.1 (8)	Cu1B^ii—S1—Cu1A^iii	138.9 (3)
Cu5—Cu1A—I3	153.1 (8)	Cu1B^iii—S1—Cu1A^iii	30.2 (3)
S2—Cu1A—I3	85.46 (17)	Cu2—S1—Cu1A^ii	108.29 (13)
S1^iii—Cu1A—I3	91.69 (14)	Cu1B^ii—S1—Cu1A^ii	30.2 (3)
S1^ii—Cu1A—I3	91.69 (14)	Cu1B^iii—S1—Cu1A^ii	138.9 (3)
Cu1B—Cu1A—Cu1A^vi	154.3 (6)	Cu1A^iii—S1—Cu1A^ii	128.0 (2)
Cu5^vi—Cu1A—Cu1A^vi	22.6 (10)	Cu2—S1—Cu5^iii	144.0 (6)
Cu5—Cu1A—Cu1A^vi	22.6 (10)	Cu1B^ii—S1—Cu5^iii	135.6 (6)
S2—Cu1A—Cu1A^vi	79.53 (15)	Cu1B^iii—S1—Cu5^iii	70.3 (6)
S1^iii—Cu1A—Cu1A^vi	94.86 (13)	Cu1A^iii—S1—Cu5^iii	40.6 (5)
S1^ii—Cu1A—Cu1A^vi	94.86 (13)	Cu1A^ii—S1—Cu5^iii	107.0 (5)
I3—Cu1A—Cu1A^vi	164.99 (18)	Cu2—S1—Cu5^ix	144.0 (6)
Cu1A—Cu1B—I3	119.2 (8)	Cu1B^ii—S1—Cu5^ix	70.3 (6)
Cu1A—Cu1B—S1^ii	75.0 (4)	Cu1B^iii—S1—Cu5^ix	135.6 (6)
I3—Cu1B—S1^ii	115.6 (3)	Cu1A^iii—S1—Cu5^ix	107.0 (6)
Cu1A—Cu1B—S1^iii	75.0 (4)	Cu1A^ii—S1—Cu5^ix	40.6 (5)
I3—Cu1B—S1^iii	115.6 (3)	Cu5^iii—S1—Cu5^ix	71.5 (11)
S1^ii—Cu1B—S1^iii	128.3 (7)	Cu2—S1—Bi1^i	88.28 (14)
Cu1A—Cu1B—S4	117.5 (14)	Cu1B^ii—S1—Bi1^i	112.4 (3)
I3—Cu1B—S4	1.7 (13)	Cu1B^iii—S1—Bi1^i	112.4 (3)
S1^ii—Cu1B—S4	115.5 (3)	Cu1A^iii—S1—Bi1^i	108.37 (11)
S1^iii—Cu1B—S4	115.5 (3)	Cu1A^ii—S1—Bi1^i	108.37 (11)
Cu1A—Cu1B—Cu5^vi	19.6 (5)	Cu5^iii—S1—Bi1^i	87.56 (11)
I3—Cu1B—Cu5^vi	132.2 (5)	Cu5^ix—S1—Bi1^i	87.56 (11)
S1^ii—Cu1B—Cu5^vi	57.5 (6)	Cu3C—S2—Cu1A	109.5 (4)
S1^iii—Cu1B—Cu5^vi	83.2 (7)	Cu3C—S2—Cu3B	22.5 (3)
S4—Cu1B—Cu5^vi	130.5 (12)	Cu1A—S2—Cu3B	131.9 (3)
Cu1A—Cu1B—Cu5	19.6 (5)	Cu3C—S2—Cu3A	17.8 (3)
I3—Cu1B—Cu5	132.2 (5)	Cu1A—S2—Cu3A	91.7 (3)
S1^ii—Cu1B—Cu5	83.2 (7)	Cu3B—S2—Cu3A	40.3 (3)
S1^iii—Cu1B—Cu5	57.5 (6)	Cu3C—S2—Cu5^vi	144.1 (4)
S4—Cu1B—Cu5	130.5 (12)	Cu1A—S2—Cu5^vi	39.5 (2)
Cu5^vi—Cu1B—Cu5	26.9 (12)	Cu3B—S2—Cu5^vi	162.1 (5)
Cu1A—Cu1B—Cu2^iii	124.9 (5)	Cu3A—S2—Cu5^vi	127.5 (3)
I3—Cu1B—Cu2^iii	94.1 (4)	Cu3C—S2—Cu5	144.1 (4)
S1^ii—Cu1B—Cu2^iii	130.7 (5)	Cu1A—S2—Cu5	39.5 (2)
S1^iii—Cu1B—Cu2^iii	50.37 (16)	Cu3B—S2—Cu5	162.1 (5)
S4—Cu1B—Cu2^iii	95.2 (9)	Cu3A—S2—Cu5	127.5 (3)
Cu5^vi—Cu1B—Cu2^iii	127.4 (6)	Cu5^vi—S2—Cu5	28.7 (13)
Cu5—Cu1B—Cu2^iii	105.9 (6)	Cu3C—S2—Bi1^ii	107.2 (2)
Cu1A—Cu1B—Cu2^ii	124.9 (5)	Cu1A—S2—Bi1^ii	115.83 (11)
I3—Cu1B—Cu2^ii	94.1 (4)	Cu3B—S2—Bi1^ii	93.27 (18)
S1^ii—Cu1B—Cu2^ii	50.37 (16)	Cu3A—S2—Bi1^ii	117.09 (16)
S1^iii—Cu1B—Cu2^ii	130.7 (5)	Cu5^vi—S2—Bi1^ii	82.6 (5)
S4—Cu1B—Cu2^ii	95.2 (9)	Cu5—S2—Bi1^ii	104.6 (5)
Cu5^vi—Cu1B—Cu2^ii	105.9 (6)	Cu3C—S2—Bi1^iii	107.2 (2)
Cu5—Cu1B—Cu2^ii	127.4 (6)	Cu1A—S2—Bi1^iii	115.83 (11)
Cu2^iii—Cu1B—Cu2^ii	91.5 (4)	Cu3B—S2—Bi1^iii	93.27 (18)
S3—Cu2—S1	140.0 (2)	Cu3A—S2—Bi1^iii	117.09 (16)
S3—Cu2—I1^iv	106.00 (11)	Cu5^vi—S2—Bi1^iii	104.6 (5)
S1—Cu2—I1^iv	101.32 (10)	Cu5—S2—Bi1^iii	82.6 (5)
S3—Cu2—I1^v	106.00 (11)	Bi1^ii—S2—Bi1^iii	100.48 (12)
S1—Cu2—I1^v	101.32 (10)	Cu2—S3—Bi2B	108.3 (2)
I1^iv—Cu2—I1^v	92.47 (11)	Cu2—S3—Bi2A	118.36 (19)
S3—Cu2—Cu1B^iii	106.4 (3)	Bi2B—S3—Bi2A	10.02 (8)
S1—Cu2—Cu1B^iii	51.2 (2)	Cu2—S3—Bi2A^iv	120.90 (11)
I1^iv—Cu2—Cu1B^iii	147.6 (3)	Bi2B—S3—Bi2A^iv	103.95 (12)
I1^v—Cu2—Cu1B^iii	79.03 (18)	Bi2A—S3—Bi2A^iv	97.44 (11)
S3—Cu2—Cu1B^ii	106.4 (3)	Cu2—S3—Bi2A^v	120.90 (11)
S1—Cu2—Cu1B^ii	51.2 (2)	Bi2B—S3—Bi2A^v	103.95 (12)
I1^iv—Cu2—Cu1B^ii	79.03 (18)	Bi2A—S3—Bi2A^v	97.44 (11)
I1^v—Cu2—Cu1B^ii	147.6 (3)	Bi2A^iv—S3—Bi2A^v	96.47 (16)
Cu1B^iii—Cu2—Cu1B^ii	91.5 (4)	Cu2—S3—Bi2B^iv	127.10 (13)
S3—Cu2—Bi1^i	170.52 (18)	Bi2B—S3—Bi2B^iv	102.63 (15)
S1—Cu2—Bi1^i	49.44 (10)	Bi2A—S3—Bi2B^iv	95.29 (13)
I1^iv—Cu2—Bi1^i	67.89 (7)	Bi2A^iv—S3—Bi2B^iv	6.69 (5)
I1^v—Cu2—Bi1^i	67.89 (7)	Bi2A^v—S3—Bi2B^iv	90.49 (15)
Cu1B^iii—Cu2—Bi1^i	80.0 (3)	Cu2—S3—Bi2B^v	127.10 (13)
Cu1B^ii—Cu2—Bi1^i	80.0 (3)	Bi2B—S3—Bi2B^v	102.63 (15)
Cu3C—Cu3A—Cu3B	5.4 (8)	Bi2A—S3—Bi2B^v	95.29 (13)
Cu3C—Cu3A—Cu4	100.4 (11)	Bi2A^iv—S3—Bi2B^v	90.49 (15)
Cu3B—Cu3A—Cu4	105.8 (7)	Bi2A^v—S3—Bi2B^v	6.69 (5)
Cu3C—Cu3A—S4	172.6 (15)	Bi2B^iv—S3—Bi2B^v	84.37 (16)

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