catena-Poly[μ2-iodido-diiodidobis(μ3-pyridine-2-thione-κ3S:S:S)(μ2-pyridine-2-thione-κ2S:S)tricopper(I)]

Ke, F.; Wu, W.

doi:10.1107/S1600536812052051

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 2| February 2013| Page m87

doi:10.1107/S1600536812052051

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catena-Poly[μ₂-iodido-diiodidobis(μ₃-pyridine-2-thione-κ³S:S:S)(μ₂-pyridine-2-thione-κ²S:S)tricopper(I)]

Fang Ke ^a ^* and Wen Wu ^b

^aCollege of Pharmacy, Fujian Medical University, Fuzhou 350004, People's Republic of China, and ^bXiamen Maternity and Child Health Care Hospital, Xiamen 361001, People's Republic of China
^*Correspondence e-mail: carsten.ke@hotmail.com

(Received 29 November 2012; accepted 29 December 2012; online 9 January 2013)

In the title compound, [Cu₃I₃(C₅H₅NS)₃]_n, a polymeric structure is formed along [100] through bridging iodide and pyridine-2-thione ligands. The metal atoms are engaged in [Cu₃S₃] and [Cu₂S₂] rings sharing Cu—S edges, with the [Cu₂S₂] rings located about inversion centers. Cu^I atoms bridged by iodide ions exhibit the shortest Cu⋯Cu separation in the polymer [2.8590 (14) Å]. The three independent Cu^I atoms all display distorted tetrahedral coordination geometries.

Related literature

For applications of Cu^I complexes and coordination compounds based on 1H-pyridine-2-thione, see: Kitagawa et al. (1990 ); Raper (1996 , 1997 ); García-Vázquez et al. (1999 ); Akrivos (2001 ); Lobana & Castineiras (2002 ). For the structure of a polymer isoformular to the title compound, see: Lobana et al. (2003 ).

Experimental

Crystal data

[Cu₃I₃(C₅H₅NS)₃]
M_r = 904.80
Triclinic, $[P \overline 1]$
a = 10.035 (1) Å
b = 10.9220 (11) Å
c = 12.2500 (15) Å
α = 105.956 (2)°
β = 100.088 (3)°
γ = 109.377 (3)°
V = 1164.1 (2) Å³
Z = 2
Mo Kα radiation
μ = 6.97 mm⁻¹
T = 298 K
0.40 × 0.23 × 0.15 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.167, T_max = 0.421
6013 measured reflections
4009 independent reflections
3215 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.115
S = 1.06
4009 reflections
244 parameters
H-atom parameters constrained
Δρ_max = 1.33 e Å⁻³
Δρ_min = −1.45 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—S3	2.315 (2)
Cu1—S1	2.356 (2)
Cu1—S1ⁱ	2.480 (2)
Cu1—I1	2.5917 (11)
Cu1—Cu2	2.8590 (14)
Cu1—Cu1ⁱ	2.928 (2)
Cu2—S2	2.315 (2)
Cu2—S1ⁱ	2.367 (2)
Cu2—I2	2.5632 (11)
Cu2—I1	2.6896 (12)
Cu3—S3	2.273 (2)
Cu3—S2ⁱ	2.290 (2)
Cu3—I3	2.5726 (11)
Cu3—S2ⁱⁱ	2.639 (3)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x-1, y, z.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812052051/bh2469sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812052051/bh2469Isup2.hkl

checkCIF report

Comment top

The coordination chemistry of Cu(I) is of considerable interest because these complexes have luminescence properties, antimicrobial activity, and potential applications in catalysis, photography, and electrochemical processes (Kitagawa et al., 1990; Raper, 1996, 1997). On the other hand, pyridine-2-thiolate can bind to a metal or a group of metals via a variety of bonding modes, and this versatility is attributed to the size of the S atom and its proximity to the pyridyl N atom (García-Vázquez et al., 1999; Akrivos, 2001; Lobana et al., 2002). The large size of the S atom makes it easier to adopt different coordination angles in complexes, which is necessary in order to match different geometries.

We report here the crystal structure of the title compound, which displays a polymeric chain structure (Fig. 1 and 2). The polymer is isoformular, although not isostructural to that previously described by Lobana et al. (2003). Two sulfur atoms S1 and S2 act as µ₃-S donor atoms, while S3 acts as a µ₂-S donor atom. There are three independent Cu atoms in the asymmetric unit; Cu1 and Cu3 are coordinated to S1, S3, I1, S1ⁱ and S3, I3, S2ⁱ, S2ⁱⁱ, respectively. Atom Cu2 is coordinated to I1, I2, S2 and S1ⁱ (symmetry codes: i: 1-x, 1-y, 1-z; ii: x-1, y, z). From bond lengths and angles around Cu centers, these metals are placed in a distorted tetrahedral coordination geometry. Moreover, metal–metal interactions are observed, with Cu1···Cu1ⁱ and Cu1···Cu2 separations of 2.928 and 2.859 Å, shorter than metal–metal contacts in the isoformular polymer (Lobana et al., 2003).

Related literature top

For applications of Cu^I complexes and coordination compounds based on 1H-pyridine-2-thione, see: Kitagawa et al. (1990); Raper (1996, 1997); García-Vázquez et al. (1999); Akrivos (2001); Lobana & Castineiras (2002). For the structure of a polymer isoformular to the title compound, see: Lobana et al. (2003).

Experimental top

An oven-dried Schlenk tube was charged with CuI (0.4 mmol), and pyridine-2-thione (0.4 mmol). The tube was evacuated and backfilled with N₂. The reaction mixture was stirred at 333 K for 4 h and then allowed to cool to room temperature. The insoluble residues were removed by filtration, and the filtrate was evaporated slowly at room temperature for about one month, to yield yellow crystals. Crystals suitable for single-crystal X-ray diffraction were selected directly from the sample as prepared.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids. H atoms have been omitted for clarity.
	Fig. 2. View of the one-dimensional extended chain structure in the title compound.

catena-Poly[µ₂-iodido-diiodidobis(µ₃-pyridine-2-thione- κ³S:S:S)(µ₂-pyridine-2-thione- κ²S:S)tricopper(I)] top

Crystal data top

[Cu₃I₃(C₅H₅NS)₃]	Z = 2
M_r = 904.80	F(000) = 840
Triclinic, P1	D_x = 2.581 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.035 (1) Å	Cell parameters from 3445 reflections
b = 10.9220 (11) Å	θ = 2.2–26.0°
c = 12.2500 (15) Å	µ = 6.97 mm⁻¹
α = 105.956 (2)°	T = 298 K
β = 100.088 (3)°	Block, yellow
γ = 109.377 (3)°	0.40 × 0.23 × 0.15 mm
V = 1164.1 (2) Å³

Data collection top

Bruker SMART CCD diffractometer	4009 independent reflections
Radiation source: fine-focus sealed tube	3215 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.167, T_max = 0.421	k = −12→12
6013 measured reflections	l = −14→10

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0556P)² + 2.5913P] where P = (F_o² + 2F_c²)/3
4009 reflections	(Δ/σ)_max < 0.001
244 parameters	Δρ_max = 1.33 e Å⁻³
0 restraints	Δρ_min = −1.45 e Å⁻³
0 constraints

Crystal data top

[Cu₃I₃(C₅H₅NS)₃]	γ = 109.377 (3)°
M_r = 904.80	V = 1164.1 (2) Å³
Triclinic, P1	Z = 2
a = 10.035 (1) Å	Mo Kα radiation
b = 10.9220 (11) Å	µ = 6.97 mm⁻¹
c = 12.2500 (15) Å	T = 298 K
α = 105.956 (2)°	0.40 × 0.23 × 0.15 mm
β = 100.088 (3)°

Data collection top

Bruker SMART CCD diffractometer	4009 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3215 reflections with I > 2σ(I)
T_min = 0.167, T_max = 0.421	R_int = 0.028
6013 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.06	Δρ_max = 1.33 e Å⁻³
4009 reflections	Δρ_min = −1.45 e Å⁻³
244 parameters

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

	x	y	z	U_iso*/U_eq
Cu1	0.48634 (11)	0.50567 (10)	0.61815 (8)	0.0417 (3)
Cu2	0.79614 (11)	0.58824 (10)	0.71789 (8)	0.0432 (3)
Cu3	0.14805 (12)	0.65287 (11)	0.57965 (8)	0.0495 (3)
I1	0.58333 (6)	0.39571 (5)	0.75952 (5)	0.04314 (17)
I2	0.95579 (7)	0.79131 (6)	0.91260 (5)	0.0568 (2)
I3	0.16049 (6)	0.90228 (5)	0.63917 (5)	0.04906 (18)
N1	0.1790 (7)	0.0857 (6)	0.3003 (6)	0.0479 (17)
H1	0.1089	0.1095	0.2766	0.057*
N2	1.0746 (7)	0.3244 (7)	0.6514 (6)	0.0422 (15)
H2	1.0476	0.2886	0.5751	0.051*
N3	0.3203 (7)	0.7738 (6)	0.8801 (5)	0.0410 (15)
H3	0.2341	0.7575	0.8377	0.049*
S1	0.3069 (2)	0.35003 (18)	0.43695 (15)	0.0328 (4)
S2	0.9240 (2)	0.4776 (2)	0.61847 (16)	0.0403 (5)
S3	0.3492 (2)	0.6317 (2)	0.67672 (16)	0.0422 (5)
C1	0.3003 (8)	0.1836 (7)	0.3837 (6)	0.0325 (16)
C2	0.4146 (10)	0.1418 (8)	0.4198 (7)	0.047 (2)
H2A	0.5022	0.2054	0.4778	0.057*
C3	0.3937 (11)	0.0047 (9)	0.3675 (8)	0.055 (2)
H3A	0.4690	−0.0231	0.3900	0.066*
C4	0.2641 (11)	−0.0914 (8)	0.2828 (8)	0.053 (2)
H4	0.2506	−0.1836	0.2491	0.063*
C5	0.1579 (11)	−0.0491 (8)	0.2500 (9)	0.058 (2)
H5	0.0695	−0.1122	0.1926	0.069*
C6	1.0204 (8)	0.4156 (8)	0.7040 (6)	0.0360 (16)
C7	1.0588 (9)	0.4641 (8)	0.8276 (7)	0.0438 (19)
H7	1.0206	0.5237	0.8674	0.053*
C8	1.1536 (11)	0.4235 (10)	0.8911 (8)	0.061 (3)
H8	1.1787	0.4547	0.9736	0.073*
C9	1.2119 (11)	0.3342 (11)	0.8293 (9)	0.063 (3)
H9	1.2795	0.3095	0.8705	0.075*
C10	1.1695 (10)	0.2871 (9)	0.7138 (9)	0.055 (2)
H10	1.2054	0.2260	0.6729	0.066*
C11	0.4100 (8)	0.7287 (7)	0.8249 (6)	0.0334 (16)
C12	0.5518 (9)	0.7651 (8)	0.8966 (7)	0.045 (2)
H12	0.6184	0.7385	0.8625	0.053*
C13	0.5946 (11)	0.8381 (9)	1.0143 (8)	0.061 (3)
H13	0.6904	0.8635	1.0603	0.074*
C14	0.4937 (11)	0.8752 (9)	1.0667 (7)	0.056 (2)
H14	0.5207	0.9219	1.1482	0.067*
C15	0.3594 (11)	0.8436 (9)	0.9995 (7)	0.053 (2)
H15	0.2922	0.8689	1.0337	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0459 (6)	0.0397 (5)	0.0395 (5)	0.0245 (5)	0.0052 (4)	0.0097 (4)
Cu2	0.0466 (6)	0.0423 (6)	0.0382 (5)	0.0235 (5)	0.0080 (4)	0.0064 (4)
Cu3	0.0618 (7)	0.0513 (6)	0.0355 (5)	0.0371 (5)	0.0002 (4)	0.0065 (4)
I1	0.0422 (3)	0.0431 (3)	0.0480 (3)	0.0177 (2)	0.0081 (2)	0.0245 (2)
I2	0.0619 (4)	0.0487 (4)	0.0412 (3)	0.0151 (3)	0.0040 (3)	0.0043 (3)
I3	0.0481 (3)	0.0371 (3)	0.0573 (4)	0.0208 (3)	0.0090 (3)	0.0095 (2)
N1	0.034 (4)	0.029 (3)	0.063 (4)	0.009 (3)	0.004 (3)	0.004 (3)
N2	0.051 (4)	0.043 (4)	0.047 (4)	0.030 (3)	0.016 (3)	0.024 (3)
N3	0.039 (4)	0.037 (3)	0.039 (3)	0.015 (3)	0.009 (3)	0.005 (3)
S1	0.0351 (9)	0.0281 (9)	0.0313 (9)	0.0152 (8)	0.0038 (7)	0.0058 (7)
S2	0.0494 (11)	0.0546 (12)	0.0292 (9)	0.0364 (10)	0.0111 (8)	0.0142 (8)
S3	0.0396 (11)	0.0502 (12)	0.0335 (10)	0.0285 (9)	0.0024 (8)	0.0026 (8)
C1	0.040 (4)	0.032 (4)	0.032 (4)	0.021 (3)	0.013 (3)	0.011 (3)
C2	0.058 (5)	0.038 (4)	0.042 (4)	0.023 (4)	0.005 (4)	0.012 (4)
C3	0.077 (6)	0.048 (5)	0.055 (5)	0.043 (5)	0.018 (5)	0.020 (4)
C4	0.075 (6)	0.029 (4)	0.058 (5)	0.026 (4)	0.023 (5)	0.013 (4)
C5	0.060 (6)	0.026 (4)	0.068 (6)	0.009 (4)	0.012 (5)	0.002 (4)
C6	0.037 (4)	0.040 (4)	0.040 (4)	0.019 (3)	0.014 (3)	0.021 (3)
C7	0.054 (5)	0.046 (5)	0.032 (4)	0.021 (4)	0.009 (3)	0.017 (3)
C8	0.066 (6)	0.066 (6)	0.037 (5)	0.010 (5)	−0.002 (4)	0.030 (4)
C9	0.056 (6)	0.072 (7)	0.076 (7)	0.032 (5)	0.006 (5)	0.049 (6)
C10	0.060 (6)	0.057 (6)	0.084 (7)	0.044 (5)	0.032 (5)	0.046 (5)
C11	0.041 (4)	0.023 (3)	0.032 (4)	0.012 (3)	0.007 (3)	0.007 (3)
C12	0.039 (4)	0.044 (5)	0.048 (5)	0.027 (4)	0.000 (3)	0.009 (4)
C13	0.063 (6)	0.049 (5)	0.060 (6)	0.029 (5)	−0.017 (5)	0.013 (4)
C14	0.079 (7)	0.045 (5)	0.026 (4)	0.012 (5)	0.005 (4)	0.007 (4)
C15	0.067 (6)	0.044 (5)	0.045 (5)	0.015 (4)	0.029 (5)	0.012 (4)

Geometric parameters (Å, º) top

Cu1—S3	2.315 (2)	S2—Cu3ⁱ	2.290 (2)
Cu1—S1	2.356 (2)	S2—Cu3ⁱⁱⁱ	2.639 (3)
Cu1—S1ⁱ	2.480 (2)	S3—C11	1.708 (7)
Cu1—I1	2.5917 (11)	C1—C2	1.414 (10)
Cu1—Cu2	2.8590 (14)	C2—C3	1.384 (11)
Cu1—Cu1ⁱ	2.928 (2)	C2—H2A	0.9300
Cu2—S2	2.315 (2)	C3—C4	1.376 (13)
Cu2—S1ⁱ	2.367 (2)	C3—H3A	0.9300
Cu2—I2	2.5632 (11)	C4—C5	1.337 (13)
Cu2—I1	2.6896 (12)	C4—H4	0.9300
Cu3—S3	2.273 (2)	C5—H5	0.9300
Cu3—S2ⁱ	2.290 (2)	C6—C7	1.393 (10)
Cu3—I3	2.5726 (11)	C7—C8	1.385 (12)
Cu3—S2ⁱⁱ	2.639 (3)	C7—H7	0.9300
N1—C1	1.330 (9)	C8—C9	1.412 (14)
N1—C5	1.357 (10)	C8—H8	0.9300
N1—H1	0.8600	C9—C10	1.300 (13)
N2—C10	1.353 (10)	C9—H9	0.9300
N2—C6	1.354 (9)	C10—H10	0.9300
N2—H2	0.8600	C11—C12	1.396 (10)
N3—C11	1.355 (9)	C12—C13	1.351 (12)
N3—C15	1.365 (10)	C12—H12	0.9300
N3—H3	0.8600	C13—C14	1.399 (13)
S1—C1	1.728 (7)	C13—H13	0.9300
S1—Cu2ⁱ	2.367 (2)	C14—C15	1.326 (13)
S1—Cu1ⁱ	2.480 (2)	C14—H14	0.9300
S2—C6	1.721 (7)	C15—H15	0.9300

S3—Cu1—S1	95.70 (7)	Cu3ⁱ—S2—Cu3ⁱⁱⁱ	87.07 (8)
S3—Cu1—S1ⁱ	109.08 (8)	Cu2—S2—Cu3ⁱⁱⁱ	112.17 (9)
S1—Cu1—S1ⁱ	105.53 (6)	C11—S3—Cu3	112.4 (3)
S3—Cu1—I1	118.52 (7)	C11—S3—Cu1	113.8 (3)
S1—Cu1—I1	116.47 (6)	Cu3—S3—Cu1	133.81 (9)
S1ⁱ—Cu1—I1	110.13 (5)	N1—C1—C2	116.4 (6)
S3—Cu1—Cu2	126.14 (6)	N1—C1—S1	118.1 (5)
S1—Cu1—Cu2	135.86 (6)	C2—C1—S1	125.6 (6)
S1ⁱ—Cu1—Cu2	52.03 (5)	C3—C2—C1	118.9 (8)
I1—Cu1—Cu2	58.89 (3)	C3—C2—H2A	120.6
S3—Cu1—Cu1ⁱ	110.90 (7)	C1—C2—H2A	120.6
S1—Cu1—Cu1ⁱ	54.69 (6)	C4—C3—C2	121.5 (8)
S1ⁱ—Cu1—Cu1ⁱ	50.84 (5)	C4—C3—H3A	119.3
I1—Cu1—Cu1ⁱ	130.56 (5)	C2—C3—H3A	119.3
Cu2—Cu1—Cu1ⁱ	93.24 (5)	C5—C4—C3	118.5 (7)
S2—Cu2—S1ⁱ	97.69 (7)	C5—C4—H4	120.8
S2—Cu2—I2	114.82 (7)	C3—C4—H4	120.8
S1ⁱ—Cu2—I2	115.43 (6)	C4—C5—N1	120.0 (8)
S2—Cu2—I1	107.63 (7)	C4—C5—H5	120.0
S1ⁱ—Cu2—I1	110.49 (6)	N1—C5—H5	120.0
I2—Cu2—I1	110.04 (4)	N2—C6—C7	117.0 (7)
S2—Cu2—Cu1	120.62 (6)	N2—C6—S2	119.4 (5)
S1ⁱ—Cu2—Cu1	55.70 (5)	C7—C6—S2	123.3 (6)
I2—Cu2—Cu1	124.49 (4)	C8—C7—C6	120.0 (8)
I1—Cu2—Cu1	55.59 (3)	C8—C7—H7	120.0
S3—Cu3—S2ⁱ	110.21 (7)	C6—C7—H7	120.0
S3—Cu3—I3	114.83 (7)	C7—C8—C9	119.3 (8)
S2ⁱ—Cu3—I3	118.15 (7)	C7—C8—H8	120.4
S3—Cu3—S2ⁱⁱ	104.12 (8)	C9—C8—H8	120.4
S2ⁱ—Cu3—S2ⁱⁱ	92.93 (8)	C10—C9—C8	119.0 (8)
I3—Cu3—S2ⁱⁱ	113.75 (6)	C10—C9—H9	120.5
Cu1—I1—Cu2	65.52 (3)	C8—C9—H9	120.5
C1—N1—C5	124.8 (7)	C9—C10—N2	121.9 (8)
C1—N1—H1	117.6	C9—C10—H10	119.1
C5—N1—H1	117.6	N2—C10—H10	119.1
C10—N2—C6	122.8 (7)	N3—C11—C12	116.0 (7)
C10—N2—H2	118.6	N3—C11—S3	120.9 (6)
C6—N2—H2	118.6	C12—C11—S3	123.1 (6)
C11—N3—C15	123.5 (7)	C13—C12—C11	121.5 (8)
C11—N3—H3	118.3	C13—C12—H12	119.2
C15—N3—H3	118.3	C11—C12—H12	119.2
C1—S1—Cu1	117.6 (3)	C12—C13—C14	119.5 (8)
C1—S1—Cu2ⁱ	111.4 (2)	C12—C13—H13	120.3
Cu1—S1—Cu2ⁱ	125.91 (8)	C14—C13—H13	120.3
C1—S1—Cu1ⁱ	104.9 (3)	C15—C14—C13	119.7 (8)
Cu1—S1—Cu1ⁱ	74.47 (6)	C15—C14—H14	120.1
Cu2ⁱ—S1—Cu1ⁱ	72.26 (6)	C13—C14—H14	120.1
C6—S2—Cu3ⁱ	112.1 (3)	C14—C15—N3	119.7 (8)
C6—S2—Cu2	112.9 (3)	C14—C15—H15	120.1
Cu3ⁱ—S2—Cu2	126.77 (9)	N3—C15—H15	120.1
C6—S2—Cu3ⁱⁱⁱ	98.9 (3)

S3—Cu1—Cu2—S2	−164.32 (10)	S2ⁱ—Cu3—S3—Cu1	−1.65 (19)
S1—Cu1—Cu2—S2	−6.01 (13)	I3—Cu3—S3—Cu1	−138.06 (12)
S1ⁱ—Cu1—Cu2—S2	−77.56 (9)	S2ⁱⁱ—Cu3—S3—Cu1	96.91 (15)
I1—Cu1—Cu2—S2	91.21 (8)	S1—Cu1—S3—C11	162.0 (3)
Cu1ⁱ—Cu1—Cu2—S2	−45.38 (9)	S1ⁱ—Cu1—S3—C11	−89.3 (3)
S3—Cu1—Cu2—S1ⁱ	−86.77 (10)	I1—Cu1—S3—C11	37.7 (3)
S1—Cu1—Cu2—S1ⁱ	71.55 (11)	Cu2—Cu1—S3—C11	−32.9 (3)
I1—Cu1—Cu2—S1ⁱ	168.77 (6)	Cu1ⁱ—Cu1—S3—C11	−143.7 (3)
Cu1ⁱ—Cu1—Cu2—S1ⁱ	32.17 (6)	S1—Cu1—S3—Cu3	−17.16 (16)
S3—Cu1—Cu2—I2	12.56 (11)	S1ⁱ—Cu1—S3—Cu3	91.46 (15)
S1—Cu1—Cu2—I2	170.87 (8)	I1—Cu1—S3—Cu3	−141.50 (12)
S1ⁱ—Cu1—Cu2—I2	99.32 (7)	Cu2—Cu1—S3—Cu3	147.85 (12)
I1—Cu1—Cu2—I2	−91.91 (5)	Cu1ⁱ—Cu1—S3—Cu3	37.13 (17)
Cu1ⁱ—Cu1—Cu2—I2	131.49 (6)	C5—N1—C1—C2	0.8 (12)
S3—Cu1—Cu2—I1	104.47 (9)	C5—N1—C1—S1	179.9 (7)
S1—Cu1—Cu2—I1	−97.22 (9)	Cu1—S1—C1—N1	162.9 (5)
S1ⁱ—Cu1—Cu2—I1	−168.77 (6)	Cu2ⁱ—S1—C1—N1	−40.6 (7)
Cu1ⁱ—Cu1—Cu2—I1	−136.59 (5)	Cu1ⁱ—S1—C1—N1	−117.0 (6)
S3—Cu1—I1—Cu2	−117.13 (8)	Cu1—S1—C1—C2	−18.1 (8)
S1—Cu1—I1—Cu2	129.49 (7)	Cu2ⁱ—S1—C1—C2	138.4 (6)
S1ⁱ—Cu1—I1—Cu2	9.41 (5)	Cu1ⁱ—S1—C1—C2	61.9 (7)
Cu1ⁱ—Cu1—I1—Cu2	64.56 (7)	N1—C1—C2—C3	0.0 (12)
S2—Cu2—I1—Cu1	−115.48 (6)	S1—C1—C2—C3	−179.0 (7)
S1ⁱ—Cu2—I1—Cu1	−9.89 (5)	C1—C2—C3—C4	−0.9 (14)
I2—Cu2—I1—Cu1	118.74 (4)	C2—C3—C4—C5	1.1 (15)
S3—Cu1—S1—C1	−149.4 (3)	C3—C4—C5—N1	−0.3 (15)
S1ⁱ—Cu1—S1—C1	99.0 (3)	C1—N1—C5—C4	−0.7 (15)
I1—Cu1—S1—C1	−23.6 (3)	C10—N2—C6—C7	−4.2 (12)
Cu2—Cu1—S1—C1	48.0 (3)	C10—N2—C6—S2	169.9 (7)
Cu1ⁱ—Cu1—S1—C1	99.0 (3)	Cu3ⁱ—S2—C6—N2	15.5 (7)
S3—Cu1—S1—Cu2ⁱ	57.90 (12)	Cu2—S2—C6—N2	166.3 (5)
S1ⁱ—Cu1—S1—Cu2ⁱ	−53.73 (9)	Cu3ⁱⁱⁱ—S2—C6—N2	−75.0 (6)
I1—Cu1—S1—Cu2ⁱ	−176.24 (7)	Cu3ⁱ—S2—C6—C7	−170.8 (6)
Cu2—Cu1—S1—Cu2ⁱ	−104.64 (10)	Cu2—S2—C6—C7	−20.0 (8)
Cu1ⁱ—Cu1—S1—Cu2ⁱ	−53.73 (9)	Cu3ⁱⁱⁱ—S2—C6—C7	98.7 (7)
S3—Cu1—S1—Cu1ⁱ	111.63 (8)	N2—C6—C7—C8	2.8 (12)
S1ⁱ—Cu1—S1—Cu1ⁱ	0.0	S2—C6—C7—C8	−171.0 (7)
I1—Cu1—S1—Cu1ⁱ	−122.51 (6)	C6—C7—C8—C9	0.7 (14)
Cu2—Cu1—S1—Cu1ⁱ	−50.91 (9)	C7—C8—C9—C10	−3.2 (15)
S1ⁱ—Cu2—S2—C6	179.4 (3)	C8—C9—C10—N2	2.0 (15)
I2—Cu2—S2—C6	56.7 (3)	C6—N2—C10—C9	1.8 (14)
I1—Cu2—S2—C6	−66.2 (3)	C15—N3—C11—C12	−3.8 (11)
Cu1—Cu2—S2—C6	−126.1 (3)	C15—N3—C11—S3	175.5 (6)
S1ⁱ—Cu2—S2—Cu3ⁱ	−34.96 (14)	Cu3—S3—C11—N3	19.6 (7)
I2—Cu2—S2—Cu3ⁱ	−157.63 (10)	Cu1—S3—C11—N3	−159.8 (5)
I1—Cu2—S2—Cu3ⁱ	79.47 (13)	Cu3—S3—C11—C12	−161.2 (6)
Cu1—Cu2—S2—Cu3ⁱ	19.54 (16)	Cu1—S3—C11—C12	19.4 (8)
S1ⁱ—Cu2—S2—Cu3ⁱⁱⁱ	68.67 (9)	N3—C11—C12—C13	1.5 (12)
I2—Cu2—S2—Cu3ⁱⁱⁱ	−54.00 (9)	S3—C11—C12—C13	−177.8 (7)
I1—Cu2—S2—Cu3ⁱⁱⁱ	−176.90 (5)	C11—C12—C13—C14	1.7 (14)
Cu1—Cu2—S2—Cu3ⁱⁱⁱ	123.16 (7)	C12—C13—C14—C15	−2.8 (14)
S2ⁱ—Cu3—S3—C11	179.1 (3)	C13—C14—C15—N3	0.7 (14)
I3—Cu3—S3—C11	42.7 (3)	C11—N3—C15—C14	2.7 (13)
S2ⁱⁱ—Cu3—S3—C11	−82.3 (3)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z; (iii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	[Cu₃I₃(C₅H₅NS)₃]
M_r	904.80
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	10.035 (1), 10.9220 (11), 12.2500 (15)
α, β, γ (°)	105.956 (2), 100.088 (3), 109.377 (3)
V (Å³)	1164.1 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	6.97
Crystal size (mm)	0.40 × 0.23 × 0.15

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.167, 0.421
No. of measured, independent and observed [I > 2σ(I)] reflections	6013, 4009, 3215
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.115, 1.06
No. of reflections	4009
No. of parameters	244
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.33, −1.45

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—S3	2.315 (2)	Cu2—S1ⁱ	2.367 (2)
Cu1—S1	2.356 (2)	Cu2—I2	2.5632 (11)
Cu1—S1ⁱ	2.480 (2)	Cu2—I1	2.6896 (12)
Cu1—I1	2.5917 (11)	Cu3—S3	2.273 (2)
Cu1—Cu2	2.8590 (14)	Cu3—S2ⁱ	2.290 (2)
Cu1—Cu1ⁱ	2.928 (2)	Cu3—I3	2.5726 (11)
Cu2—S2	2.315 (2)	Cu3—S2ⁱⁱ	2.639 (3)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z.

Acknowledgements

The authors thank the Fujian Provincial Foundation (2012-J05150) and the Research Fund of Fujian Medical University (2011BS006) for financial support.

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