Bis(μ-di-2-pyridyl disulfide-κ3N,S:N′)di-μ3-iodido-di-μ2-iodido-tetra­copper(I)

Wang, Y.-H.; Zhu, X.-H.

doi:10.1107/S160053681105152X

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page m18

doi:10.1107/S160053681105152X

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Bis(μ-di-2-pyridyl disulfide-κ³N,S:N′)di-μ₃-iodido-di-μ₂-iodido-tetracopper(I)

Yu-Hong Wang ^a ^* and Xue-Hua Zhu ^a

^aSchool of Chemistry and Bioengineering, Suzhou University of Science and Technology, Suzhou 215009, People's Republic of China
^*Correspondence e-mail: wangyuhong@mail.usts.edu.cn

(Received 27 September 2011; accepted 30 November 2011; online 7 December 2011)

In the centrosymmetric tetranuclear title compound, [Cu₄I₄(C₁₀H₈N₂S₂)₂], there are two different Cu^I atoms with tetrahedral coordination geometries. One is chelated by a pyridine N atom and an S-donor from one di-2-pyridyl disulfide ligand and coordinated by two I atoms, while the second Cu^I atom is coordinated by a pyridine-N and three I atoms. Iodine bridges between the Cu^I atoms form a tetranuclear structure.

Related literature

For the structures and luminescence properties of Cu(I) complexes, see: Caradoc-Davies & Hanton (2003 ); Ford et al. (1999 ); Rath et al. (1986 ); Song et al. (2003 ); Song, Sun & Yang (2011); Song, Sun, Yang & Yang (2011 ); Su et al. (1997 ). For metal complexes with di-2-pyridyl disulfide, see: Bell et al. (2000 ); Delgado et al. (2007 ); Kadooka et al. (1976 ); Niu et al. (2007 ); Wu et al. (2011 ).

Experimental

Crystal data

[Cu₄I₄(C₁₀H₈N₂S₂)₂]
M_r = 1202.37
Orthorhombic, P b c a
a = 10.460 (6) Å
b = 14.434 (8) Å
c = 19.908 (12) Å
V = 3006 (3) Å³
Z = 4
Mo Kα radiation
μ = 7.20 mm⁻¹
T = 223 K
0.38 × 0.11 × 0.10 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ) T_min = 0.171, T_max = 0.533
10455 measured reflections
3410 independent reflections
2944 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.087
S = 1.16
3410 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.73 e Å⁻³
Δρ_min = −0.68 e Å⁻³

Data collection: CrystalClear (Rigaku, 2001 ); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku, 2001); 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/S160053681105152X/mw2029sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681105152X/mw2029Isup2.hkl

checkCIF report

Comment top

Polynuclear Cu^I compounds with luminescent properties have been designed and synthesized by reaction of Cu^I cations and suitable bridging ligands (Ford et al., 1999). Flexible heterocyclic ligands containing nitrogen donors can form metal complexes with considerable structural diversity and reports of Cu^I complexes with such ligands have increased in recent years (Caradoc-Davies & Hanton, 2003; Rath et al., 1986; Song et al., 2003; Song, Sun & Yang, 2011; Song, Sun, Yang & Yang, 2011; Song, Sun, & Yang, 2011; Su et al., 1997). di-2-pyridyl disulfide is a interesting heterocyclic ligand. A number of metal complexes of it and related ligands have been reported (Bell et al., 2000; Delgado et al., 2007; Kadooka et al., 1976; Niu et al., 2007; Wu et al., 2011). The present study details the structure of a CuI adduct of di-2-pyridyl disulfide.

The title compound, (I), is a tetranuclear complex, [Cu₄I₄(L)₂] having crystallographically-imposed centrosymmetry (Fig. 1). In the unique ligand, S(2) and N(1) chelate to Cu(1) while N(2) coordinates to Cu(2A). Doubly-bridging I2 and triply-bridging I1 serve to complete the formation of the tetranuclear core in which each copper adopts approximately tetrahedral geometry. Cu(1) is coordinated by a pyridine N atom and an S donor from one L ligand and two iodine atoms while Cu(2) is coordinated by a pyridine N atom from the second L ligand and three iodine atoms. The bond angles around Cu(2) range from 104.38 (4) to 114.42 (5)° and are normal for a slightly distorted tetrahedral geometry while Cu(1) exists in a more distorted tetrahedral environment with the angles around Cu(1) in the range 88.58 (17) to 122.55 (7)°. All the Cu—N and Cu—S bond distances are comparable with those of other tetrameric clusters (Rath et al., 1986; Song et al., 2003; Su et al., 1997). The Cu—I bond lengths show significant differences depending on the Cu(I) environment. Cu(2) bonds to three iodine atoms with Cu—I bond distances ranging from 2.6864 (15) to 2.7623 (17) Å, while Cu(1) bonds to two iodine atoms with equivalent shorter Cu—I bond distances averaging 2.5764 (14) Å. The Cu···Cu distance of 2.6648 (18) Å is shorter than the sum of their van der Waals radii (2.83 Å), indicating the existence of Cu···Cu interactions. Such short Cu···Cu separations have been observed in some complexes such as [Cu₄I₄(quin)₄] [2.582 (10)Å](Rath et al., 1986), [Cu₄I₄(MPTQ)₂] [2.607 (1)Å] (Su et al., 1997), [Cu₄I₄(C₁₉H₃₆N₂S₂)₂]_n [2.734 (2)Å] (Song, Sun & Yang, 2011), [Cu₄I₄(C₁₅H₁₂N₂S)₂] [2.743 (1)Å] (Song et al., 2003) and [CuI(bbbm)]_n [2.7683 (9)Å] (Niu et al., 2007).

The tetrameric Cu₄I₄ core adopts a distorted chair-like structure which is defined by three Cu—I edges from different Cu₂I₂ moieties: the strictly planar Cu(2)—I(1A)—Cu(2A)—I(1) unit and the non-planar Cu(1)—I(2)—Cu(2)—I(1) and symmetry-related Cu(1A)—I( A)—Cu(2A)—I(1A) units. Similar results were also found in related tetranuclear complexes (Rath et al., 1986; Song et al., 2003; Su et al., 1997).

Related literature top

For the structures and luminescence properties of Cu(I) complexes, see: Caradoc-Davies & Hanton (2003); Ford et al. (1999); Rath et al. (1986); Song et al. (2003); Song, Sun & Yang (2011); Song, Sun, Yang & Yang (2011); Su et al. (1997). For metal complexes with di-2-pyridyl disulfide, see: Bell et al. (2000); Delgado et al. (2007); Kadooka et al. (1976); Niu et al. (2007); Wu et al. (2011).

Experimental top

The ligand di-2-pyridyl disulfide (22.0 mg, 0.1 mmol) in CHCl₃ (3 ml) was added to CuI (17.8 mg, 0.1 mmol) dissolved in MeCN (5 ml). The reaction mixture was kept in the dark and allowed to evaporate slowly. Yellow block-shaped single crystals suitable for X-ray analysis were obtained in 58% yield. Analysis found: C 20.39, H 1,40, N 4.84%; calculated for C₂₀H₁₆Cu₄I₄N₄S₄: C 19.98, H 1.34, N 4.66%.

Computing details top

Data collection: CrystalClear (Rigaku, 2001); cell refinement: CrystalClear (Rigaku, 2001); data reduction: CrystalStructure (Rigaku, 2001); 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. View of (I) shown with 30% probability displacement ellipsoids and small spheres for the H atoms.

Bis(µ-di-2-pyridyl disulfide-κ³N,S:N')di-µ₃-iodido- di-µ₂-iodido-tetracopper(I) top

Crystal data top

[Cu₄I₄(C₁₀H₈N₂S₂)₂]	F(000) = 2224
M_r = 1202.37	D_x = 2.657 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 8826 reflections
a = 10.460 (6) Å	θ = 3.0–27.5°
b = 14.434 (8) Å	µ = 7.20 mm⁻¹
c = 19.908 (12) Å	T = 223 K
V = 3006 (3) Å³	Block, yellow
Z = 4	0.38 × 0.11 × 0.10 mm

Data collection top

Rigaku Saturn diffractometer	3410 independent reflections
Radiation source: fine-focus sealed tube	2944 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
Detector resolution: 14.63 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ω scans	h = −9→13
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −11→18
T_min = 0.171, T_max = 0.533	l = −23→25
10455 measured reflections

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.087	H-atom parameters constrained
S = 1.16	w = 1/[σ²(F_o²) + (0.0286P)²] where P = (F_o² + 2F_c²)/3
3410 reflections	(Δ/σ)_max = 0.001
163 parameters	Δρ_max = 0.73 e Å⁻³
0 restraints	Δρ_min = −0.68 e Å⁻³

Crystal data top

[Cu₄I₄(C₁₀H₈N₂S₂)₂]	V = 3006 (3) Å³
M_r = 1202.37	Z = 4
Orthorhombic, Pbca	Mo Kα radiation
a = 10.460 (6) Å	µ = 7.20 mm⁻¹
b = 14.434 (8) Å	T = 223 K
c = 19.908 (12) Å	0.38 × 0.11 × 0.10 mm

Data collection top

Rigaku Saturn diffractometer	3410 independent reflections
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	2944 reflections with I > 2σ(I)
T_min = 0.171, T_max = 0.533	R_int = 0.041
10455 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.087	H-atom parameters constrained
S = 1.16	Δρ_max = 0.73 e Å⁻³
3410 reflections	Δρ_min = −0.68 e Å⁻³
163 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
I1	0.28885 (4)	0.00696 (3)	0.52344 (2)	0.03779 (13)
I2	0.56758 (4)	0.03336 (3)	0.68154 (2)	0.04152 (14)
Cu1	0.43879 (8)	0.11605 (5)	0.58888 (4)	0.0440 (2)
Cu2	0.52112 (8)	−0.05428 (6)	0.56063 (5)	0.0430 (2)
S1	0.55004 (18)	0.33204 (12)	0.60075 (10)	0.0472 (5)
S2	0.57511 (16)	0.22524 (11)	0.53450 (9)	0.0381 (4)
N1	0.3452 (5)	0.2256 (4)	0.6339 (3)	0.0409 (13)
N2	0.4533 (4)	0.1941 (3)	0.4210 (3)	0.0300 (11)
C1	0.2348 (6)	0.2116 (5)	0.6675 (4)	0.0504 (19)
H1	0.1960	0.1530	0.6644	0.061*
C2	0.1761 (7)	0.2779 (6)	0.7059 (4)	0.058 (2)
H2	0.1002	0.2647	0.7293	0.069*
C3	0.2316 (7)	0.3650 (6)	0.7093 (4)	0.057 (2)
H3	0.1933	0.4124	0.7347	0.069*
C4	0.3452 (7)	0.3811 (5)	0.6745 (4)	0.0514 (19)
H4	0.3844	0.4397	0.6756	0.062*
C5	0.3986 (6)	0.3093 (4)	0.6386 (3)	0.0400 (16)
C6	0.3900 (6)	0.2177 (4)	0.3649 (3)	0.0374 (15)
H6	0.3637	0.1702	0.3357	0.045*
C7	0.3617 (6)	0.3078 (4)	0.3479 (4)	0.0432 (17)
H7	0.3157	0.3215	0.3085	0.052*
C8	0.4027 (6)	0.3779 (4)	0.3903 (4)	0.0424 (17)
H8	0.3860	0.4401	0.3796	0.051*
C9	0.4671 (6)	0.3565 (4)	0.4474 (4)	0.0399 (16)
H9	0.4960	0.4031	0.4767	0.048*
C10	0.4893 (5)	0.2629 (4)	0.4615 (3)	0.0307 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.0346 (2)	0.0420 (3)	0.0368 (3)	−0.00164 (19)	−0.00135 (19)	−0.0036 (2)
I2	0.0539 (3)	0.0378 (2)	0.0329 (3)	−0.0041 (2)	−0.0081 (2)	0.00119 (19)
Cu1	0.0558 (5)	0.0339 (4)	0.0423 (6)	0.0019 (4)	−0.0071 (4)	−0.0047 (4)
Cu2	0.0515 (5)	0.0329 (4)	0.0447 (6)	0.0009 (4)	−0.0026 (4)	0.0002 (4)
S1	0.0593 (11)	0.0411 (10)	0.0411 (11)	−0.0087 (9)	−0.0065 (9)	−0.0111 (8)
S2	0.0420 (9)	0.0368 (9)	0.0354 (10)	0.0018 (8)	−0.0076 (8)	−0.0033 (7)
N1	0.045 (3)	0.041 (3)	0.037 (4)	0.008 (3)	−0.008 (3)	−0.001 (3)
N2	0.034 (3)	0.027 (3)	0.029 (3)	0.001 (2)	0.003 (2)	0.001 (2)
C1	0.047 (4)	0.059 (5)	0.045 (5)	−0.002 (4)	−0.005 (3)	−0.004 (4)
C2	0.049 (4)	0.089 (6)	0.036 (5)	0.016 (4)	−0.009 (4)	−0.011 (4)
C3	0.063 (5)	0.060 (5)	0.050 (5)	0.028 (4)	−0.016 (4)	−0.015 (4)
C4	0.071 (5)	0.044 (4)	0.039 (5)	0.014 (4)	−0.011 (4)	−0.008 (3)
C5	0.054 (4)	0.037 (4)	0.028 (4)	0.006 (3)	−0.010 (3)	−0.003 (3)
C6	0.037 (3)	0.041 (4)	0.033 (4)	0.005 (3)	−0.009 (3)	−0.005 (3)
C7	0.047 (4)	0.039 (4)	0.044 (4)	0.017 (3)	−0.008 (3)	0.004 (3)
C8	0.049 (4)	0.034 (3)	0.044 (4)	0.014 (3)	−0.007 (3)	0.002 (3)
C9	0.038 (3)	0.039 (4)	0.043 (4)	−0.004 (3)	0.000 (3)	−0.007 (3)
C10	0.029 (3)	0.029 (3)	0.034 (4)	0.001 (3)	0.000 (3)	−0.005 (3)

Geometric parameters (Å, º) top

I1—Cu1	2.5760 (13)	N2—Cu2ⁱ	2.068 (5)
I1—Cu2ⁱ	2.6868 (15)	C1—C2	1.370 (10)
I1—Cu2	2.6892 (16)	C1—H1	0.9400
I2—Cu1	2.5772 (13)	C2—C3	1.385 (11)
I2—Cu2	2.7623 (17)	C2—H2	0.9400
Cu1—N1	2.064 (5)	C3—C4	1.395 (10)
Cu1—S2	2.385 (2)	C3—H3	0.9400
Cu1—Cu2	2.6650 (18)	C4—C5	1.377 (9)
Cu2—N2ⁱ	2.068 (5)	C4—H4	0.9400
Cu2—I1ⁱ	2.6868 (15)	C6—C7	1.377 (8)
Cu2—Cu2ⁱ	2.912 (2)	C6—H6	0.9400
S1—C5	1.785 (7)	C7—C8	1.386 (9)
S1—S2	2.046 (3)	C7—H7	0.9400
S2—C10	1.792 (6)	C8—C9	1.357 (9)
N1—C5	1.334 (8)	C8—H8	0.9400
N1—C1	1.350 (9)	C9—C10	1.399 (8)
N2—C10	1.334 (7)	C9—H9	0.9400
N2—C6	1.341 (7)

Cu1—I1—Cu2ⁱ	73.10 (5)	C1—N1—Cu1	120.4 (5)
Cu1—I1—Cu2	60.77 (4)	C10—N2—C6	117.0 (5)
Cu2ⁱ—I1—Cu2	65.59 (5)	C10—N2—Cu2ⁱ	125.6 (4)
Cu1—I2—Cu2	59.76 (4)	C6—N2—Cu2ⁱ	117.4 (4)
N1—Cu1—S2	88.52 (17)	N1—C1—C2	123.7 (7)
N1—Cu1—I1	113.53 (16)	N1—C1—H1	118.1
S2—Cu1—I1	122.57 (7)	C2—C1—H1	118.1
N1—Cu1—I2	106.96 (16)	C1—C2—C3	118.3 (8)
S2—Cu1—I2	108.56 (6)	C1—C2—H2	120.9
I1—Cu1—I2	113.40 (5)	C3—C2—H2	120.9
N1—Cu1—Cu2	162.08 (17)	C2—C3—C4	118.9 (7)
S2—Cu1—Cu2	108.70 (7)	C2—C3—H3	120.5
I1—Cu1—Cu2	61.71 (4)	C4—C3—H3	120.5
I2—Cu1—Cu2	63.57 (4)	C5—C4—C3	118.5 (7)
N2ⁱ—Cu2—Cu1	154.75 (15)	C5—C4—H4	120.7
N2ⁱ—Cu2—I1ⁱ	105.23 (13)	C3—C4—H4	120.7
Cu1—Cu2—I1ⁱ	97.82 (4)	N1—C5—C4	123.2 (7)
N2ⁱ—Cu2—I1	119.11 (13)	N1—C5—S1	120.5 (5)
Cu1—Cu2—I1	57.52 (3)	C4—C5—S1	116.2 (6)
I1ⁱ—Cu2—I1	114.41 (5)	N2—C6—C7	123.5 (6)
N2ⁱ—Cu2—I2	105.64 (15)	N2—C6—H6	118.3
Cu1—Cu2—I2	56.67 (3)	C7—C6—H6	118.3
I1ⁱ—Cu2—I2	107.23 (5)	C6—C7—C8	118.2 (6)
I1—Cu2—I2	104.38 (4)	C6—C7—H7	120.9
N2ⁱ—Cu2—Cu2ⁱ	133.76 (15)	C8—C7—H7	120.9
Cu1—Cu2—Cu2ⁱ	68.25 (5)	C9—C8—C7	119.9 (6)
I1ⁱ—Cu2—Cu2ⁱ	57.25 (4)	C9—C8—H8	120.0
I1—Cu2—Cu2ⁱ	57.17 (3)	C7—C8—H8	120.0
I2—Cu2—Cu2ⁱ	120.18 (6)	C8—C9—C10	118.0 (6)
C5—S1—S2	104.3 (2)	C8—C9—H9	121.0
C10—S2—S1	103.3 (2)	C10—C9—H9	121.0
C10—S2—Cu1	105.6 (2)	N2—C10—C9	123.4 (6)
S1—S2—Cu1	97.40 (10)	N2—C10—S2	114.0 (4)
C5—N1—C1	117.3 (6)	C9—C10—S2	122.6 (5)
C5—N1—Cu1	121.7 (5)

Cu2ⁱ—I1—Cu1—N1	128.20 (18)	I1—Cu1—S2—C10	33.8 (2)
Cu2—I1—Cu1—N1	−160.76 (18)	I2—Cu1—S2—C10	169.2 (2)
Cu2ⁱ—I1—Cu1—S2	24.03 (6)	Cu2—Cu1—S2—C10	101.6 (2)
Cu2—I1—Cu1—S2	95.07 (7)	N1—Cu1—S2—S1	22.68 (17)
Cu2ⁱ—I1—Cu1—I2	−109.45 (5)	I1—Cu1—S2—S1	139.91 (8)
Cu2—I1—Cu1—I2	−38.41 (4)	I2—Cu1—S2—S1	−84.72 (9)
Cu2ⁱ—I1—Cu1—Cu2	−71.04 (4)	Cu2—Cu1—S2—S1	−152.27 (7)
Cu2—I2—Cu1—N1	163.59 (17)	S2—Cu1—N1—C5	−19.2 (5)
Cu2—I2—Cu1—S2	−102.17 (6)	I1—Cu1—N1—C5	−144.4 (4)
Cu2—I2—Cu1—I1	37.66 (4)	I2—Cu1—N1—C5	89.8 (5)
N1—Cu1—Cu2—N2ⁱ	−11.1 (6)	Cu2—Cu1—N1—C5	145.1 (4)
S2—Cu1—Cu2—N2ⁱ	152.3 (3)	S2—Cu1—N1—C1	169.7 (5)
I1—Cu1—Cu2—N2ⁱ	−90.1 (3)	I1—Cu1—N1—C1	44.5 (6)
I2—Cu1—Cu2—N2ⁱ	50.3 (3)	I2—Cu1—N1—C1	−81.3 (5)
N1—Cu1—Cu2—I1ⁱ	−167.0 (5)	Cu2—Cu1—N1—C1	−26.0 (9)
S2—Cu1—Cu2—I1ⁱ	−3.57 (6)	C5—N1—C1—C2	−0.4 (11)
I1—Cu1—Cu2—I1ⁱ	114.03 (5)	Cu1—N1—C1—C2	171.2 (6)
I2—Cu1—Cu2—I1ⁱ	−105.52 (5)	N1—C1—C2—C3	1.5 (12)
N1—Cu1—Cu2—I1	79.0 (5)	C1—C2—C3—C4	−0.9 (11)
S2—Cu1—Cu2—I1	−117.60 (7)	C2—C3—C4—C5	−0.7 (11)
I2—Cu1—Cu2—I1	140.45 (3)	C1—N1—C5—C4	−1.4 (10)
N1—Cu1—Cu2—I2	−61.4 (5)	Cu1—N1—C5—C4	−172.8 (5)
S2—Cu1—Cu2—I2	101.95 (7)	C1—N1—C5—S1	175.7 (5)
I1—Cu1—Cu2—I2	−140.45 (3)	Cu1—N1—C5—S1	4.3 (7)
N1—Cu1—Cu2—Cu2ⁱ	143.0 (5)	C3—C4—C5—N1	1.9 (11)
S2—Cu1—Cu2—Cu2ⁱ	−53.58 (6)	C3—C4—C5—S1	−175.3 (5)
I1—Cu1—Cu2—Cu2ⁱ	64.02 (4)	S2—S1—C5—N1	16.5 (6)
I2—Cu1—Cu2—Cu2ⁱ	−155.53 (5)	S2—S1—C5—C4	−166.2 (5)
Cu1—I1—Cu2—N2ⁱ	150.78 (17)	C10—N2—C6—C7	0.1 (9)
Cu2ⁱ—I1—Cu2—N2ⁱ	−125.65 (17)	Cu2ⁱ—N2—C6—C7	177.3 (5)
Cu2ⁱ—I1—Cu2—Cu1	83.57 (5)	N2—C6—C7—C8	1.2 (11)
Cu1—I1—Cu2—I1ⁱ	−83.57 (5)	C6—C7—C8—C9	−1.0 (10)
Cu2ⁱ—I1—Cu2—I1ⁱ	0.0	C7—C8—C9—C10	−0.3 (10)
Cu1—I1—Cu2—I2	33.31 (3)	C6—N2—C10—C9	−1.6 (9)
Cu2ⁱ—I1—Cu2—I2	116.88 (6)	Cu2ⁱ—N2—C10—C9	−178.5 (4)
Cu1—I1—Cu2—Cu2ⁱ	−83.57 (5)	C6—N2—C10—S2	−179.2 (4)
Cu1—I2—Cu2—N2ⁱ	−160.06 (14)	Cu2ⁱ—N2—C10—S2	4.0 (6)
Cu1—I2—Cu2—I1ⁱ	88.08 (5)	C8—C9—C10—N2	1.7 (10)
Cu1—I2—Cu2—I1	−33.68 (3)	C8—C9—C10—S2	179.1 (5)
Cu1—I2—Cu2—Cu2ⁱ	26.43 (5)	S1—S2—C10—N2	−157.5 (4)
C5—S1—S2—C10	83.7 (3)	Cu1—S2—C10—N2	−55.7 (5)
C5—S1—S2—Cu1	−24.3 (2)	S1—S2—C10—C9	25.0 (6)
N1—Cu1—S2—C10	−83.4 (3)	Cu1—S2—C10—C9	126.7 (5)

Symmetry code: (i) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu₄I₄(C₁₀H₈N₂S₂)₂]
M_r	1202.37
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	223
a, b, c (Å)	10.460 (6), 14.434 (8), 19.908 (12)
V (Å³)	3006 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	7.20
Crystal size (mm)	0.38 × 0.11 × 0.10

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (REQAB; Jacobson, 1998)
T_min, T_max	0.171, 0.533
No. of measured, independent and observed [I > 2σ(I)] reflections	10455, 3410, 2944
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.087, 1.16
No. of reflections	3410
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.73, −0.68

Computer programs: CrystalClear (Rigaku, 2001), CrystalStructure (Rigaku, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors thank Suzhou University of Science and Technology for financial support.

References

Bell, N. A., Gelbrich, T., Hursthouse, M. B., Light, M. E. & Wilson, A. (2000). Polyhedron, 19, 2539–2546. Web of Science CSD CrossRef CAS Google Scholar
Caradoc-Davies, P. L. & Hanton, L. R. (2003). Dalton Trans. pp. 1754–1758. Web of Science CSD CrossRef Google Scholar
Delgado, S., Molina-Ontoria, A., Medina, M. E., Pastor, C. J., Jimenez-Aparicio, R. & Priego, J. L. (2007). Polyhedron, 26, 2817–2828. Web of Science CSD CrossRef CAS Google Scholar
Ford, P. C., Cariati, E. & Bourassa, J. (1999). Chem. Rev. 99, 3625–3648. Web of Science CrossRef PubMed CAS Google Scholar
Jacobson, R. (1998). REQAB. Private communication to the Rigaku Corporation, Tokyo, Japan. Google Scholar
Kadooka, M. M., Warner, L. G. & Seff, K. (1976). J. Am. Chem. Soc. 98, 7569–7578. CSD CrossRef CAS PubMed Web of Science Google Scholar
Niu, Y., Zhang, N., Hou, H., Zhu, Y., Tang, M. & Ng, S. W. (2007). J. Mol. Struct. 827, 195–200. Web of Science CSD CrossRef CAS Google Scholar
Rath, N. P., Holt, E. M. & Tanimura, K. (1986). J. Chem. Soc. Dalton Trans. pp. 2303–2310. CSD CrossRef Web of Science Google Scholar
Rigaku (2001). CrystalClear and CrystalStructure. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Song, R.-F., Sun, Y.-Y. & Yang, J. (2011). J. Inorg. Organomet. Polym. 21, 143–149. Web of Science CrossRef CAS Google Scholar
Song, R.-F., Sun, Y.-Y., Yang, J. & Yang, X.-Y. (2011). J. Inorg. Organomet. Polym. 21, 237–243. Web of Science CSD CrossRef CAS Google Scholar
Song, R.-F., Xie, Y.-B., Li, J.-R. & Bu, X.-H. (2003). CrystEngComm, 7, 249–254. Web of Science CrossRef Google Scholar
Su, C. Y., Kang, B.-S. & Sun, J. (1997). Chem. Lett. pp. 821–822. CSD CrossRef Web of Science Google Scholar
Wu, S., Jiang, W., Li, F. & Liu, L. (2011). Acta Cryst. E67, m285. Web of Science CSD CrossRef IUCr Journals Google Scholar

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