Bis(μ-di-2-pyridyl disulfide-κN,S:N')di-μ(3)-iodido-di-μ(2)-iodido-tetra-copper(I).

In the centrosymmetric tetra-nuclear title compound, [Cu(4)I(4)(C(10)H(8)N(2)S(2))(2)], there are two different Cu(I) atoms with tetra-hedral 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 tetra-nuclear 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 = 1202.37

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.087

S = 1.16

3410 reflections

163 parameters

H-atom parameters constrained

Δρmax = 0.73 e Å−3

Δρmin = −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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681105152X/mw2029sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu4I4(C10H8N2S2)2]	F(000) = 2224
Mr = 1202.37	Dx = 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

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

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(Fo2) + (0.0286P)2] where P = (Fo2 + 2Fc2)/3
3410 reflections	(Δ/σ)max = 0.001
163 parameters	Δρmax = 0.73 e Å−3
0 restraints	Δρmin = −0.68 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)

	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)

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)