Hexa-kis-(μ(3)-1-methyl-thio-urea-κ(3)S:S:S)hexa-kis-[iodidocopper(I)].

The title compound, [Cu(6)I(6)(C(2)H(6)N(2)S)(6)], was obtained from the reaction of copper(I) iodide with N-methyl-thio-urea (Metu) in equimolar amounts in acetonitile. The complex consists of two six-membered trinuclear Cu(3)S(3)I(3) cores that combine through triply bridging Metu, forming a hexa-nuclear core which has -3 symmetry. The Cu(II) atom is coordinated by three S atoms of Metu and one iodide ion in a distorted tetra-hedral geometry. The crystal structure is stabilized by N-H⋯I hydrogen bonds and cuprophilic inter-actions [Cu⋯Cu = 3.0264 (9) Å].

Related literature

For crystal structures of copper(I) complexes of thio­urea-type ligands, see: Ahmad et al. (2010 ▶); Bowmaker et al. (2009 ▶); Li et al. (2005 ▶); Lobana et al. (2003 ▶, 2005 ▶); Khan et al. (2007 ▶); Mufakkar et al. (2007 ▶, 2009 ▶, 2011 ▶); Stocker et al. (1997 ▶); Zoufala et al. (2007 ▶). For van der Waals radii and cuprophilic inter­actions, see: Siemeling et al. (1997 ▶); Singh et al. (1997 ▶).

Experimental

Crystal data

[Cu6I6(C2H6N2S)6]

M = 1683.65

Trigonal,

a = 21.7517 (1) Å

c = 7.6269 (1) Å

V = 3125.11 (5) Å3

Z = 3

Mo Kα radiation

μ = 7.79 mm−1

T = 296 K

0.28 × 0.15 × 0.14 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.179, T max = 0.338

14898 measured reflections

1995 independent reflections

1649 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.061

S = 1.06

1995 reflections

65 parameters

H-atom parameters constrained

Δρmax = 1.32 e Å−3

Δρmin = −1.64 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812043437/rz5016sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812043437/rz5016Isup2.hkl

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

[Cu6I6(C2H6N2S)6]	Dx = 2.684 Mg m−3
Mr = 1683.65	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 4617 reflections
Hall symbol: -R 3	θ = 2.2–26.6°
a = 21.7517 (1) Å	µ = 7.79 mm−1
c = 7.6269 (1) Å	T = 296 K
V = 3125.11 (5) Å3	Block, colourless
Z = 3	0.28 × 0.15 × 0.14 mm
F(000) = 2340

Bruker SMART APEXII CCD area-detector diffractometer	1995 independent reflections
Radiation source: fine-focus sealed tube	1649 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
φ and ω scans	θmax = 29.8°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −30→30
Tmin = 0.179, Tmax = 0.338	k = −30→30
14898 measured reflections	l = −10→10

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.061	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0202P)2 + 17.0381P] where P = (Fo2 + 2Fc2)/3
1995 reflections	(Δ/σ)max < 0.001
65 parameters	Δρmax = 1.32 e Å−3
0 restraints	Δρmin = −1.64 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	0.082885 (13)	0.829523 (13)	0.17796 (4)	0.04164 (9)
Cu1	0.04125 (3)	0.91805 (3)	0.12398 (9)	0.05416 (16)
N1	−0.10312 (17)	0.76485 (17)	0.3103 (5)	0.0478 (8)
H1N1	−0.1264	0.7232	0.3455	0.057*
H2N1	−0.0616	0.7805	0.2909	0.057*
N2	−0.19615 (15)	0.78569 (16)	0.2972 (4)	0.0394 (7)
H1N2	−0.2067	0.8151	0.2721	0.047*
C1	−0.12810 (18)	0.80754 (17)	0.2777 (5)	0.0330 (7)
C2	−0.2500 (2)	0.7132 (2)	0.3356 (6)	0.0489 (10)
H2A	−0.2945	0.7111	0.3573	0.073*
H2B	−0.2363	0.6970	0.4375	0.073*
H2C	−0.2549	0.6834	0.2375	0.073*
S1	−0.07031 (4)	0.89448 (4)	0.21477 (14)	0.0388 (2)

	U11	U22	U33	U12	U13	U23
I1	0.04018 (14)	0.03935 (13)	0.05508 (16)	0.02713 (11)	0.00274 (11)	0.00505 (11)
Cu1	0.0380 (3)	0.0348 (2)	0.0945 (4)	0.0218 (2)	−0.0005 (3)	0.0007 (3)
N1	0.0340 (16)	0.0398 (17)	0.071 (2)	0.0197 (14)	0.0127 (16)	0.0209 (17)
N2	0.0316 (14)	0.0353 (15)	0.0534 (19)	0.0182 (13)	0.0053 (13)	0.0115 (14)
C1	0.0318 (16)	0.0306 (16)	0.0369 (17)	0.0157 (13)	0.0033 (14)	0.0031 (13)
C2	0.0305 (17)	0.042 (2)	0.063 (3)	0.0101 (16)	0.0039 (18)	0.0181 (19)
S1	0.0266 (4)	0.0264 (4)	0.0635 (6)	0.0133 (3)	0.0024 (4)	0.0039 (4)

I1—Cu1	2.5379 (5)	N2—C1	1.317 (4)
Cu1—S1i	2.3164 (10)	N2—C2	1.449 (5)
Cu1—S1	2.3210 (10)	N2—H1N2	0.8028
Cu1—S1ii	2.6057 (13)	C1—S1	1.735 (3)
Cu1—Cu1iii	3.0264 (9)	C2—H2A	0.9600
Cu1—Cu1ii	3.0264 (9)	C2—H2B	0.9600
N1—C1	1.313 (4)	C2—H2C	0.9600
N1—H1N1	0.8316	S1—Cu1iv	2.3164 (10)
N1—H2N1	0.8039	S1—Cu1iii	2.6057 (13)
S1i—Cu1—S1	98.22 (5)	C1—N2—C2	124.5 (3)
S1i—Cu1—I1	122.56 (3)	C1—N2—H1N2	113.8
S1—Cu1—I1	120.95 (3)	C2—N2—H1N2	121.2
S1i—Cu1—S1ii	102.80 (4)	N1—C1—N2	120.7 (3)
S1—Cu1—S1ii	102.67 (4)	N1—C1—S1	119.5 (3)
I1—Cu1—S1ii	106.80 (3)	N2—C1—S1	119.7 (3)
S1i—Cu1—Cu1iii	118.09 (3)	N2—C2—H2A	109.5
S1—Cu1—Cu1iii	56.49 (3)	N2—C2—H2B	109.5
I1—Cu1—Cu1iii	118.39 (2)	H2A—C2—H2B	109.5
S1ii—Cu1—Cu1iii	47.86 (3)	N2—C2—H2C	109.5
S1i—Cu1—Cu1ii	56.52 (3)	H2A—C2—H2C	109.5
S1—Cu1—Cu1ii	118.03 (3)	H2B—C2—H2C	109.5
I1—Cu1—Cu1ii	119.84 (2)	C1—S1—Cu1iv	115.65 (12)
S1ii—Cu1—Cu1ii	47.96 (3)	C1—S1—Cu1	115.53 (12)
Cu1iii—Cu1—Cu1ii	85.08 (3)	Cu1iv—S1—Cu1	123.88 (5)
C1—N1—H1N1	126.2	C1—S1—Cu1iii	98.60 (12)
C1—N1—H2N1	116.1	Cu1iv—S1—Cu1iii	75.63 (3)
H1N1—N1—H2N1	117.6	Cu1—S1—Cu1iii	75.55 (3)
C2—N2—C1—N1	−7.1 (6)	Cu1iii—Cu1—S1—C1	92.76 (14)
C2—N2—C1—S1	174.9 (3)	Cu1ii—Cu1—S1—C1	154.78 (14)
N1—C1—S1—Cu1iv	171.7 (3)	S1i—Cu1—S1—Cu1iv	57.15 (8)
N2—C1—S1—Cu1iv	−10.3 (4)	I1—Cu1—S1—Cu1iv	−166.73 (4)
N1—C1—S1—Cu1	15.6 (4)	S1ii—Cu1—S1—Cu1iv	−48.03 (7)
N2—C1—S1—Cu1	−166.4 (3)	Cu1iii—Cu1—S1—Cu1iv	−61.20 (5)
N1—C1—S1—Cu1iii	93.6 (3)	Cu1ii—Cu1—S1—Cu1iv	0.83 (8)
N2—C1—S1—Cu1iii	−88.4 (3)	S1i—Cu1—S1—Cu1iii	118.35 (4)
S1i—Cu1—S1—C1	−148.90 (13)	I1—Cu1—S1—Cu1iii	−105.53 (3)
I1—Cu1—S1—C1	−12.78 (15)	S1ii—Cu1—S1—Cu1iii	13.17 (4)
S1ii—Cu1—S1—C1	105.92 (14)	Cu1ii—Cu1—S1—Cu1iii	62.03 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···I1v	0.83	2.95	3.744 (3)	161
N1—H2N1···I1	0.80	2.90	3.698 (4)	173
N2—H1N2···I1iv	0.80	2.95	3.756 (3)	177

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯I1i	0.83	2.95	3.744 (3)	161
N1—H2N1⋯I1	0.80	2.90	3.698 (4)	173
N2—H1N2⋯I1ii	0.80	2.95	3.756 (3)	177

Symmetry codes: (i) ; (ii) .