Tetra-μ(3)-iodido-tetra-kis-{[ethyl 2-(1H-benzimidazol-1-yl)acetate-κN(3)]copper(I)}.

The complex mol-ecule of the tetra-nuclear cubane-type title compound, [Cu(4)I(4)(C(11)H(12)N(2)O(2))(4)], has crystallographically imposed fourfold inversion symmetry. The Cu(I) ions are coordinated in a distorted tetra-hedral geometry by an N atom of a benzimidazole ring system and three μ(3)-iodide ions, forming a Cu(4)I(4) core. In the crystal, complex mol-ecules are connected into a three-dimensional network by C-H⋯O hydrogen bonds involving H and O atoms of adjacent eth-oxy-carbonyl groups.

Related literature

For potential applications in physiological and pharmacological fields of benzimidazoyl derivatives or complexes based on the benzimidazoyl unit, see: Ramla et al. (2007 ▶); Barreca et al. (2007 ▶); Cetinkaya et al. (1999 ▶); Snyderwine et al. (1997 ▶); Skog & Solyakov (2002 ▶); Garner et al. (1999 ▶). For applications of copper complexes in biology or medicine, see: Sorrell 1989 ▶. For related structures, see: Sun et al. (2011 ▶); Liu et al. (2011 ▶); Toth et al. (1987 ▶).

Experimental

Crystal data

[Cu4I4(C11H12N2O2)4]

M = 1578.66

Tetragonal,

a = 21.196 (11) Å

c = 11.581 (7) Å

V = 5203 (5) Å3

Z = 4

Mo Kα radiation

μ = 4.04 mm−1

T = 296 K

0.24 × 0.22 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.768, T max = 0.784

13042 measured reflections

2422 independent reflections

2018 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.023

wR(F 2) = 0.053

S = 1.03

2422 reflections

155 parameters

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.32 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681202257X/rz2757sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681202257X/rz2757Isup2.hkl

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

[Cu4I4(C11H12N2O2)4]	Dx = 2.015 Mg m−3
Mr = 1578.66	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/a	Cell parameters from 4922 reflections
Hall symbol: -I 4ad	θ = 2.7–27.9°
a = 21.196 (11) Å	µ = 4.04 mm−1
c = 11.581 (7) Å	T = 296 K
V = 5203 (5) Å3	Block, red
Z = 4	0.24 × 0.22 × 0.18 mm
F(000) = 3040

Bruker APEXII CCD diffractometer	2422 independent reflections
Radiation source: fine-focus sealed tube	2018 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
φ and ω scans	θmax = 25.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −14→25
Tmin = 0.768, Tmax = 0.784	k = −25→24
13042 measured reflections	l = −13→14

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.053	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0216P)2 + 3.0196P] where P = (Fo2 + 2Fc2)/3
2422 reflections	(Δ/σ)max = 0.004
155 parameters	Δρmax = 0.35 e Å−3
0 restraints	Δρmin = −0.32 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	1.102882 (10)	0.771393 (11)	0.517267 (18)	0.04331 (9)
O2	0.78785 (12)	1.08340 (12)	0.5233 (2)	0.0575 (7)
C9	0.81754 (17)	1.02891 (18)	0.5439 (3)	0.0471 (9)
C11	0.7103 (2)	1.1347 (3)	0.4120 (7)	0.143 (3)
H11A	0.7103	1.1719	0.4593	0.214*
H11B	0.6699	1.1302	0.3753	0.214*
H11C	0.7425	1.1383	0.3541	0.214*
C8	0.88524 (16)	1.04277 (16)	0.5783 (3)	0.0506 (9)
H8A	0.9052	1.0679	0.5186	0.061*
H8B	0.8855	1.0671	0.6493	0.061*
C10	0.72251 (18)	1.0806 (2)	0.4824 (4)	0.0664 (11)
H10A	0.7160	1.0424	0.4379	0.080*
H10B	0.6939	1.0800	0.5477	0.080*
O1	0.79545 (12)	0.97762 (12)	0.5333 (2)	0.0598 (7)
N2	0.92099 (13)	0.98507 (12)	0.5952 (2)	0.0443 (7)
N1	0.96375 (13)	0.89215 (13)	0.5503 (2)	0.0435 (7)
C7	0.93802 (16)	0.94424 (16)	0.5110 (3)	0.0440 (8)
H7	0.9321	0.9523	0.4328	0.053*
C5	0.93545 (16)	0.95618 (15)	0.7004 (3)	0.0428 (8)
C6	0.96267 (15)	0.89832 (15)	0.6711 (3)	0.0405 (8)
C4	0.92889 (18)	0.97605 (18)	0.8156 (3)	0.0556 (10)
H4	0.9111	1.0148	0.8347	0.067*
C3	0.95049 (19)	0.9346 (2)	0.8988 (3)	0.0626 (11)
H3	0.9472	0.9457	0.9762	0.075*
C1	0.98362 (18)	0.85733 (18)	0.7569 (3)	0.0538 (10)
H1	1.0014	0.8185	0.7385	0.065*
C2	0.97706 (18)	0.87645 (19)	0.8701 (3)	0.0603 (10)
H2	0.9907	0.8499	0.9289	0.072*
Cu1	0.98756 (2)	0.81434 (2)	0.45656 (4)	0.04928 (13)

	U11	U22	U33	U12	U13	U23
I1	0.03946 (14)	0.04686 (15)	0.04360 (13)	−0.00175 (11)	−0.00630 (9)	−0.00031 (10)
O2	0.0476 (15)	0.0452 (15)	0.0798 (18)	0.0054 (13)	−0.0103 (13)	0.0033 (13)
C9	0.047 (2)	0.047 (2)	0.0474 (19)	0.003 (2)	0.0016 (17)	−0.0051 (17)
C11	0.068 (3)	0.104 (4)	0.256 (9)	0.012 (4)	−0.033 (4)	0.080 (5)
C8	0.047 (2)	0.0350 (19)	0.070 (2)	0.0048 (18)	−0.0008 (18)	−0.0054 (17)
C10	0.050 (2)	0.074 (3)	0.076 (3)	0.004 (2)	−0.011 (2)	0.006 (2)
O1	0.0576 (17)	0.0428 (15)	0.0789 (18)	−0.0059 (14)	−0.0057 (14)	−0.0100 (13)
N2	0.0445 (17)	0.0343 (15)	0.0542 (17)	0.0042 (14)	−0.0006 (14)	−0.0027 (13)
N1	0.0467 (17)	0.0391 (16)	0.0446 (15)	0.0054 (14)	−0.0011 (13)	−0.0027 (13)
C7	0.042 (2)	0.043 (2)	0.0469 (19)	0.0004 (17)	−0.0031 (16)	−0.0032 (16)
C5	0.0369 (18)	0.042 (2)	0.049 (2)	−0.0038 (16)	0.0005 (16)	−0.0007 (16)
C6	0.0400 (19)	0.0360 (18)	0.0456 (18)	0.0006 (16)	0.0008 (15)	−0.0037 (15)
C4	0.057 (2)	0.053 (2)	0.058 (2)	0.002 (2)	0.0094 (19)	−0.0157 (19)
C3	0.071 (3)	0.074 (3)	0.043 (2)	−0.002 (2)	0.0065 (19)	−0.007 (2)
C1	0.062 (3)	0.044 (2)	0.055 (2)	0.003 (2)	−0.0007 (18)	0.0030 (17)
C2	0.068 (3)	0.062 (3)	0.051 (2)	−0.001 (2)	0.001 (2)	0.009 (2)
Cu1	0.0551 (3)	0.0414 (2)	0.0513 (3)	0.0049 (2)	0.0002 (2)	−0.0078 (2)

I1—Cu1	2.7015 (14)	N1—C6	1.406 (4)
I1—Cu1i	2.7244 (16)	N1—Cu1	2.038 (3)
I1—Cu1ii	2.7334 (14)	C7—H7	0.9300
O2—C9	1.337 (4)	C5—C6	1.397 (4)
O2—C10	1.465 (4)	C5—C4	1.406 (5)
C9—O1	1.190 (4)	C6—C1	1.392 (5)
C9—C8	1.518 (5)	C4—C3	1.383 (5)
C11—C10	1.432 (6)	C4—H4	0.9300
C11—H11A	0.9600	C3—C2	1.395 (5)
C11—H11B	0.9600	C3—H3	0.9300
C11—H11C	0.9600	C1—C2	1.379 (5)
C10—H10A	0.9700	C1—H1	0.9300
C10—H10B	0.9700	C2—H2	0.9300
C8—N2	1.452 (4)	Cu1—I1iii	2.7244 (16)
C8—H8A	0.9700	Cu1—Cu1iii	2.7252 (13)
C8—H8B	0.9700	Cu1—Cu1i	2.7252 (13)
N2—C7	1.353 (4)	Cu1—I1ii	2.7334 (14)
N2—C5	1.397 (4)	Cu1—Cu1ii	2.7780 (17)
N1—C7	1.313 (4)
Cu1—I1—Cu1i	60.299 (15)	C1—C6—C5	120.5 (3)
Cu1—I1—Cu1ii	61.477 (17)	C1—C6—N1	130.3 (3)
Cu1i—I1—Cu1ii	59.912 (15)	C5—C6—N1	109.3 (3)
C9—O2—C10	117.9 (3)	C3—C4—C5	116.0 (3)
O1—C9—O2	125.9 (3)	C3—C4—H4	122.0
O1—C9—C8	125.1 (3)	C5—C4—H4	122.0
O2—C9—C8	108.9 (3)	C4—C3—C2	122.0 (4)
C10—C11—H11A	109.5	C4—C3—H3	119.0
C10—C11—H11B	109.5	C2—C3—H3	119.0
H11A—C11—H11B	109.5	C2—C1—C6	117.5 (3)
C10—C11—H11C	109.5	C2—C1—H1	121.2
H11A—C11—H11C	109.5	C6—C1—H1	121.2
H11B—C11—H11C	109.5	C1—C2—C3	121.8 (4)
N2—C8—C9	111.5 (3)	C1—C2—H2	119.1
N2—C8—H8A	109.3	C3—C2—H2	119.1
C9—C8—H8A	109.3	N1—Cu1—I1	110.98 (8)
N2—C8—H8B	109.3	N1—Cu1—I1iii	104.30 (9)
C9—C8—H8B	109.3	I1—Cu1—I1iii	114.311 (17)
H8A—C8—H8B	108.0	N1—Cu1—Cu1iii	138.82 (8)
C11—C10—O2	108.8 (4)	I1—Cu1—Cu1iii	110.146 (17)
C11—C10—H10A	109.9	I1iii—Cu1—Cu1iii	59.43 (4)
O2—C10—H10A	109.9	N1—Cu1—Cu1i	147.54 (8)
C11—C10—H10B	109.9	I1—Cu1—Cu1i	60.27 (4)
O2—C10—H10B	109.9	I1iii—Cu1—Cu1i	60.21 (4)
H10A—C10—H10B	108.3	Cu1iii—Cu1—Cu1i	61.29 (3)
C7—N2—C5	106.8 (3)	N1—Cu1—I1ii	103.14 (8)
C7—N2—C8	125.5 (3)	I1—Cu1—I1ii	110.098 (19)
C5—N2—C8	126.9 (3)	I1iii—Cu1—I1ii	113.280 (17)
C7—N1—C6	105.1 (3)	Cu1iii—Cu1—I1ii	59.88 (4)
C7—N1—Cu1	126.8 (2)	Cu1i—Cu1—I1ii	109.193 (17)
C6—N1—Cu1	127.6 (2)	N1—Cu1—Cu1ii	147.30 (8)
N1—C7—N2	113.5 (3)	I1—Cu1—Cu1ii	59.827 (16)
N1—C7—H7	123.2	I1iii—Cu1—Cu1ii	107.917 (17)
N2—C7—H7	123.2	Cu1iii—Cu1—Cu1ii	59.357 (16)
C6—C5—N2	105.3 (3)	Cu1i—Cu1—Cu1ii	59.357 (16)
C6—C5—C4	122.3 (3)	I1ii—Cu1—Cu1ii	58.696 (16)
N2—C5—C4	132.4 (3)
C10—O2—C9—O1	−0.9 (5)	C5—C6—C1—C2	−0.7 (5)
C10—O2—C9—C8	176.7 (3)	N1—C6—C1—C2	179.2 (3)
O1—C9—C8—N2	1.1 (5)	C6—C1—C2—C3	0.0 (6)
O2—C9—C8—N2	−176.6 (3)	C4—C3—C2—C1	0.4 (6)
C9—O2—C10—C11	−150.6 (4)	C7—N1—Cu1—I1	135.7 (3)
C9—C8—N2—C7	68.8 (4)	C6—N1—Cu1—I1	−54.4 (3)
C9—C8—N2—C5	−100.2 (4)	C7—N1—Cu1—I1iii	12.1 (3)
C6—N1—C7—N2	1.2 (4)	C6—N1—Cu1—I1iii	−177.9 (3)
Cu1—N1—C7—N2	173.0 (2)	C7—N1—Cu1—Cu1iii	−47.5 (3)
C5—N2—C7—N1	−1.7 (4)	C6—N1—Cu1—Cu1iii	122.5 (2)
C8—N2—C7—N1	−172.6 (3)	C7—N1—Cu1—Cu1i	68.4 (3)
C7—N2—C5—C6	1.5 (3)	C6—N1—Cu1—Cu1i	−121.6 (3)
C8—N2—C5—C6	172.1 (3)	C7—N1—Cu1—I1ii	−106.4 (3)
C7—N2—C5—C4	179.3 (4)	C6—N1—Cu1—I1ii	63.5 (3)
C8—N2—C5—C4	−10.0 (6)	C7—N1—Cu1—Cu1ii	−157.8 (2)
N2—C5—C6—C1	179.2 (3)	C6—N1—Cu1—Cu1ii	12.1 (4)
C4—C5—C6—C1	1.0 (5)	Cu1i—I1—Cu1—N1	−145.25 (9)
N2—C5—C6—N1	−0.8 (4)	Cu1ii—I1—Cu1—N1	145.04 (9)
C4—C5—C6—N1	−178.9 (3)	Cu1i—I1—Cu1—I1iii	−27.64 (3)
C7—N1—C6—C1	179.8 (4)	Cu1ii—I1—Cu1—I1iii	−97.34 (2)
Cu1—N1—C6—C1	8.2 (5)	Cu1i—I1—Cu1—Cu1iii	36.98 (3)
C7—N1—C6—C5	−0.2 (4)	Cu1ii—I1—Cu1—Cu1iii	−32.73 (3)
Cu1—N1—C6—C5	−171.9 (2)	Cu1ii—I1—Cu1—Cu1i	−69.703 (11)
C6—C5—C4—C3	−0.6 (5)	Cu1i—I1—Cu1—I1ii	101.19 (3)
N2—C5—C4—C3	−178.2 (3)	Cu1ii—I1—Cu1—I1ii	31.49 (3)
C5—C4—C3—C2	−0.1 (6)	Cu1i—I1—Cu1—Cu1ii	69.703 (11)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···O1iv	0.97	2.60	3.531 (5)	162

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10A⋯O1i	0.97	2.60	3.531 (5)	162

Symmetry code: (i) .