Hexa-μ-chlorido-μ(4)-oxido-tetra-kis-({1-[(pyridin-2-yl)meth-yl]-1H-benzimidazole-κN}copper(II)).

The title tetra-nuclear complex, [Cu(4)Cl(6)O(C(13)H(11)N(3))(4)], features a tetra-hedral arrangement of copper(II) ions bonded to the central O atom (site symmetry [Formula: see text]). Each of the six edges of the Cu(4) tetra-hedron is bridged by a chloride ion (one of which has site symmetry 2), so that each copper ion is linked to the other three metal ions through the central O atom and through three separate chloride-ion bridges. The fifth coord-ination position, located on the central Cu-O axis on the outside of the cluster, is occupied by an N atom of the mono-dentate 1-(pyridin-2-ylmeth-yl)-1H-benzimidazole ligand. The resulting coordination geometry of the metal ion is a distorted trigonal bipyramid with the O and N atoms in the axial positions. The dihedral angle between the benzimidazole ring system and the pendant pyridine ring is 61.0 (2)°.

Related literature

For background to polynuclear copper halides, see: Willett (1991 ▶); Chivers et al. (2005 ▶); Li et al. (2009 ▶).

Experimental

Crystal data

[Cu4Cl6O(C13H11N3)4]

M = 1319.85

Tetragonal,

a = 13.8532 (12) Å

c = 14.507 (3) Å

V = 2784.1 (6) Å3

Z = 2

Mo Kα radiation

μ = 1.85 mm−1

T = 294 K

0.25 × 0.23 × 0.20 mm

Data collection

Rigaku Mercury CCD diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ▶) T min = 0.637, T max = 0.691

7149 measured reflections

2467 independent reflections

2178 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.028

wR(F 2) = 0.062

S = 1.06

2467 reflections

170 parameters

H-atom parameters constrained

Δρmax = 0.34 e Å−3

Δρmin = −0.17 e Å−3

Absolute structure: Flack (1983) ▶, 1172 Friedel pairs

Flack parameter: 0.005 (15)

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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/S1600536811035252/hb6384sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811035252/hb6384Isup2.hkl

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

[Cu4Cl6O(C13H11N3)4]	Dx = 1.574 Mg m−3
Mr = 1319.85	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4	Cell parameters from 3492 reflections
a = 13.8532 (12) Å	θ = 2.8–25.3°
c = 14.507 (3) Å	µ = 1.85 mm−1
V = 2784.1 (6) Å3	T = 294 K
Z = 2	Block, brown
F(000) = 1332	0.25 × 0.23 × 0.20 mm

Rigaku Mercury CCD diffractometer	2467 independent reflections
Radiation source: fine-focus sealed tube	2178 reflections with I > 2σ(I)
graphite	Rint = 0.033
Detector resolution: 9 pixels mm-1	θmax = 25.0°, θmin = 2.0°
ω scans	h = −14→16
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −16→14
Tmin = 0.637, Tmax = 0.691	l = −17→17
7149 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.028	H-atom parameters constrained
wR(F2) = 0.062	w = 1/[σ2(Fo2) + (0.0286P)2] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
2467 reflections	Δρmax = 0.34 e Å−3
170 parameters	Δρmin = −0.17 e Å−3
0 restraints	Absolute structure: Flack (1983), 1172 Friedel pairs
0 constraints	Flack parameter: 0.005 (15)
Primary atom site location: structure-invariant direct methods

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
Cu1	0.42929 (3)	0.41004 (3)	0.07467 (3)	0.03400 (12)
Cl1	0.28847 (6)	0.47255 (6)	−0.00384 (7)	0.0473 (2)
Cl2	0.5000	0.5000	0.20129 (8)	0.0637 (4)
N3	0.3550 (2)	0.3189 (2)	0.1515 (2)	0.0412 (7)
C1	0.3592 (3)	0.2243 (3)	0.1520 (3)	0.0498 (10)
H1	0.3992	0.1887	0.1133	0.060*
C2	0.2867 (3)	0.3436 (3)	0.2180 (2)	0.0485 (10)
C7	0.2518 (3)	0.2588 (3)	0.2595 (3)	0.0533 (10)
N2	0.2998 (3)	0.1839 (2)	0.2144 (2)	0.0548 (9)
C6	0.1844 (3)	0.2627 (4)	0.3322 (3)	0.0736 (15)
H6	0.1636	0.2068	0.3616	0.088*
C3	0.2513 (3)	0.4325 (3)	0.2461 (3)	0.0663 (13)
H3	0.2726	0.4892	0.2184	0.080*
C4	0.1837 (4)	0.4350 (4)	0.3161 (4)	0.0844 (16)
H4	0.1593	0.4940	0.3359	0.101*
C5	0.1515 (4)	0.3495 (5)	0.3574 (4)	0.0899 (18)
H5	0.1056	0.3532	0.4040	0.108*
C8	0.2900 (4)	0.0806 (3)	0.2368 (3)	0.0755 (15)
H8A	0.2343	0.0721	0.2764	0.091*
H8B	0.3465	0.0601	0.2711	0.091*
O1	0.5000	0.5000	0.0000	0.0292 (9)
C9	0.2789 (3)	0.0170 (3)	0.1543 (3)	0.0563 (10)
C10	0.1944 (4)	−0.0195 (4)	0.1286 (4)	0.0846 (16)
H10	0.1380	−0.0038	0.1600	0.102*
N1	0.3632 (4)	−0.0017 (4)	0.1100 (4)	0.1075 (18)
C12	0.2815 (9)	−0.1018 (5)	0.0115 (5)	0.128 (3)
H12	0.2863	−0.1449	−0.0374	0.154*
C11	0.1926 (7)	−0.0858 (5)	0.0487 (5)	0.116 (2)
H11	0.1364	−0.1138	0.0261	0.139*
C13	0.3600 (8)	−0.0601 (5)	0.0405 (6)	0.140 (4)
H13	0.4172	−0.0730	0.0093	0.168*

	U11	U22	U33	U12	U13	U23
Cu1	0.0374 (2)	0.0322 (2)	0.03237 (19)	−0.00702 (17)	0.0024 (2)	0.00311 (19)
Cl1	0.0319 (5)	0.0549 (5)	0.0552 (5)	−0.0045 (4)	−0.0026 (4)	0.0094 (5)
Cl2	0.0911 (11)	0.0707 (10)	0.0294 (6)	−0.0472 (9)	0.000	0.000
N3	0.0419 (18)	0.0393 (18)	0.0425 (16)	−0.0130 (14)	0.0009 (14)	0.0065 (14)
C1	0.061 (3)	0.045 (2)	0.043 (2)	−0.0162 (19)	−0.006 (2)	0.0044 (19)
C2	0.045 (2)	0.058 (3)	0.042 (2)	−0.0166 (19)	−0.0002 (18)	0.007 (2)
C7	0.054 (2)	0.060 (3)	0.045 (2)	−0.021 (2)	0.001 (2)	0.010 (2)
N2	0.068 (2)	0.048 (2)	0.048 (2)	−0.0231 (17)	−0.0028 (18)	0.0152 (17)
C6	0.064 (3)	0.096 (4)	0.061 (3)	−0.035 (3)	0.005 (2)	0.030 (3)
C3	0.073 (3)	0.060 (3)	0.066 (3)	−0.015 (2)	0.021 (3)	0.003 (2)
C4	0.083 (4)	0.080 (4)	0.091 (4)	−0.003 (3)	0.037 (3)	0.002 (3)
C5	0.084 (4)	0.102 (5)	0.084 (4)	−0.016 (3)	0.040 (3)	0.002 (3)
C8	0.108 (4)	0.054 (3)	0.065 (3)	−0.030 (3)	−0.008 (3)	0.021 (2)
O1	0.0293 (14)	0.0293 (14)	0.029 (2)	0.000	0.000	0.000
C9	0.064 (3)	0.042 (2)	0.064 (3)	−0.002 (2)	0.010 (2)	0.020 (2)
C10	0.093 (4)	0.081 (4)	0.081 (4)	−0.020 (3)	0.010 (3)	0.001 (3)
N1	0.107 (4)	0.085 (3)	0.130 (5)	0.035 (3)	0.033 (3)	0.025 (3)
C12	0.229 (11)	0.066 (4)	0.090 (5)	−0.007 (6)	0.033 (7)	0.000 (4)
C11	0.158 (7)	0.092 (5)	0.097 (5)	−0.030 (5)	−0.005 (5)	0.008 (4)
C13	0.202 (10)	0.064 (5)	0.154 (8)	0.052 (5)	0.079 (7)	0.012 (5)

Cu1—O1	1.9199 (4)	C4—C5	1.400 (7)
Cu1—N3	1.974 (3)	C4—H4	0.9300
Cu1—Cl1i	2.3961 (10)	C5—H5	0.9300
Cu1—Cl1	2.4192 (10)	C8—C9	1.494 (7)
Cu1—Cl2	2.4263 (10)	C8—H8A	0.9700
Cl1—Cu1ii	2.3961 (9)	C8—H8B	0.9700
Cl2—Cu1iii	2.4263 (10)	O1—Cu1iii	1.9199 (4)
N3—C1	1.313 (4)	O1—Cu1i	1.9199 (4)
N3—C2	1.394 (5)	O1—Cu1ii	1.9199 (4)
C1—N2	1.345 (5)	C9—C10	1.328 (6)
C1—H1	0.9300	C9—N1	1.358 (6)
C2—C3	1.386 (6)	C10—C11	1.480 (8)
C2—C7	1.407 (5)	C10—H10	0.9300
C7—N2	1.395 (6)	N1—C13	1.293 (9)
C7—C6	1.409 (6)	C12—C13	1.301 (12)
N2—C8	1.474 (5)	C12—C11	1.362 (10)
C6—C5	1.337 (8)	C12—H12	0.9300
C6—H6	0.9300	C11—H11	0.9300
C3—C4	1.382 (6)	C13—H13	0.9300
C3—H3	0.9300
O1—Cu1—N3	179.14 (9)	C3—C4—H4	119.7
O1—Cu1—Cl1i	85.68 (3)	C5—C4—H4	119.7
N3—Cu1—Cl1i	95.10 (9)	C6—C5—C4	122.3 (5)
O1—Cu1—Cl1	85.03 (3)	C6—C5—H5	118.8
N3—Cu1—Cl1	94.25 (9)	C4—C5—H5	118.8
Cl1i—Cu1—Cl1	120.483 (17)	N2—C8—C9	113.9 (4)
O1—Cu1—Cl2	83.56 (2)	N2—C8—H8A	108.8
N3—Cu1—Cl2	96.40 (9)	C9—C8—H8A	108.8
Cl1i—Cu1—Cl2	117.17 (3)	N2—C8—H8B	108.8
Cl1—Cu1—Cl2	119.88 (3)	C9—C8—H8B	108.8
Cu1ii—Cl1—Cu1	80.69 (3)	H8A—C8—H8B	107.7
Cu1—Cl2—Cu1iii	81.58 (4)	Cu1iii—O1—Cu1i	108.564 (12)
C1—N3—C2	105.8 (3)	Cu1iii—O1—Cu1	111.30 (2)
C1—N3—Cu1	128.2 (3)	Cu1i—O1—Cu1	108.564 (12)
C2—N3—Cu1	126.0 (2)	Cu1iii—O1—Cu1ii	108.564 (12)
N3—C1—N2	113.1 (4)	Cu1i—O1—Cu1ii	111.30 (2)
N3—C1—H1	123.5	Cu1—O1—Cu1ii	108.564 (12)
N2—C1—H1	123.5	C10—C9—N1	123.5 (5)
C3—C2—N3	131.4 (3)	C10—C9—C8	122.7 (5)
C3—C2—C7	119.6 (4)	N1—C9—C8	113.8 (5)
N3—C2—C7	108.9 (4)	C9—C10—C11	118.1 (6)
N2—C7—C2	104.9 (4)	C9—C10—H10	121.0
N2—C7—C6	134.1 (4)	C11—C10—H10	121.0
C2—C7—C6	121.0 (5)	C13—N1—C9	117.3 (7)
C1—N2—C7	107.4 (3)	C13—C12—C11	123.7 (8)
C1—N2—C8	127.5 (4)	C13—C12—H12	118.1
C7—N2—C8	125.1 (4)	C11—C12—H12	118.1
C5—C6—C7	117.8 (4)	C12—C11—C10	113.3 (7)
C5—C6—H6	121.1	C12—C11—H11	123.3
C7—C6—H6	121.1	C10—C11—H11	123.3
C4—C3—C2	118.6 (4)	N1—C13—C12	123.9 (8)
C4—C3—H3	120.7	N1—C13—H13	118.0
C2—C3—H3	120.7	C12—C13—H13	118.0
C3—C4—C5	120.6 (5)
O1—Cu1—Cl1—Cu1ii	−1.10 (2)	N2—C7—C6—C5	−178.9 (5)
N3—Cu1—Cl1—Cu1ii	178.42 (9)	C2—C7—C6—C5	3.0 (7)
Cl1i—Cu1—Cl1—Cu1ii	−83.12 (4)	N3—C2—C3—C4	−178.9 (4)
Cl2—Cu1—Cl1—Cu1ii	78.54 (4)	C7—C2—C3—C4	1.4 (7)
O1—Cu1—Cl2—Cu1iii	0.0	C2—C3—C4—C5	−0.2 (8)
N3—Cu1—Cl2—Cu1iii	−179.13 (9)	C7—C6—C5—C4	−1.8 (9)
Cl1i—Cu1—Cl2—Cu1iii	81.77 (3)	C3—C4—C5—C6	0.5 (9)
Cl1—Cu1—Cl2—Cu1iii	−80.48 (3)	C1—N2—C8—C9	−48.8 (6)
O1—Cu1—N3—C1	150 (6)	C7—N2—C8—C9	135.3 (4)
Cl1i—Cu1—N3—C1	−4.5 (3)	N3—Cu1—O1—Cu1iii	88 (6)
Cl1—Cu1—N3—C1	116.6 (3)	Cl1i—Cu1—O1—Cu1iii	−117.99 (3)
Cl2—Cu1—N3—C1	−122.7 (3)	Cl1—Cu1—O1—Cu1iii	120.87 (3)
O1—Cu1—N3—C2	−31 (6)	Cl2—Cu1—O1—Cu1iii	0.0
Cl1i—Cu1—N3—C2	174.8 (3)	N3—Cu1—O1—Cu1i	−153 (6)
Cl1—Cu1—N3—C2	−64.1 (3)	Cl1i—Cu1—O1—Cu1i	1.44 (3)
Cl2—Cu1—N3—C2	56.7 (3)	Cl1—Cu1—O1—Cu1i	−119.70 (3)
C2—N3—C1—N2	−0.7 (4)	Cl2—Cu1—O1—Cu1i	119.434 (8)
Cu1—N3—C1—N2	178.8 (2)	N3—Cu1—O1—Cu1ii	−32 (6)
C1—N3—C2—C3	−178.6 (4)	Cl1i—Cu1—O1—Cu1ii	122.58 (3)
Cu1—N3—C2—C3	2.0 (6)	Cl1—Cu1—O1—Cu1ii	1.43 (3)
C1—N3—C2—C7	1.2 (4)	Cl2—Cu1—O1—Cu1ii	−119.434 (8)
Cu1—N3—C2—C7	−178.3 (2)	N2—C8—C9—C10	−102.8 (6)
C3—C2—C7—N2	178.6 (4)	N2—C8—C9—N1	78.9 (5)
N3—C2—C7—N2	−1.2 (4)	N1—C9—C10—C11	1.4 (7)
C3—C2—C7—C6	−2.8 (6)	C8—C9—C10—C11	−176.8 (4)
N3—C2—C7—C6	177.4 (4)	C10—C9—N1—C13	−1.6 (7)
N3—C1—N2—C7	−0.1 (4)	C8—C9—N1—C13	176.8 (5)
N3—C1—N2—C8	−176.6 (4)	C13—C12—C11—C10	−2.7 (10)
C2—C7—N2—C1	0.8 (4)	C9—C10—C11—C12	0.6 (8)
C6—C7—N2—C1	−177.6 (5)	C9—N1—C13—C12	−0.5 (10)
C2—C7—N2—C8	177.4 (4)	C11—C12—C13—N1	2.8 (13)
C6—C7—N2—C8	−1.0 (8)

Table 1

Selected bond lengths (Å)

Cu1—O1	1.9199 (4)
Cu1—N3	1.974 (3)
Cu1—Cl1i	2.3961 (10)
Cu1—Cl1	2.4192 (10)
Cu1—Cl2	2.4263 (10)

Symmetry code: (i) .