Bis(1H-benzimidazole-κN3)bis­(4-methyl­benzoato-κ2O,O′)copper(II)

Song, W.-D.; Huang, X.-H.; Wang, H.

doi:10.1107/S1600536808012440

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page m764

doi:10.1107/S1600536808012440

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Bis(1H-benzimidazole-κN³)bis(4-methylbenzoato-κ²O,O′)copper(II)

Wen-Dong Song,^a ^* Xiang-Hu Huang ^b and Hui Wang ^b

^aCollege of Science, Guang Dong Ocean University, Zhan Jiang 524088, People's Republic of China, and ^bCollege of Fisheries, Guang Dong Ocean University, Zhan Jiang 524088, People's Republic of China
^*Correspondence e-mail: songwd60@126.com

(Received 17 April 2008; accepted 29 April 2008; online 3 May 2008)

In the title mononuclear complex, [Cu(C₈H₇O₂)₂(C₇H₆N₂)₂], the Cu^II atom lies on an inversion centre and is coordinated by two O atoms of two monodentate 4-methylbenzoate ligands and two N atoms of two benzimidazole ligands in a square-planar geometry. The molecules are linked into chains running parallel to the b axis by intermolecular N—H⋯O hydrogen bonds and by π–π stacking interactions [centroid–centroid distance = 3.669 (2) Å] involving centrosymmetrically related imidazole rings.

Related literature

For related literature, see: Song et al. (2007 ).

Experimental

Crystal data

[Cu(C₈H₇O₂)₂(C₇H₆N₂)₂]
M_r = 570.10
Triclinic, $[P \overline 1]$
a = 7.2623 (2) Å
b = 7.6068 (1) Å
c = 12.9624 (2) Å
α = 99.687 (2)°
β = 96.390 (1)°
γ = 104.776 (3)°
V = 673.54 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.85 mm⁻¹
T = 296 (2) K
0.40 × 0.30 × 0.20 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.726, T_max = 0.848
8200 measured reflections
2743 independent reflections
2445 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.121
S = 0.88
2743 reflections
179 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2ⁱ	0.86	1.95	2.780 (2)	163
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808012440/rz2208sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808012440/rz2208Isup2.hkl

checkCIF report

Comment top

In the structural investigation of 4-methylbenzate complexes, it has been found that 4-methylbenzoic acid can act as a multidentate ligand (Song et al., 2007), with versatile binding and coordination modes. In this paper, we report the crystal structure of the title compound, a new Cu complex obtained by the reaction of 4-methylbenzoic acid, benzimidazole and copper chloride in alkaline aqueous solution.

As illustrated in Fig. 1, the complex molecule has an inversion symmetry where the Cu^II atom exists in a square planar coordination geometry, defined by two carboxyl O atoms from two monodentate 4-methylbenzate ligands and two N atoms from two benzimidazole ligands. In the crystal structure, intermolecular N—H···O hydrogen bonding interactions (Table 1) and π-π stacking interactions (centroid-centroid distance = 3.669 (2) Å) occurring between the imidazole rings of centrosymmetrically-related complexes form chains running parallel to the b axis (Fig. 2).

Related literature top

For related literature, see: Song et al. (2007).

Experimental top

A mixture of copper chloride (1 mmol), 4-methylbenzoic acid (1 mmol), benzimidazole (1 mmol), NaOH (1.5 mmol) and H₂O (12 ml) was placed in a 23 ml Teflon reactor and heated to 433 K for three days. After cooling to room temperature at a rate of 10 K h^-1, the crystals obtained were washed with water and dryed in air.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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. The molecular structure of the title compound, showing the atom-numbering scheme and 30% probability displacement ellipsoids. Unlabelled atoms are related to the labelled atoms by the symmetry operator (1-x, 2-y, 1-z).
	Fig. 2. Packing diagram of the title compound viewed approximately along the a axis. Dashed lines indicate hydrogen bonds.

Bis(1H-benzimidazole-κN³)bis(4-methylbenzoato- κ²O,O')copper(II) top

Crystal data top

[Cu(C₈H₇O₂)₂(C₇H₆N₂)₂]	Z = 1
M_r = 570.10	F(000) = 295
Triclinic, P1	D_x = 1.406 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2623 (2) Å	Cell parameters from 3600 reflections
b = 7.6068 (1) Å	θ = 1.4–28°
c = 12.9624 (2) Å	µ = 0.85 mm⁻¹
α = 99.687 (2)°	T = 296 K
β = 96.390 (1)°	Block, blue
γ = 104.776 (3)°	0.40 × 0.30 × 0.20 mm
V = 673.54 (3) Å³

Data collection top

Bruker APEXII area-detector diffractometer	2743 independent reflections
Radiation source: fine-focus sealed tube	2445 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ϕ and ω scans	θ_max = 26.5°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.726, T_max = 0.848	k = −9→9
8200 measured reflections	l = −16→16

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.121	H-atom parameters constrained
S = 0.88	w = 1/[σ²(F_o²) + (0.1115P)²] where P = (F_o² + 2F_c²)/3
2743 reflections	(Δ/σ)_max = 0.045
179 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

[Cu(C₈H₇O₂)₂(C₇H₆N₂)₂]	γ = 104.776 (3)°
M_r = 570.10	V = 673.54 (3) Å³
Triclinic, P1	Z = 1
a = 7.2623 (2) Å	Mo Kα radiation
b = 7.6068 (1) Å	µ = 0.85 mm⁻¹
c = 12.9624 (2) Å	T = 296 K
α = 99.687 (2)°	0.40 × 0.30 × 0.20 mm
β = 96.390 (1)°

Data collection top

Bruker APEXII area-detector diffractometer	2743 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2445 reflections with I > 2σ(I)
T_min = 0.726, T_max = 0.848	R_int = 0.026
8200 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.121	H-atom parameters constrained
S = 0.88	Δρ_max = 0.31 e Å⁻³
2743 reflections	Δρ_min = −0.22 e Å⁻³
179 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
C1	0.3775 (3)	0.6448 (3)	0.56672 (17)	0.0404 (5)
H1	0.4583	0.6988	0.6312	0.048*
C2	0.1775 (3)	0.4328 (3)	0.43989 (18)	0.0397 (5)
C3	0.0533 (4)	0.2729 (3)	0.3739 (2)	0.0516 (6)
H3	0.0277	0.1586	0.3942	0.062*
C4	−0.0289 (4)	0.2922 (4)	0.2778 (2)	0.0602 (7)
H4	−0.1113	0.1882	0.2313	0.072*
C5	0.0079 (4)	0.4657 (4)	0.2474 (2)	0.0553 (7)
H5	−0.0517	0.4739	0.1818	0.066*
C6	0.1304 (3)	0.6235 (3)	0.31304 (18)	0.0449 (5)
H6	0.1530	0.7380	0.2931	0.054*
C7	0.2189 (3)	0.6062 (3)	0.40969 (17)	0.0355 (4)
C15	0.5949 (3)	0.8828 (3)	0.31242 (16)	0.0400 (5)
C16	0.5876 (4)	0.8343 (3)	0.19460 (17)	0.0404 (5)
C17	0.4260 (4)	0.8288 (3)	0.12438 (18)	0.0462 (5)
H17	0.3205	0.8574	0.1503	0.055*
C18	0.4215 (4)	0.7808 (4)	0.01597 (18)	0.0553 (7)
H18	0.3117	0.7766	−0.0299	0.066*
C19	0.5742 (5)	0.7394 (3)	−0.02547 (19)	0.0548 (7)
C20	0.7351 (5)	0.7454 (4)	0.0439 (2)	0.0631 (8)
H20	0.8405	0.7179	0.0172	0.076*
C21	0.7426 (4)	0.7920 (4)	0.1535 (2)	0.0547 (6)
H21	0.8522	0.7947	0.1990	0.066*
C22	0.5672 (6)	0.6885 (4)	−0.1443 (2)	0.0736 (9)
H22A	0.4408	0.6111	−0.1768	0.110*
H22B	0.6610	0.6226	−0.1589	0.110*
H22C	0.5955	0.7996	−0.1725	0.110*
Cu1	0.5000	1.0000	0.5000	0.03466 (16)
N1	0.3479 (3)	0.7375 (2)	0.49250 (13)	0.0363 (4)
N2	0.2793 (3)	0.4642 (3)	0.54000 (15)	0.0423 (4)
H2	0.2800	0.3829	0.5787	0.051*
O1	0.4718 (2)	0.9625 (2)	0.34485 (11)	0.0403 (4)
O2	0.7185 (3)	0.8455 (2)	0.37312 (13)	0.0503 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0484 (12)	0.0394 (11)	0.0344 (10)	0.0100 (9)	0.0095 (9)	0.0123 (9)
C2	0.0398 (11)	0.0345 (11)	0.0472 (12)	0.0092 (9)	0.0146 (9)	0.0120 (9)
C3	0.0490 (13)	0.0304 (11)	0.0703 (17)	0.0020 (10)	0.0139 (12)	0.0077 (11)
C4	0.0503 (14)	0.0473 (14)	0.0661 (17)	−0.0060 (12)	0.0027 (12)	0.0001 (12)
C5	0.0482 (13)	0.0559 (15)	0.0496 (14)	0.0006 (12)	−0.0038 (10)	0.0070 (11)
C6	0.0436 (12)	0.0433 (12)	0.0450 (12)	0.0051 (10)	0.0048 (9)	0.0134 (10)
C7	0.0347 (10)	0.0322 (10)	0.0387 (10)	0.0064 (8)	0.0083 (8)	0.0077 (8)
C15	0.0504 (12)	0.0264 (10)	0.0361 (11)	−0.0028 (9)	0.0011 (9)	0.0122 (8)
C16	0.0547 (13)	0.0270 (10)	0.0367 (11)	0.0063 (9)	0.0049 (9)	0.0081 (8)
C17	0.0549 (13)	0.0463 (13)	0.0353 (11)	0.0118 (11)	0.0060 (9)	0.0068 (9)
C18	0.0672 (16)	0.0571 (14)	0.0345 (11)	0.0113 (13)	0.0016 (11)	0.0039 (11)
C19	0.0819 (19)	0.0394 (12)	0.0422 (13)	0.0155 (12)	0.0152 (12)	0.0046 (10)
C20	0.079 (2)	0.0590 (17)	0.0591 (16)	0.0291 (15)	0.0263 (15)	0.0094 (13)
C21	0.0649 (16)	0.0508 (14)	0.0498 (14)	0.0200 (13)	0.0067 (12)	0.0100 (11)
C22	0.114 (3)	0.0659 (18)	0.0417 (14)	0.0259 (18)	0.0221 (15)	0.0049 (13)
Cu1	0.0445 (2)	0.0294 (2)	0.0273 (2)	0.00483 (15)	0.00285 (14)	0.00858 (14)
N1	0.0443 (10)	0.0329 (9)	0.0307 (8)	0.0074 (8)	0.0053 (7)	0.0091 (7)
N2	0.0533 (11)	0.0344 (9)	0.0461 (10)	0.0143 (8)	0.0149 (8)	0.0197 (8)
O1	0.0508 (9)	0.0359 (8)	0.0310 (7)	0.0067 (7)	0.0045 (6)	0.0076 (6)
O2	0.0587 (10)	0.0457 (9)	0.0455 (9)	0.0101 (8)	−0.0018 (7)	0.0202 (7)

Geometric parameters (Å, º) top

C1—N1	1.315 (3)	C16—C17	1.390 (3)
C1—N2	1.342 (3)	C17—C18	1.386 (3)
C1—H1	0.9300	C17—H17	0.9300
C2—N2	1.371 (3)	C18—C19	1.368 (4)
C2—C3	1.394 (3)	C18—H18	0.9300
C2—C7	1.407 (3)	C19—C20	1.379 (4)
C3—C4	1.368 (4)	C19—C22	1.516 (3)
C3—H3	0.9300	C20—C21	1.396 (4)
C4—C5	1.410 (4)	C20—H20	0.9300
C4—H4	0.9300	C21—H21	0.9300
C5—C6	1.378 (3)	C22—H22A	0.9600
C5—H5	0.9300	C22—H22B	0.9600
C6—C7	1.386 (3)	C22—H22C	0.9600
C6—H6	0.9300	Cu1—O1ⁱ	1.9630 (14)
C7—N1	1.402 (3)	Cu1—O1	1.9630 (14)
C15—O2	1.246 (3)	Cu1—N1	2.0007 (16)
C15—O1	1.272 (3)	Cu1—N1ⁱ	2.0007 (16)
C15—C16	1.501 (3)	N2—H2	0.8600
C16—C21	1.384 (4)

N1—C1—N2	113.20 (19)	C19—C18—H18	119.1
N1—C1—H1	123.4	C17—C18—H18	119.1
N2—C1—H1	123.4	C18—C19—C20	118.2 (2)
N2—C2—C3	132.2 (2)	C18—C19—C22	121.0 (3)
N2—C2—C7	105.66 (19)	C20—C19—C22	120.8 (3)
C3—C2—C7	122.2 (2)	C19—C20—C21	121.2 (3)
C4—C3—C2	116.8 (2)	C19—C20—H20	119.4
C4—C3—H3	121.6	C21—C20—H20	119.4
C2—C3—H3	121.6	C16—C21—C20	120.2 (3)
C3—C4—C5	121.7 (2)	C16—C21—H21	119.9
C3—C4—H4	119.2	C20—C21—H21	119.9
C5—C4—H4	119.2	C19—C22—H22A	109.5
C6—C5—C4	121.3 (2)	C19—C22—H22B	109.5
C6—C5—H5	119.3	H22A—C22—H22B	109.5
C4—C5—H5	119.3	C19—C22—H22C	109.5
C5—C6—C7	117.9 (2)	H22A—C22—H22C	109.5
C5—C6—H6	121.0	H22B—C22—H22C	109.5
C7—C6—H6	121.0	O1ⁱ—Cu1—O1	180.00 (10)
C6—C7—N1	131.56 (19)	O1ⁱ—Cu1—N1	88.20 (6)
C6—C7—C2	120.1 (2)	O1—Cu1—N1	91.80 (6)
N1—C7—C2	108.32 (19)	O1ⁱ—Cu1—N1ⁱ	91.80 (6)
O2—C15—O1	123.3 (2)	O1—Cu1—N1ⁱ	88.20 (6)
O2—C15—C16	119.9 (2)	N1—Cu1—N1ⁱ	180.00 (11)
O1—C15—C16	116.81 (19)	C1—N1—C7	105.17 (17)
C21—C16—C17	118.4 (2)	C1—N1—Cu1	122.68 (15)
C21—C16—C15	120.2 (2)	C7—N1—Cu1	131.45 (14)
C17—C16—C15	121.3 (2)	C1—N2—C2	107.64 (18)
C18—C17—C16	120.3 (2)	C1—N2—H2	126.2
C18—C17—H17	119.9	C2—N2—H2	126.2
C16—C17—H17	119.9	C15—O1—Cu1	109.52 (13)
C19—C18—C17	121.8 (3)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2ⁱⁱ	0.86	1.95	2.780 (2)	163

Symmetry code: (ii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu(C₈H₇O₂)₂(C₇H₆N₂)₂]
M_r	570.10
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.2623 (2), 7.6068 (1), 12.9624 (2)
α, β, γ (°)	99.687 (2), 96.390 (1), 104.776 (3)
V (Å³)	673.54 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.85
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.726, 0.848
No. of measured, independent and observed [I > 2σ(I)] reflections	8200, 2743, 2445
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.121, 0.88
No. of reflections	2743
No. of parameters	179
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.22

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2ⁱ	0.86	1.95	2.780 (2)	163.4

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

The authors acknowledge Guang Dong Ocean University for supporting this work.

References

Bruker (2004). APEX2 and SMART. Bruker AXS Inc, Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Song, W.-D., Gu, C.-S., Hao, X.-M. & Liu, J.-W. (2007). Acta Cryst. E63, m1023–m1024. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar