Bis(2-chloro­benzoato-κO)bis­(1-vinyl­imidazole-κN3)copper(II)

Zhao, J.

doi:10.1107/S1600536808030237

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page m1321

doi:10.1107/S1600536808030237

Open

access

Bis(2-chlorobenzoato-κO)bis(1-vinylimidazole-κN³)copper(II)

Juan Zhao ^a ^*

^aCollege of Mechanical Engineering, Qingdao Technological University, Qingdao 266033, People's Republic of China
^*Correspondence e-mail: zhaojuanqd@163.com

(Received 14 September 2008; accepted 19 September 2008; online 24 September 2008)

In the title compound, [Cu(C₇H₄ClO₂)₂(C₅H₆N₂)₂], each Cu^II ion, located on an inversion center, has a slightly distorted square-planar coordination geometry formed by two 1-vinylimidazole molecules [Cu—N = 1.954 (6) Å] and two 2-chlorobenzoate anions [Cu—O = 1.958 (6) Å]. Weak intermolecular C—H⋯O hydrogen bonds contribute to the crystal packing stability.

Related literature

A square-planar coordination environment of Cu^II was also observed in bis(3-hydroxybenzoato-κO)bis(1H-imidazole-κN³)copper(II), see: Liu et al. (2006 ).

Experimental

Crystal data

[Cu(C₇H₄ClO₂)₂(C₅H₆N₂)₂]
M_r = 562.89
Monoclinic, P 2₁ /c
a = 7.9360 (16) Å
b = 11.236 (2) Å
c = 14.190 (3) Å
β = 104.36 (3)°
V = 1225.8 (5) Å³
Z = 2
Mo Kα radiation
μ = 1.15 mm⁻¹
T = 293 (2) K
0.20 × 0.10 × 0.10 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.803, T_max = 0.894
2204 measured reflections
2115 independent reflections
1620 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.073
wR(F²) = 0.192
S = 1.04
2115 reflections
154 parameters
49 restraints
H-atom parameters constrained
Δρ_max = 0.73 e Å⁻³
Δρ_min = −0.89 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O2ⁱ	0.93	2.56	3.484 (10)	174
C3—H3A⋯O1ⁱⁱ	0.93	2.49	2.918 (8)	108
C5—H5A⋯O2ⁱ	0.93	2.45	3.342 (9)	160
C11—H11A⋯O2ⁱⁱⁱ	0.93	2.60	3.460 (9)	155
Symmetry codes: (i) x-1, y, z; (ii) -x, -y, -z; (iii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); 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 local programs.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808030237/cv2449sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808030237/cv2449Isup2.hkl

checkCIF report

Comment top

In the title compound, (I) (Fig. 1), each Cu ion is coordinated by a pair of 1-vinylimidazole ligands and a pair of monodentate carboxylate groups, affording a square planar N₂O₂ coordination geometry. The CuN₂O₂ core involving the central atoms is almost perfectly square planar. The trans angles are all 180° for symmetry requirements and the cis ones are 89.52 (19)° and 90.48 (19)° for N—Cu—O, respectively. The Cu—N(imidazole) distance is 1.954 (6)Å and The Cu—O bond distance is 1.958 (4) Å. These bond distances are comparable with the reported data (Liu et al., 2006). The five atoms of CuN₂O₂ are coplanar. Distances and angles in 1-vinylimidazole are normal. The weak intermolecular C—H···O interactions (Table 1) stabilize the structure.

Related literature top

A square-planar coordination environment of Cu^II was also observed in bis(3-hydroxybenzoato-κO)bis(1H-imidazole-κN³)copper(II), see: Liu et al. (2006).

Experimental top

Copper(II) acetate hydrate(2.00 g, 10 mmol), 1-vinylimidazole(0.99 g, 10 mmol) and 2-chlorobenzoic acid(1.55 g, 10 mmol) were dissolved in water(40 ml). The pH of the solution was adjusted to 7 with 0.2M sodium hydroxide. The solution was filtered; blue single crystals of (I) were isolated after several days.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and local programs.

Figures top

Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme. The unlabelled atoms are related with the labelled ones by symmetry operation (-x, -y, -z).

Bis(2-chlorobenzoato-κO)bis(1-vinylimidazole-κN³)copper(II) top

Crystal data top

[Cu(C₇H₄ClO₂)₂(C₅H₆N₂)₂]	F(000) = 574
M_r = 562.89	D_x = 1.525 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 7.9360 (16) Å	θ = 10–14°
b = 11.236 (2) Å	µ = 1.15 mm⁻¹
c = 14.190 (3) Å	T = 293 K
β = 104.36 (3)°	Block, blue
V = 1225.8 (5) Å³	0.20 × 0.10 × 0.10 mm
Z = 2

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	2115 independent reflections
Radiation source: fine-focus sealed tube	1620 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
Thin–slice ω scans	θ_max = 25.2°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −9→9
T_min = 0.803, T_max = 0.894	k = 0→13
2204 measured reflections	l = 0→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)] = 0.073	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.192	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.07P)² + 6P] where P = (F_o² + 2F_c²)/3
2115 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.73 e Å⁻³
49 restraints	Δρ_min = −0.89 e Å⁻³

Crystal data top

[Cu(C₇H₄ClO₂)₂(C₅H₆N₂)₂]	V = 1225.8 (5) Å³
M_r = 562.89	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.9360 (16) Å	µ = 1.15 mm⁻¹
b = 11.236 (2) Å	T = 293 K
c = 14.190 (3) Å	0.20 × 0.10 × 0.10 mm
β = 104.36 (3)°

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	2115 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1620 reflections with I > 2σ(I)
T_min = 0.803, T_max = 0.894	R_int = 0.039
2204 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.073	49 restraints
wR(F²) = 0.192	H-atom parameters constrained
S = 1.04	Δρ_max = 0.73 e Å⁻³
2115 reflections	Δρ_min = −0.89 e Å⁻³
154 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
Cu	0.0000	0.0000	0.0000	0.0439 (4)
Cl	0.3736 (3)	−0.36078 (18)	0.02395 (17)	0.0794 (6)
O1	0.0066 (5)	−0.1740 (3)	0.0077 (3)	0.0455 (10)
N1	−0.3796 (8)	0.0695 (5)	0.1425 (4)	0.0550 (14)
C1	−0.6165 (13)	0.1373 (8)	0.2115 (6)	0.088 (3)
H1A	−0.6754	0.0655	0.1961	0.105*
H1B	−0.6638	0.1972	0.2422	0.105*
O2	0.1925 (7)	−0.1406 (4)	0.1509 (3)	0.0647 (14)
N2	−0.1911 (7)	0.0008 (4)	0.0642 (4)	0.0527 (14)
C2	−0.4664 (11)	0.1540 (7)	0.1896 (5)	0.066 (2)
H2A	−0.4120	0.2270	0.2063	0.079*
C3	−0.2436 (8)	0.0933 (6)	0.1068 (5)	0.047
H3A	−0.1907	0.1676	0.1114	0.057*
C4	−0.3049 (9)	−0.0881 (6)	0.0741 (5)	0.0504 (15)
H4A	−0.3010	−0.1654	0.0513	0.060*
C5	−0.4234 (9)	−0.0489 (6)	0.1212 (5)	0.0537 (16)
H5A	−0.5138	−0.0917	0.1360	0.064*
C6	0.1057 (9)	−0.2068 (5)	0.0889 (5)	0.0501 (16)
C7	0.1031 (8)	−0.3403 (5)	0.1088 (4)	0.0433 (13)
C8	0.2177 (9)	−0.4153 (6)	0.0813 (4)	0.0513 (15)
C9	0.2146 (11)	−0.5370 (6)	0.0999 (6)	0.0662 (19)
H9A	0.2926	−0.5882	0.0812	0.079*
C10	0.0945 (11)	−0.5801 (6)	0.1461 (6)	0.0676 (19)
H10A	0.0906	−0.6613	0.1580	0.081*
C11	−0.0196 (11)	−0.5057 (7)	0.1749 (5)	0.0648 (18)
H11A	−0.0990	−0.5360	0.2071	0.078*
C12	−0.0162 (10)	−0.3853 (6)	0.1558 (5)	0.0580 (17)
H12A	−0.0943	−0.3344	0.1746	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu	0.0696 (7)	0.0204 (5)	0.0350 (5)	0.0026 (5)	0.0001 (5)	0.0014 (4)
Cl	0.1031 (15)	0.0558 (11)	0.0838 (14)	0.0230 (11)	0.0319 (12)	0.0061 (10)
O1	0.060 (2)	0.030 (2)	0.043 (2)	0.0052 (19)	0.0066 (19)	0.0033 (18)
N1	0.088 (4)	0.033 (3)	0.035 (3)	0.009 (3)	−0.004 (3)	0.002 (2)
C1	0.115 (7)	0.071 (6)	0.079 (6)	0.004 (5)	0.029 (6)	−0.011 (5)
O2	0.094 (4)	0.029 (2)	0.058 (3)	−0.003 (2)	−0.006 (3)	−0.009 (2)
N2	0.075 (3)	0.024 (2)	0.048 (3)	0.008 (3)	−0.008 (3)	0.001 (2)
C2	0.096 (6)	0.054 (5)	0.042 (4)	0.004 (4)	0.004 (4)	0.007 (3)
C3	0.047	0.047	0.047	0.000	0.012	0.000
C4	0.068 (4)	0.035 (3)	0.043 (3)	0.008 (3)	0.006 (3)	0.003 (3)
C5	0.067 (4)	0.043 (3)	0.045 (4)	−0.001 (3)	0.001 (3)	0.009 (3)
C6	0.074 (4)	0.020 (3)	0.050 (4)	−0.004 (3)	0.004 (3)	0.000 (3)
C7	0.064 (3)	0.028 (3)	0.031 (3)	0.002 (2)	−0.001 (2)	−0.002 (2)
C8	0.072 (4)	0.037 (3)	0.040 (3)	0.011 (3)	0.004 (3)	−0.002 (3)
C9	0.091 (5)	0.039 (3)	0.062 (4)	0.017 (3)	0.008 (4)	−0.001 (3)
C10	0.091 (5)	0.035 (3)	0.063 (4)	−0.005 (3)	−0.007 (3)	0.007 (3)
C11	0.086 (4)	0.053 (4)	0.051 (4)	−0.017 (3)	0.010 (3)	0.013 (3)
C12	0.085 (4)	0.042 (3)	0.047 (3)	−0.002 (3)	0.017 (3)	0.007 (3)

Geometric parameters (Å, º) top

Cu—N2ⁱ	1.954 (6)	C3—H3A	0.9300
Cu—N2	1.954 (6)	C4—C5	1.356 (9)
Cu—O1ⁱ	1.958 (4)	C4—H4A	0.9300
Cu—O1	1.958 (4)	C5—H5A	0.9300
Cl—C8	1.751 (7)	C6—C7	1.528 (8)
O1—C6	1.278 (7)	C7—C8	1.366 (8)
N1—C3	1.327 (8)	C7—C12	1.383 (9)
N1—C5	1.389 (9)	C8—C9	1.394 (10)
N1—C2	1.433 (9)	C9—C10	1.372 (11)
C1—C2	1.317 (10)	C9—H9A	0.9300
C1—H1A	0.9300	C10—C11	1.367 (11)
C1—H1B	0.9300	C10—H10A	0.9300
O2—C6	1.225 (7)	C11—C12	1.381 (9)
N2—C3	1.320 (8)	C11—H11A	0.9300
N2—C4	1.377 (8)	C12—H12A	0.9300
C2—H2A	0.9300

N2ⁱ—Cu—N2	180.0 (3)	C4—C5—N1	104.5 (6)
N2ⁱ—Cu—O1ⁱ	89.52 (19)	C4—C5—H5A	127.7
N2—Cu—O1ⁱ	90.48 (19)	N1—C5—H5A	127.7
N2ⁱ—Cu—O1	90.48 (19)	O2—C6—O1	125.6 (5)
N2—Cu—O1	89.52 (19)	O2—C6—C7	119.7 (6)
O1ⁱ—Cu—O1	180.0 (4)	O1—C6—C7	114.6 (5)
C6—O1—Cu	109.9 (4)	C8—C7—C12	119.8 (6)
C3—N1—C5	107.1 (6)	C8—C7—C6	120.9 (6)
C3—N1—C2	125.1 (6)	C12—C7—C6	119.4 (6)
C5—N1—C2	127.8 (6)	C7—C8—C9	120.4 (7)
C2—C1—H1A	120.0	C7—C8—Cl	120.9 (5)
C2—C1—H1B	120.0	C9—C8—Cl	118.6 (5)
H1A—C1—H1B	120.0	C10—C9—C8	118.9 (7)
C3—N2—C4	103.6 (6)	C10—C9—H9A	120.5
C3—N2—Cu	125.9 (4)	C8—C9—H9A	120.5
C4—N2—Cu	130.4 (4)	C11—C10—C9	121.1 (7)
C1—C2—N1	125.6 (8)	C11—C10—H10A	119.4
C1—C2—H2A	117.2	C9—C10—H10A	119.4
N1—C2—H2A	117.2	C10—C11—C12	119.6 (7)
N2—C3—N1	113.2 (6)	C10—C11—H11A	120.2
N2—C3—H3A	123.4	C12—C11—H11A	120.2
N1—C3—H3A	123.4	C11—C12—C7	120.1 (7)
C5—C4—N2	111.6 (6)	C11—C12—H12A	119.9
C5—C4—H4A	124.2	C7—C12—H12A	119.9
N2—C4—H4A	124.2

N2ⁱ—Cu—O1—C6	92.5 (4)	Cu—O1—C6—O2	−4.0 (9)
N2—Cu—O1—C6	−87.5 (4)	Cu—O1—C6—C7	172.6 (4)
O1ⁱ—Cu—N2—C3	−17.5 (5)	O2—C6—C7—C8	−92.3 (8)
O1—Cu—N2—C3	162.5 (5)	O1—C6—C7—C8	90.9 (7)
O1ⁱ—Cu—N2—C4	160.1 (5)	O2—C6—C7—C12	87.2 (8)
O1—Cu—N2—C4	−19.9 (5)	O1—C6—C7—C12	−89.6 (7)
C3—N1—C2—C1	168.6 (8)	C12—C7—C8—C9	0.4 (10)
C5—N1—C2—C1	−8.3 (11)	C6—C7—C8—C9	179.9 (6)
C4—N2—C3—N1	0.2 (7)	C12—C7—C8—Cl	−178.6 (5)
Cu—N2—C3—N1	178.3 (4)	C6—C7—C8—Cl	0.9 (8)
C5—N1—C3—N2	−0.6 (7)	C7—C8—C9—C10	0.1 (10)
C2—N1—C3—N2	−178.0 (5)	Cl—C8—C9—C10	179.0 (6)
C3—N2—C4—C5	0.3 (7)	C8—C9—C10—C11	−0.8 (11)
Cu—N2—C4—C5	−177.7 (4)	C9—C10—C11—C12	1.1 (11)
N2—C4—C5—N1	−0.7 (7)	C10—C11—C12—C7	−0.7 (11)
C3—N1—C5—C4	0.8 (7)	C8—C7—C12—C11	0.0 (10)
C2—N1—C5—C4	178.0 (6)	C6—C7—C12—C11	−179.6 (6)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O2ⁱⁱ	0.93	2.56	3.484 (10)	174
C3—H3A···O1ⁱ	0.93	2.49	2.918 (8)	108
C5—H5A···O2ⁱⁱ	0.93	2.45	3.342 (9)	160
C11—H11A···O2ⁱⁱⁱ	0.93	2.60	3.460 (9)	155

Symmetry codes: (i) −x, −y, −z; (ii) x−1, y, z; (iii) −x, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Cu(C₇H₄ClO₂)₂(C₅H₆N₂)₂]
M_r	562.89
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.9360 (16), 11.236 (2), 14.190 (3)
β (°)	104.36 (3)
V (Å³)	1225.8 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.15
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART 1K CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.803, 0.894
No. of measured, independent and observed [I > 2σ(I)] reflections	2204, 2115, 1620
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.073, 0.192, 1.04
No. of reflections	2115
No. of parameters	154
No. of restraints	49
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.73, −0.89

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008) and local programs.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O2ⁱ	0.93	2.56	3.484 (10)	174
C3—H3A···O1ⁱⁱ	0.93	2.49	2.918 (8)	108
C5—H5A···O2ⁱ	0.93	2.45	3.342 (9)	160
C11—H11A···O2ⁱⁱⁱ	0.93	2.60	3.460 (9)	155

Symmetry codes: (i) x−1, y, z; (ii) −x, −y, −z; (iii) −x, y−1/2, −z+1/2.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant No. 20601015) and the Natural Science Foundation of Shandong Province (Y2006B12).

References

Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Liu, J.-W., Zhu, B. & Ng, S. W. (2006). Acta Cryst. E62, m3514–m3515. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2004). 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