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Acta Cryst. (2007). E63, m2441    [ doi:10.1107/S1600536807042109 ]

catena-Poly[[bis(1-vinyl-1H-imidazole-[kappa]N3)copper(II)]-[mu]-phthalato-[kappa]2O:O']

F.-Q. Liu, R.-X. Li, S.-X. Li, L.-S. Sun and G.-Y. Liu

Abstract top

The title compound, [Cu(C8H4O4)(C5H6N2)2]n, exhibits a polymeric zigzag chain structure extended along the c axis in the solid state. Each CuII ion is located on a crystallographic center of symmetry and is coordinated by two N [Cu-N = 1.993 (3) Å] and two O [Cu-O = 1.952 (2) Å] atoms in a distorted square-planar geometry. Weak C-H...O interactions contribute to the crystal packing stability.

Comment top

In the title compound, (I) (Fig. 1), the copper(II) centers are bridged by the carboxylate groups of o-phthalate ligiands and saturated by two 1-vinylimidazole ligands. Each CuII ion is located on a crystallographic center of symmetry being coordinated by two N [Cu—N 1.993 (3) Å] and two O [Cu—O 1.952 (2) Å] atoms in a distorted square-planar geometry. All these values agree well with those observed in [Cu(phthalato)(1-methylimidazole)2] (Baca et al., 2004), where CuII ions have a distorted tetrahedral environment. Each o-phthalate dianion acts as a bidentate ligand to bridge two CuII ions through two monodentate carboxylate groups, building a zigzag infinate chain structure along the c axis. The metal-metal distances across each polymer backbone are 7.231 (6) Å.

In the crystal, weak C—H···O (Table 1) interactions contribute to the crystal packing stability.

Related literature top

In the corresponding compound [Cu(phthalato)(1-methylimidazole)2] (Baca et al., 2004), CuII ions have a distorted tetrahedral environment.

Experimental top

The reaction of CuCl2·2H2O(0.85 g, 5 mmol) with o-phthalic acid (0.83 g, 5 mmol) in an aqueous-alcohol(3:1) solution(40 ml) at 363 K for 30 min produced a blue solution, to which 1-vinylimidazole (0.94 g, 10 mmol) was added. The reaction solution was kept at room temperature after stirring for an hour at 333 K. Blue crystals were obtained after a few days.

Refinement top

All H atoms were positioned geometrically (C—H = 0.93 Å) and allowed to ride on their parent atoms with Uiso(H) = 1.2 Ueq(C).

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, 2001); program(s) used to refine structure: SHELXTL (Sheldrick, 2001); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2001) and local programs.

Figures top
[Figure 1] Fig. 1. A portion of polymeric chain in (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme [symmetry codes: (A) −x, −y, −z; (B) x + 1/2, y + 1/2, z; (C) x + 1/2, y + 1/2, z − 1].
[Figure 2] Fig. 2. The packing of (I), viewed down the b axis. Dashed lines denote hydrogen bonds.
catena-Poly[[bis(1-vinyl-1H-imidazole-κN3)copper(II)]-µ-phthalato-κ2O:O'] top
Crystal data top
[Cu(C8H4O4)(C5H6N2)2]F000 = 852
Mr = 415.90Dx = 1.537 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3318 reflections
a = 16.527 (3) Åθ = 2.5–25.1º
b = 8.1800 (16) ŵ = 1.25 mm−1
c = 14.463 (3) ÅT = 293 (2) K
β = 113.19 (3)ºBlock, blue
V = 1797.3 (7) Å30.30 × 0.20 × 0.10 mm
Z = 4
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		1768 independent reflections
Radiation source: fine-focus sealed tube1344 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.023
T = 293(2) Kθmax = 26.0º
thin–slice ω scansθmin = 2.7º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −20→20
Tmin = 0.706, Tmax = 0.885k = 0→10
3525 measured reflectionsl = −17→17
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.136  w = 1/[σ2(Fo2) + (0.0844P)2 + 0.9237P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
1768 reflectionsΔρmax = 0.75 e Å−3
124 parametersΔρmin = −0.63 e Å−3
40 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Cu(C8H4O4)(C5H6N2)2]V = 1797.3 (7) Å3
Mr = 415.90Z = 4
Monoclinic, C2/cMo Kα
a = 16.527 (3) ŵ = 1.25 mm−1
b = 8.1800 (16) ÅT = 293 (2) K
c = 14.463 (3) Å0.30 × 0.20 × 0.10 mm
β = 113.19 (3)º
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		1768 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		1344 reflections with I > 2σ(I)
Tmin = 0.706, Tmax = 0.885Rint = 0.023
3525 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04840 restraints
wR(F2) = 0.136H-atom parameters constrained
S = 1.00Δρmax = 0.75 e Å−3
1768 reflectionsΔρmin = −0.63 e Å−3
124 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
xyzUiso*/Ueq
Cu0.00000.00000.00000.0333 (2)
O1−0.06590 (16)−0.0922 (3)0.14946 (17)0.0480 (6)
O20.01489 (15)−0.2039 (3)0.07497 (16)0.0423 (5)
N10.11711 (18)0.0724 (4)0.0994 (2)0.0431 (6)
C60.1839 (3)0.1421 (6)0.0812 (3)0.0679 (12)
H6A0.18180.16660.01750.081*
C1−0.0087 (3)−0.6538 (5)0.1984 (3)0.0627 (11)
H1A−0.0156−0.75190.16370.075*
C2−0.0155 (3)−0.5079 (4)0.1493 (3)0.0486 (9)
H2B−0.0253−0.50850.08140.058*
C3−0.00809 (19)−0.3593 (4)0.1982 (2)0.0341 (7)
C4−0.0211 (2)−0.2048 (4)0.1387 (2)0.0375 (7)
C50.1469 (2)0.0592 (5)0.1980 (3)0.0478 (8)
H5A0.11530.01480.23280.057*
N20.22960 (19)0.1189 (4)0.2419 (2)0.0533 (8)
C70.2538 (3)0.1709 (7)0.1679 (3)0.0728 (13)
H7A0.30740.21690.17520.087*
C80.2838 (3)0.1327 (6)0.3459 (3)0.0695 (12)
H8A0.34220.16380.36390.083*
C90.2577 (4)0.1057 (9)0.4147 (4)0.107 (2)
H9C0.19970.07450.39900.128*
H9A0.29630.11680.48160.128*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu0.0317 (3)0.0411 (4)0.0270 (3)0.0012 (2)0.0114 (2)0.0024 (2)
O10.0608 (15)0.0420 (14)0.0393 (13)0.0160 (11)0.0178 (11)0.0031 (10)
O20.0444 (12)0.0481 (14)0.0360 (11)0.0018 (10)0.0176 (10)0.0065 (10)
N10.0390 (14)0.0504 (16)0.0354 (14)−0.0037 (13)0.0098 (11)0.0025 (13)
C60.050 (2)0.103 (3)0.047 (2)−0.020 (2)0.0159 (17)0.002 (2)
C10.090 (3)0.038 (2)0.070 (3)−0.0032 (19)0.042 (3)−0.0090 (18)
C20.059 (2)0.045 (2)0.046 (2)−0.0037 (16)0.0252 (18)−0.0069 (15)
C30.0355 (15)0.0318 (16)0.0368 (16)−0.0003 (12)0.0161 (13)0.0005 (13)
C40.0365 (15)0.0401 (17)0.0311 (15)−0.0041 (13)0.0082 (13)−0.0012 (13)
C50.0463 (19)0.0520 (19)0.0411 (17)−0.0077 (16)0.0129 (15)0.0031 (16)
N20.0452 (16)0.063 (2)0.0390 (15)−0.0081 (14)0.0029 (13)−0.0029 (14)
C70.048 (2)0.105 (4)0.063 (2)−0.026 (2)0.0194 (19)0.000 (2)
C80.052 (2)0.090 (3)0.052 (2)−0.018 (2)0.0054 (19)−0.002 (2)
C90.084 (4)0.165 (6)0.061 (3)−0.039 (4)0.017 (3)−0.019 (4)
Geometric parameters (Å, °) top
Cu—O21.952 (2)C2—C31.387 (4)
Cu—O2i1.952 (2)C2—H2B0.9300
Cu—N1i1.993 (3)C3—C3ii1.415 (6)
Cu—N11.993 (3)C3—C41.496 (4)
O1—C41.228 (4)C5—N21.351 (4)
O2—C41.280 (4)C5—H5A0.9300
N1—C51.317 (4)N2—C71.351 (5)
N1—C61.358 (5)N2—C81.420 (5)
C6—C71.350 (6)C7—H7A0.9300
C6—H6A0.9300C8—C91.250 (7)
C1—C21.371 (5)C8—H8A0.9300
C1—C1ii1.405 (8)C9—H9C0.9300
C1—H1A0.9300C9—H9A0.9300
O2—Cu—O2i180.00 (13)C2—C3—C4118.9 (3)
O2—Cu—N1i91.21 (11)C3ii—C3—C4122.22 (16)
O2i—Cu—N1i88.79 (11)O1—C4—O2124.1 (3)
O2—Cu—N188.79 (11)O1—C4—C3121.2 (3)
O2i—Cu—N191.21 (11)O2—C4—C3114.6 (3)
N1i—Cu—N1180.0 (2)N1—C5—N2110.9 (3)
C4—O2—Cu114.3 (2)N1—C5—H5A124.5
C5—N1—C6105.0 (3)N2—C5—H5A124.5
C5—N1—Cu126.9 (2)C7—N2—C5107.6 (3)
C6—N1—Cu128.1 (2)C7—N2—C8123.6 (3)
C7—C6—N1110.9 (4)C5—N2—C8128.8 (3)
C7—C6—H6A124.6C6—C7—N2105.6 (3)
N1—C6—H6A124.6C6—C7—H7A127.2
C2—C1—C1ii119.4 (2)N2—C7—H7A127.2
C2—C1—H1A120.3C9—C8—N2123.8 (4)
C1ii—C1—H1A120.3C9—C8—H8A118.1
C1—C2—C3121.7 (4)N2—C8—H8A118.1
C1—C2—H2B119.2C8—C9—H9C120.0
C3—C2—H2B119.2C8—C9—H9A120.0
C2—C3—C3ii118.8 (2)H9C—C9—H9A120.0
N1i—Cu—O2—C4−84.6 (2)C2—C3—C4—O1135.5 (3)
N1—Cu—O2—C495.4 (2)C3ii—C3—C4—O1−42.0 (5)
O2—Cu—N1—C5−44.5 (3)C2—C3—C4—O2−42.0 (4)
O2i—Cu—N1—C5135.5 (3)C3ii—C3—C4—O2140.5 (4)
O2—Cu—N1—C6133.9 (4)C6—N1—C5—N20.3 (5)
O2i—Cu—N1—C6−46.1 (4)Cu—N1—C5—N2179.1 (3)
C5—N1—C6—C70.1 (5)N1—C5—N2—C7−0.6 (5)
Cu—N1—C6—C7−178.7 (3)N1—C5—N2—C8177.6 (4)
C1ii—C1—C2—C3−1.9 (8)N1—C6—C7—N2−0.4 (6)
C1—C2—C3—C3ii0.9 (6)C5—N2—C7—C60.6 (5)
C1—C2—C3—C4−176.6 (4)C8—N2—C7—C6−177.7 (4)
Cu—O2—C4—O14.0 (4)C7—N2—C8—C9169.9 (6)
Cu—O2—C4—C3−178.59 (18)C5—N2—C8—C9−8.1 (9)
Symmetry codes: (i) −x, −y, −z; (ii) −x, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C5—H5A···O1ii0.932.333.243 (5)167
C6—H6A···O1i0.932.503.158 (5)128
C8—H8A···O2iii0.932.433.342 (6)168
C9—H9C···O1iv0.932.453.349 (8)162
Symmetry codes: (ii) −x, y, −z+1/2; (i) −x, −y, −z; (iii) −x+1/2, y+1/2, −z+1/2; (iv) −x, y, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C5—H5A···O1i0.932.333.243 (5)167
C6—H6A···O1ii0.932.503.158 (5)128
C8—H8A···O2iii0.932.433.342 (6)168
C9—H9C···O1iv0.932.453.349 (8)162
Symmetry codes: (i) −x, y, −z+1/2; (ii) −x, −y, −z; (iii) −x+1/2, y+1/2, −z+1/2; (iv) −x, y, −z+1/2.
Acknowledgements top

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

references
References top

Baca, S. G., Filippova, I. G., Gherco, O. A., Gdaniec, M., Simonov, Y. A., Gerbeleu, N. V., Franz, P., Baster, R. & Decurtins, S. (2004). Inorg. Chim. Acta, 357, 3419–3429.

Bruker (2001). SMART (Version 5.628) and SAINT (Version 6.45). Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2001). SHELXTL. Version 5.0. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.