Tetra­kis(μ-2-anilinobenzoato)bis­[methano­lcopper(II)](Cu—Cu)

Chun-Wei Xin; Fu-Chen Liu

doi:10.1107/S1600536808038063

. 2008 Nov 22;64(Pt 12):m1589. doi: 10.1107/S1600536808038063

Tetrakis(μ-2-anilinobenzoato)bis[methanolcopper(II)](Cu—Cu)

Chun-Wei Xin ^a, Fu-Chen Liu ^a,^*

PMCID: PMC2960117 PMID: 21581189

Abstract

The title compound, [Cu₂(C₁₃H₁₀NO₂)₄(CH₄O)₂], has been prepared by the reaction of 2-anilinobenzoic acid, HL, with copper(II) nitrate in methanol. This dinuclear complex is arranged around an inversion center. Each Cu atom displays a distorted trigonal–pyramidal coordination with four O atoms from the four ligands L and one axial O atom of the methanol solvent molecule. Each carboxylate group of the ligands L links two Cu atoms, building a dinuclear complex with a Cu—Cu distance of 2.5774 (10) Å. There are intramolecular N—H⋯O hydrogen bonds, and the H atom of the methanol molecule is involved in weak bifurcated hydrogen-bonding interactions with two carboxylate O atoms of related molecules, forming a chain developing parallel to the a axis.

Related literature

For general background, see: Melnik et al. (1998 ▶); Facchin et al. (1998 ▶); Martin & Greenwood (1997 ▶); Moulton et al. (2003 ▶). For a related structure, see: Churchill et al. (1985 ▶).

Experimental

Crystal data

[Cu₂(C₁₃H₁₀NO₂)₄(CH₄O)₂]
M _r = 1040.06
Monoclinic,
a = 7.2467 (14) Å
b = 14.171 (3) Å
c = 23.813 (5) Å
β = 97.11 (3)°
V = 2426.6 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.94 mm⁻¹
T = 293 (2) K
0.22 × 0.20 × 0.15 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: none
23688 measured reflections
5568 independent reflections
3886 reflections with I > 2σ(I)
R _int = 0.073

Refinement

R[F ² > 2σ(F ²)] = 0.059
wR(F ²) = 0.115
S = 1.05
5568 reflections
316 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT-Plus (Bruker, 1998 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶) and ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808038063/dn2398sup1.cif

e-64-m1589-sup1.cif^{(21KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808038063/dn2398Isup2.hkl

e-64-m1589-Isup2.hkl^{(272.6KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.83	2.04	2.690 (4)	135
N2—H2⋯O3	0.83	2.05	2.688 (4)	133
O5—H5A⋯O1ⁱ	0.84	2.54	3.306 (4)	152
O5—H5A⋯O4ⁱ	0.84	2.55	3.260 (4)	143

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors acknowledge financial support from Tianjin Municipal Education Commission (grant No. 20060503)

supplementary crystallographic information

Comment

There is an increasing interest in the design of metal complexes based on polydentate ligands(Martin & Greenwood, 1997). 2-anilinobenzoato and its derivatives with multifunctional sites can bridge metal ions in different mode allowing a large variety of structures (Melnik et al., 1998). In the copper carboxylate based complexes dinuclear tetracarboxylate paddlewheel clusters have been frequently observed (Moulton et al., 2003 and references therein). Several dimer complexes having similar structure to the title complex were reported (Facchin et al., 1998 and references therein).

The dinuclear copper complex is built up around inversion center. Each copper atom displays a trigonal-bipyramidal coordination with four oxygen atoms from the four ligands L and one axial methanol solvent. Each carboxylate groups of the ligands L link two Cu atoms building a dinuclear complex (Fig. 1) with a Cu-Cu distance of 2.5774 (10) Å , typical of tetracarboxylate paddlewheel Cu dinuclear complex(Churchill et al., 1985).

There are intramolecular N-H···O hydrogen bond whereas the H atom of the methanol is in weak bifurcated interactions with two carboxyalte O atoms of related molecule forming a chain developping parallel to the a axis (Table 1).

Experimental

The title compound was prepared by adding 10 ml of methanol solution of copper nitrate (1 mmol) to 10 ml of methanol solution of L(0.5 mmol) neutralized by sodium aeide(1 mmol). The mixture was stirred for about 2 h and filtered.The filtrate was slowly evaporated at room temperture to yield cubic black crystals of (I) suitable for X-ray analysis. Yield 30% based on copper(II).