(Benzoato-κ2 O,O′)(quinoline-2-carboxyl­ato-κ2 N,O)(quinoline-2-carboxylic acid-κ2 N,O)copper(II)

Nuno D Martins; Manuela Ramos Silva; Joana A Silva; Ana Matos Beja; Abilio J FN Sobral

doi:10.1107/S1600536808014268

. 2008 May 21;64(Pt 6):m829–m830. doi: 10.1107/S1600536808014268

(Benzoato-κ² O,O′)(quinoline-2-carboxylato-κ² N,O)(quinoline-2-carboxylic acid-κ² N,O)copper(II)

Nuno D Martins ^a, Manuela Ramos Silva ^a,^*, Joana A Silva ^b, Ana Matos Beja ^a, Abilio J FN Sobral ^b

PMCID: PMC2961369 PMID: 21202511

Abstract

The crystal structure of the title compound, [Cu(C₁₀H₆NO₂)(C₇H₅O₂)(C₁₀H₇NO₂)], contains copper(II) ions five-coordinated in a distorted trigonal-bipyramidal environment. The equatorial plane is occupied by three O atoms, one from the carboxylate group of the benzoate ion considered as occupying a single coordination site, the other two from two carboxylate groups of the quinaldic acid and quinaldate ligands. The axial positions are occupied by the N atoms of the quinoline ring system. The metal ion lies on a twofold axis that bisects the benzoate ion. The quinaldate and quinaldic acid ligands are equivalent by symmetry, and the carboxylate/carboxyl groups are disordered. The disordered H atom is shared between the carboxylate groups of adjacent quinaldic acid molecules. Such hydrogen bonds delineate zigzag chains that run along the c axis. The structure is very similar to that of the Mn^II analog.

Related literature

For related literature, see: Zurowska et al. (2007 ▶); Dobrzynska et al. (2005 ▶); Kumar & Gandotra (1980 ▶); Catterick et al. (1974 ▶); Martins et al. (2008 ▶).

Experimental

Crystal data

[Cu(C₁₀H₆NO₂)(C₇H₅O₂)(C₁₀H₇NO₂)]
M _r = 529.97
Monoclinic,
a = 19.1140 (9) Å
b = 11.4665 (5) Å
c = 12.1885 (8) Å
β = 118.788 (1)°
V = 2341.2 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.98 mm⁻¹
T = 293 (2) K
0.26 × 0.22 × 0.20 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ▶) T _min = 0.75, T _max = 0.82
27106 measured reflections
2928 independent reflections
2536 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.104
S = 1.06
2928 reflections
178 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808014268/bt2705sup1.cif

e-64-0m829-sup1.cif^{(21.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808014268/bt2705Isup2.hkl

e-64-0m829-Isup2.hkl^{(143.8KB, 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
O3—H1⋯O4ⁱ	0.82	1.76	2.560 (3)	165

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by Fundação para a Ciência e a Tecnologia (FCT) under project POCI/FIS/57876/2004.

supplementary crystallographic information

Comment

Some compounds with quinoline derivatives, transition metal ions and halide ions exhibit interesting magnetic properties related with the formation of low dimensional elements (Zurowska et al., 2007; Dobrzynska et al., 2005; Kumar & Gandotra, 1980; Catterick et al., 1974). The crystal structure of the title compound, I, Cu (C₇H₅O₂) (C₁₀H₇NO₂)(C₁₀H₆NO₂), consists of copper(II) ions five-coordinated in a distorted trigonal-bipyramidal environment (Fig. 1). The equatorial plane is occupied by three oxygen atoms with Cu—O distances of 1.970 (3) and 2.0553 (16) Å. One equatorial O atom belongs to the carboxylate group of the benzoate ion and each of the two quinoline molecules supply another O atom to the Cu coordination environment. The axial positions are occupied by the nitrogen atoms of the quinoline ring system, with distance 2.0424 (16) Å. There is a two fold axis running through the metal positions and almost longitudinally through the benzoate ion, that is thus disordered over two positions. The non-coordinating benzoate O atom is situated at a 2.678 (3)Å distance from the metal ion. With the exception of above mentioned benzoate disorder, the title compound shows a very similar arrangement to that of the Mn(II) analog (Martins et al., 2008). The complexes are joined together by hydrogen bonds between the carboxylate/carboxyl groups of adjacent quinaldate/quinaldic acid molecules, forming zigzag chains that run along the c axis (Fig. 2). The shared hydrogen atom is disordered and the quinoline molecules are statistically neutral or negatively charged.

Experimental

Approximately 0.12 mmol of 2-quinolinecarboxaldehyde (Sigma, 97%) was added to 0.12 mmol of copper chloride in an 10 ml dimethylformamide/benzoic acid solution. After a few weeks, single crystals of suitable quality were grown from the solution. The refined structure shows that the crystals incorporated a different quinoline derivative than that expected showing the material purchased from Sigma was contaminated.