Bis{(E)-4-chloro-2-[(2-chloro-3-pyrid­yl)imino­methyl-κN]phenolato-κO}copper(II)

Yu-Jie Ding; Jun-Feng Tong; Wen-Kui Dong; Yin-Xia Sun; Jian Yao

doi:10.1107/S1600536809029651

. 2009 Jul 31;65(Pt 8):m1013. doi: 10.1107/S1600536809029651

Bis{(E)-4-chloro-2-[(2-chloro-3-pyridyl)iminomethyl-κN]phenolato-κO}copper(II)

Yu-Jie Ding ^a, Jun-Feng Tong ^b, Wen-Kui Dong ^b,^*, Yin-Xia Sun ^b, Jian Yao ^b

PMCID: PMC2977127 PMID: 21583310

Abstract

In the title complex, [Cu(C₁₂H₇Cl₂N₂O)₂], the Cu^II center is tetracoordinated by two phenolic O and two azomethine N atoms from two bidentate 4-chloro-2-[(2-chloro-3-pyridyl)iminomethyl]phenolate (L) ligands. In the crystal structure, the Cu^II atom has a distorted square-planar coordination environment. The dihedral angles between the benzene and pyridyl rings are 54.39 (3) and 80.14 (4)°, indicating that the pyridine ring has a considerably weaker steric hindrance. The packing of the molecule is controlled by C—H⋯π(Ph) interactions and short O⋯Cl interactions [3.196 (4) Å], linking the molecules into a chain-like structure along the c axis.

Related literature

For background to Schiff bases, see: Soliman & Mohamed (2004 ▶); Abd El-Wahab et al. (2004 ▶). For the synthesis, see: Dong et al. (2009d ▶). For related structures, see: Dong et al. (2009a ▶,b ▶,c ▶).

Experimental

Crystal data

[Cu(C₁₂H₇Cl₂N₂O)₂]
M _r = 595.73
Monoclinic,
a = 20.236 (2) Å
b = 11.4821 (14) Å
c = 10.5458 (9) Å
β = 90.132 (2)°
V = 2450.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 1.36 mm⁻¹
T = 298 K
0.40 × 0.14 × 0.09 mm

Data collection

Buker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.613, T _max = 0.888
12294 measured reflections
4320 independent reflections
2614 reflections with I > 2σ(I)
R _int = 0.058

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.065
S = 1.02
4320 reflections
316 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); 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.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809029651/at2850sup1.cif

e-65-m1013-sup1.cif^{(23.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809029651/at2850Isup2.hkl

e-65-m1013-Isup2.hkl^{(211.7KB, 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
C22—H22⋯Cg1ⁱ	0.93	2.89	3.753 (3)	155

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Symmetry code: (i) Inline graphic . Cg1 is the centroid of the C2–C7 ring.

Acknowledgments

This work was supported by the Foundation of the Education Department of Gansu Province (No. 0904-11) and the ‘Jing Lan’ Talent Engineering Funds of Lanzhou Jiaotong University, which are gratefully acknowledged.

supplementary crystallographic information

Comment

Schiff bases are a versatile class of ligands in the field of modern coordination chemistry (Soliman & Mohamed, 2004), which can coordinate to transition or rare earth ions yielding complexes with interesting properties that are useful in materials science and in biological systems (Abd El-Wahab et al., 2004). As an extension of our work on the complexes between transition metals and Schiff base ligands (Dong et al., 2009a; Dong et al., 2009b), we report here the synthesis and crystal structures of the title complex, bis{(E)-[4-chloro-2-((2-chloropyridin-3-ylimino)methyl-κN)] phenolato-κO¹}copper(II) (Fig. 1).

In asymmetric molecule unit of the title complex, the Cu^II center is tetracoordinated by two phenolic O and two azomethine N atoms from two ligand (L^-) units and has a distorted square-planar coordination environment, which is similar to the reported copper complex with (E)-[4-bromo-2-((2-chloropyridin-3-ylimino)methyl)]phenol (Dong et al., 2009c). The interplane dihedral angles are found to be as follows: 54.39 (3)° between the benzene ring (C2—C7) and pyridyl ring (N2/C8—C12), 80.14 (4)° between benzene ring (C14—C19) and pyridyl ring (N4/C20—C24), indicating the pyridine ring having a considerable weaker steric hindrance. Besides, the dihedral angle between the coordination plane of O1—Cu1—N1 and O2—Cu1—N3 is 27.96 (3)°, indicating slight distortion toward tetrahedral geometry from the square planar structure. The packing of the molecule is controlled by C—H···π(Ph) interactions and short O···Cl interactions linking molecules into infinite one-dimensional supramolecular structure along c axis (Fig. 2).

Experimental

(E)-[4-Chloro-2-((2-chloropyridin-3-ylimino)methyl)]phenol (HL) was prepared according to previously reported procedure (Dong et al., 2009d). A blue solution of copper(II) acetate monohydrate (4.2 mg, 0.021 mmol) in ethanol (2 ml) was added dropwise to a pale-yellow solution of HL (11.2 mg, 0.042 mmol) in ethanol (4 ml) at room temperature. The colour of the mixing solution turned to brown immediately, then allowed to stand at room temperature for several days. With evaporation of the solvent, brown needle-like single crystals suitable for X-ray crystallographic analysis were obtained. IR: ν C=N, 1610 cm^-1, ν Ar—O, 1236 cm^-1, ν Cu—N, 459 cm^-1 and ν Cu—O, 426 cm^-1.