Bis[3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato-κ3 O,N,N′]copper(II) tetra­hydrate

Kai Zhao; Xian-Hong Yin; Fei-Long Hu; Cui-Wu Lin; Shang-Shang Zhang; Ru-Wen Qing

doi:10.1107/S1600536807068110

. 2008 Jan 4;64(Pt 2):m284–m285. doi: 10.1107/S1600536807068110

Bis[3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato-κ³ O,N,N′]copper(II) tetrahydrate

Kai Zhao ^a,^b, Xian-Hong Yin ^a,^*, Fei-Long Hu ^a, Cui-Wu Lin ^b, Shang-Shang Zhang ^a, Ru-Wen Qing ^a

PMCID: PMC2960233 PMID: 21201264

Abstract

In the title complex, [Cu(C₁₁H₉ClN₃O₂)₂]·4H₂O, the Cu^II atom is in a distorted octahedral coordination environment, coordinated by four N atoms and two O atoms from two tridentate 3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinate ligands. The molecules are linked via intermolecular O—H⋯O hydrogen bonds involving water molecules to form extended chains along [010], and there are short Cl⋯Cl contacts [3.153 (4) Å].

Related literature

For related literature, see: Aliev et al. (1988 ▶); Bhatia et al. (1981 ▶); Costamagna et al. (1992 ▶); Kai et al. (2007 ▶); Kuang et al. (1997 ▶); Ramazani et al. (2002 ▶); Xu et al. (2001 ▶); Yaghi & Li (1996 ▶); Yin et al. (2007 ▶); Zhao et al. (2007 ▶).

Experimental

Crystal data

[Cu(C₁₁H₉ClN₃O₂)₂]·4H₂O
M _r = 636.93
Triclinic,
a = 9.6578 (9) Å
b = 11.2637 (14) Å
c = 14.3127 (18) Å
α = 92.349 (2)°
β = 106.090 (2)°
γ = 114.065 (3)°
V = 1344.7 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.07 mm⁻¹
T = 298 (2) K
0.59 × 0.52 × 0.50 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.571, T _max = 0.617 (expected range = 0.543–0.586)
7014 measured reflections
4664 independent reflections
3789 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.101
S = 1.03
4664 reflections
352 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a ▶); molecular graphics: SHELXTL (Sheldrick, 1997b ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807068110/rn2033sup1.cif

e-64-0m284-sup1.cif^{(27.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807068110/rn2033Isup2.hkl

e-64-0m284-Isup2.hkl^{(228.4KB, 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
O5—H5A⋯O6	0.85	1.96	2.804 (4)	170
O5—H5B⋯O4ⁱ	0.85	1.98	2.818 (4)	170
O6—H6A⋯O2	0.85	2.24	3.090 (5)	176
O6—H6B⋯O7ⁱⁱ	0.85	1.85	2.697 (4)	176
O8—H8A⋯O5	0.85	2.10	2.947 (5)	178
O8—H8B⋯O5ⁱⁱⁱ	0.85	1.98	2.825 (5)	179

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The authors thank the National Natural Science Foundation of China (grant No. 20761002). This research was sponsored by the Talent Highland research program of Guangxi University (grant No. 205121), the Science Foundation of the State Ethnic Affairs Commission (grant No. 07GX05), the Development Foundation Guangxi Research Institute of Chemical Industry, and the Science Foundation of Guangxi University for Nationalities (grant Nos. 0409032, 0409012 and 0509ZD047).

supplementary crystallographic information

Comment

Transition metal compounds containing pyrazolyl pyridine ligands have been of great interest for many years (Kuang et al., 1997; Ramazani et al., 2002). These compounds play an important role in the development of coordination chemistry related to catalysis and enzymatic reactions, magnetism and molecular architectures (Costamagna et al., 1992; Bhatia et al., 1981). Inorganic supramolecular chemistry, and in particular the construction of polymeric coordination networks, is an extremely topical area of research (Xu et al.., 2001; Yaghi et al.., 1996) and the construction of a wide variety of network topologies has been achieved through ligand design and the use of different counter-anions. Our work is aimed at obtaining multidimensional metal complexes. On the basis of the above-mentioned considerations, we designed and synthesized the flexible tridentate ligand 3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinic acid (CDPA) (Kai et al., 2007), which offers advantages over rigid ligands in that it can adopt a different coordination modes according to the geometric needs of the coordination environment of the transition metal. Recently we reported the crystal structures of bis(6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato)zinc(II)trihydrate (Yin et al., 2007). As a continuation of these investigations, we report in this paper the crystal structure of bis(6-(3-chloro-(3,5-dimethyl-1H-pyrazol-1-yl))picolinato) copper(II)tetra-hydrate, (I), Fig. 1.

The title complex, (I), is an asymmetric electronically neutral mononuclear compound with four uncoordinated water molecules (Fig. 1). The Cu^II atom is coordinated by four N atoms and two O atoms from two tridentate, 6-(3-chloro-(3,5-dimethyl-1H-pyrazol- 1-yl))picolinic acid (CDPA) ligands, respectively. that define a distorted octahedral environment for the copper atom. The Cu—O bond length is 2.073 (2)and 2.176 (2) Å, The Cu—N distances range from 1.969 (2) to 2.214 (2) Å, the C5—C6 and C9—C10 bond lengths are 1.388 (4) and 1.398 (5) Å; they are longer than the normal C=C bond length (1.38 Å) because they participate in the C—N conjugated system. There are many stacking interactions involving the CDPA ligand forming a supramolecular structure.

In the crystal structure, all oxygen atoms, except O1 and O3, bound to the metal center, contribute to the formation of intermolecular hydrogen bonds involving the solvate water molecules (Zhao et al., 2007), and there are short Cl···Cl contacts (Cl2—Cl2= 3.153 Å), their distances are much shorter than the van der Waal distance(Aliev et al., 1988). (Fig.2. for symmetry codes see Table 2). A great number of H-bonds and short Cl···Cl contacts join the complex to form a three-dimensional supramolecular network structure along b axis.

Experimental

6-(3-chloro-(3,5-dimethyl-1H-pyrazol-1-yl))picolinic acid, and CuSO₄. 6H₂O were available commercially and were used without further purification. Equimolar 6-(3-chloro-(3,5-dimethyl-1H-pyrazol-1-yl))picolinic acid (1 mmol, 217 mg) was dissolved in anhydrous alcohol (15 ml). The mixture was stirred to give a clear solution, To this solution was added CuSO₄.6H₂O (0.5 mmol, 119 mg) in anhydrous alcohol (10 ml). After keeping the resulting solution in air to evaporate about half of the solvents, blue blocks of the title compound were formed. The crystals were isolated, washed with alcohol three times and dried in a vacuum desiccator using silica gel (Yield 72%). Elemental analysis: found: C, 53.708; H, 4.20; N, 17.04;; calc. for C₂₂H₂0_CuCl_N6_O4: C, 53.78; H, 4.10; N, 17.10.