Bis[4-(4-chloro­benzo­yl)-3-methyl-1-phenyl-1H-pyrazol-5-olato-κ2 O,O′]bis­(methanol-κO)nickel(II)

Xin Zhang; Meng Huang; Cong Du; Junjing Han

doi:10.1107/S1600536810038973

. 2010 Oct 9;66(Pt 11):m1361. doi: 10.1107/S1600536810038973

Bis[4-(4-chlorobenzoyl)-3-methyl-1-phenyl-1H-pyrazol-5-olato-κ² O,O′]bis(methanol-κO)nickel(II)

Xin Zhang ^a,^*, Meng Huang ^a, Cong Du ^a, Junjing Han ^a

PMCID: PMC3008993 PMID: 21588804

Abstract

The molecular structure of the neutral mononuclear title complex, [Ni(C₁₇H₁₂ClN₂O₂)₂(CH₃OH)₂], is centrosymmetric. The Ni^II atom, which is located on an inversion center, is in a distorted octahedral coordination, defined by four O atoms from two ligands as well as two O atoms from two methanol molecules. Intermolecular O—H⋯N hydrogen bonds between the hydroxy group of methanol and a pyrazole N atom link the molecules, forming a two-dimensional network parallel to (100).

Related literature

For general background to Schiff base compounds in coordination chemistry, see: Harrop et al. (2003 ▶); Yu et al. (1993 ▶); Wu et al. (1993 ▶). For the antibacterial properties of Schiff bases derived from 4-acyl-5-pyrazolones and their metal complexes, see: Li et al. (1997 ▶, 2004 ▶).

Experimental

Crystal data

[Ni(C₁₇H₁₂ClN₂O₂)₂(CH₄O)₂]
M _r = 746.27
Monoclinic,
a = 11.8398 (7) Å
b = 12.3162 (7) Å
c = 13.2104 (8) Å
β = 114.706 (1)°
V = 1750.03 (18) Å³
Z = 2
Mo Kα radiation
μ = 0.76 mm⁻¹
T = 296 K
0.24 × 0.22 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T _min = 0.834, T _max = 0.872
8808 measured reflections
3089 independent reflections
2534 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.094
S = 1.03
3089 reflections
225 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: SMART (Bruker, 1999 ▶); cell refinement: SAINT (Bruker, 1999 ▶); 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 I, global. DOI: 10.1107/S1600536810038973/bh2312sup1.cif

e-66-m1361-sup1.cif^{(19.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810038973/bh2312Isup2.hkl

e-66-m1361-Isup2.hkl^{(151.6KB, 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
O3—H3A⋯N2ⁱ	0.85	2.00	2.795 (2)	156

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the National Natural Science Foundation of China (No. 20771083).

supplementary crystallographic information

Comment

In recent years, Schiff base complexes with metals have generated a wide interest because they possess a large spectrum of biological, pharmaceutical and catalytic properties, such as antitumor and antioxidative activities, as well as the inhibition of lipid peroxidation, among others (Harrop et al., 2003; Yu et al., 1993; Wu et al., 1993). The Schiff bases derived from 4-acyl-5-pyrazolones and their metal complexes have also been widely studied for their high antibacterial activity (Li et al., 1997, 2004). In this paper, we report the synthesis and crystal structure of the title compound, (I), containing a β-ketoamine ligand with organic chlorine, based on a pyrazolone derivative.

The molecular structure of (I) reveals a neutral centrosymmetric mononuclear complex, with the asymmetric unit comprising a half molecule (Fig. 1). The distorted octahedral Ni^II center, which locates on a crystallographic inversion center, is coordinated to four O donors from a couple of ligands, and two O atoms from two methanol molecules. The equatorial Ni—O bond lengths are comparable with an average value of 2.0345 (6) Å, which are significantly shorter than that of the axial Ni—O distance of 2.0651 (16) Å. The cis bond angles around the Ni^II center range from 88.47 (7) to 91.53 (7)°. Intermolecular hydrogen bonds (Table 1) link the molecules together, forming a two-dimensional network (Fig. 2).

Experimental

A mixture of Ni(OAc)₂.4H₂O (24.8 mg, 0.10 mmol), 4(Z)-4-((4-chlorophenyl)(hydroxy)methylene)-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one (62.6 mg, 0.20 mmol) and methanol (12 ml) was heated at 433 K for 2 days in a sealed Teflon-lined stainless steel vessel (20 mL) under autogenous pressure. After the reaction system was slowly cooled down to the room temperature, it was placed to stand at room temperature for a period of four weeks, affording green block crystals in 60% yield.