Di-μ-acetato-κ4 O:O-bis­({N′-[(E)-phen­yl­(pyridin-2-yl-κN)methyl­idene]benzo­hydrazidato-κ2 N′,O}copper(II))

M C Vineetha; M Sithambaresan; Jinsa Mary Jacob; M R Prathapachandra Kurup

doi:10.1107/S1600536812031467

. 2012 Jul 18;68(Pt 8):m1086–m1087. doi: 10.1107/S1600536812031467

Di-μ-acetato-κ⁴ O:O-bis({N′-[(E)-phenyl(pyridin-2-yl-κN)methylidene]benzohydrazidato-κ² N′,O}copper(II))

M C Vineetha ^a, M Sithambaresan ^b,^*, Jinsa Mary Jacob ^a, M R Prathapachandra Kurup ^a

PMCID: PMC3414141 PMID: 22904748

Abstract

The binuclear molecule of the title compound, [Cu₂(C₁₉H₁₄N₃O)₂(CH₃COO)₂], resides on a crystallographic inversion centre. It has an E conformation with respect to the azomethine double bond and a Z conformation about the amide C=N bond. The Cu^II atom has a slightly distorted square-pyramidal coordination geometry. The crystal packing involves intermolecular C—H⋯O, C—H⋯N and C—H⋯π and two types of π–π interactions, with centroid–centroid distances of 3.9958 (10) and 3.7016 (13) Å.

Related literature

For the applications of benzohydrazide compounds, see: El-Sayed et al. (2011 ▶); Bakir & Brown (2002 ▶). For similar structures, see: Mangalam & Kurup (2011 ▶). For the synthesis of related compounds, see: Mangalam et al. (2010 ▶).

Experimental

Crystal data

[Cu₂(C₁₉H₁₄N₃O)₂(C₂H₃O₂)₂]
M _r = 845.85
Monoclinic,
a = 9.5758 (3) Å
b = 13.1009 (4) Å
c = 15.2124 (5) Å
β = 100.718 (1)°
V = 1875.13 (10) Å³
Z = 2
Mo Kα radiation
μ = 1.19 mm⁻¹
T = 296 K
0.35 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.706, T _max = 0.788
14426 measured reflections
3300 independent reflections
2981 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.079
S = 1.06
3300 reflections
254 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2010 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812031467/fj2577sup1.cif

e-68-m1086-sup1.cif^{(27.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812031467/fj2577Isup2.hkl

e-68-m1086-Isup2.hkl^{(161.9KB, hkl)}

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

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

Cg2, Cg3, Cg5, Cg8 and Cg9 are the centroids of the Cu1/O1/C13/N3/N2, Cu1/O3/Cu1A/O3A, Cu1/N1/C5/C6/N2, C7–C12 and C14–C19 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15⋯N3	0.93	2.43	2.752 (3)	101
C8—H8⋯O1ⁱ	0.93	2.51	3.416 (2)	166
C15—H15⋯O2ⁱ	0.93	2.37	3.116 (4)	137
C1—H1⋯Cg3	0.93	2.85	3.1701	102
C3—H3⋯Cg8ⁱⁱ	0.93	2.86	3.5543	132
C12—H12⋯Cg9ⁱⁱ	0.93	3.12	3.8426	136
C21—H21A⋯Cg5ⁱⁱⁱ	0.96	3.14	3.5809	110
C21—H21B⋯Cg2ⁱⁱⁱ	0.96	2.96	3.6761	133

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

Acknowledgments

The authors thank the Sophisticated Analytical Instument Facility, Cochin University of Science and Technology, Kochi-22, for providing single-crystal XRD data. MCV and JMJ thank the Council of Scientific and Industrial Research, New Delhi, India, for awarding a Junior Research Fellowship and Senior Research Fellowship, respectively.

supplementary crystallographic information

Comment

Derivatives of benzohydrazides and their metal complexes possess pronounced biological activities. They also have versatile binding properties and show inhibitory activity against ovine COX-2 (El-Sayed et al., 2011). Derivatives of benzohydrazides and their metal complexes have received considerable attention during the last decade because of their versatile applications in nonlinear optics and molecular sensing (Bakir & Brown, 2002).The present report is an extension of our earlier studies in this area (Mangalam & Kurup, 2011).

The compound crystallizes in monoclinic space group P2₁/n. The labeled diagrams of the asymmetric unit and the dimeric molecule are shown in Figs. 1 and 2 respectively. This molecule adopts an E configuration with respect to C6—N2 bond and it exists in enolate form with C13—O1 bond length of 1.276 (2) Å which is very close to a formal C—O bond length [1.31 Å]. The dihedral angle between pyridine and the phenyl (comprising atoms C14—C19) rings is 4.78 (11)°. O1 and N2 are in Z configuration with respect to C13—N3 bond having a torsional angle of 1.6 (3)°.

A non-conventional intermolecular hydrogen bond (Fig. 3) is present in the molecular system between the H atoms attached to the C8, C15 atoms and O1, O2 aoms of another molecule with D···A distances of 3.416 (2) and 3.116 (3) Å respectively (Table 1). Moreover, there are C–H···π interactions between the H atoms attached at the C1, C3, C12 and C21 atoms and the corresponding aromatic and metal chelate rings of the same or another molecule (Fig. 4) with the minimum distance of 3.170 (2) Å between the carbon atoms and the corresponding rings involving interactions. There are two types of π–π interactions within the dimeric molecule (T-shaped arrangement) and also between the adjacent molecules (slipped arrangement) with the centroid-centroid distances of 3.9958 (10) and 3.7016 (13) Å respectively between the rings involving interactions as shown in Fig. 5.

Packing of molecules (Fig. 6) is predominantly favored by two types of non-classical intermolecular hydrogen bonding and C–H···π interactions involving the H atoms from C3 and C12 atoms and a π–π interaction between the adjacent molecules in slipped arrangement.

Experimental

The title complex was prepared by adapting a reported procedure (Mangalam et al., 2010) by refluxing a mixture of methanolic solutions of N'-[(E)-phenyl(pyridin-2-yl)methylidene]benzohydrazide (0.301 g, 1 mmol) and Cu(OAc)₂.H₂O (0.199 g, 1 mmol) for three hours. After two days, green colored crystals were collected, washed with few drops of methanol and dried over P₄O₁₀in vacuo. Single crystals of the title complex suitable for X-ray analysis were obtained after two days from the mother liquor by slow evaporation.