A dinuclear zinc complex with (E)-4-dimethyl­amino-N′-(2-hy­droxy­benzyl­idene)benzohydrazide

Jie Ma; Wei-Zhen Fan; Li-Rong Lin

doi:10.1107/S1600536811014462

. 2011 Apr 22;67(Pt 5):m624–m625. doi: 10.1107/S1600536811014462

A dinuclear zinc complex with (E)-4-dimethylamino-N′-(2-hydroxybenzylidene)benzohydrazide

Jie Ma ^a, Wei-Zhen Fan ^a, Li-Rong Lin ^a,^*

PMCID: PMC3089200 PMID: 21754335

Abstract

The title compound, bis[μ-(E)-2-({2-[4-(dimethylamino)benzoyl]hydrazinylidene}methyl)phenolato]bis[formatozinc], [Zn₂(C₁₆H₁₆N₃O₂)₂(CHO₂)₂], is a dinuclear Zn^II complex containing two Zn^II cations, two monovalent anions of a Schiff base ligand, 4-dimethylamino-N′-(2-hydroxybenzylidene)benzohydrazide (L), and two formate ions. Each Zn^II atom chelates with the hydroxy O atom of salicylaldehyde, the imine N atom, the carbonyl O atom, the formate carboxylate O atom and the hydroxy O atom of the salicylaldehyde moiety in a symmetry-related unit. The five-coordinate Zn^II atoms form a dimeric centrosymmetric unit with a central parallelepiped Zn₂O₂ core and parallel faces derived from the Schiff base ligands. The crystal packing is stabilized by intermolecular N—H⋯O hydrogen bonds between the amide N atom and the formate carboxylate O atom.

Related literature

For details of Zn complexes and related applications, see: Shamsipur et al. (2001 ▶); Cametti et al. (2008 ▶); Winter et al. (2009 ▶); Shi et al. (2009 ▶); Rai et al. (2009 ▶). For potential applications in luminescence materials, see: Erxleben (2001 ▶). For recent advances in biosensory and medicinal therapeutic applications of Zn^II complexes, see: Drewry & Gunning (2011 ▶). For other applications of Schiff base–zinc complexes, see: Costamagna et al. (1992 ▶); Sunatsuki et al. (2002 ▶); Jiang et al. (2010 ▶); Li et al. (2010 ▶). For details of the synthesis of the Schiff base ligand, see: Pouralimardan et al. (2007 ▶). For related literature on zinc complex applications, see: Consiglio et al. (2010 ▶); Kwok et al. (2004 ▶).

Experimental

Crystal data

[Zn₂(C₁₆H₁₆N₃O₂)₂(CHO₂)₂]
M _r = 785.41
Monoclinic,
a = 14.556 (3) Å
b = 6.7607 (14) Å
c = 17.085 (3) Å
β = 101.63 (3)°
V = 1646.8 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.52 mm⁻¹
T = 173 K
0.10 × 0.10 × 0.08 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.863, T _max = 0.888
13433 measured reflections
3213 independent reflections
2679 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.077
S = 1.07
3213 reflections
228 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 2004 ▶); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; 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: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811014462/jj2088sup1.cif

e-67-0m624-sup1.cif^{(24.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811014462/jj2088Isup2.hkl

e-67-0m624-Isup2.hkl^{(157.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811014462/jj2088Isup3.cdx

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
N2—H8⋯O3ⁱ	0.88	2.00	2.838 (2)	158

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported financially by the Natural Science Foundation of Fujian Province (grant Nos. 2009S0063 and 2010J01048).

supplementary crystallographic information

Comment

Zinc(II) Schiff base compounds, which are thermally stable, structurally diverse and easily modified, have attracted great interest due to their potential applications in luminescence materials (Andrea, 2001), biosensory and medicinal therapeutic (Drewry & Gunning, 2011). As part of our ongoing work in the biosensory area, the title Zn-Schiff base complex was synthesized by solvothermal methods and the crystal structure is herein reported. The title molecule consists of two subparallel, tridentate Schiff base ligands, two five coodinate zinc cations and two formyl groups (from the decomposion of dimethylformamide (DMF)). The center plane assumes a parallelogram geometry which is comprised of the alternate atoms of Zn and O atoms (Fig. 1). Crystal packing is stabilized by weak N—H···O intermolecular hydrogen bonds between the amide nitrogen atom and the formate carboxyl oxygen atom (Table 1).

Experimental

A mixture of ethyl-4-(dimethylamino) benzoate(10 mmol) and hydrazinium hydroxide (50%, 70ml) was stirred at 120 °C for 3h and then filtered. The resulting white residues were recrystallization by ethanol. Then, 2-hydroxybenzaldehyde (2 mmol) was added to the solution of the above powder (2 mmol) in 50 ml ethanol and refluxed for 3h to obtain the crude product. The crude product was purified by recrystallization with the ethanol and dichloromethane mixed solvent(v/v=2:1) to give white solid Schiff base ligand (N-(2-hydroxybenzylidene)-4-(dimethylamino)benzohydrazide, HL) with 85% yield. A DMF solution containing HL (0.2 mmol) and Zn(ClO₄)₂^.6H₂O (0.1 mmol) was stirred at room temperature for 5h and then was sealed in a 20 ml Teflon-lined stainless-steel autoclave, which was heated to 110^o and kept at this temperature for 35h. Yellow block crystals were obtained after the reactor was cooled to room temperature in about 40h.