Abstract

A tetra-nuclear ZnII complex, [Zn4(C13H11N6O)2Cl6(H2O)2] or {[Zn2(HL)(H2O)(Cl2)](μCl)2[Zn2(HL)(H2O)(Cl)]}2, was synthesized by mixing an equimolar amount of a methanol solution containing ZnCl2 and a methanol solution containing the ligand H2 L [1,5-bis-(pyridin-2-yl-methyl-ene)carbono-hydrazide]. In the tetra-nuclear complex, each of the two ligand mol-ecules forms a dinuclear unit that is connected to another dinuclear unit by two bridging chloride anions. In each dinuclear unit, one ZnII cation is penta-coordinated in a N2OCl2 in a distorted square-pyramidal geometry, while the other ZnII cation is hexa-coordinated in a N3OCl2 environment with a distorted octa-hedral geometry. The basal plane around the penta-coordinated ZnII cation is formed by one chloride anion, one oxygen atom, one imino nitro-gen atom and one pyridine nitro-gen atom with the apical position occupied by a chloride anion. The basal plane of the hexa-coordinated ZnII cation is formed by one chloride anion, one hydrazinyl nitro-gen atom, one imino nitro-gen atom and one pyridine nitro-gen atom with the apical positions occupied by a water oxygen atom and a bridged chloro anion from another dinuclear unit, leading to a tetra-nuclear complex. A series of intra-molecular C-H⋯Cl hydrogen bonds is observed in each tetra-nuclear unit. In the crystal, the tetra-nuclear units are connected by inter-molecular C-H⋯Cl, C-H⋯O and N-H⋯O hydrogen bonds, forming a planar two-dimensional structure in the ac plane.

Highlights

  • Thierno Moussa Seck,a Papa Aly Gaye,b* Cheikh Ndoye,a Ibrahima Elhadji Thiam,a Ousmane Diouf,a Pascal Retailleauc and Mohamed Gayea

  • Each of the two ligand molecules forms a dinuclear unit that is connected to another dinuclear unit by two bridging chloride anions

  • One ZnII cation is pentacoordinated in a N2OCl2 in a distorted square-pyramidal geometry, while the other ZnII cation is hexacoordinated in a N3OCl2 environment with a distorted octahedral geometry

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Summary

Chemical context

Symmetrical dicarbonohydrazide Schiff bases possess two cavitiess, which make them versatile. The presence of an amidic bond in these molecules leads to the keto-enol tautomer, which can act in neutral or deprotonated forms These compounds can adopt two different configurations, e.g. S-cis or S-trans, yielding different structures with the same metal cation. In these complexes, -O and -N,N atoms bridge the metal ions, which display N4O2 or N5O octahedral environments (Shuvaev et al, 2010). Symmetrical dicarbonohydrazide ligands, we have synthesized and characterized a new tetranuclear zinc(II) complex formulated as {[Zn2(HL)(H2O)(Cl2)](Cl)2[Zn2(HL)(H2O)(Cl)]}2 where H2L is 1,5-bis(pyridin-2-ylmethylene)carbonohydrazide

Structural commentary
Supramolecular features
Database survey
Synthesis and crystallization
Refinement
Full Text
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