Asymmetric chlorine-bridged zig-zag Cu(II) chains linked together in 2D sheets by strong Watson-Crick type intermolecular double hydrogen bonds of bis(pyrimidin-2-yl)amine ligands: synthesis, structure and antiferromagnetism

摘要

A novel polymeric, asymmetric chloro-bridged copper chain with general formula [mu-Cl-CuCl(dipm](n) (in which dipm = bis(pyrimidin-2-yl)amine) has been synthesized and characterised by X-ray crystallography and infrared spectroscopy. The chains are organized in 2D sheets by intermolecular double H bonds between pairs of dipm molecules. In addition, EPR and magnetic measurements have been performed, and these have been related to the dinuclear structural details.The geometry around the copper(II) ion is distorted square pyramidal with the basal plane formed by the two nitrogen atoms of the dipm ligand and two chloride atoms, one of which is bridging. The Cu-N distances are 2.0342(15) and 2.0125(15) Angstrom and Cu-Cl distances are 2.2899(6) and 2.2658(6) Angstrom. The apical position of Cu is occupied by a chloride atom of a neighbouring unit atom at a distance of 2.6520(6) Angstrom, resulting in the polynuclear array in which one chloride anion and the copper ion forms a zig-zag chain. The magnetic interaction between the Cu-Cu atoms is weak antiferromagnetic with a singlet-triplet separation (J) of -3.2(1) cm(-1). (C) 2004 Elsevier B.V. All rights reserved.