Synthesis, crystal structure and property of a novel azide-bridged one-dimensional chain copper(II) complex with a dinucleating macrocyclic polyamine

An azide-bridged polymeric cationic chain complex, [LCu2(N-3)(2)](n)(ClO4)( 2n). n(H2O)**, where L=the dinucleating macrocyclic ligand bis-p-xylylBISDI EN, has been prepared and characterized by x-ray crystallography, u.v.-vis and i.r. spectra, and by magnetic measurements. The structure consists of c ationic azide-bridged [LCu2(N-3)(2)](2+) (unit) chains, non-coordinated per chlorate anions and crystallized water molecules. The azide anion is bound to two copper atoms in neighboring units with an end-to-end bridging mode. In each unit, the copper atoms have a different coordination geometry; Cu(1 ) is a four-coordinated, distorted square-planar geometry, whereas Cu(2) is a five-coordinated, distorted square-pyramid. The electronic spectra of th e title complex differ in anhydrous and in aqueous MeCN solutions, indicati ng that dissociation and solvation occur in aqueous solutions. The characte ristic i.r. absorptions of azides and perchlorates are described. Magnetic moments vary from 2.05 (B.M.) at 300 K to 2.01 (B.M.) at 80 K, which sugges ts that very weak interactions exist between the metals.