Magnetic exchange interactions in dinuclear copper(II) and nickel(II) complexes with μ-oxalato bridges. The structure of μ-oxalato(O,O′,O″O‴)-bis{[1,8-di(2-pyridyl)-3,6- dithiaoctane-N,N′,S,S′]nickel(II)} dinitrate dihydrate

Abstract

A copper(II) and two nickel(II) dinuclear oxalato-bridged compounds of formulae [{Cu(bpdto)}2(μ-ox)](ClO4)2 (1), [{Ni(bpdto)]2(μ-ox)](ClO4)2(2), and [{Ni(bpdto)}2(μ-ox)](NO3)2·2H 2O (3), where bpdto = 1,8-bis(2-pyridyl)-3,6-dithiaoctane and ox = oxalate = C2O42- anion, have been synthesized and characterized. The crystal structure of 3 was determined by single-crystal X-ray analysis. It is a dinuclear complex with i symmetry in which the oxalate ligand is coordinated in bis(didentate) fashion to the inversion centre-related nickel atoms. The distorted octahedral environment of each nickel atom is completed by two sulphur atoms in the equatorial plane and by two pyridyl nitrogen atoms in axial positions. Magnetic susceptibility measurements over the range 5 - 299K, show antiferromagnetic interactions that are weak in 1 (J = -12.8 cm-1) and strong in 2 and 3 (J = -37.8 and -40.9 cm-1, respectively), which in the case of 3 is in keeping with the observed structural parameters.