Preparation, structures and properties of dinuclear and trinuclear copper(II) complexes bridged by one oximato and one hydroxo ligands

The dinuclear and trinuclear copper(II) complexes [Cu2(L)(OH)(ClO4)(phen)(H2O)]ClO4 · [Cu2(L)(OH)(ClO4)2(phen)(CH3OH)] (1) and [Cu3(L)2(OH)2(H2O)2](NO3)2 (2) (HL=2-[2-(α-pyridyl)ethyl]imino-3-butanone oxime and phen=1,10-phenanthroline) were prepared and their crystal structures have been determined by X-ray crystallography. Complex 1 is composed of [Cu2(L)(OH)(ClO4)(phen)(H2O)]ClO4 (1a) and [Cu2(L)(OH)(ClO4)2(phen)(CH3OH)] (1b). In 1a and 1b, one oximato of L and one hydroxo group bridge two copper(II) ions. The linear trinuclear cation [Cu3(L)2(OH)2(H2O)2]2+ in 2 is centrosymmetric, and one oximato and one hydroxo group bridge the central and terminal copper(II) ions. The strong antiferromagnetic interactions within the dinuclear and trinuclear complexes 1 and 2 have been observed (2J=∼−900 cm−1 for 1 and 2, respectively, H=−2JS1·S2).