Synthesis, spectroscopic characterization, X-ray crystal structure and magnetic properties of oxalato-bridged copper(II) dinuclear complexes with di-2-pyridylamine

Abstract

The syntheses and characterization of a series of dinuclear μ-oxalato copper(II) complexes of the general type [(NN)1or2Cu(C2O4)Cu(NN)1or2]2+, where NN=didentate dpyam (di-2-pyridylamine) ligand, are described. The crystal structures of three representative complexes have been determined. The dinuclear-oxalate bridged compounds [Cu(dpyam)4(C2O4)](ClO4)2(H2O)3(1) and [Cu2(dpyam)4(C2O4)](BF4)2(H2O)3(2) crystallize in the non-centrosymmetric triclinic space group P1 which are isomorphous and isostructural. The compound [Cu2(dpyam)2(C2O4)(NO3)2((CH3)2SO)2] (3) crystallizes in the centrosymmetric monoclinic space group P1 with all Cu-oxalate contacts in the equatorial plane. All three complexes contain six-coordinate copper centres bridged by planar bis-didentate oxalate groups from the equatorial position of one chromophore to the equatorial position of the other one. Both chromophores in 1 and 2 exhibit the compressed octahedral Cu(II) geometry, while 3 displays an elongated octahedral Cu(II) environment. The IR, ligand field and EPR measurements are in agreement with the structures found. The magnetic susceptibility measurements, measured from 5 to 280 K, revealed a very weak ferromagnetic interaction between the Cu(II) atoms for compound 1 and 2, with a singlet-triplet energy gap (J) of 2.42 and 3.38 cm-1, for compounds 1 and 2, respectively. Compound 3 has a strong antiferromagnetic interaction with a J of -305.1 cm-1, in agreement with coplanarity of the magnetic orbitals. © 2003 Elsevier B.V. All rights reserved.