Spectroscopic and magnetic properties of copper(II) complexes derived frompyridine-2-carbaldehyde thiosemicarbazone. Structures of [Cu(NO3)(C7H8N4S)(H2O)](NO3) and [{Cu(NCS)(C7H7N4S)}(2)]

Complexes with the formula CuX(L) (X=N-3 1, NCO 2 and NCS 3) and [Cu(NO3)(H L)(H2O)](NO3) 4, where HL=C7H8N4S, (pyridine-2-carbaldehyde thiosemicarbazo ne), have been characterised. Single-crystal X-ray diffraction studies on c ompounds 3 and 4 have been carried out. The structure of compound 4 consist s of monomeric distorted square pyramidal copper(II) species. The copper(II ) ions are coordinated to the NNS atoms from the tridentate thiosemicarbazo ne ligand and one oxygen atom of a nitrate group in the equatorial position . The oxygen atom of the water molecule occupies the apical position. The s tructure of compound 3 consists of non-centrosymmetric {Cu-2(mu-SR)(2)} ent ities in which the copper(II) ions exhibit five-coordinate square-pyramidal geometry. The thiosemicarbazone ligand and one nitrogen atom from the thio cyanate ion are in a basal position. The sulfur atom of the tridentate liga nd acts as a bridge occupying the apical position. Structural and spectrosc opic results suggest the presence of relevant a ligand-to-metal charge tran sfer and metal-to-ligand pi-backdonation character in these compounds. The ESR spectra of compounds 3 and 4 show rhombic symmetry. For complexes 1 and 2 the ESR spectra exhibit axial signals. Magnetic measurements on compound s 1, 2 and 3 show antiferromagnetic couplings. The susceptibility data were fitted by the Bleaney-Bowers' equation for copper(II) dimers. The obtained J/k values are -4.22, -6.10 and -7.33 K for compounds 1, 2 and 3, respecti vely. (C) 1999 Elsevier Science Ltd. All rights reserved.