Reaction of the binucleating ligand 6,6'-bis(5'-amino-3, '4'-benzo-2'-thiapentyl)-1, 11-diamino-2, 3:9,10-dibenzo-4, 8-dithiaundecane (H-4 L) with copper(II) salts in dried methanol (MeOH) results in the isolation of the mixtures of copper(I) and (II) complexes with Cl- and ClO4- counterions. The major products were the copper(I) complexes obtained pure after recrystallization from DMSO-MeOH. The ligands lose four protons from the amine functions to form copper(I) complexes of the general formula (Cu2L)X(2), where X = Cl-, ClO4-. The complexes were oxidized to (Cu-2,L)X(4) with hydrogen peroxide in DMF. Cu(NO3)(2), on the other hand, gave [Cu-2(H-4 L) (NO3)(2)](NO3)(2). The structure consists of two copper(I) and copper(II) atoms, each of which is coordinated through two thioether and two primary amine atoms. The two copper sites are linked through a saturated spiro carbon atom. The copper complexes were characterized by elemental analyses, molar conductivities, magnetic moments, and spectra (UV-Vis, IR). (C) 1997 Elsevier Science Inc.