STRUCTURE OF A MIXED-VALENCE COPPER COMPLEX WITH 1,10-PHENANTHROLINE AND PSEUDOHALOGENIDE LIGANDS

The reaction of Cu(NO3)2, NH4OH, 1,10-phenanthroline (phen), KSCN and KSeCN in the molar ratio 1:10:2:2:2 in a water-ethanol solution gives a new mixed-valence compound, mu-cyano-1 kappaN:2kappaC-(seleno,thio)cyanato-2kappaN-tris(1, 10-phenanthroline)-1kappa4N,N';2kappa2N,N'-dicopper(I,II) (seleno,thio)-cyanate semiethanolate, for which the X-ray structure analysis reveals the composition [Cu(II)-Cu(I)(phen)3(CN)(SeCN)0.65(SCN)0.35]+(SeCN)0.45--(SCN)0.55.0.5C2H5OH. The [Cu(II)(phen)2]2+ and [Cu(I)(phen){(Se,S)CN}] moieties are bridged by CN-, giving rise to a binuclear cation with deformed trigonal-bipyramidal and deformed tetrahedral coordination for the bivalent and monovalent Cu atoms, respectively.