BIS(1,10-PHENANTHROLINE)COPPER(II)-MU-CYANO-CYANO(1,10-PHENANTHROLINE)COPPER(I) THIOCYANATE DIHYDRATE

By reaction of Cu(NO3)2, NH4OH, phen (1,10-phenanthroline), KSCN and KCN in the molar ratio 1:40:2:1:1 in a water ethanol solution a new mixed-valence complex, mu-cyano-1kappaN:2kappaC-cyano-2kappaN-tris(1, 10-phenanthroline)-1kappa4N,N';2kappa2N,N'-dicopper-(I,II) thiocyanate dihydrate, [Cu2(phen)3(CN)2](SCN.2H2O, was prepared. The [Cu(II)(phen)2]2+ and [Cu(I)(phen)CN] moieties are bridged by a CN- ion giving rise to a binuclear cation with deformed trigonal-bipyramidal and deformed tetrahedral coordination for the divalent and univalent Cu atoms, respectively. SCN- anions do not enter the inner coordination sphere of the Cu atoms. Uncoordinated H2O molecules are held together by hydrogen bonds forming a four-membered ring. Two SCN- anions are bonded, also by hydrogen bonds, to this ring for-ming a central [SCN-4(H2O)-NCS]2-grouping. The latter is further attached by two other HOH...NC hydrogen bonds to the binuclear cations forming a centrosymmetric adduct of composition {[Cu2(phen)3(CN)2](NCS)(H2O)2}2. These adducts are packed by van der Waals forces in the crystal structure.