Structure of a mixed‐valence copper complex with 1,10‐phenanthroline and pseudohalogenide ligands

The reaction of Cu(NO 3 ) 2 , NH 4 OH, 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, μ-cyano-1κN:2κC-(seleno,thio)cyanato-2κN-tris(1,10-phenanthroline)-1κ 4 N,N';2κ 2 N,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 .5C 2 H 5 OH. 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