Coexistence of five different copper(II)-phenanthroline species in the crystal packing of inorganic-metalorganic hybrids based on Keggin polyoxometalates and copper(II)-phenanthroline-oxalate complexes

Reaction of in situ generated copper(II)-monosubstituted Keggin polyoxometalates and copper(II)-phenanthroline-oxalato complexes in ammonium or rubidium acetate buffers led to the formation of the hybrid inorganic-metalorganic compounds E4Cu(phen)(H2O)4]2Cu4(phen)4(H2O)4(ox)3]0.6Cu2(phen)2(H2O)4(ox)]0.4Cu(phen)(ox)]0.8{SiW11O39Cu(H2O)}2{Cu2(phen)2(ox)}].20H2O E: Rb (1), NH4 (2)]. The two compounds have been characterized by means of elemental analysis, thermogravimetry, infrared and electron paramagnetic resonance spectroscopies, and magnetic susceptibility measurements, and their structures have been established by single-crystal X-ray diffraction. Both compounds are isostructural, and they contain a discrete bimolecular hybrid polyanion and several types of copper-phenanthroline complexes of variable nuclearity. The main structural features of these compounds are the presence of the new hybrid POM {SiW11O39Cu(H2O)}2{Cu2(phen)2(mu-ox)}]10-, where the dinuclear copper-oxalato complex is sandwiched by two copper-monosubstituted POMs, and the coexistence of five different copper-phenanthroline species with nuclearities ranging from one to four.