Structural variability of copper-1,10-phenanthroline–oxovanadate hybrid inorganic–organic compounds

Reactions in the CuSO4–phen–KVO3–H2O–(KOH) systems under non-hydrothermal conditions yielded seven new compounds: [Cu2(H2O)2(OH)2(phen)2][Cu2(OH)2(phen)2(V4O12)] · 6H2O (3), [Cu2(phen)4(V4O12)] · 4H2O (4), [Cu2(phen)4(V4O12)] · 6H2O (5), [Cu2(phen)4(VO3)4] · 10H2O (6), [Cu(phen)3]2V4O12 · phen · 22H2O (7), [Cu(phen)(VO3)2] (9) and [Cu2(phen)4(V4O12)] · 4H2O (12). The prepared compounds were characterized by elemental analyses and IR spectra. The characteristic bands in the IR spectra corresponding to the V–O stretching modes enabled the different oxovanadate groups present in the structures to be unequivocally distinguished. Compounds 3, 4, 5, 6, 7 and 12 were characterized by X-ray single crystal diffraction. The structure of compound 3 consists of isolated dinuclear [(phen)(H2O)Cu(μ-OH)2Cu(phen)(H2O)]2+ ions and [(phen)Cu(OH)2Cu(phen)]2+ moieties attached to V4O124- rings. The structures of compounds 4, 5 and 12 contain [Cu2(phen)4(V4O12)] clusters with different bonding modes of Cu(phen)22+ and V4O124- moieties. The structure of compound 7 is constructed by isolated [Cu(phen)3]2+ and V4O124- ions as well as molecules of uncoordinated 1,10-phenanthroline and water of crystallization, while a polymeric structure containing (VO3)nn- chains, to which Cu(phen)22+ fragments are attached through Cu–O bonds, was found for 6.

The single crystal X-ray diffraction of seven new compounds, [Cu2(H2O)2(OH)2(phen)2] [Cu2(OH)2(phen)2(V4O12)] · 6H2O, [Cu2(phen)4(V4O12)] · 4H2O, [Cu2(phen)4(V4O12)] · 6H2O, [Cu2(phen)4(VO3)4] · 10H2O, [Cu(phen)3]2V4O12 · phen · 22H2O, [Cu(phen)(VO3)2] and [Cu2(phen)4(V4O12)] · 4H2O, revealed a variability in mutual bonding interactions between the cationic and anionic units.Figure optionsDownload as PowerPoint slide