Structural influences of 1,10-phenanthroline on one- and two-dimensional organicinorganic hybrid materials of the copper-oxovanadium-phosphate family

The hydrothermal reactions of CuCl2.H2O, Na3VO4, 1,10-phenanthroline (phen), H3PO4 and H2O yield a family of one- and two-dimensional organic-inorganic hybrid materials. When the reaction is carried out at 180°C for 46.8h, a mixture of blue crystals of the one-dimensional chain [Cu(phen)(VO2)(PO4)] (1) and of green plates of [{Cu (phen)}2(VO2)3(OH)(PO4)2] (2), a layered material, is obtained. Attempts to prepare monophasic samples of 1 and 2 by varying stoichiometry and temperature yielded a third phase, dark green crystals of [{Cu(phen)}2(VO)3(PO4)2(HPO4)2].2H2O (3.2H2O), a two-dimensional material. The structures of 1 and 2 contain {(VO)2(PO4)2} rings linked by copper(II) phenanthroline square pyramids into one- and two-dimensional architectures, respectively. In contrast, the structure of 3 exhibits a two-dimensional {(VO)3(PO4)2(HPO4)2}4 substructure with {Cu(phen)}2+ units decorating the surfaces of this vanado-phosphate layer. Crystal data: (1) C24H16N4O12P2V2Cu2 monoclinic, C2/c: a=20.213(1)?, b=11.5997(6)?, c=14.5259(8)?, (beta)=126.920(1)°, V=2722.9(3)?3 (2) C24H17N4O15P2V3Cu, triclinic, P1: a=8.0547(7)?, b=9.1862(8)?, c=10.2380(9)?, (alpha)=97.375(2)°, (beta)=100.673(2)°, (gamma)=104.269(2)°, V=709.3(1)?3 (3) C12H14N2O10.50P2V1.50Cu, triclinic, P1: a=8.1209(6)?, b=9.7032(7)?, c=12.0664(8)?, (alpha)=102.507(1)°, (beta)=102.833(1)°, (gamma)=110.621(1)°, V=821.1(2)?3.