Solid state coordination chemistry: temperature dependence of the crystal chemistry of the oxovanadium-phenylphosphonate-copper(II)-2,2′-bipyridine system. Crystal structures of the one-dimensional [{Cu(bpy)}VO 2(O 3PC 6H 5)(HO 3PC 6H 5)], [{Cu 3(bpy) 3(H 2O)}V 4O 9(O 3PC 6H 5) 4], [{Cu(bpy)} 2V 3O 6(O 3PC 6H 5) 3(HO 3PC 6H 5)] and [{Cu(bpy)}VO(O 3PC 6H 5) 2

Abstract

The temperature dependence of the hydrothermal chemistry of the oxovanadium-phenylphosphonate/copper(II)-bipyridine system has been investigated. Reactions of identical compositions of CuSO 4⋅5H 2O, bipyridine, C 6H 5PO 3H 2 and Na 3VO 4 in H 2O yielded [{Cu(bpy)}VO 2(O 3PC 6H 5)(HOC 6H 5)] ( 1), [{Cu 3(bpy) 3(H 2O)}V 4O 9(O 3PC 6H 5) 4]⋅3.9H 2O ( 2⋅3.9H 2O) and [{Cu(bpy)}VO(O 3PC 6H 5) 2] ( 4) at 120 °C, 150 °C and 180–230 °C, respectively. Furthermore, variations in stoichiometry at 150 °C provided yet a fourth one-dimensional phase [{Cu(bpy)} 2V 3O 6(O 3PC 6H 5) 3(HO 3PC 6H 5)] ( 3). Substitution of a methyl substituent for the phenyl group yielded another one-dimensional material [{Cu(bpy)}V 2O 4(O 3PCH 3) 2⋅H 2O ( 5⋅H 2O). The structural chemistry is discussed in terms of the polyhedral variability of vanadium oxides, the tendency of oxovanadium polyhedra to form oligomeric arrays, the variable modes of polyhedral connectivity associated with vanadium square pyramids and phosphorus tetrahedra and the steric influences of the copper(II)-bpy subunit.