Hydrothermal synthesis and crystal structure of a hybrid material based on [Co4(phen)8(H2O)2(HPO3)2]4+ and a highly reduced polyoxoanion

An unusual composite hybrid material [Co4(phen)8(H2O)2(HPO3)2](H3O)3[PMoVI8VIV4O40(VIVO)2] 1 (phen = 1,10-phenanthroline) has been hydrothermally synthesized from a mixture of NH4VO3, Na2MoO4·2H2O, CoCl2·6H2O, phen, H3PO3 and water. It was characterized by elemental analysis, IR, UV-vis, XPS, EPR, TG and single crystal X-ray diffraction. The title compound is constructed from the organic–inorganic hybrid [Co4(phen)8(H2O)2(HPO3)2]4+ and highly reduced bi-capped pseudo-Keggin [PMoVI8VIV4O40(VIVO)2]7− polyoxoanions The structure exhibits an extended 2D network through hydrogen bonds among cations, anions and H2O, combining polyoxometalates with metal phosphonates for the first time.