Solid state coordination chemistry in the design of molybdenum oxides:: The hydrothermal synthesis and structure of a layered copper-molybdenum oxide, [Cu(tpytrz)2Mo4O13] (tpytrz = tripyridyltriazine)

The hydrothermal reaction of CuSO4 . 5H(2)O, tripyridyltriazine (tpytrz), MoO3, and H2O in the mole ratio 2.1 : 1.0 : 1.9 : 3470 for 84 h at 160 degrees C yields green needles of [Cu(tpytrz)(2)Mo4O13] (MOXI-37). The structure of MOXI-37 consists of bimetallic {CuMo4O13} layers buttressed by tpytrz ligands occupying the interlamellar region. The overall structure adopts the motif of alternating inorganic and organic subunits characteristic of many organic-inorganic composite materials, The inorganic network is constructed from {Mo4O13} chains of corner-sharing octahedra and tetrahedra, linked by octahedral {CuN2O} units into a two-dimensional structure. The structure of MOXI-37 may be compared to other examples of copper-molybdate networks sandwiching bridging organonitrogen ligands, namely, [Cu(dpe)MoO4] (MOXI-1) and [Cu(bpa)(0.5)MoO4] (MOXI-24). In contrast to the net work connectivity of MOXI-37, the layer structure of [Cu(dpe)MoO4] consists of corner-sharing {MoO4} tetrahedra and {CuN2O5} trigonal bipyramids, while the two-dimensional oxide substructure [Cu(bpa)(0.5)MoO4] is constructed from tetranuclear copper clusters linked through {MoO4} tetrahedra. (C) 2000 Academic Press.