Ligand influences of the structures of molybdenum oxide networks.

The influence of organonitrogen ligands on the network structure of molybdenum oxides was examined by preparing three new molybdenum oxide phases [MoO3(4,4'-bpy)0.5] (MOXI-8), [HxMoO3(4,4'-bpy)0.5] (MOXI-9), and [MoO3(triazole)0.5] (MOXI-32). The structure of [MoO3(4,4'-bpy)0.5) consists of layers of corner-sharing MoO5N octahedra, buttressed by bridging 4,4'-bipyridyl ligands into a three-dimensional covalently bonded organic-inorganic composite material. Partial reduction of [MoO3(4,4'-bpy)0.5] yields the mixed-valence material [HxMoO3(4,4'-bpy)0.5] (x approximately 0.5). The most apparent structural change upon reduction is found in the Mo-ligand bond lengths of the MoO5N octahedra, which exhibit the usual (2 + 2 + 2) pattern in [MoO3(4,4'-bpy)0.5] and a more regular (5 + 1) pattern in [HxMoO3(4,4'-bpy)0.5]. Substitution of triazole for 4,4'-bipyridine yields [MoO3(triazole)0.5], which retains the layer motif of corner-sharing MoO5N octahedra but with distinct sinusoidal ruffling in contrast to planar layers of [MoO3(4,4'-bpy)0.5] and [HxMoO3(4,4'-bpy)0.5]. The folding reflects the ligand constraints imposed by the triazole ligand that bridges adjacent Mo sites within a layer. MOXI-8, C5H4NMoO3: monoclinic P2(1)/c, a = 7.5727(6) A, b = 7.3675(7) A, c = 22.433(3) A, beta = 90.396(8) degrees, Z = 8. MOXI-9, C5H4.5NMoO3: monoclinic I2/m, a = 5.2644(4) A, b = 5.2642(4) A, c = 22.730(2) A, beta = 90.035(1) degrees, Z = 4. MOXI-32, C2H3N3Mo2O6: orthorhombic Pbcm, a = 3.9289(5) A, b = 13.850(2) A, c = 13.366(2) A, Z = 4.

An Inorganic Double Helix: Hydrothermal Synthesis, Structure, and Magnetism of Chiral [(CH3)2NH2]K4[V10O10(H2O)2(OH)4(PO4)7]{middle dot}4H2O.

Very complicated inorganic solids can be self-assembled from structurally simple precursors as illustrated by the hydrothermal synthesis of the vanadium phosphate, [(CH(3))(2)NH(2)]K(4)[V(10)O(10)(H(2)O)(2)(OH)(4)(PO(4))(7)].4H(2)O, 1, which contains chiral double helices formed from interpenetrating spirals of vanadium oxo pentamers bonded together by P(5+). These double helices are in turn intertwined with each other in a manner that generates unusual tunnels and cavities that are filled with (CH(3))(2)NH(2)(+) and K(+) cations, respectively. The unit cell contents of dark blue phosphate 1, which crystallizes in the enantiomorphic space group P4(3) with lattice constants a = 12.130 and c = 30.555 angstroms, are chiral; only one enantiomorph is present in a given crystal. Magnetization measurements show that 1 is paramagnetic with ten unpaired electrons per formula unit at higher temperatures and that antiferromagnetic interactions develop at lower temperatures.

Structure of a three-dimensional, microporous molybdenum phosphate with large cavities.

The synthesis, single-crystal x-ray structural characterization, and sorption properties of a microporous molybdenum phosphate, (Me(4)N)(1.3)(H(3)O)(0.7)[Mo(4)O(8)(PO(4))(2)] . 2H(2)O (Me, methyl), are presented. The three-dimensional framework is built up from Mo(4)O(8)(4+) cubes and PO(4)(3-) tetrahedra that are connected in such a way that large, cation-filled voids are generated; these voids constitute 25% of the volume of the solid. Absorption isotherms for water show the completely reversible uptake of 4 to 5 percent by weight water into the micropores of this compound, which corresponds to 10 to 12 percent by volume.