Ligand influences on the structures of molybdenum oxide networks

Pamela J. Hagrman, Robert L. LaDuca, H. J. Koo, Randy Rarig, Robert C. Haushalter, Myung Hwan Whangbo, Jon Zubieta

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Abstract

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), [H(x)MoO3(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 [H(x)MoO3(4,4'-bpy)0.5] (x ≃ 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 [H(x)MoO3(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 [H(x)MoO3(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 P21/c, a = 7.5727(6) Å, b = 7.3675(7) Å, c = 22.433(3) Å, β = 90.396(8)°, Z = 8. MOXI-9, C5H4.5NMoO3: monoclinic I2/m, a = 5.2644(4) Å, b = 5.2642(4) Å, c = 22.730(2) Å, β = 90.035('1)°, Z = 4. MOXI-32, C2H3N3Mo2O6: orthorhombic Pbcm, a = 3.9289(5) Å, b = 13.850(2) Å, c = 13.366(2) Å, Z = 4.

Original languageEnglish (US)
Pages (from-to)4311-4317
Number of pages7
JournalInorganic Chemistry
Volume39
Issue number19
DOIs
StatePublished - Sep 18 2000

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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    Hagrman, P. J., LaDuca, R. L., Koo, H. J., Rarig, R., Haushalter, R. C., Whangbo, M. H., & Zubieta, J. (2000). Ligand influences on the structures of molybdenum oxide networks. Inorganic Chemistry, 39(19), 4311-4317. https://doi.org/10.1021/ic000496l