Ligand influences on copper molybdate networks: The structures and magnetism of [Cu(3,4′-bpy)MoO4], [Cu(3,3′-bpy)0.5MoO4], and [Cu(4,4′-bpy)0.5 MoO4]·1.5H2O

Randy S. Rarig, Robert Lam, Peter Y. Zavalij, J. Katana Ngala, Robert L. LaDuca, John E. Greedan, Jon Zubieta

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The reactions of a Cu(II) salt, MoO3, and the appropriate bipyridine ligand yield a series of bimetallic oxides, [Cu(3,4′-bpy)MoO4] (1), [Cu(3,3′-bpy)0.5MoO4] (2), and [Cu(4,4′-bpy)0.5MoO4]·1.5H2O (3·1.5H2O). The structures of 1-3 exhibit three-dimensional covalent frameworks, constructed from bimetallic oxide layers tethered by the dipodal organoimine ligands. However, the {CuMoO4} networks are quite distinct. For structure 1, the layer consists of corner-sharing {MoO4} tetrahedra and {CuN2O3} square pyramids, while the layer of 2 is constructed from {MoO4} tetrehedra and binuclear {Cu2O6N2} units of edge-sharing copper square pyramids. The oxide substructure of 3 consists of {MoO4} tetrahedra corner-sharing with tetranuclear clusters of edge-sharing {CuO5N} octahedra. Crystal data: C10H8N2O4CuMo (1), orthorhombic Pbca, a = 12.4823(6) Å, b = 9.1699(4) Å, c = 19.5647(9) Å, V = 2239.4(1) Å3, Z = 8; C5H4NO4CUMO (2), triclinic P1, a = 5.439(1) Å, b = 6.814(1) Å, c = 10.727(2) Å, α = 73.909(4)°, β = 78.839(4)°; γ = 70.389(4)°; V = 357.6(1) Å3, Z = 2; C10H8N2O8Cu 2Mo2·1.5H2O, triclinic P1, a = 7.4273(7) Å, b = 9.2314(8) Å, c = 13.880(1) Å, α = 71.411(2)°, β= 88.528(2)°, γ = 73.650(2)°, V = 863.4(1) Å3, Z = 2. The magnetic properties of 1-3 arise solely from the presence of the Cu(ll) sites, but reflect the structural differences within the bimetallic oxide layers. Compound 1 exhibits magnetic behavior consistent with ferromagnetic chains which couple antiferromagnetically at low temperature. Compound 2 exhibits strong antiferromagnetic dimeric interactions, with the magnetic susceptibility data consistent with the Bleaney-Bowers equation. Similarly, the magnetic susceptibility of 3 is dominated by antiferromagnetic interactions, which may be modeled as a linear S = 1/2 Heisenberg tetramer.

Original languageEnglish (US)
Pages (from-to)2124-2133
Number of pages10
JournalInorganic Chemistry
Issue number8
StatePublished - Apr 22 2002

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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