Synthesis and structure of dodecamolybdates of tetravalent cerium, thorium, uranium, neptunium, and plutonium

Resumo

A series of isostructural compounds of the composition Na₇H[EMo₁₂O₄₂]·12H₂O, where E(IV) = Ce, Th, U, Np, or Pu, were synthesized and structurally characterized. In the [EMo₁₂O₄₂]^8– heteropolyanion (HPA), the central E(IV) atom is surrounded by six Mo₂O₉ groups, each constituted by two octahedra sharing a common face. The coordination polyhedron (CP) of the central atom is a weakly distorted icosahedron with the mean E(IV)–О bond lengths of 2.498, 2.529, 2.500, 2.490, and 2.488 Å for Ce, Th, U, Np, and Pu, respectively. In the structure of the compounds Na₇H[EMo₁₂O₄₂]·12H₂O, there are two crystallographically independent sodium atoms: Na(1) and Na(2). The oxygen surrounding of the Na(1) atom is formed by the terminal oxygen atoms of two heteropolyanions adjacent along [001], and its coordination polyhedron is an octahedron. The surrounding of the Na(2) atom (a six-vertex polyhedron) is formed by three terminal oxygen atoms of three Mo₂O₉ groups belonging to the same HPA and by three water molecules. The coordination polyhedra of the Na(2) atoms are linked with each other via common oxygen atoms of O_w(2) water molecules to form a chain “winding” around the 3₁ screw axis. The heteropolyanions and Na⁺ cations in the crystal form a framework constructed in a fashion characteristic of Dexter–Silverton type anions, with the coordination via three terminal oxygen atoms of three Mo₂O₉ groups. Excess negative charge of HPA is compensated by the proton localized on one of the six bridging O atoms. In the Mo₂O₉ doubled octahedra, the Mo–O bonds with the О atoms bonded to E(IV) and forming the edge of the common face are sensitive to the kind of the central atom.