Organically Templated Vanadium Oxide Phases: Synthesis and Structures of [H3NCH2CH2NH3][V2O6] and [HN(CH2CH2)3NH][VV2VIV4O14]·H2O

Abstract

The synthesis and crystal structures of [H3NCH2CH2NH3][V2O6] (1) and [HN(CH2CH2)3NH][VV2VIV4O14]·H2O (2) are described. The structure of the oxidized compound 1 consists of parallel stacks of vanadium oxide chains of corner sharing {VO4} tetrahedra. The chains are stabilized by extensive hydrogen bonding involving oxide ligands of the chains and ethylenediammonium ions which fill the space between the stacks of chains. The structure of compound 2 consists of vanadium oxide layers separated by doubly protonated 1,4-diazabicyclo[2.2.2]octane and lattice water. The vanadium oxide layers, containing mixed-valence vanadium (VV and VIV) centers, are composed of zigzag ribbons of edge-sharing {VO5} square pyramids interconnected by {VO4} tetrahedra. Crystal data. C2H10N2O6V2 , 1: monoclinic, space group P21/c (No. 14), a=5.5359(5), b=12.9430(12), c=5.6856(5) A, α=90, β=97.460(2), γ=90°, V=403.93(6) A3, Z=2. A total of 2506 reflections (θmax=27.89°) was collected, of which 954 were used to resolve the structure. The structure was solved by direct methods and least-squares refinement converged at R=0.0592. C6H16N2O15V6, 2: monoclinic, space group C2 (No. 5), a=19.303(4), b=6.667(2), c=7.579(2) A, α=90, β=111.31(2), γ=90°, V=908.4(4) A3, Z=2. A total of 1779 reflections was collected, of which 1591 unique reflections were used for structural elucidation. The structure was solved by direct methods and least-squares refinement converged at R=0.0314.