Organically templated vanadium oxide phases: Synthesis and structures of [H3NCH2CH2NH3][V2O6] and [HN(CH2CH2)(3)NH][(V2V4O14)-V-V-O-IV]center dot H2O

The synthesis and crystal structures of [H-3,NCH2,CH2NH3] [V2O6] (l)and [HN (CH2CH2)(3)NH] [(V2V4O14)-V-V-O-IV] . H2O (2) are described. The structure of the oxidized compound 1 consists of parallel stacks of vanadium oxide ch ains of corner sharing {VO4} tetrahedra. The chains are stabilized by exten sive hydrogen bonding involving oxide ligands of the chains and ethylenedia mmonium ions which fill the space between the stacks of chains. The structu re of compound 2 consists of vanadium oxide layers separated by doubly prot onated 1.4-diazabicyclo[2.2.2] octane and lattice water. The vanadium oxide layers, containing mixed-valence vanadium (V-V and V-IV) centers, are comp osed of zigzag ribbons of edge-sharing {VO5} square pyramids interconnected by {VO4} tetrahedra. Crystal data C2H10N2O6V2 ,1: monoclinic, space group P2(1)/c ( No. 14), a= 5.5359(5), h = 12.9430(12), c = 5.6856(5) A, alpha = 90, beta = 97.460(2), 90 degrees, V= 403.93(6) A(3), Z=2. A total of 2506 r eflections (0(max) = 27.89 degrees) was collected. of which 954 were used t o resolve the structure. The structure was solved by direct methods and lea st-squares refinement converged at R = 0.0592. C6H16N2O15V6 2: monoclinic, space group C2 (No. 5), a=19.303(4). h= 6.657(2), c = 7.579(2) A, alpha = 9 0. beta = 111.31(2), gamma =90 degrees, V= 908.4(4) A(3), 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.