Structural influences of organonitrogen ligands on vanadium oxide solids. Hydrothermal syntheses and structures of the terpyridine vanadates [V₂O₄(terpy)₂]₃[V₁₀O₂₈], [VO₂(terpy)][V₄O₁₀], and [V₉O₂₂(terpy)₃]

Hydrothermal reactions of the V₂O₅/2,2':6':2''-terpyridine/ZnO/H₂O system under a variety of conditions yielded the organic-inorganic hybrid materials [V₂O₄(terpy)₂]₃[V₁₀O₂₈]·2H₂O (VOXI-10), [VO₂(terpy)][V₄O₁₀] (VOXI-11), and [V₉O₂₂(terpy)₃] (VOXI-12). The structure of VOXI-10 consists of discrete binuclear cations [V₂O₄-(terpy)₂]²⁺ and one-dimensional chains [V₁₀O₂₈]^6-, constructed of cyclic [V₄O₁₂]^4- clusters linked through {VO₄} tetrahedra. In contrast, the structure of VOXI-11 exhibits discrete mononuclear cations [VO₂(terpy)]¹⁺ and a two-dimensional vanadium oxide network, [V₄O¹⁰]^1-. The structure of the oxide layer is constructed from ribbons of edge-sharing square pyramids; adjacent ribbons are connected through comer-sharing interactions into the two-dimensional architecture. VOXI-12 is also a network structure; however, in this case the terpy ligand is incorporated into the two-dimensional oxide network whose unique structure is constructed from cyclic [V₆O₁₈]^6- clusters and linear {V₃O₅(terpy)₃} moieties of corner-sharing vanadium octahedra. The rings form chains through comer-sharing linkages; adjacent chains are connected through the trinuclear units. Crystal data: VOXI-10, C₉₀H₇₀N₁₈O₄₂V₁₆, triclinic P1, a = 12.2071(7) Å, b = 13.8855(8) Å, 16.9832(10) Å, α = 69.584(1)°, β = 71.204(1)°, γ = 84.640(1)°, Z = 1; VOXI-11, C₁₅H₁₁N₃O₁₂V₅, monoclinic, P2₁/n, a = 7.7771(1) Å, b = 10.3595(2) Å, c = 25.715(4) Å, β = 92.286(1)°, Z = 4; VOXI-12, C₄₅H₃₃N₉O₂₂V₉, monoclinic C2/c, a = 23.774(2) Å, b = 9.4309(6) Å, c = 25.380(2) Å, β = 112.047(1)°, Z = 4.