Hydrothermal Synthesis and Structural Characterization of a Series of One-Dimensional Organic/Inorganic Hybrid Materials of the [(MoO3)n(2,2‘-bipy)m] Family: [MoO3(2,2‘-bipy)], [Mo2O6(2,2‘-bipy)], and [Mo3O9(2,2‘-bipy)2]

Three one-dimensional molybdenum oxide/2,2'-bipyridine species have been prepared by hydrothermal methods and structurally characterized. The reaction of MoO3, 2,2'-bipyridine, and H2O in the mole ratio 1:0.68:680 at 160 °C for 120 h in a 23 mL Teflon-lined Parr acid digestion bomb produces colorless rods of [MoO3(2,2'-bipy)] (1) mixed with colorless octahedra of [Mo3O9(2,2'-bipy)2] (3). The structure of 1 consists of one-dimensional chains of corner-sharing distorted {MoO4N2} octahedra. [Mo2O6(2,2'-bipy)] (2) was prepared from a mixture of Na2MoO4·2H2O, MoO3, 2,2'-bipyridine, MnCl2·4H2O, and H2O in the mole ratio 1:1:2:1.9:263 and was isolated as colorless plates. In contrast to the structure of 1, compound 2 consists of a chain of alternating corner-sharing {MoO4N2} octahedra and {MoO4} tetrahedra. Compound 3 was isolated as colorless octahedra. The structure of 3 consists of a chain of corner-sharing {MoO4N2} octahedra and {MoO4} tetrahedra that alternate such that each {MoO4N2} octahedron corner-shares with another such octahedron and a {MoO4} tetrahedron; consequently, each {MoO4} unit corner shares with two {MoO4N2} octahedra. Crystal data: 1: monoclinic Cc, a = 14.246(3), b = 9.628(2), c = 7.344(1) Å, β = 101.26(3)°, V = 987.9(3) Å3, Z = 4, Dcalc = 2.018 g cm-3; structure solution and refinement based on 1346 reflections converged at R = 0.026; 2: monoclinic P21/m, a = 9.0875(6), b = 6.8286(5), c = 10.5441(7) Å, β = 99.307(2)°, V = 645.70(8) Å3, Z = 2, Dcalc = 2.284 g cm-3, structure solution and refinement based on 1607 reflections converged at R = 0.062; 3: monoclinic P21/n, a = 13.5468(3), b = 10.1407(2), c = 17.8346(1) Å, β = 104.888(1)°, V = 2367.76(7) Å3, Z = 4, Dcalc = 2.088 g cm-3, structure solution and refinement based on 5581 reflections converged at R = 0.054.