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 MoO 3, 2,2‘-bipyridine, and H 2 O 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 [MoO 3 (2,2‘-bipy)] ( 1 ) mixed with colorless octahedra of [Mo 3 O 9 (2,2‘-bipy) 2 ] ( 3 ). The structure of 1 consists of one-dimensional chains of corner-sharing distorted {MoO 4 N 2 } octahedra. [Mo 2 O 6 (2,2‘-bipy)] ( 2 ) was prepared from a mixture of Na 2 MoO 4 ·2H 2 O, MoO 3, 2,2‘-bipyridine, MnCl 2 ·4H 2 O, and H 2 O 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 {MoO 4 N 2 } octahedra and {MoO 4 } tetrahedra. Compound 3 was isolated as colorless octahedra. The structure of 3 consists of a chain of corner-sharing {MoO 4 N 2 } octahedra and {MoO 4 } tetrahedra that alternate such that each {MoO 4 N 2 } octahedron corner-shares with another such octahedron and a {MoO 4 } tetrahedron; consequently, each {MoO 4 } unit corner shares with two {MoO 4 N 2 } 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) Å 3, Z = 4, D calc = 2.018 g cm - 3; structure solution and refinement based on 1346 reflections converged at R = 0.026; 2: monoclinic P2 1 /m, a = 9.0875(6), b = 6.8286(5), c = 10.5441(7) Å, β = 99.307(2)°, V = 645.70(8) Å 3, Z = 2, D calc = 2.284 g cm - 3, structure solution and refinement based on 1607 reflections converged at R = 0.062; 3: monoclinic P2 1 /n, a = 13.5468(3), b = 10.1407(2), c = 17.8346(1) Å, β = 104.888(1)°, V = 2367.76(7) Å 3, Z = 4, D calc = 2.088 g cm - 3, structure solution and refinement based on 5581 reflections converged at R = 0.054.