A Series of Inorganic−Organic Hybrid Composite Solids Based on Molybdenum Oxide Chains

Six inorganic−organic compounds based on [Mo_xO_y]^n- chains, [Ag₂(quinoxaline)₂Mo₄O₁₃] (1), [Cu₂(DMPz)₂Mo₄O₁₃] (2) (DMPz = 2,5-dimethylpyrazine), [Cu₂(4-PBIM)₂Mo₄O₁₃] (3) [4-PBIM = 2-(4-pyridyl)benzimidazole], [Cu(OPBIM)(H₂O) Mo₃O₁₀]·H₂O (4) [OPBIM = 2-(2-ol-3-pyridinio)benzimidazole], [Co(3-HPBIM)₂ (H₂O)₂Mo₆O₂₀] (5) [3-HPBIM = 2-(3-pyridyl)benzimidazolium], [Ni(3-HPBIM)₂(H₂O)₂Mo₆O₂₀] (6), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Compounds 1 and 2 represent the first two examples of three-dimensional frameworks constructed from [Mo₈O₂₆]_n^4n- anion chains integrated by M−L polymeric cation chains. Compounds 3 and 4 reveal the peripheral decorated [Mo₈O₂₆]_n^4n- and [Mo₃O₁₀]_n^2n- one-dimensional chains, respectively. The isostructural compounds 5 and 6 feature two-dimensional networks formed from [Mo₃O₁₀]_2n^4n- infinite chains linked by [Co(3-HPBIM)₂]⁴⁺ fragments. The molybdate chains in compounds 1−3 and 4−6 represent three isomeric forms of [Mo₈O₂₆]_n^4n- and two [Mo₃O₁₀]_n^2n- chains, respectively.