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

Six inorganic−organic compounds based on [Mo<i><sub>x</sub></i>O<i><sub>y</sub></i>]<i><sup>n</sup></i><sup>-</sup> chains, [Ag<sub>2</sub>(quinoxaline)<sub>2</sub>Mo<sub>4</sub>O<sub>13</sub>] (<b>1</b>), [Cu<sub>2</sub>(DMPz)<sub>2</sub>Mo<sub>4</sub>O<sub>13</sub>] (<b>2</b>) (DMPz = 2,5-dimethylpyrazine), [Cu<sub>2</sub>(4-PBIM)<sub>2</sub>Mo<sub>4</sub>O<sub>13</sub>] (3) [4-PBIM = 2-(4-pyridyl)benzimidazole], [Cu(OPBIM)(H<sub>2</sub>O) Mo<sub>3</sub>O<sub>10</sub>]·H<sub>2</sub>O (<b>4</b>) [OPBIM = 2-(2-ol-3-pyridinio)benzimidazole], [Co(3-HPBIM)<sub>2</sub> (H<sub>2</sub>O)<sub>2</sub>Mo<sub>6</sub>O<sub>20</sub>] (<b>5</b>) [3-HPBIM = 2-(3-pyridyl)benzimidazolium], [Ni(3-HPBIM)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>Mo<sub>6</sub>O<sub>20</sub>] (<b>6</b>), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Compounds <b>1</b> and <b>2</b> represent the first two examples of three-dimensional frameworks constructed from [Mo<sub>8</sub>O<sub>26</sub>]<i><sub>n</sub></i><sup>4</sup><i><sup>n</sup></i><sup>-</sup> anion chains integrated by M−L polymeric cation chains. Compounds <b>3</b> and <b>4</b> reveal the peripheral decorated [Mo<sub>8</sub>O<sub>26</sub>]<i><sub>n</sub></i><sup>4</sup><i><sup>n</sup></i><sup>-</sup> and [Mo<sub>3</sub>O<sub>10</sub>]<i><sub>n</sub></i><sup>2</sup><i><sup>n</sup></i><sup>-</sup> one-dimensional chains, respectively. The isostructural compounds <b>5</b> and <b>6</b> feature two-dimensional networks formed from [Mo<sub>3</sub>O<sub>10</sub>]<sub>2</sub><i><sub>n</sub></i><sup>4</sup><i><sup>n</sup></i><sup>-</sup> infinite chains linked by [Co(3-HPBIM)<sub>2</sub>]<sup>4+</sup> fragments. The molybdate chains in compounds <b>1</b>−<b>3</b> and <b>4</b>−<b>6</b> represent three isomeric forms of [Mo<sub>8</sub>O<sub>26</sub>]<i><sub>n</sub></i><sup>4</sup><i><sup>n</sup></i><sup>-</sup> and two [Mo<sub>3</sub>O<sub>10</sub>]<i><sub>n</sub></i><sup>2</sup><i><sup>n</sup></i><sup>-</sup> chains, respectively.