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The crystal structure of the title compound, (C12H12N2)(C12H11N2)[Mo(CN)8]·4H2O, consists of 4,4′-(ethene-1,2-di­yl)dipyridinium and 4-[2-(pyridin-4-yl)ethen­yl]pyridinium cations disordered over the same site, an [Mo(CN)8]3− anion and four water mol­ecules of crystallization. The eight-coordinate [Mo(CN)8]3− unit exhibits a slightly distorted square-anti­prismatic geometry. In the structure, the cations (crystallographic symmetry, 2) and anions (crystallographic symmetry, 222) are arranged alternately by N—H...O and O—H...N hydrogen bonds, forming layers parallel to the bc plane. These layers are further linked through O—H...N hydrogen bonds, generating a three-dimensional supra­molecular network.

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The structure of the title compound, (C16H17N2)3[Co(CN)6]·5H2O, consists of three 3,4,7,8-tetra­methyl-1,10-phenanthrolin-1-ium cations, a [Co(CN)6]3− anion and five water mol­ecules of crystallization, one of which is disordered over two sets of sites in a 0.587 (15):0.413 (15) ratio. The [Co(CN)6]3− anion exhibits an octa­hedral geometry. In the structure, cations and anions are linked alternatively through O—H...O, O—H...N, N—H...O and N—H...N hydrogen bonds, π–π inter­actions [centroid–centroid distances = 3.523 (2)–4.099 (2) Å] and van der Waals forces, forming a three-dimensional supra­molecular network.
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