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The title compound, [CoNa4(C6H5O7)2]n, was obtained under hydro­thermal conditions as a minor product. The Co2+ cation is located on a crystallographic inversion center and is coordinated by six O atoms from two different citrate units, forming a [Co(C6H5O7)2]4− building unit with Co—O bond lengths between 2.0578 (17) and 2.0813 (16) Å. The structure features two crystallographically independent Na+ ions. The first Na+ cation is five-coordinated by O atoms of five carboxylate groups from four different citrate anions. The second Na+ cation is surrounded by six O atoms of five carboxylate groups from five different citrate anions. The carboxylate groups of the citrate are completely depronona­ted, the hydroxyl group, however, is not. It is coordinated to the Co2+ cation, and through an O—H...O hydrogen bond connected to a neighboring [Co(C6H5O7)2]4− building unit. The coordination modes of the carboxyl­ate O atoms vary, with one O atom being coordinated to three different Na+ cations, three are bridging O atoms bound to two Na+ cations and two are connected to a Co2+ cation and a Na+ cation, respectively. Through these inter­connections, the basic [Co(C6H5O7)2]4− building units are linked with each other through coordination of their carboxyl­ate groups to the Na+ cations, forming a three-dimensional framework.
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