Summary: | The title compounds, calcium perchlorate tetrahydrate and calcium perchlorate hexahydrate, were crystallized at low temperatures according to the solid–liquid phase diagram. The structure of the tetrahydrate consists of one Ca2+ cation eightfold coordinated in a square-antiprismatic fashion by four water molecules and four O atoms of four perchlorate tetrahedra, forming chains parallel to [01-1] by sharing corners of the ClO4 tetrahedra. The structure of the hexahydrate contains two different Ca2+ cations, each coordinated by six water molecules and two O atoms of two perchlorate tetrahedra, forming [Ca(H2O)6(ClO4)]2 dimers by sharing two ClO4 tetrahedra. The dimers are arranged in sheets parallel (001) and alternate with layers of non-coordinating ClO4 tetrahedra. O—H...O hydrogen bonds between the water molecules as donor and ClO4 tetrahedra and water molecules as acceptor groups lead to the formation of a three-dimensional network in the two structures. Ca(ClO4)2·6H2O was refined as a two-component inversion twin, with an approximate twin component ratio of 1:1 in each of the two structures.
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