Crystal structures of Ca(ClO4)2·4H2O and Ca(ClO4)2·6H2O

Abstract

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 ClO4tetrahedra. 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)]2dimers by sharing two ClO4tetrahedra. The dimers are arranged in sheets parallel (001) and alternate with layers of non-coordinating ClO4tetrahedra. O—H...O hydrogen bonds between the water molecules as donor and ClO4tetrahedra 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.