Abstract: | The structure of the polymeric title compound, CaCo(C3H2O4)2(H2O)4]n, consists of CaO8 and CoO6 polyhedra linked together by malonate groups. The Co atom lies on a centre of symmetry in an octahedral arrangement, and is coordinated by four malonate O atoms in a planar arrangement and two water molecules in a trans conformation. The geometry around the Ca atom, which lies on a twofold axis, may be described as a distorted square antiprism, which involves two water molecules and six malonate O atoms. The Co—O and Ca—O bond lengths are in the ranges 2.0711 (12)–2.1004 (14) and 2.3775 (12)–2.6329 (12) Å, respectively. |