Abstract
Robertsite, ideally Ca(2)Mn(3)O(2)(PO(4))(3)·3H(2)O [calcium manganese(III) tris-(orthophosphate) trihydrate], can be associated with the arseniosiderite structural group characterized by the general formula Ca(2)A(3)O(2)(TO(4))(3)·nH(2)O, with A = Fe, Mn; T = As, P; and n = 2 or 3. In this study, single-crystal X-ray diffraction data were used to determine the robertsite structure from a twinned crystal from the type locality, the Tip Top mine, Custer County, South Dakota, USA, and to refine anisotropic displacement parameters for all atoms. The general structural feature of robertsite resembles that of the other two members of the arseniosiderite group, the structures of which have previously been reported. It is characterized by sheets of [MnO(6)] octa-hedra in the form of nine-membered pseudo-trigonal rings. Located at the center of each nine-membered ring is a PO(4) tetra-hedron, and the other eight PO(4) tetra-hedra sandwich the Mn-oxide sheets. The six different Ca(2+) ions are seven-coordinated in form of distorted penta-gonal bipyramids, [CaO(5)(H(2)O)(2)], if Ca-O distances less than 2.85 Å are considered. Along with hydrogen bonding involving the water mol-ecules, they hold the manganese-phosphate sheets together. All nine [MnO(6)] octa-hedra are distorted by the Jahn-Teller effect.