New Structure Type among Octahydrated Rare-Earth Sulfates, β-Ce2(SO4)3·8H2O, and a new Ce2(SO4)3·4H2O Polymorph

Syntheses, crystal structures and thermal behavior of two new hydrated cerium(III) sulfates are reported, Ce2(SO4)3·4H2O (I) and β-Ce2(SO4)3·8H2O (II), both forming three-dimensional networks. Compound I crystallizes in the space group P21/n. There are two non-equivalent cerium atoms in the structure of I, one nine- and one ten-fold coordinated to oxygen atoms. The cerium polyhedra are edge sharing, forming helically propagating chains, held together by sulfate groups. The structure is compact, all the sulfate groups are edge-sharing with cerium polyhedra and one third of the oxygen atoms, belonging to sulfate groups, are in the S-Oμ3-Ce2 bonding mode. Compound II constitutes a new structure type among the octahydrated rare-earth sulfates which belongs to the space group Pn. Each cerium atom is in contact with nine oxygen atoms, these belong to four water molecules, three corner sharing and one edge sharing sulfate groups. The crystal structure is built up by layers of [Ce(H2O)4(SO4)]nn+ held together by doubly edge sharing sulfate groups. The dehydration of II is a three step process, forming Ce2(SO4)3·5H2O, Ce2(SO4)3·4H2O and Ce2(SO4)3, respectively. During the oxidative decomposition of the anhydrous form, Ce2(SO4)3, into the final product CeO2, small amount of CeO(SO4) as an intermediate species was detected.