A reinvestigation of quaternary layered bismuth oxyhalides of the Sillen X1 type

A family of layered bismuth oxyhalides, LI0.5Bi1.5O2X and LIIBiO2X has been reinvestigated. Formation of X1-type Sillen compounds has been established for LI=Li, Na, LII=Ca, Sr, Ba, and X=Cl, Br, I, but the details of their crystal structures are different. While all LI0.5Bi1.5O2X, CaBiO2Br, and CaBiO2I adopt the disordered tetragonal Nd2O2Te structure, all compounds of LII=Sr and Ba are orthorhombic and isostructural to PbSbO2Cl, due to L/Bi cation ordering. Crystal structures have been determined for CaBiO2I, SrBiO2Br, SrBiO2I, and BaBiO2I. We discuss the factors which determine the occurrence and type of cation ordering in the quaternary bismuth and antimony X1-type oxyhalides. We also predict that more isostructural compounds can be prepared with antimony