ASc[SeO3]2 (A = Na – Cs): Pure Alkali‐Metal Scandium Oxoselenates(IV) and Their Representatives With Mixed Alkali‐Metal Occupation

Abstract

Alkali‐metal scandium oxoselenates(IV) ASc[SeO3]2 (A = Na – Cs) are known since a few years and a hydrothermal synthesis was used to obtain them. In our new studies we applied a flux‐supported solid‐state reaction and produced colorless single crystals as well. All representatives ASc[SeO3]2 with A = Na – Cs crystallize in the orthorhombic space group Pnma, in contrast to earlier reports for hexagonal RbSc[SeO3]2. Furthermore we have extended this field with some crystals showing a mixed occupation on the alkali‐metal site, namely (K,Na)Sc[SeO3]2, (Rb,K)Sc[SeO3]2, and (Cs,Rb)Sc[SeO3]2. Since all of them contain [ScO6]9– octahedra and [SeO3]2– ψ1‐tetrahedra the diverse connectivity of the distinct alkali‐metal centered oxygen polyhedra differentiates the compounds with the smaller alkali metals (A′ = Na and K) from those with the bigger ones (A′′ = Rb and Cs). For the mixed crystals the amount of smaller or bigger alkali metal is responsible, which design is chosen by the system. This forces the mixed crystal (Rb,K)Sc[SeO3]2 with a higher amount of potassium instead of rubidium to crystallize isotypically with KSc[SeO3]2 and NaSc[SeO3]2, whereas the pure rubidium compound RbSc[SeO3]2 adopts the CsSc[SeO3]2‐type structure. These findings are supported by single‐crystal Raman spectroscopy.