Single crystals of CaNa[ReO4]3 : serendipitous formation and systematic characterization

Abstract

In an attempt to crystallize Ce[ReO4]4·xH2O from aqueous solutions of equimolar amounts of Ce[SO4]2 and Ba[ReO4]2 via salt‐metathesis the serendipitous formation of colorless, transparent, rod‐shaped single crystals of CaNa[ReO4]3 was observed as a result of calcium and sodium impurities within the improperly deionized water used. Structure analysis by X‐ray diffraction lead to the conclusion that the title compound crystallizes in the ThCd[MoO4]3 structure type with the hexagonal space group P63/m and the lattice parameters a = 991.74(6) pm, c = 636.53(4) pm, c/a = 0.642 for Z = 2. The crystal structure contains purely oxygen surrounded and crystallographically unique cations, namely Ca2+ in tricapped trigonal prismatic (d(Ca-O) = 6 × 249 pm + 3 × 254 pm), Na+ in octahedral (d(Na-O) = 6 × 241 pm), and Re7+ in tetrahedral coordination (d(Re-O) = 171-173 pm). Furthermore, it was possible to yield an almost phase‐pure microcrystalline powder of the title compound from a melt of equimolar amounts of Na[ReO4] and Ca[ReO4]2 stemming from aquatically obtained precursors.