Abstract: | Single Crystals of the Cerium(IV) Oxotellurate(IV) CeTe2O6 Orange‐red, coffin‐shaped single crystals of CeTe2O6 (monoclinic, P21/n; a = 703.71(5), b = 1106.32(8), c = 735.24(5) pm, β = 108.066(6)°; Z = 4) were obtained by the reaction of admixtures of cerium dioxide and tellurium dioxide (CeO2, TeO2; molar ratio 1 : 2) in the presence of fluxing CsCl (750 °C, 4 d) in evacuated silica tubes. The crystal structure contains eightfold coordinated Ce4+ cations, which are surrounded by irregular trigonal dodecahedra of oxygen atoms. The interconnection of these CeO8] polyhedra occurs via two edges (O2–O2′ and O3–O3′) with equatorial orientation relative to each other forming zigzag chains {CeO4/1O4/2]8–} which run parallel to 100] and arrange as a hexagonal packing of rods. Both crystallographically different Te4+ cations exhibit trigonal non‐planar coordination figures (ψ1 tetrahedra) with three oxygen atoms each as a result of the stereochemical activity of the non‐binding electron pairs (“lone pairs”). They also are responsible for the necessary cross‐linkage of the anionic {CeO6]8–} chains. The isotypical relationship with Ce(SeO3)2 therefore justifies the formulation Ce(TeO3)2 for CeTe2O6. |