Goerigk, Felix C.Schleid, Thomas2024-07-122024-07-1220191521-37490044-2313189551553Xhttp://nbn-resolving.de/urn:nbn:de:bsz:93-opus-ds-146561http://elib.uni-stuttgart.de/handle/11682/14656http://dx.doi.org/10.18419/opus-14637The quaternary halide‐containing samarium(III) oxidoantimonates(III) Sm1.3Sb1.7O4Cl and Sm1.5Sb1.5O4Br were synthesized through solid‐state reactions from the binary components (Sm2O3, Sb2O3 and SmX3, X = Cl and Br) at 750 °C in evacuated fused silica ampoules. They crystallize tetragonally in the space group P4/mmm, like the basically isotypic bismuthate(III) compounds SmBi2O4Cl and SmBi2O4Br, but show larger molar volumes and therefore contradict an ideal composition of “SmSb2O4X” (X = Cl and Br). Both single‐crystal X‐ray diffraction and quantitative electron‐beam microprobe analysis revealed the actual compositions of the investigated antimony(III) compounds, which can be understood as heavily Sm3+‐doped derivatives of “SmSb2O4X” hosts at the Sb3+ site. (Sm1)3+ is coordinated eightfold by oxygen atoms in the shape of a cube. The mixed‐occupied (Sb/Sm2)3+ cation has four oxygen atoms and four halide anions as neighbors forming a square antiprism. The oxygen atoms and anions establish alternating layers parallel to the ab‐plane, which alternate when stacked along [001].eninfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/4.0/540article2023-11-14