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Composition and Crystal Structure of SmSb 2 O 4 Cl Revisited – and the Analogy of Sm 1.5 Sb 1.5 O 4 Br
Author(s) -
Goerigk Felix C.,
Schleid Thomas
Publication year - 2019
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201900139
Subject(s) - crystallography , crystal structure , samarium , antimony , chemistry , halide , electron microprobe , bond length , analytical chemistry (journal) , inorganic chemistry , mineralogy , chromatography
The quaternary halide‐containing samarium(III) oxidoantimonates(III) Sm 1.3 Sb 1.7 O 4 Cl and Sm 1.5 Sb 1.5 O 4 Br were synthesized through solid‐state reactions from the binary components (Sm 2 O 3 , Sb 2 O 3 and Sm X 3 , X = Cl and Br) at 750 °C in evacuated fused silica ampoules. They crystallize tetragonally in the space group P 4/ mmm , like the basically isotypic bismuthate(III) compounds SmBi 2 O 4 Cl and SmBi 2 O 4 Br, but show larger molar volumes and therefore contradict an ideal composition of “SmSb 2 O 4 X ” ( 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 Sm 3+ ‐doped derivatives of “SmSb 2 O 4 X ” hosts at the Sb 3+ 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].