Single crystals of ternary chalcogenides with the composition BaLu 2 Ch 4 ( Ch = S, Se and Te; orthorhombic, Pnma; a = 1211.4–1353.6, b = 395.6–438.5, c = 1427.8–1593.6 pm) could be obtained after attempts to synthesize ternary lutetium(III) nitride chalcogenides using the elements (Lu and Ch) along with BaN 3Cl as a nitrogen source. Their crystal structures are isotypic with CaFe 2O 4 containing two sorts of {[Lu Ch Ch] 8–} chains built up of edge-linked [(Lu1)( Ch2)( Ch3) 3( Ch4) 2] 9– and [(Lu2)( Ch1) 3( Ch2) 2( Ch4)] 9– octahedra, respectively. A further interconnection via the chalcogenide anions ( Ch3) 2– and ( Ch1) 2– leads to double chains, where either (Lu1) 3+ or (Lu2) 3+ coordinates these chalcogenide anions as well. The three-dimensional framework {[Lu 2 Ch 4] 2–} emerges from the corner-linkage of the two kinds of double chains forming large channels apt to take up the Ba 2+ cations. These divalent cations exhibit eight contacts to chalcogenide anions resulting in the formation of bicapped trigonal prisms [Ba Ch 8] 14–.
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