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Single crystals of the ternary copper(I) lanthanide(III) sulfides with the composition CuMS 2  (M = Dy - Lu) are formed within seven days at 750 °C by oxidation of elemental copper and lanthanide metal with sulfur (molar ratio: 1 : 1 : 2, evacuated silica tubes) in equimolar quantities of CsCl, CsBr or CsI as fluxing agents. The CuYS 2 -type crystal structures (orthorhombic, Pnma, Z = 4; e. g. CuDyS 2 : a = 1342.51(9), b = 397.96(3), c = 627.43(5) pm and CuLuS 2 : a = 1315.06(9), b = 391.04(3), c = 624.18(5) pm) exhibit chains of cis edge-linked [CuS 4 ] 7−  tetrahedra with the composition  1  ∞ {[Cu(S1) 3/3 (S2) 1/1 ] 3− } which run parallel to [010] and show hexagonal rod packing. Charge compensation and three-dimensional interconnection of these anionic strands occur via octahedrally coordinated M 3+  cations surrounded by six S 2−  anions. These [MS 6 ] 9−  octahedra share vertices and edges to form a three-dimensional network  3  ∞ {[M(S1) 3/3 (S2) 3/3 ] − } with the ramsdellite-type topology of γ-MnO 2 . The metal sulfur distances within the [MS 6 ] polyhedra are very similar (M-S: 263 - 279 pm), whereas those within the [CuS 4 ] units cover the ranges 227 - 230 (Cu-S 2 ) and 231 - 233 (Cu-S1) as well as 250 - 252 pm (Cu-S1′, 2×). The present work is the first comprehensive X-ray single crystal diffraction study of the complete isotypic B-type series CuMS 2  (M = Dy - Lu).

zeitschrift für naturforschung b

Münzmetall-Lanthanid-Chalkogenide: II. Kupfer(I)-Lanthanid(III)- Sulfide der Zusammensetzung CuMS 2  (M = Dy – Lu) im orthorhombischen B-Typ / Coinage Metal Lanthanide Chalcogenides: II. Copper(I) Lanthanide(III) Sulfides of the Composition CuMS 2  (M = Dy – Lu) with the Orthorhombic B-Type Structure