Publication Date:
2012-08-31
Description:
The polysulfides Ln S 1.9 and polyselenides Ln Se 1.9 of the lanthanide metals from gadolinium to thulium were prepared by high-pressure high-temperature synthesis. The compounds adopt the tetragonal CeSe 1.9 structure type in space group P 4 2 / n (No. 86) with lattice parameters of 8.531 Å ≤ a ≤ 8.654 Å and 15.563 Å ≤ c ≤ 15.763 Å for the sulfides and 8.869 Å ≤ a ≤ 9.076 Å and 16.367 Å ≤ c ≤ 16.611 Å for the selenides. The atomic pattern consists of puckered double slabs [ LnX ] + and planar chalcogenide layers with ten possible chalcogen positions, of which eight are occupied by chalcogen atoms forming dinuclear X 2 2– dianions, one by a single X 2– ion and one remaining vacant. This resembles a √5×√5 × 2 superstructure of the ZrSSi aristotype. Structural relationships to the aristotype and the related lanthanide polychalcogenides LnX 2– δ ( Ln = La–Tm, X = S–Te, δ = 0 – 0.3) are discussed. The samples synthesized under high-pressure conditions ( p 〉 1 GPa) decompose slowly under release of sulfur or selenium at ambient conditions. The crystal structure of a partially degraded thulium-polysulfide sample can be described as an incommensurate variant of the original TmS 1.9 motif. Additionally, the isostructural ternary compound Gd(S 1–x Se x ) 1.9 was synthesized and characterized by powder X-ray diffraction.
Print ISSN:
0044-2313
Electronic ISSN:
1521-3749
Topics:
Chemistry and Pharmacology
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