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Syntheses, Crystal Structures, and Energetics of a Complete Series of Lithium Salts of Binary or Ternary Hexachalcogenodistannates(IV), Li 4 Sn 2 E 6 · 8 en (E = S, Se, Te), Li 4 Sn 2 S 1.36 Se 4.64 · 8 en , Li 4 Sn 2 Se 2 Te 4 · 8 en , Li 4 Sn 2 Se 2 Te 4 · 9 en , and Li 4 Sn 2 S 2 Te 4 · 10 en
Author(s) -
Dehnen Stefanie,
Zimmermann Christian,
Anson Christopher E.
Publication year - 2002
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 - 10.1002/1521-3749(200201)628:1<279::aid-zaac279>3.0.co;2-l
Subject(s) - monoclinic crystal system , crystallography , triclinic crystal system , crystal structure , chemistry , ternary operation , lithium (medication) , medicine , computer science , programming language , endocrinology
En ‐coordinated lithium salts of binary or ternary hexachalcogenodistannates(IV), Li 4 Sn 2 E 6 · 8 en (E = S ( 1 ), Se ( 2 ), Te ( 3 )), Li 4 Sn 2 S 1.36 Se 4.64 · 8 en ( 4 ), Li 4 Sn 2 Se 2 Te 4 · 8 en (5 a), Li 4 Sn 2 Se 2 Te 4 · 9 en ( 5 b ), and Li 4 Sn 2 S 2 Te 4 · 10 en ( 6 ) ( en = 1,2‐diaminoethane) were synthesized by extraction of Li/Sn/E or Li/Sn/E/E′ phases (E, E′ = S, Se, Te) with en , and were structurally characterized by single crystal X‐ray diffraction. 1 – 4 and 5 a crystallize isotypically in the monoclinic space group C 2/c. The Li/Sn/Se/Te quaternary species 5 b crystallizes in a second, triclinic crystal structure in the space group P1. The stannate with sulfur as well as tellurium ligands, 6 , crystallizes as a third structure type, in the monoclinic space group P 2 1 / n . The compounds are the first chalcogeno stannates to be isolated and structurally characterized that contain lithium counterions in the crystal lattice. Along with anions [Sn 2 E 6 ] 4– or [Sn 2 E x E $^{\prime}_{6-{\it x}}$ 4– ( x = 1.36, 2), from the first of which several Group 14/16 analogs are known, 1 – 6 exhibit complex Li + ‐ en aggregates. Thus, the crystal structures differ significantly from those of known phases A 4 M 2 E 6 (A = Na, K, Rb, Cs, Tl, NMe 4 , NEt 4 , en H 2 ; M = Ge, Sn; E = S, Se, Te) that all feature discrete, sometimes complexed cations. Quantum chemical calculations at the MP2 level helped to explain the exclusive formation of ternary anions instead of different binary ones upon extracting quaternary phases, the endo‐exo ‐situation of the chalcogenide ligands found in those species, and the S/Se disorder observed for 4 . Here we present the results of the single crystal X‐ray structural analyses and the MP2 calculations, and discuss the differences between three new structure types.