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Cs 10 Tl 6 SiO 4 , Cs 10 Tl 6 GeO 4 , and Cs 10 Tl 6 SnO 3 – First Oxotetrelate Thallides, Double Salts Containing “Hypoelectronic” [Tl 6 ] 6– Clusters
Author(s) -
Saltykov Vyacheslav,
Nuss Jürgen,
Jansen Martin
Publication year - 2011
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.201000358
Subject(s) - octahedron , crystallography , tin , atom (system on chip) , crystal structure , electron counting , tantalum , quenching (fluorescence) , oxidation state , jahn–teller effect , materials science , chemistry , electron , physics , metal , ion , fluorescence , organic chemistry , quantum mechanics , computer science , metallurgy , embedded system
Cs 10 Tl 6 TtO 4 (Tt = Si, Ge) and Cs 10 Tl 6 SnO 3 were synthesized by the reaction of appropriate starting materials at 623–673 K, followed by fast cooling or quenching to room temperature, in arc‐welded tantalum ampoules. According to single‐crystal X‐ray analyses, the compounds crystallize in new structure types (Cs 10 Tl 6 TtO 4 (Tt = Si, Ge), P 2 1 / c and Cs 10 Tl 6 SnO 3 , Pnma ), consisting of [Tl 6 ] 6– clusters, which can be characterized as distorted octahedra compressed along one of the fourfold axes of an originally unperturbed octahedron, and [SiO 4 ] 4– , [GeO 4 ] 4– or [SnO 3 ] 4– anions. The oxotetrelate thallides can be regarded as “double salts”, which consist of Cs 6 Tl 6 on one side and respective oxosilicates, ‐germanates and ‐stannates on the other, showing almost not any direct interaction between the two anionic moieties, as might be expressed e.g. by the formula [Cs 6 Tl 6 ][Cs 4 SiO 4 ]. In contrast to the silicon and germanium compounds, where the oxidation state of the tetrel atom is unambiguously 4+, for the threefold coordinated tin atom in Cs 10 Tl 6 SnO 3 an oxidation state of 2+ has to be assumed. Thus, the latter reveal further evidence that the so called “hypoelectronic” [Tl 6 ] 6– cluster does not require additional electrons and is intrinsically stable. The distortion of [Tl 6 ] 6– can be understood in terms of the Jahn–Teller theorem. According to magnetic measurements all title compounds are diamagnetic.