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The isostructural compounds Tl 4 TiS 4 , Tl 4 SnS 4  and Tl 4 TiSe 4  crystallize in the monoclinic system, space group P2 1 /c with a = 8.328, b = 8.191, c = 15.248 Å, β = 104.53°; a = 8.395, b = 8.280, c = 15.398 A, ft = 103.69°, and a = 8.517, b = 8.389, c = 15.672 Å, β = 103.50°, respectively. There are four formula units in the unit cell. The crystal structures were determined and refined from single crystal diffractometer data. They are characterized by isolated tetrahedral thioanions which are connected with each other by Tl +  ions. The mean bond lengths are Ti-S = 2.26 Å, Sn-S = 2.40 Å and Ti -Se = 2.38 Å. The Tl atoms are surrounded by six and seven chalcogen atoms, respectively, in an irregular and polar arrangement, thus indicating stereochemical activity of the lone electron pair of the Tl +  ions. Tl-S distances vary from 2.93 to 3.98 Å, Tl-Se distances from 3.03 to 3.96 Å. The Tl atoms have nearest Tl neighbours at distances ranging from 3.46 to 3.65 Å. The crystal structure can be described as built from pseudotetragonal slabs oriented parallel to (001) which contain the cations and the tetrahedral anions. It is shown that a similar description is valid also for the crystal structures of Tl 4 GeS 4  [1] and Na 4 SnS 4  [2, 3].

zeitschrift für naturforschung b

Darstellung und Kristallstruktur von Tl 4 TiS 4 , TI 4 SnS 4  und Tl 4 TiSe 4  / Preparation and Crystal Structure of Tl 4 TiS 4 , TI 4 SnS 4  and Tl 4 TiSe 4