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Tl 2 TiS 4  is orthorhombic, space group Pbca, with a = 22.176(7), b = 9.484(4), c = 6.3977(9) Å, Z = 8. The crystal structure was solved by direct methods and refined to a conventional R of0.058 for 704 reflections with I ≥3σ(I). The crystal structure is characterized by infinite perthioanions,  ∞  1 -[TiS  4/2  (S2) 2-  ], which are separated by Tl +  -cations. The anion chains are built up by distorted octahedra which share two skew edges to form infinite cis-chains running along [001], The two unshared S-atoms of each octahedron are connected via a S -S-single bond of 2.10 Å length. The crystal structure is described as a mixed packing of TI-and S-atoms, composed of puckered TlS 2  -layers, in which the Ti-atoms occupy the octahedral interstices. The relationship of the  ∞  1 -[TiS 4  2-  -]-chains to the anionic groups of Cs 2 TiS 3  is discussed.

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Darstellung und Kristallstruktur von Tl 2 TiS 4  : Ein Perthiotitanat(IV) mit  ∞  1 -[TiS 4  2- ]-Ketten Preparation and Crystal Structure of Tl 2 TiS 4  : A Perthiotitanate(IV) with   ∞  1 -[TiS 4  2- ]-Chains