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The known crystal structures of the mixed valence compounds In 6 S 7  and Sn 0.5 In 5 S 7  are characterized by the existence of indium atoms in different valence states: In + -ions (Sn 2+ ), dumbbell shaped In 2  4+  groups and In 3+ -ions. The In 2  4+  and In 3+  species are embedded in a characteristic coordination of sulfur atoms found separately in comparable simpler non-mixed-valence chalcogenides of indium. In 6 S 7  however is so far the only example with monovalent indium in a surrounding of sulfur. The question whether  P 2 1  or  P 2 1 / m  is the correct space group for the description of In 6 S 7  (or Sn 0.5 In 5 S 7 ) cannot be answered clearly on the basis of the existing experimental data because it only affects a small possible deviation of the “lone pair cation” In +  (Sn 2+ ) from a mirror plane. This may however be of great importance for futural studies of the physical properties. We prove the crystal structure of Sn 0.5 In 5 S 7  and In 6 S 7  to be actually isotypic. Moreover we show, that the pure tin containing compound does not exist, but is indeed In 6 S 7  in which In + -ions are partly (max. 50%) substituted by Sn 2+ .

Strukturchemie und Valenz von In 6 S 7 : Neubestimmung der Kristallstruktur