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Octachalcogen Cations Te82+, Se82+, and Mixed (Te8-xSex)82+ Stabilized by Chlorometallates of Bi, Zr, and Hf: Synthesis and Crystal Structures of Se8[Bi4Cl14] and E8[MCl6] (E = Se, Te; M = Zr, Hf)
-
A. Baumann
and
T. Hilbert
Published/Copyright:
June 2, 2014
The title compounds were obtained by the reaction of elemental chalcogens E (E = Se, Te) with the respective tetrachlorides ECl4 and the Lewis acidic metal halides ZrCl4, HfCl4, and BiCl3. An alternative way, particularly for the preparation of mixed Se/Te-species, is the enlargement of smaller cationic rings in E4MCl6] (M = Zr, Hf) by adding the respective complementary chalcogen. All reactions were carried out in sealed, evacuated glass ampoules at temperatures between 120 °C and 220 °C, and yielded black crystals of Se8[Bi4Cl14], (Te5.0Se3.0)[HfCl6], (Te5.3 Se2.7)[ZrCl6], (Te6.5Se1.5)[ZrCl6] and Te8[HfCl6], which have been identified by crystal structure analyses. All five compounds contain eight-membered chalcogen rings in an endo-exo-conformation which are isostructural to the known octachalcogen dications E82+ (E = S, Se, Te). While in (Te5 .0Se3.0)[HfCl6], (Te5.3Se2 .7 )[ZrCl6], (Te6 .5Se1.5 )[ZrCl6] and Te8[HfCl6] the molecular polycations are surrounded by discrete, octahedral [MCl6]2- counterions, Se4[Bi4Cl14] contains a two-dimensional polymeric anion ([Bi4Cl14]2-)n built of a variety of vertex and edge-sharing BiClx-polyhedra (x = 6, 7). The Bi-Cl bond lengths are spread over a wide range between 250 and 350 pm.
Keywords : Octaselenium(2+); Octatellurium(2+); Chalcogen Polycations; Halogenobismutates(III); Crystal Structure
Received: 1999-7-15
Published Online: 2014-6-2
Published in Print: 1999-10-1
© 1946 – 2014: Verlag der Zeitschrift für Naturforschung
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Keywords for this article
Octaselenium(2+);
Octatellurium(2+);
Chalcogen Polycations;
Halogenobismutates(III);
Crystal Structure
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