The Bicyclic Polyselenium Cation Se102+ in the Structure of Se10[Bi4Cl14]
Résumé
In the ternary system Se / Bi / Cl a new polycation containing phase besides the already known Se4[Bi4Cl14] Se8[Bi4Cl14], and Se10[Bi5Cl17] was discovered. Red, transparent, plate shaped crystals of Se10[Bi4Cl14] were formed by reaction of Se / SeCl4 / BiCl3 in 15 / 1 / 8 molar ratio in evacuated glass ampoules applying a temperature gradient from 90 to 80 °C. The crystal structure consists of bicyclic Se102+ cations and of layered chloridobismutate anions with the cations located between the anionic planes. The atoms of the cation form a six membered ring with a Se4 chain bridging over the 1,4 positions of the Se6 ring. The anions are made up of BiCl7 polyhedra connected via common edges to layers [Bi4Cl142–]. Se4[Bi4Cl14], Se8[Bi4Cl14], Se10[Bi4Cl14], and Te8[Bi4Cl14] all contain an anion of identical formula and two-dimensional connectivity, but these polymeric chloridobismutates are not isostructural. The structural differences are discussed on basis of the different topologies of the nets made up by the Bi atoms.
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