Selen-Polykationen stabilisiert durch polymere Chlorobismutat-Anionen: Synthesen und Kristallstrukturen von Se4[Bi4Cl14] und Se10[Bi5Cl17]

Abstract

Die Reaktion von Selen, Selen(IV)‐chlorid und Bismut(III)‐chlorid in geschlossenen, evakuierten Glasampullen führt bei Temperaturen zwischen 110 und 155 °C zu mehreren Verbindungen, die aus diskreten Selen‐Polykationen und polymeren Chlorobismutat‐Anionen zusammengesetzt sind. Nach Se8[Bi4Cl14] konnten jetzt zwei weitere Vertreter dieser Verbindungsklasse anhand von Kristallstrukturanalysen als Se4[Bi4Cl14] (tetragonal, P4/n, a = 1089,1(2) pm, c = 993,7(2) pm, Z = 2) und Se10[Bi5Cl17] (monoklin, P21/c, a = 1079,24(8) pm, b = 2062,9(2) pm, c = 1676,1(2) pm, β = 90,87(1)°, Z = 4) identifiziert werden. Se4[Bi4Cl14], welches in Form roter, transparenter Kristallplättchen erhalten wurde, enthält Se42+‐Ionen mit der für (Chalkogen4)2+‐Ionen erstmals im Festkörper beobachteten exakt quadratisch‐planaren Struktur mit der Molekülsymmetrie D4h. Die Kationen sind umgeben von zweidimensional‐polymeren Anionen [Bi4Cl14]2–. Se10[Bi5Cl17] bildet dunkelrote, nahezu schwarze Kristalle. Neben dem bekannten bicyclischen Polykation Se102+, welches über zwei Positionen lagefehlgeordnet auftritt, enthält die Struktur mit [Bi5Cl17]2– das erste dreidimensional‐polymere Chlorobismutat‐Anion. Die Verknüpfung der BiClx‐Einzelpolyeder erfolgt über gemeinsame Ecken, Kanten und Flächen.

Homopolyatomic Chalcogen Radical Cations of Selenium and Tellurium

“…For some dicationic structures X‐ray data in the solid state are available for comparison. The square planar cycle for [Ch 4 ] 2+ , the exo‐endo ring with a transannular Ch ··· Ch contact for [Ch 8 ] 2+ and the boat conformation of the six‐membered tellurium dication were reproduced well by our calculations and are in accord with other literature data , , . Thus the reliability of the theoretical method used in this study for this class of compounds can be assumed.…”

“…A number of salts of the selenium analogues [Se 4 ] 2+ and [Se 8 ] 2+ could be prepared and their structures were determined in the salts [Se 4 ] 2 [Sb 4 F 17 ][SbF 6 ] 3 , [Se 4 ][ReCl 6 ], [Se 4 ][HS 2 O 7 ] 2 , and [Se 8 ][AlCl 4 ] 2 , , , . Moreover, the existence of the larger cations [Se 10 ] 2+ and [Se 17 ] 2+ was demonstrated , . Tellurium shows the highest number of dicationic structures in this series, which are substantially different to the structures of the lighter chalcogens.…”

A One-Dimensional Polymeric Form of the Polycation Te8 2+ in the Structure of Te8[Bi4Cl14]

“…Here a small increase of Bi-Cl distances is present, starting with two short bonds Bi( 1 )-Cl ( 1) and Bi(l)-Cl(3) of averaged 249 pm. Since two of the Cl atoms (Cl(13), Cl (14)) do not exhibit BiCl bonds shorter than 283 pm, the structure of the chlorobismutate [Bi4Cli42 -]" can be interpreted as an aggregate of B iC^ molecules and C l-ions with the formula [(BiCl3>4 (Cl_ )2]n-It is remarkable that now three compounds built of chalcogen polyca tionic clusters and a chlorobismutate of the for mula Bi4C li42~ are known, namely Se4[Bi4C li4] [6], Se8[Bi4Cli4] [7], and Te8[Bi4Cli4]. The com mon structural feature of all three anions is the link ing of irregular Bi-Cl polyhedra with coordination number 7 and 8 to two-dimensional arrangements.…”

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“…In a similar vein, new examples of salts of the [Se 4 ] 2+ and [Se 10 ] 2+ cations have been shown to result from the reaction of selenium with SeCl 4 and BiCl 3 . 43 A different class of polysulfur system comes in the form of new sulfanes isolated from the reaction of organosulfur chlorides with transition metal sulfide complexes. 44 47 and the trimeric [Te 3 O 6 F 3 ] 32 anion.…”