Untersuchungen zur Polymorphie der Cäsium-Dodekahalogeno-closo-Dodekaborate Cs2[B12X12] (X = Cl–I)

Ioannis Tiritiris; Kevin U. Bareiß; Thomas Schleid

doi:10.1515/znb-2020-0096

Published by De Gruyter August 12, 2020

Untersuchungen zur Polymorphie der Cäsium-Dodekahalogeno-closo-Dodekaborate Cs₂[B₁₂X₁₂] (X = Cl–I)

Investigations on the polymorphism of the cesium dodecahalogeno-closo-dodecaborates Cs₂[B₁₂X₁₂] (X = Cl–I)

Ioannis Tiritiris , Kevin U. Bareiß and Thomas Schleid

From the journal Zeitschrift für Naturforschung B

https://doi.org/10.1515/znb-2020-0096

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Abstract

Thermoanalytic DSC and temperature-dependent X-ray diffraction investigations on the cesium dodecahalogeno-closo-dodecaborates Cs₂[B₁₂X₁₂] (X = Cl–I) have revealed solid-solid phase transitions from their trigonal room-temperature α-forms (e.g. α-Cs₂[B₁₂Cl₁₂]: a = 959.67(3) pm, c = 4564.2(2) pm, Z = 6, space group R3¯) into cubic high-temperature modifications. The isotypic title compounds crystallize in the space group Pm3¯n (e.g. β-Cs₂[B₁₂Cl₁₂]: a = 1051.98(6) pm, Z = 2) with a W₃O-type defect structure. The statistic occupation of six possible positions with only four Cs⁺ cations results in a cation-deficient A₂B arrangement for Cs₂[B₁₂X₁₂]. Upon cooling the β-phase, a third polymorph was observed, which also crystallizes in the cubic system, but now in the space group Ia3¯d (e.g. γ-Cs₂[B₁₂Cl₁₂]: a = 2102.2(3) pm, Z = 16), and has to be regarded as a phase with only a partially disordered cation substructure. In this crystal structure the [B₁₂X₁₂]²⁻ anions exhibit a NaTl-type arrangement, in which the Cs⁺ cations occupy suitable interstices. The phase transitions of the differently halogenated cesium salts follow no specific trend as the transition from the trigonal α- to the cubic β-form occurs at 178 °C for the chlorinated, at 270 °C for the iodinated and at 325 °C for the brominated examples. On further heating however, β-Cs₂[B₁₂I₁₂] starts to decompose at 945 °C first, followed by β-Cs₂[B₁₂Br₁₂] and β-Cs₂[B₁₂Cl₁₂] at 959 °C and 983 °C, respectively.

Keywords: cesium salts; crystal structures; dodecahalogeno-closo-dodecaborates; phase transitions; thermal DSC analyses

Widmung: Professor Peter Paetzold zum 85. Geburtstag.

Corresponding author: Thomas Schleid, Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany, E-mail: schleid@iac.uni-stuttgart.de

Danksagung: Wir danken Herrn Dr. Falk Lissner (AOR) für die Einkristallmessungen, Herrn Christof Schneck (CTA) für die DSC-Messungen sowie dem Land Baden-Württemberg (Stuttgart) und der Deutschen Forschungsgemeinschaft (Bonn) im Rahmen der Förderung des Graduiertenkollegs „Moderne Methoden der magnetischen Resonanz in der Materialforschung“ an der Universität Stuttgart für die großzügige Unterstützung mit Personal- und Sachmitteln.
Author contribution: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: None declared.
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Erhalten: 2020-06-05

Angenommen: 2020-06-11

Online erschienen: 2020-08-12

Erschienen im Druck: 2020-09-25

Untersuchungen zur Polymorphie der Cäsium-Dodekahalogeno-closo-Dodekaborate Cs₂[B₁₂X₁₂] (X = Cl–I)

Abstract

References

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