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

  • Ioannis Tiritiris , Kevin U. Bareiß and Thomas Schleid EMAIL logo
Published/Copyright: August 12, 2020
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Zeitschrift für Naturforschung B
From the journal Zeitschrift für Naturforschung B Volume 75 Issue 8

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:

  1. 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.

  2. Author contribution: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  3. Research funding: None declared.

  4. 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

© 2020 Walter de Gruyter GmbH, Berlin/Boston

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https://doi.org/10.1515/znb-2020-0096
Keywords for this article
cesium salts; crystal structures; dodecahalogeno-closo-dodecaborates; phase transitions; thermal DSC analyses

Articles in the same Issue

  1. Frontmatter
  2. In this issue
  3. Research Articles
  4. Na2MgSnS4 – a new member of the A2IBIICIVX4 family of compounds
  5. Synthesis, crystal structure, luminescence, and photocatalytic properties of a 2D Cu(II) metal-organic frameworks based on 3,5-di(1H-benzimidazol-1-yl)pyridine and 4,4′-oxybis(benzoate) ligands
  6. Synthesis and structural characterization of a three-dimensional two-fold interpenetrated coordination polymer constructed from bis(4-(1H-imidazol-1-yl)phenyl)methanone and 1,1ʹ-biphenyl-2,2ʹ-dicarboxylate ligands for cadmium(II)
  7. Impact of aging on the hydration of tricalcium aluminate (C3A)/gypsum blends and the effectiveness of retarding admixtures
  8. Influence of meso-linker attachment on the formation of core···π interactions in urea-functionalized porphyrins
  9. Single-crystal investigation of Ce5AgxGe4−x (x = 0.1−1.08) with Sm5Ge4 type
  10. Wirt-Gast-Komplexe von [bfu.bfu.bfu]: Vorhersage von Ionenselektivitäten mittels quantenchemischer Rechnungen XIII
  11. Untersuchungen zur Polymorphie der Cäsium-Dodekahalogeno-closo-Dodekaborate Cs2[B12X12] (X = Cl–I)
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  14. Sc14Co3.10In2.59 – the representative of the Lu14Co3In3 type with the smallest rare earth element
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