Die unerwartete Kristallstruktur des Cäsium-Dodekahydro-Monocarba-closo-Dodekaborats Cs[CB11H12]
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Kevin U. Bareiß
Abstract
The cesium dodecahydro-monocarba-closo-dodecaborate Cs[CB11H12] crystallizes with an unexpected trigonal crystal structure having the lattice parameters a = 2094.73(3) and c = 1324.56(2) pm (c/a = 0.632) for Z = 18. The non-centrosymmetric space group R3 allows an ordering of the unsymmetric [CB11H12]– anions in a way that the least electronegative vertices of the pseudo-icosahedral cages avoid close proximity to the Cs+ cations. Hence there are channels at [0 0 z], [1/32/3z] and [2/31/3z], into which the C–H bonds of the [CB11H12]– units are pointing. There are two crystallographically independent Cs+ cations and [CB11H12]– anions present with unsurprising interatomic distances (d(C–B) = 166–181 pm, d(B–B) = 170–183 pm, d(B–H) = d(C–H) ≈ 110 pm) for the latter. Both Cs+ cations have contact to 18 hydrogen atoms (d(Cs–H) = 296–427 pm) stemming from six unevenly face-grafting [CB11H12]– anions, where only B–H bonds are involved. This fact is nicely reflected by IR and Raman spectroscopy. According to a 6/6 motif of the ions with highly distorted mutual octahedral coordination spheres of their centres of gravity, the crystal structure of Cs[CB11H12] follows roughly a rock salt-like arrangement. This becomes even more evident, when order-disorder transitions starting at T = 60 °C lead to more highly symmetrical structures with orientationally disordered [CB11H12]– anions.
Widmung: Professor Todd B. Marder zum 65. Geburtstag gewidmet.
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 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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Artikel in diesem Heft
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- Synthesis, crystal structure and photoluminescence of a binuclear rhenium(I) carbonyl complex incorporated in a framework of a distorted salophen ligand
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Artikel in diesem Heft
- Frontmatter
- In this issue
- Research Articles
- A zinc(II) coordination polymer based on a flexible bis(benzimidazole) ligand: synthesis, crystal structure and fluorescence study
- A study of antituberculosis activities and crystal structures of (E)-2-[2-(arylidene)hydrazinyl]pyrimidine and (E)-N1-(arylidene)pyrimidine-2-carbohydrazide derivatives
- Pt3Ni/C and Pt3Co/C cathodes as electrocatalysts for use in oxygen sensors and proton exchange membrane fuel cells
- Selective cyclization modes of methyl 3′-heteroarylamino-2′-(2,5-dichlorothiophene-3-carbonyl)acrylates. Synthesis of model (thienyl)pyrazolo- and triazolo[1,5-α]pyrimidines
- Synthesis and crystal structures of two new lead(II) complexes with the pincer-type ligand 4′-(4-chlorophenyl)-2,2′:6′,2″-terpyridine (Cl-Ph-tpy): subtle interplay of weak intermolecular interactions
- Die unerwartete Kristallstruktur des Cäsium-Dodekahydro-Monocarba-closo-Dodekaborats Cs[CB11H12]
- Synthesis, crystal structure and photoluminescence of a binuclear rhenium(I) carbonyl complex incorporated in a framework of a distorted salophen ligand
- 1-Trifluoromethyl-prop-2-yne 1-iminium salts and 1-imines: reactions with the mesoionic „Nitron“
- Note
- YIrIn with ZrNiAl-type structure
