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N(nPr)4[B5O6(OH)4][B(OH)3]2 and N(nBu)4[B5O6(OH)4][B(OH)3]2: Clathrates with a diamondoid arrangement of hydrogen-bonded pentaborate anions

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Abstract

Single-crystal X-ray structure analyses of N(nPr)4[B5O6(OH)4][B(OH)3]2,1, and N(nBu)4 [B5O6(OH)4][B(OH)3]2,2, reveal that these materials are novel clathrates, the isotypic host structures of which are three-dimensional assemblies of hydrogen-bonded [B5O6(OH)4]− ionsand B(OH)3 molecules. The assembly of only the pentaborate anions is a distorted (i.e., along [102] elongated) fourconnected diamond-related network. The N(nPr) +4 and N(nBu) +4 ions are trapped within the complex three-dimensional channel systems of the host frameworks. Both1 and2 crystallize monoclinically with space groupP21/c andZ=4. The cell constants are:1:a=13.592(5),b=12.082(2),c=17.355(6) Å, β=106.60(2)° (298K);2:a=13.874(3),b=12.585(1),c=17.588(4) Å, β=107.04(1)° (238 K). The results obtained by both11B and13C MAS NMR spectroscopy are discussed. Thermogravimetric studies under a flowing inert-gas atmosphere suggest that water, stemming from polycondensation of the hydrous borate species, is released from the clathrates at ca. 443 K (1) and 398 K (2) before the decomposition of the organic cations starts at ca. 603 K (1) and 603 K (2).

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Authors and Affiliations

  1. Faculty of Chemistry, University of Konstanz, P.O. Box 5560, 78434, Konstanz, Germany

    Clemens C. Freyhardt, Michael Wiebcke & Jürgen Felsche

  2. Institute of Chemical Technology I, University of Stuttgart, Pfaffenwaldring 55, 70550, Stuttgart, Germany

    Günter Engelhardt

Authors
  1. Clemens C. Freyhardt
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  2. Michael Wiebcke
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  3. Jürgen Felsche
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  4. Günter Engelhardt
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Author for correspondence.

Supplementary Data relating to this article are deposited with the British Library as supplementary publication No. SUP 82172 (82 pages).

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Freyhardt, C.C., Wiebcke, M., Felsche, J. et al. N(nPr)4[B5O6(OH)4][B(OH)3]2 and N(nBu)4[B5O6(OH)4][B(OH)3]2: Clathrates with a diamondoid arrangement of hydrogen-bonded pentaborate anions. Journal of Inclusion Phenomena and Molecular Recognition in Chemistry 18, 161–175 (1994). https://doi.org/10.1007/BF00705819

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