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Chlorotrinitromethane and its exceptionally short carbon–chlorine bond

Nature Chemistry volume 1, pages 229–235 (2009)Cite this article

Abstract

Compounds that deviate from the normal range of bonding can help to assess the strengths and weaknesses of the models currently used to describe chemical bonds. Furthermore, computer simulations of molecules require experimental data to describe accurately the energies and forces between interacting molecules. Compounds that contain the trinitromethyl group, with three nitro groups bonded to one carbon atom, show remarkable inter- and intramolecular effects. In this paper, we report the structural features of chlorotrinitromethane in the solid state and present the first reliable solid-state geometry parameters of an α-halogen derivative of the trinitromethyl pseudohalogen. We found several intriguing geometrical features in terms of intra- and intermolecular interactions, as well as an exceptionally short carbon–chlorine bond (1.694(1) Å). Using a combined crystallographic and computational approach, we show that these effects can be described in terms of the computed electrostatic potential of the molecular surface.

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Figure 1: The structure of chlorotrinitromethane.
Figure 2: Carbon–chlorine bond lengths.
Figure 3: The molecular electrostatic potential of chlorotrinitromethane.

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Acknowledgements

Financial support of this work by the Ludwig-Maximilian University of Munich (LMU) and the Fonds der Chemischen Industrie is gratefully acknowledged. M.G. thanks the Cusanuswerk for a fellowship. P.P. and J.S.M. appreciate a Defence Threat Reduction Agency grant. We thank R. Harcourt for many inspired valence bond discussions.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, Ludwig-Maximilian University of Munich, Butenandtstr. 5-13 (D), Munich, 81377, Germany

    Michael Göbel, Boris H. Tchitchanov & Thomas M. Klapötke

  2. Department of Chemistry, University of New Orleans, New Orleans, 70148, LA, USA

    Jane S. Murray & Peter Politzer

  3. Department of Chemistry, Cleveland State University, Cleveland, 44115, OH, USA

    Jane S. Murray & Peter Politzer

  4. Departments of Mechanical Engineering and Chemistry/Biochemistry, CECD, University of Maryland College Park, 20742, MD, USA

    Thomas M. Klapötke

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Contributions

M.G. conceived, designed and carried out the experiment, analysed the data, interpreted and discussed the results and wrote the paper. B.H.T. provided the visualization of the molecular electrostatic potentials as well as NBO calculations. T.M.K. provided NBO calculations as well as the increased valence bond description and discussed the results. J.S.M. and P.P. provided the molecular electrostatic potential calculations, analysed the data, discussed the results and co-wrote the paper.

Corresponding authors

Correspondence to Peter Politzer or Thomas M. Klapötke.

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Crystallographic data for compound 1, chlorotrinitromethane (CIF 10 kb)

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Göbel, M., Tchitchanov, B., Murray, J. et al. Chlorotrinitromethane and its exceptionally short carbon–chlorine bond. Nature Chem 1, 229–235 (2009). https://doi.org/10.1038/nchem.179

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