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The structure of tris(chloromethyl)amine in the gas phase using quantum chemical calculations and gas electron diffraction and as a solid and melt using Raman spectroscopy

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Abstract

The equilibrium structure of tris(chloromethyl)amine, N(CH2Cl)3, has been determined in the gas phase using electron diffraction. Single-step distance corrections (representing the differences between the interatomic distances from the equilibrium structure and those from the vibrationally averaged structure) and amplitudes of vibration have been computed using semi-empirical molecular dynamics (SE-MD) simulations in order to treat accurately the description of the low-frequency, large-amplitude vibrational modes associated particularly with one CH2Cl group. A series of complementary theoretical calculations using the SOGGA11-X DFT functional with correlation-consistent basis sets of double-, triple-, and quadruple-ζ quality is also presented. The agreement between the experimental and theoretical equilibrium structural parameters attests to the accuracy of the applied theoretical calculations and of our gas-phase structural solution. Raman spectra have been recorded over a range of temperatures, allowing the solid and the melt to be studied, and the Raman-active intramolecular modes to be identified. Free from the influence of intermolecular interaction, the structure of tris(chloromethyl)amine in the gas phase is markedly different to that reported in the literature for the single crystal. This is discussed, and evidence for the anomeric effect in tris(chloromethyl)amine is evaluated.

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Acknowledgments

C.D.R thanks João Pedro Nunes for useful discussions on data extraction and provision of the data extraction package xstract. We extend our thanks the staff at the York Advanced Research Computing Cluster (YARCC) and the UK National Service for Computational Chemistry Software (NSCCS) for the provision of computational resources.

Funding

D.A.W and C.D.R thank the EPSRC for funding the gas electron diffraction and theoretical research at the University of York, UK, for funding a fellowship for D.A.W. (EP/I004122), and for funding the studentship of C.D.R. S.J.A thanks the Department of Chemistry, University of Canterbury, NZ, for funding a studentship, and for the award of the inaugural Betty Wignall Scholarship.

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Authors and Affiliations

  1. Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK

    Conor D. Rankine & Derek A. Wann

  2. School of Physical and Chemical Sciences, University of Canterbury, Private Bag 4800, Christchurch, 8140, New Zealand

    Sandra J. Atkinson & Sarah L. Masters

  3. Institute of Fundamental Sciences, Massey University, Private Bag 11 222, Palmerston North, 4442, New Zealand

    Mark R. Waterland

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  1. Conor D. Rankine
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  2. Sandra J. Atkinson
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  3. Mark R. Waterland
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Correspondence to Sarah L. Masters or Derek A. Wann.

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Electronic supplementary material

ESM 1

Supporting Information: Summary of parameters for the GED data collection (Table S1); the Cartesian coordinates and energies of A and B as optimized at the SOGGA11-X level (Tables S2–S4); the Cartesian coordinates and energies of TS A,B as optimized at the SOGGA11-X level (Tables S5–S7); summary of parameters for the GED data refinement (Table S8); least-squares correlation matrix for the GED data refinement (Table S9); the Cartesian coordinates and energies of A as optimized at the B3LYP (Tables S10–S12), B3P86 (Tables S13–S15), B3PW91 (Tables S16–S18) and wB97XD (Tables S19–S21) levels; the Cartesian coordinates and energies of methenamine as optimized at the SOGGA11-X level (Tables S22–S24); details of the molecular model used in the least-squares refinement procedure; refined parameters, and SARACEN restraints (Table S25); interatomic distances, GED-determined and theoretical amplitudes of vibration, and MD-derived distance corrections (Table S26); the refined GED structure of TCMA in Cartesian coordinates (Table S27). (DOCX 131 kb)

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Rankine, C.D., Atkinson, S.J., Waterland, M.R. et al. The structure of tris(chloromethyl)amine in the gas phase using quantum chemical calculations and gas electron diffraction and as a solid and melt using Raman spectroscopy. Struct Chem 29, 803–813 (2018). https://doi.org/10.1007/s11224-018-1089-1

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