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Energetic study of bromobenzonitrile isomers: insights on the intermolecular interactions, aromaticity and electronegativity

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Abstract

The standard (p o = 0.1 MPa) molar enthalpies of formation, in the gaseous phase, of 2-, 3- and 4-bromobenzonitrile isomers were calculated from the combination of the following two parameters experimentally determined: the standard molar enthalpy of formation in the condensed phase, derived from the standard molar energy of combustion in oxygen at T = 298.15 K, measured by rotating-bomb combustion calorimetry, and the standard molar enthalpy of sublimation at the same reference temperature, derived from vapour pressure studies at several temperatures, as measured by mass-loss Knudsen effusion. The computational calculations complement the energetic study and analysis of the electron delocalization allows a comparison between the fluorine and bromine benzonitrile isomers. The harmonic oscillator model of aromaticity and nucleus-independent chemical shift aromaticity criteria and the natural bond orbital analysis were applied and related with the intramolecular enthalpic interactions. The intermolecular interactions in the crystal packing were analysed in terms of enthalpic and entropic contributions, using the crystallographic structures available in literature.

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Acknowledgments

Thanks are due to Fundação para a Ciência e Tecnologia (FCT), Lisbon, Portugal and to European Social Fund for financial support to Centro de Investigação em Química, University of Porto (strategic project PEst-C/QUI/UI0081/2011). I.M.R and T.L.P.G. thank FCT and European Social Fund (ESF) under the Community Support Framework (CSF) for the award of Ph.D. fellowship (SFRH/BD/61915/2009) and (SFRH/BD/62231/2009), respectively.

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Authors and Affiliations

  1. Centro de Investigação em Química, Department of Chemistry and Biochemistry, Faculty of Science, University of Porto, Rua do Campo Alegre, 687, 4169-007, Porto, Portugal

    Inês M. Rocha, Tiago L. P. Galvão, Maria D. M. C. Ribeiro da Silva & Manuel A. V. Ribeiro da Silva

Authors
  1. Inês M. Rocha
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  2. Tiago L. P. Galvão
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  3. Maria D. M. C. Ribeiro da Silva
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  4. Manuel A. V. Ribeiro da Silva
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Corresponding author

Correspondence to Maria D. M. C. Ribeiro da Silva.

Electronic supplementary material

Below is the link to the electronic supplementary material.

11224_2013_278_MOESM1_ESM.doc

This supplementary information includes all the rotating-bomb combustion calorimetry experiments for 2-, 3- and 4-bromobenzonitrile isomers as well as the areas of the orifices of the cells used and the vapour pressure obtained by mass-loss Knudsen effusion method for each studied compound. Cartesian coordinates of the optimized structures for the three bromobenzonitrile isomers and all the auxiliaries molecules at MP2/cc-pVTZ level of theory, as well as the computed enthalpies for the compounds studied are also listed. Some explanations of Donor–acceptor propagation method calculations and the second-order perturbation energies interactions for each compound are presented. (DOC 538 kb)

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Rocha, I.M., Galvão, T.L.P., Ribeiro da Silva, M.D.M.C. et al. Energetic study of bromobenzonitrile isomers: insights on the intermolecular interactions, aromaticity and electronegativity. Struct Chem 24, 1935–1944 (2013). https://doi.org/10.1007/s11224-013-0278-1

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  • DOI: https://doi.org/10.1007/s11224-013-0278-1

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