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Theoretical study on O⋯Br and O⋯Cl halogen bonds in some small model molecular systems

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Abstract

Halogen bonding interactions of type X⋯O=C are important in various fields including biological systems. In this work, theoretical calculations were carried out using B3LYP/6-31 ++G**, MP2/6-31 ++G** and MP2/aug-cc-pVDZ methods on a series of O⋯X halogen bonds between CH2O and CH3CHO as halogen bond acceptor with X-Y (X = Cl, Br; Y = CF3, CF2H, CFH2, CN, CCH, CCCN) as halogen bond donors. The strength of interaction energy for O⋯Br halogen-bonded complexes varies from −2.16 to −5.26 kcal/mol while for O⋯Cl complexes, it is between −1.65 to −3.67 kcal/mol, which indicate the O⋯Br bond to be stronger in comparison to O⋯Cl bond. SAPT analysis suggests that the strength of halogen bonding arises from the electrostatic and induction forces while dispersion is playing a comparatively smaller role. The halogen-bonded interaction energies were found to correlate well with positive electrostatic potential VS,max, halogen bonded distances, and the change in s-character of C-X bond. The halogen-bonded interaction energies were also evaluated for O⋯I bonded complexes and thus these complexes were found to be stronger than O⋯Br and O⋯Cl bonded complexes.

Theoretical calculations were carried out on halogen bonded complexes CH2O⋯X-Y and CH3CHO⋯X-Y (X = Cl, Br, I; Y = CF3, CF2H, CFH2, CN, CCH, CCCN). The interaction energies increase in the order O⋯Cl < O⋯Br < O⋯I. The interaction energies were found to be correlate well with the VS,max, halogen bonded distances, and the change in s-character of C-X bond.

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Acknowledgement

We are highly thankful to the Department of Science and Technology (DST) (INSPIRE Fellowship Programme) for the financial assistance.

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  1. Department of Chemistry, Guru Nanak Dev University, Amritsar, 143005, India

    DAMANJIT KAUR & RAJINDER KAUR

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Supplementary Information

The differences of the halogen bonding distances between the values in the complex and in the isolated molecule for C-X bond of X-Y molecules and for C=O bond of carbonyl molecules are given in table S1 at MP2/aug-cc-pVDZ level. Tables S2–S19 include the optimized parameters for the CH2O and CH3CHO along with their complexes with X-Y (X = Cl, Br; Y = CF3, CF2H, CFH2, CN, CCH and CCCN) at B3LYP/6-31 ++G** and MP2/aug-cc-pVDZ theoretical levels. Table S21 lists the percentage s-character of C in C-X bond of the halogen donors for the monomers and the complexes at MP2/aug-cc-pVDZ level. The atomic charges on the halogen bonding atoms obtained using NBO analysis at MP2/aug-cc-pVDZ level are given in table S22. Figure S1 shows a correlation between SAPT-based interaction energies and interaction energies obtained at MP2/cc-pVDZ level for both CH2O and CH3CHO complexes under study. The optimized parameters for O ⋯I bond complexes of CH2O and CH3CHO at MP2/cc-pVDZ-PP level are reported in tables S23–S28.

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KAUR, D., KAUR, R. Theoretical study on O⋯Br and O⋯Cl halogen bonds in some small model molecular systems. J Chem Sci 126, 1763–1779 (2014). https://doi.org/10.1007/s12039-014-0717-6

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