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Comparison of halogen bonds in MXN contacts (M=C, Si, Ge and X=Cl, Br)

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The halogen bonds (XB) formed between some Si−X- and Ge−X- (X is Cl and Br) containing molecules and NCH (as a Lewis base) have been investigated and compared with C−X⋯N halogen bond. Although, in all cases, the existence of a positive electrostatic potential (σ-hole) along the extension of M−X was responsible for halogen bond formation, multipole expansion of electrostatic potential reveals that these positive potentials originate from different atomic multipole moments. Indeed, in addition to the monopole moment of M atoms, the quadrupole moment of X in C−X molecules, the dipole moment of the halogen in Si−X molecules and both the dipole and quadrupole moments of X in Ge−X molecules are mainly responsible for the existence of the σ-hole along the extension of the M−X bond. From a different point of view, the distribution of the Laplacian of electron density shows that all the studied M−X⋯N halogen bonds can be regarded as “lump-hole” interactions; a region of charge depletion (hole) in the valence shell charge concentration (VSCC) of the halogen atom interacts with a region of charge concentration (lump) in the VSCC of nitrogen and forms a halogen bond. On the other hand, interacting quantum atoms (IQA) analysis of atomic energies indicates that, in contrast to C−X⋯N contacts, in which the interaction between halogen and nitrogen is attractive, there is a net repulsive interaction between X and N in Si−X⋯N and Ge−X⋯N complexes. Indeed, the attraction between Si/Ge and nitrogen is mainly responsible for the formation of these halogen bonds.

Contour map of the Laplacian of the electron density (∇2 ρ) of FCGeBr. The arrow indicates the hole in the valence shell charge concentration of bromine

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This paper was extracted from a research project entitled Electron Density and It’s Laplacian in Halogen bonds of Ge-X and Si-X Containing Molecules (X= F, Cl, Br). Financial assistance from the Mahshahr Branch, Islamic Azad University is gratefully acknowledged.

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Correspondence to Hossein Jalali Jahromi or Kiamars Eskandari.

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Jahromi, H.J., Eskandari, K. & Alizadeh, A. Comparison of halogen bonds in MXN contacts (M=C, Si, Ge and X=Cl, Br). J Mol Model 21, 112 (2015).

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