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Exploring the simultaneous ?-hole/?-hole bonding characteristics of a Br?? interaction in an ebselen derivative via experimental and theoretical electron-density analysis.

ABSTRACT: In this study, the nature and characteristics of a short Br?? interaction observed in an ebselen derivative, 2-(2-bromophenyl)benzo[d][1,2]selenazol-3(2H)-one, has been explored. The electronic nature of this Br?? interaction was investigated via high-resolution X-ray diffraction and periodic density functional theory calculations using atoms-in-molecules (AIM) analysis. This study unravels the simultaneous presence of ?-hole and ?-hole bonding characteristics in the same interaction. The dual characteristics of this unique Br?? interaction are further established via molecular electrostatic potentials (MESPs) and natural bond orbitals (NBOs).

SUBMITTER: Shukla R

PROVIDER: S-EPMC6126650 | biostudies-literature | 2018 Sep

REPOSITORIES: biostudies-literature

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Exploring the simultaneous σ-hole/π-hole bonding characteristics of a Br⋯π interaction in an ebselen derivative via experimental and theoretical electron-density analysis.

Shukla Rahul R Claiser Nicolas N Souhassou Mohamed M Lecomte Claude C Balkrishna Shah Jaimin SJ Kumar Sangit S Chopra Deepak D

IUCrJ 20180901 Pt 5

In this study, the nature and characteristics of a short Br⋯π interaction observed in an ebselen derivative, 2-(2-bromophenyl)benzo[d][1,2]selenazol-3(2H)-one, has been explored. The electronic nature of this Br⋯π interaction was investigated via high-resolution X-ray diffraction and periodic density functional theory calculations using atoms-in-molecules (AIM) analysis. This study unravels the simultaneous presence of σ-hole and π-hole bonding characteristics in the same in ...[more]

PMID: 30224967

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Project description:In the present work, a number of R-X⋯NH3 (X = Cl, Br, and I) halogen bonded systems were theoretical studied by means of DFT calculations performed at the ωB97XD/6-31+G(d,p) level of theory in order to get insights on the effect of the electron-donating or electron-withdrawing character of the different R substituent groups (R = halogen, methyl, partially fluorinated methyl, perfluoro-methyl, ethyl, vinyl, and acetyl) on the stability of the halogen bond. The results indicate that the relative stability of the halogen bond follows the Cl < Br < I trend considering the same R substituent whereas the more electron-withdrawing character of the R substituent the more stable the halogen bond. Refinement of the latter results, performed at the MP2/6-31+G(d,p) level showed that the DFT and the MP2 binding energies correlate remarkably well, suggesting that the Grimme's type dispersion-corrected functional produces reasonable structural and energetic features of halogen bond systems. DFT results were also observed to agree with more refined calculations performed at the CCSD(T) level. In a further stage, a more thorough analysis of the R-Br⋯NH3 complexes was performed by means of a novel electron localization/delocalization tool, defined in terms of an Information Theory, IT, based quantity obtained from the conditional pair density. For the latter, our in-house developed C++/CUDA program, called KLD (acronym of Kullback-Leibler divergence), was employed. KLD results mapped onto the one-electron density plotted at a 0.04 a.u. isovalue, showed that (i) as expected, the localized electron depletion of the Br sigma-hole is largely affected by the electron-withdrawing character of the R substituent group and (ii) the R-X bond is significantly polarized due to the presence of the NH3 molecule in the complexes. The afore-mentioned constitutes a clear indication of the dominant character of electrostatics on the stabilization of halogen bonds in agreement with a number of studies reported in the main literature. Finally, the cooperative effects on the [Br-CN]n system (n = 1-8) was evaluated at the MP2/6-31+G(d,p) level, where it was observed that an increase of about ~14.2% on the complex stability is obtained when going from n = 2 to n = 8. The latter results were corroborated by the analysis of the changes on the Fermi-hole localization pattern on the halogen bond zones, which suggests an also important contribution of the electron correlation in the stabilization of these systems.

Dataset Information

Exploring the simultaneous ?-hole/?-hole bonding characteristics of a Br?? interaction in an ebselen derivative via experimental and theoretical electron-density analysis.

Publications

Exploring the simultaneous σ-hole/π-hole bonding characteristics of a Br⋯π interaction in an ebselen derivative <i>via</i> experimental and theoretical electron-density analysis.

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