Evaluation of Halogenopyridinium Cations As Halogen Bond Donors

Overview

Journal Cryst Growth Des

Publisher American Chemical Society

Date 2021 Dec 9

PMID 34880714

Authors

Luka Fotovic

Nikola Bedekovic

Vladimir Stilinovic

Affiliations

Soon will be listed here.

Abstract

We have performed a database survey and a structural and computational study of the potential and the limitations of halogenopyridinium cations as halogen bond donors. The database survey demonstrated that adding a positive charge on a halogenopyridine ring increases the probability that the halogen atom will participate in a halogen bond, although for chloropyridines it remains below 60%. Crystal structures of both protonated and -methylated monohalogenated pyridinium cations revealed that the iodo- and bromopyridinium cations always form halogen-bonding contacts with the iodide anions shorter than the sum of the vdW radii, while chloropyridinium cations mostly participate in longer contacts or fail to form halogen bonds. Although a DFT study of the electrostatic potential has shown that both protonation and -methylation of halogenopyridines leads to a considerable increase in the ESP of the halogen σ-hole, it is generally not the most positive site on the cation, allowing for alternate binding sites.

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