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Evaluation of Halogenopyridinium Cations as Halogen Bond Donors.

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 N-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 N-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.

SUBMITTER: Fotovic L

PROVIDER: S-EPMC8641392 | biostudies-literature | 2021 Dec

REPOSITORIES: biostudies-literature

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Evaluation of Halogenopyridinium Cations as Halogen Bond Donors.

Fotović Luka L Bedeković Nikola N Stilinović Vladimir V

Crystal growth & design 20211108 12

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 <i>N</i>-methylated monohalogenated pyridinium cations revealed t ...[more]

PMID: 34880714

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