Halogen Bonding in N-Alkyl-3-halogenopyridinium Salts

We performed a structural study of N-alkylated halogenopyridinium cations to examine whether choice of the N-substituent has any considerable effect on the halogen bonding capability of the cations. For that purpose, we prepared a series of N-ethyl-3-halopyridinium iodides and compared them with their N-methyl-3-halopyridinium analogues. Structural analysis revealed that N-ethylated halogenopyridinium cations form slightly shorter C-X...I- halogen bonds with iodide anion. We have also attempted synthesis of ditopic symmetric bis-(3-iodopyridinium) dications. Although successful in only one case, the syntheses have afforded two novel ditopic asymmetric monocations with an iodine atom bonded to the pyridine ring and another on the aliphatic N-substituent. Here, the C-I...I- halogen bond lengths involving pyridine iodine atom were notably shorter than those involving an aliphatic iodine atom as a halogen bond donor. This trend in halogen bond lengths is in line with the charge distribution on the Hirshfeld surfaces of the cations-the positive charge is predominantly located in the pyridine ring making the pyridine iodine atom sigma-hole more positive than the one on the alkyl chan.

Automated summary

The study showed that N-ethylated halogenopyridinium cations form shorter halogen bonds with iodide anions, and two novel asymmetric monocations were obtained during the synthesis process.