Work

Supramolecular Organization of Diaryliodonium Dicyanoargentates(I) Provided by Iodine(III)–Cyanide Halogen Bonding

Year: 2025

Type: article

Abstract: Three diaryliodonium dicyanoargentates(I), [MesIAr][Ag(CN)2] (Ar = Ph 1, Mes 2, 4-MeC6H4 3; Mes = 2,4,6-Me3C6H2), were prepared by anion metathesis. The X-ray structural analyses for these crystals revealed C–IIII∙∙∙N≡C halogen bonds (abbreviated as XB) between I atoms of diaryliodonium cations and N atoms of cyano groups, which provide different supramolecular organization. The noncovalent nature of these interactions was studied by density functional theory (DFT) calculations and topological analysis of the electron density distribution in the framework of the quantum theory of atoms in molecules (QTAIM) at the PBE-D3/jorge-DZP-DKH level of theory both in gas phase and crystal models. The philicities of partners in these contacts were confirmed by electron localization function (ELF) projections, electron density/electrostatic potential (ED/ESP) profiles, and Hirshfeld surfaces analysis. An analysis of the available crystallographic data from the literature allows us to find other examples of σ-hole interactions including the dicyanoargentate(I) anion, and the C–X∙∙∙N≡C (X = Br, I, Te) bonding were also confirmed theoretically.

Source: Inorganics

DOI: 10.3390/inorganics13050157

Authors: Irina S. Aliyarova, Anastasiia V. Koziakova, Daniil M. Ivanov, Natalia S. Soldatova, Pavel S. Postnikov

Institutions: St Petersburg University, Tomsk Polytechnic University

Language: English

Topic: Crystallography and molecular interactions

Subfield: Physical and Theoretical Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: gold

Estimated APC paid: $2,654

Funders: Saint Petersburg State University, Russian Science Foundation