Supramolecular Organization of Diaryliodonium Dicyanoargentates(I) Provided by Iodine(III)–Cyanide Halogen Bonding
Three diaryliodonium dicyanoargentates(I), [MesIAr][Ag(CN)<sub>2</sub>] (Ar = Ph <b>1</b>, Mes <b>2</b>, 4-MeC<sub>6</sub>H<sub>4</sub> <b>3</b>; Mes = 2,4,6-Me<sub>3</sub>C<sub>6</sub>H<sub>2</s...
Saved in:
| Main Authors: | , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2025-05-01
|
| Series: | Inorganics |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2304-6740/13/5/157 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1850257067185537024 |
|---|---|
| author | Irina S. Aliyarova Anastasiia V. Koziakova Daniil M. Ivanov Natalia S. Soldatova Pavel S. Postnikov |
| author_facet | Irina S. Aliyarova Anastasiia V. Koziakova Daniil M. Ivanov Natalia S. Soldatova Pavel S. Postnikov |
| author_sort | Irina S. Aliyarova |
| collection | DOAJ |
| description | Three diaryliodonium dicyanoargentates(I), [MesIAr][Ag(CN)<sub>2</sub>] (Ar = Ph <b>1</b>, Mes <b>2</b>, 4-MeC<sub>6</sub>H<sub>4</sub> <b>3</b>; Mes = 2,4,6-Me<sub>3</sub>C<sub>6</sub>H<sub>2</sub>), were prepared by anion metathesis. The X-ray structural analyses for these crystals revealed C–I<sup>III</sup>∙∙∙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. |
| format | Article |
| id | doaj-art-219747433d9d452cbb063db9aa381cf6 |
| institution | OA Journals |
| issn | 2304-6740 |
| language | English |
| publishDate | 2025-05-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Inorganics |
| spelling | doaj-art-219747433d9d452cbb063db9aa381cf62025-08-20T01:56:31ZengMDPI AGInorganics2304-67402025-05-0113515710.3390/inorganics13050157Supramolecular Organization of Diaryliodonium Dicyanoargentates(I) Provided by Iodine(III)–Cyanide Halogen BondingIrina S. Aliyarova0Anastasiia V. Koziakova1Daniil M. Ivanov2Natalia S. Soldatova3Pavel S. Postnikov4Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 7/9, Saint Petersburg 199034, RussiaInstitute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 7/9, Saint Petersburg 199034, RussiaInstitute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 7/9, Saint Petersburg 199034, RussiaResearch School of Chemistry and Applied Biomedical Sciences, Tomsk Polytechnic University, Tomsk 634034, RussiaResearch School of Chemistry and Applied Biomedical Sciences, Tomsk Polytechnic University, Tomsk 634034, RussiaThree diaryliodonium dicyanoargentates(I), [MesIAr][Ag(CN)<sub>2</sub>] (Ar = Ph <b>1</b>, Mes <b>2</b>, 4-MeC<sub>6</sub>H<sub>4</sub> <b>3</b>; Mes = 2,4,6-Me<sub>3</sub>C<sub>6</sub>H<sub>2</sub>), were prepared by anion metathesis. The X-ray structural analyses for these crystals revealed C–I<sup>III</sup>∙∙∙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.https://www.mdpi.com/2304-6740/13/5/157diaryliodoniumdicyanoargentate(I)halogen bondingcrystal engineering |
| spellingShingle | Irina S. Aliyarova Anastasiia V. Koziakova Daniil M. Ivanov Natalia S. Soldatova Pavel S. Postnikov Supramolecular Organization of Diaryliodonium Dicyanoargentates(I) Provided by Iodine(III)–Cyanide Halogen Bonding Inorganics diaryliodonium dicyanoargentate(I) halogen bonding crystal engineering |
| title | Supramolecular Organization of Diaryliodonium Dicyanoargentates(I) Provided by Iodine(III)–Cyanide Halogen Bonding |
| title_full | Supramolecular Organization of Diaryliodonium Dicyanoargentates(I) Provided by Iodine(III)–Cyanide Halogen Bonding |
| title_fullStr | Supramolecular Organization of Diaryliodonium Dicyanoargentates(I) Provided by Iodine(III)–Cyanide Halogen Bonding |
| title_full_unstemmed | Supramolecular Organization of Diaryliodonium Dicyanoargentates(I) Provided by Iodine(III)–Cyanide Halogen Bonding |
| title_short | Supramolecular Organization of Diaryliodonium Dicyanoargentates(I) Provided by Iodine(III)–Cyanide Halogen Bonding |
| title_sort | supramolecular organization of diaryliodonium dicyanoargentates i provided by iodine iii cyanide halogen bonding |
| topic | diaryliodonium dicyanoargentate(I) halogen bonding crystal engineering |
| url | https://www.mdpi.com/2304-6740/13/5/157 |
| work_keys_str_mv | AT irinasaliyarova supramolecularorganizationofdiaryliodoniumdicyanoargentatesiprovidedbyiodineiiicyanidehalogenbonding AT anastasiiavkoziakova supramolecularorganizationofdiaryliodoniumdicyanoargentatesiprovidedbyiodineiiicyanidehalogenbonding AT daniilmivanov supramolecularorganizationofdiaryliodoniumdicyanoargentatesiprovidedbyiodineiiicyanidehalogenbonding AT nataliassoldatova supramolecularorganizationofdiaryliodoniumdicyanoargentatesiprovidedbyiodineiiicyanidehalogenbonding AT pavelspostnikov supramolecularorganizationofdiaryliodoniumdicyanoargentatesiprovidedbyiodineiiicyanidehalogenbonding |