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Isostructural Halogen Exchange and Halogen Bonds: The Case of N-(4-Halogenobenzyl)-3-halogenopyridinium Halogenides
[Image: see text] Six N-(4-halogenobenzyl)-3-halogenopyridinium cations were prepared by reacting meta-halogenopyridines (Cl, Br, and I) with (4-halogenobenzyl) bromides (Br and I) and were isolated as bromide salts, which were further used to obtain iodides and chlorides. Sixteen compounds (out of...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2022
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8889897/ https://www.ncbi.nlm.nih.gov/pubmed/35250388 http://dx.doi.org/10.1021/acs.cgd.1c01285 |
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author | Fotović, Luka Bedeković, Nikola Stilinović, Vladimir |
author_facet | Fotović, Luka Bedeković, Nikola Stilinović, Vladimir |
author_sort | Fotović, Luka |
collection | PubMed |
description | [Image: see text] Six N-(4-halogenobenzyl)-3-halogenopyridinium cations were prepared by reacting meta-halogenopyridines (Cl, Br, and I) with (4-halogenobenzyl) bromides (Br and I) and were isolated as bromide salts, which were further used to obtain iodides and chlorides. Sixteen compounds (out of 18 possible cation/anion combinations) were obtained; two crystallized as hydrates and 14 as solvent free salts, 11 of which belonged to one isostructural series and 3 to another. All crystal structures comprise halogen-bonded chains, with the anion as an acceptor of two halogen bonds, with the pyridine and the benzyl halogen substituents of two neighboring cations. The halogen bonds with the pyridine halogen show a linear correlation between the relative halogen bond length and angle, which primarily depend on the donor halogen. The parameters of the other halogen bonds vary with all three halogens, indicating that the former halogen bond is the dominant interaction. This is also in accord with the calculated electrostatic potential in the σ-holes of the halogens and the thermal properties of the solids. The second isostructural group comprises combinations of the best halogen bond donors and acceptors, and features a more favorable halogen bond geometry of the dominant halogen bond, reaffirming its significance as the main factor in determining the structure. |
format | Online Article Text |
id | pubmed-8889897 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-88898972022-03-02 Isostructural Halogen Exchange and Halogen Bonds: The Case of N-(4-Halogenobenzyl)-3-halogenopyridinium Halogenides Fotović, Luka Bedeković, Nikola Stilinović, Vladimir Cryst Growth Des [Image: see text] Six N-(4-halogenobenzyl)-3-halogenopyridinium cations were prepared by reacting meta-halogenopyridines (Cl, Br, and I) with (4-halogenobenzyl) bromides (Br and I) and were isolated as bromide salts, which were further used to obtain iodides and chlorides. Sixteen compounds (out of 18 possible cation/anion combinations) were obtained; two crystallized as hydrates and 14 as solvent free salts, 11 of which belonged to one isostructural series and 3 to another. All crystal structures comprise halogen-bonded chains, with the anion as an acceptor of two halogen bonds, with the pyridine and the benzyl halogen substituents of two neighboring cations. The halogen bonds with the pyridine halogen show a linear correlation between the relative halogen bond length and angle, which primarily depend on the donor halogen. The parameters of the other halogen bonds vary with all three halogens, indicating that the former halogen bond is the dominant interaction. This is also in accord with the calculated electrostatic potential in the σ-holes of the halogens and the thermal properties of the solids. The second isostructural group comprises combinations of the best halogen bond donors and acceptors, and features a more favorable halogen bond geometry of the dominant halogen bond, reaffirming its significance as the main factor in determining the structure. American Chemical Society 2022-01-05 2022-02-02 /pmc/articles/PMC8889897/ /pubmed/35250388 http://dx.doi.org/10.1021/acs.cgd.1c01285 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Fotović, Luka Bedeković, Nikola Stilinović, Vladimir Isostructural Halogen Exchange and Halogen Bonds: The Case of N-(4-Halogenobenzyl)-3-halogenopyridinium Halogenides |
title | Isostructural Halogen Exchange and Halogen Bonds:
The Case of N-(4-Halogenobenzyl)-3-halogenopyridinium
Halogenides |
title_full | Isostructural Halogen Exchange and Halogen Bonds:
The Case of N-(4-Halogenobenzyl)-3-halogenopyridinium
Halogenides |
title_fullStr | Isostructural Halogen Exchange and Halogen Bonds:
The Case of N-(4-Halogenobenzyl)-3-halogenopyridinium
Halogenides |
title_full_unstemmed | Isostructural Halogen Exchange and Halogen Bonds:
The Case of N-(4-Halogenobenzyl)-3-halogenopyridinium
Halogenides |
title_short | Isostructural Halogen Exchange and Halogen Bonds:
The Case of N-(4-Halogenobenzyl)-3-halogenopyridinium
Halogenides |
title_sort | isostructural halogen exchange and halogen bonds:
the case of n-(4-halogenobenzyl)-3-halogenopyridinium
halogenides |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8889897/ https://www.ncbi.nlm.nih.gov/pubmed/35250388 http://dx.doi.org/10.1021/acs.cgd.1c01285 |
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