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Halides with Fifteen Aliphatic C–H···Anion Interaction Sites

Since the aliphatic C–H···anion interaction is relatively weak, anion binding using hydrophobic aliphatic C–H (C(ali)–H) groups has generally been considered not possible without the presence of additional binding sites that contain stronger interactions to the anion. Herein, we report X-ray structu...

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Autores principales: Shi, Genggongwo, Aliakbar Tehrani, Zahra, Kim, Dongwook, Cho, Woo Jong, Youn, Il-Seung, Lee, Han Myoung, Yousuf, Muhammad, Ahmed, Nisar, Shirinfar, Bahareh, Teator, Aaron J., Lastovickova, Dominika N., Rasheed, Lubna, Lah, Myoung Soo, Bielawski, Christopher W., Kim, Kwang S.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group 2016
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4957075/
https://www.ncbi.nlm.nih.gov/pubmed/27444513
http://dx.doi.org/10.1038/srep30123
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author Shi, Genggongwo
Aliakbar Tehrani, Zahra
Kim, Dongwook
Cho, Woo Jong
Youn, Il-Seung
Lee, Han Myoung
Yousuf, Muhammad
Ahmed, Nisar
Shirinfar, Bahareh
Teator, Aaron J.
Lastovickova, Dominika N.
Rasheed, Lubna
Lah, Myoung Soo
Bielawski, Christopher W.
Kim, Kwang S.
author_facet Shi, Genggongwo
Aliakbar Tehrani, Zahra
Kim, Dongwook
Cho, Woo Jong
Youn, Il-Seung
Lee, Han Myoung
Yousuf, Muhammad
Ahmed, Nisar
Shirinfar, Bahareh
Teator, Aaron J.
Lastovickova, Dominika N.
Rasheed, Lubna
Lah, Myoung Soo
Bielawski, Christopher W.
Kim, Kwang S.
author_sort Shi, Genggongwo
collection PubMed
description Since the aliphatic C–H···anion interaction is relatively weak, anion binding using hydrophobic aliphatic C–H (C(ali)–H) groups has generally been considered not possible without the presence of additional binding sites that contain stronger interactions to the anion. Herein, we report X-ray structures of organic crystals that feature a chloride anion bound exclusively by hydrophobic C(ali)–H groups. An X-ray structure of imidazolium-based scaffolds using C(ali)–H···A(−) interactions (A(−) = anion) shows that a halide anion is directly interacting with fifteen C(ali)–H groups (involving eleven hydrogen bonds, two bidentate hydrogen-bond-type binding interactions and two weakly hydrogen-bonding-like binding interactions). Additional supporting interactions and/or other binding sites are not observed. We note that such types of complexes may not be rare since such high numbers of binding sites for an anion are also found in analogous tetraalkylammonium complexes. The C(ali)–H···A(−) interactions are driven by the formation of a near-spherical dipole layer shell structure around the anion. The alternating layers of electrostatic charge around the anion arise because the repulsions between weakly positively charged H atoms are reduced by the presence of the weakly negatively charged C atoms connected to H atoms.
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spelling pubmed-49570752016-07-26 Halides with Fifteen Aliphatic C–H···Anion Interaction Sites Shi, Genggongwo Aliakbar Tehrani, Zahra Kim, Dongwook Cho, Woo Jong Youn, Il-Seung Lee, Han Myoung Yousuf, Muhammad Ahmed, Nisar Shirinfar, Bahareh Teator, Aaron J. Lastovickova, Dominika N. Rasheed, Lubna Lah, Myoung Soo Bielawski, Christopher W. Kim, Kwang S. Sci Rep Article Since the aliphatic C–H···anion interaction is relatively weak, anion binding using hydrophobic aliphatic C–H (C(ali)–H) groups has generally been considered not possible without the presence of additional binding sites that contain stronger interactions to the anion. Herein, we report X-ray structures of organic crystals that feature a chloride anion bound exclusively by hydrophobic C(ali)–H groups. An X-ray structure of imidazolium-based scaffolds using C(ali)–H···A(−) interactions (A(−) = anion) shows that a halide anion is directly interacting with fifteen C(ali)–H groups (involving eleven hydrogen bonds, two bidentate hydrogen-bond-type binding interactions and two weakly hydrogen-bonding-like binding interactions). Additional supporting interactions and/or other binding sites are not observed. We note that such types of complexes may not be rare since such high numbers of binding sites for an anion are also found in analogous tetraalkylammonium complexes. The C(ali)–H···A(−) interactions are driven by the formation of a near-spherical dipole layer shell structure around the anion. The alternating layers of electrostatic charge around the anion arise because the repulsions between weakly positively charged H atoms are reduced by the presence of the weakly negatively charged C atoms connected to H atoms. Nature Publishing Group 2016-07-22 /pmc/articles/PMC4957075/ /pubmed/27444513 http://dx.doi.org/10.1038/srep30123 Text en Copyright © 2016, Macmillan Publishers Limited http://creativecommons.org/licenses/by/4.0/ This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/
spellingShingle Article
Shi, Genggongwo
Aliakbar Tehrani, Zahra
Kim, Dongwook
Cho, Woo Jong
Youn, Il-Seung
Lee, Han Myoung
Yousuf, Muhammad
Ahmed, Nisar
Shirinfar, Bahareh
Teator, Aaron J.
Lastovickova, Dominika N.
Rasheed, Lubna
Lah, Myoung Soo
Bielawski, Christopher W.
Kim, Kwang S.
Halides with Fifteen Aliphatic C–H···Anion Interaction Sites
title Halides with Fifteen Aliphatic C–H···Anion Interaction Sites
title_full Halides with Fifteen Aliphatic C–H···Anion Interaction Sites
title_fullStr Halides with Fifteen Aliphatic C–H···Anion Interaction Sites
title_full_unstemmed Halides with Fifteen Aliphatic C–H···Anion Interaction Sites
title_short Halides with Fifteen Aliphatic C–H···Anion Interaction Sites
title_sort halides with fifteen aliphatic c–h···anion interaction sites
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4957075/
https://www.ncbi.nlm.nih.gov/pubmed/27444513
http://dx.doi.org/10.1038/srep30123
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