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How the Position of Substitution Affects Intermolecular Bonding in Halogen Derivatives of Carboranes: Crystal Structures of 1,2,3- and 8,9,12-Triiodo- and 8,9,12-Tribromo ortho-Carboranes

The crystal structures of two isomeric triiodo derivatives of ortho-carborane containing substituents in the three most electron-withdrawing positions of the carborane cage, 1,2,3-I(3)-1,2-C(2)B(10)H(9), and the three most electron-donating positions, 8,9,12-I(3)-1,2-C(2)B(10)H(9), as well as the cr...

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Autores principales: Suponitsky, Kyrill Yu., Anufriev, Sergey A., Sivaev, Igor B.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9865681/
https://www.ncbi.nlm.nih.gov/pubmed/36677932
http://dx.doi.org/10.3390/molecules28020875
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author Suponitsky, Kyrill Yu.
Anufriev, Sergey A.
Sivaev, Igor B.
author_facet Suponitsky, Kyrill Yu.
Anufriev, Sergey A.
Sivaev, Igor B.
author_sort Suponitsky, Kyrill Yu.
collection PubMed
description The crystal structures of two isomeric triiodo derivatives of ortho-carborane containing substituents in the three most electron-withdrawing positions of the carborane cage, 1,2,3-I(3)-1,2-C(2)B(10)H(9), and the three most electron-donating positions, 8,9,12-I(3)-1,2-C(2)B(10)H(9), as well as the crystal structure of 8,9,12-Br(3)-1,2-C(2)B(10)H(9), were determined by single-crystal X-ray diffraction. In the structure of 1,2,3-I(3)-1,2-C(2)B(10)H(9), an iodine atom attached to the boron atom (position 3) donates its lone pairs simultaneously to the σ-holes of both iodine atoms attached to the carbon atoms (positions 1 and 2) with the I⋯I distance of 3.554(2) Å and the C-I⋯I and B-I⋯I angles of 169.2(2)° and 92.2(2)°, respectively. The structure is additionally stabilized by a few B-H⋯I-shortened contacts. In the structure of 8,9,12-I(3)-1,2-C(2)B(10)H(9), the I⋯I contacts of type II are very weak (the I⋯I distance is 4.268(4) Å, the B8-I8⋯I12 and B12-I12⋯I8 angles are 130.2(3)° and 92.2(3)°) and can only be regarded as dihalogen bonds formally. In comparison with the latter, the structure of 8,9,12-Br(3)-1,2-C(2)B(10)H(9) demonstrates both similarities and differences. No Br⋯Br contacts of type II are observed, while there are two Br⋯Br halogen bonds of type I.
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spelling pubmed-98656812023-01-22 How the Position of Substitution Affects Intermolecular Bonding in Halogen Derivatives of Carboranes: Crystal Structures of 1,2,3- and 8,9,12-Triiodo- and 8,9,12-Tribromo ortho-Carboranes Suponitsky, Kyrill Yu. Anufriev, Sergey A. Sivaev, Igor B. Molecules Article The crystal structures of two isomeric triiodo derivatives of ortho-carborane containing substituents in the three most electron-withdrawing positions of the carborane cage, 1,2,3-I(3)-1,2-C(2)B(10)H(9), and the three most electron-donating positions, 8,9,12-I(3)-1,2-C(2)B(10)H(9), as well as the crystal structure of 8,9,12-Br(3)-1,2-C(2)B(10)H(9), were determined by single-crystal X-ray diffraction. In the structure of 1,2,3-I(3)-1,2-C(2)B(10)H(9), an iodine atom attached to the boron atom (position 3) donates its lone pairs simultaneously to the σ-holes of both iodine atoms attached to the carbon atoms (positions 1 and 2) with the I⋯I distance of 3.554(2) Å and the C-I⋯I and B-I⋯I angles of 169.2(2)° and 92.2(2)°, respectively. The structure is additionally stabilized by a few B-H⋯I-shortened contacts. In the structure of 8,9,12-I(3)-1,2-C(2)B(10)H(9), the I⋯I contacts of type II are very weak (the I⋯I distance is 4.268(4) Å, the B8-I8⋯I12 and B12-I12⋯I8 angles are 130.2(3)° and 92.2(3)°) and can only be regarded as dihalogen bonds formally. In comparison with the latter, the structure of 8,9,12-Br(3)-1,2-C(2)B(10)H(9) demonstrates both similarities and differences. No Br⋯Br contacts of type II are observed, while there are two Br⋯Br halogen bonds of type I. MDPI 2023-01-15 /pmc/articles/PMC9865681/ /pubmed/36677932 http://dx.doi.org/10.3390/molecules28020875 Text en © 2023 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Suponitsky, Kyrill Yu.
Anufriev, Sergey A.
Sivaev, Igor B.
How the Position of Substitution Affects Intermolecular Bonding in Halogen Derivatives of Carboranes: Crystal Structures of 1,2,3- and 8,9,12-Triiodo- and 8,9,12-Tribromo ortho-Carboranes
title How the Position of Substitution Affects Intermolecular Bonding in Halogen Derivatives of Carboranes: Crystal Structures of 1,2,3- and 8,9,12-Triiodo- and 8,9,12-Tribromo ortho-Carboranes
title_full How the Position of Substitution Affects Intermolecular Bonding in Halogen Derivatives of Carboranes: Crystal Structures of 1,2,3- and 8,9,12-Triiodo- and 8,9,12-Tribromo ortho-Carboranes
title_fullStr How the Position of Substitution Affects Intermolecular Bonding in Halogen Derivatives of Carboranes: Crystal Structures of 1,2,3- and 8,9,12-Triiodo- and 8,9,12-Tribromo ortho-Carboranes
title_full_unstemmed How the Position of Substitution Affects Intermolecular Bonding in Halogen Derivatives of Carboranes: Crystal Structures of 1,2,3- and 8,9,12-Triiodo- and 8,9,12-Tribromo ortho-Carboranes
title_short How the Position of Substitution Affects Intermolecular Bonding in Halogen Derivatives of Carboranes: Crystal Structures of 1,2,3- and 8,9,12-Triiodo- and 8,9,12-Tribromo ortho-Carboranes
title_sort how the position of substitution affects intermolecular bonding in halogen derivatives of carboranes: crystal structures of 1,2,3- and 8,9,12-triiodo- and 8,9,12-tribromo ortho-carboranes
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9865681/
https://www.ncbi.nlm.nih.gov/pubmed/36677932
http://dx.doi.org/10.3390/molecules28020875
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