Halogen Bonds in 2,5-Dihalopyridine-Copper(I) Halide Coordination Polymers

Two series of 2,5-dihalopyridine-Cu(I)A (A = I, Br) complexes based on 2-X-5-iodopyridine and 2-X-5-bromopyridine (X = F, Cl, Br and I) are characterized by using single-crystal X-ray diffraction analysis to examine the nature of C2−X2···A−Cu and C5&...

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Main Authors:	Carolina von Essen, Kari Rissanen, Rakesh Puttreddy
Format:	Article
Language:	English
Published:	MDPI AG 2019-10-01
Series:	Materials
Subjects:	halogen bond copper pyridine halopyridines dihalopyridine
Online Access:	https://www.mdpi.com/1996-1944/12/20/3305

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spelling	doaj-47dabc80149943e8b496e4818fcd18352020-11-25T01:58:27ZengMDPI AGMaterials1996-19442019-10-011220330510.3390/ma12203305ma12203305Halogen Bonds in 2,5-Dihalopyridine-Copper(I) Halide Coordination PolymersCarolina von Essen0Kari Rissanen1Rakesh Puttreddy2Department of Chemistry, University of Jyvaskyla, P.O. Box 35, FI-40014 Jyväskylä, FinlandDepartment of Chemistry, University of Jyvaskyla, P.O. Box 35, FI-40014 Jyväskylä, FinlandDepartment of Chemistry, University of Jyvaskyla, P.O. Box 35, FI-40014 Jyväskylä, FinlandTwo series of 2,5-dihalopyridine-Cu(I)A (A = I, Br) complexes based on 2-X-5-iodopyridine and 2-X-5-bromopyridine (X = F, Cl, Br and I) are characterized by using single-crystal X-ray diffraction analysis to examine the nature of C2−X2···A−Cu and C5−X5···A−Cu halogen bonds. The reaction of the 2,5-dihalopyridines and Cu(I) salts allows the synthesis of eight 1-D coordination polymers and a discrete structure. The resulting Cu(I)-complexes are linked by C−X···A−Cu halogen bonds forming 3-D supramolecular networks. The C−X···A−Cu halogen bonds formed between halopyridine ligands and copper(I)-bound halide ions are stronger than C−X···X’−C interactions between two 2,5-dihalopyridine ligands. The C5−I5···I−Cu and C5−Br5···Br−Cu halogens bonds are shorter for C2-fluorine than C2-chlorine due to the greater electron-withdrawing power of fluorine. In 2,5-diiodopyridine-Cu(I)Br complex, the shorter C2−I2···Br−Cu [3.473(5) Å] distances are due to the combined polarization of C2-iodine by C2−I2···Cu interactions and <i>para</i>-electronic effects offered by the C5-iodine, whilst the long halogen bond contacts for C5−I5···Br−Cu [3.537(5) Å] are indicative that C2-iodine has a less <i>para</i>-electronic influence on the C5-iodine. In 2-fluoro-5-X-pyridine-Cu(I) complexes, the C2-fluorine is halogen bond passive, while the other C2-halogens in 2,5-dihalopyridine-Cu(I), including C2-chlorine, participate in halogen bonding interactions.https://www.mdpi.com/1996-1944/12/20/3305halogen bondcopperpyridinehalopyridinesdihalopyridine
collection	DOAJ
language	English
format	Article
sources	DOAJ
author	Carolina von Essen Kari Rissanen Rakesh Puttreddy
spellingShingle	Carolina von Essen Kari Rissanen Rakesh Puttreddy Halogen Bonds in 2,5-Dihalopyridine-Copper(I) Halide Coordination Polymers Materials halogen bond copper pyridine halopyridines dihalopyridine
author_facet	Carolina von Essen Kari Rissanen Rakesh Puttreddy
author_sort	Carolina von Essen
title	Halogen Bonds in 2,5-Dihalopyridine-Copper(I) Halide Coordination Polymers
title_short	Halogen Bonds in 2,5-Dihalopyridine-Copper(I) Halide Coordination Polymers
title_full	Halogen Bonds in 2,5-Dihalopyridine-Copper(I) Halide Coordination Polymers
title_fullStr	Halogen Bonds in 2,5-Dihalopyridine-Copper(I) Halide Coordination Polymers
title_full_unstemmed	Halogen Bonds in 2,5-Dihalopyridine-Copper(I) Halide Coordination Polymers
title_sort	halogen bonds in 2,5-dihalopyridine-copper(i) halide coordination polymers
publisher	MDPI AG
series	Materials
issn	1996-1944
publishDate	2019-10-01
description	Two series of 2,5-dihalopyridine-Cu(I)A (A = I, Br) complexes based on 2-X-5-iodopyridine and 2-X-5-bromopyridine (X = F, Cl, Br and I) are characterized by using single-crystal X-ray diffraction analysis to examine the nature of C2−X2···A−Cu and C5−X5···A−Cu halogen bonds. The reaction of the 2,5-dihalopyridines and Cu(I) salts allows the synthesis of eight 1-D coordination polymers and a discrete structure. The resulting Cu(I)-complexes are linked by C−X···A−Cu halogen bonds forming 3-D supramolecular networks. The C−X···A−Cu halogen bonds formed between halopyridine ligands and copper(I)-bound halide ions are stronger than C−X···X’−C interactions between two 2,5-dihalopyridine ligands. The C5−I5···I−Cu and C5−Br5···Br−Cu halogens bonds are shorter for C2-fluorine than C2-chlorine due to the greater electron-withdrawing power of fluorine. In 2,5-diiodopyridine-Cu(I)Br complex, the shorter C2−I2···Br−Cu [3.473(5) Å] distances are due to the combined polarization of C2-iodine by C2−I2···Cu interactions and <i>para</i>-electronic effects offered by the C5-iodine, whilst the long halogen bond contacts for C5−I5···Br−Cu [3.537(5) Å] are indicative that C2-iodine has a less <i>para</i>-electronic influence on the C5-iodine. In 2-fluoro-5-X-pyridine-Cu(I) complexes, the C2-fluorine is halogen bond passive, while the other C2-halogens in 2,5-dihalopyridine-Cu(I), including C2-chlorine, participate in halogen bonding interactions.
topic	halogen bond copper pyridine halopyridines dihalopyridine
url	https://www.mdpi.com/1996-1944/12/20/3305
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Halogen Bonds in 2,5-Dihalopyridine-Copper(I) Halide Coordination Polymers

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