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

Abstract
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 para-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 para-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.
Main Authors
Format
Articles Research article
Published
2019
Series
Subjects
Publication in research information system
Publisher
MDPI
The permanent address of the publication
https://urn.fi/URN:NBN:fi:jyu-201910144451Käytä tätä linkitykseen.
Review status
Peer reviewed
ISSN
1996-1944
DOI
https://doi.org/10.3390/ma12203305
Language
English
Published in
Materials
Citation
  • von Essen, C., Rissanen, K., & Puttreddy, R. (2019). Halogen Bonds in 2,5-Dihalopyridine-Copper(I) Halide Coordination Polymers. Materials, 12(20), Article 3305. https://doi.org/10.3390/ma12203305
License
CC BY 4.0Open Access
Funder(s)
Research Council of Finland
Funding program(s)
Tutkijatohtori, SA
Postdoctoral Researcher, AoF
Research Council of Finland
Additional information about funding
The authors kindly acknowledge the Academy of Finland (Project numbers RP: 298817) and the University of Jyväskylä for financial support.
Copyright© 2019 by the authors.

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