Title
Interplay between halogen bonding and lone pair-π interactions : a computational and crystal packing study Interplay between halogen bonding and lone pair-π interactions : a computational and crystal packing study
Author
Faculty/Department
Faculty of Sciences. Chemistry
Faculty of Applied Engineering Sciences
Publication type
article
Publication
Subject
Chemistry
Engineering sciences. Technology
Source (journal)
ChemPlusChem
Volume/pages
79(2014) :4 , p. 552-558
ISSN
2192-6506
ISI
000334114200009
Carrier
E
Target language
English (eng)
Full text (Publishers DOI)
Affiliation
University of Antwerp
Abstract
The supramolecular organization of modified thiophenes resulting from N⋅⋅⋅I halogen bonding (XB) has been studied. X-ray diffraction analyses of two polymorphs of the same supramolecular complex showed an arrangement controlled by halogen-bonded pyridyl and tetrafluoroiodobenzene rings, one case with and the other without the presence of two different lone pair (lp)⋅⋅⋅π interactions, namely O⋅⋅⋅pyridyl and I⋅⋅⋅tetrafluoroiodobenzene contacts. To shed light on the interplay between these interactions, quantum mechanical calculations were performed at the ωB97X-D/6-31+G(d,p) level on both systems in the gas phase. The longer N⋅⋅⋅I distance observed in the crystal structure without lp⋅⋅⋅π interactions was also corroborated by dispersion-corrected DFT. These results represent the first case in which a synergy between lp⋅⋅⋅π interactions and XB is observed experimentally and confirmed by calculations.
E-info
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000334114200009&DestLinkType=RelatedRecords&DestApp=ALL_WOS&UsrCustomerID=ef845e08c439e550330acc77c7d2d848
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000334114200009&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=ef845e08c439e550330acc77c7d2d848
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000334114200009&DestLinkType=CitingArticles&DestApp=ALL_WOS&UsrCustomerID=ef845e08c439e550330acc77c7d2d848
Handle