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Title
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Interplay between halogen bonding and lone pair-π interactions : a computational and crystal packing study
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Author
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Abstract
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| 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. |
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Language
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English
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Source (journal)
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ChemPlusChem. - -
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Publication
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2014
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ISSN
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2192-6506
[online]
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DOI
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10.1002/CPLU.201400005
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Volume/pages
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79
:4
(2014)
, p. 552-558
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ISI
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000334114200009
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Full text (Publisher's DOI)
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