Evidence for the ``Amphoteric'' Nature of Fluorine in Halogen Bonds: An Instance of Cl center dot center dot center dot F Contact

This study presents unambiguous experimental evidence in support of the highly debated ``halogen bond donor'' character of organic fluorine. Two examples of intermolecular Cl center dot center dot center dot F contacts, with F-atom as halogen bond acceptor and donor, have been analyzed by in situ cryocrystallography and theoretical charge density studies.