Synthesis and Characterization of Nonclassical Interhalides Based on Bromine Monochloride

: Due to a more distinct σ-hole, BrCl is able to form stronger halogen bonds than those in polyhalogen anions based on Cl2 and Br2 . This stabilization allows the crystallographic characterization of a variety of new polyinterhalides, in which chloride functions as the central ion as shown by the molecular structures of [AsPh4 ][Cl(BrCl)3 ] and [CCl(NMe2 )2 ][Cl(BrCl)5 ]. Furthermore, the solid-state structure of an octahedrally coordinated nonclassical interhalide is reported for the first time. The tridecainterhalide monoanion [Cl(BrCl)6 ]- consists of a central chloride ion, which is coordinated by six BrCl molecules in a slightly distorted octahedral structure. All new compounds were characterized by single-crystal X-ray diffraction (XRD), NMR and Raman spectroscopy, as well as quantum-chemical calculations.