Synthesis and Characterization of Nonclassical Interhalides Based on Bromine Monochloride

Abstract Due to a more distinct σ‐hole, BrCl is able to form stronger halogen bonds than those in polyhalogen anions based on Cl 2 and Br 2 . 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 [AsPh 4 ][Cl(BrCl) 3 ] and [CCl(NMe 2 ) 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.