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A gradual change of Br⋯N bond lengths and strengths from the values typical for intermolecular associates to that characteristic of a covalent bond was observed in a series of halogen-bonded complexes. This continuum reveals a fundamental relationship between the limiting types of bonding and implies the onset of covalency in the intermolecular interactions.

Graphical abstract: Continuum of covalent to intermolecular bonding in the halogen-bonded complexes of 1,4-diazabicyclo[2.2.2]octane with bromine-containing electrophiles

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