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We describe a two-component cocrystal composition which appears in two stoichiometric variations exhibiting different supramolecular architectures: whereas one stoichiometric variation displays C–H⋯O hydrogen bonds, the second form exhibits short I⋯O halogen bonds alongside I⋯π halogen-bonded contacts; the two forms are readily prepared mechanochemically by varying the relative amounts of starting materials in a liquid-assisted grinding process.

Graphical abstract: Switching between halogen- and hydrogen-bonding in stoichiometric variations of a cocrystal of a phosphine oxide

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