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While polymorphism is a wide spread phenomenon, the number of reported polymorphic co-crystals is still very limited. Here we report the synthesis and structural characterisation of such a rare case of polymorphism with a co-crystal of benzoic acid (HBz) and sodium benzoate (NaBz). Flash evaporation yielded a new polymorph of this ionic co-crystal with a stoichiometry of 2 HBz?1 NaBz. The thermodynamic relationship between the known and the new polymorph was determined to be of enantiotropicdoi:10.15495/epub_ubt_00004751 fatcat:itbxm6ivyvbvnpnikfo4ywzukm