The crystal structures of two polymorphic forms of maltol, C6H6O3, have been determined. The polymorphs exhibit different crystal-packing arrangements through intermolecular hydrogen bonding involving the hydroxyl H atoms. Form (1) has a near planar chain of molecules linked by hydrogen bonds while form (2) has mutually hydrogen-bonded dimers. In both polymorphic forms, there are also weaker C-H⋯O bonds which give greater stability to the chains of form (1) and link the dimers in form (2).
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Burgess et al. (1996) studied this question.