The immunomodulatory agent bropirimine crystallizes from N-methylformamide (NMF) as a triply hydrogen-bonded duplex in the manner of a Watson-Crick guanine:cytosine base pair. The stoichiometry of the solvate is bropirimine:NMF (2:1) and all NMF molecules are in the Z-rotomeric form. The intermolecular hydrogen bonding is disrupted when the solvate is dissolved in deuteriated dimethyl sulphoxide at 37 degrees C. Bropirimine and other molecules which possess the 2-aminopyrimidin-4-one fragment are potentially capable of recognizing guanine or cytosine residues in single-stranded RNA or DNA by Watson-Crick bonding or double-stranded DNA by Hoogsteen bonds. The immunomodulatory properties of these compounds might be triggered by these encounters.