title: 3-Cyano-6-hydroxy-4-methyl-2-pyridone: two new pseudopolymorphs and two cocrystals with products of an in situ nucleophilic aromatic substitution.
abstract: Four crystal structures of 3-cyano-6-hydroxy-4-methyl-2-pyridone (CMP), viz. the dimethyl sulfoxide monosolvate, C7H6N2O2·C2H6OS, (1), the N,N-dimethylacetamide monosolvate, C7H6N2O2·C4H9NO, (2), a cocrystal with 2-amino-4-dimethylamino-6-methylpyrimidine (as the salt 2-amino-4-dimethylamino-6-methylpyrimidin-1-ium 5-cyano-4-methyl-6-oxo-1,6-dihydropyridin-2-olate), C7H13N4(+)·C7H5N2O2(-), (3), and a cocrystal with N,N-dimethylacetamide and 4,6-diamino-2-dimethylamino-1,3,5-triazine [as the solvated salt 2,6-diamino-4-dimethylamino-1,3,5-triazin-1-ium 5-cyano-4-methyl-6-oxo-1,6-dihydropyridin-2-olate-N,N-dimethylacetamide (1/1)], C5H11N6(+)·C7H5N2O2(-)·C4H9NO, (4), are reported. Solvates (1) and (2) both contain the hydroxy group in a para position with respect to the cyano group of CMP, acting as a hydrogen-bond donor and leading to rather similar packing motifs. In cocrystals (3) and (4), hydrolysis of the solvent molecules occurs and an in situ nucleophilic aromatic substitution of a Cl atom with a dimethylamino group has taken place. Within all four structures, an R2(2)(8) N-H...O hydrogen-bonding pattern is observed, connecting the CMP molecules, but the pattern differs depending on which O atom participates in the motif, either the ortho or para O atom with respect to the cyano group. Solvents and coformers are attached to these arrangements via single-point O-H...O interactions in (1) and (2) or by additional R4(4)(16) hydrogen-bonding patterns in (3) and (4). Since the in situ nucleophilic aromatic substitution of the coformers occurs, the possible Watson-Crick C-G base-pair-like arrangement is inhibited, yet the cyano group of the CMP molecules participates in hydrogen bonds with their coformers, influencing the crystal packing to form chains.
authors.affiliation: Institut für Organische Chemie und Chemische Biologie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main, Germany.
authors.forename: Valeska
authors.initials: V
authors.lastname: Gerhardt
authors.affiliation: Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main, Germany.
authors.forename: Michael
authors.initials: M
authors.lastname: Bolte
mesh_terms: D000081:Acetamides / Q000737:chemistry*; D003460:Crystallization; D018360:Crystallography, X-Ray; D006860:Hydrogen Bonding; D008744:Methylamines / Q000737:chemistry*; D015394:Molecular Structure; D011728:Pyridones / Q000737:chemistry*; D011743:Pyrimidines / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry; D014227:Triazines / Q000737:chemistry
chemical_list: C000599030:2-amino-4-dimethylamino-6-methylpyrimidine; C000599029:3-cyano-6-hydroxy-4-methyl-2-pyridone; D000081:Acetamides; D008744:Methylamines; D011728:Pyridones; D011743:Pyrimidines; D012997:Solvents; D014227:Triazines; C013959:dimethylacetamide
keywords: 3-cyano-6-hydroxy-4-methyl-2-pyridone; CMP; crystal structure; hydrogen-bond motifs; in situ nucleophilic aromatic substitution; pseudopolymorphs