organic compounds
Hydantoin-5-acetic acid [2-(2,5-dioxoimidazolidin-4-yl)acetic acid] and orotic acid (2,6-dioxo-1,2,3,6-tetrahydropyrimidine-4-carboxylic acid) each contain one rigid acceptor-donor-acceptor hydrogen-bonding site and a flexible side chain, which can adopt different conformations. Since both compounds may be used as coformers for supramolecular complexes, they have been crystallized in order to examine their conformational preferences, giving solvent-free hydantoin-5-acetic acid, C5H6N2O4, (I), and three crystals containing orotic acid, namely, orotic acid dimethyl sulfoxide monosolvate, C5H4N2O4·C2H6OS, (IIa), dimethylammonium orotate-orotic acid (1/1), C2H8N+·C5H3N2O4-·C5H4N2O4, (IIb), and dimethylammonium orotate-orotic acid (3/1), 3C2H8N+·3C5H3N2O4-·C5H4N2O4, (IIc). The crystal structure of (I) shows a three-dimensional network, with the acid function located perpendicular to the ring. Interestingly, the hydroxy O atom acts as an acceptor, even though the carbonyl O atom is not involved in any hydrogen bonds. However, in (IIa), (IIb) and (IIc), the acid functions are only slightly twisted out of the ring planes. All H atoms of the acidic functions are directed away from the rings and, with respect to the carbonyl O atoms, they show an antiperiplanar conformation in (I) and synperiplanar conformations in (IIa), (IIb) and (IIc). Furthermore, in (IIa), (IIb) and (IIc), different conformations of the acid O=C-C-N torsion angle are observed, leading to different hydrogen-bonding arrangements depending on their conformation and composition.
organic compounds
Different tautomeric and zwitterionic forms of chelidamic acid (4-hydroxypyridine-2,6-dicarboxylic acid) are present in the crystal structures of chelidamic acid methanol monosolvate, C7H5NO5·CH4O, (Ia), dimethylammonium chelidamate (dimethylammonium 6-carboxy-4-hydroxypyridine-2-carboxylate), C2H8N+·C7H4NO5−, (Ib), and chelidamic acid dimethyl sulfoxide monosolvate, C7H5NO5·C2H6OS, (Ic). While the zwitterionic pyridinium carboxylate in (Ia) can be explained from the pKa values, a (partially) deprotonated hydroxy group in the presence of a neutral carboxy group, as observed in (Ib) and (Ic), is unexpected. In (Ib), there are two formula units in the asymmetric unit with the chelidamic acid entities connected by a symmetric O—HO hydrogen bond. Also, crystals of chelidamic acid dimethyl ester (dimethyl 4-hydroxypyridine-2,6-dicarboxylate) were obtained as a monohydrate, C9H9NO5·H2O, (IIa), and as a solvent-free modification, in which both ester molecules adopt the hydroxypyridine form. In (IIa), the solvent water molecule stabilizes the synperiplanar conformation of both carbonyl O atoms with respect to the pyridine N atom by two O—HO hydrogen bonds, whereas an antiperiplanar arrangement is observed in the water-free structure. A database study and ab initio energy calculations help to compare the stabilities of the various ester conformations.