Publication details

Crystal structure of zymonic acid and a redetermination of its precursor, pyruvic acid


HEGER Dominik EUGENE Alexis J PARKIN Sean R. GUZMAN Marcelo I.

Year of publication 2019
Type Article in Periodical
MU Faculty or unit

Faculty of Science

Keywords crystal structure; hydrogen bonding; low temperature; zymonic; pyruvic
Description The structure of zymonic acid (systematic name: 4-hydroxy-2-methyl-5-oxo-2,5-dihydrofuran-2-carboxylic acid), C6H6O5, which had previously eluded crystallographic determination, is presented here for the first time. It forms by intramolecular condensation of parapyruvic acid, which is the product of aldol condensation of pyruvic acid. A redetermination of the crystal structure of pyruvic acid (systematic name: 2-oxopropanoic acid), C3H4O3, at low temperature (90 K) and with increased precision, is also presented [for the previous structure, see: Harata et al. (1977). Acta Cryst. B33, 210-212]. In zymonic acid, the hydroxylactone ring is close to planar (r.m.s. deviation = 0.0108 angstrom) and the dihedral angle between the ring and the plane formed by the bonds of the methyl and carboxylic acid carbon atoms to the ring is 88.68 (7)degrees. The torsion angle of the carboxylic acid group relative to the ring is 12.04 (16)degrees. The pyruvic acid molecule is almost planar, having a dihedral angle between the carboxylic acid and methyl-ketone groups of 3.95 (6)degrees. Intermolecular interactions in both crystal structures are dominated by hydrogen bonding. The common R-2(2) (8) hydrogen-bonding motif links carboxylic acid groups on adjacent molecules in both structures. In zymonic acid, this results in dimers about a crystallographic twofold of space group C2/c, which forces the carboxylic acid group to be disordered exactly 50: 50, which scrambles the carbonyl and hydroxyl groups and gives an apparent equalization of the C-O bond lengths [1.2568 (16) and 1.2602 (16) angstrom]. The other hydrogen bonds in zymonic acid (O-H center dot center dot center dot O and weak C-H center dot center dot center dot O), link molecules across a 2(1)-screw axis, and generate an R-2(2)(9) motif. These hydrogen-bonding interactions propagate to form extended pleated sheets in the ab plane. Stacking of these zigzag sheets along c involves only van der Waals contacts. In pyruvic acid, inversion-related molecules are linked into R-2(2)(8) dimers, with van der Waals interactions between dimers as the only other intermolecular contacts.