title: Phenyl- and mesitylglyoxylic acids: catemeric hydrogen bonding in two alpha-keto acids
abstract: alpha-Oxobenzeneacetic (phenylglyoxylic) acid, C(8)H(6)O(3), adopts a transoid dicarbonyl conformation in the solid state, with the carboxyl group rotated 44.4 (1) degrees from the nearly planar benzoyl moiety. The heterochiral acid-to-ketone catemers [O.O = 2. 686 (3) and H.O = 1.78 (4) A] have a second, longer, intermolecular O-H.O contact to a carboxyl sp(3) O atom [O.O = 3.274 (2) and H.O = 2.72 (4) A], with each flat ribbon-like chain lying in the bc plane and extending in the c direction. In alpha-oxo-2,4, 6-trimethylbenzeneacetic (mesitylglyoxylic) acid, C(11)H(12)O(3), the ketone is rotated 49.1 (7) degrees from planarity with the aryl ring and the carboxyl group is rotated a further 31.2 (7) degrees from the ketone plane. The solid consists of chiral conformers of a single handedness, aggregating in hydrogen-bonding chains whose units are related by a 3(1) screw axis, producing hydrogen-bonding helices that extend in the c direction. The hydrogen bonding is of the acid-to-acid type [O.O = 2.709 (6) and H.O = 1.87 (5) A] and does not formally involve the ketone; however, the ketone O atom in the acceptor molecule has a close polar contact with the same donor carboxyl group [O.O = 3.005 (6) and H.O = 2.50 (5) A]. This secondary hydrogen bond is probably a major factor in stabilizing the observed cisoid dicarbonyl conformation. Several intermolecular C-H.O close contacts were found for the latter compound.
authors.affiliation: Carl A. Olson Memorial Laboratories, Department of Chemistry, Rutgers University, Newark, NJ 07102, USA.
authors.initials: CD
authors.lastname: Chen
authors.initials: AP
authors.lastname: Brunskill
authors.initials: SS
authors.lastname: Hall
authors.initials: RA
authors.lastname: Lalancette
authors.initials: HW
authors.lastname: Thompson