Crystal and molecular structure of glutaconic acid

Abstract

Crystals of Glutaconic acid, C₅O₄H₆, are triclinic, space group P ${\bar 1}$, with the cell dimensions (294 K), a = 4.843(1) Å, b = 10.188(1) Å, c = 12.609(1) Å, α = 83.46(1)°, β = 80.02(1)°, γ = 78.71(1)°, V = 598.8(3) ų with D _m = 1.47, D _x = 1.443 g⋅cm ⁻³. There are two independent molecules in the asymmetric unit. The crystal structure was solved by multi solution techniques with three-dimensional data collected (to the limit of 2θ_max of 154° for Cu Kα) on a CAD-4 diffractometer. The crystal structure was refined by full matrix least squares method to a final R value of 0.058 for 1894 reflections (I ≥ 2σ). The two independent molecules are conformationally similar. In both the molecules, the carboxyl ends are trans to each other with respect to the central C=C double bond in the structure. The molecules are self-paired through dimeric type of hydrogen bonding involving the terminal carboxyl groups, characteristic of many dicarboxylic acid structures. The crystal structure is stabilized by a series of O–H⋅⋅⋅O hydrogen bonds of the glutaconic acid dimeric units. Free radicals have been shown to be involved in a number of chemical and biological processes and lipid peroxidation is one such process. Glutaconic acid was chosen as a simple unsaturated model of a fatty acid. When irradiated with X-rays, it was found to form a stable free radical structure. ESR (electron spin resonance) and ENDOR (electron nuclear double resonance) studies were used to characterize the free radical structure and correlate with the X-ray structure. The free radical was found to be HOOC–CH=CH–CH–COOH with the glutaconic acid in the trans conformation. The damage occurs at the α-carbon atom (the first carbon of the double bond). The damage consists of a loss of an hydrogen atom. This results in an unpaired electron in the p-orbital delocalized over the three central carbon atoms. The two α-proton couplings were resolved in the ENDOR spectrum. ESR spectra show that the two molecules are magnetically similar that is in agreement with the crystal structure that reveals that the two independent molecules are conformationally similar. This is the characteristic type of damage that occurs in lipids when they form free radicals that in turn reacts with oxygen and other compounds and ultimately results in cellular damage.