Experimental and theoretical characterization of chelidonic acid structure

Chelidonic acid (4-oxo-4H-pyran-2,6-dicarboxylic acid) is present in plants of Papaveraceae family, especially in Chelidonium majus . Due to its anticancer, antibacterial, hepatoprotective, and antioxidant properties, it has been used in medical treatments. In this work, the X-ray structure of methanol solvate of chelidonic acid was determined. Layers of chelidonic acid are held by hydrogen bonds via COOH and C = O fragments and additionally bridged by methanol. The formed H-bond network between two acid units is different from typical –COOH dimers observed, e.g., in crystals of isophtalic acid. The molecular structure of 2,6-dimethyl-γ-pyrone (2Me4PN) and chelidonic acid, a 2,6-dicarboxylic derivate of γ-pyrone (4PN), was verified in silico using density functional theory (DFT-B3LYP) combined with large correlation-consistent basis sets. The impact of –CH 3 and –COOH substituents on 4PN ring structure, dipole moments, geometric/magnetic indexes of aromaticity, and NBO charges was assessed following unconstrained geometry optimization in the gas phase, chloroform, methanol, DMSO, and water with solvent effect introduced using the polarized continuous model (PCM). H-bond network formed in chelidonic acid–methanol complex was analyzed and their interaction energy estimated. Theoretical modeling enabled prediction of accurate structural parameters, dipole moments, and geometric/magnetic indexes of aromaticity of the studied 4PN, 2Me4PN, and chelidonic acid molecules.