Supramolecular Cocrystal of 2-Amino-4-Chloro-6- Methylpyrimidine with 4-Methylbenzoic Acid: Synthesis, Structural Determinations and Quantum Chemical Investigations

The 1:1 cocrystal of 2-amino-4-chloro-6methylpyrimidine (2A4C6MP) with 4-methylbenzoic acid (4MBA) (I) has been prepared by slow evaporation method in methanol, which was crystallized in monoclinic C2/c space group, Z = 8, and a = 28.431 (2) Å, b = 7.3098 (5) Å, c = 14.2622 (10) Å and β = 109.618 (3)°. The presence of unionized –COOH functional group in cocrystal I was identified both by spectral methods (1H and 13C NMR, FTIR) and X-ray diffraction structural analysis. The 2A4C6MP molecule interact with the carboxylic group of the respective 4MBA molecule through N—H⋯O and O—H⋯N hydrogen bonds, forming a cyclic hydrogen–bonded motif R2(8). The crystal structure was stabilized by Npyrimidine—H⋯O=C and C=O—H⋯Npyrimidine types hydrogen bonding interactions. Theoretical investigations have been computed by HF and density function (B3LYP) method with 6–311+G (d,p)basis set. The vibrational frequencies together with 1H and 13C NMR chemical shifts have been calculated on the fully optimized geometry of cocrystal I. Theoretical calculations are in good agreement with the experimental results. Solvent–free formation of this cocrystal I is confirmed by powder X-ray diffraction analysis. Keywords—Supramolecular Cocrystal, 2-amino-4-chloro-6methylpyrimidine, Hartree-Fock and DFT Studies, Spectroscopic Analysis.