In acid-aminopyrimidine continuum: experimental and computational studies of furan tetracarboxylate-2-aminopyrimidinium salt.

ABSTRACT

Salts and cocrystals are the two important solid forms when a carboxylic acid crystallizes with an aminopyrimidine base such that the extent of proton transfer distinguishes between them. The ΔpK a value (pK a(base) - pK a(acid)) predicts whether the proton transfer will occur or not. However, the ΔpK a range, 0 < ΔpK a < 3, is elusive where the formation of cocrystal or salt cannot be predicted. The current study has been done to obtain a generalization in this elusive range with the Cambridge Structural Database (CSD). Based on the generalization, a novel salt (FTCA)-(2-AP)+ of furantetracarboxylic acid (FTCA) with 2-aminopyrimidine (2-AP) is obtained. The structural confirmation was done by single-crystal X-ray diffraction (SCXRD). Density functional theory (DFT) calculations were performed at the IEF-PCM-B3LYP-D3/6-311G(d,p) level to optimize the geometrical coordinates of salt for frontier molecular orbitals (FMOs) and molecular electrostatic potential (MESP). The geometrical parameters of most of the atoms of the optimized salt structure were comparable with SCXRD data. Additionally, results of other computational methods such as ab initio (Hartree-Fock; HF and second-order-Møller-Plesset perturbation; MP2) and semi-empirical were also compared with experimental results of the salt. Quantum theory of atoms in molecules (QTAIM), reduced density gradient (RDG), and natural bond orbital (NBO) analyses were done to calculate the strength and nature of non-covalent interactions present in the salt. Furthermore, Hirshfeld surface analysis, interaction energy calculations, and total energy frameworks were performed for qualitative and quantitative estimations of strong and weak intermolecular interactions.