Near Supramolecular Isomorphism Involving Homologous Solvents: Pyrimethaminium Terephthalate Methanol Solvate and Pyrimethaminium Terephthalate Ethanol Solvate

Abstract

Two nearly isostructural pseudopolymorphic forms of pyrimethaminium terephthalate have been synthesized and their supramolecular architectures analyzed. In both the crystals, the protonated pyrimethamine (PMN) cation interacts with the carboxylate anion via N–H···O hydrogen bonds to form the robust R ²₂ (8) motif. The centrosymmetrically (N–H···N) paired PMN cations are bridged on either sides by interaction of the solvent molecules with the amino groups (N–H···O) of PMN cations. The combination of two R ²₂ (8) motifs formed between the PMN cations and PMN cation solvent, leads to the formation of the complementary DADA (D = hydrogen bonded donor, A = hydrogen bonded acceptor) array of quadruple hydrogen bonds. The solvent molecule further interacts with the corresponding anion via O–H···O hydrogen bonds. Moreover, both the solvates exhibit several edge to face stacking interactions. They have in common, two C–H···π interactions; one between the symmetry related cations and other between the cation and anion. The molecular packing of the ethanol solvate is further strengthened by C–H···O and C–H···π interaction between the solvent and the ions.

Graphical Abstract

Isomorphous supramolecular architectures in the crystal structures of pyrimethaminium terephthalate solvates.