Synthesis, Crystal Structure and Supramolecular Features of Novel 2,4-Diaminopyrimidine Salts

Abstract

The crystal structures and the supramolecular architectures of a series of novel salts originating from 2,4-diaminopyrimidine and four different chain dicarboxylic acids are reported. For this purpose, 2,4-diaminopyrimidin-1-ium 2,2′-thio(acetic)acetate (1), 2,4-diaminopyrimidin-1-ium monoglutarate (2), 2,4-diaminopyrimidin-1-ium 3,3′-dithio(propionic)propionate (3) and 2,4-diaminopyrimidin-1-ium suberate (4) were synthesized in good to high yields from 2,4-diaminopyrimidine and appropriate dicarboxylic acids (2,2′-thiodiacetic acid, glutaric acid, 3,3′-dithiodipropionic acid and suberic acid, respectively). Each of the compounds were formed as a monohydrate and compound 4 additionally co-crystallized with the suberic acid molecule. Despite the similar structures of compounds 1 and 2 as well as 3 and 4, subtle but important differences are observed in their crystal packing and H-bonding patterns, especially between 3 and 4. Supramolecular self-assemblies can be distinguished through different interactions considering anions, leading to diverse H-bonding motifs, which also include sulphur atoms in 1 and 3, at the upper level of supramolecular architecture. Notably, the basic motif is always the same—2,4-diaminopyrimidine-based homosynthon R22(8) via N-H∙∙∙N interactions. The impact of diverse types of intermolecular interactions was evaluated by Hirshfeld analysis, while the propensity of atom pairs of elements to build interactions was calculated using enrichment ratios. Although compounds 1 and 3 contain S-atoms, the percentage of S-derived interactions is rather low. In 1, the contribution of S∙∙∙H/H∙∙∙S, S∙∙∙C/C∙∙∙S, S∙∙∙N/N∙∙∙S intermolecular contacts is 5.7%. In 2, the contribution of S∙∙∙H/H∙∙∙S accounts for only 0.6%.