Structural insights into supramolecular interactions in isostructural salts of 2,4,6-triaminopyrimidinium with various heterocyclic carboxylates

2,4,6-Triaminopyrimidine is an interesting and challenging molecule due to the presence of multiple hydrogen-bond donors and acceptors. Its noncovalent interactions with a variety of carboxylic acids provide several supramolecular aggregates with frequently occurring molecular synthons. The present work focuses on the supramolecular interactions of 2,4,6-triaminopyrimidinium 3-(indol-3-yl)propionate–3-(indol-3-yl)propionic acid (1/1), C 4 H 8 N 5 + ·C 11 H 10 NO 2 − ·C 11 H 11 NO 2 , (I), 2,4,6-triaminopyrimidinium 2-(indol-3-yl)acetate, C 4 H 8 N 5 + ·C 10 H 8 NO 2 − , (II), 2,4,6-triaminopyrimidinium 5-bromothiophene-2-carboxylate, C 4 H 8 N 5 + ·C 5 H 2 BrO 2 S − , (III), and 2,4,6-triaminopyrimidinium 5-chlorothiophene-2-carboxylate, C 4 H 8 N 5 + ·C 5 H 2 ClO 2 S − , (IV). All four salts exhibit robust homomeric and heteromeric R 2 2 (8) ring motifs. Salts (I) and (II) develop sextuple [in (I)] and quadruple [in (I) and (II)] hydrogen-bonded arrays through fused-ring motifs. Salt (II) exhibits a rosette-like architecture. Salt (IV) is isostructural and isomorphous with salt (III), exhibiting an identical crystal structure with a different composition and an identical supramolecular architecture. In salts (III) and (IV), a linear hetero-tetrameric motif is formed and, in addition, both salts exhibit halogen–π interactions which enhance the crystal stability. All four salts develop a supramolecular hydrogen-bonded pattern facilitated by several N—H...O and N—H...N hydrogen bonds with multiple furcated donors and acceptors.