Crystal structures and supramolecular and Hirshfeld surface analysis of three novel 2,4,6-triaminopyrimidine salts

Three new hydrous molecular salts, namely, 2,4,6-triaminopyrimidin-1-ium anthranilate (2-aminobenzoate) monohydrate, C 4 H 8 N 5 + ·C 7 H 6 NO 2 − ·H 2 O (I), 2,4,6-triaminopyrimidin-1-ium 5-aminoisophthalate monohydrate, C 4 H 8 N 5 + ·C 8 H 6 NO 4 − ·H 2 O (II), and bis(2,4,6-triaminopyrimidin-1-ium) 4-aminophthalate trihydrate, 2C 4 H 8 N 5 + ·C 8 H 5 NO 4 2− ·3H 2 O (III), have been synthesized and characterized by single-crystal X-ray diffraction techniques. In all three crystal structures, protonation of the pyrimidine moiety occurs at the N1 position and is reflected in a widening of the C—N—C bond angle. In all three cases, protonation of the triaminopyrimidine (TAP) molecule leads to the formation of the robust charge-assisted R 2 2 (8) TAP–carboxylate heterosynthon, which acts as the primary supramolecular building unit. In salt I, TAP base pairing and water-mediated contacts produce tetrameric aggregates and a DDDA ( D is donor and A is acceptor) supramolecular array that propagates into a 3D hydrogen-bonded sheet structure. Salt II exhibits a combination of R 2 2 (8), R 3 2 (8) and R 2 4 (8) motifs that fuse to form a continuous hydrogen-bonded chain characterized by a DDDAAA supramolecular array. These chains further assemble into extended sheets which are interconnected by higher-order ring motifs and are reinforced by π–π stacking interactions between the pyrimidine ring and the aromatic anion. The structure of salt III displays the most complex architecture. Multiple hydrogen-bonded arrays, including DADA -type quadruple motifs and large fused-ring motifs, arise through co-operative N—H...O, N—H...N and O—H...O interactions involving the cations, anion and water molecules, resulting in a densely interconnected 3D framework. Hirshfeld surface analysis reveals that H...H contacts dominate the crystal packing, while O...H/H...O and N...H/H...N interactions play a crucial role in directing the supramolecular assembly. The study highlights how anion topology and hydration influence hydrogen-bond hierarchy and supramolecular dimensionality in TAP-based salts.