Supramolecular Organization of Two 2,4‐Diamino‐6‐Phenyl‐1,3,5‐Triazin‐1‐Ium Salts With Fluorine‐Containing Anions: Crystal Structure and Hirshfeld Surface Analysis

ABSTRACT Two salts of 2,4‐diamino‐6‐phenyl‐1,3,5‐triazine (Tris) with fluorine‐containing anions, trifluoroacetate and tetrafluoroborate, with the compositions (TrisH)(CF 3 COO) ( 1 ) and (TrisH)(BF 4 ) . H 2 O ( 2 ) were obtained and characterised by single‐crystal x‐ray diffraction. The binary salt‐like adduct 1 comprises H‐bonded tapes built of the cation‐anion centrosymmetric hetero‐tetramers through N˗H⋯O hydrogen bonds in the form of the R 4 4 (12) cyclic motif alternating with the (TrisH) 2 centrosymmetric dimers associated via a couple of NH…N hydrogen bonds through the R 2 2 (8) graph set. All hydrogen bonds are realised within the infinite tapes. The more complicated three‐dimensional H‐bonding supramolecular network was realised in 2 due to the larger number of available H‐donor and H‐acceptor binding sites (water molecule and BF 4 − anion). The (TrisH) 2 centrosymmetric dimers preserve as a robust fragment of the H‐bonded infinite tape in 2 sustained by the interplay of NH…N, OH…F, and also by NH…O and NH…F hydrogen bonds. The impact of H···F and F···F short contacts, alongside π – π stacking interactions, in rigidifying the crystal lattice and eliminating the Tris conformational continuum—thereby facilitating the crystallization of the thermodynamically favorable crystal form—was evaluated using Hirshfeld surface analysis.