Synthesis and structural studies on the supramolecular architecture of two novel proton transfer molecular salts of 2−aminopyridine

• Published in: Journal of molecular structure 2023-02, Vol.1274, p.134426, Article 134426
• Main Authors: Srijana, P.J., Narayana, B., Sarojini, B.K., Wong, Qin Ai, Quah, Ching Kheng, Likhitha, U.
• Format: Article
• Language: English
• Subjects: Heterosynthon; Hirshfeld surfaces; Hydrogen bonding; Molecular salts; Single crystal XRD
• ISSN: 0022-2860; 1872-8014
• DOI: 10.1016/j.molstruc.2022.134426

•The synthesis and crystal structures of AP−PHBA and AP−NA are illustrated.•Molecular salts are characterized by Single crystal XRD, PXRD, FTIR, UV-Vis, NMR and computational methods.•Hydrogen bonding assembly is described with the help of graph set notations.•Intermolecular interactions are analyzed through Hirshfeld surfaces. Herein, synthesis, analytical and structural characterization of two new molecular salts (AP−PHBA and AP−NA) of 2−aminopyridine (AP) using GRAS molecules i.e, p−hydroxybenzoic acid (PHBA) and nicotinic acid (NA) has been envisaged. The TGA/DSC revealed that both molecular salts were thermally more stable than the AP molecule. In the UV-Vis spectrum of AP−PHBA there observed a bathochromic shift (λmax 298 nm to 305 nm) caused by extended conjugation due to the hydroxy group at the para position of PHBA which might influence the photophysical property and no such shift was observed in AP−NA (λmax=298 nm). Both the salts were found to be dominated by the two−point charge assisted acid−pyridine heterosynthonic ring motif with graph set notation R22(8). This was held via N+−H···O− and N−H···O linkages that formed between the 2−aminopyridinium cation and carboxylate anions. In both crystals, a ribbon synthon linking the ring synthon via N2A—H2AB/AC···O3B hydrogen bonds was noted with the chain motifs C21(6) and C22(6). Furthermore, the C1A—H1AA···N1B and N2A—H2AC···O3B networks were associated to build a large tetramer with R44(22) was seen in the AP−NA salt system. From Hirshfeld surfaces analysis, it was noteworthy that the variation in the percentage contribution of O···H (20.8% in AP−PHBA and 15.8% in AP−NA) and N···H (1.9% in AP−PHBA and 12.1% in AP−NA) interconnects signify the importance of hydroxy group (PHBA) and pyridine N (NA) in stabilizing the crystal systems. Hence, a complete analysis of crystal structure and supramolecular packing of the two molecular salts AP−PHBA and AP−NA was presented. [Display omitted]