Crystal Structure, Spectroscopic Characterization, DFT, Hirshfeld Surface and Energy Framework Analyses of (E)-4-bromo-5-methoxy-2-(((2-methoxyphenyl)imino)methyl)phenol monohydrate
Abstract
In this study, a bromine-substituted Schiff base derivative was effectively synthesized and its crystal structure was identified by single-crystal X-ray diffraction. The supramolecular properties of the compound were comprehensively investigated using experimental and theoretical approaches. A high degree of agreement was observed between the experimentally determined molecular geometry and the computationally optimized structure at the B3LYP/6-31G(d,p) level, confirming the reliability of the computational model. Fourier transform infrared spectroscopy revealed the presence of an azomethine bond and a strong intramolecular O-H···N hydrogen bonding, while UV–Visible spectroscopic analysis exhibited characteristic π→π*, n→π*, and intramolecular charge transfer transitions associated with the conjugated molecular framework. Hirshfeld surface analysis and fingerprint maps revealed that O-H···O and crystal water-mediated Ow-H···O hydrogen bonds have a significant role in crystal packing, whereas weaker interactions such as C-H···Br and C-H···O contacts contribute cooperatively to the stabilization of the supramolecular architecture. Energy framework analysis revealed that the dispersion energy is the major contributor to the total interaction energy, consistent with the presence of π···π stacking and van der Waals interactions. Furthermore, void analysis indicated a low void content within the unit cell, suggesting efficient molecular packing. Overall, the crystal stability of the investigated compound arises from the combined effects of strong hydrogen bonding and dispersion-driven interactions.
Keywords
Schiff base, X-ray diffraction, density functional theory, Hirshfeld surface analysis, FT-IR and UV-Vis spectroscopy
Supporting Institution
No financial support was received for this study. The research was conducted using the existing laboratory facilities and infrastructure of the authors’ affiliated institution. No external funding, grant, sponsorship, or financial contribution from any public, commercial, or non-profit organization was obtained during the preparation of this manuscript.
Ethical Statement
Ethics committee approval was not required for this study.
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References
- L. Fabbrizzi, Beauty in chemistry: making artistic molecules with Schiff bases, The Journal of Organic Chemistry 85 (19) (2020) 12212–12226.
- J. Jorge, K. F. Del Pino Santos, F. Timóteo, R. R. Piva Vasconcelos, O. I. Ayala Cáceres, I. J. Arantes Granja, D. M. de Souza, T. E. Allievi Frizon, G. Di Vaccari Botteselle, …, J. Rafique, Recent advances on the antimicrobial activities of Schiff bases and their metal complexes: An updated overview, Current Medicinal Chemistry 31 (17) (2024) 2330–2344.
- E. Raczuk, B. Dmochowska, J. Samaszko-Fiertek, J. Madaj, Different Schiff bases—structure, importance and classification, Molecules 27 (3) (2022) 787.
- V. K. Juyal, A. Pathak, M. Panwar, S. C. Thakuri, O. Prakash, A. Agrwal, V. Nand, Schiff base metal complexes as a versatile catalyst: A review, Journal of Organometallic Chemistry 999 (2023) 122825.
- T. Shiga, N. Mihara, M. Nihei, Cyanide-bridged assemblies with tricyanometalates, Coordination Chemistry Reviews 472 (2022) 214763.
- C. Redshaw, Use of metal catalysts bearing Schiff base macrocycles for the ring opening polymerization (ROP) of cyclic esters, Catalysts 7 (5) (2017) 165.
- P. Mahadevi, S. Sumathi, Schiff base metal complexes: Synthesis, optoelectronic, biological studies, fabrication of zinc oxide nanoparticles and its photocatalytic activity, Results in Chemistry 6 (2023) 101026.
- C. Boulechfar, H. Ferkous, A. Delimi, A. Djedouani, A. Kahlouche, A. Boublia, A. S. Darwish, T. Lemaoui, R. Verma, Y. Benguerba, Schiff bases and their metal complexes: A review on the history, synthesis, and applications, Inorganic Chemistry Communications 150 (2023) 110451.
- M. Kumar, A. K. Singh, A. K. Singh, R. K. Yadav, S. Singh, A. P. Singh, A. Chauhan, Recent advances in 3d-block metal complexes with bi, tri, and tetradentate Schiff base ligands derived from salicylaldehyde and its derivatives: Synthesis, characterization and applications, Coordination Chemistry Reviews 488 (2023) 215176.
- D. W. Roberts, T. W. Schultz, A. M. Api, Skin sensitization QMM for HRIPT NOEL data: Aldehyde Schiff-base domain, Chemical Research in Toxicology 30 (6) (2017) 1309–1316.