A new perfluoromethyl aminoenone derivative and the role of the hydrogen bonding in the intra- and intermolecular interactions

• Published in: Journal of fluorine chemistry Vol. 208; pp. 36 - 47
• Main Authors: Rocha, Mariana, Gil, Diego M., Echeverría, Gustavo A., Piro, Oscar E., Jios, Jorge L., Ulic, Sonia E.
• Format: Journal Article
• Language: English
• Published: LAUSANNE Elsevier B.V 01.04.2018; Elsevier; Elsevier BV
• Subjects: Carbonyls; Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Conformation; Crystal structure; DFT calculations; Electronic spectra; Hirshfeld surface analysis; Hydrogen; Hydrogen bonding; Hydrogen bonds; Molecular chains; Molecular conformation; Phenolic compounds; Phenols; Physical Sciences; Science & Technology; Single crystals; Spectrum analysis; Vibration; X-ray diffraction; β-Aminoenone tautomer; β-Aminoenone tautomer; Hirshfeld surface analysis; Hydrogen bonding; DFT calculations; Crystal structure; CRYSTAL-STRUCTURE; BEHAVIOR; COMPLEXES; ORGANIC FLUORINE; beta-Aminoenone tautomer; ENAMINONES; RESONANCE; ANTICONVULSANT ACTIVITY; DENSITY-FUNCTIONAL THEORY; ENERGIES
• ISSN: 0022-1139; 1873-3328
• DOI: 10.1016/j.jfluchem.2018.01.001

[Display omitted] •A new perfluoromethyl aminoenone has been synthesized and characterized.•The crystal structure was solved by XRD methods.•A detail analysis of the main intermolecular interactions in the solid was performed.•The experimental data were compared with those obtained by DFT calculations. The structure of a new perfluoromethyl derivative, (Z)-4,4,4-trifluoro-1-(2-hydroxyphenyl)-3-(methylamino)-2-buten-1-one (1), was investigated in both crystalline state and solution since the prototropy enable the existence of three tautomeric species in equilibrium. The preference in the configurational E/Z arrangement is strongly dependent on the intramolecular hydrogen bond interactions. The vibrational and electronic spectra of 1 were discussed and assigned by using DFT calculations. The crystal, solved by single-crystal X-ray diffraction, shows the prevalence of the tautomer aminoenone over the imino-enol and imino-ketone forms. Therefore, an almost planar molecular conformation is observed due to the formation of two intramolecular amino and phenolic hydrogen bonds to the same carbonyl oxygen acceptor atom that stabilize the Z configuration. The molecular packing is held by the OH⋯O(keto) and NH⋯O hydrogen bonds, F⋯F, CH⋯π and π-stacking interactions that contribute to the crystal stabilization. The intra and intermolecular contacts were also characterized by Natural Bond Orbital (NBO) analysis and Atoms in Molecules (AIM) approach. Hirshfeld surfaces and their associated fingerprint plots were generated for 1 and for a related structure, to visualize different intermolecular interactions and their relative contributions to the total surface.