Supramolecular self-assembly of a new multi-conformational Schiff base through hydrogen bonds: Crystal structure, spectroscopic and theoretical investigation

Autores
Rocha, Mariana; Di Santo, A.; Echeverría, Gustavo Alberto; Piro, Oscar Enrique; Cukiernik, F. D.; Ulic, Sonia Elizabeth; Gil, Diego M.
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The compound 4-(4-dimethylaminobenzylidene)aminoacetophenone was synthesized by condensation of 4-aminoacetophenone and 4-(dimethylamino) benzaldehyde in ethanol. This compound was characterized by CG-MS, infrared, Raman, UVeVis, 1H and 13C NMR spectroscopy. The crystal structure was solved by single-crystal X-ray diffraction methods. The crystallographic data reveals that there are four independent molecules per asymmetric unit, that mainly differ from one another in rotations around the σ-bond of the azomethine N-atom with the phenyl ring. A detailed analysis of the intermolecular interactions in the four conformers of the compound has been performed using Hirshfeld surfaces and their associated two-dimensional fingerprint plots. The optimized geometrical parameters and calculated spectroscopic features obtained by quantum chemical calculations at B3LYP method show a very good agreement with the experimental data. Moreover, Natural Bond Orbital (NBO) analysis confirms the strong hyper-conjugative LP N(n1) → σ* C(n9)–H interaction between the lone pair located in the N-atom of the azomethine group and the C–H bond. Liquid crystalline properties of the Schiff base were studied by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and Powder X-ray diffraction techniques. Mesomorphic behaviour was observed in this unsymmetrical azomethine. Based on POM and DSC measurements, the hexatic Smetic B phase was detected.
Facultad de Ciencias Exactas
Centro de Química Inorgánica
Instituto de Física La Plata
Materia
Ciencias Exactas
Química
Física
Schiff bases
crystal structure
quantum chemical calculations
IR and Raman spectroscopy
Hirshfeld surface analysis
mesomorphic properties
Nivel de accesibilidad
acceso abierto
Condiciones de uso
http://creativecommons.org/licenses/by-nc-sa/4.0/
Repositorio
SEDICI (UNLP)
Institución
Universidad Nacional de La Plata
OAI Identificador
oai:sedici.unlp.edu.ar:10915/108943
Acceder
id SEDICI_027706c6c8c7593e7adbf4b168d55e61
oai_identifier_str oai:sedici.unlp.edu.ar:10915/108943
network_acronym_str SEDICI
repository_id_str 1329
network_name_str SEDICI (UNLP)
spelling Supramolecular self-assembly of a new multi-conformational Schiff base through hydrogen bonds: Crystal structure, spectroscopic and theoretical investigationRocha, MarianaDi Santo, A.Echeverría, Gustavo AlbertoPiro, Oscar EnriqueCukiernik, F. D.Ulic, Sonia ElizabethGil, Diego M.Ciencias ExactasQuímicaFísicaSchiff basescrystal structurequantum chemical calculationsIR and Raman spectroscopyHirshfeld surface analysismesomorphic propertiesThe compound 4-(4-dimethylaminobenzylidene)aminoacetophenone was synthesized by condensation of 4-aminoacetophenone and 4-(dimethylamino) benzaldehyde in ethanol. This compound was characterized by CG-MS, infrared, Raman, UVeVis, <sup>1</sup>H and <sup>13</sup>C NMR spectroscopy. The crystal structure was solved by single-crystal X-ray diffraction methods. The crystallographic data reveals that there are four independent molecules per asymmetric unit, that mainly differ from one another in rotations around the σ-bond of the azomethine N-atom with the phenyl ring. A detailed analysis of the intermolecular interactions in the four conformers of the compound has been performed using Hirshfeld surfaces and their associated two-dimensional fingerprint plots. The optimized geometrical parameters and calculated spectroscopic features obtained by quantum chemical calculations at B3LYP method show a very good agreement with the experimental data. Moreover, Natural Bond Orbital (NBO) analysis confirms the strong hyper-conjugative LP N(n1) → σ* C(n9)–H interaction between the lone pair located in the N-atom of the azomethine group and the C–H bond. Liquid crystalline properties of the Schiff base were studied by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and Powder X-ray diffraction techniques. Mesomorphic behaviour was observed in this unsymmetrical azomethine. Based on POM and DSC measurements, the hexatic Smetic B phase was detected.Facultad de Ciencias ExactasCentro de Química InorgánicaInstituto de Física La Plata2017info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdf24-36http://sedici.unlp.edu.ar/handle/10915/108943enginfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/abs/pii/S0022286016312571info:eu-repo/semantics/altIdentifier/issn/0022-2860info:eu-repo/semantics/altIdentifier/doi/10.1016/j.molstruc.2016.11.071info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-sa/4.0/Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2025-10-22T17:05:36Zoai:sedici.unlp.edu.ar:10915/108943Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-10-22 17:05:36.304SEDICI (UNLP) - Universidad Nacional de La Platafalse
dc.title.none.fl_str_mv Supramolecular self-assembly of a new multi-conformational Schiff base through hydrogen bonds: Crystal structure, spectroscopic and theoretical investigation
title Supramolecular self-assembly of a new multi-conformational Schiff base through hydrogen bonds: Crystal structure, spectroscopic and theoretical investigation
spellingShingle Supramolecular self-assembly of a new multi-conformational Schiff base through hydrogen bonds: Crystal structure, spectroscopic and theoretical investigation
Rocha, Mariana
Ciencias Exactas
Química
Física
Schiff bases
crystal structure
quantum chemical calculations
IR and Raman spectroscopy
Hirshfeld surface analysis
mesomorphic properties
title_short Supramolecular self-assembly of a new multi-conformational Schiff base through hydrogen bonds: Crystal structure, spectroscopic and theoretical investigation
title_full Supramolecular self-assembly of a new multi-conformational Schiff base through hydrogen bonds: Crystal structure, spectroscopic and theoretical investigation
title_fullStr Supramolecular self-assembly of a new multi-conformational Schiff base through hydrogen bonds: Crystal structure, spectroscopic and theoretical investigation
title_full_unstemmed Supramolecular self-assembly of a new multi-conformational Schiff base through hydrogen bonds: Crystal structure, spectroscopic and theoretical investigation
title_sort Supramolecular self-assembly of a new multi-conformational Schiff base through hydrogen bonds: Crystal structure, spectroscopic and theoretical investigation
dc.creator.none.fl_str_mv Rocha, Mariana
Di Santo, A.
Echeverría, Gustavo Alberto
Piro, Oscar Enrique
Cukiernik, F. D.
Ulic, Sonia Elizabeth
Gil, Diego M.
author Rocha, Mariana
author_facet Rocha, Mariana
Di Santo, A.
Echeverría, Gustavo Alberto
Piro, Oscar Enrique
Cukiernik, F. D.
Ulic, Sonia Elizabeth
Gil, Diego M.
author_role author
author2 Di Santo, A.
Echeverría, Gustavo Alberto
Piro, Oscar Enrique
Cukiernik, F. D.
Ulic, Sonia Elizabeth
Gil, Diego M.
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv Ciencias Exactas
Química
Física
Schiff bases
crystal structure
quantum chemical calculations
IR and Raman spectroscopy
Hirshfeld surface analysis
mesomorphic properties
topic Ciencias Exactas
Química
Física
Schiff bases
crystal structure
quantum chemical calculations
IR and Raman spectroscopy
Hirshfeld surface analysis
mesomorphic properties
dc.description.none.fl_txt_mv The compound 4-(4-dimethylaminobenzylidene)aminoacetophenone was synthesized by condensation of 4-aminoacetophenone and 4-(dimethylamino) benzaldehyde in ethanol. This compound was characterized by CG-MS, infrared, Raman, UVeVis, <sup>1</sup>H and <sup>13</sup>C NMR spectroscopy. The crystal structure was solved by single-crystal X-ray diffraction methods. The crystallographic data reveals that there are four independent molecules per asymmetric unit, that mainly differ from one another in rotations around the σ-bond of the azomethine N-atom with the phenyl ring. A detailed analysis of the intermolecular interactions in the four conformers of the compound has been performed using Hirshfeld surfaces and their associated two-dimensional fingerprint plots. The optimized geometrical parameters and calculated spectroscopic features obtained by quantum chemical calculations at B3LYP method show a very good agreement with the experimental data. Moreover, Natural Bond Orbital (NBO) analysis confirms the strong hyper-conjugative LP N(n1) → σ* C(n9)–H interaction between the lone pair located in the N-atom of the azomethine group and the C–H bond. Liquid crystalline properties of the Schiff base were studied by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and Powder X-ray diffraction techniques. Mesomorphic behaviour was observed in this unsymmetrical azomethine. Based on POM and DSC measurements, the hexatic Smetic B phase was detected.
Facultad de Ciencias Exactas
Centro de Química Inorgánica
Instituto de Física La Plata
description The compound 4-(4-dimethylaminobenzylidene)aminoacetophenone was synthesized by condensation of 4-aminoacetophenone and 4-(dimethylamino) benzaldehyde in ethanol. This compound was characterized by CG-MS, infrared, Raman, UVeVis, <sup>1</sup>H and <sup>13</sup>C NMR spectroscopy. The crystal structure was solved by single-crystal X-ray diffraction methods. The crystallographic data reveals that there are four independent molecules per asymmetric unit, that mainly differ from one another in rotations around the σ-bond of the azomethine N-atom with the phenyl ring. A detailed analysis of the intermolecular interactions in the four conformers of the compound has been performed using Hirshfeld surfaces and their associated two-dimensional fingerprint plots. The optimized geometrical parameters and calculated spectroscopic features obtained by quantum chemical calculations at B3LYP method show a very good agreement with the experimental data. Moreover, Natural Bond Orbital (NBO) analysis confirms the strong hyper-conjugative LP N(n1) → σ* C(n9)–H interaction between the lone pair located in the N-atom of the azomethine group and the C–H bond. Liquid crystalline properties of the Schiff base were studied by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and Powder X-ray diffraction techniques. Mesomorphic behaviour was observed in this unsymmetrical azomethine. Based on POM and DSC measurements, the hexatic Smetic B phase was detected.
publishDate 2017
dc.date.none.fl_str_mv 2017
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
Articulo
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://sedici.unlp.edu.ar/handle/10915/108943
url http://sedici.unlp.edu.ar/handle/10915/108943
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/abs/pii/S0022286016312571
info:eu-repo/semantics/altIdentifier/issn/0022-2860
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.molstruc.2016.11.071
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
dc.format.none.fl_str_mv application/pdf
24-36
dc.source.none.fl_str_mv reponame:SEDICI (UNLP)
instname:Universidad Nacional de La Plata
instacron:UNLP
reponame_str SEDICI (UNLP)
collection SEDICI (UNLP)
instname_str Universidad Nacional de La Plata
instacron_str UNLP
institution UNLP
repository.name.fl_str_mv SEDICI (UNLP) - Universidad Nacional de La Plata
repository.mail.fl_str_mv alira@sedici.unlp.edu.ar
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