Supramolecular Packing of a Series of N-Phenylamides and the Role of NH···O=C Interactions

[Image: see text] A series of seven N-phenylamides [R–C(O)NHPh, in which R: CH(3), C(CH(3))(3), Ph, CF(3), CCl(3), CBr(3), and H] were used as models in this study. Molecular packing and intermolecular interactions were evaluated by theoretical calculations, solution NMR, and quantum theory of atoms...

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Autores principales: Pagliari, Anderson B., Orlando, Tainára, Salbego, Paulo R. S., Zimmer, Geórgia C., Hörner, Manfredo, Zanatta, Nilo, Bonacorso, Helio G., Martins, Marcos A. P.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2018
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6645157/
https://www.ncbi.nlm.nih.gov/pubmed/31458083
http://dx.doi.org/10.1021/acsomega.8b01801
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author Pagliari, Anderson B.
Orlando, Tainára
Salbego, Paulo R. S.
Zimmer, Geórgia C.
Hörner, Manfredo
Zanatta, Nilo
Bonacorso, Helio G.
Martins, Marcos A. P.
author_facet Pagliari, Anderson B.
Orlando, Tainára
Salbego, Paulo R. S.
Zimmer, Geórgia C.
Hörner, Manfredo
Zanatta, Nilo
Bonacorso, Helio G.
Martins, Marcos A. P.
author_sort Pagliari, Anderson B.
collection PubMed
description [Image: see text] A series of seven N-phenylamides [R–C(O)NHPh, in which R: CH(3), C(CH(3))(3), Ph, CF(3), CCl(3), CBr(3), and H] were used as models in this study. Molecular packing and intermolecular interactions were evaluated by theoretical calculations, solution NMR, and quantum theory of atoms in molecules analyses. Crystallization mechanisms were proposed based on the energetic and topological parameters using the supramolecular cluster as demarcation. Concentration-dependent (1)H NMR experiments corroborated the proposed interactions between molecules. For all compounds (except for R: H, which initially formed tetramers), layers (two-dimensional) or chains (one-dimensional) were formed in the first stage of the proposed crystallization mechanisms. The presence of strong intermolecular NH···O=C interactions promoted the first stages. The study in solution provided different values of association constant (K(ass)) governed by the hydrogen bond NH···O=C, showing that the stronger interactions are directly influenced by the substituent steric hindrance. A correlation between K(ass(NH···O=C)) from the solution and the NH···O=C interaction energy in the crystal showed a good trend.
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spelling pubmed-66451572019-08-27 Supramolecular Packing of a Series of N-Phenylamides and the Role of NH···O=C Interactions Pagliari, Anderson B. Orlando, Tainára Salbego, Paulo R. S. Zimmer, Geórgia C. Hörner, Manfredo Zanatta, Nilo Bonacorso, Helio G. Martins, Marcos A. P. ACS Omega [Image: see text] A series of seven N-phenylamides [R–C(O)NHPh, in which R: CH(3), C(CH(3))(3), Ph, CF(3), CCl(3), CBr(3), and H] were used as models in this study. Molecular packing and intermolecular interactions were evaluated by theoretical calculations, solution NMR, and quantum theory of atoms in molecules analyses. Crystallization mechanisms were proposed based on the energetic and topological parameters using the supramolecular cluster as demarcation. Concentration-dependent (1)H NMR experiments corroborated the proposed interactions between molecules. For all compounds (except for R: H, which initially formed tetramers), layers (two-dimensional) or chains (one-dimensional) were formed in the first stage of the proposed crystallization mechanisms. The presence of strong intermolecular NH···O=C interactions promoted the first stages. The study in solution provided different values of association constant (K(ass)) governed by the hydrogen bond NH···O=C, showing that the stronger interactions are directly influenced by the substituent steric hindrance. A correlation between K(ass(NH···O=C)) from the solution and the NH···O=C interaction energy in the crystal showed a good trend. American Chemical Society 2018-10-22 /pmc/articles/PMC6645157/ /pubmed/31458083 http://dx.doi.org/10.1021/acsomega.8b01801 Text en Copyright © 2018 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
spellingShingle Pagliari, Anderson B.
Orlando, Tainára
Salbego, Paulo R. S.
Zimmer, Geórgia C.
Hörner, Manfredo
Zanatta, Nilo
Bonacorso, Helio G.
Martins, Marcos A. P.
Supramolecular Packing of a Series of N-Phenylamides and the Role of NH···O=C Interactions
title Supramolecular Packing of a Series of N-Phenylamides and the Role of NH···O=C Interactions
title_full Supramolecular Packing of a Series of N-Phenylamides and the Role of NH···O=C Interactions
title_fullStr Supramolecular Packing of a Series of N-Phenylamides and the Role of NH···O=C Interactions
title_full_unstemmed Supramolecular Packing of a Series of N-Phenylamides and the Role of NH···O=C Interactions
title_short Supramolecular Packing of a Series of N-Phenylamides and the Role of NH···O=C Interactions
title_sort supramolecular packing of a series of n-phenylamides and the role of nh···o=c interactions
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6645157/
https://www.ncbi.nlm.nih.gov/pubmed/31458083
http://dx.doi.org/10.1021/acsomega.8b01801
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