Solid State Structure and Solution Thermodynamics of Three-Centered Hydrogen Bonds (O∙∙∙H∙∙∙O) Using N-(2-Benzoyl-phenyl) Oxalyl Derivatives as Model Compounds
Intramolecular hydrogen bond (HB) formation was analyzed in the model compounds N-(2-benzoylphenyl)acetamide, N-(2-benzoylphenyl)oxalamate and N(1),N(2)-bis(2-benzoylphenyl)oxalamide. The formation of three-center hydrogen bonds in oxalyl derivatives was demonstrated in the solid state by the X-ray...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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MDPI
2014
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6270700/ https://www.ncbi.nlm.nih.gov/pubmed/25221868 http://dx.doi.org/10.3390/molecules190914446 |
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author | Gómez-Castro, Carlos Z. Padilla-Martínez, Itzia I. García-Báez, Efrén V. Castrejón-Flores, José L. Peraza-Campos, Ana L. Martínez-Martínez, Francisco J. |
author_facet | Gómez-Castro, Carlos Z. Padilla-Martínez, Itzia I. García-Báez, Efrén V. Castrejón-Flores, José L. Peraza-Campos, Ana L. Martínez-Martínez, Francisco J. |
author_sort | Gómez-Castro, Carlos Z. |
collection | PubMed |
description | Intramolecular hydrogen bond (HB) formation was analyzed in the model compounds N-(2-benzoylphenyl)acetamide, N-(2-benzoylphenyl)oxalamate and N(1),N(2)-bis(2-benzoylphenyl)oxalamide. The formation of three-center hydrogen bonds in oxalyl derivatives was demonstrated in the solid state by the X-ray diffraction analysis of the geometric parameters associated with the molecular structures. The solvent effect on the chemical shift of H6 [δH6(DMSO-d(6))–δH6(CDCl(3))] and Δδ(ΝΗ)/ΔT measurements, in DMSO-d(6) as solvent, have been used to establish the energetics associated with intramolecular hydrogen bonding. Two center intramolecular HB is not allowed in N-(2-benzoylphenyl)acetamide either in the solid state or in DMSO-d(6) solution because of the unfavorable steric effects of the o-benzoyl group. The estimated ΔHº and ΔSº values for the hydrogen bonding disruption by DMSO-d(6) of 28.3(0.1) kJ·mol(−1) and 69.1(0.4) J·mol(−1)·K(−1) for oxalamide, are in agreement with intramolecular three-center hydrogen bonding in solution. In the solid, the benzoyl group contributes to develop 1-D and 2-D crystal networks, through C–H∙∙∙A (A = O, π) and dipolar C=O∙∙∙A (A = CO, π) interactions, in oxalyl derivatives. To the best of our knowledge, this is the first example where three-center hydrogen bond is claimed to overcome steric constraints. |
format | Online Article Text |
id | pubmed-6270700 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2014 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-62707002018-12-27 Solid State Structure and Solution Thermodynamics of Three-Centered Hydrogen Bonds (O∙∙∙H∙∙∙O) Using N-(2-Benzoyl-phenyl) Oxalyl Derivatives as Model Compounds Gómez-Castro, Carlos Z. Padilla-Martínez, Itzia I. García-Báez, Efrén V. Castrejón-Flores, José L. Peraza-Campos, Ana L. Martínez-Martínez, Francisco J. Molecules Article Intramolecular hydrogen bond (HB) formation was analyzed in the model compounds N-(2-benzoylphenyl)acetamide, N-(2-benzoylphenyl)oxalamate and N(1),N(2)-bis(2-benzoylphenyl)oxalamide. The formation of three-center hydrogen bonds in oxalyl derivatives was demonstrated in the solid state by the X-ray diffraction analysis of the geometric parameters associated with the molecular structures. The solvent effect on the chemical shift of H6 [δH6(DMSO-d(6))–δH6(CDCl(3))] and Δδ(ΝΗ)/ΔT measurements, in DMSO-d(6) as solvent, have been used to establish the energetics associated with intramolecular hydrogen bonding. Two center intramolecular HB is not allowed in N-(2-benzoylphenyl)acetamide either in the solid state or in DMSO-d(6) solution because of the unfavorable steric effects of the o-benzoyl group. The estimated ΔHº and ΔSº values for the hydrogen bonding disruption by DMSO-d(6) of 28.3(0.1) kJ·mol(−1) and 69.1(0.4) J·mol(−1)·K(−1) for oxalamide, are in agreement with intramolecular three-center hydrogen bonding in solution. In the solid, the benzoyl group contributes to develop 1-D and 2-D crystal networks, through C–H∙∙∙A (A = O, π) and dipolar C=O∙∙∙A (A = CO, π) interactions, in oxalyl derivatives. To the best of our knowledge, this is the first example where three-center hydrogen bond is claimed to overcome steric constraints. MDPI 2014-09-12 /pmc/articles/PMC6270700/ /pubmed/25221868 http://dx.doi.org/10.3390/molecules190914446 Text en © 2014 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution license (http://creativecommons.org/licenses/by/3.0/). |
spellingShingle | Article Gómez-Castro, Carlos Z. Padilla-Martínez, Itzia I. García-Báez, Efrén V. Castrejón-Flores, José L. Peraza-Campos, Ana L. Martínez-Martínez, Francisco J. Solid State Structure and Solution Thermodynamics of Three-Centered Hydrogen Bonds (O∙∙∙H∙∙∙O) Using N-(2-Benzoyl-phenyl) Oxalyl Derivatives as Model Compounds |
title | Solid State Structure and Solution Thermodynamics of Three-Centered Hydrogen Bonds (O∙∙∙H∙∙∙O) Using N-(2-Benzoyl-phenyl) Oxalyl Derivatives as Model Compounds |
title_full | Solid State Structure and Solution Thermodynamics of Three-Centered Hydrogen Bonds (O∙∙∙H∙∙∙O) Using N-(2-Benzoyl-phenyl) Oxalyl Derivatives as Model Compounds |
title_fullStr | Solid State Structure and Solution Thermodynamics of Three-Centered Hydrogen Bonds (O∙∙∙H∙∙∙O) Using N-(2-Benzoyl-phenyl) Oxalyl Derivatives as Model Compounds |
title_full_unstemmed | Solid State Structure and Solution Thermodynamics of Three-Centered Hydrogen Bonds (O∙∙∙H∙∙∙O) Using N-(2-Benzoyl-phenyl) Oxalyl Derivatives as Model Compounds |
title_short | Solid State Structure and Solution Thermodynamics of Three-Centered Hydrogen Bonds (O∙∙∙H∙∙∙O) Using N-(2-Benzoyl-phenyl) Oxalyl Derivatives as Model Compounds |
title_sort | solid state structure and solution thermodynamics of three-centered hydrogen bonds (o∙∙∙h∙∙∙o) using n-(2-benzoyl-phenyl) oxalyl derivatives as model compounds |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6270700/ https://www.ncbi.nlm.nih.gov/pubmed/25221868 http://dx.doi.org/10.3390/molecules190914446 |
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