TY - JOUR
T1 - Solid state structure and solution thermodynamics of three-centered hydrogen bonds (O⋯H⋯O) using N-(2-benzoyl-phenyl) oxalyl derivatives as model compounds
AU - Gómez-Castro, Carlos Z.
AU - Padilla-Martínez, Itzia I.
AU - García-Báez, Efrén V.
AU - Castrejón-Flores, José L.
AU - Peraza-Campos, Ana L.
AU - Martínez-Martínez, Francisco J.
N1 - Publisher Copyright:
© Molecules 2014.
PY - 2014/9/12
Y1 - 2014/9/12
N2 - Intramolecular hydrogen bond (HB) formation was analyzed in the model compounds N-(2-benzoylphenyl)acetamide, N-(2-benzoylphenyl)oxalamate and N1,N2-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-d6)-δH6(CDCl3)] and Δδ(NH)/ΔT measurements, in DMSO-d6as 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-d6solution because of the unfavorable steric effects of the o-benzoyl group. The estimated ΔH° and ΔS° values for the hydrogen bonding disruption by DMSO-d6of 28.3(0.1) kJ·mol-1and 69.1(0.4) J·mol-1·K-1for 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.
AB - Intramolecular hydrogen bond (HB) formation was analyzed in the model compounds N-(2-benzoylphenyl)acetamide, N-(2-benzoylphenyl)oxalamate and N1,N2-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-d6)-δH6(CDCl3)] and Δδ(NH)/ΔT measurements, in DMSO-d6as 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-d6solution because of the unfavorable steric effects of the o-benzoyl group. The estimated ΔH° and ΔS° values for the hydrogen bonding disruption by DMSO-d6of 28.3(0.1) kJ·mol-1and 69.1(0.4) J·mol-1·K-1for 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.
KW - Cooperativity
KW - Oxalamate
KW - Oxalamide
KW - Proton mobility
KW - Solvent effect
KW - Steric effect
KW - Three-center hydrogen bond
UR - http://www.scopus.com/inward/record.url?scp=84907096709&partnerID=8YFLogxK
U2 - 10.3390/molecules190914446
DO - 10.3390/molecules190914446
M3 - Artículo
C2 - 25221868
AN - SCOPUS:84907096709
SN - 1420-3049
VL - 19
SP - 14446
EP - 14460
JO - Molecules
JF - Molecules
IS - 9
ER -