Solid State Structure and Solution Thermodynamics of Three-Centered Hydrogen Bonds (O∙∙∙H∙∙∙O) Using N-(2-Benzoyl-phenyl) Oxalyl Derivatives as Model Compounds

Molecules

Carlos Z. Gómez-Castro²  Itzia I. Padilla-Martínez²  Efrén V. Garc໚-Bพz²  José L. Castrejón-Flores²  Ana L. Peraza-Campos¹ 

[1] Laboratorio de Posgrado, Facultad de Ciencias Químicas, Universidad de Colima, Km 9 Carretera Colima-Coquimatlán, Colima 28400, Mexico; E-Mail:;Departamento de Ciencias Básicas, Unidad Profesional Interdisciplinaria de Biotecnología del Instituto Politécnico Nacional, Av. Acueducto s/n Barrio la Laguna Ticomán, México D.F. 07340, Mexico; E-Mails:

关键词: three-center hydrogen bond;    oxalamide;    oxalamate;    steric effect;    solvent effect;    proton mobility;    cooperativity;   

DOI  :  10.3390/molecules190914446

来源: mdpi

【 摘 要 】

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(ΝΗ)/ΔT measurements, in DMSO-d₆ 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-d₆ 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-d₆ 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.

【 授权许可】

CC BY   
© 2014 by the authors; licensee MDPI, Basel, Switzerland.