کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
1406038 | 1501819 | 2011 | 6 صفحه PDF | دانلود رایگان |
The location of H-atoms sites in carboxylic-acid dimers has been related to the crystal environment. It has been shown that the H-sites are coupled to the orientation of carboxylic-acid groups. Consequently, the H-bonds can be strained and the H-atoms destabilized and disordered by the symmetric crystal environment of symmetric molecules. The coupling results in the O⋯O distance contraction by about 0.015 Å in carboxylic acids with disordered H-atoms, this magnitude calculated from H-bonds strain being consistent with that observed in crystal structures. This strain analysis provides an easy method of locating the H-atoms in hydrogen bonds between carboxyl groups, verifying experimental data determined by X-ray diffraction, calculating the magnitudes of O⋯O distance contraction and molecular reorientations induced by the H-atoms disordering structural effects, and predicting properties related to the H-atom dynamics. The survey of carboxylic-acid structures corroborates the effects of the molecular environment on the H-sites and hydrogen-bond dimensions.
► Interdependence between H-sites and orientation of OH···O bonded carboxyl groups and molecules.
► A new method for predicting details of molecular arrangement in crystals.
► Understanding the dynamics of disordered H-atoms in hydrogen bonds.
► Validation of crystal structures of carboxylic acids.
► Systematic differences between hydrogen bonds in carboxylic acids with H-atoms ordered and disordered.
Journal: Journal of Molecular Structure - Volume 995, Issues 1–3, 31 May 2011, Pages 29–34