Comparative study of NH···O and NH···S intramolecular hydrogen bonds in β-aminoacrolein, β-thioaminoacrolein and their halogenated derivatives by some usual methods

A Critical Overview of Current Theoretical Methods of Estimating the Energy of Intramolecular Interactions

“…This means that the conformer change should not lead to significant changes in the values of geometric parameters. In order to overcome any inaccuracies, another approach is to use more than just two conformers of a given molecule [ 47 , 60 , 61 , 62 , 63 ]. This idea will be shown on the example of 3-aminopropenal (3-aminoacrolein), which has four conformers.…”

“…This idea will be shown on the example of 3-aminopropenal (3-aminoacrolein), which has four conformers. The N-H⋯O hydrogen bond energy in the ZZ conformer of 3-aminoacrolein was quite often estimated [ 47 , 61 , 63 , 64 , 65 ], but the methods used did not take into account changes in the values of geometric parameters when switching from the bound system (ZZ-3-aminoacrolein) to reference forms (in particular, to ZE-3-aminoacrolein) [ 64 , 65 ]. The specific system of conjugated double bonds and, hence, the presence of four conformers (see Figure 9 ), allowed for proposing a method that was derived from the analysis of the mutual energy relations between the four conformers of 3-aminoacrolein ( Figure 9 ) [ 47 ].…”

“…It should be mentioned that RRM [ 47 , 60 ] has been readily adopted by Nowroozi et al [ 61 , 62 , 63 ], who called it the Related Rotamers Method (RRM) and in this review it functions under that name. However, even a little earlier, practically the same method was used by Lipkowski et al [ 60 ] to estimate the energy of O-H⋯N intramolecular hydrogen bonds in some chloro-derivatives of 2-(N-dimethylaminomethyl)-phenols, but they used the term “thermodynamic cycle”.…”

“…and their halogenated derivatives, Nowroozi and Masumian claimed that GCM performs worse than RBM and RRM, in particular [63]. However, it is enough to look at their Scheme 3 to realize that they used wrong conformers labeled as EZ and EE.…”

Estimations of FH···X hydrogen bond energies from IR intensities: Iogansen's rule revisited

“…Badger and Bauer proposed the linear correlation between the enthalpy of complex formation ∆ H and ∆ ν s for a set of complexes formed by OH group of acids or alcohols as hydrogen bond donors 19 . During the following decades, this correlation has been mentioned in literature as the “Badger‐Bauer rule” and has been used for numerous investigations 20–26 . However, in some works it was noted that the dependency ∆ H (∆ ν s ) is nonlinear, 27,28 while others reported the absence of a strict correlation between ∆ H and ∆ ν s at all 29–31 .…”