|
ИСТИНА |
Войти в систему Регистрация |
ИСТИНА ИНХС РАН |
||
Internal rotation and intramolecular hydrogen bonding in thiosalicylamide: gas phase electron diffraction study supported by quantum chemical calculationsстатья
Информация о цитировании статьи получена из
Web of Science,
Scopus
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 11 ноября 2019 г.
- Авторы: Kolesnikova Inna N., Rykov Anatolii N., Shuvalov Maxim V., Shishkov Igor F.
- Журнал: Structural Chemistry
- Том: 30
- Год издания: 2019
- Издательство: Springer-Verlag
- Местоположение издательства: Heidelberg, Germany
- Первая страница: 1993
- Последняя страница: 2001
- DOI: 10.1007/s11224-019-01369-y
- Аннотация: The molecular structure of thiosalicylamide (2-hydroxythiobenzamide) was investigated in the gas phase at 401 K by means of gas electron diffraction (GED) combined with quantum chemical (QC) calculations. Special attention was paid to the internal rotation of the thioamide group. Structural refinement was performed taking into account rovibrational corrections to the thermal-average internuclear distances calculated with harmonic and anharmonic (cubic) MP2/cc-pVTZ force constants in terms of static and dynamic models. It was shown that both models fitted the GED data equally well. The results of the GED refinement revealed that in the equilibrium structure the thioamide group is twisted by about 30° with respect to the phenol ring plane. This is the result of an interatomic repulsion of hydrogen atom in the amide group from the closest hydrogen atom of the benzene ring, which overcomes the energy gain from the π−π conjugation of the thioamide group and the aromatic system of thiosalicylamide. NBO analysis and comparison of the thiosalicylamide molecular structure with those of related compounds revealed hydrogen bonded fragment between the hydroxyl and thiocarbonyl groups. The structure of thiosalicylamide in the gas phase was found to be markedly different from that in the solid phase due to the effect of intermolecular hydrogen bonding in the crystal.
- Добавил в систему: Колесникова Инна Николаевна