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Intramolecular hydrogen bonding and molecular geometry of 2-nitrophenol from a joint gas-phase electron diffraction and ab initio molecular orbital investigationстатья
Информация о цитировании статьи получена из
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Дата последнего поиска статьи во внешних источниках: 14 февраля 2019 г.
- Авторы: Borisenko K.B., Bock C.W., Hargittai I.
- Журнал: The Journal of physical chemistry
- Том: 98
- Номер: 5
- Год издания: 1994
- Издательство: American Chemical Society
- Местоположение издательства: United States
- Первая страница: 1442
- Последняя страница: 1448
- DOI: 10.1021/j100056a012
- Аннотация: The molecular geometry of 2-nitrophenol has been determined by a joint investigation of gas-phase electron diffraction and ab initio molecular orbital calculations. RHF/6-31G*, RHF/6-31G**, and MP2/6-31G* optimizations were used to determine small parameter differences, such as ΔA(N=O), Δ(C-C), and Δ(C-N=O), which in turn were utilized as constraints in an electron diffraction structure analysis. The present experimental and calculated geometries are consistent regarding (i) the planarity of the molecule and (ii) all the structural features including strong hydrogen bonding between the nitro group oxygen and hydroxy hydrogen and the structural changes in the rest of the molecule as compared with phenol and nitrobenzene on the one hand and 2-nitroresorcinol on the other. Whereas the structural changes in 2-nitrophenol are less pronounced than those in 2-nitroresorcinol, they are consistent with a resonance form that implies the hydrogen bond and some redistribution of electron density in the benzene ring. The (N=)O⋯H(-O) and (N=)O⋯O(-H) nonbonded distances are 1.72 ± 0.02 and 2.58 ± 0.01 Å, respectively, and they do not differ, within experimental error, from those of 2-nitroresorcinol. The molecular geometry is characterized by the following bond lengths (rg) and angles, obtained in the electron diffraction analysis incorporating the constraints from the molecular orbital calculations: (C-H)mean, 1.089 ± 0.007 Å;(C-C)mean, 1.399 ± 0.003 Å; C1-C2, 1.411 ± 0.012 Å; C2-C3, 1.406 ± 0.013 Å; C3-C4, 1.388 ± 0.021 Å; C4-C5, 1.399 ± 0.027 Å; C5-C6, 1.387 ± 0.020 Å; C1-C6, 1.402 ± 0.016 Å; C-O, 1.359 ± 0.009 Å; O-H, 0.969 ± 0.012 Å; C-N, 1.464 ± 0.005 Å; (N=O)mean, 1.233 ± 0.003 Å; N=O14, 1.241 ± 0.009 Å; N=O15, 1.225 ± 0.009 Å; ∠C6-C1-C2, 121.4 ± 0.5°; ∠C1-C2-C3, 119.4 ± 0.8° ∠C2-C3-C4, 118.1 ± 1.6°; ∠C3-C4-C5, 122.9 ± 0.9°; ∠C4-C5-C6, 119.3 ± 0.8°, ∠C1-C6-C5, 119.0 ± 0.8° ∠C1-C2-O, 123.9 ± 0.8°; ∠C-O-H, 104.4 ± 2.2°; ∠C2-C1-N, 120.8 ± 0.7°; (∠C-N=O)mean, 118.4 ± 0.3° ∠C-N=O14, 118.2 ± 1.0°; ∠C-N=O15, 118.6 ± 1.0°; ∠O=N=O, 123.3 ± 0.4°; nitro group torsion, 7.3 ± 5.7°. © 1994 American Chemical Society.
- Добавил в систему: Borisenko Konstantin B.