Intramolecular hydrogen bonding and molecular geometry of 2-nitrophenol from a joint gas-phase electron diffraction and ab initio molecular orbital investigation

Konstantin B. Borisenko, Charles W. Bock, I. Hargittai

Research output: Contribution to journalArticle

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Abstract

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°.

Original languageEnglish
Pages (from-to)1442-1448
Number of pages7
JournalJournal of Physical Chemistry
Volume98
Issue number5
Publication statusPublished - 1994

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Molecular orbitals
Electron diffraction
Orbital calculations
molecular orbitals
Hydrogen bonds
electron diffraction
Gases
vapor phases
Geometry
hydrogen
geometry
Molecules
Nitrobenzene
Bond length
Phenol
Benzene
Torsional stress
Phenols
Carrier concentration
nitrobenzenes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Intramolecular hydrogen bonding and molecular geometry of 2-nitrophenol from a joint gas-phase electron diffraction and ab initio molecular orbital investigation. / Borisenko, Konstantin B.; Bock, Charles W.; Hargittai, I.

In: Journal of Physical Chemistry, Vol. 98, No. 5, 1994, p. 1442-1448.

Research output: Contribution to journalArticle

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title = "Intramolecular hydrogen bonding and molecular geometry of 2-nitrophenol from a joint gas-phase electron diffraction and ab initio molecular orbital investigation",
abstract = "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 {\AA}, 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 {\AA};(C-C)mean, 1.399 ± 0.003 {\AA}; C1-C2, 1.411 ± 0.012 {\AA}; C2-C3, 1.406 ± 0.013 {\AA}; C3-C4, 1.388 ± 0.021 {\AA}; C4-C5, 1.399 ± 0.027 {\AA}; C5-C6, 1.387 ± 0.020 {\AA}; C1-C6, 1.402 ± 0.016 {\AA}; C-O, 1.359 ± 0.009 {\AA}; O-H, 0.969 ± 0.012 {\AA}; C-N, 1.464 ± 0.005 {\AA}; (N=O)mean, 1.233 ± 0.003 {\AA}; N=O14, 1.241 ± 0.009 {\AA}; N=O15, 1.225 ± 0.009 {\AA}; ∠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°.",
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TY - JOUR

T1 - Intramolecular hydrogen bonding and molecular geometry of 2-nitrophenol from a joint gas-phase electron diffraction and ab initio molecular orbital investigation

AU - Borisenko, Konstantin B.

AU - Bock, Charles W.

AU - Hargittai, I.

PY - 1994

Y1 - 1994

N2 - 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°.

AB - 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°.

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