Electronographic study of structure of molecule of o-chloronitrobenzene in gaseous phase

Batyukhnova, O.G.; Sadova, N. I.; Vilkov, L. V.; Pankrushev, Yu. A.

doi:10.1007/bf00773279

Cited by 3 publications

(2 citation statements)

References 6 publications

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“…The C−F bond in 2-fluoroanisole is also of nearly the same length as in fluorobenzene, r s = 1.354(10) Å and r g = 1.356(4) Å . The same tendency is found in 2-chloroanisole: 11 there are no differences in the C−Cl, C Ph −O, and C Me −O bond lengths in comparison with anisole 3 and chlorobenzene. , It should be noted that, unlike the methoxy group, the nitro group produces an essential shortening of the C−F bond in 2-fluoronitrobenzene by 0.05 Å and of the C−Cl bond in 2-chloronitrobenzene by 0.016 Å as compared with fluoro- and chlorobenzene, respectively.…”

Section: Discussionmentioning

confidence: 68%

Conformational Properties of 2-Fluoroanisole in the Gas Phase

2003

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Molecular structure and conformational properties of 2-fluoroanisole have been studied by gas electron diffraction and quantum chemical methods (HF/6-31G*, MP2/6-31G*, and B3LYP/6-31G*). All methods predict the existence of two minima on the potential to internal rotation around the C(sp 2 )-O bond corresponding to planar and nonplanar forms, but they give rather different results on the geometry and the relative energy of the nonplanar conformation. The electron diffraction data were treated with two different procedures for obtaining the scattering intensities (scanner and densitometer) and two different procedures of structural analysis used in laboratories of Moscow and Tu ¨bingen. With all data sets and procedures used in analysis, geometrical parameters and conformational composition were found to be very close. The preferred conformation of 2-fluoroanisole is a planar anti form, 70 ( 12%, whereas the minor conformation is a nonplanar form with the CH 3 group rotated toward the F atom with φ(CdC-O-C) ) 57( 8)°. The structural parameters are compared with those obtained for related compounds. Stereochemical peculiarities in ortho derivatives of anisole, which result in the existence of a nonplanar conformer, are discussed in terms of a natural bond orbital (NBO) analysis.

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Section: Discussionmentioning

confidence: 68%

Conformational Properties of 2-Fluoroanisole in the Gas Phase

2003

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“…Molecular structure studies performed on fluoronitrobenzenes by Correll et al and by Shishkov et al, using rotational spectroscopy and gas-phase electron diffraction, respectively, both detected rotation of the nitro group and determined the angle of rotation: 31.7° and 37.6°, respectively. Electronographic studies performed by Batyukhnova et al on 2-chloronitrobenzene confirmed that the gaseous molecule is not planar, with a dihedral angle of 33.9°, between the planes of the benzene ring and of the nitro group. Batyukhnova et al also studied the 2-bromonitrobenzene by gas-phase electron diffraction, and obtained a dihedral angle of 43.3° for this molecule.…”

Section: Resultsmentioning

confidence: 94%

Experimental and Computational Thermodynamic Study of Three Monofluoronitrobenzene Isomers

et al. 2010

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The present work reports the thermodynamic study performed on three monofluorinated nitrobenzene derivatives by a combination of experimental techniques and computational approaches. The standard (p degrees = 0.1 MPa) molar enthalpies of formation in the liquid phase of the three isomers of fluoronitrobenzene were derived from the standard molar energies of combustion, in oxygen, at T = 298.15 K, measured by rotating bomb combustion calorimetry. The vapor pressure study of the referred compounds was done by a static method and, from the obtained results, the phase diagrams were elaborated, and the respective triple point coordinates, as well as the standard molar enthalpies of vaporization, sublimation and fusion, at T = 298.15 K, were determined. The combination of some of the referred thermodynamic parameters yielded the standard (p degrees = 0.1 MPa) molar enthalpies of formation in the gaseous phase, at T = 298.15 K, of the studied compounds: Delta(f)H(m)(o) (2-fluoronitrobenzene, g) = -(102.4 +/- 1.5) kJ x mol(-1), Delta(f)H(m)(o) (3-fluoronitrobenzene, g) = -(128.0 +/- 1.7) kJ x mol(-1), and Delta(f)H(m)(o) (4-fluoronitrobenzene, g) = -(133.9 +/- 1.4) kJ x mol(-1). Using the empirical scheme developed by Cox, values of standard molar enthalpies of formation in the gaseous phase were estimated and afterwards compared with the ones obtained experimentally, and both were interpreted in terms of the molecular structure of the compounds. The theoretically estimated gas-phase enthalpies of formation were calculated from high-level ab initio molecular orbital calculations at the G3(MP2)//B3LYP level of theory. The computed values compare very well with the experimental results obtained in this work and show that 4-fluoronitrobenzene is the most stable isomer from the thermodynamic point of view. Furthermore, this composite approach was also used to obtain information about the gas-phase basicities, proton and electron affinities and, finally, adiabatic ionization enthalpies.

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The Structural Chemistry of Carbon—Halogen Bonds

Oberhammer

2009

Patai's Chemistry of Functional Groups

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Electronographic study of structure of molecule of o-chloronitrobenzene in gaseous phase

Cited by 3 publications

References 6 publications

Conformational Properties of 2-Fluoroanisole in the Gas Phase

Conformational Properties of 2-Fluoroanisole in the Gas Phase

Experimental and Computational Thermodynamic Study of Three Monofluoronitrobenzene Isomers

The Structural Chemistry of Carbon—Halogen Bonds

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