Determination of properties of hydrogen-bonded dimers by rotational spectroscopy and a classfication of dimer geometries

Legon, A. C.; Millen, D. J.

doi:10.1039/dc9827300071

Cited by 258 publications

(125 citation statements)

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“…This observation is consistent with MO computations ( 5 ) , which indicate that the proton donor molecule can move in this plane without a large loss in energy of interaction, and with experimental electron density maps of the lone-pair region of an epoxide (2). In the gas phase, F-H.. .O bonds display a (weak) preference for the lone-pair directions (6,7). For N-H.. .O=C bonds in solids, formation along the direction of the sp2 lone pairs is apparent (3).…”

Section: Introductionsupporting

confidence: 90%

Concerning lone-pair stereospecificity of intramolecular OH hydrogen bonds to oxygen and sulfur in solution

Schaefer¹,

McKinnon²,

Sebastian³

et al. 1987

Can. J. Chem.

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The 1H nuclear magnetic resonance spectra for CCl4 solutions are analyzed for 2-(thioethyl)phenol, 2,3-dimethoxyphenol, and 8-hydroxythiochroman. The chemical shifts of the hydroxyl protons in these compounds, in 2,3-dihydroxyanisole, and 2-hydroxybenzyl methyl ether are discussed in terms of stereospecific intramolecular OH hydrogen bonds to lone-pair electrons on oxygen and sulfur. The O—H … O hydrogen bonds can be adequately discussed in terms of equivalent lone pairs on oxygen. There is very little difference between the hydrogen bond energies for 2,3-dihydroxyanisole and 2,3-dimethoxyphenol. In the latter the central hydrogen bonded methoxy group lies nearly perpendicular to the ring plane. The O—H … S hydrogen bonds are best described in terms of nonequivalent, 3s and 3p, lone pairs on sulfur. It is estimated that an O—H … H 3s hydrogen bond is at least 8 kJ/mol weaker than an O—H … 3p hydrogen bond. The former is predominant in the thiochroman derivative and the latter in the thioethylphenol, in which the thioethyl group prefers a plane perpendicular to the benzene ring. The long-range benzylic coupling constants in the thiochroman derivative indicate inversion of the saturated ring between distorted half-chair conformations. The boat conformation can be ruled out.

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Section: Introductionsupporting

confidence: 90%

Concerning lone-pair stereospecificity of intramolecular OH hydrogen bonds to oxygen and sulfur in solution

Schaefer¹,

McKinnon²,

Sebastian³

et al. 1987

Can. J. Chem.

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“…observed frequently (Legon & Millen, 1982;Taylor et al, 1983) and can be ascribed, primarily, to optimization of the electrostatic attraction which is the largest energy contribution to hydrogen-bond formation. It is difficult to draw a general conclusion from the study by Baranovskii et al (1985), however, as water molecules appear to have special donor features by comparison with other (aliphatic) hydroxyl donors (Tse et al, 1980; Kroon-Bateburg & van Duijneveldt, 1986;Zheng & Merz, 1992).…”

Section: Introductionmentioning

confidence: 99%

Hydrogen Bonding to Thiocyanate Anions: Statistical and Quantum-Chemical Analyses

Lommerse¹,

Cole²

1998

Acta Crystallogr Sect B

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A statistical analysis of entries from the CSD (Cambridge Structural Database) showed that the average hydrogen-bond geometry to the nitrogen acceptor atom of the thiocyanate anion was not collinear with respect to the molecular axis of the anion and so not collinear with the nitrogen lone pair [Tchertanov & Pascard (1996). Acta Cryst. B52, 685-690]. This somewhat unexpected result has been investigated further using theoretical energy calculations applying Intermolecular Perturbation Theory in combination with a more detailed statistical analysis of an appropriate CSD dataset. The energy calculations pointed to the formation of the strongest hydrogen bonds in the nitrogen lone-pair direction. The statistical analysis showed that this directionality occurs in cases where the N atom accepts one hydrogen bond only. The non-linear average hydrogen-bond geometry observed in the earlier study can be attributed to multiple hydrogen bonding to the N atom. In such cases, there is a shift away from the optimum orientation.observed frequently (Legon & Millen, 1982;Taylor et al., 1983) and can be ascribed, primarily, to optimization of the electrostatic attraction which is the largest energy contribution to hydrogen-bond formation. It is difficult to draw a general conclusion from the study by Baranovskii et al. (1985), however, as water molecules appear to have special donor features by comparison with other (aliphatic) hydroxyl donors (Tse et al., 1980; Kroon-Bateburg & van Duijneveldt, 1986;Zheng & Merz, 1992). In theoretical calculations (Lommerse et al., 1997) ether O atoms accept water hydroxyl donors in the direction of one of their lone pairs, but methanol hydroxyl donors between their lone pairs. This paper presents a more detailed study of hydrogen bonding to thiocyanate anions. A further statistical survey of CSD information is presented which considers the effect of hydrogen-bond coordination on the mean hydrogen-bond geometry to thiocyanate anions. Theoretical energy calculations using Intermolecular Perturbation Theory (IMPT: Hayes & Stone, 1984) for a suitable model system are also presented.

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“…The structures of many complexes, particularly those of the H-bonded type, have been determined by high-resolution spectroscopy (1)(2)(3). A b initio calculations have been used to predict or confirm structures of small complexes with some success, e.g., refs.…”

Section: Introductionmentioning

confidence: 99%

A model for the geometries of Van der Waals complexes

Buckingham¹,

1985

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Determination of properties of hydrogen-bonded dimers by rotational spectroscopy and a classfication of dimer geometries

Cited by 258 publications

References 0 publications

Concerning lone-pair stereospecificity of intramolecular OH hydrogen bonds to oxygen and sulfur in solution

Concerning lone-pair stereospecificity of intramolecular OH hydrogen bonds to oxygen and sulfur in solution

Hydrogen Bonding to Thiocyanate Anions: Statistical and Quantum-Chemical Analyses

A model for the geometries of Van der Waals complexes

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