Crystalline ethane-1,2-diol does not have intra-molecular hydrogen bonding: Experimental and theoretical charge density studies

Chopra, Deepak; Row, Tayur N. Guru; Arunan, E.; Klein, Roger A.

doi:10.1016/j.molstruc.2009.11.021

Cited by 77 publications

(114 citation statements)

References 70 publications

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“…Thus, solvophilic solvation consisting mainly of the formation of the O-H· · ·N bonds, as well as the association of the complexes, is a characteristic for aqueous and 1,2-ethanediolic solutions of pyridine and its derivatives. Similar to water, 1,2-ethanediol forms a three-dimensional, hydrogen-bonded network in crystals [6][7][8]. This supports the idea of the solvent-induced aggregation of pyridines in both solvents.…”

Section: Introductionsupporting

confidence: 74%

Volumetric Properties of Binary Mixtures of 2,4,6-Trimethylpyridine with 1,2-Ethanediol, Methanol, and Water, and the Association Energies of the O–H· · ·N Bonded Complexes

2012

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2,4,6-Trimethylpyridine forms 1:1 complexes with methanol, 1,2-ethanediol, and water due to the O-H· · ·N bonds. The association energy of the complexes was calculated using MP2 and DFT methods. The complexes with 1,2-ethanediol and water aggregate in the liquid phase as a result of the O-H· · ·O bonds. In spite of the higher O-H· · ·N bond energy, the aggregation of the ethanediolic complexes is less pronounced than that of the aqueous ones. That is probably caused by the weaker induction effect due to the C-C chain separating the hydroxyl groups in the diol molecule. Aggregation is impossible in the methanolic system, because of the lack of proton-donating functional groups. Differences in the hydrogen bond energy and in the ability to aggregate are manifested in the volumetric properties of the mixtures.

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Section: Introductionsupporting

confidence: 74%

Volumetric Properties of Binary Mixtures of 2,4,6-Trimethylpyridine with 1,2-Ethanediol, Methanol, and Water, and the Association Energies of the O–H· · ·N Bonded Complexes

2012

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“…27,37 An interesting question which arises from all these reports is that whether IHB is found between vicinal hydroxyl groups in 1,2-ED in the gas phase or not. Chopra et al 5 Most of these previous studies are silent about intensity changes which are expected to be there due to IHB formation. We have chosen two specific diol systems namely 1,2-ED and 1,4-BD to investigate if intensities play an important role in dictating the most prevalent conformer 7 in the ground state of the diols.…”

Section: Introductionmentioning

confidence: 99%

“…16,17,18,19,20,21,22,23,24,25,26,27,28 Electron density topological analysis has not shown a bond critical point (BCP) and atomic bond path corresponding to IHB in 1,2-ED. 5,29,30 However, Klein argues that the absence of a bond critical point does not imply that the absence of a bond although the presences need not necessarily indicate the presence of a bond. 23 The quantum diffusion Monte Carlo (QDMC) simulations in the past 31 and X-ray crystallographic studies on crystalline 1,2-ED suggests that the intramolecular hydrogen bond (IHB) does not exist in this molecule.…”

Section: Introductionmentioning

confidence: 99%

“…23 The quantum diffusion Monte Carlo (QDMC) simulations in the past 31 and X-ray crystallographic studies on crystalline 1,2-ED suggests that the intramolecular hydrogen bond (IHB) does not exist in this molecule. 5 Cheng et al did the conformational analysis with 1,2-ED, 1,3-PD (propane diol) and 1,4-BD using B3LYP/6-31+G(d,p) and QCISD/6-311++G(3df,3pd) computational method to 5 find the origin of disappearing of hydrogen bonded O−H peak in overtone spectra of diols. 28 They have pointed out that higher energy conformers are needed to reproduce the experimental overtone spectra of diols.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Conformational Stability and Intramolecular Hydrogen Bonding in 1,2-Ethanediol and 1,4-Butanediol

Das

Arunan

2015

J. Phys. Chem. A

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The gas-phase infrared spectra of 1,2-ED and 1,4-BD have been recorded at three different temperatures using a multipass gas cell of 6 m optical path length. DFT calculation has also been carried out using 6-311++G** and aug-cc-pVDZ basis sets to look for the existence of intramolecular hydrogen bonding in them from the red shift and infrared absorption intensity enhancement of the bonded O-H band compared to that of the free O-H band. Equilibrium population analysis with 10 conformers of 1,2-ED and 1,4-BD at experimental temperatures were carried out for the reconstruction of the observed vibrational spectra at that temperature using standard statistical relationships. The most abundant conformer at experimental temperatures was identified. In 1,2-ED a red shift of 45 cm(-1) in the intramolecularly interacting O-H stretching vibrational band position and no significant intensity enhancement compared to that of the free O-H have been observed. On the contrary, in one of the hydrogen-bonded conformers of 1,4-BD, a 124 cm(-1) red shift in the O-H stretching frequency and a 8.5 times intensity enhancement for the "bonded" O-H compared to that of the "free" O-H is seen. On the basis of this comparative study, we have concluded that strong intramolecular hydrogen bonding exists in 1,4-BD. But there appears to be weak intramolecular hydrogen bonding in 1,2-ED at temperatures of 303, 313, and 323 K in the gas phase. We have found that most stable hydrogen-bonded conformers of 1,4-BD are less populated than some of the non-hydrogen-bonded conformers. Even for the 1,4-BD, the relative population of the g'GG'Gt conformer, which has a strong intramolecular hydrogen bond, is less than what is predicted. Perhaps the intramolecular hydrogen bond plays a less significant role in the relative stability of the various conformers than what has been predicted from calculations and prevails in the literature.

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“…NMR has been utilized to investigate molecular dynamics [17,9,18] and conformational equilibria of polyalcohols [19][20][21][22][23][24][25][26]. Among ten non-equivalent isomers of EG with different dihedral angles in one C-C and two C-O torsion angles, theoretical calculations have shown that two gauche conformers with a C-C torsion angle at possible potential minima, 60 and 300 , are favorable rather than trans conformers with a torsion angle of 180 [27][28][29][30][31][32][33][34][35]. The two-bond J-couplings in 1 H NMR measurements support the predominant gauche state [19][20][21][22][23][24][25][26].…”

Section: Introductionmentioning

confidence: 99%

Zero-field nuclear magnetic resonance spectroscopy of viscous liquids

Shimizu

Blanchard

Pustelny

et al. 2015

Journal of Magnetic Resonance

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a b s t r a c tWe report zero-field NMR measurements of a viscous organic liquid, ethylene glycol. Zero-field spectra were taken showing resolved scalar spin-spin coupling (J-coupling) for ethylene glycol at different temperatures and water contents. Molecular dynamics strongly affects the resonance linewidth, which closely follows viscosity. Quantum chemical calculations have been used to obtain the relative stability and coupling constants of all ethylene glycol conformers. The results show the potential of zero-field NMR as a probe of molecular structure and dynamics in a wide range of environments, including viscous fluids.

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Crystalline ethane-1,2-diol does not have intra-molecular hydrogen bonding: Experimental and theoretical charge density studies

Cited by 77 publications

References 70 publications

Volumetric Properties of Binary Mixtures of 2,4,6-Trimethylpyridine with 1,2-Ethanediol, Methanol, and Water, and the Association Energies of the O–H· · ·N Bonded Complexes

Volumetric Properties of Binary Mixtures of 2,4,6-Trimethylpyridine with 1,2-Ethanediol, Methanol, and Water, and the Association Energies of the O–H· · ·N Bonded Complexes

Conformational Stability and Intramolecular Hydrogen Bonding in 1,2-Ethanediol and 1,4-Butanediol

Zero-field nuclear magnetic resonance spectroscopy of viscous liquids

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