High-Energy X-ray Diffraction Study on the Intramolecular Structure of 2-Aminoethanol in the Liquid State

Kameda, Yasuo; Deguchi, Hiroshi; Kubota, Y.; Furukawa, Hirotoshi; Yagi, Yasuyuki; Imai, Yoshihiro; Tatsumi, Masahiko; Yamazaki, Noriko; Watari, Noriko; Hirata, Tatsumi; Matubayasi, Nobuyuki

doi:10.1246/bcsj.20120222

Cited by 4 publications

(7 citation statements)

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“…Intramolecular hydrogen bonding in 2-aminoethanol and 3-aminopropanol has been the subject of several experimental − and computational investigations. − The experimental techniques used in previous investigations include infrared and Raman spectroscopies, − microwave spectroscopy, , photoelectron spectroscopy, Penning ionization electron spectroscopy, , and electron diffraction . These studies agree that the conformation with hydrogen bond interaction from the OH group to the N atom of the amino group (OH–N) is the dominant structure in both 2-aminoethanol and 3-aminopropanol.…”

Section: Introductionmentioning

confidence: 97%

Intramolecular Interactions in 2-Aminoethanol and 3-Aminopropanol

et al. 2013

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Gas-phase vibrational spectra of 2-aminoethanol and 3-aminopropanol were recorded up to the third OH-stretching overtone using Fourier transform infrared spectroscopy, cavity ringdown spectroscopy, and intracavity laser photoacoustic spectroscopy. The experimental investigation was supplemented by local mode calculations, and the intramolecular interactions were investigated using atoms in molecules (AIM) and noncovalent interactions (NCI) theories. All calculations were performed at the CCSD(T)-F12a/VDZ-F12 level of theory. For both compounds the most abundant conformer has a structure that allows for hydrogen bond interaction from the OH group to the N atom of the amino group (OH-N). The spectra show signals from both hydrogen bonded and free OH stretches, implying the presence of several conformers. We observe hydrogen-bond-like interactions in both compounds. The red shift of the bonded OH-stretching frequency and intensity enhancement of the fundamental transition suggest that the hydrogen bond interaction is more pronounced in 3-aminopropanol. AIM analysis supports the presence of a hydrogen bond in 3-aminopropanol but not in 2-aminoethanol, whereas NCI analysis shows hydrogen bonding in both compounds with the stronger interaction found in 3-aminopropanol.

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Section: Introductionmentioning

confidence: 97%

Intramolecular Interactions in 2-Aminoethanol and 3-Aminopropanol

et al. 2013

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“…The present values of r ND (1.01 ± 0.02 Å) and r NC (1.47 ± 0.02 Å) are in good agreement with those obtained from the gas phase microwave (r ND = 1.017 ± 0.005 Å and r NC = 1.475 ± 0.023 Å) 37 and high-energy X-ray studies for pure liquid MEA (r NC = 1.46 ± 0.02 Å). 36 The dihedral angle ∠OCC−CCN was obtained to be 45 ± 3°, suggesting that an intramolecular hydrogen bond within the MEA should form in the aqueous solution. The present value of ∠OCC−CCN is slightly smaller than the value determined in the pure liquid MEA (53 ± 3°), 36 which may reflect the effect of intermolecular hydrogen bonds between the MEA and neighboring water molecules.…”

Section: ■ Results and Discussionmentioning

confidence: 97%

“…36 The dihedral angle ∠OCC−CCN was obtained to be 45 ± 3°, suggesting that an intramolecular hydrogen bond within the MEA should form in the aqueous solution. The present value of ∠OCC−CCN is slightly smaller than the value determined in the pure liquid MEA (53 ± 3°), 36 which may reflect the effect of intermolecular hydrogen bonds between the MEA and neighboring water molecules.…”

Section: ■ Results and Discussionmentioning

confidence: 97%

“…Then intramolecular N•••α distance was evaluated. In the present analysis, structural parameters, except for independent parameters described above, were fixed to the values determined from our previous X-ray study of pure liquid MEA 36 and values from microwave studies. 37,38 (e) The normalization factor, γ, was treated as an independent parameter.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Hydration Structure of CO₂-Absorbed 2-Aminoethanol Studied by Neutron Diffraction with the ¹⁴N/¹⁵N Isotopic Substitution Method

et al. 2014

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Neutron diffraction measurements were carried out for CO2-absorbed aqueous 11 mol % 2-aminoethanol (MEA) D2O solutions (corresponding to 30 wt % MEA solution) in order to obtain information on both the intramolecular structure and intermolecular hydration structure of the MEA carbamate molecule in the aqueous solution. Neutron scattering cross sections observed for (MEA)0.11(D2O)0.89, (MEA)0.11(D2O)0.89(CO2)0.06, and (MEA)0.11(D2O)0.89(DCl)0.11 solutions with different (14)N/(15)N ratios were used to derive the first-order difference function, ΔN(Q), which involves environmental structural information around the nitrogen atom of the MEA molecule. Intramolecular geometry and intermolecular hydration structure of MEA, protonated MEA (MEAD(+)), and MEA carbamate (MEA-CO2) molecules were obtained through the least-squares fitting of the observed Δ(N)(Q) in the high-Q region and the intermolecular difference function, Δ(N)(inter)(Q), respectively. In the aqueous solution, the MEA molecule takes the gauche conformation (dihedral angle, ∠NCCO = 45 ± 3°), suggesting that an intramolecular hydrogen bond is formed. On the other hand, values of the dihedral angle ∠NCCO determined for MEAD(+) and MEA-CO2 molecules were 193 ± 4° and 214 ± 8°, respectively. These results imply that the intermolecular hydrogen bonds are dominated for MEAD(+) and MEA-CO2 molecules. The intermolecular nearest neighbor N···O(D2O) distance for the MEA molecule was determined to be 3.13 ± 0.01 Å, which suggests weak intermolecular interaction between the amino-nitrogen atom of MEA and water molecules in the first hydration shell. The nearest-neighbor N···O(D2O) distances for MEAD(+) and MEA-CO2 molecules, 2.79 ± 0.03 and 2.87 ± 0.04 Å, clearly indicate strong hydrogen bonds are formed among the amino group of these molecules and neighboring water molecules.

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“…For 2 , IR, , electron diffraction, , microwave spectroscopy, and computational chemistry − find that 2-gGt is lowest in energy followed closely by 2-gGg . For 3 , IR, , microwave, photoelectron spectroscopy, Penning ionization spectroscopy, electron diffraction, near IR, and computational chemistry , find 3-gGg to be lowest in energy. While the values of Δ E are well established within a reasonably small range, the origins of Δ E are still being debated.…”

Section: Introductionmentioning

confidence: 99%

Can 2-X-Ethanols Form Intramolecular Hydrogen Bonds?

Rosenberg

2019

J. Phys. Chem. A

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For 2-X-ethanols, where X = F, OH, or NH 2 , the gauche conformer is favored over the trans conformer by at least 2 kcal/mol. Initially, this preference, ΔE, was attributed to an intramolecular hydrogen bond, IMHB, between the OH and X groups. Over the years, this conclusion has been challenged by two major arguments. One claim is that the entirety of ΔE can be accounted for by the gauche effect. Against this, calculations using five different methods show that the maximum contribution of the gauche effect to ΔE is less than 1 kcal/ mol. A second argument employs the quantum theory of atoms in molecules to contend that the absence of a bond critical point (BCP) between the OH and X groups in 2-X-ethanols denotes the lack of an IMHB. By looking at the 2-X-ethanols at fixed XCCO torsional angles ranging from 0°to 60°, it is shown that the BCP criterion is inconsistent with other properties such as energy, bond lengths, and stretching frequencies. These inconsistencies are removed when the theory of noncovalent interactions is used. The IMHBs in 2-X-ethanols are found to be similar in form but smaller in magnitude than their intermolecular counterparts. This work concludes that 2-X-ethanols form IMHBs.

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High-Energy X-ray Diffraction Study on the Intramolecular Structure of 2-Aminoethanol in the Liquid State

Cited by 4 publications

References 15 publications

Intramolecular Interactions in 2-Aminoethanol and 3-Aminopropanol

Intramolecular Interactions in 2-Aminoethanol and 3-Aminopropanol

Hydration Structure of CO₂-Absorbed 2-Aminoethanol Studied by Neutron Diffraction with the ¹⁴N/¹⁵N Isotopic Substitution Method

Can 2-X-Ethanols Form Intramolecular Hydrogen Bonds?

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High-Energy X-ray Diffraction Study on the Intramolecular Structure of 2-Aminoethanol in the Liquid State

Cited by 4 publications

References 15 publications

Intramolecular Interactions in 2-Aminoethanol and 3-Aminopropanol

Intramolecular Interactions in 2-Aminoethanol and 3-Aminopropanol

Hydration Structure of CO2-Absorbed 2-Aminoethanol Studied by Neutron Diffraction with the 14N/15N Isotopic Substitution Method

Can 2-X-Ethanols Form Intramolecular Hydrogen Bonds?

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Product

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Hydration Structure of CO₂-Absorbed 2-Aminoethanol Studied by Neutron Diffraction with the ¹⁴N/¹⁵N Isotopic Substitution Method