Structure and dynamics of the symmetric hydrogen bond in potassium hydrogen maleate: a neutron scattering study

Fillaux, F.; Leygue, Nadine; Tomkinson, J.; Cousson, A.; Paulus, Werner

doi:10.1016/s0301-0104(99)00153-6

Cited by 65 publications

(64 citation statements)

References 35 publications

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“…For KHM, it was speculated that the hydrogen bond could be broken at a rather modest energy cost, thanks to the internal strain of the ring. 27 However, this view was not confirmed with density functional theory calculations. 23 Furthermore, there is no internal strain for intermolecular SSHBs, so this option must be abandoned.…”

Section: Discussionmentioning

confidence: 93%

“…The prototypical intramolecular strong-symmetric hydrogen bond ͑SSHB͒ in the crystal of potassium hydrogen maleate, KH͑OOC u CH v CH u COO͒ or KHM, has been thoroughly investigated with x-ray or neutron diffraction, [25][26][27] infrared and Raman, [28][29][30][31] inelastic neutron scattering ͑INS͒, 27,32-34 NMR, 35,36 and calorimetry. 37 The linear hydrogen bond is very short ͓R OO = 2.427͑1͒ Å at 5 K͔ and crystallographically symmetrical.…”

Section: Introductionmentioning

confidence: 99%

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A neutron scattering study of strong-symmetric hydrogen bonds in potassium and cesium hydrogen bistrifluoroacetates: Determination of the crystal structures and of the single-well potentials for protons

Cousson

Archilla

Tomkinson

2008

The Journal of Chemical Physics

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The crystal structures of potassium and cesium bistrifluoroacetates, KH͑CF 3 COO͒ 2 and CsH͑CF 3 COO͒ 2 , respectively, were determined at room and cryogenic temperatures with the single crystal neutron diffraction technique. The crystals belong to the monoclinic space groups, I2 / a and A2 / a, respectively, and there is no evidence of any structural phase transition. In both crystals, trifluoroacetate entities in centrosymmetric dimers are linked by very short hydrogen bonds lying across a center of inversion. The thermal parameters provide no evidence of any double minimum potential for hydrogen bond protons. Single-minimum potentials were determined via best fitting to the inelastic neutron scattering spectral profiles of the stretching vibrations. They comprise a narrow well for the ground state and a very broad quasiharmonic well for excited states. The spread out of the wave functions of these states shows that protons are no longer confined between the oxygens. Presumably, they are attracted by the lone pairs of oxygen atoms. These potentials emphasize the covalent nature of the OO bond and the ionic character of the hydrogen bond proton.

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Section: Discussionmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

A neutron scattering study of strong-symmetric hydrogen bonds in potassium and cesium hydrogen bistrifluoroacetates: Determination of the crystal structures and of the single-well potentials for protons

Cousson

Archilla

Tomkinson

2008

The Journal of Chemical Physics

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“…In the short intramolecular O-H···O [2.404(3) ] bond, the hydrogen is situated almost midway along the bond and the single 13 C chemical shift is consistent with the presence of a symmetrical hydrogen bond. [62] As previously described, [57] the anhydrous phase of dabco-maleate 1:1 (III) converts into dabco-maleate 1:1 hydrate [HN(mCH 2 , were obtained from a solution in ethanol, and the crystal structure determined. No significant differences were observed between our crystal structure and that previously published.…”

Section: Resultsmentioning

confidence: 99%

Hydrogen Bonding and Dynamic Behaviour in Crystals and Polymorphs of Dicarboxylic–Diamine Adducts: A Comparison between NMR Parameters and X‐ray Diffraction Studies

Gobetto

Nervi

Chierotti

et al. 2005

Chemistry A European J

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Fumaric, malonic, maleic, and hydromuconic (HOOCCH2(CH)2CH2COOH) acids were used to prepare a series of hydrogen-bonded adducts or salts, depending on whether acid-base proton transfer takes place, with the dibase [N(muCH2CH2)3N] in various stoichiometric ratios. The resulting compounds have been investigated by using the 1H MAS, 15N, and 13C cross polarisation magic-angle spinning (CPMAS) methods and discussed in relation to X-ray diffraction studies to ascertain the nature of the O-HO, NH-O, and N+-HO- hydrogen bonds between the various species. In addition, two polymorphic forms of the malonic compound and a hydrate in the maleic case were examined. We also present the correlations between the chemical shifts of the hydrogen-bonded protons and those from the proton transfer reaction (acid-to-base) with the heavy atom distances. The dynamic behaviour in the solid-state of the [N(muCH2CH2)3N] adducts with fumaric 2:1, maleic 1:1 hydrate, and hydromuconic acids, and a malonate 2:1 polymorph adduct have been investigated by using variable-temperature 1H spin-lattice relaxation times. A substantial agreement between the activation energies obtained from fitting the T1 data and the results of potential energy barrier calculations demonstrates that the facile reorientation of the [N(muCH2CH2)3N] molecule occurs in several of the adducts.

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“…Recent inelastic neutron scattering (INS) experiments pointed out the existence of low energy bands near 500 cm 1 above the ground state in relation to the OHO asymmetric stretching [11]; this energy relation allows the occupation of excited state by 8%, and in the case of such a low energy excitation, the above mechanism may work. For a more quantitative estimation, more detailed calculations concerning the vibrational excited states and experiments at lower temperatures would be required.…”

Section: Discussionmentioning

confidence: 99%

“…Crystalline potassium hydrogen maleate belongs to the orthorhombic Pbcm space group [10,11]. A maleate anion forms a 7-member ring by intramolecular hydrogen bonds between two carboxyl groups.…”

Section: Potassium Hydrogen Maleatementioning

confidence: 99%

Temperature Dependence of ²H Nuclear Quadrupole Interaction in Very Short Hydrogen Bonds in Some Organic Acidic Salt Crystals

Miyakubo¹,

Nakamura

2002

Zeitschrift Für Naturforschung A

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The 2 H nuclear quadrupole interaction parameters, 2 and , are closely related to the shape of the potential energy surface at hydrogen bonds and depend sensitively on their geometry. We measured the temperature dependence of the 2 H NMR spectra of the crystalline acidic salts KDCO 3 , KD acetylenedicarboxylate, RbD acetylenedicarboxylate, and KD maleate, which contain very short O-D O type hydrogen bonds. The temperature coefficient decreases with increase in the O O distance in the hydrogen bond. Ab inito molecular orbital calculations of the electric field gradient tensor based on the temperature dependent structure of each crystal indicate that thermal expansion of the hydrogen bond geometry is not responsible for this tendency. Ab initio calculations also predict that a fictitious off center shift of the hydrogen position in a symmetric hydrogen bond causes very high

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Structure and dynamics of the symmetric hydrogen bond in potassium hydrogen maleate: a neutron scattering study

Cited by 65 publications

References 35 publications

A neutron scattering study of strong-symmetric hydrogen bonds in potassium and cesium hydrogen bistrifluoroacetates: Determination of the crystal structures and of the single-well potentials for protons

A neutron scattering study of strong-symmetric hydrogen bonds in potassium and cesium hydrogen bistrifluoroacetates: Determination of the crystal structures and of the single-well potentials for protons

Hydrogen Bonding and Dynamic Behaviour in Crystals and Polymorphs of Dicarboxylic–Diamine Adducts: A Comparison between NMR Parameters and X‐ray Diffraction Studies

Temperature Dependence of ²H Nuclear Quadrupole Interaction in Very Short Hydrogen Bonds in Some Organic Acidic Salt Crystals

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Structure and dynamics of the symmetric hydrogen bond in potassium hydrogen maleate: a neutron scattering study

Cited by 65 publications

References 35 publications

A neutron scattering study of strong-symmetric hydrogen bonds in potassium and cesium hydrogen bistrifluoroacetates: Determination of the crystal structures and of the single-well potentials for protons

A neutron scattering study of strong-symmetric hydrogen bonds in potassium and cesium hydrogen bistrifluoroacetates: Determination of the crystal structures and of the single-well potentials for protons

Hydrogen Bonding and Dynamic Behaviour in Crystals and Polymorphs of Dicarboxylic–Diamine Adducts: A Comparison between NMR Parameters and X‐ray Diffraction Studies

Temperature Dependence of 2H Nuclear Quadrupole Interaction in Very Short Hydrogen Bonds in Some Organic Acidic Salt Crystals

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Temperature Dependence of ²H Nuclear Quadrupole Interaction in Very Short Hydrogen Bonds in Some Organic Acidic Salt Crystals