Infrared and Raman spectra of some acid salts containing crystallographically symmetric hydrogen bonds

Hadži, D.; Orel, B.; Novák, A.

doi:10.1016/0584-8539(73)80126-6

Cited by 76 publications

(24 citation statements)

References 17 publications

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“…2.4 Å expected on the basis of other O-O hydrogen bonding distances involving short strong, symmetric hydrogen bonds. [35][36][37][38][39] This extrapolation may well be non-linear, however, so the intercept is at a longer O-O distance. In any case the trend of the effect of increasing the length of the hydrogen bonded chain on the internal structure of the CHD unit appears to agree qualitatively with expectations based on short-strong symmetric hydrogen-bonded systems.…”

Section: Discussionmentioning

confidence: 99%

The Crystalline Enol of 1,3-Cyclohexanedione and Its Complex with Benzene: Vibrational Spectra, Simulation of Structure and Dynamics and Evidence for Cooperative Hydrogen Bonding

et al. 2004

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The inelastic incoherent neutron scattering spectra of 1,3-cyclohexanedione (CHD) in its crystalline enol form and its cyclamer complexes with benzene and benzene-d 6 are compared with each other, with IR and Raman spectra and with the results of calculations using density functional theory (DFT). The crystal packing of the CHD enol is a linear hydrogen-bonded chain with conjugated donor and acceptor groups analogous to that found in peptide hydrogen bonding. The benzene complex is a closed hexameric hydrogen-bonded cycle. A DFT treatment is applied to the full hexamer of the benzene complex. The CHD chain is treated as a series of finite linear clusters by DFT, while the infinite one-dimensional chain and the three-dimensional crystal are treated by periodic DFT. Comparison is made with both the observed crystal structures and the vibrational spectra. The very good to excellent agreement of the computed vibrational spectra with experiment demonstrates that the models and computational treatments used are reliable. The theoretical treatment of the linear chain clusters exhibits a continuous change in structure with increasing chain length, converging to values near the observed structure. Emphasis is placed on the cooperative nature of hydrogen bonding in CHD as revealed by these systematic trends. The ability of DFT methods to treat hydrogen bonding in solids appears to be roughly as accurate as the crystal structure determinations.1,3-Cyclohexanedione (CHD) exists in its enol form in the solid state where it forms hydrogen-bonded chains with an antianti configuration having short (2.56 Å) O-O hydrogen bonding distances. 1 This structure is of interest for several reasons including the ordered hydrogen bonding arrangement, an orderdisorderphasetransitionthatinvolveshydrogenbondinterchange, 2-6 and indications derived from examination of crystal structures that CHD is an example of a resonance-assisted, cooperative hydrogen bonding network. [7][8][9][10][11][12][13] This cooperativity arises from the fact that when the enol of CHD forms a hydrogen bond, this polarizes the molecule such that the formation of an additional hydrogen bond with another CHD is more favorable. This may be thought of as due to an enhanced contribution of the ionic resonance form. When crystallized from benzene, this material forms a unique cyclamer structure (CHD 6 Bz) in which six CHD molecules form a syn-anti hydrogen bonded ring surrounding a central benzene molecule. 14 The related 1,3-cyclopentanedione (CPD) 15 forms an antianti linear chain structure very much like that of CHD. Methyl substitution of CPD or CHD can result in changes to the hydrogen-bonding pattern. 2-Methyl-CPD forms a linear chain with an anti-syn arrangement. 16 In this case the methyl-CHD molecules in a given linear chain all point in the same direction. This is in contrast to the anti-anti chain of CPD and CHD (Figure 1) where alternate molecules are oriented in opposite directions. The 2-methyl derivative of CHD has a structure similar to that of CHD 17 but t...

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Section: Discussionmentioning

confidence: 99%

The Crystalline Enol of 1,3-Cyclohexanedione and Its Complex with Benzene: Vibrational Spectra, Simulation of Structure and Dynamics and Evidence for Cooperative Hydrogen Bonding

et al. 2004

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“…42 At room temperature, trifluoroacetate dimers, H͑CF 3 COO͒ 2 − , are linked by crystallographically symmetric hydrogen bonds with R OO = 2.435͑7͒ or 2.38͑3͒ Å, respectively. The vibrational spectra of these salts at a very low temperature 19,43,44 evidence several ͉x a ͘ n states in the same frequency range as for KHM ͑500-1100 cm −1 ͒ but with quite different profiles of intensity. In a previous work, 44 it was suggested that CTFA could be a LBHB case, but there is no neutron diffraction data to support this proposal.…”

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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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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“…[11] Therefore, the title compound reported herein provides a novel and previously unreported type of a hybrid one-dimensional organic-inorganic polymeric arrangement in uranyl oxysalts, where interaction between inorganic and organic subunits is mediated by ionic K + -O bonds.…”

Section: Wwwzaacwiley-vchde Short Communicationmentioning

confidence: 99%

Hybrid One‐Dimensional 15‐Crown‐5‐ether‐uranyl‐selenate Polymers in [K@(C₁₀H₂₀O₅)][(UO₂)(SeO₄)(HSeO₄)(H₂O)]: Synthesis and Characterization

Gurzhiy

Tyumentseva

Krivovichev

et al. 2015

Zeitschrift anorg allge chemie

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Infrared and Raman spectra of some acid salts containing crystallographically symmetric hydrogen bonds

Cited by 76 publications

References 17 publications

The Crystalline Enol of 1,3-Cyclohexanedione and Its Complex with Benzene: Vibrational Spectra, Simulation of Structure and Dynamics and Evidence for Cooperative Hydrogen Bonding

The Crystalline Enol of 1,3-Cyclohexanedione and Its Complex with Benzene: Vibrational Spectra, Simulation of Structure and Dynamics and Evidence for Cooperative Hydrogen Bonding

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

Hybrid One‐Dimensional 15‐Crown‐5‐ether‐uranyl‐selenate Polymers in [K@(C₁₀H₂₀O₅)][(UO₂)(SeO₄)(HSeO₄)(H₂O)]: Synthesis and Characterization

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Infrared and Raman spectra of some acid salts containing crystallographically symmetric hydrogen bonds

Cited by 76 publications

References 17 publications

The Crystalline Enol of 1,3-Cyclohexanedione and Its Complex with Benzene: Vibrational Spectra, Simulation of Structure and Dynamics and Evidence for Cooperative Hydrogen Bonding

The Crystalline Enol of 1,3-Cyclohexanedione and Its Complex with Benzene: Vibrational Spectra, Simulation of Structure and Dynamics and Evidence for Cooperative Hydrogen Bonding

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

Hybrid One‐Dimensional 15‐Crown‐5‐ether‐uranyl‐selenate Polymers in [K@(C10H20O5)][(UO2)(SeO4)(HSeO4)(H2O)]: Synthesis and Characterization

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Hybrid One‐Dimensional 15‐Crown‐5‐ether‐uranyl‐selenate Polymers in [K@(C₁₀H₂₀O₅)][(UO₂)(SeO₄)(HSeO₄)(H₂O)]: Synthesis and Characterization