Powder neutron diffraction analysis of the hydrogen bonding in deutero-oxalic acid dihydrate at high pressures

Putkonen, Matti; Feld, R.; Vettier, C.; Lehmann, M. S.

doi:10.1107/s0108768185001598

Cited by 18 publications

(7 citation statements)

References 6 publications

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“…The early results were corrected by Robertson and Ubbelohde who also investigated some other physical properties of α-OADH . Several studies were done in the following decades, including XRD measurements at higher accuracy, alternative models and improved refinement, , isotope effects, , neutron diffraction structure determination, − and high resolution electron density studies. − A series of results was obtained within the project organized by the International Union of Crystallography . This exercise was primarily focused on the electron density and its deformation caused by the hydrogen bonding (H-bonding) but has also yielded improved structural data, including temperature effects .…”

Section: Introductionmentioning

confidence: 99%

Cooperativity Assisted Shortening of Hydrogen Bonds in Crystalline Oxalic Acid Dihydrate: DFT and NBO Model Studies

Stare

Hadži

2014

J. Chem. Theory Comput.

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The distance of ∼2.49 Å separating the carboxylic OH oxygen from the water oxygen atom in the α-polymorph of crystalline oxalic acid dihydrate is by ∼0.1 Å shorter than the average distance in carboxylic acid monohydrates. It is also by ∼0.2 Å shorter than the corresponding distance presently calculated for the heterotrimer consisting of one acid and two water molecules. The large difference between RO···O in the heterotrimer and in the crystal is attributed to the cooperative effect in the latter; this is supported by calculations carried out on clusters constituted of an increasing number of acid and water molecules. The present DFT calculations with geometry optimization include seven isolated model clusters, the largest of which contains five acid and eight water molecules. The RO···O of the short hydrogen bond shortens progressively with increasing the number of cluster constituents; in the largest cluster, it reaches 2.50 Å. This is remarkably close to both the experimental distance as well as to the distance obtained by the periodic DFT calculation. The electronic effects were studied by Natural Bond Orbital analysis, revealing an enhancement of hydrogen bonding on extending the network by increased polarization of the carbonyl group and by the increased delocalization interaction between the lone electron pair on the acceptor oxygen atom and the OH antibond orbital. The formation of circular motifs appears to be the most important factor in the cooperative shortening of the hydrogen bonds. In agreement with the measured hydrogen bond distances, inspection of the electron density reveals a notable difference in hydrogen bond shrinking tendency between the two known polymorphs of the title system.

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Section: Introductionmentioning

confidence: 99%

Cooperativity Assisted Shortening of Hydrogen Bonds in Crystalline Oxalic Acid Dihydrate: DFT and NBO Model Studies

Stare

Hadži

2014

J. Chem. Theory Comput.

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“…We decided to carry an investigation on 1, which was extensively studied by X-rays and neutron scattering at room pressure. 6 A small but significant shortening of the OÁ Á ÁO distance between oxalic acid and water was observed at low T. 7 Putkonen et al 8 carried out a HP crystallographic study on a powder sample (up to 0.5 GPa only), but no special changes were observed.…”

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confidence: 99%

Hydrogen migration in oxalic acid di-hydrate at high pressure?

2009

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“…Since the initial studies dealing with hydrogen bonding in oxalic acid (Putkonen et al, 1985) several reports have been published, illustrating the sensitivity of hydrogen-bonding networks to high pressure (Yan et al, 2012;Mishra et al, 2020). Analogous to hydrogen bonding, halogen bonding is another class of non-covalent interactions widely exploited by the crystal engineering community (Desiraju et al, 2013;Cavallo et al, 2016).…”

Section: Introductionmentioning

confidence: 99%

N-Iodosaccharin–pyridine co-crystal system under pressure: experimental evidence of reversible twinning

Vijayakumar-Syamala¹,

Aubert²,

Deutsch³

et al. 2022

Acta Crystallogr Sect B

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This work presents a single-crystal X-ray diffraction study of an organic co-crystal composed of N-iodosaccharin and pyridine (NISac·py) under hydrostatic pressure ranging from 0.00 (5) GPa to 4.5 (2) GPa. NISac·py crystallizes in the monoclinic system (space group B21/e). The unconventional setting of the space group is adopted (the conventional setting is P21/c, No. 14) to emphasise the strongly pseudo-orthorhombic symmetry of the lattice, with a β angle very close to 90°. The crystal structure contains one molecule each of N-iodosaccharin (NISac) and pyridine (py) in the asymmetric unit (Z′ = 1), linked via an Nsac...I...N′py halogen-bonding motif. A gradual modification of this motif is observed under pressure as a result of changes in the crystalline environment. Mechanical twinning is observed under compression and the sample splits into two domains, spanning an unequal volume that is mapped by a twofold rotation about the [100] direction of the B21/e unit cell. The twinning is particularly significant at high pressure, being reversible when the pressure is released. The structure of the twinned sample reveals the continuity of a substantial substructure across the composition plane. The presence of this common substructure in the two orientations of the twinned individuals can be interpreted as a structural reason for the formation of the twin and is the first observed example in a molecular crystal. These results indicate that the anisotropy of intermolecular interactions in the crystal structure results in an anisotropic strain generated upon the action of hydrostatic compression. Periodic density functional theory calculations were carried out by considering an isotropic external pressure, the results showing good agreement with the experimental findings. The bulk modulus of the crystal was obtained from the equations of state, being 7 (1) GPa for experimental data and 6.8 (5) GPa for theoretical data.

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Powder neutron diffraction analysis of the hydrogen bonding in deutero-oxalic acid dihydrate at high pressures

Cited by 18 publications

References 6 publications

Cooperativity Assisted Shortening of Hydrogen Bonds in Crystalline Oxalic Acid Dihydrate: DFT and NBO Model Studies

Cooperativity Assisted Shortening of Hydrogen Bonds in Crystalline Oxalic Acid Dihydrate: DFT and NBO Model Studies

Hydrogen migration in oxalic acid di-hydrate at high pressure?

N-Iodosaccharin–pyridine co-crystal system under pressure: experimental evidence of reversible twinning

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