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Journal ArticleDOI

The hydrogen bond in the solid state.

Thomas Steiner
- 04 Jan 2002 - 
- Vol. 41, Iss: 1, pp 48-76
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TLDR
The hydrogen bond is the most important of all directional intermolecular interactions, operative in determining molecular conformation, molecular aggregation, and the function of a vast number of chemical systems ranging from inorganic to biological.
Abstract
The hydrogen bond is the most important of all directional intermolecular interactions. It is operative in determining molecular conformation, molecular aggregation, and the function of a vast number of chemical systems ranging from inorganic to biological. Research into hydrogen bonds experienced a stagnant period in the 1980s, but re-opened around 1990, and has been in rapid development since then. In terms of modern concepts, the hydrogen bond is understood as a very broad phenomenon, and it is accepted that there are open borders to other effects. There are dozens of different types of X-H.A hydrogen bonds that occur commonly in the condensed phases, and in addition there are innumerable less common ones. Dissociation energies span more than two orders of magnitude (about 0.2-40 kcal mol(-1)). Within this range, the nature of the interaction is not constant, but its electrostatic, covalent, and dispersion contributions vary in their relative weights. The hydrogen bond has broad transition regions that merge continuously with the covalent bond, the van der Waals interaction, the ionic interaction, and also the cation-pi interaction. All hydrogen bonds can be considered as incipient proton transfer reactions, and for strong hydrogen bonds, this reaction can be in a very advanced state. In this review, a coherent survey is given on all these matters.

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Citations
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Fingerprinting intermolecular interactions in molecular crystals

TL;DR: In this paper, a two-dimensional mapping of the Hirshfeld surfaces of a molecular molecule is presented, which summarizes quantitatively the nature and type of intermolecular interaction experienced by a molecule in the bulk, and presents it in a convenient graphical format.
Journal ArticleDOI

Proton-Coupled Electron Transfer

TL;DR: Proton-coupled electron transfer is an important mechanism for charge transfer in a wide variety of systems including biology- and materials-oriented venues and several are reviewed.
Journal ArticleDOI

Novel tools for visualizing and exploring intermolecular interactions in molecular crystals.

TL;DR: A new way of exploring packing modes and intermolecular interactions in molecular crystals is described, using Hirshfeld surfaces to partition crystal space, using identifiable patterns of interaction between small molecules to rationalize the often complex mix of interactions displayed by large molecules.
Journal ArticleDOI

Asymmetric catalysis by chiral hydrogen-bond donors.

TL;DR: This review documents the structural and mechanistic features that contribute to high enantioselectivity in hydrogen-bond-mediated catalytic processes in small-molecule, synthetic catalyst systems.
References
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Journal ArticleDOI

A crystallographic AM1 and PM3 SCF-MO investigation of strong OH ⋯π-alkene and alkyne hydrogen bonding interactions

TL;DR: In this paper, a search of the Cambridge structural database reveals eleven alkenes and two alkynes in which particularly short OH ⋯π-facial hydrogen bonding occurs, a feature largely unrecognised in the original reports of these structures.
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Trifluoroacetic acid tetrahydrate: A unique change from an ionic to a molecular crystal structure on deuteration

TL;DR: In this paper, a trifluoroacetic acid has been found from DTA, DSC, and temperature-dependent X-ray powder diffraction to form, besides other stable and metastable hydrates, both an undeuterated (reinvestigation) and perdeuterated stable tetrahydrate.
Journal ArticleDOI

Correlation between crystallographic and spectroscopic properties for C-H|O bonds in terminal acetylenes

TL;DR: In this article, non-bonded C-H|O distances and infrared c-H stretching frequencies correlate well in a series of terminal acetylenes demonstrating the attractive nature of the CH-O interaction in these compounds.
Journal ArticleDOI

Structural evidence for resonance-assisted O–H···S hydrogen bonding

TL;DR: By far the shortest hydrogen bonds of the O −H···S type occur in monothio-s-diketones and related substances (H·· ·S distances 1.9 −2.0 A); it was shown with crystal correlation techniques that this very short hydrogen bonding facilitated by resonance assistance similar to that occurring in the oxygen analogues as mentioned in this paper.
Journal ArticleDOI

First example of cooperative O–H⋯CC–H⋯Ph hydrogen bonding: crystalline 7-ethynyl-6,8-diphenyl-7H-benzocyclohepten-7-ol

TL;DR: In the crystalline title compound, molecular dimers are joined by a system of interconnected O-H⋯CC-H and CC-H ⋯Ph hydrogen bonds for which IR spectra indicate considerable strength as mentioned in this paper.
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