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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

Metal-bound chlorine often accepts hydrogen bonds

TL;DR: In this paper, crystallographically characterised hydrogen bonds containing M-Cl, C-Cl or Cl-Cl and either HO or HN groups were analyzed and it was shown that M−Cl moieties are good, anisotropic hydrogen-bond acceptors forming hydrogen bonds similar in length to those of the chloride anion.
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Identifying and Analyzing Intermolecular Bonding Interactions in van der Waals Molecules

TL;DR: In this article, the role of the intermolecular charge density in binding was investigated in a set of 36 configurations of 11 van der Waals dimers and a trimer, none of which contained a hydrogen bond.
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How Strong Is the Cα−H···OC Hydrogen Bond?

TL;DR: In this article, a linear correlation between C−H···O bond energies and gas-phase anion proton affinities was reported and used to estimate values of De = −4.0 ± 0.5
Journal ArticleDOI

CH/π Interaction in the Crystal Structure of Organic Compounds. A Database Study

TL;DR: The CH/π interaction is a weak molecular force occurring between CH groups and π-groups as mentioned in this paper, and it has been found that the CH hydrogen atoms tend to point toward the center of the aromatic ring.
Journal ArticleDOI

Covalency of the Hydrogen Bond in Ice: A Direct X-Ray Measurement

TL;DR: In this paper, the Compton profile anisotropies of ordinary ice were found to correspond to distances of 1.72 and 2.85, which are close to the hydrogen bond length and the nearest-neighbor O-O distance, respectively.
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