Journal ArticleDOI
The C-h···o hydrogen bond: structural implications and supramolecular design.
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It is clearly no longer necessary to justify the relevance of C-H’‚‚O hydrogen bonds, so widely invoked are they in small-molecule and biological crystallography and supramolecular synthesis and crystal engineering.Abstract:
The C-H‚‚‚O hydrogen bond is so well-established in structural chemistry that it seems difficult now to believe that when Sutor proposed the existence of this type of hydrogen bond in the early 1960s,1,2 her suggestion was drowned in scepticism, if not outright hostility.3 It was only two decades later, with Taylor and Kennard’s paper, that the subject was properly revived.4 Shortly thereafter, an Account appeared from this laboratory describing the role of the C-H‚‚‚O interaction in crystal engineering.5 Subsequently, one felt confident enough to term these erstwhile “interactions” hydrogen bonds, in a second Account.6 A recent invitation to contribute another Account and the many recent efforts in this direction by my students and postdoctorals have led to the present paper. It is clearly no longer necessary to justify the relevance of C-H‚‚‚O hydrogen bonds, so widely invoked are they in small-molecule and biological crystallography. The presence of O-atoms in a large majority of organic molecules means that this hydrogen bond is widespread, even if not identified in many cases. However, other questions concerning these weak hydrogen bonds could be posed: (1) What is their upper distance limit? (2) Are very short, bent bonds significant? (3) Why do C-H‚‚‚O bonds sometimes disturb the strong O-H‚‚‚O and N-H‚‚‚O network? Alternatively, why do hydrogen bond donors and acceptors not always pair in descending order of strength? (4) How important is cooperativity for weak hydrogen bonds? (5) Are C-H‚‚‚O hydrogen bonds responsible for crystal packing, or are they the forced consequences of packing? (6) Are weak hydrogen bonds robust enough for supramolecular synthesis and crystal engineering? (7) Does the C-H‚‚‚O hydrogen bond have any biological significance? These difficult questions cannot be answered fully. This Account attempts to address some of them, but better answers can only follow from further work.read more
Citations
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Journal ArticleDOI
The hydrogen bond in the solid state.
TL;DR: 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.
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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.
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Artificial Molecular Machines.
TL;DR: The aim of this review is to present a unified view of the field of molecular machines by focusing on past achievements, present limitations, and future perspectives.
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
Hydrogen bridges in crystal engineering: interactions without borders.
TL;DR: The aim of this article is to highlight some features common to all hydrogen bonds and further to suggest that the term hydrogen bridge is perhaps a better descriptor for them.
References
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MonographDOI
Supramolecular Chemistry: Concepts and Perspectives
TL;DR: From molecular to supramolescular chemistry: concepts and language of supramolecular chemistry, molecular recognition, information, complementarity molecular receptors - design principles and more.
Journal ArticleDOI
Supramolecular Synthons in Crystal Engineering—A New Organic Synthesis
TL;DR: In this article, the authors show that crystal engineering is a new organic synthesis, and that rather than being only nominally relevant to organic chemistry, this subject is well within the mainstream, being surprisingly similar to traditional organic synthesis in concept.
Journal ArticleDOI
Characterization of c-h-o hydrogen-bonds on the basis of the charge-density
Uwe Koch,Paul L. A. Popelier +1 more
TL;DR: In this paper, a set of criteria are proposed based on the theory of "atoms in molecules" to establish hydrogen bonding, even for multiple interactions involving C-H-O hydrogen bonds.
Journal ArticleDOI
Crystallographic evidence for the existence of CH.cntdot..cntdot..cntdot.O, CH.cntdot..cntdot..cntdot.N and CH.cntdot..cntdot..cntdot.Cl hydrogen bonds
Robin Taylor,Olga Kennard +1 more
Journal Article
Crystal engineering : the design of organic solids
TL;DR: The Atom-Atom Potential Method and the Close-Packing Model for Molecular Crystals as mentioned in this paper have been used to predict the crystal structures of organic molecules using the Kitaigorodskii model.