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Crystalline Molecular Complexes and CompoundsStructures and Principles$
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Frank H. Herbstein

Print publication date: 2005

Print ISBN-13: 9780198526605

Published to Oxford Scholarship Online: September 2007

DOI: 10.1093/acprof:oso/9780198526605.001.0001

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Hydrogen bonded molecular complexes and compounds

Hydrogen bonded molecular complexes and compounds

(p.851) Chapter 12 Hydrogen bonded molecular complexes and compounds
Crystalline Molecular Complexes and Compounds

Frank H. Herbstein

Oxford University Press

Hydrogen bonding, one of the most important secondary interactions between molecules of the same kind, is no less important among the binary adducts, and most of the same principles apply. Among the most important hydrogen bond donors are -OH, >NH, and -NH2, while >C=O, >O, -Cl, and >S are important acceptors together with charged analogues. The major structural distinction is between ‘Appendage Structures’, where one component forms a framework to which the second component is hydrogen bonded, and ‘Mixed Framework Structures’, where both components form part of an alternating framework. The latter group can have the two components hydrogen bonded in pairs or in larger discrete groupings, the crystals being molecular crystals from a structural point of view, in linear chains, in layers, or in three dimensional frameworks, where many complex arrangements are possible, especially if a third component such as water is present. Finally, the question of the circumstances under which proton transfer takes place (the formation of ions) is considered.

Keywords:   hydrogen bonding, appendage structures, mixed-framework structures, proton transfer

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