The Weak Hydrogen Bond In Structural Chemistry and Biology

by Desiraju, Gautam R.; Steiner, Thomas

• ISBN13: 9780198509707
• ISBN10: 0198509707
• Edition: Reprint
• Format: Paperback
• Copyright: 2001-08-09
• Publisher: International Union of Crystallography

Summary

The weak or non-conventional hydrogen bond has been the subject of intense scrutiny over recent years. Although the existence of this type of hydrogen bond was suggested many years ago, research has traditionally focused on the stronger and more well-known forms of hydrogen bonds. However, a growing body of experimental and theoretical evidence now confirms that hydrogen bonds like C-H...O, O-H..., C-H... and even bonds such as O-H...metal play distinctive roles in structural chemistry and biology. This book provides a critical assessment of this interesting and occasionally controversial interaction type. It will be a useful resource for a wide range of researchers in structural and supramolecular science.

Author Biography

Gautam R. Desiraju is Professor at the School of Chemistry, University of Hyderabad Thomas Steiner is Lecturer at the Institut fur Kristallographie, Freie Universitat Berlin

Table of Contents

Acknowledgements	xiii
Introduction	1	(28)
The hydrogen bond	1	(10)
Historical background	1	(4)
Geometrical parameters and definitions	5	(4)
Energetic parameters and definitions	9	(2)
The weak or non-conventional hydrogen bond -- scope of this work	11	(10)
Classification of hydrogen bonds	12	(4)
The nature of the hydrogen bond interaction and its limits	16	(3)
Differences between strong and weak hydrogen bonds	19	(2)
Methods of studying weak hydrogen bonds	21	(7)
Crystal structure analysis and statistical treatment of these results	21	(5)
Vibrational spectroscopy	26	(1)
Gas-phase rotational spectroscopy	27	(1)
Computation	27	(1)
Summary	28	(1)
Archetypes of the weak hydrogen bond -- C --- H ... O and C --- H ... N interactions in organic and organometallic systems	29	(93)
Historical developments	29	(11)
Sutor's study	32	(3)
The dark ages	35	(3)
The Taylor--Kennard paper	38	(2)
General properties	40	(82)
Vibrational spectroscopy	40	(4)
Length properties	44	(14)
Angular properties	58	(10)
C --- H bond lengthening	68	(2)
Reduction of thermal vibrations	70	(3)
Computational studies and hydrogen bond energies	73	(7)
Cooperativity	80	(6)
Hardness and softness	86	(3)
Intramolecular phenomena	89	(8)
Influence on crystal packing	97	(11)
Repulsive and destabilizing C --- H ... O contacts	108	(8)
Weak hydrogen bonds in liquids and solution	116	(4)
Recapitulation	120	(2)
Other weak and non-conventional hydrogen bonds	122	(171)
π-Acceptors	122	(80)
What is a π-acceptor?	122	(2)
Solution and gas phase experiments	124	(6)
Phenyl groups	130	(34)
Alkynes	164	(21)
Alkenes	185	(5)
Heterocycles	190	(3)
Other π-acceptors	193	(9)
Weak atomic acceptors	202	(44)
Group VII elements -- covalent halogen	202	(22)
Group VI elements -- S, Se and Te	224	(14)
Group V elements -- P, As and Sb	238	(4)
Group IV elements -- isonitriles, carbanions, carbenes and silylenes	242	(4)
Halide anions	246	(7)
Weak donors	253	(17)
S --- H	253	(14)
P --- H and P+ --- H	267	(2)
Se --- H, As --- H and Si --- H	269	(1)
Organometallics	270	(11)
Metal atoms as acceptors -- X --- H ... M hydrogen bonds	271	(6)
Metal atom groups as donors -- M --- H ... A hydrogen bonds	277	(3)
Agostic interactions -- M ... (H --- C)	280	(1)
Other varieties	281	(11)
The dihydrogen bond -- X --- H ... H --- M	283	(8)
The inverse hydrogen bond -- X --- H- ... A+	291	(1)
Summary	292	(1)
The weak hydrogen bond in supramolecular chemistry	293	(50)
The solid state -- influence of weak hydrogen bonds on packing	294	(9)
The crystal as a supermolecule	294	(2)
Crystal structures wherein weak hydrogen bonds are important	296	(7)
Inclusion complexes	303	(12)
Crown ethers	303	(7)
Oligoaryl hosts	310	(1)
Cyclodextrins (cycloamyloses)	311	(4)
Crystal engineering -- promises and problems	315	(21)
From molecular to crystal structure	316	(5)
The computational approach	321	(1)
The experimental approach -- database research	322	(1)
Crystal engineering in practice -- supramolecular synthons	323	(13)
Recognition in solution and related phenomena	336	(7)
Supramolecular assistance to molecular synthesis	337	(1)
Drug design and biological recognition	338	(5)
The weak hydrogen bond in biological structures	343	(98)
Introduction	343	(3)
Biological structures are not time-stable	344	(1)
The crystallographic resolution problem	345	(1)
Peptides and proteins	346	(39)
The building blocks -- amino acids	346	(4)
C --- H ... O hydrogen bonds	350	(13)
X --- H ...π hydrogen bonds	363	(13)
Protein--ligand interactions	376	(5)
Enzymatic activity	381	(4)
Nucleic acids	385	(22)
Nucleic acid constituents	389	(4)
Polymeric DNA and RNA	393	(14)
Carbohydrates	407	(5)
Chemical constitution	407	(1)
Hydrogen bond geometry	408	(2)
Functionally important C --- H ... O hydrogen bonds	410	(2)
Water molecules	412	(29)
Organic hydrates	414	(12)
Are there water molecules with vacant hydrogen bond potentials?	426	(1)
Macromolecular structures	427	(14)
Conclusions	441	(5)
Appendix Some bibliographic statistics	446	(1)
References	447	(54)
Index	501