Hydrogen-bond geometry and directionality

Allen, F. H.; Cole, J. C.; Verdonk, M. L.

doi:10.1107/97809553602060000713

International
Tables for
Crystallography
Volume F
Crystallography of biological macromolecules
Edited by M. G. Rossmann and E. Arnold

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International Tables for Crystallography (2006). Vol. F. ch. 22.4, p. 562 | 1 | 2 |

Section 22.4.5.2. Hydrogen-bond geometry and directionality

F. H. Allen,^a ^* J. C. Cole^a and M. L. Verdonk^a

^aCambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, England
Correspondence e-mail: allen@ccdc.cam.ac.uk

22.4.5.2. Hydrogen-bond geometry and directionality

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The hydrogen bond is the strongest and most frequently studied of the non-covalent interactions that are observed in crystal structures. As with intramolecular geometries, the first surveys of non-bonded interaction geometries all concerned hydrogen bonds, and were reported long before the CSD existed (Pauling, 1939; Donohue, 1952; Robertson, 1953; Pimentel & McClellan, 1960). The review by Donohue (1952) already contained a plot of N···O distances versus C—N···O angles in crystal structures (the C—N groups are terminal charged amino groups), while the review by Pimentel & McClellan (1960) contained histograms of hydrogen-bond distances. Up to the mid-1970s, numerous other studies appeared, e.g. Balasubramanian et al. (1970), Kroon & Kanters (1974) and Kroon et al. (1975), in which all of the statistical analyses were performed manually.

With the advent of the CSD and its developing software system, these kinds of studies became much more accessible and easier to perform, although the non-bonded search facility was only generalized and fully integrated within Quest3D in 1992. Thus, Taylor and colleagues reported studies on N—H···O=C hydrogen bonds (Taylor & Kennard, 1983; Taylor et al., 1983, 1984a,b), Jeffrey and colleagues reported detailed studies on the O—H···O hydrogen bond (Ceccarelli et al., 1981), hydrogen bonds in amino acids (Jeffrey & Maluszynska, 1982; Jeffrey & Mitra, 1984), and hydrogen bonding in nucleosides and nucleotides, barbiturates, purines and pyrimidines (Jeffrey & Maluszynska, 1986), while Murray-Rust & Glusker (1984) studied the directionalities of O—H···O hydrogen bonds to ethers and carbonyls. These studies indicated that hydrogen bonds are often very directional. For example, the distribution of the O—H···O hydrogen-bond angle, after correction for a geometrical factor, peaks at 180° (i.e. there is a clear preference for linear hydrogen bonds) and, in carbonyls and carboxylate groups, hydrogen bonds tend to form along the lone-pair directions of the O-atom acceptors (Fig. 22.4.5.1). For ethers, however, lone-pair directionality is not observed, as is illustrated in Fig. 22.4.5.2.

Figure 22.4.5.1| top | pdf |

The IsoStar knowledge-based library of intermolecular interactions: interaction of O—H donors (contact groups) with one of the >C=O acceptors of a carboxylate group (the central group). (a) Direct scatter plot derived from CSD data, (b) contoured scatter plot derived from CSD data and (c) direct scatter plot derived from PDB data.

Figure 22.4.5.2| top | pdf |

Distribution of O—H donors around ether oxygen acceptors (CSD data from the IsoStar library, see text).

Software availability has facilitated CSD studies of a wide range of individual hydrogen-bonded systems in the recent literature, including studies of resonance-assisted hydrogen bonds (Bertolasi et al., 1996) and resonance-induced hydrogen bonding to sulfur (Allen, Bird et al., 1997a). These statistical studies are often combined with molecular-orbital calculations of interaction energies. Some of these studies are cited in this chapter, but the monograph of Jeffrey & Saenger (1991) and the CCDC's DBUSE database are valuable reference sources.

References

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International Tables for Crystallography (2006). Vol. F. ch. 22.4, p. 562