On the electrostatic directionality of NH…OC hydrogen bonding

✍ Scribed by J.B.O. Mitchell; S.L. Price

• Publisher: Elsevier Science
• Year: 1989
• Tongue: English
• Weight: 470 KB
• Volume: 154
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(89)87461-5

✦ Synopsis

The accessible minima in the electrostatic interaction energy of 29 bimolecular complexes containing N-H...O=C hydrogen bonds have been calculated, using ab initio distributed multipoles. The hydrogen bond geometries corresponding to these minima show the same statistical trends as found in crystal structures, namely a tendency towards planarity with a C=O...H angle around the classical lone pair position. However, the geometries of the complexes are generally based on structural motifs containing two separate intermolecular contacts. Thus we believe that the geometrical constraints involved in maximising the number of favourable electrostatic contacts are more important than any lone pair electrostatic effects in determining the geometry of N-H...O=C hydrogen bonds.