Acta Crystallographica Section B

Structural Science

Volume 64, Part 4 (August 2008)

research papers

Acta Cryst. (2008). B64, 491-496 [ doi:10.1107/S0108768108015437 ]

Interaction geometries and energies of hydrogen bonds to C=O and C=S acceptors: a comparative study

P. A. Wood, E. Pidcock and F. H. Allen

Abstract: The occurrence, geometries and energies of hydrogen bonds from N-H and O-H donors to the S acceptors of thiourea derivatives, thioamides and thiones are compared with data for their O analogues - ureas, amides and ketones. Geometrical data derived from the Cambridge Structural Database indicate that hydrogen bonds to the C=S acceptors are much weaker than those to their C=O counterparts: van der Waals normalized hydrogen bonds to O are shorter than those to S by 0.25 Å. Further, the directionality of the approach of the hydrogen bond with respect to S, defined by the C=SH angle, is in the range 102-109°, much lower than the analogous C=OH angle which lies in the range 127-140°. Ab initio calculations using intermolecular perturbation theory show good agreement with the experimental results: the differences in hydrogen-bond directionality are closely reproduced, and the interaction energies of hydrogen bonds to S are consistently weaker than those to O, by 12 kJ mol^-1, for each of the three compound classes. There are no CSD examples of hydrogen bonds to aliphatic thiones, (Csp³)₂C=S, consistent with the near-equality of the electronegativities of C and S. Thioureas and thioamides have electron-rich N substituents replacing the Csp³ atoms. Electron delocalization involving C=S and the N lone pairs then induces a significant >C⁺=S^- dipole, which enables the formation of the medium-strength C=SH bonds observed in thioureas and thioamides.

Keywords: interaction geometry; hydrogen bonding; Cambridge Structural Database; electron delocalization.