Acta Crystallographica Section B

Structural Science

Volume 54, Part 3 (June 1998)

research papers

Acta Cryst. (1998). B54, 320-329 [ doi:10.1107/S0108768198001463 ]

Carbonyl-Carbonyl Interactions can be Competitive with Hydrogen Bonds

F. H. Allen, C. A. Baalham, J. P. M. Lommerse and P. R. Raithby

Abstract: The geometries and attractive energies of carbonyl-carbonyl interactions have been investigated using crystallographic data and ab initio molecular-orbital calculations. Analysis of crystallographic data for 9049 carbon-substituted >C=O groups shows that 1328 (15%) form contacts with other >C=O groups, in which d(CO) < 3.6 Å. Three common interaction motifs are observed in crystal structures: (a) a slightly sheared antiparallel motif (650 instances) involving a pair of short CO interactions, together with (b) a perpendicular motif (116 instances) and (c) a highly sheared parallel motif (130 instances), which both involve a single short CO interaction. Together, these motifs account for 945 (71%) of the observed interactions. Ab-initio-based molecular-orbital calculations (6-31G** basis sets), using intermolecular perturbation theory (IMPT) applied to a bis-propanone dimer model, yield an attractive interaction energy of -22.3 kJ mol^-1 for a perfect rectangular antiparallel dimer having both d(CO) = 3.02 Å and attractive energies < -20 kJ mol^-1 over the d(CO) range 2.92-3.32 Å. These energies are comparable to those of medium-strength hydrogen bonds. The IMPT calculations indicate a slight shearing of the antiparallel motif with increasing d(CO). For the perpendicular motif, IMPT yields an attractive interaction energy of -7.6 kJ mol^-1, comparable in strength to a C-HO hydrogen bond and with the single d(CO) again at 3.02 Å.