Acta Crystallographica Section B

Structural Science

Volume 52, Part 5 (October 1996)

research papers

Acta Cryst. (1996). B52, 882-891 [ doi:10.1107/S0108768196007409 ]

Symmetry-modified conformational mapping and classification of the medium rings from crystallographic data. IV. Cyclooctane and related eight-membered rings

F. H. Allen, J. A. K. Howard and N. A. Pitchford

Abstract: Crystallographic observations of eight-membered ring conformations, retrieved from the Cambridge Structural Database, have been mapped and classified using symmetry-adapted deformation coordinates, principal component analysis and cluster analysis. Seven subsets of eight-membered rings, containing 11-32 conformational observations, have been analysed: cyclooctane (dataset 8C1), cyclooctene (8C2), cycloocta-1,3-diene (8C3), mono-exo-unsaturated carbocycles (8C4), monohetero (8A1), 1,5-dihetero (8A2) and 1,3,5,7-tetrahetero rings (8A3). The energetically preferred (by ~7 kJ mol^-1) boat-chair form is adopted by 26 of the 32 examples of 8C1, although varying degrees of twist are induced by fusion to rings of sizes three, four and five. Crystallographic results for other subsets also populate the lower-energy areas of the appropriate potential energy hypersurface, but the analyses are complicated by the effects of ring fusion and by the small numbers of relevant crystal structures in some cases.