Über die kristall- und molekülstruktur und die absolute konfiguration des (+)-14-epicorynolin-bromacetats

The crystal structure and absolute configuration of ( + )-14-epicorynoline bromoacetate have been elucidated by X-ray diffraction method. The title compound forms monoclinic needles of space group P2₁, with a = 10.056, b = 7.400, c = 13.959 Å, β = 94.09°, and two molecules in the unit cell. The structure was determined by the heavy-atom method and refined by the least-squares method to R =0.082 for 1195 reflections collected by counter diffractometer techniques. Using the anomalous dispersion effect of the bromine atom, the absolute configuration was also determined as 11S, 13R and 14S. The mode of B/C-ring connection is trans; the rings B and C form half-chair and twist-half-chair conformations, respectively. The dihedral angle between the A- and D-rings is 11°. The hydroxyl-group at C-ll is trans to the methyl-group at C-13. The methyl-group at N-5 has an axial orientation and a 1,3-diaxial relationship to the angular methyl-group at C-13, which causes an unusual short distance of 3.11 Å between these methyl-groups.