The molecular structure of solstitialin, C15H2005, a new, toxic sesquiterpenoid from Centaurea solstitialis L., has been elucidated via its crystal structure. Solstitialin crystallizes in the orthorhombic system with a = 10-007 (4), b = 22.789 (4), c = 5.844 (3)/~, space group P212121 with four molecules in the unit cell. Copper K~ data were gathered by use of a Picker automatic diffractometer. The structure was solved by symbolic addition and tangent formula procedures and refined by Fourier and full-matrix least-squares methods to a final R index of 0.026 (1506 reflections). Estimated standard deviations of the bond lengths not involving hydrogen are 0.002-0.003 A. The absolute configuration was determined by use of the anomalous scattering from oxygen. Solstitialin possesses the guaianolide structure H,, t "and has the absolute configuration shown. The lactone carbonyl group is involved in intermolecular hydrogen bonding directed in a plane about 65 ° from the plane of the lactone group.