STRUCTURES OF 3 DERIVATIVES OF 5,12-METHANO[2.2.2]PARACYCLOPHANE

5,12-Methano[2.2.2]paracyclophan-25-one (1), C25H22O, M(r) = 338.4, monoclinic, P2(1)/c, a = 10.677 (2), b = 26.122 (3)(10) angstrom = 13.053 (2) angstrom, beta = 92.96 (2)-degrees, V = 3635.7 (10) angstrom3, Z = 8, D(x) = 1.237 Mg m-3, lambda(Cu Kalpha) = 1.54178 angstrom, mu = 0.57 mm-1, F(000) = 1440, T = 293 K, R = 0.051 for 5400 reflections. There are two independent molecules in the asymmetric unit which differ only in slight relative ring rotations. The approximate threefold symmetry of the parent [2.2.2]paracyclophane is lost on formation of the methano bridge. No disorder of the ethano bridges is observed. endo-5,12-Methano[2.2.2]paracyclophan-25-ol (2), C25H24O, M(r) = 340.4, monoclinic, Cc, a = 15.714 (2), b = 31.126 (5), c = 11.476 (2) angstrom, beta = 96.51 (2)-degrees, V = = 340.4 angstrom3 monoclinic, Cc, a = 15.714 (2), b = 31.126(5), c= 11.476(2) angstrom, beta=96.51 (2)-degrees, V= 5577(3)angstrom3,Z=12,D(x)=1.216 Mg m-3, lambda (Mo Kalpha) =0.71069 angstrom, mu=0.07 mm-1, F(000)=2184, T= 293 K, R = 0.071 for 5288 reflections. There are three independent molecules in the asymmetric unit. The conformation of the seven-membered ring differs but otherwise the molecules are similar in conformation to each other and to compound (1). Two of the molecules are linked by a hydrogen bond of 2.97 angstrom between the hydroxyl O atoms. endo-25-Methyl-5,12-methano[2.2.2]paracyclophan-25-ol (3), C26H26O, M(r) = 354.5, rhombohedral, R3, a = 23.978 (4), c = 8.918 (2) angstrom (hexagonal axes), V = 4440 (3) angstrom3, Z = 9, D(x) = 1.193 Mg m-3, lambda(Mo Kalpha) = 0.71069 angstrom, mu = 0.07 mm-1, F(000) = 1710, T = 293 K, R = 0.034 for 2819 reflections. The molecule exhibits a conformation very similar to molecule 2 of compound (2) and has close to (non-crystallographic) mirror symmetry. Hydrogen bonds of 3.09 A link the molecules around the threefold axes.