Structures of N-substituted 1,2-oxazines .2. Bicyclic Bridged Derivatives

摘要

(I) 2-(2-Oxa-3-azabicyclo[2.2.2]oct-5-en-3-yl)-1,1-ethylenedicarbonitrile, C10H9N3O, M(r) = 187.20, orthorhombic, Pnam, a = 8.933 (1), b = 13.088 (1), c = 8.002 (2) angstrom, V = 935.6 (3) angstrom3, Z = 4, D(x) = 1.33 g cm-3, lambda-(Cu K-alpha) = 1.5418 angstrom, mu = 7.5 cm-1, F(000) = 392, T = 291 K, R = 0.056 for 642 observed reflections. (II) 2-(tert-Butylthio)-3-(2-oxa-3-azabicyclo[2.2.2]octan-3-yl)acrylonitrile, C-13H20N2OS, M(r) = 252.38, monoclinic, P2(1), a = 12.098 (4), b = 17.770 (5), c = 10.926 (5) angstrom, beta = 112.44 (3)-degrees, V = 2171 (1) angstrom 3, Z = 6, D(x) = 1.16 g cm-3, lambda-(Mo K-alpha) = 0.71069 angstrom, mu = 2.1 cm-1, F(000) = 816, T = 291 K, R = 0.064 for 3441 observed reflections. (III) 2-(tert-Butylthio)-3-(6-oxa-7-azabicyclo[3.2.2]non-8-en-7-yl)acrylonitrile, C-14H20N2OS, M(r) = 264.39, orthorhombic, P2(1)2(1)2(1), a = 9.962 (3), b = 12.576 (3), c = 11.766 (4) angstrom, V = 1474.1 (7) angstrom 3, Z = 4, D(x) = 1.19 g cm-3, lambda-(Mo K-alpha) = 0.71069 angstrom, mu = 2.10 cm-1, F(000) = 568, T = 291 K, R = 0.051 for 1259 observed reflections. The E configuration of the double bond is observed for both (II) and (III). Some geometrical parameters indicate clearly that the conjugation between the olefin and the ring system is less in molecule (III) than in the other two derivatives.