(I) S(equatorial)-Allyl-3-hydroxy-17-thioniamorphinan perchlorate, C19H25OS+.C1O4-, Mr = 400.91, monoclinic, P2(1)/n, a = 9.4171 (8), b = 10.7425 (10), c = 19.096 (2) A, beta = 95.666 (7) degrees, V = 1922.4 (3) A3, Z = 4, Dx = 1.385 Mg m-3, lambda (Mo K alpha) = 0.70930 A, mu = 0.33 mm-1, F(000) = 847.92, room temperature, final R = 0.052 for 1742 observed reflections. (II) S(axial)-Allyl-3-hydroxy-17-thioniamorphinan perchlorate, C19H25OS+.C1O4-, Mr = 400.91, monoclinic, P2(1), a = 8.4554 (10), b = 11.658 (3), c = 9.5831 (21) A, beta = 95.620 (10) degrees, V = 940.1 (3) A 3, Z = 2, Dx = 1.416 Mg m-3, lambda (Mo K alpha) = 0.70930 A, mu = 0.33 mm-1, F(000) = 423.96, room temperature, final R = 0.054 for 1015 observed reflections. The molecular structures of (I) and (II) are differentiated only by the orientation of the S-allyl substituent: the S-allyl group is equatorial in (I) and axial in (II). It has been shown that the activities as potent and selective blockers of kappa opioid receptors (kappa 2 subtype) are to be attributed to the alpha-thiamorphinan isomer (I). The inactive compound (II) is the beta-isomer. The fused ring systems are almost identical in the two molecules.