The structure of 15-membered polyfunctional macroheterocycles

Abstract

Three isomers of I have the same melting point, 133°, and diagnostically different, but not interpretable, infrared spectra.Stability constants for formation of complexes with potassium bromide in methanol are 1.5 x ~0 8 , 3.2 x 10 6 and 4.5 x 10 4 1 mol-1 . The third isomer also yields from methanol crystals of a 1:1 solvate with an infrared spectrum indicating no hydrogen bonding by the OH group.The configuration of each of the three isomers has been determined by X-ray diffraction.Intensities were measured on a CAD4 diffractometer with Mo-Ka radiation; the phase problem 1ms solved by direct methods and final parameters obtained by full matrix refinement.Hydrogen atoms were located unequivocally.There is a cis substitution at the cyclohexane bridges, at each of---which the hydrogen atoms may be on the same or the opposite side as the OCH 2 CH 2 oc 6 H 4 0CH 2 CH 2 0 link. The configurations provide a basis for understanding their behaviour as ligands.Ia Monoclinic,~= 15.613 (2), ~ = 21.492(4), £ = 8.021(1) A, S = 96.99°, l = 4 in P2 1 /a. R = 0.078 for 2163 reflections. Ib Tric1inic, ~ = 8.842(2), ~ = 16. 702(6), £ = 10.050(3), a= 114.10(3), S = 98.97(2), £ = 91.22(2) 0 , Z = 2 in Pl. 2666 observed reflections. R = 0.060 for Ic, CH 3 0H Monoclinic,~= 14.520(2), £_ = 15.391(3), £ = 12.754(2), S = 95.02(2) 0 , l = 4 in P2 1 /n. R = 0.062 for 2071 observed reflections. The shortest (hydroxy) H ... 0 (ligand) distances are 2.37 and 2.31(10) .ill. Crystal structures of complexes Hi th alkali metal salts are being investigated.

Structure of 1,4-dioxa-10,13-dithia-7,16-diazacyclooctadecane-6,17-dione

“…Similar treatment of the N(1)-C(5) [O(5)]--C(6) amide moiety gives an average deviation of <0.007 A with atoms C(4) (0.105 ./k) and H(N1) (0.050,/k) close to the calculated plane. The amide bond lengths and bond angles are in the respective ranges: C(sp3)-C(sp2), 1.505-1.532; C=O, 1-218-1.237; C(sp2)-N, 1-320-1.379 ,~; C-C=O, 117.9-122.3; N-C--O, 122.1-124.9; C-C-N, 115.0-119.1 °, found for a variety of other macrocyclic amides (Samuel & Weiss, 1970;Northolt & Alexander, 1968;Simonov et al, 1981;Ganin et al, 1981Ganin et al, , 1984. The least-squares planes of the two amide segments have a dihedral angle of 40.5 (2) ° .…”