Heavy Metal Complexes of Oxa-Crowned Derivatives of Dithiomaleonitrile Academic Article uri icon


  • An improved synthesis of 1,4,7-trioxa-10,13-dithiacyclopentadec-11-en-11,12-dicarbonitrile, 2, and 1,4,7,10-tetraoxa-13,16-dithiacyclooctadec-14-en-14,15-dicarbonitrile, 3, and their coordination chemistry with Ag(I) are presented. The metal complexes have been investigated by X-ray structural and spectroscopic methods. The complex [2·Ag]bf4, 6, forms colorless crystals in the triclinic space group P1 with unit cell parameters a = 8.020(4) Å, b = 16.032(5) Å, c = 16.116(7) Å, α = 116.62(2)°,β= 102.34(2)°, γ = 91.71(2)°, and Z = 4. The structure of 6 contains two unique, cocrystallized, 1:1 Ag complexes, a polymeric form and a discrete monomelic form. In both cases, the five macrocyclic donor atoms ligate the Ag(I) ion in an endocyclic fashion. The monomelic complex is further coordinated to a F atom from the bf4 anion, while in the polymeric form the Ag(I)-macrocycle units are linked by the coordination of a nitrile N atom from a neighboring macrocycle. The complex [3·Ag]bf4, 7, crystallizes in the orthorhombic space group P212121 with unit cell parameters a = 10.074(4) Å, b = 12.575(4) Å, c = 16.144(6) Å, and Z = 4. The structure of 7 is polymeric and consists of an endocyclic Ag(I) ion coordinated by three of the four macrocyclic O donor atoms and only one S atom. As in the polymer form of 6, the links between Ag-macrocycle units are through the coordination of a nitrile N atom from a neighboring macrocycle. NMR (13C) studies confirm that the complex persists in methanol solution, with an average structure that involves the coordination of all macrocyclic heteroatoms in both 6 and 7. © 1995, American Chemical Society. All rights reserved.

author list (cited authors)

  • Sibert, J. W., Lange, S. J., Hoffman, B. M., Williams, D. J., & Barrett, A.

citation count

  • 39

publication date

  • April 1995