Abstract
The X-ray crystallographic analysis of silver(I)-13, 14-benzo-1, 4, 8, 11-tetrathiacyclopentadec-l3-ene picrate (Ag-Bz- TTCP-Pic) was carried out. The molecular structure of its complex cation is discussed in connection with its solvent extraction behavior. The Ag-Bz-TTCP cation complex is not the simple 1:1 monomer complex cation, [Ag(bz-ttcp)]+, but the 2:2 dimeric complex cation, [Ag2(bz-ttcp)2]2+. Each silver(I) ion has the coordination number 5 and binds with five sulfur atoms: four sulfur atoms in one Bz-TTCP molecule and one sulfur atom in another Bz-TTCP, to form a distorted square pyramidal configuration. Thus two silver(I) ions are sandwiched between two Bz-TTCP molecules so that they look as if they were surrounded with two cyclic polythioether rings and two benzene rings. The charge on two silver(I) ions is delocalized on the dimeric complex. Thus the formation of the ion pair complex with two picrate anions is so stabilized that silver(I) will be almost completely extracted.
