Synthesis and structural characterization of crown thioether complexes of silver(I) and copper(II)

Abstract

The crown thioether silver(I) complexes {[Ag{(OH)2[16]aneS4}]NO3}∞1 and {[Ag{(OH)2[16]aneS4}][O2CMe]}∞2 and the copper(II) complex [Cu{(OH)2[16]aneS4}][ClO4]23, where (OH)2[16]aneS4= 1,5,9,13-tetrathiacyclohexadecane-3,11-diol, have been prepared by reaction of (OH)2[16]aneS4 with the appropriate metal salt. The two silver structures are not isomorphous. Complex 1 crystallizes in the monoclinic space group C2 with a= 13.500(4), b= 9.178(2), c= 8.695(4)A, β= 121.99(2)° and Z= 2. Silver(I) is tetrahedrally bound with four thioether group from four symmetry-related macrocycles and each ligand molecule in turn co-ordinates to four separate silver(I) ions in an exodentate fashion to yield a three-dimensional tetrahedral polymeric network. Complex 2 crystallizes in the orthorhombic space group Pccn with a= 14.121(9), b= 17.203(8), c= 15.940(3)A and Z= 8. It contains two types of crystallographically different silver(I) ions, both of which are co-ordinated by four sulfur atoms from four symmetry-related macrocycles in a rather distorted-tetrahedral fashion. The silver atoms are in a two-dimensional sheet arrangement interconnected by the macrocycle. Complex 3 crystallizes in the monoclinic space group P21/c with a= 7.820(2), b= 13.853(2), c= 9.627(2)A, β= 90.85(2)° and Z= 2. The molecule is a discrete monomer in which the tetradentate macrocycle is in the endodentate conformation with four thioether donors in a precisely square-planar arrangement around the copper.