Co-ordination of the crown thioether 2,5,8-trithia[9]-o-benzenophane (L1). Synthesis and crystal structures of [CuL1(CI)] and [NiL12][BF4]2

Abstract

The co-ordination abilities of 2,5,8-trithia[9]-o-benzenophane (L¹) are compared with several S₃-crown macrocycles by structural, spectral and electrochemical techniques. Ligand L¹ shows intermediate behaviour relative to the well known ligands 1,4,7-trithiacyclononane and 1,5,9-trithiacyclododecane. The synthesis and characterization of Cu^II, Cu^I, Ni^II and Co^II complexes with L¹ are carried out. Crystal and molecular structures of two complexes are determined: [CuL¹(Cl)], monoclinic, space group P2₁/a, a= 13.562(6), b= 8.046(1), c= 13.770(6)Å, β= 109.96(2)°, Z= 4, R= 0.041 and R′= 0.045; [NiL₂¹][BF₄]₂, monoclinic, space group P2₁/c, a= 9.430(2), b= 14.879(2), c= 11.451(2)Å, β= 113.59(1)°, Z= 2, R= 0.058 and R′= 0.057.