Discrete Mercury(II) Complexes, One-Dimensional and Palladium(II)-Mediated Two-Dimensional Silver(I) Coordination Polymers of NS2-Macrocycle: Synthesis and Structural Characterization

A range of thiaphilic mononuclear (Hg(2+) and Ag(+)) and heterobinuclear (Ag(+)/Pd(2+)) complexes (1-6) of an NS(2)-donor macrocycle L with discrete and networked forms were prepared and structurally characterized. Reaction of L with HgCl(2) afforded a unique 1:1 (cationic/anionic) complex [Hg(2)(L)Cl(5)][Hg(L)Cl] (1). Reaction of L with Hg(ClO(4))(2) yielded the sandwich-type 1:2 (metal-to-ligand) complex [Hg(L)(2)](ClO(4))(2) (2). Contrasting with the mercury(II) salts, the reactions of L with AgX (X = NO(3)(-) and CF(3)SO(3)(-)) yielded an isostructural one-dimensional (1D) zigzag networks [Ag(L)X](n) (3; X = NO(3)(-) and 4; X = CF(3)SO(3)(-)) in which each ring of L is exo-coordinated via two S atoms and one N atom to a silver ion which is also bound to one S atom in the neighboring L such that the overall coordination geometry about each silver is four-coordinate. Whereas, reaction of L with K(2)PdCl(4) gave a discrete exocyclic complex 5, [cis-Cl(2)Pd(L)]. Through a successive reaction of the complex 5 with AgNO(3), a heterobinuclear two-dimensional (2D) coordination polymer 6, [Pd(L)Ag(2.5)(NO(3))(4.5)(H(2)O)(0.5)](n), utilizing exocyclic Pd(II) and Ag(I) was isolated and characterized.