A range of thiaphilic mononuclear (Hg2+ and Ag+) and heterobinuclear (Ag+/Pd2-) complexes (1-6) of an NS2-donor macrocycle L with discrete and networked forms were prepared and structurally characterized. Reaction of L with HgCl2 afforded a unique 1:1 (cationic/anionic) complex [Hg-2(L)Cl-5][Hg(L)Cl] (1). Reaction of L with Hg(ClO4)(2) yielded the sandwich-type 1:2 (metal-to-ligand) complex [Hg(L)(2)](ClO4)(2) (2). Contrasting with the mercury(II) salts, the reactions of L with AgX (X=NO3- and CF3SO3-) yielded an isostructural one-dimensional (1 D) zigzag networks [Ag(L)X](n)(3; X=NO3- and 4 X=CF3SO3-) inwhich each ringof Lisexo-coordinatedviatwo S atomsandone Natom 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 K2PdCl4 gave a discrete exocyclic complex 5, [cis-Cl2Pd(L)]. Through a successive reaction of the complex 5 with AgNO3, a heterobinuclear two-dimensional (2D) coordination polymer 6, [Pd(L)Ag-2.5(NO3)(4.5)(H2O)(0.5)](n), utilizing exocyclic Pd(II) and Ag(I) was isolated and characterized.