As ditopic host system incorporating hard base and soft base domains, an 18-membered (L¹ and a 20-membered (L²)^2-4 N₂O₂S₂-macrocycles and their supramolecular complexes are reported. The reactions of ZnBr₂ and CdBr₂ with L¹ afforded mononuclear complexes [Zn(L¹)][ZnBr₄] (1) and [Cd(L¹)Br₂] (2), respectively. When HgBr₂ was used, a dinuclear complex [Hg₂(L¹)Br₄] (3) was obtained. While, Hg(NO₃)₂ gave a 1-D CP {[Hg₂(L¹)](NO₃)₂}_n (4, see below) as a first example of the infinite macrocyclic mercury(I) complex. The reaction of a mixture of ZnBr₂ and CdBr₂ afforded two solubility-dependent Cd(II) complexes (2 and 5) including a half dumbbell-type complex [Cd(L¹)(μ-Br)(CdBr₃)] (5). Interestingly, one-pot reaction of a mixture of CdBr₂ and HgBr₂ afforded a dumbbell-type heterometallic product [(CdL¹)₂(μ-Hg₂Br₆)](Hg₂Br₆) (6, see below). In the equimolar reaction of L², AgPF₆ afforded a typical endocyclic complex [Ag(L²)(PF₆)] (7). However, the use of three equivalents or above amount of AgPF6, gave an endo/exocyclic 1-D CP {[Ag₄(L²)₂](PF₆)₄∙2CH₂Cl₂}_n (8a, see below). Upon removal of the lattice dichloromethane molecules in the ambient condition, conversion of the coordination geometry of the exo-Ag atom from linear (8a) to trigonal plane (8b, {[Ag₄(L²)₂(PF₆)₂](PF₆)₂}_n) as well as sliding of the 1-D chains were observed in an SCSC manner.