A ditopic 23-membered NO₄S₂-macrocycle (L) incorporating rigid and flexible binding sites and its soft metal complexes exhibiting different stoichiometries and coordination modes were synthesized and structurally characterized. First, silver(I) perchlorate reacts with L to afford an endocyclic mononuclear complex [Ag(L)]ClO₄ (1) in which the silver(I) ion locates at the rigid binding site of the macrocyclic cavity adopting a penta-coordinated SP geometry. NMR titration for the corresponding system also shows of an 1:1 (metal-to-ligand) stoichiometry in solution. Interestingly, reaction of L with HgI₂ led to the isolation of two tetranuclear bis(macrocycle) complexes, [(^exoHgLI₂)₂(μ-Hg₂I₄)] (2a) and [(^endoHgLI₂)₂(μ-Hg₂I₄)] (2b), as a kinetic and a thermodynamic product, respectively (see below). In both products, two exocyclic (2a) and two endocyclic (2b) mercury(II) complex units are linked by tetraiododimercury(II) core, (μ-Hg₂I₄), to give a 4:2 stoichiometry. The reaction of L with copper(I) chloride yielded a greenish complex of the formula [Cu^II(L)Cl₂]·CH₃CN (3), exhibiting the oxidation of copper(I) to copper(II). When a mixture of CdI₂ and HgI₂ was used in the reaction with L, a discrete type complex with two separated parts of the formula [Cd(L)I]₂[Hg₂I₆] (4) was isolated.