A ditopic 23-membered NO₄S₂-macrocycle (L) incorporating a rigid and a flexible binding sites was synthesized and its silver(I) and mercury(II) complexes exhibiting different stoichiometries and coordination modes were prepared 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 square pyramidal geometry. The ¹H-NMR titration results for the silver(I) complexation agree with the solid state data. Interestingly, reaction of L with HgI₂ led to the isolation of two tetranuclear bis(macrocycle) complexes, [(^exoHgLI₂)₂(μ-Hg₂I₄)] (2) and [(^endoHgLI₂)₂(μ-Hg₂I₄)] (3), as a kinetic and a thermodynamic product, respectively (see below). These two products are configurational isomers which show different coordination modes. In both products, for example, two exocyclic (2) and two endocyclic (3) mercury(II) complex units are linked by tetraiododimercury(II) core, (μ-Hg₂I₄), to give a 4:2 (metal-to-ligand) stoichiometry. It is profound that the exo- and endo-coordinated macrocyclic complexes (configurational isomers) are isolated and characterized as a kinetic product and a thermodynamic product, respectively.