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Two novel d10 metal coordination polymers [Cd2(Hmna)4] n ( 1), [Zn2(ddca)2 (dpe)] n ·nH2O ( 2) (H2mna = 6-mercaptonicotinic acid, H2ddca = 6, 6'-dithiodinicotinic acid, dpe = 1, 2-bis(4-pyridyl)ethylene), were hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Compound 1 is a cyclic double chain structure containing 16-number and 32-number circles with (Hmna)- ligands as bridges, in which the starting H2ddca reagent was unprecedentedly converted into H2mna ligands via in situ cleavage of S-S bonds during the course of hydrothermal treatment. In compound 2, two five-coordinate zinc centers are connected with carboxylate groups of H2ddca ligands to give a binuclear [Zn2(CO2)4] unit, which are linked by dpe ligands to form a 2D network structure. It is worth noting that compound 2 displays a twofold 2D+2D parallel interpenetration framework containing a polyrotaxane-like motif. In addition, the thermal stablities and photoluminescence properties of compounds 1 and 2 were also studied. [ABSTRACT FROM AUTHOR]