The synthesis, structural characterization, and electrochemical properties of a Ni-II complex derived from the template reaction of N,N’-bis(2-mercaptoethyl)-1,5-diazacyclooctans nickel(II). Ni-1, with ICH2CO2Na are described. Blue N-(3-thiabutyl)-N’-(3-thiapentanoate)-1,5-diazacpclooctanenickel(II)iodide, [(tbtp-daco)Ni][I], [5]I, contains Ni-II in an octahedral environment with N2S2O2 donor atoms; one oxygen is from an adjacent [(tbtp-daco)Ni] ion and has the same distance to Ni-II as the intramolecular oxygen, resulting in a coordination polymer. Complex [5]. H2O, C13H27N2O3S2NiI, crystallizes in the orthorhombic space group Pbca with a = 10.898(3), b = 18.103(5), c = 19.020(5), and Z = 8. The extent to which the polymer is retained in solution is counterion dependent, which influences redox properties (accessibility of Ni-I and Ni-III).