Two Mn-4 single-molecule-magnet (SMM)-based coordination polymers, {[Mn4O(salox)(3)(N-3)(3)-(DMF)(2)(H2O)(dpp)]center dot 0.5MeOH}(n) (1,0.5MeOH; H(2)salox = salicylaldoxime; dpp = 1,3-di-4-pyridylpropane; DMF = N, N-dimethylformamide) and {[Mn4O(Me-salox)(3)(N-3)(3)-(dpp)(1.5)]center dot 1.5Et(2)O}(n) (2.1.5Et(2)O; Me-H(2)salox = hydroxypheny-lethanone oxime), are self-assembled from Mn(ClO4)(2)center dot 6H(2)O/H(2)salox and Mn(ClO4)(2)center dot 6H(2)O/Me-H(2)salox systems with dpp and NaN3 in DMF/MeOH, respectively. Both compounds comprise a mixed-valence tetranuclear manganese core, [(MnMn3O)-Mn-II-O-III](9+), which serves as a building unit for subsequent assembly via oximate and azido ligands. The flexible dpp ligand links with a Mn-4 unit, leading to the formation of a one-dimensional helical structure in 1.0.5MeOH and a three-dimensional pcu network in 2.1.5Et(2)O. The magnetic data analysis shows that antiferromagnetic interactions within the Mn-4 units resulted in S = 3/2 and 7/2 ground states for 1.0.5MeOH and 2.1.5Et(2)O, respectively. Both compounds show SMM behavior, as evidenced by frequency-dependent out-of-phase signals in alternating-current magnetic susceptibility and magnetic hysteresis loop studies with an energy barrier of U-eff = 37 K for 2.1.5Et(2)O.