Three new coordination polymers, {[Mn-3(pzbtz)(2)(Cl)(2)(H2O)(2)]center dot 4H(2)O}(n) (1), {Mn-2(pzbtz)(SO4)(H2O)(3)]center dot 3H(2)O}(n) (2), and {[Mn-3(pzbtz)(3)(H2O)(3)]center dot 1.5DMA center dot 2H(2)O}(n) (3), have been solvothermally synthesized with MnCl2/MnSO4 and a bitriazole ligand, 5'-(pyrazin-2-yl)-2H,4'H-3,3'-bi(1,2,4-triazole) (H(2)pzbtz), in different solvent systems. H(2)pzbtz shows different geometrical configurations and coordination modes, leading to the diverse three-dimensional (3D) frameworks of 1-3. Complex 1 contains the trinuclear Mn-3(tr)(4)X-2 (X = Cl or H2O) clusters and reveals an unobserved (3,4,8)-connected sqc929 topological framework with two types of cages. Complex 2 is a new (3,4,6)-connected network based on dinuclear Mn-2(tr)(2) clusters, and 3 shows an 8-connected bcu topology with a novel tetranuclear Mn-4(tr)(6) cluster. Complexes 1 and 2 show antiferromagnetic properties, while 3 reveals spin-canting magnetic behavior with an uncommonly high T-c around 44 K. In addition, 1 also possesses good adsorption selectivity for CO2 over CH4 and N-2 and an uncommon gate-opening phenomenon.