The reactions of 2-(4-pyridyl) thiazole-4-carboxylic acid (Hptca) and CuCl(2)6H(2)O have led to a novel 3D mixed-valence, four-copper-center, metalorganic framework (MOF) [Cu8Cl2(ptca)(10)17H(2)O](n) (1). The topology analysis using ToposPro software package for 1 resulted in three chain-based topology types of sra (4(2), 6(3), 8), pcu (4(12), 6(3)), and dia (6(6)) via choosing corresponding connection atoms as central atoms. The study indicates that connection atoms associated directly with multiple coordination centers are applicable to act as central atoms. This unique topology analysis approach is conceptually different from the current analytical methods which use node atoms as central atoms. In addition, complex 1 exhibits significant selective adsorption of CO2 over N-2. This study provides a great example of the topological analysis of MOFs with multiple coordination centers.