Four novel coordination polymers, [Mn2(cptc)(2,2′-bpy)(H2O)]·H2O (1), [Mn2(cptc)(phen)(H2O)]·H2O (2), Mn4(cptc)2(phen)4(H2O)2]·3H2O (3) and [Cd2(cptc)(H2O)3] (4) (H4cptc = cyclopentane-1,2,3,4-tetracarboxylic acid, 2,2′-bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline), have been synthesized by hydrothermal reactions of flexible (1S,2S,3R,4R)-H4cptc with MnCl2/CdCl2. By breaking the mirror plane of symmetry, the meso-cptc ligand is successfully converted into two pairs of enantiomers, the (1R,2S,3S,4R)- and (1S,2R,3R,4S)-cptc groups in 1–3 are unprecedented while the documented (1R,2R,3R,4S)- and (1S,2S,3S,4R)-cptc enantiomers exhibit an unprecedented μ6-mode in 4. Layered 1 and 2 show similar structures and are constructed by centrosymmetric tetranuclear units. 3 is a binodal (3,4)-connected layer with Schlafli symbols of (53)2(54·82), in which cptc exhibits two types of μ5-mode bonding. 4 has a 3-D pillar layered structure composed of neutral [Cd(cptc)]n layers and octahedral CdO6 pillars. The presence probability of different enantiomers is in agreement with the relative stability of different conformations of cptc calculated by time-dependent density functional theory (TD-DFT).