Abstract: | Two coordination polymers {Cd(phen)](C6H8O4)3/3} ( 1 ) and {Cd(phen)](C7H10O4)3/3} · 2H2O ( 2 ) were structurally characterized by single crystal X‐ray diffraction methods. In 1 (C2/c (no. 15), a = 16.169(2)Å, b = 15.485(2)Å, c = 14.044(2)Å, β = 112.701(8)°, U = 3243.9(7)Å3, Z = 8), the Cd atoms are coordinated by two N atoms of one phen ligand and five O atoms of three adipato ligands to form mono‐capped trigonal prisms with d(Cd‐O) = 2.271‐2.583Å and d(Cd‐N) = 2.309, 2.390Å. The Cd(phen)] moieties are bridged by adipato ligands to generate {Cd(phen)](C6H8O4)3/3} chains, which, via interchain π—π stacking interactions, are assembled into layers. Complex 2 (P1¯(no. 2), a = 9.986(1)Å, b = 10.230(3)Å, c = 11.243(1)Å, α = 66.06(1)°, β = 87.20(1)°, γ = 66.71(1)°, U = 955.7(2)Å3, Z = 2) consists of {Cd(phen)](C7H10O4)3/3} chains and hydrogen bonded H2O molecules. The Cd atoms are pentagonal bipyramidally coordinated by two N atoms of one phen ligand and five O atoms of three pimelato ligands with d(Cd‐O) = 2.213—2.721Å and d(Cd‐N) = 2.329, 2.372Å. Through interchain π—π stacking interactions, the {Cd(phen)](C7H10O4)3/3} chains resulting from Cd(phen)] moieties bridged by pimelato ligands are assembled in to layers, between which the hydrogen bonded H2O molecules are sandwiched. |