Two new coordination polymers constructed with the 1,10-phenanthroline derivative 2-(2-chloro-6-fluorophenyl)-1H-imidazo[4,5][1,10]-phenanthroline (L) and different carboxylates, namely, [Cd-2(L)(2)(1,3,5-BTC)(Cl)]center dot H2O (1) and [Co-2(L)(2)(1,2,4,5-BTC)(H2O)(2)] (2), have been synthesized under hydrothermal conditions (1,3,5-BTC = 1,3,5-benzenetricarboxylate anion and 1,2,4,5-BTC = 1,2,4,5-benzenetetracarboxylate anion). Crystal data for 1: C47H25Cd2Cl3F2N8O7, triclinic, space group P (1) over bar, a = 10.1084(5), b = 14.9285(7), c = 15.2930(4) angstrom, alpha = 72.1050(10), beta = 86.160(2), gamma = 79.6000(10)degrees, V = 2159.88(16) angstrom(3), Z = 2. Crystal data for 2: C24H13ClCoFN4O5, triclinic, space group P (1) over bar, a = 7.4767(15), b = 10.094(2), c = 14.772(3) angstrom, alpha = 91.23(3), beta = 100.95(3), gamma = 106.57(3)degrees, V = 1045.8(4)angstrom(3), Z = 2. Their crystal structures have been determined by single-crystal X-ray diffraction analyses, and the compounds further characterized by physico-chemical and spectroscopic methods. In 1, each 1,3,5-BTC anion connects five Cd(II) atoms to form a double chain. These chains are extended into 2D supramolecular networks through pi-pi interactions. N - H center dot center dot center dot Cl N - H center dot center dot center dot O and O - H center dot center dot center dot N hydrogen bonding interactions further stabilize the network of 1. In 2, each 1,2,4,5-BTC anion bridges four Co(II) atoms to yield a chain. pi-pi interactions among adjacent chains result in a 2D supramolecular architecture.