Six coordination compounds constructed by two structurally related flexible nitrogen-containing polycarboxylate ligands 2,2'-(2,2'-(ethane-1,2-diylbis(oxy))bis(2,1-phenylene))bis(methylene)bis(azanediyl)dibenzoic acid (H(2)L1) and 5,5'-(2,2'-(ethane-1,2-diylbis(oxy))bis(2,1-phenylene))bis(methylene)bis(azanediyl)diisophthalic acid (H(4)L2) have been synthesized: [Ni(H2O)(6)] center dot L1 center dot (C2H5OH)(0.5) center dot H2O (1), [Co(L1)(L3)] center dot CH3OH (2), [Ni(L1)(L3)] center dot CH3OH (3), [Zn(L1)(L3)] center dot CH3OH (4), [Cd(L1)(L3)] center dot CH3OH (5), and [Zn(L2)(0.5)(phen)] center dot C2H5OH (6), where L3 = 3,4 : 9,10 : 17,18 : 23,24-tetrabenzo-1,12,15,26-tetraaza-5,8,19,22-tetraoxacyclooctacosan and phen = 1,10-phenanthroline. The crystal structures have been determined by single-crystal X-ray diffraction. Compound 1 displays a discrete structure, which is further linked by hydrogen bonds to form a 2-D supramolecular layer. Compounds 2-5 display similar structures. These compounds possess 1-D meso-chain structures linked by L1 and metals. The C-H center dot center dot center dot pi interactions from neighboring chains extend the chains in different directions, giving a 3-D plywood network. Compound 6 possesses 2-D layers, which are further linked by hydrogen-bonding interactions to generate a 3-D supramolecular architecture.