Coordination compounds with a 4,4'-azobis(pyridine) (azpy) ligand, {[M-2(azpy)(6)(H2O)(5)](.)4PF(6)(.)azpy-H2O}(n) (M = Ni-II, (1) or Co-II (2)) (0-dimensional (0-D) dimer), {[Zn(azpy)(3)(H2O)(2)](.)2PF(6)(.)2azpy-4H(2)O}(n) (3) (1-dimensional (1-D) fishbone-type chain), {[Ag(azpy)](PF6)-P-.}(4) (1-D linear chain), {[Mn(NCS)(2)(azpy)(2)](.)azpy}, (5) (2-dimensional (2-D) grid sheet), and {[Ni(NCS)(2)(azpy)(2)](.)3toluene}, (6) (2-D grid sheet), were synthesized and structurally characterized. Compounds 1 and 2 have a 0-D dimer motif, in which one M-II (M-II = N-II or Co-II) coordination site is shared by unidentate azpy and H2O ligands, each with half-occupancy, i.e., exhibiting static disorder. Compounds 3 and 4 afford 1-D fishbone-type and 1-D linear chain motifs, respectively. Azpy mediates pi-pi and pi-p interactions between these low-dimensional structures. Compounds 5 and 6 possess a 2-D grid sheet motif. These sheets assemble to form microporous frameworks that incorporate aromatic guests, such as coordination-free azpy (5) and toluene (6), There exist not only pi-pi and pi-p interactions but also CH-pi interactions between the framework azpy ligands and guests. It should be noted that the azpy ligand is a good candidate for the construction of new assembling systems of coordination compounds through its aromatic interactions.