Eight novel coordination polymers based on the 6-methylpyridine-2,4-dicarboxylic acid N-oxide (MPDCO) ligand, [M(MPDCO)(H2O)x]n (M = Mn2+, x = 1 (1); M = Cu2+, x = 2 (2)), [M(MPDCO)(bpy)(H2O)·(H2O)]n (M = Co2+ (3), Ni2+ (4)), [M(MPDCO)(TPB)0.5(H2O)·(H2O)x]n (M = Co2+(5), Ni2+ (6), Zn2+ (7), Cd2+ (8)) (bpy = 4,4′-bipyridine, TPB = 1,2,3,4-tetra-(4-pyridyl)-butane) have been prepared and structurally characterized. Compounds 1 and 2 are both two-dimensional (2-D) layers, which are further stacked via strong interlayer hydrogen-bond interactions to form three-dimensional (3-D) supramolecular structures. Compounds 3 and 4, which contain 3-fold interpenetrating nets, are isostructural and feature 3-D (10,3)-d open frameworks. In isomorphous compounds 5–8, 2-D sheets with nonequivalent nodes of (42·62·82)(4·62)2 topology were constructed from metal cations, MPDCO, and the four-connecting ligand 1,2,3,4-tetra-(4-pyridyl)-butane (TPB). Then the inclined interpenetration of these 2-D sheets leads to 3-D porous arc...