We report the supramolecular chemistry of several metal complexes of N-(4-pyridyl)benzamide (NPBA) with the general formula [M_a(NPBA)₂A_bS_c], where M = Co²⁺, Ni²⁺, Zn²⁺, Mn²⁺, Cu²⁺, Ag⁺; A = NO₃^-, OAc^-; S = MeOH, H₂O; a = 0, 1, 2; b = 0, 1, 2, 4; and c = 0, 2. NPBA contains structural features that can engage in three modes of intermolecular interactions:  (1) metal−ligand coordination, (2) hydrogen bonding, and (3) π−π stacking. NPBA forms one-dimensional (1-D) chains governed by hydrogen bonding, but when reacted with metal ions, it generates a wide variety of supramolecular scaffolds that control the arrangement of periodic nanostructures and form 1- (2−4), 2- (5), or 3-D (6−10) solid-state networks of hydrogen bonding and π−π stacking interactions in the crystal. Isostructural 7−9 exhibit a 2-D hydrogen bonding network that promotes topotaxial growth of single crystals of their isostructural family and generates crystal composites with two (11) and three (12) different components. Furthermore, 7−9 can also form crystalline solid solutions (M,M‘)(NPBA)₂(NO₃)₂(MeOH)₂ (M, M‘ = Co²⁺, Ni²⁺, or Zn²⁺, 13−16), where mixtures of Co²⁺, Ni²⁺, and Zn²⁺ share the same crystal lattice in different proportions to allow the formation of materials with modulated magnetic moments. Finally, we report the effects that multidimensional noncovalent networks exert on the magnetic moments between 2 and 300 K of 1-D (4), 2-D (5), and 3-D (7, 8, 10, and 13−16) paramagnetic networks.