Reaction of manganese(II) with the electron-deficient ligand 3,6-bis(4-pyridyl)-1,2,4,5-tetrazine (pbptz) leads to distinct coordination networks whose topologies are influenced by the nature of the anions used. As anticipated, the linear ditopic ligand pbptz is involved in various types of supramolecular π interactions, i.e. π⋯π, lone pair⋯π and C–H⋯π interactions, which clearly play a role in the formation of the different solid-state architectures obtained, as shown by DFT calculations.