A remarkable twosome: Four-coordinate square-planar complexes based on [Zn(salen)] derivatives are conveniently captured inside a crystal matrix using a supramolecular protecting strategy (see figure). The four-coordinate species is accompanied by a five-coordinate complex that binds an axial ligand able to hydrogen bond to an N-heterocycle positioned in the axial region of the coordinative unsaturated derivative. The size of the N-heterocycle is a decisive stabilization parameter.