The title bis-piperidine, C26H28N2O3, was unexpectedly obtained via a dimerization mechanism promoted by acetic acid when performing the Dieckmann cyclization of a chiral amido ester. The S,S configuration was assigned by reference to the enanti-omerically pure starting material. In the mol-ecule, two core heterocycles are linked by a σ bond. One ring includes a keto-enol group, while the other presents an enone functionality. Both rings present a conformation inter-mediate between envelope and screw-boat, and the dihedral angle between the mean planes passing through the rings [48.9 (1)°] is large enough to avoid hindrance between ring substituents. The enol tautomeric form in one ring favors the formation of strong inter-molecular O-H⋯O=C hydrogen bonds. The resulting one-dimensional supra-molecular structure features single-stranded helices running along the 21 screw axis parallel to [100].