Abstract 4,4′-Dichloro-3,3′-diquinolinyl sulfide 3 underwent ring closure reactions with divalent nucleophiles to pentacyclic heterocycles: dithiin 4, thiopyran 5, thiazine 6, oxathiin 7 and thiaselenin 8 in good yield (76–100%). The chemical shift of the H-1 and H-13 protons in 1H NMR spectra is a result of the interaction between these atoms and the Z-atom.