Supramolecular derivatives of chlorostannate(IV) and -plumbate(IV) with {Cl-2} units, Cat(2){[MCl6](Cl-2)(x)} (1-5; M = Sn, Pb, cat = 1-methylpyridinium (1-MePy), tetramethylammonium (TMA)) were prepared and characterized by X-ray diffractometry and Raman spectroscopy. In particular, the TMA-containing complexes demonstrate remarkable thermal stability, releasing Cl-2 only at elevated temperatures.