The barium sulfonate network presented herein, [[Ba2(L)(H2O)5]Cl]infinity (1), represents the first metal sulfonate compound to possess a cationic framework. The network is layered with channels between pillaring ligands in which chloride ions reside. Compound 1 contracts slightly upon dehydration but retains its overall structural motif to 420 degrees C. Significantly, the chloride ions of the structure can be exchanged in 80% yield for fluoride ions in a facile manner. This exchange is quantified by elemental analyses, gravimetric determination, and 19F NMR spectroscopy. Confirmation of retention of structure is provided by standardized powder X-ray diffraction experiments. This last point is notable as the F-analogue of the structure is not attainable by a direct synthesis. These results illustrate one of the hallmark features of supramolecular chemistry, that a robust and functional framework can result through cooperative interactions between more weakly interacting units.