[18-Crown-6 Na](2)S2O4 complex was prepared in methanol solution but dissociates into 18-Crown-6 ((s)) and Na2S2O4 ((s)) on removal of the solvent. Evidence for complexation in methanol is supported by a quantitative mass analysis and the dissociation in the solid state by vibrational spectroscopy and powder X-ray diffraction. These observations are accounted for by investigating the energetics of complexation in solution and dissociation in the solid state using calculated density functional theory (DFT) gas phase binding enthalpies and free energies combined with conductor-like screening model (COSMO) solvation energies and lattice enthalpy and free energy terms derived from volume based thermodynamics (VBT). Our calculations show that complexation of alkali metal dianion salts to crown ethers are much less favorable than that of the corresponding monoanion salts in the solid state and that the formation of alkali metal crown complexes of stable simple oxy-dianion (e.g., CO32-, SO42-) salts is unlikely. The roles of complexation with 18-Crown-6 and ion pair formation in the process of dissolution of Na2S2O4 to methanol are discussed.