Reversible solid-state reaction between 18-Crown[6] and M[H2PO4](M = K, Rb, Cs) and an investigation of the decomplexation process.

On heating the hydrated complexes 18-Crown[6].M[H(2)PO(4)].xH(2)O (x= 2 for M = K, Rb; x= 1.5 for M = Cs), quantitatively prepared by mechanical mixing of crystalline 18-Crown[6] and M[H(2)PO(4)], to ca. 60 degrees C, water loss takes place, accompanied by the extrusion of the crown ether from the crystalline complex and followed by reconstruction of the inorganic phase M[H(2)PO(4)](M = K, Rb, Cs); the resulting solid mixture reverts to 18-Crown[6].M[H(2)PO(4)].xH(2)O (x= 2 for M = K, Rb; x= 1.5 for M = Cs) upon grinding in air.