The minerals of the kröhnkite, talmessite and fairfieldite groups plus dondoellite, general formula X2M2+(TO4)2(H2O)2 where X = Na, Ca; M2+ = Mg, Fe, Mn, Co, Ni, Zn, Cu; and T = S, P, As; have been consolidated into the IMA-approved kröhnkite supergroup. The cell dimensions and space-group symmetries of the minerals in these three groups and dondoellite are distinct but the structures of these minerals are strongly related as they have topologically identical structural units. Differences in structure between the different groups involve the disposition of adjacent [M2+(TO4)2(H2O)2] chains and the stereochemical details of the hydrogen bonds that link adjacent [M2+(TO4)2(H2O)2] chains. The ions that form the interstitial complex of a mineral and the structural unit must satisfy the principle of correspondence of Lewis acidity–basicity whereby stable structures will form where the Lewis acidity of the structural unit closely matches the Lewis basicity of the interstitial complex. For pentavalent T cations (P5+or As5+), the Lewis acidity of Ca2+ shows the closest match of all cations to the Lewis basicity of the structural unit. For hexavalent T cations (S6+), the Lewis acidity of Na+ shows the closest match of all cations to the Lewis basicity of the structural unit.