Three groups of minerals are discussed, which are typified by pyroaurite and sjögrenitc, hydrocalumite, and ettringite. All show interesting structural features. In the pyroaurite-sjögrenite group, brucite-likc layers carrying a net positive charge alternate with layers in which the oxygen atoms of carbonate groups and water molecules are statistically distributed on a single set of sites; other anions may replace the carbonate, especially in synthetic phases. Hydrocalumite and related synthetic phases also have layer structures in which positively charged main layers alternate with intermediate layers containing anions and water molecules; the anions occur in cavities and their nature can again vary widely. In the ettringite group, the structures are based on positively charged columns, between which occur channels containing anions and sometimes also water molecules. This group includes thaumasite, the only natural mineral known to contain silicon six-coordinated by oxygen that is not a high-pressure phase. The thermal dehydration behaviour in each group is briefly considered.