Hydroxide
The hydroxides of the transition metals and post-transition metals usually have the metal in the +2 (M = Mn, Fe, Co, Ni, Cu, Zn) or +3 (M = Fe, Ru, Rh, Ir) oxidation state. None are soluble in water, and many are poorly defined. One complicating feature of the hydroxides is their tendency to undergo further condensation to the oxides, a process called olation. Hydroxides of metals in the +1 oxidation state are also poorly defined or unstable. For example, silver hydroxide Ag(OH) decomposes spontaneously to the oxide (AgO). Copper(I) and gold(I) hydroxides are also unstable, although stable adducts of CuOH and AuOH are known. The polymeric compounds M(OH) and M(OH) are in general prepared by increasing the pH of an aqueous solutions of the corresponding metal cations until the hydroxide precipitates out of solution. On the converse, the hydroxides dissolve in acidic solution. Zinc hydroxide Zn(OH) is amphoteric, forming the tetrahydroxidozincate ion in strongly alkaline solution.
Hydroxide
The amphoteric hydroxide Al(OH) has four major crystalline forms: gibbsite (most stable), bayerite, nordstrandite, and doyleite.
All these polymorphs are built up of double layers of hydroxide ions – the aluminium atoms on two-thirds of the octahedral holes between the two layers – and differ only in the stacking sequence of the layers. The structures are similar to the brucite structure. However, whereas the brucite structure can be described as a close-packed structure in gibbsite the OH groups on the underside of one layer rest on the groups of the layer below. This arrangement led to the suggestion that there are directional bonds between OH groups in adjacent layers. This is an unusual form of hydrogen bonding since the two hydroxide ion involved would be expected to point away from each other. The hydrogen atoms have been located by neutron diffraction experiments on α-AlO(OH) (diaspore). The O–H–O distance is very short, at 265 pm; the hydrogen is not equidistant between the oxygen atoms and the short OH bond makes an angle of 12° with the O–O line. A similar type of hydrogen bond has been proposed for other amphoteric hydroxides, including Be(OH), Zn(OH), and Fe(OH).