Anhydrates and/or hydrates in nitrate, sulphate and phosphate salts of 4-aminopyridine, (4-AP) and 3,4-diaminopyridine (3,4-DAP): The role of the water molecules in the hydrates

Several salt forms of 4-aminopyridine and 3,4-diaminopyridine with nitric, sulfuric, and phosphoric acids, comprising anhydrates and some hydrates, have been prepared and structurally characterized, and the role of water assessed in the latter cases. Our study has confirmed that anhydrates can be obtained even when water is present in the crystallizing solution. Protonation of the aminopyridines is consistent with ΔpK_a differences. 4-Aminopyridine uniquely forms a mono cation only, with protonation at the pyridine nitrogen, whilst 3,4-diaminopyridine forms both a mono cation, again with protonation at the pyridine nitrogen, and a dication, with the second protonation at the 3-amino position. Thus, 4-aminopyridine forms a 1:1 nitrate anhydrate, a 1:1 bisulphate anhydrate, a 2:1 sulfate hydrate and a 1:1 dihydrogen phosphate hydrate. 3,4-Diaminopyridine forms a 1:1 nitrate anhydrate and 1:2 nitrate anhydrate and hydrate, 2:1 and 1:1 sulfate hydrates and a 1:1 dihydrogen phosphate anhydrate. Analysis of the structures found suggests that the H-bonding capability of the water O-H donors and O acceptor components have similar tendencies to N-H donors and other O acceptors. At the same time, we recognise that, whilst water molecules may occasionally be structure forming, they also act as spacers or fillers in the development of the primary H-bonded assemblies. These will mainly be controlled by the stoichiometries and H-bonding possibilities of the anion/cation components. It is also possible that, in some circumstances, the inclusion or otherwise of water in structures may be competitive with supplementary weak interactions such as C-H⋯O hydrogen bonding.