The solvation energies of the pyridine(center dot+) radical cation by 1-4 H2O molecules were determined by equilibrium measurements in a drift cell. The binding energies of the pyridine(center dot+)(H2O)(n) clusters are similar to the binding energies of protonated pyridine-water clusters, (C5H5NH+)(H2O)(n), which involve NH+center dot center dot OH2 bonds and different from those of the solvated benzene radical cation-water clusters, C6H6 center dot+(H2O)(n), which involve CH delta+center dot center dot OH2 bonds. These relations indicate that the observed pyridine(center dot+) ions have the distonic (C5H4NH+)-C-center dot structures that can form NH+center dot center dot OH2 bonds. The observed thermochemistry and ab initio calculations show that these bonds are not affected significantly by an unpaired electron at another site of the ion. Similar observations also identify the 2-fluoropyridine(center dot+) distonic ion. The distonic structure is also consistent with the reactivity of pyridine(center dot+) in H atom transfer, intra-cluster proton transfer and deprotonation reactions. The results present the first measured stepwise solvation energies of distonic ions, and demonstrate that cluster thermochemistry can identify distonic structures.