Infrared (IR) photodissociation spectra of mass-selected aniline(+)-(N-2)(n) complexes with n less than or equal to 5, produced in an electron-impact (EI) cluster ion source, are presented in the range of the N-H stretch, vibrations of the aniline cation (An(+)). Analysis of the An(+)-N-2 spectrum is consistent with a H-bound structure in which the N-2 ligand forms a nearly linear hydrogen bond to one proton of the NH2 group of An(+). No other isomers are observed in the n = 1 spectrum, implying that H-bound An(+)-N-2 corresponds to the global minimum of the, dimer potential. This conclusion is supported by ab initio calculations at the UMP2/6-311G(2df,2pd) level, which predict H-bound An(+)-N-2 (De = 1431 cm(-1)) to be more stable than other local minima. Systematic vibrational frequency shifts in the spectra of the larger An(+)-(N-2) clusters provide information about the microsolvation process of An(+) in a quadrupolar solvent. The first two N-2 ligands fill a first subshell by solvating the protons of the amino group (H bonds), whereas further ligands bind to the aromatic ring of An(+) (7 bonds). Analysis of the photofragmentation branching ratios yields approximate dissociation energies of the H and pi bonds of D-0(H) similar to 1100 +/- 300 cm(-1) and D-0(pi) similar to 700 +/- 200 cm(-1), respectively.