The first excited neutral and ground cationic states of the 2-aminopyridine-argon van der Waals complex have been studied using a combination of (1 + 1') REMPI and ZEKE spectroscopy, supported by ab initio molecular orbital calculations. In addition to an updated ionisation energy of 65 265 +/- 3 cm(-1) an analysis of the intermolecular vibrational structure observed in both REMPI and ZEKE spectra supports an assignment to a pi-bound complex. The pyramidal conformation of the amino group in the electronic ground state allows for the possibility of anti and syn pi-bound conformers: this is discussed in the context of the related molecule, aniline-Ar. (C) 2004 Elsevier B.V. All rights reserved.