Magic-number-like behavior in the ammonia constituents has been observed in mixed-ligand metal complexes M(+)(NH3)(m)(CH3OH)(n) prepared by reactions of several metal ions with ammonia-methanol binary clusters, using a laser ablation-molecular beam (LAMB) method. In typical cases it appears as the preponderance of ions with a certain number of ammonia constituents. It indicates preferred coordination and the metal-specific coordination number of ammonia ligands in the first coordination sphere in these mixed-ligand metal complexes in the gas phase.