Two isomorphous series including the adducts trans-[PdI₂(CNC₆H₄-4-X)₂]·2I₂ [(1-3)·2I₂; X = Cl 1, Br 2, I 3] and the complexes cis-[PdCl₂(CNC₆H₄-4-X)(PPh₃)] (4-6; X = Cl 4, Br 5, I 6) were characterized by X-ray crystallography. Inspection of the X-ray diffraction data allowed the identification of halogen-bonding C-X···I-I in (1-3)·2I₂ and C-X···Cl-[Pd] in 4-6 thus providing a rare example of the triple Cl/Br/I exchange of σ-hole donating halogens. In accord with the conducted theoretical considerations, the strength of these XBs are in the range of 0.9-2.8 kcal/mol, and these contacts are of a noncovalent nature. The calculated maximum electrostatic potentials on the σ-hole donating X centers of CNC₆H₄-4-X on the 0.001 au molecular surfaces for both (1-3)·2I₂ and 4-6 series are increased along with the decrease of relative XB lengths. These data are consistent with Politzer and co-workers conclusions that are based exclusively on theoretical ground.