The simultaneous cooperation of pi-pi stacking and pnicogen bonding the formation of Pyr parallel to X-PhPS2 perpendicular to pyr ternary complexes has been investigated via a computational chemistry at MP2/aug-cc-pVDZ level of theory. We proved by computational NMR data the effect of electron-withdrawing and donating substituents on (1P)J(N-P) across N-15 center dot center dot center dot P-31 pnicogen bond. The interaction energy contributions of Pyr parallel to X-PhPS2 and X-PhPS2 perpendicular to pyr dimers have been investigated by symmetry adapted perturbation theory (SAPT) energy decomposition method. In addition, atoms in molecules (AIM), natural bond orbital analysis (NBO) and molecular electrostatic potentials (MEP) have been performed to unveil the mechanism of these interactions in the title complexes.