In this manuscript we report high level ab initio calculations [RI-MP2(full)/aug-cc-pVDZ] and experimental evidence that demonstrate that important synergistic effects between two relevant non covalent interactions that are omnipresent in biological systems, i.e., pi-pi and X-H/pi interactions (X = C,N,O), occur when the interactions coexist in the same complex. In particular, we study how the pi-pi interaction influences the X-H/pi interaction and vice versa by computing the genuine non additivity energies of the ternary X-H/p-p complexes.