A solid-state complex utilizing non-covalent interactions between two aromatic cations is synthesized and characterized. The X-ray study of the structure shows that the anion templated pi(+)-pi(+) interactions are the major driving force in the crystal packing, while pi(+)-pi, pi-pi, pi-anion and pi(+)-anion interactions assist the overall stabilization of self-assembly. In addition, we also identify the cation-mediated non-covalent interaction between two pi anions (pi(-)-pi(-) interaction). The interaction energies of the important driving forces (pi(+)-pi(+), pi(+)-pi, pi-anion, pi(+)-anion, and pi(-)-pi(-) interactions) observed in the crystal structure are calculated using dispersion-corrected density functional theory (DFT-D).