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 π⁺–π⁺ interactions are the major driving force in the crystal packing, while π⁺–π, π–π, π–anion and π⁺–anion interactions assist the overall stabilization of self-assembly. In addition, we also identify the cation-mediated non-covalent interaction between two π anions (π⁻–π⁻ interaction). The interaction energies of the important driving forces (π⁺–π⁺, π⁺–π, π–anion, π⁺–anion, and π⁻–π⁻ interactions) observed in the crystal structure are calculated using dispersion-corrected density functional theory (DFT-D).

A two component new coordination complex having formula {[Mn(phen)₂Cl(H₂O)]⁺ [Mn(phen)(btc)(H₂O)₃]⁻(CH₃OH)·2(H₂O)} (1) [btc = 1,3,5-benzenetricarboxylate trianion; phen = 1,10-phenanthroline] has been synthesized and characterized by X-ray single crystal structure, which reveals that one of the components is positively charge and the other is negatively charged. Complex 1 is a rare example of a coordination complex consisting of coordination ion pairs. The btc containing anionic subunits give rise to a 3D supramolecular host based on a coordination driven hydrogen bonding synthon. Cationic subunits occupy the 1D channels of the anionic supramolecular host.