AbstractThe direct mixing of CoCl2, sodium 2,6‐pyridinedicarboxylate (Na2(2,6‐pda)), KSCN, and 1,2‐bis(4‐pyridyl)ethane (bpye) in water at the ambient temperature afforded purple crystals readily. The crystal structure, as determined by X‐ray diffraction crystallography, consists of discrete inorganic [Co2(η3‐2,6‐pda)2(μ‐SCN)2(H2O)2] and organic bpye molecules. Adjacent dicobalt molecules are connected via intermolecular hydrogen bonds, to form one‐dimensional hydrophobic channels in the solid state, which serve as a host framework to incarcerate bpye guests inside. Every organic molecule attaches to four adjacent inorganic species via arene‐arene interactions. The facile approach in assembling the dicobalt and bpye molecules together into an inorganic clat