Abstract: 2-((pyridine-4-ylthio)methyl)pyridine and azide were applied as ligands for the atmospheric temperature volatilization self-assembly synthesis of one novel coordination compound 1D Co(C₁₁H₁₁N₂S)₂(N₃)_2n. According to result of single-crystal X-ray diffraction analysis, the compound crystallizes in the triclinic space group Pī. The compound exhibits a one-dimensional chain in which Co(Ⅱ) are alternatively linked by the double end-on (EO) and double end-to-end (EE) azide bridges. These chains are further interlinked by hydrogen bonds into a three-dimensional supermolecule architecture. The temperature dependence of the magnetic susceptibility measurement reveals the antiferromagnetic interaction among metal centers of the compound.