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A new cobalt(II) coordination polymer containing 4,4′‐bipyridine and azide as bridging ligand, [CoII(4,4′‐bpy)(N3)2]n (1) was synthesized under mild hydrothermal conditions and was characterized by single‐crystal X‐ray diffraction studies and magnetic susceptibility measurements. It exhibits an acentric structure, in which cobalt(II) ions are linked through end‐to‐end (EE) azido groups. The 4,4′‐bpy ligands are coordinated on the axial positions of the octahedral environment reinforcing the intermetallic connections and resulting in a network. Circular dichroism spectra of the compound exhibit a maximum negative Cotton effect at 260 nm, which indicates the chiral nature of 1. Variable temperature magnetic susceptibility measurements in the temperature range 2–300 K reveal the existence of antiferromagnetic couplings in the framework.

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