Peculiar magnetic behavior was found for 1D-polymeric seven coordinate pentagonal bipyramidal Fe(II) complex {[Fe(L)(mu(1,3)-N-3)](ClO4)}(n) (1) with a pentadentate macrocyclic ligand L (3,12,18-triaza-6,9-dioxabicyclo[12.3.1]octadeca-1(18),14,16-triene) coordinated in the pentagonal equatorial plane and with end-to-end bridging azido ligands in axial positions. The static and dynamic magnetic data revealed that spin-canting in the 1D-chain of 1 results in the single-chain magnet (SCM) behavior with high spin-reversal energy barrier U-eff (Delta(tau)) = 87.S K, exhibiting magnetic hysteresis below 4 K and coexistence with the metamagnetism altogether resulting in weak 3D-ferromagnetic behavior. This is the first reported example of the exclusively azido-bridged homospin Fe(II)-based SCM.