A new cyanide-bridged FeIII–MnII heterobimetallic coordination polymer (CP), namely catena-poly[[[N,N′-(1,2-phenylene)bis(pyridine-2-carboxamidato)-κ4
N,N′,N′′,N′′′]iron(III)]-μ-cyanido-κ2
C:N-[bis(4,4′-bipyridine-κN)bis(methanol-κO)manganese(II)]-μ-cyanido-κ2
N:C], {[FeMn(C18H12N4O2)(CN)2(C10H8N2)2(CH3OH)2]ClO4}
n
, (1), was prepared by the self-assembly of the trans-dicyanidoiron(III)-containing building block [Fe(bpb)(CN)2]− [bpb2− = N,N′-(1,2-phenylene)bis(pyridine-2-carboxamidate)], [Mn(ClO4)2]·6H2O and 4,4′-bipyridine, and was structurally characterized by elemental analysis, IR spectroscopy, single-crystal X-ray crystallography and powder X-ray diffraction (PXRD). Single-crystal X-ray diffraction analysis shows that CP 1 possesses a cationic linear chain structure consisting of alternating cyanide-bridged Fe–Mn units, with free perchlorate as the charge-balancing anion, which can be further extended into a two-dimensional supramolecular sheet structure via inter-chain π–π interactions between the 4,4′-bipyridine ligands. Within the chain, each MnII ion is six-coordinated by an N6 unit and is involved in a slightly distorted octahedral coordination geometry. Investigation of the magnetic properties of 1 reveals an antiferromagnetic coupling between the cyanide-bridged FeIII and MnII ions. A best fit of the magnetic susceptibility based on the one-dimensional alternating chain model leads to the magnetic coupling constants J
1 = −1.35 and J
2 = −1.05 cm−1, and the antiferromagnetic coupling was further confirmed by spin Hamiltonian-based density functional theoretical (DFT) calculations.