The novel mononuclear complex PPh4-mer- [Fe-III(bpca)(3)(CN)(3)].H2O (1) [PPh4+ = tetraphenylphosphonium cation and bpca = bis(2-pyridylcarbonyl)amidate anion] and ladder-like chain compound {[Fe-III(bpca)(mu-CN)(3)Mn-II(H2O)(3)] [Fe-III(bpca)(CN)(3)]}.3H(2)O (2) have been prepared and characterized by X-ray diffraction analysis. Compound 1 is a low-spin iron(Ill) compound with three cyanide ligands in mer arrangement and a tridentate N-donor ligand building a distorted octahedral environment around the iron atom. Compound 2 is an ionic salt made up of cationic ladder-like chains {[Fe-III(bpca)(mu-CN)(3)Mn-II(H2O)(3)]}(+) and uncoordinated anions [Fe-III(bpca)(3)(CN)(3)](-). The magnetic properties of 2 correspond to those of a ferrimagnetic chain with significant intrachain antiferromagnetic coupling between the low-spin iron(III) centers and the high-spin manganese(II) cations. This compound exhibits ferrimagnetic ordering below 2.0 K.