The structural and electronic properties of two high-spin iron (III) Schiff-base complexes [(imd)Fe(salen)(NCS)] (I) and [(imd)Fe(salen)(N₃)] (II) are described. Crystals ofI as a hemimethanol solvate, (C₃H₄N₂)Fe(C₁₆H₁₄N₂O₂)(NCS). 0·5 CH₃OH, crystallize in the triclinic space group$$P\bar 1$$ with unit cell dimensionsa=14·278(4),b=16·932(4),c=9·057(4) Å, α=97·40(3), β=92·07(3), γ=85·32(2)° andZ=4. The structure was refined by a block-matrix least-squares procedure to finalR 0·050 andR_w 0·057 using 3127 unique reflections with I>2·5 σ(I). Complex I is one of the few structurally characterized examples of six-coordinate Lewis-base adducts in which there are two different axial ligands. The in-plane Fe-N distances, 2·12 Å (av) are characteristic ofS=5/2 Fe^III. The Fe-N (imidazole) distance of 2·149(5) Å is similar to that in related high-spin imidazole-Fe^III complexes. Non-linear Fe-NCS bonding is observed (Fe-N-C=159·0(5)°) as in related six-coordinate Fe^III porphyrin and methemoglobin isothiocyanate species. Mössbauer spectra ofI andII between 295 and 4·2 K are symptomatic ofS=5/2 Fe^III. The nature of the asymmetry of the quadrupole doublet as a function of temperature points to zero field splitting of the⁶A₁ ground state having a negative value of the axial ZFS parameter,D. These are new additions to the few known examples of negativeD in Fe^III-tetradentate chelating systems, and contrast for instance with aquo-imidazole Fe^III salen adducts which we have recently shown to have positiveD values. Spin-hamiltonian analyses of the 300-4·2 K_χFe/T data, assuming rhombic ligand field symmetry, yielded the following parameter sets;I:g=1·98±0·02,D=−2·4±0·2 cm⁻¹,E=0·6±0·2 cm⁻¹.II:g=2·00±0·01,D=−1·4±0·2 cm⁻¹,E=0·4±0·2 cm⁻¹. In the 77 KX-band ESR spectra of neat powdered samples ofII: a line atg=4·4 confirms the rhombic splitting, while the related spectrum forI shows a broad line atg∼2·1. This somewhat unusual line position probably arises through solid state exchange effects since ag 4·3 signal is observed for a frozen glass spectrum.