Crystal structure, paramagnetic anisotropy, and zero-field splitting in intermediate-spin chlorobis(NN-di-isopropyldithiocarbamato)iron(III)–chloroform (1/1)

Abstract

The crystal structure of the title complex has been determined by single-crystal X-ray diffraction at 295(1) K and refined by least-squares procedures to R 0.072 for 4 066 observed reflections. Crystals are triclinic, with space group P, unit-cell dimensions a= 1 350.5(5), b= 1 070.6(3), c= 986.2(3) pm, α= 96.12(2), β= 93.13(2), γ= 108.72(2)°, and Z= 2. The molecular structure is similar to those observed in other [FeX(S₂CNR₂)₂] derivatives, the iron atom lying in a pseudo-square-pyramidal environment with apical Cl [Fe–Cl 228.1(3), mean Fe–S 228_.7 pm]. The lattice contains a chloroform solvent molecule with occupancy 0.8₇. The magnetic anisotropy has been studied in the range 80–300 K. The rhombic molecular anisotropies have been deduced following the method of Ghose, and found to be similar to those of [FeCl(S₂CNEt₂)₂], their signs establishing a ⁴A₂ ground state. The zero-field splitting parameters have been deduced from the experimental data, and found to be consistent with previous e.s.r. studies.