A series of penta-coordinate bis(N,N-dialkyldithiocarbamato) iron (III) halides have been prepared in which the ground iron (III) term is an orbital singlet and spin quartet. The quartet ground term results from the low symmetry (C2v) local environment of the iron. The Mössbauer technique was employed to study several homologues closely related to the basic unit, bis(N,N-diethyldithiocarbamato) iron (III) chloride, which exhibits a ferromagnetic ordering at low temperatures (TC= 2.5°K). While the paramagnetic character of the ground quartet remains independent of small structural changes, no new magnetically ordered systems were found. However, low-temperature Mössbauer data show that the small zero-field splitting of the quartet manifold is markedly affected by the halo-constituent of the penta-coordinate complex. Effects of a small external polarizing field on the Mössbauer spectra of these complexes is also considered.