A new paramagnetic ligand, betaDTDA, and its coordination complex with Fe(hfac)2 are reported (betaDTDA = 4-(benzothiazol-2'-yl)-1,2,3,5-dithiadiazolyl; hfac = 1,1,1,5,5,5-hexafluoroacetylacetonato-). The neutral radical betaDTDA is the first dithiadiazolyl ligand designed to include an electropositive sulphur moiety outside the thiazyl heterocycle, increasing the capacity for supramolecular, structure-directing electrostatic contacts and enabling new pathways for magnetic exchange. The Fe(hfac)2(betaDTDA) complex is composed of a hs-Fe(ii) center with the three bidentate ligands arranged about the ion in a distorted octahedral 6-coordinate environment. The magnetic properties of crystalline Fe(hfac)2(betaDTDA) are consistent with strong antiferromagnetic (AF) coupling between the metal and ligand moments, giving rise to a well-defined Stotal = 3/2 ground state that is the only thermally populated state below 40 K. Below 4 K, this complex exhibits slow relaxation of the magnetization detected by ac susceptibility measurements consistent with a single-molecule magnet (SMM) behaviour.