The early lanthanide benzenefluorothiolates (Ln(SC6F5)(3); Ln = La, Ce, Pr, Nd, Sm, Gd) react with Hg(SC6F5)(2) in DIVE to form ionic heterometallic compounds with Ln cations and Hg anions. X-ray diffraction analyses of all compounds reveal an isostructural series with the general formula [(DME)(3)Ln(SC6F5)(2)](2)[Hg-2(SC6F5)(6)]. In the structures, a fluorothiolate ligand has been extracted from the Ln coordination sphere that is saturated with three neutral DME donor ligands and a dative interaction between one ortho fluorine and the Ln. Distances between Ln and F do not vary simply with Ln ionic radius. There are two Ln cations with charge balanced by a Hg-2(SC6F5)(6) dianion composed of two distinctly nonideal Hg(II) tetrahedra, all connected through a series of pi-pi interactions that link cations with anions in a one-dimensional array and anions to anions in a more complex 2D network.