The ionic salts (p-rad) 2 [ReCl 6 ] (1) and (m-rad) 2 [ReCl 6 ] (2) (p/m-rad=2-(4/3-N-methylpyridinium)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl-3-N-oxide) have been prepared and their crystal structures determined by single-crystal X-ray diffraction. The nitronyl nitroxide cations in compound 1 show a layered disposition, whereas the [ReCl 6 ] 2− units are placed between these layers. The nitronyl nitroxide cations in compound 2 adopt an hexagonal array but they do not result in layers. Bulk magnetic properties of 1 and 2 have been investigated in the temperature range 2–300K. Both compounds show weak but significant intermolecular antiferromagnetic interactions.