The β-phase of the radical p-NCC6F4CNSSN (1β) crystallizes in the orthorhombic space group Fdd2 and orders as a canted antiferromagnet with TN = 36 K. Computational studies (B3LYP or M06-2X functional with the cc-pVTZ-PP(-F)+basis set) of the microscopic nearest-neighbour magnetic exchange coupling in 1β and in the hypothetical isomorphous phase of the selenium radical p-NCC6F4CNSeSeN (2β) revealed that replacement of S by Se should lead to a significant enhancement in the magnetic ordering temperature by ca. 20% (B3LYP) - 30% (M06-2X). Recrystallization of 2 from solution or via vacuum sublimation afforded only the known diamagnetic, dimeric phase, 2α. Computational studies indicated that both the molecular geometry and charge distribution for 1 and 2 are extremely similar and experimental approaches to form alloys of the general form 11-x2x were explored: attempts to cosublime 1 and 2in vacuo were unsuccessful, forming only 1β due to the low volatility of 2. Crystallization of pure 1 by solution evaporation was found to afford polymorph 1α (triclinic, P1̄) selectively, irrespective of the solvent employed (CH2Cl2, MeCN, PhMe or THF) but 1α transformed to 1β upon subsequent vacuum sublimation. Crystallization of 1 in the presence of 2 (up to 20 mol%) from solution evaporation was examined. At 20 mol% there was clear evidence for formation of both 1α and 2α as distinct crystallographic phases by powder X-ray diffraction (PXRD) but some evidence for doping of 2 into 1α at low concentration (≤15 mol percent) was observed. Attempts to sublime a sample of 10.920.1 led to phase separation with the isolation of needle-shaped crystals of pure 1β characterized by X-ray diffraction.