1-(4-[N-tert-Butylaminoxyl]-2,3,5,6-tetrafluorophenyl)pyrrole (BNPPF4) was synthesized and characterized by X-ray crystallography, electron spin resonance (ESR), and magnetism. It is unusually stable by comparison to related systems. Its crystallography shows strong twisting of the nitroxide group, and dyad π-stacking that is probably assisted by fluoroarene/pyrrole interactions. There are crystallographic nitroxide chains of >5.5Å distance between nitroxides, and chains of nitroxide to tert-butyl contacts. BNPPF4 magnetic behavior is consistent with a spin-pairing model having 2J/k=(−)8.7±0.2K, but not with a simple 1D AFM chain model.