Bis(methylsulfamido) sulfone, SO2(NHSO2CH3)2 (1) is synthesized from imido-bis(sulfonylchloride) HN(SO2Cl)2 and bis(trimethylsilyl) methane CH2(Si(CH3)3)2 in trimethylchlorsilane solution. In the solid state there are two independent molecules linked by two N-H....O hydrogen bridges into infinite chains parallel to the b-axis. Bis(trifluoromethylsulfamido)sulfone, SO2(NHSO2CF3)2 (2) is formed by the reaction of trichlorophosphazo-sulfuryl trifuoromethane Cl3PNSO2CF3 with fluorosulfonic acid FSO3H. The molecules are bonded by bifurcated N-H....O bridges into infinite layers parallel to the [001] plane.