Bis(methylsulfonamido) sulfone, C(2)H(8)N(2)O(6)S(3) or SO(2)(NHSO(2)CH(3))(2), was synthesized from imidobis(sulfonyl chloride), HN(SO(2)Cl)(2), and bis(trimethylsilyl)methane, CH(2)[Si(CH(3))(3)](2), in chlorotrimethylsilane 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. The central S atoms of the independent molecules each lie on a twofold axis. Bis(trifluoromethylsulfonamido) sulfone, C(2)H(2)F(6)N(2)O(6)S(3) or SO(2)(NHSO(2)CF(3))(2), was formed by the reaction of trichlorophosphazosulfuryl trifluoromethane, Cl(3)PNSO(2)CF(3), with fluorosulfonic acid, FSO(3)H. The molecules are connected by bifurcated N-H...O bridges into infinite layers parallel to the [001] plane. The central S atom lies on a twofold axis.