AbstractThe crystal structure of pyridinium 6-methyl-1,2,3,-oxathiazine-4(3H)-one-2,2-dioxide [(C5NH6)(C4H4NO4S)], for short, pyH(ace), was determined by X-ray diffraction methods. It crystallizes as a twin in the monoclinic space group P21/c with a=6.9878(9), b=7.2211(7), c=21.740(2) Å, β=91.67(1)° and Z=4 molecules per unit cell. The structure was determined employing 1599 reflections with I>2σ(I) from one of the twin domains and refined employing 2092 reflections from both crystal domains to an agreement R1 factor of 0.0466. Besides electrostatic attractions, intermolecular pyH···O=C(ace) hydrogen bonds stabilize the acesulfamate anion and the pyridinium cation into planar discrete units parallel to the (100) crystal plane. The units form stacks of alternating ace− and pyH+ ions along the a axis that favors inter-ring π–π interactions. The Fourier transform-infrared (FT-IR) spectrum of the compound was recorded and is briefly discussed. Some comparisons with related pyridinium saccharinate salts are also made.