Abstract: | The crystal structure of the first acesulfame–metal complex, namely tetraaquabis6‐methyl‐1,2,3‐oxathiazin‐4(3H)‐onato 2,2‐dioxide‐κN]cobalt(II), Co(C4H4NO4S)2(H2O)4], is reported. The CoII ion resides on a twofold axis and is coordinated by four aqua ligands defining the basal plane and by two monodentate acesulfamate ligands, via their ring N atoms, in the axial positions. Two intra‐ and three intermolecular hydrogen‐bonding interactions stabilize the crystal structure and form an infinite three‐dimensional lattice. |