Abstract: | The reaction of the CuII and NiII complexes of saccharin with dicyandiamide (cyanoguanidine, cnge) in methanol produces the addition of methanol to the nitrile moiety of this molecule. Furthermore, the product of the reaction coordinates the metal centers generating two new complexes containing saccharinate as the counter anion. The crystal structures of [Cu(cnge‐OCH3)2](sac)2 and of [Ni(cnge‐OCH3)2](sac)2·2H2O (cnge‐OCH3 = 1‐amidino‐O‐methylurea) were solved by single crystal X‐ray diffractometry. Both complexes crystallize in the triclinic space group and the metallic cations present a quite similar centrosymmetric planar conformation. The complexes were characterized by means of electronic and infrared spectroscopy and also their magnetic and thermal behavior was investigated. |