Template synthesis is a gateway to some of coordinating agents or organic compounds, which cannot be obtained by usual methods. A real interest for coordination chemistry shows bis(salicylidene)-S-methylisothiosemicarbazide (H2L), an organic compound close to salen type ligands which are widely used in the synthesis of single molecule magnets. Therefore this one represents a potential precursor for the synthesis of new magnetic materials. The template synthesis of H2L takes place in the presence of 3d metal ions (Ni2+, Cu2+, VO2+) [1, 2]. The final step supposes the demetallation of intermediate compounds with HCl gas. At the one of the stages of demetallation an intermediate form double-protonated H2L·2HCl appears [3]. The neutralization with sodium acetate of double protonated intermediate leads to the free linear H2L ligand [4]. Obviously, it is important by theoretical and practical point of view to determine the structure of the intermediate H2L·2HCl. X-ray diffraction study, carried out on single crystal, obtained by recrystallization from methanol of H2L·2HCl, shows the separation of the compound with the formula H2L·HCl·CH3OH. This represents a mono-protonated form of bis(salicylidene)S-methylisothiosemicarbazide where thiosemicarbazidic fragment is involved in the formation of a triazole ring (Figure). NMR spectroscopic studies (1H-NMR, 13C-NMR and 1H-COSY-NMR) of this show that the structure keeps cyclic form also in solution. Decyclization takes place only after neutralizing of H2L·2HCl or H2L·HCl·CH3OH intermediates with alkaline agents. These results complete knowledge of template synthesis of H2L ligand, stereodynamic changes in the configuration during of demetallation or formation of the coordination compounds with metals, which do not manifest template properties.