Thiazolo[5,4-d]thiazole-2,5-dicarboxylic acid, C6H2N2O4S2, and its coordination polymers

Thiazolo[5,4-d]thiazole-2,5-dicarboxylic acid, C6H2N2O4S2, was isolated as a polycrystalline material, and its crystal structure was determined by ab-initio X-ray powder diffraction (XRPD) methods. This species, upon deprotonation, was subsequently used in preparing the new coordination polymers Ag2(C6N2O4S2), Mn(C6N2O4S2)(H2O)2, Co(C6N2O4S2)(H2O)2, Cu(C6N2O4S2)(H2O) and Zn(C6N2O4S2)(H2O)2, fully characterized by analytical, thermal and XRPD structural methods - including in situ thermodiffractometry and simultaneous TGA and DSC. In the first-row transition metal derivatives, the [C6N2O4S2]2- anion systematically prefers the N,O-chelating, vs. the expected O,O′-bridging, coordination mode, not allowing the formation of porous 3D frameworks. Indeed, these species are dense 1D coordination polymers. At variance, the silver derivative possesses a complex, dense 3D framework, due to the presence of μ6-[C6N2O4S2]2- ligands showing two μ2-bridging carboxylates and two monohapto N-donor sites. When dehydration is viable, materials of En(C6N2O4S2) formulation are irreversibly recovered (n = 1 for E = Mn, Co, Zn, Cu; n = 2, for E = H).