Novel Copper(II) Thiodibenzoic Acid Coordination Polymers by in situ Extrusion of Sulfur from 2,2′‐Dithiodibenzoic Acid and the Unique Oxidation of Disulfide to Sulfate

Slow diffusion reaction of 2,2′‐dithiodibenzoic acid (dtdb) with CuCl 2 in the presence of N‐donor ligands results in the formation of different coordination polymers where both S–S and C–S scission and oxidation of S is observed. X‐ray diffraction analysis of [Cu(tdb)(phen)(H 2 O)] 2 · 2H 2 O.2DMF] ( 1 ), [Cu(tdb)(py) 2 (H 2 O)] 2 ( 3 ), and [Cu(tdb)(bipy)(H 2 O)] 2 · 0.5H 2 O ( 4 ) (tdb = thiodibenzoic acid, phen = phenanthroline, py = pyridine, bipy = 2,2′‐bipyridine) show that the metal ions are coordinated to the carboxylate oxygen atoms of the in situ generated tdb ligand in a monodenate fashion. In [Cu(phen)(SO 4 ) 2 (H 2 O) 2 ] n ( 2 ) and [Cu(bipy)(SO 4 ) 2 (H 2 O) 2 ] n ( 5 ), the sulfur is oxidized to sulfate ions prior to coordination with the metal. Complex 1 has a dimeric structure with π–π interactions between the phen ligands, whereas 3 and 4 form 1D polymeric chains.