Crystal Structures of Triazine-3-thione Derivatives by Reaction with Copper and Cobalt Salts

The reaction of 5-methoxy-5,6-diphenyl-4,5-dihydro-2<i>H</i>-[1,2,4]triazine-3-thione <b>L</b><b><sup>1</sup></b><sup></sup><b>H</b><b><sub>2</sub></b><b>OCH</b><b><sub>3</sub></b> with copper(II) chloride leads to the formation of an organic molecule <b>L</b><b><sup>2</sup></b><sup></sup> containing two triazine rings linked by a new S−S bond. A binuclear copper(II) complex, <b>1</b>, containing <b>L</b><b><sup>1</sup></b><sup></sup> is also isolated. The reaction of <b>L</b><b><sup>1</sup></b><sup></sup><b>H</b><b><sub>2</sub></b><b>OCH</b><b><sub>3</sub></b> with copper(I) chloride yields a hexanuclear cluster of copper(I), <b>2</b>, in which the copper atoms form a distorted octahedron with the ligand <b>L</b><b><sup>1</sup></b><sup></sup> acting as an NS chelate and sulfur bridge, giving to the copper ion a trigonal geometry by one N and two S atoms. In any reaction of the disulfide <b>L</b><b><sup>2</sup></b><sup></sup> with metal salts, complexes containing this molecule are isolated. Reactions with copper(I) and copper(II) chloride and nickel(II) and cadmium(II) nitrate produce the S−S bond cleavage, giving complexes containing the triazine <b>L</b><b><sup>1</sup></b><sup></sup> behaving as the NS anion, which show spectroscopic characteristics identical with those formed by reaction with <b>L</b><b><sup>1</sup></b><sup></sup><b>H</b><b><sub>2</sub></b><b>OCH</b><b><sub>3</sub></b>. However, the reaction with cobalt(II) nitrate gives a low-spin octahedral cobalt(III) complex, in which an asymmetric rupture of the disulfide <b>L</b><b><sup>2</sup></b><sup></sup> has been produced, giving an unexpected complex with a new ligand and keeping the S−S bond.