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-2H-[1,2,4]triazine-3-thione L1H2OCH3 with copper(II) chloride
leads to the formation of an organic molecule L2 containing two triazine rings linked by a new S−S bond. A
binuclear copper(II) complex, 1, containing L1 is also isolated. The reaction of L1H2OCH3 with copper(I) chloride
yields a hexanuclear cluster of copper(I), 2, in which the copper atoms form a distorted octahedron with the ligand
L1 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 L2 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 L1 behaving as the NS anion, which show spectroscopic characteristics identical
with those formed by reaction with L1H2OCH3. However, the reaction with cobalt(II) nitrate gives a low-spin octahedral
cobalt(III) complex, in which an asymmetric rupture of the disulfide L2 has been produced, giving an unexpected
complex with a new ligand and keeping the S−S bond.