Syntheses of bis(organomercury) 1,3-dithiole-2-thione-4,5-dithiolates and related compounds: Crystal structure of bis(phenylmercury) 1,3-dithiole-2-one-4,5-dithiolate

The syntheses, IR and UV spectra and thermal analysis are reported of the organomercury 1,2-dithiolates, bis-(organomercury) 1,3-dithiole-2-thione-4,5-dithiolates [(RHg)(2)(dmit)], 1,3-dithiole-2-one-4,5-dithiolates [(RHg)(2)(dmio)], and 1,2-dithiole-3-thione-4,5-dithiolates [(RHg)(2)(dmt)], (R = Me or Ph). As shown by TGA, the onset of thermal decomposition occurs in all cases below 160 degrees C: in each case, thermal decomposition occurs in various stages with loss of R2Hg. A single crystal structure determination of [(PhHg)(2)(dmio)] revealed the presence of centrosymmetric dimeric units, which are linked via (SS)-S-..., p(...)p and Hg(...)p into a layered structure. Within the dimer, there are two distinct T'' shaped Hg(II) environments: Hg1 is asymmetrically chelated to the dmio ligand with bond lengths Hg1-S1 and Hg1-S2 = 2.3813(13) and 2.9315(12) angstrom and with a chelate bite angle of 84.17(4) and a near linear S1-Hg1-C11 bond angle of 172.30(13)degrees. Atom, Hg2, is bonded to a single thiolato atom, S2, of one dmio ligand [Hg2-S2 = 2.3853(12)] and to the carbonyl oxygen of the other dmio unit in the dimer: [ Hg2-O1 = 2.738(4)angstrom], with bond angles 171.23(16)degrees , 97.53(9)degrees and 91.05(17)degrees, respectively for S2-Hg2-C21, S2-Hg2-O1 and C21-Hg2-O1. All the compounds appear polymeric and are poorly soluble in organic solvents. (C) 2015 Elsevier B.V. All rights reserved.