Verschiedene strukturen von β-diketonderivaten des quecksilbers

Mercury(II) Complexes Containing the [Hg(L)2]2–, [Hg(L)(HL)]−, and [Hg(HL)2] Units [H2L = 3-(2-Chlorophenyl)-2-sulfanylpropenoic Acid]. Structural and Spectroscopic Effects of the Different Degrees of Ligand Protonation

“…Recent surveys of Hg(II) thiolate structures show values for these Hg–S distances in the range 2.32–2.36 Å for linear [Hg(SR) 2 ] complexes, 2.42–2.45 Å for trigonal [Hg(SR) 3 ] − species and 2.52–2.58 Å for tetrahedral [Hg(SR) 4 ] 2– ones. The data for 1 and 2 , as well as for other equivalent sulfanylcarboxylates (or in other complexes with S,O-donor ligands ,,− ), show that the increase in the Hg–S bond length is not significant when the coordination number increases on the basis of the O-donor atom but that the S–Hg–S angle is quasi-linear. A similar situation also occurs when the Hg atom of an [Hg(SR) 2 ] thiolate bonds pyridine to give a tricoordinated T-shaped complex, a carboxylate group to give a seesaw-shaped geometry, or when, as in 3· 4H 2 O, a secondary intermolecular interaction increases the Hg coordination number.…”

“…The two chelate HgSCCO rings (rms 0.137) are coplanar and make angles of 49.8(1)° with the Cl–C 6 H 4 plane. The data were compared with those for the equivalent neutral examples containing S,O-bidentate ligands available in the literature, including complexes of thiosalicylic acid, , monothioderivatives of 2,2,6,6-tetramethyl-3,5-heptanedione, , 2-dimethylamino-3,4-dioxo-cyclobut-1-en thiolate, and N -(piperidyl-thiocarbonyl)benzamide . The closest situation for the Hg kernel is that of the thiosalicylic acid complex described in ref , which was isolated as a dioxane solvate.…”