Correlation of a Solution-State Conformational Change between Mercuric Chloride Complexes of Tris[(2-(6-methylpyridyl))methyl]amine with X-ray Crystallographic Structures.

Solution-state NMR and X-ray crystallography were used to investigate the complexation of HgCl(2) by the potentially tetradentate ligand tris[(6-methyl-2-pyridyl)methyl]amine (TLA) in acetonitrile. A change in the ligand conformation as a function of the metal-to-ligand ratio could be indirectly monitored through large changes in (3)J((1)H(199)Hg) to the methylene protons at -40 degrees C. The solution-state NMR were correlated with two solid-state structures. The five-coordinate complex [Hg(TLA)Cl(2)] (1) crystallizes in the triclinic space group P&onemacr; with a = 8.663(3) Å, b = 11.539(4) Å, c = 13.739(3) Å, alpha = 80.81(2) degrees, beta = 75.84(2) degrees, gamma = 80.97(3) degrees, and Z = 2. The Hg-N(amine) distance of 2.505(7) Å for the tridentate ligand is the same as the average Hg-N(lutidyl) distance of 2.50(3) Å for the two bound lutidyl nitrogens. Hg(TLA)Cl(Hg(2)Cl(6)) (2) also crystallizes in P&onemacr; with a = 10.606(2) Å, b = 15.104(3) Å, c = 17.785(4) Å, alpha = 67.46(3) degrees, beta = 83.52(3) degrees, gamma = 80.29(3) degrees, and Z = 2. The ligand is tetradentate in the two crystallographically unique cations which are arranged in a dimer-like orientation. The average Hg-Cl distance is 2.37 (1) Å, and the average interionic Hg-Cl distance is 3.51(1) Å. The Hg- N(lutidyl) distances are of two types: two have an average distance of 2.36(3) Å, nearly the same as the Hg-N(amine) distance of 2.35(2) Å. The remaining four N(lutidyl) distances have an average distance of 2.56(5) Å.