Structure and solvation of mercury(II) iodide, bromide, and chloride in pyridine solution; refinement of the crystal structure of di-iodobis(pyridine)mercury(II), [HgI2(py)2]

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Abstract
The structure of the neutral mercury(II) halides in pyridine (py) solution has been studied by X-ray diffraction methods and vibrational spectroscopy. Pseudo-tetrahedral HgX2(py)2 species (X = I, Br, or Cl) are formed in solution with approximately C2V symmetry. Relevant bond lengths are Hg–I 2.665(2), Hg–Br 2.497(2), and Hg–Cl 2.375(10)Å. The IHgI angle was found to be 143(2)° and BrHgBr 151(3)°, including estimated corrections for shrinkage effects. The two pyridine molecules have Hg–N distances of 2.43(2), 2.45(2), and 2.47(2)Å in the iodide, bromide, and chloride species, respectively. The crystal structure of [HgI2(py)2] has been refined to an R value of 0.031 for 744 observations. It consists of monomeric pseudo-tetrahedral [HgI2(py)2] species with Hg–I bond lengths of 2.664(1) and 2.668(1)Å and an IHgI angle of 142.7(1)°. The two pyridine ligands are related by a mirror plane which contains the HgI2 entity. The Hg–N distance is 2.424(9)Å. Raman and i.r. spectra of the pyridine solutions and of the HgX2(py)2 solids are consistent with structural models based on the diffraction data.

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