Metal Iodides in Polyiodide Networks: Synthesis and Structure of Binary Metal Iodide-Iodine Compounds Stable under Ambient Conditions

Inorg Chem. 1999 Jul 12;38(14):3390-3393. doi: 10.1021/ic981348m.

Abstract

The reaction between HgI(2)(C(6)N(4)H(12)) and HI in ethanol solution results in the binary metal iodide-iodine complexes [C(6)N(4)H(13)](2)(Hg(2)I(6))(1/2)(HgI(3)).(1)/(2)I(2), which are stable under ambient conditions. The structure consists of C(6)N(4)H(13)(+) cations, discrete trigonal HgI(3)(-) ions, and.Hg(2)I(6)(2)(-).I(2).Hg(2)I(6)(2)(-). chains in the crystallographic b direction, which are formed by I(2) molecules connecting the bridging iodines of the Hg(2)I(6)(2)(-) dimers. The intra- and intermolecular I-I distances of iodine in the chain are 2.7402(15) and 3.438(1) Å, respectively. The Raman spectrum of [C(6)N(4)H(13)](2)(Hg(2)I(6))(1/2)(HgI(3)).(1)/(2)I(2) confirms the interaction between the iodine molecules and Hg(2)I(6)(2)(-) ions. The structure of [NH(4)](HgI(3)).H(2)O, obtained during the synthesis of [C(6)N(4)H(13)](2)(Hg(2)I(6))(1/2)(HgI(3)).(1)/(2)I(2), is also reported. Crystal data for [C(6)N(4)H(13)](2)(Hg(2)I(6))(1/2)(HgI(3)).(1)/(2)I(2): a = 14.275(3) Å, b = 19.721(4) Å, c = 10.416(2) Å, orthorhombic space group Pbam; Z = 4. Crystal data for [NH(4)](HgI(3)).H(2)O: a = 8.7246(4) Å, b = 9.7860(3) Å, c = 11.1103(4) Å, orthorhombic space group Ama2; Z = 4.