Reactivity of Ammonium Chloride/Mercuric Chloride Mixtures with Monel Containers . The new Compounds (NH_4)_2(NH_3)_x[Ni(NH_3)_2Cl_4] and (NH_4)_5Cl_2[CuCl_2][CuCl_4]

摘要

Ammonium chloride/mercuric chlorde mixtures (molar ratio 2:1) react at 350 deg C with Monel (Cu68 Ni32) to yield (NH_4)NiCl_3 and mercury and copper amalgam respectively. With larger amounts of (NH_4)Cl in the reaction mixture, dark green (NH_4)_2(NH_3)_x[Ni(NH_3)_2Cl_4] (x aoorox =0.77) (1) is alos formed as a main product. Light the crystals of the mixed-valent copper(I,II) chloride (NH_4)_5Cl_2[CuCl_2][CuCl_4] (2) were obtained as a minor byproduct from a 4:1 reaction mixture . The crystal structures were determined from single crystal X-ray data; (1) tetragonal, 14/mmm, a=770.9(1),c=794.2(2)pm, 190 reflections, R_1=0.0263; (2): tetragonal, 14/mcm, a=874.8(1), c=2329.2(3)pm,451 reflctions, R_1=0.0736. In (1)Ni~(2+) resides in trans-[Ni(NH_3)_2Cl_4]~(2-) octahedra, and in (2) copper (I) is linearly two-coordinated in [CuCl_2]~- and copper (II) resides in a flattened tetrahedron [CuCl_4]~- with a tetrahedricity of 89%