Abstract
The copper(I) zirconium(IV) halide, [H2NMe2]CuZrCl6 (1), has been synthesized, and its single-crystal X-ray structure was determined. The crystal undergoes a phase transition at −60 °C giving a room-temperature structure with a = 10.1105(6) A, b = 9.9463(5) A, c = 12.7254(8) A, β = 110.287(5)° in the monoclinic space group C2/c, Z = 4, and a low-temperature structure (−116 °C) with a = 10.234(2) A, b = 9.427(1) A, c = 12.691(2) A, β = 109.90(2)° in the monoclinic space group P21/c, Z = 4. [H2NMe2]CuZrCl6 is constructed from unique one-dimensional chains with zirconium and copper in alternating octahedral and tetrahedral coordination environments, respectively. The structural relationship between (CuCl4)3- and (PS4)3- is demonstrated by the analogy of this structure to that of KNiPS4. The phase transition, which occurs at approximately −60 °C, results in altered configurations of the dimethylammonium to metal−chloride hydrogen bonding. In addition, a remarkable distortion in the cuprous chloride tetrahedra...
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