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 degrees C giving a room-temperature structure with a 10.1105(6) Angstrom, b = 9.9463(5) Angstrom, c = 12.7254(8) Angstrom, beta = 110.287(5)degrees in the monoclinic space group C2/c, Z = 4, and a low-temperature structure (-116 degrees C) with a 10.234(2) Angstrom, b = 9.427(1) Angstrom, c 12.691(2) Angstrom, beta = 109.90(2)degrees in the monoclinic space group P2(1)/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 degrees C, results in altered configurations of the dimethylammonium to metal-chloride hydrogen bonding. In addition, a remarkable distortion in the cuprous' chloride tetrahedral unit is observed in the room-temperature structure, whereas the zirconium chloride octahedron is distorted in the low-temperature crystal structure. These distortions are discussed in terms of hydrogen-bond driven second-order Jahn-Teller-type distortions.