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The title compound, {(C9H14N)2[Cu3Cl8]}n, consists of parallel chains of alternating quasiplanar Cu2Cl6 and planar CuCl4 complexes separated by trimethylphenylammonium cations. Both inorganic complexes possess inversion symmetry. Pairs of neighboring chloride ions of the CuCl4 complex each form a symmetric bridge and an asymmetric bridge to Cu2Cl6 complexes on either side. The Cu2Cl6 complex contains two symmetric chloride bridges between the copper cations with a terminal chloride bound to each five‐coordinated CuII ion. The CuCl4 complex completes its coordination environment by forming two long semicoordinate contacts to the bridging chloride ions of neighboring Cu2Cl6 complexes. The use of the bridging rather than the terminal chloride ions to form semicoordinate contacts generates a new zigzag chain structure that differs from the straight chain structures found for other A2Cu3Cl8 compounds. The zigzag chain structure is adopted so as to conform to the shorter repeat distance dictated by stacking of the organic cations.
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