1-Dimensional halocuprate(I) chains [(Cu₂X₄)^2–]_n (= [(CuX₂)^–]_n, X = Cl, Br, I) have been synthesized under hydrothermal conditions through in-situ reduction of Cu^IIX₂ with Fe^IIX₂ or as phase pure materials through comproportionation of Cu^IIX₂ or Cu^IIO with Cu⁰ metal in the presence of the respective aqueous hydrogen halide HX and a templating amine. Chains of trans edge-sharing tetrahedra are obtained with piperazinium or ethylenediammonium dications, while the 4,4′-bipyridinium dication gave chains of cis edge-sharing tetrahedra. Two monoprotonated piperazinium groups act as cationic ligands (Hpipz⁺) towards copper atoms in a molecular [Cu₄(μ-Br₆)(Hpipz)₂] cluster. Electrical crystal conductivities of the halocuprate [(Cu₂X₄)^2–]_n (= [(CuX₂)^–]_n) chains (X = Cl, Br, I) are around 10^–8 S·cm^–1 at room temperature.

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