The crystal structures of piperidinium trichlorocuprate(II)[Hpip][CuCl₃], and piperazinium hexachlorodicuprate(II), [H₂pipz][Cu₂Cl₆], have been determined by X-ray diffraction techniques. [Hpip][CuCl₃] is monoclinic, space group C2/c, with a= 18.385(7), b= 8.439(4), c= 11.878(5)Å, and β= 103.63(5)° while [H₂pipz][Cu₂Cl₆] is triclinic, P, with a= 7.984(4), b= 7.054(4), c= 6.104(3)Å, α= 111.23(8), β= 99.95(9), γ= 81.26(7)°. Both salts contain infinite chains of [Cu₂Cl₆]^2– dimers. The [Cu₂Cl₆]^2– dimers show significant distortions from planarity due to formation of semi-co-ordinate bonds between adjacent dimers, with a larger distortion for the Hpip salt. This bifold distortion gives each copper(II) ion a (4 + 1) co-ordination geometry. The chains have slightly different configurations. In the H₂pipz salt, adjacent dimers are related by unit-cell translations, while in the Hpip salt they are related by a c-glide operation. Magnetic susceptibility measurements show that the H₂pipz salt is an alternating antiferromagnetic chain with J/k=–13.35(7) K and J′/k=–7.6(3) K, while the Hpip salt is an alternating ferro- antiferro-magnetic chain with J/k= 26(3) K and J′/k=–0.24(1) K. Thus, the intradimer coupling (J) becomes less antiferromagnetic as the distortion from planarity increases. Comparison with other bifolded dimers confirms correlation of J with the bifold angle, both experimentally and theoretically. Electrical measurements reveal the presence of an activated process for electrical conduction with activation parameters of 0.44 eV for [Hpip][CuCl₃] and 0.34 eV for [H₂pipz][Cu₂Cl₆]. The charge carriers are proposed to be the protons in N–H ⋯ Cl hydrogen bonds.