Transition metal complexes of Schiff base ligands have been shown to have particular application in catalysis and magnetism. The chemistry of copper complexes is of interest owing to their importance in biological and industrial processes. The reaction of copper(I) chloride with the bidentate Schiff baseN,N′-bis(trans-2-nitrocinnamaldehyde)ethylenediamine {Nca₂en, systematic name: (1E,1′E,2E,2′E)-N,N′-(ethane-1,2-diyl)bis[3-(2-nitrophenyl)prop-2-en-1-imine]} in a 1:1 molar ratio in dichloromethane without exclusion of air or moisture resulted in the formation of the title complex μ-chlorido-μ-hydroxido-bis(chlorido{(1E,1′E,2E,2′E)-N,N′-(ethane-1,2-diyl)bis[3-(2-nitrophenyl)prop-2-en-1-imine]-κ²N,N′}copper(II)) dichloromethane sesquisolvate, [Cu₂Cl₃(OH)(C₂₀H₁₈N₄O₄)₂]·1.5CH₂Cl₂. The dinuclear complex has a folded four-membered ring in an unsymmetrical Cu₂OCl₃core in which the approximate trigonal bipyramidal coordination displays different angular distortions in the equatorial planes of the two Cu^IIatoms; the chloride bridge is asymmetric, but the hydroxide bridge is symmetric. The chelate rings of the two Nca₂en ligands have different conformations, leading to a more marked bowing of one of the ligands compared with the other. This is the first reported dinuclear complex, and the first five-coordinate complex, of the Nca₂en Schiff base ligand. Molecules of the dimer are associated in pairs by ring-stacking interactions supported by C—H...Cl interactions with solvent molecules; a further ring-stacking interaction exists between the two Schiff base ligands of each molecule.