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In the title complex, [NaCu(C 22 H 18 N 2 O 4 )Cl(CH 3 OH)], the Cu atom lies nearly in the plane defined by the N 2 O 2  core of donor atoms, the out-of-plane distance being 0.001 (2) Å. The anion provides a planar cavity of four O atoms which accommodates a sodium cation. The coordination geometry around sodium is completed by the methanol O atom and a chloride ion. The four O atoms define a coordination plane containing the sodium cation [maximum displacement from the mean plane through the five atoms = 0.152 (3) Å for Na]. The crystal structure is stabilized by inter­molecular C—H⋯Cl and O—H⋯Cl hydrogen bonds, which link the mol­ecules into dimers. The crystal packing is further stabilized by weak π–π stacking inter­actions [centroid–centroid distances of 3.442 (4), 3.482 (3), 3.350 (2), 3.531 (4) 3.575 (2) and 3.604 (2) Å].

{μ-6,6′-Dimethoxy-2,2′-[1,2-phenylenebis(nitrilomethylidyne)]diphenolato}methanolcopper(II)sodium(I)