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In a new polymorph of acetato(2,2′-{imino­bis[(E)-propane-3,1-diylnitrilo­methyl­idyne]}diphenol­ato)­cobalt(III), [Co(C20H23N3O2)(C2H3O2)], in the space group P21/c, the CoIII ion is six-coordinate, with unequal Co—Ophenolate distances that average 1.908 (12) Å and more similar Co—Nimine distances averaging 1.937 (4) Å. The acetate ion occupies the sixth coordination site and forms an intra­molecular hydrogen bond (H...O = 1.95 Å) with the Co-bound NH group of the penta­dentate chelate. The extended structure is a one-dimensional (aryl)C—H...O(carbonyl) hydrogen-bonded polymer with 21 (helical) symmetry and is thus distinct from the simple hydrogen-bonded stack of the P21/n polymorph [Matsumoto, Imaizumi & Ohyoshi (1983). Polyhedron, 2, 137–139].
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