The crystal structure of a second form of green [Cu(NO2)2(phen)], where phen is 1,10‐phenanthroline (C12H8N2), containing six‐coordinate copper(II) with a distorted tetragonal [CuIIN2O4] core is reported. The first form had a crystal symmetry of C2/c [Breneman et al. (1999). Acta Cryst. C55, IUC9900158], while the form reported here is Pbcn. The nitrito ligands are bonded to the central copper through both O atoms, with short Cu—O bond distances of 1.987 (3) Å and longer Cu—O bond distances of 2.410 (4) Å. Both nitrito groups are significantly displaced from the plane defined by the 1,10‐phenanthroline and the square‐planar arrangement of the ligands around the CuII atom.
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