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In the structure of the title complex, {[CeFe(CN)6(H2O)2]·2H2O}n, the CeIII and FeIII atoms exhibit square anti­prismatic [CeN6(H2O)2] (site symmetry m2m) and octahedral [FeC6] (site symmetry 2/m) coordination geometries, respectively. The metal atoms are linked alternately through the cyanide groups, forming a three-dimensional framework in which the {Ce2Fe2(CN)4} puckered square unit is the basic building block. The crystal packing is enforced by O—H...O and O—H...N hydrogen bonds, including the uncoordinated water molecule which is located on a mirror plane.

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The asymmetric unit of the title complex, (C12H9N2)3[Fe(CN)6]·C2H5OH·3H2O, consists of two half [Fe(CN)6]3− anions located on inversion centers, three 1,10-phenanthrolin-1-ium cations, [Hphen]+, an ethanol and three water solvent mol­ecules. The average Fe—C and C—N bond lengths are 1.942 (6) and 1.154 (3) Å, respectively, while the Fe—C—N angles deviate slightly from linearity with values ranging from 177.8 (2) to 179.7 (2)°. The FeIII atoms adopt a distorted octa­hedral geometry. All the species are linked through O—H...N, N—H...O and O—H...O hydrogen-bonding inter­actions, resulting in a three-dimensional supra­molecular network.
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