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The title compound, [Co(C14H6N2O4)(H2O)3]·2H2O, has twofold crystallographic symmetry. The CoII atom is in a distorted pentagonal-bipyramidal coordination environment with two N atoms and two O atoms from a tetradentate 1,10-phenanthroline-2,9-dicarboxylate ligand and one O atom from a water molecule forming the pentagonal plane, and two O atoms from two water molecules occupying axial positions. In the crystal, adjacent molecules are linked by O—H...O hydrogen bonds, forming a three-dimensional network.

In the title compound, C20H14, a naphthalene ring system is linked at the 2-position to the 2-C atom of the five-membered ring of an azulene unit. The compound crystallizes with two reasonably similar molecules in the asymmetric unit. Neither molecule is perfectly planar: the r.m.s. deviations from the best fit planes through all non-H atoms are 0.092 and 0.091 Å for the two molecules. The dihedral angle between the molecular planes is 49.60 (4)°. The naphthalene and azulene ring systems are inclined at dihedral angles of 6.54 (12) and 5.68 (12)° in the two molecules. The crystal structure exhibits two sets of parallel layers, a typical edge-to-face herringbone packing arrangement. The structure is stabilized by an extensive series of weak C—H...π interactions.