An Ag(I) complex with HL (I), AgL (AgC23H15O3, II), has been synthesized. Compounds I and II have been studied by X-ray diffraction. The crystals are monoclinic, I: space group P21/n, a = 10.459(2) Å, b = 12.354(2) Å, c = 13.390(3) Å, β = 96.67(3)°, Z = 4; II: space group P21/c, a = 10.764(2) Å, b = 10.683(2) Å, c = 15.939(3) Å, β = 101.57(3)°, Z = 4. The structural units of the crystal of I are neutral molecules with intramolecular hydrogen bonds. In structure II, the Ag2O6 dimeric groups and the ligands form infinite openwork layers perpendicular to the x axis and containing cavities. The layers are penetrated by channels with an oblong cross section. In the crystal of II, all intermolecular distances exceed the sums of the van der Waals radii of the corresponding atoms.