Three new metal-organic complexes, [CoL2(H2O)(4)] 1, [CdL2(H2O)(2)] 2, and [CuL2(H2O)(2)] 3 [HL = 4-chlorophenyloxyacetic acid], have been synthesized and characterized by IR spectra, elemental analysis, fluorescence spectra, and single-crystal X-ray diffraction. Compounds 1, 2, and 3 are all zero-dimensional dimers. The carboxylate ligand exhibits different coordination modes in all compounds. These compounds exhibit interesting supramolecular architecture according to O-HO and C-HCl interactions. Compounds 1, 2, and 3 develop to different framework though they all are from same ligands, which will be helpful to design of different materials. [Supplemental materials are available for this article. Go to the publisher's online edition of Molecular Crystals and Liquid Crystals to view the free supplemental file: CCDC 902676, 902674, 902675 contains the supplementary crystallographic data for this article. These data can be obtained free of charge viawww.ccdc.cam.ac.uk/conts/retrieving.html(or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; Fax: C44 1223 336033; e-mail: [email protected]).]