The Co(II), Ni(II) and Cu(II) complexes with herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) were synthesized and structurally characterized. The geometry of metal-ligand interaction was refined using XAFS and DFT studies. The Co(2,4-D)(2)center dot 6H(2)O and Ni(2,4-D)2 center dot 4H(2)O complexes have octahedral geometry with two carboxylate groups of 2,4-D anions and four water molecules in the coordination sphere. The square planar geometry around metal cations formed by the carboxylate groups from two monodentate ligands and two water molecules, is observed for Cu(2,4-D)2 center dot 4H(2)O complex. In the recrystallized Ni(II) complex dinuclear 'Chinese lantern' structures with bridging carboxylate groups of 2,4-D were observed. (C) 2016 Elsevier B.V. All rights reserved.