Four new complexes [Cu^II(H₂biim)(gly)(H₂O)]Cl•H₂O (1), [Cu^II(H₂biim)(C₃H₂O₄)(H₂O)]•1.5H₂O (2), [Fe^III₂(μ-O)(H₂biim)₄(H₂O)₂](NO₃)₄•C₂H₅H (3) and [Fe^II(H₂biim)₃]SO₄ (4) (H₂biim＝2,2'-biimidazole; gly^－＝glycinate; C₃H₂O＝malonate) have been synthesized by the cooperation effect of the metal Cu(II), Fe(III) and Fe(II) with H₂biim molecule. 1～4 were characterized by elemental analysis, IR and X-ray single crystal diffraction. In the complexes 1～4, the metal ions are coordinated by chelating biimidazole molecules, glycinate and malonate. By multiple robust hydrogen bonds R(7), R(9) and R(4) formed by N—H groups of biimidazole with anions, water molecules and solvent molecules, complexes 1～4 extend multidimensional structures. 1 and 2 have 3D porous structures, while 3 has a novel binuclear center Fe—O—Fe in which the bridging O atom came from water or air. The Λ-form chiral unit of 4 forms a (10,3) net along b-axis.

Key words: 2,2-biimidazole, glycinate, malonate, hydrogen bond, copper(II) complex, crystal structure