The reactions of zinc and cadmium salts with 2,2′-biimidazole (H 2 biim) yielded a series of compounds in which the ligand is coordinated in the chelating bidentate mode. ZnCl 2 and [Ag(H 2 biim)](NO 3 ) in methanol in a 2:1 proportion produced Zn(H 2 biim)Cl 2 , in which the metal has a distorted tetrahedral coordination. A 1:2 ratio led to [Zn(H 2 biim) 2 (CH 3 OH) 2 ](NO 3 ) 2 , containing an octahedrally coordinated Zn(II) center with the O-bonded methanol ligands occupying trans positions. The corresponding [Cd(H 2 biim) 2 (CH 3 OH) 2 ](NO 3 ) 2 compound was obtained from CdCl 2 . By starting with Cd(NO 3 ) 2 and Cd(ClO 4 ) 2 in aqueous media, the related octahedral bis-chelate compounds [Cd(H 2 biim) 2 (NO 3 )(H 2 O)](NO 3 ) and Cd(H 2 biim) 2 (ClO 4 ) 2 , respectively, were isolated, the apical positions being filled by perchlorate oxygens in the latter case. With Cd(BF 4 ) 2 , the glass container participated in the reaction and a tris-chelate complex [Cd(H 2 biim) 3 ] 2 (SiF 6 )(BF 4 ) 2 ·6EtOH was isolated. The [Cd(H 2 biim) 3 ] 2+ and SiF62- ions define an extended hydrogen-bonded network, in which BF4-ions surrounded by disordered ethanol molecules occupy large cavities. The two free N–H groups provide H 2 biim with a unique ability to form hydrogen bonds and their interactions with counter anions or other acceptors play a determining role in controlling molecular packing. The IR spectra of all compounds are discussed.