Constructions of Five Noncovalent‐bonded Supramolecules from Reactions of Cadmium(II) and Zinc(II) with Imidazole/benzimidazole and Carboxylate Ligands

Five imidazole/benzimidazole‐based metal complexes, Cd(bim) 2 (L1) 2 ( 1 ) [L1 = 2‐methyl‐2‐phenoxypropionate, bim = benzimidazole], Zn(im) 2 (L2) 2 ( 2 ) [L2 = 3‐(4‐methoxyphenyl)acrylate, im = imidazole], Zn(im) 2 (L3) 2 ( 3 ) [L3 = 3,4‐(methylenedioxy)benzoate], [Cd(im) 2 (L3) 2 ] 2 · 4H 2 O ( 4 ), and Cd(Bim) 2 (L4) · CH 3 CH 2 OH · H 2 O ( 5 ) (L4 = 1,4‐cyclohexanedicarboxylate), were obtained by the introduction of the carboxylates as coligands and are structurally characterized by different techniques including elemental analysis, IR spectra, TG, and single‐crystal X‐ray diffraction analysis. The X‐ray crystal structure analyses reveal that these complexes display mononuclear to dinuclear structures with tetrahedral coordination spheres around each central zinc atom, and octahedral coordination sphere around each central cadmium atom. The imidazole ligands in all compounds are coordinated only in a monodentate fashion with their neutral nitrogen groups. The carboxylates coordinate to the metal in monodentate, chelating bidentate, and bridging bidentate fashions. The N–H ··· O hydrogen bonds from the NH donor of the neutral imidazole were found in all compounds. On the basis of X‐ray crystallographic study the rich intra‐ and intermolecular noncovalent interactions (including classical hydrogen bonds, C–H ··· O, CH 2 ··· O, CH 3 ··· O, CH 2 –N, C–H ··· π, CH 3 –π, O–H ··· π, and π–π interactions) are analyzed. The various nonbonding interactions in these compounds are responsible for different structures such as 3D network, 3D prismatic layer network, and 3D layer network structure.