New types of the flexible self-assembled metal–organic coordination polymers constructed by aliphatic dicarboxylates and rigid bidentate nitrogen ligands

Abstract

The reaction of metal ions, flexible aliphatic dicarboxylates and rigid bidentate linear ligands under mild conditions in water afford four novel metal–organic coordination polymers, [Cd(µ-mal)(µ-pyz)_0.5(H₂O)]_n1 (mal = malonate dianion, pyz = pyrazine), [Cd₂(µ-suc)₂(µ-pyz)(H₂O)₂]_n2 (suc = succinate dianion), and {[M(µ-bipy)(H₂O)₄][suc]·4H₂O}_n (M = Co, 3, M = Zn, 4, bipy = 4,4′-bipyridine). The molecular structures of 1–4 have been established by single-crystal X-ray crystallography. 1 is a 3D network being composed of layers of octahedrally coordinated Cd atoms bridged by malonate anions in syn–anti configurations within the layers and pyz molecules between layers. Unlike that in 1, each Cd atom in 2 displays uncommon pentagonal-bipyramidal geometry to form 2D infinite grid sheets with square grid dimensions of ca. 7.936 × 7.936 Å. Both 3 and 4 exhibit 1D linear –M–bipy–M–bipy– chain polymers, and these chains were packed as ⋯ABCABC⋯ layered structures. The bridging succinate ligands in 2 adopt the syn–anti mode with a torsion angle of 60.8(7)°, while the solvated succinate ligands in 3 and 4 adopt the anti–anti mode with a torsion angle of 180.0°. To our knowledge, compound 2 represents the first example of flexible self-assembled succinate–pyrazine mixed bridging ligand coordination network. 3 and 4 are the first two cases of succinate–bipy polymers with non-coordinated succinate. The magnetic behavior for 3 was studied in the temperature range of 5–300 K. The result indicates the occurrence of a weak antiferromagnetic coupling between the cobalt(II) ions.