Synthesis, crystal structure and magnetic properties of a one-dimensional Mn2+ complex constructed from (+)-dibenzoyltartaric acid and 2,2'-bipyridine. 2021

Yuan Jiao, and Fu Ning Jin, and Si Si Feng, and Ai Wang, and Ulli Englert
Institute of Molecular Science, Key Laboratory of Chemical Biology and Molecular Engineering of the Education Ministry, Shanxi University, Taiyuan, Shanxi 030006, People's Republic of China.

The self-assembly reaction of (+)-dibenzoyltartaric acid (D-H2DBTA) with 2,2'-bipyridine (bpy) and Mn(CH3CO2)2·4H2O yielded a new coordination polymer, namely, catena-poly[[[diaqua(2,2'-bipyridine-κ2N,N')manganese(II)]-μ-2,3-bis(benzoyloxy)butanedioato-κ2O2:O3] dihydrate], {[Mn(C18H12O8)(C10H8N2)(H2O)2]·2H2O}n or {[Mn(DBTA)(bpy)(H2O)2]·2H2O}n, (I). Complex (I) has been characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA) and single-crystal and powder X-ray diffraction. It crystallizes in the orthorhombic space group P212121. In the complex, the Mn2+ cation displays a distorted octahedral {MnO4N2} geometry, formed from two carboxylate O atoms of two DBTA2- ligands, two cis-oriented N atoms from one chelating 2,2'-bipyridine ligand and two trans-oriented O atoms from coordinated water molecules. The polymer displays a 1D chain with an Mn...Mn distance of 9.428 (1) Å. Due to the presence of flexible polycarboxylate and rigid bipyridyl ligands in the molecular structure, a high thermal stability of the complex is attained. The magnetic properties of (I) were analyzed based on the mononuclear Mn2+ model due to the long intramolecular Mn...Mn distance. The zero field splitting (ZFS) contribution in the high-spin Mn2+ cation is almost negligible and there are weak antiferromagnetic couplings between 1D chains [zJ' = -0.062 (5) cm-1], corresponding to an intermolecular Mn...Mn distance of 7.860 (2) Å.

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