Jiao Yuan, Jin Fu Ning, Feng Si Si, Wang Ai, Englert Ulli
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.
Acta Crystallogr C Struct Chem. 2021 Nov 1;77(Pt 11):707-712. doi: 10.1107/S2053229621010627. Epub 2021 Oct 19.
The self-assembly reaction of (+)-dibenzoyltartaric acid (D-HDBTA) with 2,2'-bipyridine (bpy) and Mn(CHCO)·4HO yielded a new coordination polymer, namely, catena-poly[[[diaqua(2,2'-bipyridine-κN,N')manganese(II)]-μ-2,3-bis(benzoyloxy)butanedioato-κO:O] dihydrate], {[Mn(CHO)(CHN)(HO)]·2HO} or {[Mn(DBTA)(bpy)(HO)]·2HO}, (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 P222. In the complex, the Mn cation displays a distorted octahedral {MnON} geometry, formed from two carboxylate O atoms of two DBTA 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 Mn model due to the long intramolecular Mn...Mn distance. The zero field splitting (ZFS) contribution in the high-spin Mn cation is almost negligible and there are weak antiferromagnetic couplings between 1D chains [zJ' = -0.062 (5) cm], corresponding to an intermolecular Mn...Mn distance of 7.860 (2) Å.
（+）-二苯甲酰酒石酸（D-HDBTA）与2,2'-联吡啶（bpy）和Mn（CH₃CO₂）₂·4H₂O的自组装反应产生了一种新的配位聚合物，即链状聚[[[二水合（2,2'-联吡啶-κN,N'）锰（II）]-μ-2,3-双（苯甲酰氧基）丁二酸根合-κO:O]二水合物]，{[Mn（C₄H₄O₆）（C₁₀H₈N₂）（H₂O）₂]·2H₂O} 或 {[Mn（DBTA）（bpy）（H₂O）₂]·2H₂O}，（I）。配合物（I）已通过元素分析、红外光谱、热重分析（TGA）以及单晶和粉末X射线衍射进行了表征。它结晶于正交晶系空间群P2₂₂₂。在该配合物中，Mn²⁺阳离子呈现出扭曲的八面体{MnN₄O₂}几何构型，由两个DBTA配体的两个羧酸根O原子、一个螯合的2,2'-联吡啶配体的两个顺式取向的N原子以及配位水分子的两个反式取向的O原子形成。该聚合物呈现出一维链状结构，Mn...Mn距离为9.428 (1) Å。由于分子结构中存在柔性的多羧酸根和刚性的联吡啶配体，该配合物具有较高的热稳定性。由于分子内Mn...Mn距离较长，基于单核Mn模型对（I）的磁性进行了分析。高自旋Mn²⁺阳离子中的零场分裂（ZFS）贡献几乎可以忽略不计，并且一维链之间存在弱的反铁磁耦合[zJ' = -0.062 (5) cm⁻¹]，对应分子间Mn...Mn距离为7.860 (2) Å。
