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Manganese(II) complexes derived from acyclic ligands having flexible alcohol arms: structural chracterization and SOD and catalase mimetic studies
Acta Crystallographica Section C ( IF 0.8 ) Pub Date : 2021-01-18 , DOI: 10.1107/s2053229621000395
Vickie McKee , Muhammet Kose

In this work, a series of seven MnII complexes of noncyclic flexible ligands derived from 2,6‐diformylpyridine and ethanolamine or alkyl‐substituted ethanolamines were prepared and characterized, six structurally by single‐crystal X‐ray diffraction studies. The complexes are dichlorido{2,2′‐[(pyridine‐2,6‐diyl)bis(nitrilomethanylylidene)]diethanol}manganese(II), [MnCl2(C11H15N3O2)] or [MnCl2(L1)], (2), bis{μ‐2,2′‐[(pyridine‐2,6‐diyl)bis(nitrilomethanylylidene)]diethanol}bis[dithiocyanatomanganese(II)], [Mn2(NCS)4(C11H15N3O2)2] or [Mn2(NCS)4(L1)2], (3), chlorido{1,1′‐[(pyridine‐2,6‐diyl)bis(nitrilomethanylylidene)]bis(propan‐2‐ol)}manganese(II) chloride monohydrate, [MnCl(C13H19N3O2)(H2O)]Cl·H2O or [MnCl(L2)(H2O)]Cl·H2O, (4), {1,1′‐[(pyridine‐2,6‐diyl)bis(nitrilomethanylylidene)]bis(propan‐2‐ol)}dithiocyanatomanganese(II), [Mn(NCS)2(C13H19N3O2)] or [Mn(NCS)2(L2)], (5), aquadichlorido{2,2′‐dimethyl‐2,2′‐[(pyridine‐2,6‐diyl)bis(nitrilomethanylylidene)]bis(propan‐1‐ol)}manganese(II) 0.3‐hydrate, [MnCl2(C15H23N3O2)(H2O)]·0.3H2O or [MnCl2(L3)(H2O)]·0.3H2O, (6), (dimethylformamide){2,2′‐dimethyl‐2,2′‐[(pyridine‐2,6‐diyl)bis(nitrilomethanylylidene)]bis(propan‐1‐ol)}dithiocyanatomanganese(II), [Mn(NCS)2(C15H23N3O2)(C3H7NO)] or [Mn(NCS)2(L3)(DMF)], (7), and (dimethylformamide){2,2′‐[(pyridine‐2,6‐diyl)bis(nitrilomethanylylidene)]bis(butan‐1‐ol)}dithiocyanatomanganese(II) dimethylformamide monosolvate, [Mn(NCS)2(C15H23N3O2)(C3H7NO)]·C3H7NO or [Mn(NCS)2(L4)(DMF)]·DMF, (8). The crystal structure of ligand L1 is also reported, but that of (5) is not. All four ligands (L1–L4) have five potential donor atoms in an N3O2 donor set, i.e. three N (pyridine/diimine donors) and two alcohol O atoms, to coordinate the MnII centre. The N3O2 donor set coordinates to the metal centre in a pentagonal planar arrangement; seven‐coordinated MnII complexes were obtained via coordination of two auxiliary ligands (anions or water molecules) at the axial positions. However, in some cases, the alcohol O‐atom donors remain uncoordinated, resulting in five‐ or six‐coordinated MnII complexes. The structurally characterized complexes were tested for their catalytic scavenging of superoxide and peroxide. The results indicated that the complexes with coordinated exogenous water or chloride ligands showed higher SOD activity than those with exogenous thiocyanate ligands.

中文翻译:

衍生自具有柔性醇臂的无环配体的锰(II)配合物:结构化学和SOD和过氧化氢酶模拟研究

在这项工作中,制备并表征了一系列由2,6-二甲酰基吡啶和乙醇胺或烷基取代的乙醇胺衍生的非环状柔性配体的七个Mn II配合物,并通过单晶X射线衍射研究对了六个结构进行了表征。络合物为二氯基{2,2'-[(吡啶-2,6-二基)双(亚硝基甲基亚甲叉基)]二乙醇}锰(II),[MnCl 2(C 11 H 15 N 3 O 2)]或[MnCl 2L 1)],(2),双{μ-2,2'-[(吡啶-2-6-二基)双(亚硝基甲基亚甲基)]二乙醇}双[二硫代氰基原子团(II)],[Mn 2(NCS)4(C 1115 N 3 O 22 ]或[Mn 2(NCS)4L 1)2 ],(3),氯基{1,1'-[(吡啶-2-6-二基)双(亚硝甲基亚甲基)] bis (丙烷-2-醇)}氯化锰(II)一水合物,[MnCl(C 13 H 19 N 3 O 2)(H 2 O)] Cl·H 2 O或[MnCl(L 2)(H 2 O) ] Cl·H 2 O,(4),{1,1'-[(吡啶-2-6-二基)双(亚硝基甲基亚甲基)]双(丙烷-2-醇)}二硫代氰基原子团蒽(II),[Mn(NCS )2(C 13H 19 N 3 O 2)]或[Mn(NCS)2L 2)],(5),aquadichlorido {2,2'-dimethyl-2-2,2'-[(吡啶-2,6-diyl)bis (亚硝基三甲叉基)]双(丙-1-醇)}锰(II)0.3水合物,[MnCl 2(C 15 H 23 N 3 O 2)(H 2 O)]·0.3H 2 O或[MnCl 2L 3)(H 2 O)]·0.3H 2 O,(6),(二甲基甲酰胺){2,2'-二甲基-2,2'-[(吡啶-2-6-二基)双(亚甲基甲叉基)] bis(propan-1-ol)}二硫代氰基原子团(II),[Mn(NCS)2(C 15 H 23 N 3 O 2)(C 3 H 7 NO)]或[Mn(NCS)2L 3)(DMF)],(7)和(二甲基甲酰胺){2,2'-[(吡啶-2,6-二基)双(亚硝基甲基亚甲叉基)双(丁-1-醇)}二硫氰基原子团蒽(II)二甲基甲酰胺单溶剂化物,[Mn(NCS)2(C 15 H 23 N 3 O 2)(C 3 H 7 NO)] C 3 H 7 NO或[Mn(NCS)2L 4)(DMF)]·DMF,(8)。还报道了配体L 1的晶体结构,但没有报道(5)的晶体结构。所有四个配体(L 1至L 4)在N 3 O 2供体组中具有五个潜在的供体原子,三个N(吡啶/二亚胺供体)和两个醇O原子,以协调Mn II中心。N 3 O 2供体组以五边形平面布置方式与金属中心坐标;通过以下方法获得了七个配位的Mn II配合物轴向位置上两个辅助配体(阴离子或水分子)的配位。但是,在某些情况下,醇O原子供体仍然不协调,导致Mn II络合物为5或6个。测试了结构表征的复合物对超氧化物和过氧化物的催化清除作用。结果表明,与具有外源硫氰酸酯配体的配合物相比,具有配位的外源水或氯化物配体的配合物显示出更高的SOD活性。
更新日期:2021-02-05
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