辅助配体对酰腙类金属Mn(II)配合物晶体结构的影响
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摘要
选择N3-苯甲酰吡啶基-2-甲酰胺腙(Hbpad)作为有机配体,以Mn(Ⅱ)离子为金属中心,构筑了一例金属配合物[Mn(bpad)2](1)。在此基础上,引入间硝基苯甲酸(Hmnb)作为辅助配体获得了第二例配合物[Mn(Hbpad)(mnb)2·(H2O)](2)。利用红外光谱,元素分析、X-射线粉末衍射和X-射线单晶衍射对两例化合物的结构和组成进行了研究。晶体结构分析表明,配合物1属于单斜晶系,P2/n空间群,最小不对称单元中的两个bpad-配体采用三齿螯合的配位模式与Mn(Ⅱ)离子结合,导致中心离子形成了一个六配位的扭曲八面体构型;配合物2属于三斜晶系P-1空间群,最小不对称单元由一个Mn(Ⅱ)离子、bpad-配体、配位水分子和两个mnb-离子组成。尽管Mn(Ⅱ)离子也呈现了六配位的扭曲八面体几何构型,但金属中心的配位环境明显不同。两例配合物中单核分子间各异的氢键相互作用堆积形成了二者的三维超分子网络结构。
Based on an acylhydrazone derivative as ligand,a new complex,[Mn(bpad)2](1),has been obtained in methanol solvent(Hbpad = N3-benzoyl hydrazone pyridin-2-carboxamide).Consequently,nitrobenzoic acid as coligand was introduced in the reaction system mentioned above,giving rise to complex 2,[Mn(Hbpad)(mnb)2·(H2 O) ](2)(Hmnb = nitrobenzoic acid). The structures of the resulting complexes were characterized by using IR,elemental analysis,X-ray powder diffraction and X-ray single crystal diffraction. X-ray single crystal diffraction analysis reveals that complex 1 belongs to monoclinic,P2/n space group. Two bpad ligands with tridentate modes connect with one Mn(Ⅱ) ion in the asymmetric unit of 1,contributing to a distorted octahedral geometry surrounding the metal center. Complex 2 exhibits monoclinic and P-1 space group,in which one Mn(Ⅱ)ion,one bpad ligand,two mnb ligands and one coordinated water exist in the asymmetric unit. The central cation also presents six-coordinated environment with distorted octahedron in 2. Comparatively,although the Mn(Ⅱ) centers in two complexes display similar geometric configurations,the coordinationenvironments are significantly different. Furthermore, several mononuclear Mn(Ⅱ) fragments are integrated by intermolecular hydrogen-bonding,constructing the 3 D supramolecular networks of two title.
Based on an acylhydrazone derivative as ligand,a new complex,[Mn(bpad)2](1),has been obtained in methanol solvent(Hbpad = N3-benzoyl hydrazone pyridin-2-carboxamide).Consequently,nitrobenzoic acid as coligand was introduced in the reaction system mentioned above,giving rise to complex 2,[Mn(Hbpad)(mnb)2·(H2 O) ](2)(Hmnb = nitrobenzoic acid). The structures of the resulting complexes were characterized by using IR,elemental analysis,X-ray powder diffraction and X-ray single crystal diffraction. X-ray single crystal diffraction analysis reveals that complex 1 belongs to monoclinic,P2/n space group. Two bpad ligands with tridentate modes connect with one Mn(Ⅱ) ion in the asymmetric unit of 1,contributing to a distorted octahedral geometry surrounding the metal center. Complex 2 exhibits monoclinic and P-1 space group,in which one Mn(Ⅱ)ion,one bpad ligand,two mnb ligands and one coordinated water exist in the asymmetric unit. The central cation also presents six-coordinated environment with distorted octahedron in 2. Comparatively,although the Mn(Ⅱ) centers in two complexes display similar geometric configurations,the coordinationenvironments are significantly different. Furthermore, several mononuclear Mn(Ⅱ) fragments are integrated by intermolecular hydrogen-bonding,constructing the 3 D supramolecular networks of two title.
引文
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[4]Liu X Y,Sun L,Zhou H L,et al.Single-Ion-Magnet Behavior in a Two-Dimensional Coordination Polymer Constructed from Co II Nodes and a Pyridylhydrazone Derivative[J].Inorganic Chemistry,2015,54:8884-8886.
[5]Liu X Y,Li F F,Ma X H,et al.Coligand Modifications Fine-tuned the Structure and Magnetic Properties of Two Triple-bridged Azido-Cu(II)Chain Compounds Exhibiting Ferromagnetic Ordering and Slow Relaxation[J].Dalton Transactions,2017,46(4):1207-1217.
[6]张书泉,张建汉,辜家芳.四个Cd配位聚合物:辅助配体对晶体结构以及荧光性能的影响[J].无机化学学报,2018,34(2):237-246.
[7]Liu X Y,Liu H X,Cen P P,et al.Hu Q L.Auxiliary Ligand-triggered Assembly of Two Dinuclear Cu(II)Compounds with a Pyridylhydrazone Derivative:Synthesis,Crystal Structure and Magnetic Property[J].Inorganica Chimica Acta,2016,447:12-17.
[8]郑长征,任立娣,丁涛,等.基于柔性芳香羧酸配体的三维镉(Ⅱ)配位聚合物的合成,晶体结构及荧光性质[J].人工晶体学报,2014,43(4):1009-1014.
[9]蒋畅,姚枫枫,康杰,等.一种新型芳香羧酸钴配合物的合成及晶体结构[J].海峡药学,2016,28(8):253-256.
[10]赵程程,阮晓文,王德成,等.芳香羧酸构筑的Pb(Ⅱ)配合物的合成及晶体结构[J].吉林师范大学学报:自然科学版,2015,36(1):111-114.
[11]Sheldrick,G M SADABS.Software for Empirical Absorption Correction;University of G9ttingen:G9ttingen,Germany,1996.
[12]Sheldrick,G M SHELXTL.Structure Determination Software Programs;Bruker Analytical X-ray System Inc.:Madison,WI,USA,1997.