一例Mn(Ⅱ)超分子配合物的合成与晶体结构

Synthesis and Crystal Structure of a Mn(Ⅱ) Supramolecular Complex

通过常规溶液法合成了一例新的Mn(Ⅱ)超分子配合物{[Mn(4,4’-bpy)2(H2O)4][Mn(H2O)4(EtOH)2]}(HASA)2#2(4,4’-bpy)#4H2O(1)(H3ASA=5-偶氮四唑水杨酸,4,4’-bpy=4,4’-联吡啶).单晶X-射线衍射分析表明配合物1属于单斜晶系,P21/c空间群,其晶胞参数为:a=2.75989(2),b=0.708862(4),c=1.801189(15)nm,β=106.7066(9)o,V=3.37507(5)nm^3,Z=2,Dc=1.483 g/cm^3,μ=3.803 mm^-1,F(000)=1572.0,R1=0.0425,wR2=0.1119.每个晶胞单元包含2个不同的阳离子单核结构[Mn(4,4’-bpy)2(H2O)4]2+和[Mn(H2O)4(EtOH)2]2+,游离的4,4’-bpy、HASA2-和水分子.5个子单元间存在O-H…O、O-H…N 2种不同的氢键和π-π堆积相互作用,这些非共价相互作用在三维超分子结构的形成和稳定性中扮演着重要的角色.

A new Mn(Ⅱ)supramolecular complex of{[Mn(4,4′-bpy)2(H2O)4][Mn(H2O)4(EtOH)2]}(HASA)2·2(4,4′-bpy)·4H2O(1)(H3 ASA=5-azotetrazolyl salicylic acid,4,4′-bpy=4,4′-bipyridine)has been synthesized via solution method and its structure was characterized by single crystal X-ray diffraction analysis.Complex 1 crystallizes in the monoclinic system,space group P21/c with a=2.75989(2),b=0.708862(4),c=1.801189(15)nm,β=106.7066(9)°,V=3.37507(5)nm^3,Z=2,Dc=1.483 g/cm^3,μ=3.803 mm^-1,F(000)=1572.0,R1=0.0425 and wR2=0.1119.Each asymmetric unit of 1 consists of two different cation mononuclear structures of[Mn(4,4′-bpy)2(H2O)4]2+and[Mn(H2O)4(EtOH)2]2+,free 4,4′-bpy,HASA2-and water molecules.Two different hydrogen bonds of O-H…O、O-H…N andπ-πstacking interactions were found between the five discrete subunits.These noncovalent interactions play a significant role in the formation and stabilization of the three-dimensional supramolecular structure.