酰胺氮桥联双核钴(Ⅲ)配合物[Co_2(bpmb)_2(CN)_2]·H_2O的合成、分子结构和超分子组装(英文)

Synthesis,Molecular Structure and Supramolecular Assembly of a Carboxamide Nitrogen-Bridged Dicobalt(Ⅲ) Complex [Co_2(bpmb)_2(CN)_2]·H_2O(bpmb^(2-)=1,2-bis(pyridine-2-carboxamido)-4-methylbenzenate)

合成了1个酰胺氮桥联的双核钴(Ⅲ)配合物[Co2(bpmb)2(CN)2].H2O(bpmb2-=1,2-bis(pyridine-2-carboxamido)-4-methylbenze-nate)(1),并通过X-射线单晶衍射分析表征其结构特征。结果表明:吡啶甲酰胺配体H2bpmb的甲酰胺氮原子脱去氢原子形成带两个负电荷的扭曲的四配位螯合配体bpmb2-。1个钴(Ⅲ)离子与2个吡啶氮原子,2个bpmb2-配体上的桥联酰胺氮原子和2个氰基碳原子配位得到六配位、变形的八面体CoN4C2;另1个钴(Ⅲ)离子与2个吡啶氮原子,配体bpmb2-上的2个未桥联甲酰胺氮原子和2个桥联的甲酰胺氮原子六配位,形成扭曲的八面体CoN6配位构型。[Co2(bpmb)2(CN)2]单元通过自由水分子和氰基氮原子和甲酰胺氧原子之间O-H…N和O-H…O氢键形成锯齿型链状超分子亚结构,这些链状亚结构通过π-π相互作用连接起来形成网状的超分子结构。

A carboxamide nitrogen-bridged binuclear cobalt（Ⅲ） complex [Co2（bpmb）2（CN）2]·H2O（bpmb2-=1,2-bis（pyridine-2-carboxamido）-4-methylbenzenate）（1） has been synthesized and structurally characterized by single X-ray diffraction analysis.In the molecular structure,the pyridine carboxamide ligand H2bpmb forms twisted tetradentate chelate ligand bpmb2-with two negative charges after the deprotonation of the two carboxamide nitrogen atoms.One Co（Ⅲ） ion is coordinated by two pyridine nitrogen,two bridging carboxamide nitrogen atoms from two bpmb2-ligands,and two cis-cyanide carbon atoms,giving distorted octahedral CoN4C2 environment.Another Co（Ⅲ） ion in 1 is six-coordinated by two pyridine nitrogen,two unbridging carboxamide nitrogen and two bridging carboxamide nitrogen atoms from two bpmb2-ligands,yielding significantly distorted octahedral CoN6 geometry.It is noteworthy that the [Co2（bpmb）2（CN）2] units are connected through two O-H…N and O-H…O hydrogen bonds involving free water molecules and cyanide nitrogen and carboxamide oxygen atoms into zigzag chain-like substructures,then these chains are linked together by intermolecular π-π interactions,giving a network supramolecular structure.CCDC： 661715.