无机化学学报
無機化學學報
무궤화학학보
JOURNAL OF INORGANIC CHEMISTRY
2012年
2期
411-416
,共6页
倪中海%聂景%李国玲%马瑞
倪中海%聶景%李國玲%馬瑞
예중해%섭경%리국령%마서
钴(Ⅲ)配合物%晶体结构%超分子组装%酰胺氮桥联
鈷(Ⅲ)配閤物%晶體結構%超分子組裝%酰胺氮橋聯
고(Ⅲ)배합물%정체결구%초분자조장%선알담교련
cobalt(Ⅲ) complex%crystal structure%supramolecular assembly%carboxamide nitrogen-bridged
合成了1个酰胺氮桥联的双核钴(Ⅲ)配合物[Co3(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.
閤成瞭1箇酰胺氮橋聯的雙覈鈷(Ⅲ)配閤物[Co3(bpmb)2(CN)2]· H2O (bpmb2-=1,2-bis(pyridine-2-carboxamido)-4-methylbenze-nate) (1),併通過X-射線單晶衍射分析錶徵其結構特徵.結果錶明:吡啶甲酰胺配體H2bpmb的甲酰胺氮原子脫去氫原子形成帶兩箇負電荷的扭麯的四配位螯閤配體bpmb2-.1箇鈷(Ⅲ)離子與2箇吡啶氮原子,2箇bpmb2-配體上的橋聯酰胺氮原子和2箇氰基碳原子配位得到六配位、變形的八麵體CoN4C2;另1箇鈷(Ⅲ)離子與2箇吡啶氮原子,配體bpmb2-上的2箇未橋聯甲酰胺氮原子和2箇橋聯的甲酰胺氮原子六配位,形成扭麯的八麵體CoN6配位構型.[Co2(bpmb)2(CN)2]單元通過自由水分子和氰基氮原子和甲酰胺氧原子之間O-H…N和O-H…O氫鍵形成鋸齒型鏈狀超分子亞結構,這些鏈狀亞結構通過(Π)-(Π)相互作用連接起來形成網狀的超分子結構.
합성료1개선알담교련적쌍핵고(Ⅲ)배합물[Co3(bpmb)2(CN)2]· H2O (bpmb2-=1,2-bis(pyridine-2-carboxamido)-4-methylbenze-nate) (1),병통과X-사선단정연사분석표정기결구특정.결과표명:필정갑선알배체H2bpmb적갑선알담원자탈거경원자형성대량개부전하적뉴곡적사배위오합배체bpmb2-.1개고(Ⅲ)리자여2개필정담원자,2개bpmb2-배체상적교련선알담원자화2개청기탄원자배위득도륙배위、변형적팔면체CoN4C2;령1개고(Ⅲ)리자여2개필정담원자,배체bpmb2-상적2개미교련갑선알담원자화2개교련적갑선알담원자륙배위,형성뉴곡적팔면체CoN6배위구형.[Co2(bpmb)2(CN)2]단원통과자유수분자화청기담원자화갑선알양원자지간O-H…N화O-H…O경건형성거치형련상초분자아결구,저사련상아결구통과(Π)-(Π)상호작용련접기래형성망상적초분자결구.
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.