一氯桥双核铜配合物:Cu2(phen)2Cl4的合成、晶体结构及性质研究

人工晶体学报, 2002, 31(4): 365-369. doi: 10.3969/j.issn.1000-985X.2002.04.009

一氯桥双核铜配合物:Cu2(phen)2Cl4的合成、晶体结构及性质研究

孙杰 ^1, , 林建利 ^2, , 郑岳青 ^3, , 王继扬 ^4,

1.宁波大学固体材料化学研究所,无机材料化学市重点实验室,宁波,315211

2.宁波大学固体材料化学研究所,无机材料化学市重点实验室,宁波,315211

3.宁波大学固体材料化学研究所,无机材料化学市重点实验室,宁波,315211

4.山东大学晶体材料国家重点实验室,济南,250100

基金项目: 浙江省自然科学基金(01J02130-1) 浙江省自然科学基金(RC99034)

关键词：晶体结构 , 双核铜配合物 , 合成 , 磁性 , 热分析

Study on the Crystal Synthesis,Structure and Properties of a Chloro-bridged Dinuclear Copper (Ⅱ) Complex-Cu2(phen)2Cl4

本文报导了Cu2(phen)2Cl4配合物的合成方法.X射线衍射分析表明标题配合物属单斜晶系,空间群Cc(no.9),晶胞参数:a=0.9864(2)nm,b=1.7860(4)nm,c=1.3398(3)nm,β=106.60(3)°,V=2.262(8)nm3,Dc=1.848g/cm3,F(000)=1256,Z=4.3064个独立衍射点中2812个满足F2o2σ(F2o),R1和wR2分别为0.0482和0.1066.标题配合物由双核[Cu2(phen)2Cl4]络分子组成,每个铜原子与邻菲NFED4啉配体的2个N原子和3个Cl原子配位形成畸变CuN2Cl3四方锥.配位多面体通过两氯原子形成共棱的Cu2N4Cl6双四方锥.通过氢键和芳环堆积作用,络分子形成三维网络结构.标题配合物为顺磁物质,在5～300K区间内遵循Curie-Weiss定律,χm(T+0.649)=0.405cm3*K*mol-1(χm为每摩尔Cu2+离子磁化率),其Cu2+离子的室温有效磁矩为1.8 B.M.,与Cu2+自由离子的磁矩基本相同,表明铜离子之间不存在磁交换作用.热分析显示该配合物在290℃以下非常稳定.

参考文献

[1]	Kitajima N;Fujisawa K;Fujimoto C et al.A New Model for Dioxygen Binding in Hemocyanin.Synthesis,Characterization,and Molecular Structure of the μ-η2:η2 Peroxo Dinuclear Copper(Ⅱ) Complexes,[Cu(HB(3,5-R2pz)3)]2(O2)(R=i-Pr and Ph)[J].Journal of the American Chemical Society,1992(114):1277.
[2]	Kruger PE.;Moubaraki B.;Berry KJ.;Murray KS.;Fallon GD. .INTRAMOLECULAR FERROMAGNETISM IN A NOVEL HEXANUCLEAR (MU-HYDROXO)(MU-CARBONATO)COPPER(II) BIPYRIDINE COMPLEX - STRUCTURE OF [CU-6(BPY)(10)(MU-CO3)(2)(MU-OH)(2)](CLO4)(6)CENTER-DOT-4H(2)O AND OF A DINUCLEAR MU-CARBONATO COMPLEX, [CU-2(BPY)(4)(MU-CO3)][J].Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics,1995(19):4808-4814.
[3]	Kitajima N;Koda T;Hashimoto S et al.Synthesis and Characterization of the Dinuclear Copper(Ⅱ) Complexes[Cu(HB(3,5-Me2pz)3)]2X(X=O2-,(OH)2-2,CO2-3,O2-2)[J].Journal of the American Chemical Society,1991(113):5664.
[4]	Ruiz E.;Alvarez S.;Cano J.;Alemany P. .STRUCTURAL MODELING AND MAGNETO-STRUCTURAL CORRELATIONS FOR HYDROXO-BRIDGED COPPER(II) BINUCLEAR COMPLEXES[J].Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics,1997(17):3683-3688.
[5]	Ruiz E;Alemany P;Alvarez S et al.Toward the Prediction of Magnetic Coupling in Molecular Systems:Hydroxo-and Alkoxo-Bridged Cu(Ⅱ) Binuclear Complexes[J].Journal of the American Chemical Society,1997(119):1297.
[6]	Hernndez-Molina M;Gonzlez-Platas J;Ruiz-Pérez C et al.Crystal Structure and Magnetic Properties of the Single-μ-chloro Copper(Ⅱ) Chain [Cu(bipy)Cl2](bipy=2,2′-bipyridine)[J].Inorganica Chimica Acta,1999,284:258.
[7]	Viossat B;Gaucher J F;Mazurier A et al.Crystal Structure of bis(μ-chloro)bis[chloro-(o-phenanthroline-N,N′)Copper(Ⅱ)],Cu2(C12H8N2)2(Cl2)2.Z kristallogr[J].NCS,1998,213:329.
[8]	Boudreaux E A;Mulay L N.Theory and Applications of Molecular Paramagnestism[M].New York:John Wiley & Sons,1976
[9]	Sheldrick G M .SHELXS-97,Programm zur Lsung von Kristallstrukturen[Z].Gttingen,1997.
[10]	Sheldrick G M;SHELXL-97 .Programm zur Verfeinerung von Kristallstrukturen[Z].Gttingen,1997.
[11]	Zheng Y-Q;Sun J;Lin J-L.Hydrogenmaleato Bridged Supramolecular Double Chains via π-π Stacking Interactions:Syntheses,Crystal Structures and Magnetic Properties of 1∞ [Cu(phen)X(HL)2/2] with X=Cl-(1),NO-3(2) and H2L=Maleaic Acid[J].Journal of Chemical Crystallography
[12]	孙杰,林建利,郑岳青.[Cu（phen）2Cl] （OH）@ 5.5H2O的合成和晶体结构（phen = 1,10-phenanthroline）[J].宁波大学学报(理工版),2001(02):13-17.

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