配合物[Cu(Mba)_2(Im)_2]的水热合成、晶体结构和量子化学研究
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摘要
通过水热法,由Hmba(Hmba=methoxybenzoic acid)、Im(Im=imidazole)与Cu~(2+)离子反应,合成标题配合物[Cu(Mba)_2(Im)_2]。单晶X射线衍射分析表明,晶体属单斜晶系,空间群为P2(1)/c,晶胞参数:a=1.429 64(4)nm,b=1.147 34(3)nm,c=1.356 92(3)nm,β=102.789(2)°,V=2.170 52(1)nm3,Z=4,μ(MoKα)=10.54cm~(-1),F(000)=1 036,R_1=0.037 4,wR_2=0.093 0[I>2σ(I)]。在配合物中,中心铜原子与配位原子构成四配位的变形平面四方形构型。最小不对称单元间通过芳环间的π-π堆积、C-H…π弱相互作用和氢键,构筑成三维网状结构。此外,利用量子化学Gaussian03程序包,在lanl2dz基组上,研究了标题配合物的稳定性、配合物的分子轨道能量以及前沿分子轨道的成键特征。
The novel complex[Cu(Mba)_2(Im)_2]has been hydrothermally synthesized by Hmba and Im with copper(II),where Hmba=methoxybenzoic acid and Im=imidazole.The crystal structure of the complex has been determined by X-ray diffraction.The crystal belong to monoclinic system,space group P2(1)/c.The cell parameters are:a=1.429 64(4)nm,b=1.147 34(3)nm,c=1.356 92(3)nm,β=102.789(2)°V=2.170 52(1)nm~3,Z=4,μ(MoKα)=10.54cm~(-1),F(000)=1 036,R_1=0.037 4,wR_2=0.093 0[I>2σ(I)].The centric copper(Ⅱ)ions are four-coordinated in the distorted planar tetragon arrangement for the complex.Three-dimensional network is formed through weak interaction ofπ-πpacking,C-H …π,and hydrogen bonds.The study on the complex has been performed with quantum chemistry calculation by means of Gaussian 03 software package and taking Lanl2 dz basis set.The stabilities of the complex,the orbital energies and bonding characteristics of some frontier molecular orbital have been investigated.
The novel complex[Cu(Mba)_2(Im)_2]has been hydrothermally synthesized by Hmba and Im with copper(II),where Hmba=methoxybenzoic acid and Im=imidazole.The crystal structure of the complex has been determined by X-ray diffraction.The crystal belong to monoclinic system,space group P2(1)/c.The cell parameters are:a=1.429 64(4)nm,b=1.147 34(3)nm,c=1.356 92(3)nm,β=102.789(2)°V=2.170 52(1)nm~3,Z=4,μ(MoKα)=10.54cm~(-1),F(000)=1 036,R_1=0.037 4,wR_2=0.093 0[I>2σ(I)].The centric copper(Ⅱ)ions are four-coordinated in the distorted planar tetragon arrangement for the complex.Three-dimensional network is formed through weak interaction ofπ-πpacking,C-H …π,and hydrogen bonds.The study on the complex has been performed with quantum chemistry calculation by means of Gaussian 03 software package and taking Lanl2 dz basis set.The stabilities of the complex,the orbital energies and bonding characteristics of some frontier molecular orbital have been investigated.
引文
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[12]石智强,季宁宁,何国芳,等.以邻氯苯甲酸及联吡啶为配体的双核铜配合物的水热合成、晶体结构及量子化学研究[J].无机化学学报,2011,27(8):1507-1512.
[13]邝代治,冯泳兰,许金生,等.茂金属配合物[(eat5-C5H4R)Mo(CO)3]2(R:SiMe3,Si2Me5)的电子结构研究[J].化学物理学报,2003,16(1):59-63.
[14]邝代治,冯泳兰,张复兴,等.铜(11)配合物[Cu(pydc)(H2O)]2:合成、结构和量子化学的研究[J].计算机与应用化学,2008,25(3):319-322.
[15]杨一心,杨宜康,白晋涛,等.稀土与丙氨酸、咪唑三元配合物的FTIR和UV/VIS光谱[J].光子学报,2002,31(9):1120-1123.
[2]陈志敏,张复兴,曾荣英,等.[Cu(m-NBA)(2,2′-bipy)(H2O)].m-NBA.H2O的合成、晶体结构及电化学性质[J].无机化学学报,2009,25(3):548-551.
[3]石敬民,廖代正,程鹏,等.2-溴代对苯二甲酸根桥联双核钴(Ⅱ)配合物的合成、磁性及抗癌活性[J].无机化学学报,1996,12(4):372-376.
[4]朱恩静,刘琦,陈群,等.二维层状铜配位聚合物[Cu2(TFBDC)2(DMF)2]2.3MeOH·2DMF的合成、晶体结构和磁性(TFBDC=四氟对苯二甲酸根;DMF=N,N-二甲基甲酰胺)[J].无机化学学报,2008,24(9):1428-1433.
[5]李东平,陈志敏,匡云飞,等.配合物[Cu(NPA)2(Im)2(H2O)]·H2O的合成、晶体结构及电化学性质[J].无机化学学报,2007,23(5):892-896.
[6]杨颖群,李昶红,李薇.化合物Mn(C6H4O2N)2(H2O)4的水热合成、晶体结构及量子化学计算[J].计算机与应用化学,2010,27(12):1669-1672.
[7]陈志敏,邹建陵,杨颖群,等.基于大茴香酸与邻菲咯啉的异双桥联双核铜配合物的水热合成、结构、荧光和电化学性质[J].无机化学学报,2011,27(11):2167-2171.
[8]S.Youngme,J.Phatchimkun,N.Wannarit,et al.New ferromagnetic dinuclear triply-dyidged Copper(Ⅱ)compouns containning carboxylato bridges:Synthesis,X-pay structure and magnetic properties[J].Polyhedron,2008,27(1):304-318.
[9]安金,陈志达,卞江,等.混合价十二核锰配合物的合成、结构及磁性研究[J].北京大学学报:自然科学版,2000,36(4):439-447.
[10]Chen Z M,Feng Y L,Yang Y Q,et al.Hydrothermal synthesis,crystal structure and fluorescence properties of a three-dimensional triply-bridged binuclear zinc(Ⅱ)complex[Zn2(Mba)3(Phen)2 EtOH)]·ClO4[J].Chinese J.Struct.Chem.,2012,31(12):1803-1809.
[11]郭辉瑞,陶朱,祝黔江,等.配位化学中的C-H…π非键弱相互作用[J].无机化学学报,2002,18(5):435-441.
[12]石智强,季宁宁,何国芳,等.以邻氯苯甲酸及联吡啶为配体的双核铜配合物的水热合成、晶体结构及量子化学研究[J].无机化学学报,2011,27(8):1507-1512.
[13]邝代治,冯泳兰,许金生,等.茂金属配合物[(eat5-C5H4R)Mo(CO)3]2(R:SiMe3,Si2Me5)的电子结构研究[J].化学物理学报,2003,16(1):59-63.
[14]邝代治,冯泳兰,张复兴,等.铜(11)配合物[Cu(pydc)(H2O)]2:合成、结构和量子化学的研究[J].计算机与应用化学,2008,25(3):319-322.
[15]杨一心,杨宜康,白晋涛,等.稀土与丙氨酸、咪唑三元配合物的FTIR和UV/VIS光谱[J].光子学报,2002,31(9):1120-1123.