配合物[RE_2(H_2L)_2(HL)_2(2,6-H_2PDA)(H_2O)_2]·2H_2O的合成、晶体结构及其与DNA作用方式初探

以N-(2-异丙酸)-邻羟基苯甲酰腙(C10H10N2O4,H3L)、2,6-吡啶二甲酸(2,6-H2PDA)与RE(NO3)3·nH2O(RE=Pr,Eu)在室温下反应,合成了配合物1[Pr2(H2L)2(HL)2(2,6-H2PDA)(H2O)2]·2H2O和配合物2[Eu2(H2L)2(HL)2(2,6-H2PDA)-(H2O)2]·2H2O,对其进行了元素分析、红外光谱、紫外光谱等表征,测定了两种配合物的晶体结构.通过紫外吸收光谱、荧光发射光谱和稳态荧光猝灭方法及其与溴化乙锭(EB)的竞争实验研究了两种配合物与小牛胸腺DNA的作用情况.结果表明,两种配合物与小牛胸腺DNA均是以插入方式结合的.     

单核铜配合物[Cu~(II)(HIPP)(pydc)(H_2O)]的合成和晶体结构

用溶剂热合成方法合成了一个单核铜配合物CuII(HIPP)(pydc)(H2O),采用元素分析法和X射线单晶衍射法对该配合物的组成和结构进行了表征.配合物CuII(HIPP)(pydc)(H2O)属于正交晶系,空间群是Pbca.a=0.663 93(18)nm,b=2.062 2(6)nm,c=2.619 1(7)nm,α=90°,β=90°,γ=90°,V=3.585 9(17)nm3,Z=8,ρc=1.693g·cm-3,F(000)=1 864,GOF=0.882,R1=0.037 4,wR2=0.111 8[I2σ(I)].中心铜原子与配体脱质子2,6-吡啶二甲酸的2个羧基氧原子和1个氮原子、HIPP的1个氮原子和1个氧原子及1个水分子中的氧原子形成六配位的变形八面体.结构分析表明晶体中分子间含有氢键.     

配合物[Co2(EGTB)Cl2]•(BF4)2•5H2O与DNA相互作用的研究

用紫外光谱法、荧光光谱法、黏度法、凝胶电泳法研究了双核钴(II)配合物[Co2(EGTB)Cl2]•(BF4)2•5H2O和DNA的相互作用, 在pH＝7.2的缓冲体系中, 求得配合物与DNA的结合常数. 结果表明, 配合物在接近生理条件下能有效地断裂pBR322DNA, 同时可使DNA的粘度增加, 使EB-DNA体系的荧光强度降低. 配合物与DNA的荧光光谱和紫外光谱表明, 配合物与DNA的作用既存在部分插入结合又存在静电结合模式.     

配合物(n-Bu)2Sn(C10H8N2O4)(C2H5OH)的合成和晶体结构

以2-羰基丙酸水杨酰腙作为配体与二正丁基氧化锡(Ⅳ)在苯/乙醇混合溶剂中反应, 合成了新型配合物(n-Bu)2Sn(C10H8N2O4)(C2H5OH)(C10H8N2O42为2-羰基丙酸水杨酰腙负二价离子)。用单晶X-射线衍射分析法测定了该配合物的晶体结构。晶体属四方晶系, I41/a空间群, 晶胞参数a = 2.5113(7), b = 2.5113(7), c = 1.5062(6) nm, V = 9.499(5) nm3, Z = 16, Dc = 1.396 g/cm3, m(MoKa) = 1.105 mm1, F (000) = 4096。对于2499 (I >2s(I))个可观测点, 最终可靠因子R = 0.0349, wR = 0.0793。在该配合物的分子结构中, 中心锡原子与3个O原子、1个N原子和2个C原子形成扭曲的八面体几何构型, 其中3个O原子和1个N原子为赤道配位原子, 而CSnC为配合物的轴。相邻配合物分子间因Sn…O的弱相互作用和分子间氢键的作用而以二聚体的结构形式存在。     

多元混配合物[Ni(NPA)2(Phen)(Ac)(H2O)]·H2O的合成、晶体结构

0引言镍是生物体中必须的痕量元素,常成为一些酶的活性中心,因而模拟镍酶并研究其结构,一直是生物无机化学等领域的重要研究课题,近年来镍配     

希土胺羧酸配合物的研究——Ⅲ.吡啶-2,6-二甲酸钕配合物{[Nd(HDPA)(DPA)(H_2O)_2]·4H_2O}_n合成及其晶体结构

关于吡啶-2,6-二甲酸希土配合物晶体结构有Na_3[Ln(DPA)_3]·yNaClO_4·xH_2O类型的报道。本文合成了{[Nd(HDPA)(DPA)(H_2O)_2]·4H_2O}_n。配合物单晶并测定了其结构。 将硝酸希土溶液与吡啶-2,6-二甲酸以1:3的摩尔比混合,加入适量蒸馏水和四甲基铵盐,加热搅拌并滴加四甲基铵碱至吡啶-2,6-二甲酸溶解。冷却后调溶液pH至2,室温下放置数天得到单晶。     

2′-(2-噻吩亚甲基)-2-羟基苯甲酰腙钴(Ⅲ)配合物的合成、表征及晶体结构

In ethanol, a mononuclear cobalt(Ⅱ) complex incorporating 2′-(2-Thienylidene)-2-Hydroxybenzoylhydra-zide has been synthesized and characterized by IR, UV-Vis, elemental analysis and X-ray crystal structure analysis. The crystal belongs to triclinic system, space group P1 with cell constant, a=1.230 69(10) nm, b=1.329 18(11) nm, c=1.330 56(11) nm, α=113.702(2)°, β=91.590(2)°, γ=100.846(2)°, V=1.944 4(3) nm³, Z=2, μ=0.662 mm^-1, D_c=1.482 g·cm^-3, F(000)=896, R_int=0.048 7. The crystal structure shows an anionic didentate ligand O and N donors in this work. The cobalt(Ⅲ) atom is hexacoordinated with oxygen atom from keto group and nitrogen atom from amide to form a cobalt atom for the core octahedral structure. CCDC: 748882.     

配合物[Ni(IDB)2]2•(SO4)2•3CH3CH2OH•CH3OH•5H2O的合成、 晶体结构及其荧光光谱的研究

标题配合物是由三齿配体N,N-二(2-苯并咪唑甲基)亚胺(IDB)与NiSO4•6H2O在甲醇-乙醇溶液中反应得到的紫色晶体. X射线衍射测定了其单晶结构. 结构分析表明, 镍(II)分别与两个IDB配体中的苯并咪唑的四个氮和胺基的两个氮配位形成畸变的八面体构型. 研究了纳米金和小牛胸腺DNA对配合物荧光的影响, 探讨了配合物的荧光猝灭与恢复的可能机理.     

二聚体配合物[(n-Bu)2Sn(C10H8N2O3)(C2H5OH)]2的合成和晶体结构

The novel seven-coordinate complex [(n-Bu)₂Sn(C₁₀H₈N₂O₃)(C₂H₅OH)]₂ (C₁₀H₈N₂O₃^2- is the dinegative ion of 2-oxo-propionic acid benzoyl hydrazone) was synthesized by the reaction of (n-Bu)₂SnO with 2-oxo-propionic acid benzoyl hydrazone in 1∶1 molar ratio in benzene-ethanol (V/V, 3/1), and its structure was characterized by X-ray single crystal diffraction. The crystal belongs to a tetragonal system with space group I4₁/a, a=2.4890(2)nm, b=2.4890(2)nm, c=1.5170(3)nm, V=9.398(2)nm³, Z=8, F(000)=3968, D_c=1.366g·cm^-3, and the structure was refined to final R₁=0.0530, wR₂=0.0971. The structure of the title complex is described as a dimer through weak interactions of Sn…O bonding and hydrogen bond. The tin atoms rendered sev-en-coordination in a distorted pentagonal bipyramid geometry structure, four oxygen atoms [O1, O2, O2^#1 and O4] and one nitrogen atom N2 formed the equatorial plane and C11-Sn1-C15 is the axis. CCDC: 212696.     

配合物[Cu(CAM)(H2O)2]的水热合成与结构表征

A copper(II) complex [Cu(CAM)(H₂O)₂], (CAM=4-hydroxypyridine-2,6-dicarboxylic acid), has been hydr-othermally synthesized and characterized by elemental analysis, IR, and X-ray diffraction single crystal structure analysis. It belongs to triclinic system, with space group P1, a=0.783 3(3) nm, b=0.796 5(3) nm, c=0.798 6(3) nm, α=100.340(6)°, β=93.768(6)°, γ=109.348(5)°, V=0.458 3(3) nm³, Z=2. The copper(II) ion is 5-coordinated and exhi bits a distorted square pyramidal coordination environment. The two coordinated aqueous molecules and the oxygen atoms from the ligand generate the intermolecular hydrogen bonds, which result in the 2D supramolecular network. CCDC: 227156.     

混配配合物[Cu(2-mpac)(SCN)(H2O)•H2O]n的合成、结构与磁性研究

在水溶液中以Cu(NO3)2•3H2O, 2-mpac和KSCN反应得到了一个通过硫氰酸根桥连的混配配合物[Cu(2-mpac)(SCN)(H2O)•H2O]n (1) (2-mpac: 5-methylpyrazine-2-carboxylic acid), 利用元素分析, 红外光谱, 单晶X射线衍射, X射线粉末衍射以及热重分析对配合物1进行了表征. 晶体学数据: 三斜晶系, P-1空间群, a＝0.5567(2) nm, b＝1.0339(3) nm, c＝1.0532(3) nm, α＝64.030(2)°, β＝77.620(3)°, γ＝85.945(3)°, V＝0.5321(3) nm3, Z＝2, S＝1.061, 最终偏离因子[I＞2σ(I)] R1＝0.0444, wR2＝0.0905, 对于全部数据R1＝0.0647, wR2＝0.0988. 变温磁化率研究表明配合物1中的Cu(II)离子之间存在弱的反铁磁相互作用.     

RE(Hsal)2•(tch)•2H2O配合物与大肠杆菌作用的热动力学研究

用TAM air微量热仪测定了新合成的稀土水杨酸硫代脯氨酸配合物RE(Hsal)2•(tch)•2H2O (RE＝La, Sm; Hsal＝C7H5O3; tch＝C4H6NO2S)在37.00 ℃时对大肠杆菌作用的产热曲线; 根据产热曲线求算了在稀土水杨酸硫代脯氨酸配合物作用下, 大肠杆菌生长代谢的最大发热功率Pmax、速率常数k、传代时间tG、抑制率I和半抑制浓度cI,50等热动力学参数. 结果表明: 稀土水杨酸硫代脯氨酸配合物在低浓度下对大肠杆菌有刺激作用, 高浓度下为抑制作用, 即稀土配合物对微生物的生长具有双向生物效应, 也称为Hormesis效应. 配合物La(Hsal)2•(tch)•2H2O和Sm(Hsal)2•(tch)•2H2O的半抑制浓度cI,50分别为7.60和1.62 mg•L－1. 即配合物Sm(Hsal)2•(tch)•2H2O的抑制效果优于La(Hsal)2•(tch)•2H2O.     

混合价配位聚合物 - [Cu(en)2H2O]2•8H2O的水热合成与晶体结构

在水热条件下合成了一个新的混合价配位聚合物 [Cu(en)2H2O]2•8H2O, 并对其进行了元素分析, IR, UV, TG-DSC等表征. X射线单晶衍射结果表明, 化合物属于单斜晶系, P21/c空间群, 晶胞参数a＝1.88678(12) nm, b＝2.30383(14) nm, c＝2.61234(16) nm, α＝90°, β＝95.844(1)°, γ＝90°, V＝11.2964(12) nm3, Z＝4, Dc＝3.954 g/cm3, R1＝0.0975, wR2＝0.2041. 结构测定结果表明, 聚合物中杂多阴离子骨架通过氧桥相连并形成一维无限链. 热性质研究表明, 形成标题化合物后杂多阴离子骨架分解温度大约在600.4 ℃, 热稳定性较母体杂多酸明显增强.     

Synthesis and Crystal Structure of [Cu2（DMF）（H2O）（C7H4NO4）2（C7H3NO4）]2·3.5DMF

A new copper（H） complex [Cu2（DMF）（H2O）（C7H4NO4）2（C7H3NO4）]2-3.5DMF has been synthesized and its structure was determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1^- with a = 10.722（3）, b = 18.170（4）, c = 20.923（7）A,α = 105.297（9）, β = 101.701（10）, γ = 105.74（1）°, V= 3615（1）A^3, Z = 2, C58.50H64.50Cu4N1l.50O3150, Mr = 1686.90, Dc = 1.550 g/cm^3,μ= 1.255 mm^-1, F（000） = 1728.00, T = 150（2） K, the final R = 0.0640 and wR = 0.173 for 11310 observed reflections with I 〉 2σ（I）. In the crystal, each formular unit consists of two dinuclear copper（H） compounds, between which the O-H…O hydrogen bonds exist. Each Cu^Ⅱ cation is six-coordinated in an octahedral geometry. The intermolecular hydrogenbonding interaction leads to a 3-D framework of the title compound.     

Synthesis and Crystal Structure of a Palladium(II) Coordination Polymer [Na_2Pd(2,6-pydc)_2(H_2O)_6]_n

A novel coordination polymer [Na2Pd(2,6-pydc)2(H2O)6]n (2,6-H2pydc = 2,6-pyri- dinedicarboxylic acid) has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/c, with a = 11.962(2), b = 6.5552(13), c = 12.673(3) , β = 91.72(3)°, V = 993.3(3) 3, Z = 2, Mr = 590.68, Dc = 1.975 g/cm3, μ = 1.059 mm-1, F(000) = 592, the final R = 0.0211 and wR = 0.0454. In the crystal the Pd(II) ion adopts a distorted four-coordinated square-planar geometry and bonds to two bidentate 2,6-pyridinedicarboxylate molecules through caronyl oxygen and pyridine nitrogen atoms. The title complex exhibits a novel three-dimensional network structure.     

Synthesis and Crystal Structure of a New Complex {[Co~(Ⅲ)L_2]·[Co~(Ⅱ)(H_2O)_6]_(0.5)·2.25H_2O}_4 (H_2L = N-(2-Hydroxyphenyl)salicylidenimine)

The reaction of Co(OAc)2·4H2O with the Schiff base H2L in a methanol solution affords the red crystals of {[CoIIIL2]·[CoII(H2O)6]0.5·2.25H2O}4 1 (H2L = N-(2-hydroxyphenyl) sali-cylidenimine). The molecular and crystal structures were determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/n, C104H114Co6N8O37, Mr = 2421.61, a = 10.625(3), b = 16.335(4), c = 15.265(4) , β = 102.990(4)o, V = 2581.6(11) 3, Z = 1, Dc = 1.558 g/cm3, μ = 1.034 mm-1, F(000) = 1252, R = 0.0414 and wR = 0.1167 for 5889 reflections. The Co(III) atom is six-coordinated by two nitrogen atoms and four oxygen atoms of two tridentate L ligands. The abundant hydrogen bonding interactions extend the complex into a one-dimensional supra-molecular framework. The uncoordinated water molecules act as space-fillers and consolidate the whole architecture through the hydrogen bonding interactions.     

新颖一维配位聚合物[Ni(3，5-pdc)(H2O)4]·(H2O)的合成与晶体结构

The hydrothermal reaction of 3,5-pyridinedicarboxylic acid and NiCl₂·6H₂O results in a novel coordination polymer， [Ni(3,5-pdc)(H₂O)₄]·(H₂O). The crystal structure of the compound was determined by X-ray single crystal diffraction. The crystal belongs to monoclinic system with space group P2₁/n, a=1.136 1(3)nm, b=0.709 8(2) nm, c=1.459 7(4) nm, β=107.538(4)°， V=1.122 4(6) nm³, D_c=1.858 g·cm^-1, Z=4, F(000)=648, R₁=0.0264, wR₂=0.0665. CCDC: 224880.     

新型二维异核配位聚合物{[NdBi(cydta)(NO3)2(H2O)4]•2.5H2O}n的 晶体结构与热分解

由Bi(Hcydta)•5H2O和Nd(NO3)•6H2O按1︰1的物质的量比, 在水溶液中合成了含Bi(III)-Nd(III)的异核配位聚合物{[(NO3)Nd(H2O)4(μ3-cydta)Bi(μ-ONO2)]•2.5H2O}n. 用元素分析、红外光谱、热重-差热和X射线单晶衍射等手段对标题配合物的组成和结构进行了表征. 该配合物属三斜晶系, 空间群 , 晶胞参数: a＝0.9235(3) nm, b＝1.0902(4) nm, c＝1.4253(5) nm, α＝71.840(4)°, β＝86.877(4)°, γ＝76.991(4)°, Z＝2, Mr＝936.65, V＝1.3284(8) nm3, Dc＝2.342 g• cm－3, μ＝8.646 mm－1, F(000)＝900, 最终偏离因子R1＝0.0406, wR2＝0.1124. 在该配合物中, 铋(III)与配体cydta4－的4O2N和1个硝酸根中1个O原子以及邻位分子的硝酸根形成8配位的畸变双帽三棱柱. 钕(III)与4个水分子的O, 1个硝酸根中2个O以及来自3个不同配体cydta4－的桥联羧基O结合, 形成9配位的三帽三棱柱构型. 羧酸根在Bi—Nd和硝酸根在Bi—Bi间的桥联作用, 使得整个配合物分子连接成无限二维框架结构. 热分析以及分解产物的红外光谱表明配合物热分解经历脱水、配体热分解、硝酸盐转变成氧化物等多步连续分解过程, 最后在625 ℃失重恒定.