Synthesis and Crystal Structure of [{Mn(IBG)(2,2'-bipy)(H_2O)}·4H_2O]_n

A novel MnⅡ complex [{Mn(IBG)(2,2'-bipy)(H2O)}·4H2O]n 1(H2IBG=isophtha-loylbisglycine and 2,2'-bipy = 2,2'-bipyridine) has been synthesized and characterized by singlecrystal X-ray diffraction,elemental analysis,IR spectra and thermogravimetric analysis.It crystallizes in monoclinic,space group P21/n,with a=13.667(2),b=14.045(2),c=14.195(2),β=101.483(3)°,V=2670.1(7)3,Z=4,C22H26N4O11Mn,Mr=577.41,Dc=1.436 g/cm3,F(000)=1196.0,μ(MoKα)=0.558 mm-1,the final R=0.0578 and wR=0.1460 for 2974 observed reflections with I2σ(I).In the structure,the MnⅡ atom is coordinated in a distorted octahedral environment arranged by one water molecule,one 2,2'-bipy ligand and two IBG ligands.     

Co(μ2-bpy)V2O6(bpy=4,4′-联吡啶)的水热合成和晶体结构

采用CoCl2·6H2O、4,4′-联吡啶和NH4VO3,以H2O作溶剂(摩尔比1:2:2:1950)在170℃下水热反应合成无机-有机杂化化合物Co(μ2-bpy)V2O6(bpy=4,4′-联吡啶),经单晶X射线衍射测定其晶体结构.此晶体属三斜晶系,空间群为Pi,晶胞常数a=0.81599(7)nm,b=0.85826(7)nm,c=1.02031(8)nm,α=87.111(2)°,β=75.305(2)°,y=74.784(2)°,Z=2.Co(μ2-bpy)V2O6是无机的双金属氧化物层,[Co2V4O12]n通过有机的桥式配体μ2-bpy以N-Co配位键桥联而成.晶体的三维共价结构含有多种开放式孔道,其中最大孔道的尺寸为0.5nm×0.7nm.漫反射光谱研究表明,此晶体具有约2.0 eV的光学能隙,属于半导体,在420℃以下是热稳定的.     

联苯四甲酸及联吡啶构筑的一维链状银(Ⅰ)配合物的合成及晶体结构

采用水热法合成了一个新颖的配合物{[Ag(4,4′-bpy)][Ag2(H3btc)(H2btc)(4,4′-bpy)2].3H2O}n(1)(H4btc=联苯-2,2′,4,4′-四甲酸;4,4′-bpy=4,4′-联吡啶),并对其进行了元素分析、红外光谱和X射线单晶衍射测定。配合物1属于三斜晶系,空间群为P1,a=1.122 51(6)nm,b=1.554 01(8)nm,c=1.774 59(9)nm,β=91.641 0(10)°,V=2.830 8(3)nm3,Z=2,Dc=1.764 g.cm-3,μ=1.113 mm-1,F(000)=1 508,R1=0.045 0,wR2=0.086 2(I>2σ(I))。在1中,一维线性[Ag(4,4′-bpy)]+阳离子链包含在一维{[Ag2(H3btc)(H2btc)(4,4′-bpy)2]-阴离子双链与游离水分子通过分子间氢键组装成的三维超分子结构中。研究了配合物的热稳定性和电化学性质。     

两个金属铜配位聚合物Cu3(2,2′-bipy)2(C8H4O4)2(C8H5O4)2和Cu(Ⅰ)Cu(Ⅱ)(4,4′-bipy)1.5(C8H4O4)(C8H5O4)混合溶剂热合成及结构与性能研究

在中温混合溶剂热条件下合成了两个金属铜配位聚合物Cu3(2,2′-bipy)2(C8H4O4)2(C8H5O4)2和Cu(Ⅰ)Cu(Ⅱ)(4,4′-bipy)1.5(C8H4O4)(C8H5O4)(bipy=联吡啶,C8H4O4=1,3-间苯二甲酸),并对其进行了单晶结构解析及相关性能表征.配合物Cu3(2,2′-bipy)2(C8H4O4)2(C8H5O4)2(1)晶体属三斜晶系,P1空间群,a=1.03314(4)nm,b=1.08350(3)nm,c=1.15826(4)nm,α=83.104(2)°,β=84.609(2)°,γ=66.125(2)°,Z=1.配合物Cu(Ⅰ)Cu(Ⅱ)(4,4′-bipy)1.5(C8H4O4)(C8H5O4)(2)晶体属三斜晶系,P1空间群,a=1.06979(3)nm,b=1.09209(3)nm,c=1.47887(3)nm,α=91.795(2)°,β=93.2460(10)°,γ=118.6170(10)°,Z=2.通过使用不同的有机碱配体(2,2′-联吡啶和4,4′-联吡啶),并调节不同有机碱配体的用量,得到了结构不同的两个目标晶体产物相.产物均可稳定到3...     

含单蝶状[2Fe2S]骨架的新型[FeFe]氢化酶模型物｛(μ-FcS)(μ-SMe)Fe_2(CO)_6｝的合成及其晶体结构

利用二茂铁基溴化镁(FcMgBr)与(μ-S2)Fe2(CO)6和MeI的反应,合成了一种新型的含二茂铁基[FeFe]氢化酶活性中心模型化合物——(μ-FcS)(μ-SMe)Fe2(CO)6(1),其结构经1H NMR,IR,元素分析和X-射线单晶衍射表征。1属于斜方晶系,Pna2(1)空间群,晶胞参数a=12.707(2),b=11.355(2),c=27.621(5),V=3 985.1(12)3,Z=8,Dc=1.813 g.cm-3,μ=2.395 mm-1,F(000)=2 176,R1=0.059 7,wR2=0.136 7。     

[Ni(2,2′-bpy)3]MoO4·7.5H2O的水热合成和晶体结构

合成了一种新的钼-氧化合物[Ni(2,2′-bpy)3]MoO4@7.5H2O,用元素分析、IR和TGA-DTA等手段进行了表征,并用X射线衍射法测定了晶体结构.结果表明,该化合物属于单斜晶系,C2/c空间群,a=23.019(5),b=13.967(3),c=23.510(5)（A）,β=107.28(3)°,V=7217(3)(A)3,Z=8,Dc=1.514 g/cm3,F(000)=3384,Mr=822.32,μ(MoKα)=0.934 mm-1.结构由直接法解出,全距阵最小二乘法修正,最终偏离因子R=0.0358,wR=0.0797.结构测定表明,结构中阴离子MoO42-与配位阳离子[Ni(2,2′-bpy)3]2+之间靠静电作用相结合,同时与H2O通过氢键构成无机阴离子层.     

Synthesis,Structure and Characterization of [Cu(2,2′-bpy)_2][{Cu(2,2′-bpy)_2}_2W_(12)O_(40)(H_2)]·4H_2O

An organic-inorganic compound [Cu(2,2′-bpy)2][{Cu(2,2′-bpy)2}2W12O40(H2)]·4H2O (Mr = 4048.00) was prepared from the hydrothermal reaction of Na2WO4·2H2O, CuCl2·2H2O, 2,2′-bipyridine (2,2′-bpy) and H2O at 160 ℃ for 4 days. The compound crystallizes in the monoclinic system, space group P21/n with a = 18.9196(8), b = 20.4212(8), c = 21.8129(9) , β = 96.992(3)°, V = 8365.0(6) 3, Dc = 3.214 g/cm3, Z = 4, μ(MoKα) = 17.269 mm-1 and F(000) = 7324. Of the 119837 total reflections, 17315 were unique (Rint = 0.0489). The final R = 0.0385 and wR = 0.0770 for 11142 observed reflections with I > 2σ(I). Single-crystal X-ray diffraction reveals that the structure is composed of [{Cu(2,2′-bpy)2}2W12O40(H2)]2- anions, discrete [Cu(2,2′-bpy)2]2+ cations and lattice water molecules, and the anion is made up of a {W12O40(H2)}6- α-Keggin core decorated with two {Cu(2,2′-bpy)2}2+ groups through bridging oxygen atoms.     

A Novel Three-dimensional Ni Coordination Polymer Based on Flexible Di-carboxylate Ligand and 4,4-Pyridine： Synthesis, Characterization and Topological Analysis

A novel Ni(II) coordination polymer [Ni(dtba)(4,4′-bpy)] (1, H2dtba = 2,2′-dithio- bisbenzoic acid, 4,4′-bpy = 4,4′-bipyridine) has been synthesized by H2dtba and Ni(CH3COO)2·4H2O with exo-bidentate rigid ligand 4,4′-bpy by using hydrothermal method, and its structure was determined by single-crystal X-ray diffraction. X-ray crystal structure analysis reveals that complex 1 crystallizes in monoclinic, space group Cc with a = 11.7624(9), b = 18.7933(19), c = 10.3071(11), β = 97.6510(10)°, V = 2258.2(4)3, Z = 4, C24H16N2NiO4S2, Mr = 519.22, Dc = 1.527 g/cm3, μ = 1.079 mm-1 and F(000) = 1064. The structure was solved by direct methods and refined to R = 0.0434 and wR = 0.1000 for 3281 observed reflections (I > 2σ(I)). The coordination environment of Ni(II) is a distorted octahedron, and a three-dimensional structure was formed with the coordination effect of dtba2- and 4,4′-bpy ligands. The topological analysis reveals that the whole framework of 1 is a 2-nodal net of (52.6)(53.64.72.8) topology. The thermal stability and XRD pattern of 1 were also investigated.     

配合物[Cd(C_9H_8O_3N)_2(2,2′-bipy)(H_2O)]_2·(H_2O)_3的合成、结构及荧光和电化学性质(英文)

以对乙酰氨基苯甲酸和2,2′-联吡啶为配体合成了一个新配合物[Cd(C9H8O3N)2(2,2′-bipy)(H2O)]2·(H2O)3。该配合物晶体属三斜晶系,空间群P1,晶胞参数:a=1.2559(3)nm,b=1.5068(3)nm,c=1.6507(3)nm,α=112.14(3)°,β=101.83(3)°,γ=93.84(3)°,V=2.7959(10)nm3,Dc=1.592g·cm-3,Z=4,μ(MoKα)=0.840mm-1,F(000)=1364,最终偏离因子R1=0.0276,wR2=0.0683。标题配合物的不对称单元由2个独立的单核结构Cd(C9H8O3N)2(2,2′-bipy)(H2O)和3个晶格水分子组成。中心镉髤离子处于六配位的变形八面体环境中。本工作测定了配合物的荧光和电化学性能。     

Hydrothermal Synthesis and Crystal Structure of a Novel Dinuclear Co(Ⅱ) Complex: [Co2(2,2(')-bpy)2((-L)2(L)2(μ-H2O)] (HL = 4-Chlorobenzoic Acid)

A new 4-chlorobenzoic acid bridge Co(Ⅱ) complex [Co2(2,2(')-bpy)2(μ-L)2(L)2(μ- H2O)] (HL = 4-chlorobenzoic acid) has been obtained by hydrothermal synthesis, and X-ray single-crystal diffraction analysis shows that it crystallizes in the monoclinic system, space group C2/c with a = 22.537(5), b = 16.212(3),c = 15.306(3)(A), β= 124.37(3)°, V = 4616.1(16) (A)3, Mr = 1070.45, Dc = 1.540 g/cm3, Z = 4, μ = 1.012 mm-1, F(000) = 2176, the final R = 0.0338 and Wr = 0.0810. The title complex is composed of dinuclear [Co2(2,2(')-bpy)2(μ-L)2(L)2(μ-H2O)] molecules. Each Co(Ⅱ) atom is coordinated by two nitrogen atoms from one 2,2'-bipyridine ligand, three oxygen atoms from three 4-chlorobenzoic ions and another oxygen atom from one water molecule. The two Co(Ⅱ) atoms are connected by two 4-chlorobenzoic ions and one bridged water molecule. The dinuclear molecules are interlinked by hydrogen bond and π-π stacking interactions into a three-dimensional supramolecular network.     

两种N-2-嘧啶基-4-氨基苯磺酰Co(Ⅱ)配合物的合成、晶体结构及电催化性能研究(英文)

水热法合成两种新的Co(Ⅱ)化合物[Co(SD)2(2,2′-bpy)](1)和{[Co(SD)2(4,4′-bpy)]·4H2O}n(2)(SD=N-2-嘧啶基-4-氨基苯磺酰,2,2′-bpy=2,2′-联吡啶,4,4′-bpy=4,4′-联吡啶),并通过元素分析、红外光谱、X射线粉末衍射、热重分析、循环伏安法进行结构和性能表征。单晶X-ray衍射分析表明化合物1是三斜晶系,空间群为P1;化合物2是单斜晶系,空间群为C2/c。电催化实验发现化合物1和2对H2O2、HCHO都具有良好的电催化活性。     

二维配位聚合物[Cu(ox)(4,4′-bpy)]n的水热合成与结构表征

采用水热方法合成出一种新型配位聚合物[Cu(ox)(4,4′-bpy)]n(ox=草酸根离子,4,4′-bpy=4,4′-联吡啶),并通过X射线单晶结构分析、元素分析以及红外光谱测定对该化合物进行了表征.结果表明,标题化合物属于单斜晶系,Cm空间群,晶胞参数a=1·1921(7)nm,b=1·153(7)nm,c=0·5155(4)nm,β=113·38(3)°,V=0·6291(7)nm3,Z=2.该化合物是一个由{Cu(ox)}n链通过桥联配体4,4′-bpy垂直相连并具有矩形格子结构的二维层状配位聚合物,层与层之间交错排列,通过C4,4′-bpy—H…Oox层间氢键作用,进一步扩展成三维超分子网络结构.     

双三苯膦铁硫原子簇配合物(μ-i-C3H7S)(μ-PhCH2S)-Fe2(CO)4(PPh3)2的合成及晶体结构

通过(μ-i-C3H7S)(μ-PhCH2S)Fe2(CO)6和三苯膦在甲苯中回流反应6h, 制得了三苯膦双取代配合物(μ-i-C3H7S)(μ-PhCH2S)Fe2(CO)4(PPh3)2(1), 并用X射线衍射技术测得其单晶结构. 晶体属三斜晶系, 空间群为PI. 晶胞参数: a=10.268(4),b=20.289(1), c=22.799(5)埃; a=94.73(1)°, β=102.98(2)°, γ=89.93(1)°;V=4610.5埃^3, Z=4, Dc=1.36g/cm^3. 晶体结构用直接法(MULTAN 82)测定, 采用块矩阵最小二乘法进行最终结构精化, 最后偏离因子R=0.059, Rw=0.068. 单晶X射线分析表明, 配合物1的簇核是由两个铁原子和两个硫原子组成的蝴蝶式结构; 两个三苯膦配体处于铁-铁弯键的反位; 异丙基和苄基分别以6键与硫相连.     

Co(2,2'-bipy)(H2O)V2O6的合成及其晶体结构

以Co(NO3)2,2,2'-联吡啶(2,2'-bipy)及NaVO3为原料,采用水热法于200 ℃合成了一种新的有机-无机杂化材料--Co(2,2'-bipy)(H2O)V2O6(1),其结构经IR,热重分析及X-射线单晶衍射表征.结果表明,1属于单钭晶系,空间群为P21/c,晶胞参数为:a=7.855 6(3)(A),b=21.056 2(5)(A),c=9.552 1(6)A,α=90.000°,β=110.236(5)°,γ=90.000°,V=1 423.65(8)(A)3,Z=2,Dc=2.126 g·cm-3,μ(Mo Kα)=2.548mm-1,R1=0.058 6,wR2=0.093 5.1为一种二维层状结构,由[VO4]四面体通过共顶点构成的一维钒氧链,链与链之间以[Co(2,2'-bipy)(H2O)]2 基团连接而成.     

Two Cd(Ⅱ)-biphenyl-3,3’-disulfonyl-4,4’-dicarboxylate-2,2’-bipyridine Compounds: Structures and Luminescence

Two coordination polymers based on the mixed ligands of biphenyl-3,3?-disul-fonyl-4,4?-dicarboxylate(BPDSDC4–)and 2,2?-bipyridine(2,2?-bpy),{[Cd(BPDSDC)0.5(2,2?-bpy)(H2O)]·(H2O)}n(1)and{[Cd(BPDSDC)0.5(2,2?-bpy)2]·(H2O)}n(2)were synthesized.Both compounds crystallize in the monoclinic system,space group P21/n.For 1,a=7.5737(2),b=17.4284(5),c=13.5982(5)?,β=90.788(3)°,V=1794.76(10)?^3,Z=4,C17H15N2O7SCd,Mr=503.77,Dc=1.864 g/cm^3,μ=1.378 mm^?1,F(000)=1004,the final R=0.0299 and wR=0.0644 for 3137 observed reflections with I>2s(I).For 2,a=13.3097(2),b=10.66240(10),c=17.6583(3)?,β=91.779(2)°,V=2504.74(6)?^3,Z=4,C27H21N4O6SCd,Mr=641.94,Dc=1.702 g/cm^3,μ=1.008 mm^?1,F(000)=1292,the final R=0.0244 and wR=0.0583 for 4594 observed reflections with I>2s(I).The Cd(II)atoms in both compounds are six-coordinated.In 1,the Cd(2,2?-bpy)units are connected by BPDSDC4–ligands to generate a one-dimensional(1D)ribbon structure.The 1D ribbons are linked by the hydrogen bonds and π···π interactions to give a three-dimensional(3D)structure.In compound 2,the Cd(2,2?-bpy)2 units are linked by the BPDSDC^4–ligands to form a 1D chain.Compounds 1 and 2 show luminescent emissions.     

一维链状配位聚合物[Ni(p-CPOA)(2,2′-bipy)(H2O)]n的合成与晶体结构

合成了一个新的配位聚合物[Ni(p-CPOA)(2,2′-bipy)(H2O)]n(p-CPOA2-= 4-羧基苯氧乙酸根,2,2′-bipy= 2,2′-联吡啶),并对其进行了元素分析、红外和单晶X-射线的表征.结果表明:配合物的化学式为C19H16N2O6Ni,晶体属单斜晶系,空间群为C2/c,晶胞参数a = 14.254(3),b = 13.085(3),c = 19.372(4)A,β = 104.89(3)°,V = 3491.8(12)A3,Z = 8,Mr = 427.05,Dc = 1.625 g/cm3,μ = 1.153mm－1,F(000) = 1760,最终R = 0.0345,wR = 0.0565。Ni原子为扭曲的六配位八面体构型,每个p-CPOA2－配体桥联2个Ni原子形成一维折叠链状结构,Ni…Ni原子之间的距离为9.675A,且通过分子间氢键将一维链连接成双链结构.     

苯并三氮唑-1-氧基乙酸、4,4′-联吡啶构筑的一维链状铜配合物的水热合成及晶体结构(英文)

水热条件下,合成了1个铜髤配位聚合物[Cu(L)(4,4′-bpy)(HCOO)(H2O)]n(HL=苯并三氮唑-1-氧基乙酸,4,4′-bpy=4,4′-联吡啶),并通过元素分析、红外光谱,热重分析,X-射线粉末衍射和X-射线单晶衍射对其进行了表征。晶体结构表明,配合物属三斜晶系,空间群P1,晶胞参数:a=0.820 26(16)nm,b=1.128 3(2)nm,c=1.159 7(2)nm,α=76.50(3)°,β=70.88(3)°,γ=76.97(3)°,V=0.973 0(3)nm3,Z=2。铜髤分别与来自2个4,4′-bipy的2个氮原子、1个苯并三氮唑-1-氧基乙酸的1个氧原子、1个甲酸根中1个氧原子和1个水分子中的1个氧原子配位,形成变形的四方锥的配位构型。由于4,4′-bipy的桥联作用,配合物在空间形成了一维链状结构,该一维链又通过分子间O-H…N和分子内O-H…O氢键作用形成了二维层状结构。     

新型共晶化合物[Cu(fiac)(2,2-bipy)]_2·(Hfiac)_2的合成、结构及性质研究

以5-氟水杨酸和2,2-联吡啶为定向配体,与乙酸铜反应经溶剂热法合成了新型共晶化合物[Cu(fiac)(2,2-bipy)]2·(Hfiac)2(Hfiac=5-氟水杨酸,2,2-bipy=2,2-联吡啶),并对其结构进行了单晶X-射线衍射表征、元素分析和红外光谱分析.配合物属于三斜晶系,Pī空间群,晶胞参数a=0.785 69(10)nm,b=1.149 97(16)nm,c=1.365 20(13)nm;α=113.841(12)°,β=90.879(9)°,γ=107.528(12)°,V=1.062 5(2)nm3,Z=1,Dc=1.656g·cm-3,R1=0.052 0,wR2=0.155 7,S=1.019.共晶化合物中的Cu(Ⅱ)离子分别与来自1个fiac配体上的2个O原子和来自1个2,2-bipy配体上的2个N原子配位,形成平面构型.对化合物的荧光性能研究结果表明其具有一定的荧光特性.     

二苯乙醇酸铜配合物的合成、晶体结构、电化学和荧光性质

以二苯乙醇酸为配体合成了1个新的化合物[Cu(2,2′-bipy)(BAA)][Cu(2,2′-bipy)(BAA)(H2O)]2.(H2O)3(BAA=二苯乙醇酸阴离子,2,2′-bipy=2,2′-联吡啶)。该化合物晶体属三斜晶系,空间群P1,晶胞参数:a=1.121 7(5)nm,b=1.360 2(6)nm,c=2.335 2(10)nm,α=99.260(6)°,β=101.223(8)°,γ=94.805(8)°,V=3.425(3)nm3,Dc=1.385 g.cm-3,Z=6,μ(Mo Kα)=0.992 mm-1,F(000)=1 474,最终偏离因子R1=0.0561,wR2=0.1128。在标题化合物的不对称单元中有3个单核铜(Ⅱ)配合物,且3个中心铜(Ⅱ)离子的配位数不完全相同,如Cu(1)离子的配位数是4,而Cu(2)和Cu(3)离子的配位数都是5。本文还测定了标题化合物的电化学性能和荧光性能,结果表明:在电化学过程中配合物的电子转移是准可逆的,电子转移数为2个;配合物在478 nm的光激发下可发射荧光。     

新型有机-无机杂化的类Dawson型多金属钨酸盐[Co(2,2''-bpy)3]2[Co(2,2''-bpy)2Cl][Co(2,2''-bpy)2]H2[SbW18O60]·4H2O的合成、晶体结构及性质

以Sb2O3、Na2WO4、CoCl2及2,2′-联吡啶为原料, 采用水热合成方法, 制得了新颖的有机-无机杂化的类Dawson型多金属氧酸盐: [Co(2,2′-bpy)3]2[Co(2,2′-bpy)2Cl][Co(2,2′-bpy)2]H2- [SbW18O60]·4H2O (2,2′-bpy = 2,2′-bipyridine), 并通过元素分析, IR, XPS, EPR, TG, 变温磁化率和X-射线单晶衍射等分析手段对化合物进行表征. X-射线单晶衍射测定表明, 该化合物属于正交晶系, Pba2空间群, 晶胞参数: a = 2.1208(2) nm, b = 2.4506(2) nm, c = 1.2931(1) nm, Z = 2, R1 = 0.0416, wR2 = 0.0771. 晶体解析表明, Sb2O3与Na2WO4在水热条件下组装成少见的类Dawson型多金属氧酸盐阴离子[SbW18O60]9-, 该阴离子的{W18}簇结构骨架中包含一个三角锥形{SbO3}基团. EPR谱分析表明, 高自旋态和低自旋态Co2+共存于标题化合物中. 磁性质研究表明标题化合物显示抗磁性.