Synthesis and Crystal Structure of a Novel Manganese Coordination Polymer： 2,5-Bis（4-pyridyl）-3,4-diaza-2,4-hexadiene

A new manganese coordination polymer 1, [Mn(H2O)4(L)]n(ClO4)2n·2nH2O·3nL (L = 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene), has been synthesized and structurally characterized. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group Pn with a = 13.9176(8), b = 15.4754(9), c = 15.9670(9) , β = 99.5010(10)o, V = 3391.8(3) 3, Z = 2, C56H68Cl2MnN16O14 , Mr = 1315.10, Dc = 1.288 g/cm3, μ = 0.344 mm-1, F(000) = 1374, R = 0.0733 and wR = 0.2035. In the crystal the manganese atom is six-coordinated by two nitrogen atoms from 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene and four oxygen atoms from water molecules, completing an octahedral geometry. The title complex exhibits a novel supramolecular layer architecture sustained by the concurrence of coordination bonds, hydrogen bonds, and π-π stacking interactions.     

配合物[Mn(2,2''-bipy)(H2O)4]·(m-phth)的水热合成和晶体结构

A mononuclear manganese complex [Mn(2,2'-bipy)(H2O)4]·(m-phth) (2,2'-bipy=2,2'-bipyridine, m-phth=isophthalate) has been synthesized by hydrothermal methods. The crystal structure was determined by singlecrystal X-ray diffraction. The crystal is of orthorhombic, space group Pnna with a=0.766 8(8) nm, b =2.050 2(2)0.027 0, R=0.028 0 and wR=0.075 5. In the crystal the manganese atom is six-coordinated by two nitrogen atoms from 2,2'-bipyradine and four oxygen atoms from water molecules, completing an octahedral coordination geometry. The isophthalate molecules are included in the lattice and connected to Mn(2,2'-bipy)(H2O)4 by hydrogen bonding interactions to form a three-dimensional supramolecular structure. CCDC:286965.     

[Zn2(C7H8O6)2(bipy)2(H2O)2]·4H2O手性配位聚合物的合成与晶体结构

采用溶剂热技术合成了一种新型手性配位聚合物[Zn2(C7H8O6)2(bipy)2(H2O)2]·4H2O(C7H8O6=2,3-氧-异丙叉基-L-酒石酸根, bipy=4,4'-联吡啶), 并通过单晶X射线衍射结构分析、元素分析、热重分析以及红外光谱进行了表征. 结构分析数据表明, 该化合物属单斜晶系, C2空间群, 晶胞参数a=2.02334(14) nm, b=1.13896(4) nm, c=1.01094(6) nm, β=117.366(3)°, V=2.0689(2) nm3. 两个晶体学独立的Zn原子均为八面体构型, 其中Zn1原子赤道配位点被2个酒石酸根中的4个羧酸根氧螯合配位, 2个酒石酸根中剩下的4个羧酸根氧中的2个分别与2个Zn2原子连接形成无限一维链, Zn2原子的另外2个反式赤道配位点被2个水分子氧占据, 同时这两种Zn原子的轴向配位点均被4,4'-联吡啶的氮原子占据, 形成具有矩形格子[0.51165(3) nm×1.13896(5) nm]的二维层状结构, 游离的2个水分子通过氢键作用形成二聚体, 并与酒石酸根中未与Zn配位的羧酸氧连接, 把二维层状结构连接成三维网状的超分子结构.     

一维链状化合物[Ag(L)]·H2O的合成、晶体结构和荧光性质

The title compound,[Ag(L)]·H2O,1,where HL=4-(isonicotinamido)benzoic acid,was synthesized in methanol solution and its crystal structure was determined by X-ray diffraction analysis.The crystal is of monoclinic.space group P21/c with a=0.571 8(8)nm,b=1.357 2(18)nm,c=1.5580(2)nm,β=91.090(2)°,V=1.2090(3)nm3,Z=4,Dc=2.009 g·cm-3,F(000)=722,Rint=0.042 9,R=0.027 1,wR=0.055 6.In complex 1,the Ag atoms are linearly coordinated by one O atom and one N atom of two ligand molecules.Each I- ligand in turn uses its one carboxylate group and one pyridinyl groups to connect two metal centers,then the one-dimensional (1D) chains is formed.On the other hand,the 1D chains are further connected by O1W-H1WB…O2 hydrogen bonds and Ag-O weak interactions to give a two-dimensional (2D) layer,finally,the 2D net extents to three-dimensional (3D) supramolecular framework by O1W-H1WB…O1 as well as N2-H2…O2 interactions.CCDC:762259.     

一个由5-硝基间苯二甲酸和1，10-啉啡咯啉构筑的锰配位聚合物的水热合成和晶体结构

通过水热法合成了1个新的金属-有机配位聚合物[Mn(NIPH)(phen)₂]·4H₂O(H₂NIPH=5-硝基间苯二甲酸,phen=1,10-邻菲咯啉)。并对其进行了元素分析、热重、红外光谱和X-射线单晶衍射测定。该配合物属于单斜晶系,P2₁/n空间群。晶体学数据：a=1.082 2(2) nm,b=2.288 3(5) nm,c=1.289 6(3) nm,β=105.11(3)°,V=3.083 2(11) nm³,C₃₂H₂₇MnN₅O₁₀,M_r=696.53,D_c=1.501 g·cm^-3,μ(Mo Kα)=0.497 mm^-1,F(000)=1 436,Z=4,最终R=0.059 2,wR=0.134 5用于4 079个可观测点。在晶体结构中,锰原子为六配位与来自2个不同的NIPH配体上的2个羧基氧原子和来自2个phen配体上的4个氮原子配位,呈现畸变的八面体几何构型。而且该配合物通过氢键和π-π堆积作用扩展成三维超分子网状结构。     

二{氧合-二[3-二茂铁基丙烯酸二正丁基锡(Ⅳ)]} 配合物的晶体结构及溶液中的 配位互变平衡机理

测定了配合物{[(n-Bu)2Sn(FcCH=CHCO2)]2O}2(Fc=Ferrocenyl)晶体结构,它属三斜晶系,空间群P1,晶胞参数a=1.3943(3)nm,b=1.4635(3)m,c=1.2792(3)nm,α=94.32(3)°,β=116.27(3)°,γ=109.08(3)°,Z=2,V=2.1362(8)nm^3,Dc=1.542g/cm^3,F(000)=1004。最终偏差因子R=0.0401,Rw=0.1076。该分子中存在着内环锡和外环锡配位单元,锡原子均形成具有假六配位的单加帽畸变三角双锥配位构型。Sn2O2中心内环与丙烯酸酯基茂环等共轭体系之间相互未能共平面。配合物中四个羧基配体划分为两类：两个为桥式双齿配位(μ-COO),跨接于一个内环锡和一个外环锡;另两个仅以单齿配位方式各连接一个外环锡。根据核磁共振谱信息表明分子在溶液中存在着配位互变异构体之间的快交换。我们提出振动模式的假说,认为可能是羧酸酯基氧在其平面内快速摇摆建立了动态平衡之故。     

Synthesis and Crystal Structure of a 1-D Chain Coordination Complex {[Mn2(HCAM)3(H2bipy)]·5H2O}n

The 1-D chain coordination complex of {[Mn2(HCAM)3(H2bipy)]·5H2O}n(H3CAM=4-hydroxypyridine-2,6-dicarboxylic acid,bipy=4,4′-bipyridine) has been synthesized by the reaction of 4-hydroxypyridine-2,6-dicarboxylic acid,4,4′-bipyridine and manganese carbonate under hydrothermal conditions,and its crystal structure was determined by X-ray diffraction method.The crystal belongs to the monoclinic system,space group P21/n with a=10.110(2),b=20.159(4),c=17.861(4) ,β=99.67(3)°,V=3.5884(12) nm3,Mr=901.47,Z=4,Dc=1.669 g·cm-3,μ=0.798 mm-1,F(000)=1840,the final R=0.0713 and wR=0.1853.The complex forms a 1-D chain bridged by HCAM,protonated 4,4-bipyridines link the 1-D chains to construct 2-D networks via N-H…O hydrogen bonds,and networks are further extended via π-π stacking and hydrogen bonds into 3-D supramolecular framework.     

苯四甲酸桥连的镍配合物[Ni(btec)(H2O)4][Ni(imi)2(H2O)4]·2H2O的合成及结构

At room temperature, a coordination polymer [Ni(btec)(H2O)4][Ni(imi)2(H2O)4]·2H2O was synthesized by reaction of NiCl2·6H2O, 1,2,4,5-benzenetetracarboxylic dianhydridc and imidazole in a water/THF solution. The structure was determined by X-ray diffraction crystal structure analysis. It crystallizes in triclinic P1 space group with the crystal cell parameters of a=0.67542 (2) nm, b=1.000 14 (1) nm, c=1.09088 (3) nm, α=74.140(2)°, β= 74.388(1)°, y=73.239(2)°, and V=0.664 09(3) nm3, Z=1. The crystal structure shows that Ni1 atom is coordinated by four water and two imidazole molecules, while Ni2 is coordinated by four water molecules and two carboxyl oxygen atoms. The 1,2,4,5-benzenetetracarboxylate ions bridge Ni2 coordination centers to form one-dimensional chain structure. Moreover, the chains are further linked together by hydrogen bonds to form a two-dimensional network. CCDC: 295873.     

以邻苯二甲酸根及邻菲咯啉衍生物构筑的锰配位聚合物的合成、晶体结构及磁性

采用水热法合成了一个配位聚合物{[Mn(Pht)(Medpq)(H2O)].0.25nH2O}n(Pht=phthalate,Medpq=2-methyldipyrido[3,2-f:2′,3′-h]quinoxaline)1,并对其进行了元素分析、红外光谱、热重表征、磁性表征和X射线单晶衍射测定。配位聚合物1属于单斜晶系,空间群为P21/c。晶胞参数为:a=1.5980(3)nm,b=2.0925(4)nm,c=0.65967(13)nm,β=93.06(3)°,V=2.2027(8)nm3。在晶体中,锰原子与4个氧原子和2个氮原子形成六配位的畸变的八面体构型。整个晶体由Pht-Mn-Medpq单元组成一维双链结构。     

一个新的噻二唑衍生物H2ADTZ与锰的二维聚合物的合成与晶体结构(英)

A new 1,3,4 thiadiazole-derivative ligand 2,5-(s-acetic acid) dimercapto-1,3,4 thiadiazole (H₂ADTZ) and its one-dimensional manganese polymer Mn(ADTZ)·4H₂O had been synthesized and structurally characterized by X-ray single crystal diffraction in this paper. The Mn(Ⅱ) ion is coordinated with a distorted octahedron by two oxygen atoms from neighboring two deprotonated ligands ADTZ^2- and other four oxygen atoms from four coordinated water molecules. The structural feature of the title compound is the formation of one-dimensional manganese chains polymer through the bridging of dioxygen O-O units. In the solid state structure of the complex, one-dimensional manganese chains are joined together by the weak intermolecular hydrogen bonds and vander Waals interactions forming a two-dimensional supramolecular compound. Furthermore, the UV spectra and electro-chemical properties of the title compound were also investigated. CCDC: 260532.     

有机锡配合物{[(n-C8H17)2Sn(O2CCH2CS2NC4H8O)]2O}2的合成，表征及晶体结构

The title complex {[(n-C₈H₁₇)₂Sn(O₂CCH₂CS₂NC₄H₈O)]₂O}₂ has been synthesized by the reaction of (morpholinylthiocarbamoylthio)acetic acid with the di-n-octyltin oxide in 1∶1 molar ratio. The complex was characterized by elemental analysis, IR and ¹H NMR. The crystal and molecular structure of complex was determined by X-ray single crystal diffraction. The crystal belongs to triclinic system with space group P1 and unit cell dimensions: a=1.201 5(9) nm, b=1.481 8(11) nm, c=1.894 1(14) nm, α=72.485(10)°, β=88.586(10)°, γ=66.893(9)°, and Z=1, μ=1.034 mm^-1, V=2.941(4) nm³, D_c=1.295 g·cm^-3, F(000)=1 196, R₁=0.058 8, wR₂=0.155 8. The complex is a centrosymmetric structure with a four-membered central endo-cyclic Sn₂O₂ unit in which two bridged oxygen atoms both connect with an exo-cyclic tin atom. The endo-cyclic tin atoms and the exo-cyclic tin atom are all five-coordinate and have coordination geometry of distorted trigonal bipyramid with an additional weak coordination carboxylate oxygen. Four carboxylate ligands are divided into two types. And two of them are monodentate and connecting to each of exo-cyclic tin atoms by using one oxygen atom, whereas the others bridge to each pair of exo-and endo-cyclic tin atoms utilizing one oxygen atom. CCDC: 277048.     

超分子钴(Ⅱ)配合物[CoL(H2O)2]n的合成与结构表征

A mononuclear Cobalt(Ⅱ) complex [CoL(H₂O)₂]_n (H₂L: 4,4′,6,6′-Tetrabromo-2,2′-[ethylenedioxybis(nitrilomethylidyne)]diphenol), has been synthesized and structurally characterized by elemental analysis, IR and X-ray diffraction single crystal structure analysis. The crystal of the complex belongs to monoclinic space group P2₁/c with a=2.516 8(3) nm, b=1.023 43(18) nm, c=0.789 17(14) nm, β=91.375(2)°, V=2.032 1(5) nm³, Z=4, D_c=2.317 Mg·m^-3, μ(Mo Kα)=8.747 mm^-1, F(000)=1 356, R₁=0.049 7, wR₂=0.110 4. The crystal structure of [CoL(H₂O)₂]_n indicates that the complex consists of one cobalt(Ⅱ) atom, one L^2- unit and two coordinated water molecules, and the coordination number of the cobalt(Ⅱ) atom is six. One-dimensional chain supramolecular structure is formed by intermolecular hydrogen bonds and π-π stacking of neighboring benzene rings. CCDC: 652649.     

基于3，4-吡啶二羧酸的二维层状聚合物的合成和晶体结构

A metal-organic coordination polymer {[La(PDC)(N-HPDC)]·H₂O}_n (1) (H₂PDC=pyridine-3,4-dicarboxylic acid) has been hydrothermally synthesized and structurally characterized by X-ray diffraction single-crystal structure determination, elemental analyses and IR spectroscopy. The complex crystallizes in the monoclinic system, space group P2₁/c with a=1.452 8(2) nm, b=0.681 59(11) nm, c=1.464 0(2) nm, β=94.270(2)°, V=1.445 6(4) nm³, D_c=2.243 Mg·m^-3, Z=4, M_r=488.14, F(000)=944, μ(Mo Kα)=3.015 mm^-1, R=0.031 0 and wR=0.076 2 for 2 424 observed reflections (I>2σ(I)). There are La-O-C-O-C-La double chains in the complex. The chelating carboxylate O atoms and pyridyl N atoms lead the compound to 2D layers structure, which is extended to 3D supramolecular architecture through intermolecular hydrogen bonds. It is interesting that the polymer containing one-dimensional channels. CCDC: 708868.     

Synthesis, Crystal Structure and Thermal Property of a Manganese(II) 4-Carboxyphenoxyacetate Complex

1 INTRODUCTION Organic aromatic carboxylic acids which com-monly possess multiple coordination modes are ex-cellent candidates for constructing supramolecularmetal complexes[1～6]. 4-Carboxyphenoxyacetic acid(4-CPOAH2), widely used in biological activitystudies, is a multidentate flexible ligand that not onlyhas versatile binding possibilities but also can formregular hydrogen bonds as both hydrogen-bond donorand acceptor. However, there have been few reportson the coordination chemistr…     

一维链状锰配位聚合物[Mn(3,5-Me2PhCO2)2(phen)]n的合成与晶体结构

A manganese coordination polymer [Mn(3,5-Me₂PhCO₂)₂(phen)]_n(phen=1,10-phenanthroline) has been synthesized by hydrothermal methods. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1 with a=0.770 3(4) nm, b=1.145 2(6) nm, c=1.537 0(9) nm, α=78.182(9)°, β=77.170(9)°, γ=89.784(9)°, V=1.292 8(12) nm³, Z=2, M_r=533.47, D_c=1.370 g·cm^-3, μ=0.549 mm^-1, F(000)=554, R_int=0.043 4, R=0.060 8 ,wR=0.148 4. In the crystal the manganese atom is six-coordinated by two nitrogen atoms from phen and four oxygen atoms from four 3,5-dimethylbenzolate molecules, completing an octahedral geometry. And the title complex forms one-dimensional chain structure through bridging 3,5-dimethylbenzolate molecules. CCDC: 642920.     

X-Ray Diffraction Study on Manganese(II) Complexes with Thiophene-2-Carboxylate and Furan-3-Carboxylate Ligands

Abstract

Mn(II) cations in the crystals of trisaquobis(μ-thiophen-2-carboxylato-O,O′)(thiophen-2-carboxylato-O)manganese(II) monohydrate are bridged by oxygen atoms donated by bidentate carboxylic groups of two thiophen-2-carboxylate ligands. In addition, each Mn(II) ion is coordinated by an oxygen atom of a monodentate carboxylic group of this ligand and three oxygen atoms of water molecules. The coordination around the Mn(II) cation is octahedral. The bridging of the ligands results in molecular ribbons propagating in the c-direction of the crystal held together by C?H…O hydrogen bonds. The crystal structure of diaquobis(μ-furan-3-carboxylato-O,O′)di(μ-furan-3-carboxylato-O,O)(μ-aqua-O)manganese(II) consists of dinuclear structural units. In each molecule Mn(II) cations are O,O′ bridged by oxygen atoms of bidentate carboxylic groups of two furan-3-carboxylate ligands and have a water located between the Mn cations. The units are O,O′ bridged to Mn(II) ions located in adjacent units by bidentate oxygen atoms, forming molecular ribbons extending in the c-direction. Octahedral coordination around each Mn(II) ion is completed by two water molecules. The octahedra around two adjacent metal ions in the unit share a common apex - the bridging oxygen atom of the water molecule. The ribbons are held together by C?H…O hydrogen bonds between furan ring oxygen atoms and the carbon atoms of adjacent furan rings.     

双甲基化大豆苷元磺酸盐的合成、晶体结构及活性研究

以大豆苷元为原料合成了强水溶性异黄酮类化合物7,4′-二甲氧基异黄酮-3′-磺酸钠(1)和7,4′-二甲氧基异黄酮-3′-磺酸铜(2).X射线单晶衍射分析表明,化合物1的分子组成为[Na(H₂O)₂](C₁₇H₁₃O₄SO₃),Na的配位数为6,且相邻钠离子以7,4′-二甲氧基异黄酮-3′-磺酸根氧原子桥连,与两个磺酸根的3个氧原子和1个S原子组成六元环,六元环通过Na-O配位键彼此稠合,在晶体结构中形成延伸的锯齿状聚合八面体配位钠离子链;这些钠离子链之间又通过配位水与配位水、磺酸根之间的氢键作用自组装成二维结构的超分子离子聚合物.化合物2的分子组成为[Cu(H₂O)₆](C₁₇H₁₃O₄SO₃)₂·8H₂O,Cu(Ⅱ)位于对称中心上.[Cu(H₂O)₆]²⁺,C₁₇H₁₃O₄SO^-₃和H₂O之间存在多种氢键;并且异黄酮环反平行排列存在π…π的堆积作用.氢键和π…π的堆积作用使化合物2自组装成三维结构的超分子.抗缺氧缺血活性试验结果表明,它们的抗缺氧缺血活性比大豆苷元的高.     

Hydrothermal Synthesis and Crystal Structure of a One-dimensional Manganese(Ⅱ) Compound Bridged by 2,6-Dichlorobenzoic Acid and Water

A novel manganese(Ⅱ) coordination polymer [Mn(L1)2(H2O)]·2H2O (HL1 = 2,6-dichlorobenzoic acid) 1 has been synthesized and structurally characterized.X-ray diffraction analyses reveal that 1 is a one-dimensional chain structure bridged by water molecules and 2,6-dichlorobenzoic acid.The crystal is of monoclinic,space group P21/c with a = 12.9701(19),b =20.592(3),c = 7.3759(10) (A),β = 102.660(2)°,V = 1.9221(5) nm3,Z = 4,C14H12Cl4MnO7,Mr=488.98,Dc = 1.690 g/cm3,μ = 1.275 mm-1,F(000) = 980,Rint = 0.0348,R = 0.0350,and wR =0.0755.In the crystal the manganese atom is six-coordinated by two oxygen atoms from water and four oxygen atoms from four 2,6-dichlorobenzolate molecules,completing an octahedral geometry.     

一维链状锰配位聚合物的合成、晶体结构与性能研究

本文合成了1个新的一维链状锰的配位聚合物{[Mn(HL)(phen)(H2O)2].1.5H2O}n,(H3L=2-羟基-5-羧基苯磺酸),并且进行了元素分析、红外、热重、荧光、紫外、粉末XRD及单晶X射线衍射等表征及研究。标题化合物属于单斜晶系,C2/c空间群,a=0.840 57(17)nm,b=1.757 5(4)nm,c=2.873 4(6)nm,β=92.54(3)°,V=4.240 7(16)nm 3,Z=4,R=0.027 0。每个Mn(Ⅱ)离子与邻菲咯啉配体的2个N原子、磺酸配体中的1个磺酸基O原子和羧基O原子以及2个配位水分子配位,展示出扭曲的八面体几何构型。2个相邻的Mn(Ⅱ)八面体单元通过1个磺酸基氧原子和1个羧基氧原子连接形成一维链状结构,该一维链进一步通过氢键作用构筑成三维网状结构。     

具有双螺旋链的新型二维无机-有机骨架晶体材料Ni(PDC)(H2O)2的合成与结构

本文报道由H2PDC合成的新型维层状无机-有机骨架晶体Ni(PDC)(H2O)2(H2PDC=吡啶-2,5-二羧酸), 该化合物的一层是由右手螺旋Ni—O—C链与左手螺旋Ni-pdc链组成, 而邻近的一层则是由左手螺旋Ni—O—C链与右手螺旋Ni-pdc链组成, 层与层之间通过氢键作用形成了三维超分子结构. 用ICP、TG、IR和X射线单晶衍射分析等手段对其结构进行表征.