Synthesis and Crystal Structure of [La（BTC）（H2O）6]n

1 INTRODUCTION desired topologies owing to their rich coordination modes[8~12] and we have been exploring the chemi- The assembly of metal-organic infinite frame- stry of coordination polymers constructed by tran- works via coordination of metal ions with multifunc- sition metals and benzoic multicarboxylic acids[13~16]. tional organic ligands is a field of increasing inte- In addition, lanthanide ions have high affinity for rest[1~4]. A rational designed and predictable coor- hard donor a…     

Synthesis, Crystal Structure and Fluorescence Property of [Y（sip）（H2O）4]n with 5-Sulfoisophthalate Ligand

1 INTRODUCTION Recently, much attention has been focused on metal- organic coordination polymers for their structural novelty and potentially important applications as advanced materials[1～3]. With the development of crystal engineering and supramolecular chemistry, it is possible to use organic ligands and metal salts to construct metal-organic coordination polymers pos- sessing some specific properties. Furthermore, inve- stigations on coordination complexes containing rare earth ion ha…     

Synthesis and Crystal Structure of Cadmium（Ⅱ） Complex [Cd（H2O）（CH3OC6H4COO）2]n

1 INTRODUCTION Cadmium (Ⅱ) complexes have been exten- sively studied from both chemical and structural views, mainly due to the capability of cadmium (Ⅱ) (shared by most d10 metal ions) to adopt different modes of coordination determined by the consideration of size, as well as electrostatic and covalent bonding forces[1]. And the field of coordination polymers has witnessed tremendous growth over the last decade[2]. Many coordination polymeric networks have been shown to posses intere…     

From Chain to Layer Structure: Zn~(II) Coordination Polymers Derived from Diphenic Acid

1 INTRODUCTION The rational design and synthesis of metal-organic coordination polymers have generated considerable interest in supramolecular chemistry and material science owing to their intriguing structural diver- sities and potential applications as functional mate- rials[1～3]. Up to now, some structural motifs with specific topologies and functions have been con- structed through rational combination of organic li- gands containing appropriate coordination sites and metal ions beari…     

Synthesis, Characterization and Fluorescence of a One-dimensional Cadmium（Ⅱ） Compound Involving Covalent and Hydrogen Bonds

1 INTRODUCTION The rational design and synthesis of new metal- organic coordination polymers have generated con- siderable interest in supramolecular chemistry and material science owing to their intriguing structural diversities and potential applications as functional materials[1～3]. Molecular self-assembly has been pro- ved to be an efficient way to construct various inte- resting coordination polymers[4～6]. The coordina- tion covalent bond, hydrogen bond or other mole- cular interact…     

Synthesis, Structure and Characterization of Manganese（ Ⅱ ） Coordination Polymer with Camphoric Acid and 1, 10-Phenanthroline

IntroductionThe syntheses of metal-organic coordination poly-mers have been attracting increasing attention owing tothe potential applications of their functional materials incatalysis,non-linear optics,magnetism sensors andmolecular recognition[1—7].Coordination polymers crys-tallized from polyaromatic acids and metal-ions are ofgreat interest for their polymeric structures and porousproperties[8—12].Their network topologies based on mo-lecular building blocks are usually controlled and mod…     

Synthesis and Crystal Structure of Mn（phen）（PhCOO）2（H2O）

1 INTRODUCTION During the last decade the manganese che- mistry has aroused great interest due to its diverse redox functions of enzymes in photosystem Ⅱ and its specially structural, magnetic and spectroscopic properties[1, 2]. A lot of manganese complexes involving carboxylate ligands have been reported, and their properties been fully explored[3, 4]. The coordination environment of the manganese site in biosystem often consists of oxygen and nitrogen atoms from the carboxylate groups…     

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

1 INTRODUCTION In recent years, coordination polymeric frame- works have attracted great attention not only due to their potential applications in the areas of magnetism, nonlinear optics, electronics, catalysis, and molecu- lar recognition and sorption but also to their intri- guing structure topologies[1～8]. The coordination polymers can be specially designed by careful selec- tion of the metal ions with definite coordination geometry, the structure of the connecting ligands, the nature…     

Syntheses, Spectroscopic Properties and Crystal Structures of （2-Cl-C6H4CH2）3SnS2CN（C5H10） and （2-Cl-C6H4CH2）3SnS2CN（C4H9N）

1 INTRODUCTION The chemistry of organotin(IV) complexes was extensively studied due to their biological activity and coordination chemistry[1～7]. More recently, phar- maceutical properties of alkyltin(IV) complexes with dithiocarbamate ligands have bee…     

Synthesis and Crystal Structure of aNovel Polymer Copper（ Ⅱ） Complex

1 INTRODUCTION One-dimensional coordination polymers of metal complexes have been extensively studied for many years owing to their unusual properties, and many efforts have been made to prepare these kinds of complexes. Study on these polymer complexes has an active field of coordination chemistry in recent years[1～5]. In this study we obtained a com- plex C14H9CuNO3CH3OH, of which the carboxy- late oxygen atom acts as the bridging ligands to coordinate to the second metal atom, fo…     

Synthesis, structures, and magnetic properties of transition metal compounds with 2,2'-dinitrobiphenyl-4,4'-dicarboxylate and N,N'-chelating ligands

Solvothermal reactions of Co(II), Ni(II), Zn(II) salts with 2,2'-dinitrobiphenyl-4,4'-dicarboxylate (dnpdc) and 2,2'-bipyridyl-like chelating ligands yielded five compounds formulated as [Co(dnpdc)(bipy)](n)·nH(2)O (1), [M(dnpdc)(phen)](n) (2, M = Co; 3, M = Ni; 4, M = Zn) and [Co(dnpdc)(biql)](n)·2nH(2)O (5) (bipy = 2,2'-bipyridine, phen = 1,10-phenanthroline and biql = 2,2'-biquinoline). With bipy or phen as coligands, compounds 1-4 exhibit isomorphous 3D M(dnpdc) metal-organic frameworks in which double carboxylate bridged chains are interlinked by the backbones of the dicarboxylate ligands. The bipy or phen ligands are involved in interchain hydrogen bonding or π-π interactions to form 1D zipper-like arrays in the rhombic channels of the frameworks, playing a templating role and determining the channel dimensions. The biql coligand is too bulky for the 1D double carboxylate bridged chain and the rhombic channel. Instead, in compound 5, the dnpdc ligands link metal ions into 1D zigzag metal-organic chains and the biql ligands are arranged into 2D (6,3) arrays through extensive π-π stacking interactions. In compounds 1-3, the double carboxylate bridges in the nonplanar syn-skew conformation mediate ferromagnetic interactions along the chains, while the chelating ligands provide supramolecular pathways for interchain antiferromagnetic interactions. The π-π interactions in 5 also evoke weak antiferromagnetic interactions.     

含氟二羧酸和含氮配体与过渡金属(Ⅱ)配合物的合成、表征及晶体结构

水热法合成了5个新的配位聚合物:[Cd(TFSA)(2,2’-bpy)2]n(1),[Mn(HFGA)(phen)2]n(2),[Co(TFSA)(bpp)2(H2O)2]n(3),[Zn(TFSA)(bpp)2(H2O)2]n(4)和[Cu(HFGA)(phen)]n(5)(TFSA=四氟丁二酸,HFGA=六氟戊二酸,2,2’-bpy=2,2’-联吡啶,phen=1,10-邻菲啰啉,bpp=1,3-二吡啶基丙烷),通过X射线单晶衍射确定了配合物的晶体结构.配合物1和2具有相似的1D链结构,四氟丁二酸和六氟戊二酸以两个单齿羧基氧原子分别配位于Cd2+和Mn2+离子,2,2’-联吡啶和1,10-邻菲啰啉分别螯合配位于Cd2+和Mn2+离子.配合物3和4具有相似的1D链结构,1,3-二吡啶基丙烷以两个端基氮原子桥联金属离子,四氟丁二酸和六氟戊二酸分别以单齿方式配位.配合物5是具有{4.82}拓扑的2D网结构,六氟丁二酸配体通过单齿/双齿-桥联模式连接Cu2+离子.5个配合物均通过分子间弱作用进一步构筑成3D超分子结构.     

Synthesis and Structure of a New Dimanganese Complex [Mn2(μ-OAc)2(phen)4](ClO4)2

A dinuclear manganese(II) complex, [Mn2(μ-Oac)2(phen)4](ClO4)2 1 (phen = phenanthroline), has been prepared by the reaction of Mn(Oac)2·4H2O, phen, tartaric acid and NaClO4·H2O in MeOH/H2O solution. The crystal structure has been determined by X-ray diffraction. The crystal is of monoclinic, space group P21/c with a = 9.6052(4), b = 14.2353(7), c = 18.8893(8)(A),β= 96.584(1)°, C52H38Cl2Mn2N8O12, Mr = 1147.68, V = 2565.8(2) (A)3, Dc = 1.486 g/cm3, F(000) = 1172, μ = 0.668 cm-1 and Z = 2. The final refinement gave R = 0.0605 and wR = 0.1619 for 3203 reflections with I > 2σ(I). The complex contains a dinuclear [Mn2(μ-Oac)2(phen)4]]2+ cation located at a centre of symmetry with two syn-anti acetate bridges between the Mn atoms. Each Mn atom is coordinated by four N atoms from two chelating phen ligands and two O atoms from a pair of bridging acetate groups to furnish a distorted octahedral geometry. Two ClO4 anions exist around the cation [Mn2(μ-Oac)2(phen)4]2+as counter ions.     

One-dimensional Supramolecular Chain Based on a Dinuclear Terbium(Ⅲ) 4-Cyanobenzoate Complex

A new dinuclear Tb(III) 4-cyanobenzoate complex [Tb2(4-cba)6(phen)2] (4-Hcba = 4-cyanobenzoic acid and phen = 1,10-phenanthroline) 1 has been synthesized by solvothermal reac- tion in an ethanol/water mixed solution at 100 ℃ and structurally characterized by single-crystal X-ray diffraction. Crystallographic data: C72H40N10O12Tb2, Mr = 1554.98, triclinic P1, a = 9.903(3), b = 11.769(8), c = 15.078(8) A, α = 111.42(12), β = 96.37(19), γ = 101.24(14)°, V = 1572(1) A3, Z = 1, Dc = 1.642 g/cm3, F(000) = 768 μ = 2.305 mm–1, the final R = 0.0205 and wR = 0.0543 for 5479 reflections with I > 2σ(I). Structural analysis shows that 1 displays an isolated dinuclear structure. Two eight-coordinated Tb(III) ions are bridged by four 4-cba ligands in the syn-syn bidentate coordination mode, and two other 4-cba ligands chelate these two Tb(III) ions. The title complex molecules are connected through π-π stacking interactions to generate a one-dimensional supra- molecular chain. The characteristic infrared spectra, luminescent properties and thermogravimetric analyses have also been discussed.     

Synthesis and Structural Chemistry of Two Novel Transition Metal Organic Phosphonates

Two novel transition metal phosphonate compounds, [Co（H2BDPP）（phen）]n 1 （BDPP = p-O3PCH2（C6H4）CH2PO3, phen = 1,10-phenanthroline） and [Pb3（BCP）2]n 2 （BCP = OOC（C6H4）CH2PO3）, have been synthesized and structurally determined by X-ray single-crystal diffraction. Compound 1 crystallizes in the monoclinic system, space group C2/c with a = 21.169（4）, b = 12.001（2）, c = 7.6211（15）A, β = 98.03（3）°, V= 1917.2（6）A^3, C20H18N2O6P2Co, Mr = 505.22, Z = 8, De= 1.737 g/cm^3, p = 1.107 mm^-1, F（000） = 1020, the final R= 0.0450 and wR = 0.1306 for 2072 observed reflections （I 〉 2σ（I）. Compound 2 crystallizes in the monoclinic system, space group C2/c with a = 4.7167（9）, b = 18.753（2）, c = 22.781（3）A, β = 91.07（3）°, V= 2014.7（14）A^, C8H6O5PPb1.5, Mr = 523.88, Z = 8, Dc = 3.454 g/cm^3, p = 25.222 mm^-1, F（000） = 1856, the final R = 0.0441 and wR = 0.1906 for 2259 observed reflections （I 〉 2σ（I）. In compound 1, the 1D chain running along the c axis is bridged by four ligands （trans- HO3PCH2C6H4CH2PO3H） in four different directions to extend the structure into a three- dimensional network. In compound 2, the Pb（II） displays 4- and 5-coordination modes. There is a one-dimensional P-O-Pb band along the a axis formed by PO3 groups and Pb（II） cations. These bands are joined by μ2-O of -COO to yield two-dimensional inorganic P-O-Pb layers which are pillared by the OOCC6HaCH2PO3 ligands to form a three-dimensional network. Moreover, compound 2 displays a strong emission band attributed to the ligand-centered （LC） transition.     

Zn(II), Cu(II), Co(II)与3,5-二硝基苯甲酸-咪唑三元超分子配合物的合成、晶体结构及性质

摘要 在水和甲醇混合溶液中合成了3个配合物[Zn(DNBC)2(Im)2](1), [Cu(DNBC)2(Im)(H2O)](2) [Co1.5(DNBC)4(Im)(CH3OH)(H2O)2](3) (DNBC = 3,5-二硝基苯甲酸, Im = 咪唑), 并进行了常规表征,单晶X-射线衍射测定了3个配合物的晶体结构。结果表明,配合物1采用四配位,且形成扭曲的四面体形式,通过分子间氢键及范德华力形成了三维网状的超分子框架结构。配合物2中金属铜原子采用五配位,分别与四个氧原子和一个咪唑氮原子配位,形成一个扭曲的四方锥体,而且通过羧基和硝基与金属铜连接形成一个一维Z字链的超分子链状结构。配合物3的空间群为p2(1)/n, a = 1.20876(7)nm, b = 2.63287(16)nm, c = 1.36466(9)nm, V = 4.3045(5)nm3, Z = 4, F(000) = 2166, Co…Co原子之间的距离为0.3587nm。在配合物3中,由八面体配位的Co(II)离子与μ-OH2组成的三核金属钴通过氢键与相邻的三核金属钴连接,Co(II)离子与μ-OH2形成一维Z字链,并且配合物的空腔中包含未配位的咪唑和甲醇分子。配合物3的磁学性质测试表明,三核金属Co(II)之间存在着很好的反铁磁交换作用。     

Synthesis and Crystal Structure of Dichlorobis(1-methylimidazoline-2(3H)-thione-S) Cobalt(II)

The reaction of anhydrous cobalt(II) dichloride with 1-methylimidazoline-2(3H)thione in dichloromethane solution gave the title complex, [Co(C4H6N2S)2Cl2]. X-ray single-crystal analysis revealed that the complex crystallizes in a monoclinic system, space group P21/c, a = 13.9707(10), b = 10.0435(7), c = 10.3910(6) (A), β = 91.181(3)o, V = 1457.70(17) (A)3, Z = 4, C8H12Cl2N4S2Co, Mr = 358.17, Dc = 1.632 g/cm3, μ = 1.813 mm-1, F(000) = 724, the final R = 0.0710 and wR = 0.1224 for 1549 observed reflections with I > 2((I). The Co atom is coordinated by two S atoms from two 1-methylimidazoline-2(3H)-thione ligands and two chloride ions in a slightly distorted tetrahedral geometry. The intramolecular classical hydrogen-bonding interactions involving chloride ions and N-H groups of the heterocyclic thione ligands are observed. The offset π-π stacking interactions between the imidazole rings of adjacent molecules with a face-to-face distance of 3.604 (A) are found in the packing diagram.     

4-氧乙酸苯乙酸构筑的双核Zn(Ⅱ)和Co(Ⅱ)配合物的合成，晶体结构及荧光性能

用水热法合成得到2个新配合物,[M₂L₂(phen)₂(H₂O)₂](L=4-氧乙酸苯乙酸,phen=1,10-邻菲咯啉,M=Zn,1;Co,2),并测定了它们的晶体结构。配合物1和2为异质同晶,单斜晶系,P2₁/c空间群。中心金属M为六配位,相邻的M(Ⅱ)通过2个桥连的配体形成双核笼状次级结构单元,通过氢键和π-π堆积弱作用链接形成二维层结构。通过对配合物1的固态荧光测试,结果表明其在紫光区显示发光效应。     

Crystal Structure,Thermal Behavior and Luminescence of a One-dimensional Coordination Polymer [Zn（4-CPOA）（Phen）（H2O）]n

A novel coordination polymer of [Zn（4-CPOA）（Phen）（H2O）]n （C21H16N2O6Zn,1,4-CPOA = 4-carboxylato-phenoxyacetate dianion and Phen = 1,10-phenanthroline） has been synthesized and characterized by elemental analysis,IR,TG,PL and single-crystal X-ray diffraction. The crystal crystallizes in the triclinic system,space group of P1 with a = 9.622（3）,b = 9.631（3）,c = 11.526（4）A,α = 67.719（5）,β = 71.203（5）,γ = 83.552（6）o,V = 935.5（5） A^3,Z = 2,Dc = 1.625 g/cm^3,μ = 1.357 mm^-1 and F（000） = 468. The Zn（II） ion is surrounded by three carboxylate O atoms from two different 4-CPOA groups,two N atoms from the Phen ligand and one water molecule,forming a distorted octahedral coordination configuration. The Zn（II） ions were alternately interlinked by carboxylate groups of 4-CPOA with chelating bisbidentate and monodentate modes into a one-dimensional zigzag chain having an intrachain distance of ca. 9.631（1） . Under the direction of supramolecular recognition and attraction,the adjacent chains yield a double-stranded chain through π-π stacking between the phen ligands,which was further expanded into a 2-D framework via strong C–H–π interaction （ca. 2.95（1） ） between the 4-CPOA ligands and into a 3-D supramolecular network by strong hydrogen bond between terminal water molecule and carboxyl group. TG/DTG shows that its chain skeleton is thermally stable up to 419 oC and the blue fluorescent emission of the complex was determined at 471 nm in a solid state with its long decay lifetime of 1.83 ns.     

Synthesis and Crystal Structure of a Novel Cobalt（Ⅱ） Coordination Polymer with 1,2,4,5-Benzenetetracarboxylate

A novel cobalt（II） coordination polymer,[Co（BTEC）1/2]n 1,has been synthesized with Co（NO3）2·6H2O and 1,2,4,5-benzenetetracarboxylic acid （H4BTEC） by the hydrothermal method,and characterized by elemental analysis,IR and single-crystal X-ray diffraction. Crystallographic data for 1： C5HO4Co,Mr = 183.99,monoclinic,space group C2/c,a = 16.619（6）,b = 7.416（3）,c = 8.040（3）A,β = 90.612（4）°,V = 990.8（6） A^3,Z = 8,Dc = 2.467 g/cm^3,μ = 3.390 mm^-1,F（000） = 720,R = 0.0307 and wR = 0.0847 for 912 observed reflections （I 〉 2σ（I））. X-ray crystal structural analysis revealed that each Co（II） adopts a tetrahedral coordination mode to link four separate BTEC ligands via uniform monodentate carboxylate groups and each BTEC ligand possesses an 8-connected geometry to connect eight Co（II） ions. Complex 1 exhibits a rare （4,8）-connected net with （45.6）2（410.614.84） topology.