[Sr(CHZ)(TNR)(H2O)(OH)]2·2H2O的晶体结构和热分解机理

The coordination compound of [Sr(CHZ)(TNR)(H₂O)(OH)]₂·2H₂O (TNR: 2,4,6-trinitroesorcinol, CHZ: carbohydrazide) was prepared by reacting CHZ solution and strontium styphnate solution (obtained through the reaction of strontium carbonate and styphnic acid). The molecular structure was characterized by using X-ray diffraction analysis, element analysis and FTIR analysis. The crystal belongs to triclinic with space group P1. The unit cell parameters were as follows: a=0.725 2(2) nm, b=1.021 2(2) nm, c=1.144 0(2) nm, α=69.50(3)°, β=78.82(3)°, γ=84.64(3)° and Z=2. The thermal decomposition of the compound is studied using differential scanning calorimetry (DSC) and thermogravimetry thermogravimetry-derivative (TG-DTG) techniques. CCDC: 269310.     

Synthesis and Crystal Structure of a Macrocycle [Cu(dadm)(mal)(H2O)]2·2H2O

The reaction of 4,4′-diaminodiphenylmethane (dadm), malonic acid (H2mal) and Cu(NO3)2 in aqueous solution results in a discrete binuclear Cu(II) macrocycle: [Cu(dadm)(mal)- (H2O)]2(2H2O. It crystallizes in monoclinic, space group P21/c with a = 15.231(3), b = 11.847(2), c = 9.801(2)A,Z= 106.75(3)o, V = 1693.5(6)A3, Z = 2, C32H40Cu2N4O12, Mr = 799.76, Dc = 1.568 g/cm3, λ(MoK() = 0.71073A, μ = 1.325 mm-1, F(000) = 828, the final R = 0.0531 and Wr = 0.1244 for 3421 observed reflections with I > 2σ(I). Each Cu(II) is coordinated by two oxygen atoms from a mal ligand, two nitrogen atoms from two dadm ligands and a water oxygen atom to form a triangle bipyramidal motif. The title compound possesses a distorted macrocycle enclosed by dadm with approximate dimensions of 8.3A× 5.9A.     

A structural and Mössbauer study of complexes with Fe(2)(micro-O(H))(2) cores: stepwise oxidation from Fe(II)(micro-OH)(2)Fe(II) through Fe(II)(micro-OH)(2)Fe(III) to Fe(III)(micro-O)(micro-OH)Fe(III)

Dinuclear non-heme iron clusters containing oxo, hydroxo, or carboxylato bridges are found in a number of enzymes involved in O(2) metabolism such as methane monooxygenase, ribonucleotide reductase, and fatty acid desaturases. Efforts to model structural and/or functional features of the protein-bound clusters have prompted the preparation and study of complexes that contain Fe(micro-O(H))(2)Fe cores. Here we report the structures and spectroscopic properties of a family of diiron complexes with the same tetradentate N4 ligand in one ligand topology, namely [(alpha-BPMCN)(2)Fe(II)(2)(micro-OH)(2)](CF(3)SO(3))(2) (1), [(alpha-BPMCN)(2)Fe(II)Fe(III)(micro-OH)(2)](CF(3)SO(3))(3) (2), and [(alpha-BPMCN)(2)Fe(III)(2)(micro-O)(micro-OH)](CF(3)SO(3))(3) (3) (BPMCN = N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane). Stepwise one-electron oxidations of 1 to 2 and then to 3 demonstrate the versatility of the Fe(micro-O(H))(2)Fe diamond core to support a number of oxidation states with little structural rearrangement. Insight into the electronic structure of 1, 2', and 3 has been obtained from a detailed M?ssbauer investigation (2' differs from 2 in having a different complement of counterions). Mixed-valence complex 2' is ferromagnetically coupled, with J = -15 +/- 5 cm(-)(1) (H = JS(1).S(2)). For the S = (9)/(2) ground multiplet we have determined the zero-field splitting parameter, D(9/2) = -1.5 +/- 0.1 cm(-)(1), and the hyperfine parameters of the ferric and ferrous sites. For T < 12 K, the S = (9)/(2) multiplet has uncommon relaxation behavior. Thus, M(S) = -(9)/(2) <--> M(S) = +(9)/(2) ground state transition is slow while deltaM(S) = +/-1 transitions between equally signed M(S) levels are fast on the time scale of M?ssbauer spectroscopy. Below 100 K, complex 2' is trapped in the Fe(1)(III)Fe(2)(II) ground state; above this temperature, it exhibits thermally assisted electron hopping into the state Fe(1)(II)Fe(2)(III). The temperature dependence of the isomer shifts was corrected for second-order Doppler shift, obtained from the study of diferrous 1. The resultant true shifts were analyzed in a two-state hopping model. The diferric complex 3 is antiferromagnetically coupled with J = 90 +/- 15 cm(-)(1), estimated from a variable-temperature M?ssbauer analysis.     

STRUCTURE OF [W(H)_2(F)(OH_2)(PMe_2)_4]F

<正> Mr = 546.3, orthorhombic, space group Cmc21, a = 14.223(4), b = 12.907(3), c = 12.343(4) A, V = 2265.746 A3, Z = 4, DC = 1.601 Mg.m-3, λ= 0.7106 A, μ(MoK(?)) = 56.86 cm-1, F(OOO) = 1048. Final R = 0.044 for 1937 observed reflections. Cation [W(H)2(F)(OH2)(PMes)4]4 has a mirror symmetry, an equatorial belt of four PMe3 groups and mutually syn fluoride and water Ugands. The mean W-P length is 2.462 (A) and P-C 1.83 (A). From the dimensions of the metal, fluoride and water system ( W(1)-F(1) = 2.08(1), W(1)-0(1) - 2.084(9), F(2)-O(1) = 2.59(2) A and F(2)-W(1)-O(1) - 76.7(4)°) an in-terligand hydrogen bond was assumed. The ligand water molecule also makes an H-bonded contact with the fluoride counter ion.     

｛[Co(4,4′-bipy)(ambdc)(H_2O)_2](4,4′-bipy)(DMF)｝_n合成与晶体结构

近年来,取代在5位上的间苯二甲酸(取代基为:-SO3H,-NH2,-OH,-NO2等)衍生物与过渡金属形成的配位聚合物,由于其具有新奇的结构,而且是潜在的功能材料而备受关注[1￣4]。Yaghi等人认为,取代基对配位聚合物的结构和性能具有重要的修饰作用[5]。因此我们在研究5-硝基间苯二甲酸、5-羟基间苯二甲酸与过渡金属形成的配位聚合物结构的同时[6,7],选择了5-氨基间苯二甲酸作为酸性配体,氨基不仅能用其氮原子与金属配位,还能形成氢键,能够提供丰富的配位方式。我们曾经报道了｛[Co(4,4′-bipy)(hmbdc)(H2O)2](4,4′-bipy)(DMF)｝n的合成与结构[8…     

Formation and isomerization of cis,cis-Ir(H)2(--Ph)(CO)(PPh3)2 and cis,cis-Ir(H)(--Ph)2(CO)(PPh3)2 in oxidative addition of hydrogen and phenylacetylene to trans-Ir(CO)(--Ph)(PPh3)2

Oxidative addition of H–R (H--Ph and H₂) to trans-Ir(--Ph)(CO)(PPh₃)₂ (2) gives the initial products, cis, cis-Ir(H)(--Ph)₂(CO)(PPh₃)₂ (3a) and cis, cis-Ir(H)₂(--Ph)(CO)(PPh₃)₂ (3b), respectively. Both cis-bis(PPh₃) complexes, 3a and 3b undergo isomerization to give the trans-bis(PPh₃) complexes, trans, trans-Ir(H)(--Ph)₂(CO)(PPh₃)₂ (4a) and cis, trans-Ir(H)₂(--Ph)(CO)(PPh₃)₂ (4b). The isomerization, 3b→4b is first order with respect to 3b with k₁=6.37×10⁻⁴ s⁻¹ at 25°C under N₂ in CDCl₃. The reaction rate (k₁) seems independent of the concentration of H₂. A large negative entropy of activation (ΔS^≠=−24.9±5.7 cal deg⁻¹ mol⁻¹) and a relatively small enthalpy of activation (ΔH^≠=14.5±3.3 kcal mol⁻¹) were obtained in the temperature range 15∼35°C for the isomerization, 3b→4b under 1 atm of H₂.     

[Cu(L-Ile)(Phen)(H2O)(ClO4)]的合成、结构及稳定性研究

合成了三元混配配合物[Cu(L-Ile)(Phen)(H20)(ClO4)](L-Ile=L-异亮氨酸,phen=1,10-邻菲咯啉),通过红外光谱、紫外-可见光谱、摩尔电导率、X射线单晶结构分析,对配合物进行了表征.该晶体属单斜晶系,P21空间群,晶胞参数:a=1.1704(5)nm,b=0.8090(5)nm,c=2.1822(5)nm,β=98.061(5)°,Z=2,Dx=1.60Mg·m-3,R1=0.0462,wR2=0.1225.每个配合物分子中Cu(Ⅱ)离子与一个L-Ile(N,O)配体、一个Phen(N,N)配体、一个H2O(O)配体及一个ClO4-(O)形成六配位的畸变八面体构型.本文还用电位滴定法测定了配合物的稳定常数,结果表明,配合物具有高的稳定性.     

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.     

Crystal Structure of Dimer Complex of 〔K (dndb)(H_2O)(NCS)〕_2

1INtrODUCTIONThecrownethercomPOundsandtheirderivativeshavecontinuouslyattractedconsiderableattentioneversincetheywerefirstreportedin1967illbecauseoftheirexcellentcapacitytoattachmetalatomstoformcomplexes.Nowadaystheyareappliedextensivelyinchemistry,biology,medicine,agriculture,metallurgyandmanyotherfields.Manypapersonsynthesesofnewcrownethers,theirstructuredeterminationandcharactersareoftenpublished.Inthestudiesthenitrifiedreactionofcrownetherisknownasasignificantwaybywhichfunctionalgroup…     

The synthesis,structure and reactions of the novel cationic bisbut-2-yne complex [W(CO)(NCMe)(S2CNC4H8)(η2-MeC2Me)2][BPh4]

The complex [WI(CO)(S₂CNC₄H₈)(η²-MeC₂Me)₂] reacts with an equimolar amount of Na[BPh₄] in acetonitrile at room temperature to give the cationic bisbut-2-yne complex [W(CO)(NCMe)(S₂CNC₄H₈)(η²-MeC₂Me)₂][BPh₄] (1) by replacement of an iodide ligand by acetonitrile. The crystal structure of 1 has been determined and reveals a pseudo-octahedral geometry with the mid points of the two cis-but-2-yne ligands approximately coplanar with the sulphur atoms of the dithiocarbamate ligand. Carbon monoxide and acetonitrile occupy the axial sites. ¹³C NMR spectroscopy shows the two but-2-yne ligands in 1 donate a total of 6 electrons to the tungsten. Preliminary studies of the chemistry of 1 are also described.     

Synthesis,Crystal Structure,Fluorescence Property and Antibacterial Activity of Two Unprecedented One-dimensional Chain Metal-organic Coordination Polymers: Zn(H-SSA)(Phen)(H_2O)_2and Cu(H-SSA)(Phen)(H_2O)_2

IntroductionSalicylicacid (2 oxybenzoicacid ,H2 Sal)anditsderivativeshavebeenknownforalongtimetopossessan ti inflammatoryactivity ,1whileithasbeenfoundthatthebiologicalactivityofawidevarietyoforganicdrugsisen hancedupontheirmetalcomplexation .2 ,3Forexample ,bis(salicylato)copper(II)isastrongeranalgesicandanti inflammatoryagentforanimalsthansalicylicaciditself,4andthecopper(II)complexofaspirin ,Cu2 (aspirin) 4,isamoreeffectiveanti inflammatoryandanti rheumatoida gentthanaspirinitself.5,6 I…     

[La(CH_2ClCOO)_2(NO_3)(phen)(H_2O)]_n的合成和晶体结构

合成了混合阴离子配合物［Ｌａ（ＣＨ２ＣｌＣＯＯ）２（ＮＯ３）（ｐｈｅｎ）（Ｈ２Ｏ）］ｎ。配合物经元素分析、ＩＲ、ＤＴＡＴＧ和ＵＶ等表征。用Ｘ射线单晶结构分析解析了标题配合物的晶体结构，三斜，空间群Ｐ１，晶胞参数为ａ＝１０５３３（２），ｂ＝１３１３６（３），ｃ＝７７７６（１），α＝９６５９（１）°，β＝９５７６（１）°，γ＝１０８４２（２）°，Ｖ＝１００３３（３）３，Ｚ＝２，Ｄｃ＝１９４０ｇ／ｃｍ３，Ｆ（０００）＝５７２，μ（ＭｏＫα）＝２４３６ｃｍ－１。     

New routes to carbonyl complexes of general formula [RuCl2(CO)(S)(PPh3)2] (S = DMA,DMF, DMSO): crystal structure of [RuCl2(CO)(DMA)(PPh3)2] · 1/2CH2Cl2

The compound [RuCl₂(CO)(DMA)(PPh₃)₂] [DMA = dimethylacetamide] was obtained from [RuCl₃(PPh₃)₂-(DMA)] · DMA and CO in DMA. Orange crystals of [RuCl₂(CO)(DMA)(PPh₃)₂] · 1/2CH₂Cl₂ were isolated by slow evaporation of a CH₂Cl₂/DMA solution and its structure was determined by single crystal X-ray diffraction. The analogous compounds containing DMF and DMSO were obtained from the precursor ttt-[RuCl₂(CO)₂(PPh₃)₂]. Characterization of the other complexes is based on i.r. and n.m.r. spectroscopy, including ³¹P{¹H} data.     

Synthesis and ligand substituion chemistry of dinuclear,phosphido-bridged complexes of manganese. X-ray crystal structures of Mn2(μ-H)(μ-Cy2P)(CO)7(PCy2H)(1) and Mn2(μ-H)(μ-Cy2P)(CO)6(PMe32

Reaction of Mn₂ (CO)₁₀ with two equivalents of dicyclohexylphosphine in toluene at 110° produces Mn₂ (μ-H)(μ-Cy₂P)(CO)₇(PCy₂H) (1) in 60% yield. Interaction of 1 with excess trimethylphosphine produces Mn₂(μ-H)(μ-Cy₂P)(CO)₆ (PMe₃)(₂ (2) in 90% yield. The X-ray crystal structures of 1 and 2 have been determined. Both structures contain two Mn atoms bridged by a Cy₂P group and a hydridge. In each case, the metal atoms exhibit distorted octahedral geometry, with the phosphines occupying positions trans to the P atom of the bridging dicyclohexylphosphine. A metal-metal distance of ca. 2.9 Å separates the manganese atoms in both complexes.     

Synthesis and Characterization of Nitrato-Triamine-Metal(II) Complexes. Conglomerate Crystallization Part 55. Crystal Structure of [Ni(dien)(O2NO)(ONO2)] (I), {[Cu(dien)-(μ-ONO2)]NO3}∞ (II), [Zn(dien)(O2NO)(ONO2)] (III), [Ni(Medpt)(O2NO)(ONO2)] (IV) and [Cu(Medpt)(ONO2)2] (V)

In absolute ethanol and in the presence of triethylorthoformate, reactions of metal(II) nitrates with linear tridentate amines afforded metal complexes of the formula M(NNN)(NO₃)₂, where M = Ni²⁺, Cu²⁺ and Zn²⁺, and NNN = dien and Medpt. The compounds fall into three categories in accordance with their stereochemistry and mode of binding of the nitrato ligands. Compounds I, [Ni(dien)(O₂NO)(ONO₂)] and III, [Zn(dien)(O₂NO)(ONO₂)] are isomorphous and isostructural. They crystallize in the monoclinic space group P2₁/n with nearly identical cell constants. The stereochemistry of these two compounds is such that the terdentate dien ligand forms a fac MN₃ moiety with the two oxygens of the bidentate nitrato ligand trans to the terminal NH₂. These ligands form the base of the octahedral arrangement in which the sixth position, trans to the secondary nitrogen of the dien, is an oxygen of the monodentate nitrato ligand. Compound IV, [Ni(Medpt)(O₂NO)(ONO₂)] falls into the same category as I and III despite the fact that the two rings in the Ni-Medpt moiety are six-membered rings, unlike those in compounds I and III which are five-membered rings. Nevertheless, the nickel-amine arrangement is fac. The bidentate nitrato-oxygens are trans to the terminal NH₂ of the amine ligand, and the oxygen of the monodentate nitrato ligand is trans to the tertiary amine-nitrogen. Such stereochemistry is prevalent for nickel and zinc compounds. Interestingly, compound IV crystallizes as a conglomerate (space group P2₁2₁2₁). Compound II, {[Cu(dien)(μ-ONO₂)]NO₃}_∞ belongs to the second category and has a polymeric structure. The repeating fragment in the polymeric chain is a Cu(dien)-O fragment with the monodentate nitrato ligand occupying an equatorial position of the base. A second oxygen of the equatorial nitrate becomes an axial ligand for an adjacent Cu-N₃O fragment. In this way the substance propagates into an infinite chain. The repeating unit has an effective square pyramidal, five-coordinate, configuration. Finally, the compound crystallizes as a racemate. The second nitrate necessary for charge compensation of this copper(II) compound is ionic and its function is to hold the infinite chains of the lattice. The third category represented by compound V, [Cu(Medpt)(ONO₂)₂] contains two molecules in the asymmetric unit of the racemic lattice (monoclinic, space group P2₁/a). The structure of Cu-Medpt is unlike that of IV in that both species present in the asymmetric unit have the amine ligand in a mer configuration which together with a monodentate oxygen of a nitrato ligand form a base plane of a square pyramid. The fifth ligand of both Cu²⁺ ions is a second monodentate nitrato ligand. The stereochemical differences between the two Cu²⁺ ions are insignificant for the Cu-Medpt fragment, which share the same conformation and configuration. The major difference between the two species is the torsional angles defined by the Cu-O-N-O angles. The difference arises from variation in the hydrogens of the primary amine moieties selected by nitrato-oxygens to form intramolecular hydrogen bonds. Finally, there is a little variation in the equatorial Cu-ONO₂ stereochemistry because of steric hindrance, imposed by the Medpt, preventing large torsional angles by these nitrato ligands. This is evident by comparing the two copper species shown in Finally, nitrate-to-Br ligand exchange was found to take place when KBr pellets are prepared for IR spectral measurements.     

[Ln(TOv)(phen)(NO3)]·2H2O的合成表征与热分解动力学

合成了三种稀土元素与牛磺酸缩邻香草醛Schiff碱的配合物[Ln（TOv）（phen）（NO3）]·2H2O（TOv：牛磺酸缩邻香草醛Schiff碱配体;phen：1,10-邻菲哕啉;Ln：Er,Tm,Yb）,并对其进行了结构表征．采用Achar微分法和Coats．Redfem积分法拟合得到了配合物的热分解动力学方程．     

Synthesis and Crystal Structure of a Macrocycle [Cu(dadm)(mal)(H_2O)]_2·02H_2O

1 INTRODUCTION Recently the self-assembly through transition metal and N-containing organic ligands has appear- ed as a popular research field in supramolecular architecture. Among the N-donor organic ligands, the rigid ligands have been well investigat…     

[Cr(Ⅲ)(SSA)(en)2]·2H2O配合物的合成、表征及性质研究

有机铬(Ⅲ)配合物具有较高的生物利用率.本文合成了一种新型磺基水杨酸铬(Ⅲ)混配配合物[Cr(SSA)(en)2]·2H2O(SSA=5-磺基水杨酸,en=乙二胺),通过红外、紫外、荧光光谱以及元素分析、电导率测定和X晶体衍射等方法对其结构进行了表征.在pH 7.4,0.05 mo1·L-1 Tris-HCl缓冲液中,利用荧光光谱研究了配合物与人血清白蛋白的结合.结果表明配合物可与人血清白蛋白以较强的分子间作用力结合,条件结合常数为(2.7±0.1)×104mol·L-1,结合位点数为3.87.在pH 7.4,0.05 mol·L-1Tris-HCl缓冲液中,观察了不同温度下EDTA和脱铁伴清蛋白为竞争剂的配体取代反应动力学行为,其中37℃时反应速率常数分别0.0142TT和0.0225 h-1.     

一维锰金属配位化合物[Mn(oba)(L)(H_2O)]·2H_2O的合成和晶体结构

以六水合氯化锰,二苯甲醚二羧酸(Hoba)和吡嗪[2,3-f]邻菲咯啉(L)为原料合成了一种新型化合物[二水合(二苯甲醚二羧酸)(吡嗪[2,3-f]邻菲咯啉)水合锰][Mn(oba)(L)(H2O)].2H2O(1),该化合物为链状结构,吡嗪[2,3-f]邻菲咯啉(L)配体间的π-π相互作用将化合物连接成二维超分子结构.     

Crystal Structure and Interaction with DNA of [Ni(phen)(mal)(H2O)2]·3H2O

A new complex [Ni(phen)(mal)(H2O)2]·3H2O (phen = 1,10-phenanthroline,mal2-= malonic acid) has been synthesized by the reaction of nickel nitrate,phen and malonic acid.EA,IR spectra and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure of the title complex.Crystal data:monoclinic system,space group P2/c,a =8.937(3),b = 12.163(5),c = 9.725(3)(A),β = 119.36°,C15H19N2O9Ni,Mr= 430.03,Z = 2,F(000) =446,V = 921.3 (A)3,Dc = 1.550 g/cm3,μ = 1.104 mm-1,-10≤h≤ 10,-12≤k≤ 14,-11 ≤l≤7,R =0.0261 and wR = 0.0609 for 4376 (Rint = 0.0203) independent reflections and 1631 observed ones (I＞ 2σ(I)).Ni(Ⅱ) exhibits an octahedral coordination geometry,with hydrogen bonds and π-π interactions stabilizing the whole structure.UV spectrum of the complex interacting with protamine DNA indicates that the title compound interacts with DNA via insertion mode with bonding constant Kb of 1.11 × 104.