阶梯状配位聚合物[Cu(μ_3-I)INH]_n的合成、晶体结构及其热稳定性研究

The complex [Cu( μ3-I)INH]n has been synthesized in DMF solution with INH, CuI, where INH=isoniazid. The crystal structure of the complex has been determined by X-ray diffraction single crystal structure analysis. The crystal belong to monoclinic system, space group P21/c. The cell parameters are: a=1.009 48(10) nm, b=0.467 51(5) nm, c=1.992 62(19) nm, β=101.413 0(10)°, and V= 0.921 81(16) nm3, Z=4, μ(Mo Kα)=5.674 mm-1, F(000)=616.0, R1=0.031 6, wR2=0.082 5 [I2σ(I)]. The copper(Ⅰ) atom locates in a distorted coordination tetrahedron. The copper(Ⅰ) atoms bridged by μ3-I to form a band stair-like chain, and INH occupying the remaining coordination site of the approximately tetrahedral. The stair-like chains extend along b axis. The results of TG analysis show the title complex was stable under 200℃.     

Synthesis,Structure and Properties of a New Terbium(Ⅲ) Complex Tb_2(C_(15)H_(11)O_3)_6(phen)_2

A new terbium(Ⅲ) complex Tb_2(C_(15)H_(11)O_3)_6(phen)_2 has been synthesized with 2-(4-methylbenzoyl)benzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2_1/n,a=15.0786(6),b=13.5762(5),c=22.9683(9) A,β=104.130(4)°,V=4559.6(3) A~3,D_c=1.540_g/cm~3,Z=2,μ(MoKα)=1.615 mm~(-1),F(000)=2136,the final R=0.0528 and wR=0.0740.The Tb(Ⅲ) ion is coordinated by eight atoms to give a distorted square antiprism coordination geometry.The complex shows four fluorescence emission bands arising from the transitions of Tb~(3+5)D_4→~7F_6(490 nm),~5D_4→~7F_5(546 nm),~5D_4→~7F_4(588 nm) and ~5D_4→~7F_3(622 nm).The complex is an antiferromagnet in the range of 300～2 K.Also reported in the paper is the thermal stability property of the title complex.     

2-(1H-1,2,4-三氮唑)乙酸Cu(Ⅱ)配合物的水热合成、晶体结构及性质

A copper(Ⅱ) complex [CuL2] [L=2-(1H-1,2,4-triazol-1-yl)acetic acid] has been synthesized by means of hydrothermal method, and characterized by elemental analysis, IR spectra and X-ray diffraction. Crystal data for this complex: monoclinic, space group P21/n, a=0.481 3(2) nm, b=1.151 1(6) nm, c=0.993 9(5) nm, β=100.528(8)°, V=0.541 4(5) nm3, Z=2, F(000)=318, Dc=1.937 g·cm-3, Final GooF=1.109, R1=0.027 6, wR2=0.075 6. The crystal structure shows the copper(Ⅱ) atom is six-coordinated by two triazole nitrogen atom and four carboxylate group oxygen atom from four distinct L- ligand, thereby forming a 2D network structure. The cyclic voltammetric behavior of the complex was described.     

SYNTHESIS AND CRYSTAL STRUCTURE OF [(η~5-C_5H_5)_2NdCl·OC_4H_8]_2

All attempts to prepare light lanthanide dicyclopeutadienyt chloride failed,due to the disproportionation reaction. The crystal complex of [(η~5-C_5H_5)_2NdCl.OC_4H_8]_2 was successfully prepared by the reaction of NdCl_3·2C_4H_8O with cyclopentadienyl sodium (molar ratio 1:1.8)in tetrahydrofuran at room temperatureThe composition of the title compound was determined by the methods of elemental analysis, infrared spectroscopy and photoelectron spectroscopy. The crystal structure of [(η~5-C_5H_5)_2NdCl·OC_4H_8]_2 was determined from single crystal X-ray diffraction. Data were collected at-60℃ under dry nitrogen atmosphere.The complex crystallizes in the monoclinic space group P2_1/c,with Z=2. Lattice parameters are: a=8.201(3), b=21.589(6),c=8.596(3),β=109.10(3)°.The structure was solved by Patterson and Fourier techniques and refined by least-squares to a final conventional R=0.0636 for 1680 reflections. There are two Nd atoms in the dimeric unit which are bridged asymmetrically by the two chlori     

Crystal Structure, Nano-particle Morphology and Interaction with ATP of [ NH3 CH2 CH（ NH2 ） CH3 ]2 [ M（ Ⅵ ） O2 （ OC6 H4 O）2 ] （M = Mo0. 6 W0. 4 ） and Its Activity to Promote DNA Cleavage

The title complex [NH_3CH_2CH(NH_2)CH_3]_2 [M(Ⅵ)O_2(OC_6H_4O)_2](M= Mo_(0.6)W_(0.4))was synthesized via a simple solution-phase chemical route.The determination of single crystal X-ray diffraction revealed that the title compound is crystallized in a monoclinic system with P2(1)/n space group,a=1.0913(10)nm,b=1.0442(10)nm,c=1.8842(19)nm,α=90°,β=96.530(17)°,γ=90°,Z=4,and V=2.133(4)nm3.The mononuclear anionic unit [M(Ⅵ)O2(OC6H4O)2]2-displays chiral pseudo-octahedral [MO_6] coordination geometry and is linked by chiral cations via hydrogen bond and π…π stacking interaction.The transmission electron microscopy images show that the title complex is comprised of nano-particles with diameters ranging from 20 to 50 nm.The NMR study shows the 1H downfield chemical shifts of [NH_3CHaHbCH(NH_2)CH_3] cations in the title complex when it is mixed with adenosine-triphosphate(ATP),and the chemical shift difference between Ha and Hb is increased greatly,and most of the catecholate ligands dissociate from the central metal atoms.The DNA cleavage activity experiment reveals that DNA cleavage promoted by the title complex is lower than that by Na_2MoO_4 which possesses antitumor pro-perty,but higher than that by Na_2WO_4.     

Synthesis,Electrochemical and Fluorescent Properties of a New Zinc(Ⅱ) Complex through Self-assembly Reaction of 2,2'-Bipyridine-3,3'-dicarboxylic Acid

A new Zn(Ⅱ) complex [Zn(Phen)_2(C_(12)H_6O_4N_2)(H_2O)]·3H_2O with 2,2?-bipyridine-3,3?-dicarboxylic acid and 1,10-phenanthroline(Phen) as ligands was synthesized, and the crystal data are as follows: monoclinic, space group P2_(1/n), a=12.5581(11), b=17.3382(17), c=15.6687(14) ?, β=110.579(2)o, M_r=731.02, V=3193.9(5) ?~3, Dc=1.520 g/cm~3, Z=4, μ(Mo Kα)=0.833 mm~(-1), F(000)=1508, the final R=0.0431 and w R=0.0936. In the title complex, the central Zn(Ⅱ) ion is located in a distorted octahedral coordination environment. The electrochemical and fluorescent properties were studied. The title complex possesses irreversible electron transfer in the electrode reaction, and it has a strong emission peak in the range of 470~505 nm, with the excitation wavelength being 488 nm.     

双核Cd(Ⅱ)配合物[Cd2(C22H14N4)2Cl2(N3)2]2·H2O的合成与晶体结构

A dinuclear Cd(Ⅱ) complex [Cdz (N3)2LzCl2]2·H2O (1) [L=4'-(4-eyanophenyl)-2,2':6',2"-terpyridine]was synthesized by reaction of ligand L with CdCl2 and NaN3 using solvothermal method and its structure was determined by X-ray crystal structure analysis. The structure indicates that the complex crystallizes in monoclinic, space group C2/c with a=1.644 5(16) nm, b=1.441 9(12) nm, c=1.9181(18) nm,β=100.349(11)°. V=4474(7) nm3, Z=2, Dc=1.570Mg·m-3,μ=1.120 mm-l, F(000)=2 100, and final R1=0.039 3, wR2=0.0811. The result shows a Cd(Ⅱ) ion was sixcoordinated by a tridentate 4'-(4-cyanophenyl)-2,2' :6',2"-terpyridine ligand and one bridging nitrogen atom of the azide group in the basal position and an chloride atom and the other bridging nitrogen atom of the azide group in the axialone, to form a distorted octahedral-pyramidal geometry. CCDC: 673291.     

Synthesis,Crystal Structure and Photoluminescence of a TADF Dinuclear Cu(Ⅰ) Complex

A binuclear Cu(Ⅰ) complex[Cu(PCNP)(mepypz)]_2(BF_4)_2 (1,PCNP=2,6-bis(diphenylphosphine)-benzonitrile,mepypz=2-methyl-6-(1H-pyrazol-3-yl)-pyridine was synthesized from the reaction of Cu(CH_3CN)_4BF_4,PCNP and mepypz in CH_2Cl_2 at room temperature.The compound was characterized by NMR,UV-vis and X-ray single-crystal structure analysis.It crystallizes in monoclinic space group P2_1/c with a=14.0139(5),b=11.8149(3),c=27.1248(10)?,β=96.686(4)°,V=4460.6(3)?~3,Z=2,M_r=1561.97,D_c=1.163 g/cm~3,F(000)=1600.0,μ=1.774 mm~(–1),GOOF=1.071,the final R=0.0523 and w R=0.1412 for 7919 observed reflections with I2σ(I).The Cu atoms in the complex are four-coordinated and adopt a distorted tetrahedral coordination geometry.In the solid state,the complex exhibits yellowish-green emission with a peak wavelength of 546 nm,a lifetime of 390μs,and a quantum yield of 0.45 at room temperature.The temperature-dependent investigation of luminescent properties suggests that the complex emits thermally activated delayed fluorescence (TADF) at room temperature.     

杂-双核配合物[CaCu(C3H2O4)2(H2O)4]n的合成、晶体结构及热稳定性

The title complex, [CaCu(C3H2O4)2(H2O)4]n, with a formula of C6H12CaCuO12 and Mr=379.78 has been sy-nthesized and characterized by single crystal X-ray diffraction structure analysis, elemental analysis, IR spectra and TG-DTG techniques. The results show that the crystal is Orthorhombic, space group Pbcn with a=0.669 21(5) nm, b=1.370 23(5) nm, c=1.322 39(10) nm, V=1.212 59(16) nm3, Dc=2.080 g·cm-3, μ=2.288 mm-1, F(000)=772 and Z=4. The final R=0.054 0 and wR=0.112 8 for 1 189 observed reflections with I>2σ(I). The structure of the title complex consists of CaO8 polyhedra and CuO6 elongated octahedra linked together by malonate ligands. The Ca(Ⅱ) cation, on a twofold axis, is coordinated by two water molecules and six malonate O atoms. The Cu(Ⅱ) cation, which lies in a centre of symmetry in an octahedral arrangement, is coordinated by four malonate O atoms and two water molecules. The structure comprises alternating layers along the [101] plane, with the shortest Cu…Cu distance of 0.762 46(6) nm. The whole 3D structure is maintained and stabilized by the presence of hydrogen bonds. Its thermo gravimetric analysis was determined by TG-DTG techniques. CCDC:663184.     

Synthesis and Crystal Structure of a New Diamine Complex CuC14（H2tn）

In an attempt to synthesize a new pyrimidine complex of copper(H) in a solution reaction of CuBr2 with 2,2‘-bis(hexahydropydmidine) and hydro-chloric acid, we unexpectedly obtained a bright yellow chip-like crystal of CuCl4(H2tn) [H2tn=(H3NCH2CH2CH2NH3)^2 ]. Its structure was determined by single-crystal X-ray diffraction analysis. The crystal belongs to orthorhombic system, space group Pnma, with cell parameters: a=0.7216(2)nm, b=1.8308(6)nm, c=0.7553(3)nm, V=0.9953(6)nm^3, Z=4, F(000)=564, Mr=281.49, Dc=1.879 g/cm^3. u(Mo Ka)=3.204 mm^-1, R1=0.0248, wR2=0.0575. The analysis of the crystal structure indicates that the complex has a three-dimensional network structure, which is formed by hydrogen bonds and electrostatic interaction.     

Molecular Structure,Theoretical Calculation and Thermal Behavior of DAG(NTO)

A new compound, [DAG(NTO)], was prepared by mixing the NaNTO•H2O aqueous solution and diaminogaunidine hydrochloride aqueous solution. Single crystals suitable for X-ray measurement were obtained by recrystallization from water at room temperature. The crystal belongs to triclinic, space group P-1 with crystal parameters of a＝0.6732(3) nm, b＝0.6745(3) nm, c＝0.9840(4) nm, α＝88.309(7)°, β＝77.255(6)°, γ＝86.520(7)°, V＝4.349(3) nm3, Z＝2, μ＝0.144 mm－1, F(000)＝228, and Dc＝1.674 g/cm3. The theoretical investigation on DAG(NTO) as a structural unit was carried out by B3LYP, MP2 and HF methods with 6-31＋G(d) basis set. The apparent activation energy and pre-exponential constant of the exothermic decomposition reaction of DAG(NTO) are 112.15 kJ•mol－1 and 109.603 s－1, respectively. The critical temperature of thermal explosion is 208.6 ℃.     

3,5-二羟基-2,4,6-三硝基苯酚氨基脲铵盐半水合物的合成、晶体结构和热分解特性

A new compound, semicarbazidium 3,5-dihydroxy-2,4,6-trinitrophenolate hemihydrate （SCDHTNP·0.5H2P）, was synthesized by the reaction of the aqueous solutions of semicarbazide with trinitrophloroglucinol. Its structure was determined by single-crystal X-ray diffraction analysis and characterized by elemental analysis, FTIR, DSC and TG-DTG techniques. The crystal is monoclinic with space group P21/n and the empirical formula C7H9N6O10.50. The unit cell parameters are： a= 1.3791（3） nm, b=0.9256（2） nm, c=2.0468（4） nm,β= 106.93（3）°, V=2.4995（9）nm^3, Z=8, Dc= 1.835 g/cm^3, Mr=345.20, F（000）= 1416, s=0.945,μ（Mo Ka）=0.174 mm^-1. The final R and wR are 0.0401 and 0.0896. Its structure consists of two semicarbazidium cations, two 3,5-dihydroxy-2,4,6-trinitrophenolate anions and one crystal water molecule, which are interconnected by electrostatic forces and hydrogen bonds into layer structure, making the title compound very stable. Under a linear heating rate, the thermal decomposition processes of SCDHTNP·0.5H2O have one endothermal dehydration stage and two intensive exothermic decomposition stages at 178-241℃ to evolve abundant gas products.     

两个N-己酰基水杨酰肼合镍(Ⅱ)配合物的合成、结构及抗菌活性的研究

The two trinuclear nickel（Ⅱ） complexes, Ni3（C13H15N2O3）2（C5H5N）4 （1） and Ni3（C13H15N2O3）2（C5H5N）2- （C3H7NO）2 （2）, were prepared by the reaction of Ni（OAc）2·4H2O with N-hexanoylsalicylhydrazide. The crystal structures of complexes were determined by X-ray diffraction analysis. Complex 1 takes triclinic symmetry with space group P-1 and cell dimensions of a=0.92377（2） nm, b= 1.08786（6） nm, c= 1.29391（3） nm, α=76.395（4）°, β=78.418（3）°, γ=67.378（4）°, V= 1.15772（7） nm^3, Z= 1,μ= 12.63 cm^-1. Complex 2 belongs to triclinic system and P2（1） space group and the crystallographic data： a= 1.4889（2） nm, b= 1.0389（1） nm, c= 1.4994（2） nm, β= 96.174（4）°, V=2.3058（5） nm^3, Z=2,μ= 12.70 cm^-1. The structures of the two molecules are similar. The three nickel atoms in each molecule of the two title complexes arrange in a strictly linear structure. The central nickel atom of the molecule adopts octahedral configuration, while the two nickel atoms on the two sides adopt square-planar configuration in each molecule. But the central nickel atoms of the two complexes have different axial ligands, which cause a slight difference in the bond distances of the octahedron. The antibacterial activity of compound 1 against seven common bacteria was investigated.     

Synthesis and Characterization of an Unexpected Asymmetric Binuclear Copper（Ⅰ） Complex Containing 4-Vinyl-pyridine

The asymmetric binuclear copper(I) complex [Cu₂(dppm)₂(C₇H₇N)(μ‐HCOO)](NO₃) (dppm=Ph₂PCH₂PPh₂, C₇H₇N=4‐vinyl‐pyridine) has been prepared and characterized by physicochemical and spectroscopic methods. The complex is photoluminescent at room temperature. It crystallizes in triclinic system, space group P‐1 with a= 1.2719(3) nm, b=1.8637(4) nm, c=1.1656(2) nm, a=97.16(3)°, β= 104.94(3)″, γ=89.39(3)°, V=2.648.1(9) nm³, D_c= 1.390 g.m^?3, Z=2, μ=0.974 mm^?1, R=0.0483 for 5716 independently observed reflections with I>2δ(I). The structure consists of [Cu₂(dppm)₂(C₇H₇N)(μ‐HCOO)]⁺cations and nitrate anions. The copper atoms show different coordination modes: Cu(1) displays a distorted trigonal and Cu(2) a tetrahedred geometry.     

Syntheses,Structures and Characterizations of Two Vanadium(V) Complexes:[2-MePyH][V^vO2(C14H9N2O3Br)] and [2-EtPyH][V^VO2(C14H9N2O3Br)]

Two new oxovanadium(V) complexes, [2‐MePyH][V^vO₂(L)] (3) and[2‐EtPyH][V^vO₂,(L)] (4) (salicylaldehyde 5‐bromo salicyloylhydrazone is abbreviated as H₂L; 2‐MePyH is protonated 2‐Mepyridine; 2‐EtPyH presents protonated 2‐Et‐pyridine) were obtained from a reaction of VOSO₄ and H₂L in acetonitrile‐methanol with small quantity of 2‐Me‐pyridine or 2‐Et‐pyridine, and characterized by X‐ray diffraction and spectroscopic methods. Crystal data: [2‐MePyH][VO₂(L)] (3), C₂₀H₁₇N₃O₅BrV, M_r = 510.2, monoclinic, P2₁/n, a = 0.7363(1) nm, 6 = 0.9514(1) nm, c = 2.8594(2) nm, β = 95.305(2)°, Z = 4 and V=1.9946(3) nm³, μ(Mo Kα) = 2.539 mm^?1; [2‐EtPyH][VO₂(L)] (4), C₂₁H₁₉N₃ O₃BrV, M_r = 524.2, triclinic, P1 , a = 0.8051(1) nm, b = 0.9413(1) nm, c = 1.4648(2) nm, α=99.1900(10)°, α = 99.4530(10)°, γ = 104.6670(10)°, Z = 2 and V= 1.0355(2) nm³, μ(Mo Kα) = 2.448 mm^?1, X‐Ray analyses revealed that the crystal structures of 3 and 4 have similar packing modes.     

一个新颖的含联二萘芬衍生物的镉配合物的合成和晶体结构

The self-assembly of a racemic exo-bidentate ligand 2,2＇-bis（4-pyridylmethyloxy）-1,1＇-binaphthyl, namely Rac-L, with cadmium（Ⅱ） salt gave rise to a new one-dimensional polymer, which has been characterized by single crystal X-ray diffraction analysis. The polymer crystallizes in a triclinic space group P-1 with unit cell parameters： a=0.6976（1） nm, b= 1.30160（14） nm, c= 1.71146（17） nrn.α= 105.141（3）°, β=94.263（5）°, γ= 100.405（4）°, V= 1.4633（2） nm^3, Z=2, C32H29CdCl2N2O4.5, M=696.88, Dc= 1.584 g/cm^3, F（000）=708,μ（Mo Kα）=0.972 mm^-1. The final R and wR are 0.0498 and 0.1282 for 5079 observed reflections with I≥2σ（I）.     

一种新型氧离子导体：La3GaMo2O12

A new oxide ion conductor,La_3GaMo_2O_(12),with a bulk conductivity of 2.7×10~(-2)S·cm~(-1) at 800 ℃ in air at-mosphere was prepared by the traditional solid-state reaction.The room temperature X-ray diffraction data could beindexed on a monoclinic cell with lattice parameters of a=0.5602(2) nm,b=0.3224(1) nm,c=1.5741(1) nm,β=102.555(0)°,V= 0.2775(2) nm~3 and space group Pc(7).Ac impedance measurements in various atmospheres furthersupport that it is an oxide ion conductor.This material was stable in various atmospheres with oxygen partial pres-sure p(O_2)ranging from 1.0×10~5 to 1.0×10~(-7) Pa at 800 ℃.A reversible polymorphic phase transition occurred atelevated temperatures as confirmed by the differential thermal analysis and dilatometric measurement.     

N-(4-甲基苯甲酰氨基) N’-[5-(2-三氟甲基苯基)-2-呋喃甲酰硫脲的合成、晶体结构测定与生物活性测定

本文首次合成标题化合物N-(4-甲基苯甲酰氨基)-N’-[5-(2-三氟甲基苯基)-2-呋喃甲酰硫脲。化合物(C21H16F3N3O3S, Mr = 447.43)单晶经测定为单斜晶体,空间群为P -1。在晶体中,存在一些分子内和分子间的相互作用,分子间还有C—H···π 的相互作用,这可能导致晶体更稳定的原因。目标产物的结构经IR, H NMR和元素分析测定确证。初步生物活性测试表明,部分化合物对棉花枯萎病、黄瓜灰霉病、苹果轮纹病和棉花炭疽病有较好的选择性杀菌活性;部分目标化合物有较好的除草活性。     

Direct Synthesis, Crystal Structure and Thermal Kinetics of Supramolecular Complex [Co（H2O）6]·（Hnip）2·（H2nip）2·（DMA）2·（H2O）8 （nip=5-nitroisophthalate, DMA=CH3NHCH3）

The crystal of [Co（H2O）6]·（Hnip）2·（H2nip）2·（OMA）2·（H2O）8 has been cultured using direct method and characterized by X-ray single crystal diffractometry, elemental analysis and FTIR spectroscopy. It crystallizes in triclinic system, P-1 space group with the cell parameters of a=0.7012（1） nm, b=1.1378（2） nm, c=1.6612（3） nm, α= 84.92（3）°, β=85.19（3）°, γ=85.91（3）°, V= 1.3128（5） nm^3, Z=1, Dc= 1.573 g·cm^-3. Final R indices [1〉2σ（I）] are： R1 =0.0279, wR2=0.0765 while R indices for all data are： R1 =0.0327, wR2=0.0806. The Co coordination octahadra are each surrounded by two Hnip, two H2nip, two DMA and eight water molecules that are linked by hydrogen bonds and π-π stacking interactions. Thermal analyses of DSC and TG-DTG have been performed on the complex to predict its thermal decomposition mechanism and determine the most probable kinetic model function using Kissinger, Ozawa, integral and differential methods.     

两个Keggin结构锗钨酸盐稀土衍生物的合成、晶体结构及表征

合成了两个基于Dy3＋阳离子和单缺位Keggin阴离子[GeW11O39]8-的锗钨酸盐, [(CH3)4N]1.5H3.5[Dy(H2O)2(GeW11O39)]×1.5H2O (1) 和[Cu(Hen)(en)]2[Cu(H2O)3]0.5{[Cu(H2en)(Hen)]