DACO-CuⅡ-SCN-三元配合物的合成、表征及结构研究（DACO=1，5-二氮环辛烷）

A new mononuclear Cu^Ⅱ complex of DACO [Cu(DACO)₂(SCN)]·(SCN)·2H₂O (1) was prepared by introducing a co-ligand SCN^- anion. The crystal structure of 1 was determined by X-ray diffraction analysis. The crystallographic data are: monoclinic, P2₁/n, a=0.728 5(4) nm, b=2.479 0(15) nm, c=1.069 7(6) nm, β=93.861(10)°, V=1.927(2) nm³, Z=4. The Cu^Ⅱ atom takes the square-pyramidal coordination geometry. The SCN^- anions adopt both monodentate coordination and uncoordinated forms in the crystal. The coordinated cation, SCN^- counter anion and the lattice water molecules are further linked through hydrogen bonds to form a one-dimensional chain motif. The spectral and thermal properties of 1 were studied. CCDC: 243104.     

一个新的双核锌配合物Zn2(dhaash)2(py)4的合成及晶体结构

The crystal of binuclear zinc complex Zn₂(dhaash)₂(py)₄ was obtained in DMF and pyridine, where H₂dhaash is 2,4-dihydroxy-5-acetylacetophenone-N-salicylhydrazone. It has been characterized by IR, UV, element analysis and X-ray single crystal diffraction. The crystallographic data were as follows: monoclinic system, space group P2₁/c, a=1.108 98(11) nm, b=1.640 84(16) nm, c=1.445 14(14) nm, β=108.617(2)°, Z=2, V=2.492 1(4) nm³, D_c=1.466 g·cm^-3, M_r=1 099.74, μ=1.031 mm^-1, F(000)=1 136 and the final R=0.044 8 and wR=0.105 8 for 4 143 observed reflections with I≥2σ(I), respectively. The X-ray crystal structure analysis revealed that, in the centrosymmetric binuclear complex molecule, two zinc(Ⅱ) centers are linked by two oxygen atoms (O(3) and O(3A)), respectively. Zn(1)…Zn(1A) distance is 0.314 81(6) nm, O(3)…O(3A) distance is 0.270 4(2) nm. Every zinc(Ⅱ) ion has an elongated octahedral coordination. For example, the two pyridine nitrogen atoms, one oxygen atom and one nitrogen atom from salicylhydrazone, one oxygen atom from 2,4-dihydroxy-5-acetylacetophenone in one dhaash^2- ligand and one oxygen atom from 2,4-dihydroxy-5-acetylacetophenone in another dhaash^2- ligand coordinated to zinc(Ⅱ) ion, respectively. Two zinc(Ⅱ) ions and all the 72 non-hydrogen atoms in the two dhaash^2- ligands are in the same plane. CCDC: 261929.     

三维异核Mn-Na配合物[MnNa(N3)4(C5H5N)4]的合成与表征

Azide-containing coordination polymers have received considerable attention for the construction of new molecule-based magnets. A three dimensional heteronuclear Mn-Na compound [MnNa(N₃)₄(C₅H₅N)₄] was obtained by reaction of [Mn₃O(O₂CCH₃)₆(py)₃]ClO₄ and NaN₃ in pyridine solvents. The title compound crystallizes in monoclinic space group C2/c, a=1.536 6(2), b=1.045 3(2), c=1.576 3(2) nm, β=90.309(3)°, V=2.531 8(6) nm³, Z=4. In the structure, each Mn³⁺ and Na⁺ ion coordinated with four N atoms from four N₃^- and two N atoms from two pyridine molecules. Each pair of Mn³⁺ and Na⁺ ion are linked by N₃^- bridges into a 3D polymer with PtS topology. CCDC: 706250.     

二维层状结构十钒酸盐[K(H2O)2Ni(H2O)6]2[V10O28]的合成及性质(英)

A novel heteropoly compound, containing two kinds of coordinated cations, [K(H₂O)₂Ni(H₂O)₆]₂[V₁₀O₂₈], has been synthesized through routine process and characterized by elemental analyses, IR, ⁵¹V NMR and single crystal X-ray diffraction. It crystallizes in the triclinic system, space group P1 with a=0.87382(17) nm, b=1.075 4(2) nm, c=1.111 1(2) nm, α=65.10(3)°, β=75.01(3)°, γ=70.63(3)°, V=0.884 8(3) nm³ and Z=1. The X-ray analysis reveals that the two kinds of coordinated cations are linked by three shared coordinated water molecules, and K⁺ cations coordinate with ten oxygen atoms: five of which come from V₁₀O₂₈^6- anion, the other five from water molecules. The title compound exhibits extended 2D array building up of V₁₀O₂₈^6- groups connected by ten-coordinated K⁺ cations. The hexahydrated nickel cations Ni(H₂O)₆²⁺ lie in neat apposition to three adjacent V₁₀O₂₈^6- clusters. CSD: 413271.     

[Mn(NH2NHCO2C2H5)3](NO3)2的晶体结构和热分解机理

[Mn(ECZ)₃](NO₃)₂ is newly prepared by the aqueous solutions of Mn(NO₃)₂ and ethyl carbazate (ECZ). The crystal structure has been determined by X-ray crystal diffraction analysis. It belongs to monoclinic with space group of P2₁/n. The crystal parameters are: a=1.3974(2) nm, b=0.8796(2) nm, c=3.4322(7) nm, β=91.25(1) °, V= 4.2175(1) nm³, Z=8. Its molecular weight is 491.30. Mn²⁺ is located on the center of the molecular structure. Ethyl carbazate serves as a bidentate ligand which coordinates to the metal cations with its carbonyl oxygen atom and the terminal hydrazine nitrogen atom, forming five-member chelating rings, and three such rings are formed in each molecule. The coordination number of the metal ion is six and the coordination configuration of the central ion is octahedral. Specially, antimer configuration phenomenon is found in the molecule. The complex is further characterized by element analysis and IR measurements. The thermal decomposition mechanism is studied by using TG-DTG and DSC techniques. CCDC: 215675.     

LiNi1-xMxVO4的红外光谱和拉曼光谱研究

The vanadates of LiNi_1-xM_xVO₄(M=Fe,Co,Ni) containing VO₄ tetrahedrons were synthesized by soft chemical method through a new mild liquid route. The samples sintered at 450℃ for 3h and at 650℃ for 3h are named for LT-LiNiVO₄ and for MT-LiNi_1-xM_xVO₄ respectively. All of the products were measured by X-ray diffraction, IR and Raman spectra respectively. In comparison with IR spectra of V₂O₅ and NiO, the LT-LiNiVO₄ has a strong and broad IR absorption band of VO₄ tetrahedrons located at 600～850cm^-1 with three small splitting peaks corresponding to the asymmetry stretching vibrations of V-O bonds. The results of IR and Raman spectra for MT-LiNi_1-xM_xVO₄ show that the cations of Ni²⁺, Co²⁺, Fe²⁺ have the influences on the frequency shifts of the V-O vibrations.     

球形La2O3∶Eu纳米晶的制备及其发光特性

The spheric La₂O₃∶Eu nanocrystals were prepared using NH₃·H₂O-NH₄HCO₃ mixture as precipitant. The material was characterized by FTIR, XRD and TEM techniques. The luminescence properties of Eu³⁺ in spheric La₂O₃ were measured by three dimension spectra, emission and excitation spectra. The results indicate that the La₂O₃∶Eu nanocrystals are in hexagonal phase by annealing at 800 ℃, the crystal size is about 30 nm. The maximum emission and excitation wavelength were determined by three dimensional spectroscopy to be at 591 nm and 394 nm, respectively. In emission spectrum the band at 591 nm and 612 nm are corresponding to ⁵D₀-⁷F₁ and ⁵D₀-⁷F₂ transition of Eu³⁺ ions. With increasing in annealing temperature the differences of intensity of the two transitions are increased. This phenomenon shows that the luminescence intensity of La₂O₃∶Eu nanocrystals can be tuned by changing annealing temperature.     

一维双核锌配合物[Zn2(SHSH)2(2-Me-py)2]的合成、晶体结构及理论研究

The crystal of one-dimensional binuclear zinc complex [Zn₂(SHSH)₂(2-Me-py)₂] was obtained in DMF and 2-methylpyridine, where SHSH is salicylaldehyde salicylhydrazone. It has been characterized by IR, UV, element analysis and X-ray diffraction analysis. The crystallographic data were as follows: monoclinic system, space group P2₁/c, a=1.144 49 nm, b=1.206 69 nm, c=1.379 39 nm, β=97.039°, Z=2, V=1.890 6 nm³, M_r=825.47, D_c=1.450 g·cm^-3, μ=1.324 mm-1, F(000)=848 and the final R=0.033 6 and wR=0.094 7 for 3 752 observed reflections with I≥2σ(I). The theoretical investigation of title complex as a structure unit was carried out at B3LYP/6-31G and HF/6-31G levels with Guassian 03W program, and the atomic charges, natural bond orbital analysis and bond energies were also discussed. CCDC: 260920.     

二维网状铜(Ⅱ)配位聚合物{Cu(μ2-C10H8N2O3)( μ2-C6H12N4)1/2}n的合成和晶体结构

The novel copper(Ⅱ) coordination polymer with 2-oxo-propionic acid benzoyl hydrazone and hexamethylenetetramine ligands, {Cu(μ₂-C₁₀H₈N₂O₃)( μ₂-C₆H₁₂N₄)_1/2}_n (C₁₀H₈N₂O₃^2- is the dinegative ion of 2-oxo-propionicacid benzoyl hydrazone), has been synthesized and characterized by elemental analysis and IR spectroscopy. The crystal structure was determined by single crystal X-ray diffraction analysis. The results show that the crystal of the title coordination polymer belongs to monoclinic space group C2/c, the cell parameters are as follows: a=1.787 5(2) nm, b=0.730 93(9) nm, c=2.038 2(2) nm, β=92.890(2)°, and V=2.659 6(5) nm³, Z=8, D_c=1.687 Mg·m^-3, μ(Mo Kα)=1.659 mm^-1, F(000)=1 384, R=0.031 1, wR=0.079 0 for 2 454 observed reflections (I>2σ(I)) out of 2887 unique reflections. In this copper(Ⅱ) coordination polymer, each copper(Ⅱ) ion is five-coordinated with a geometry of distorted square-pyramid. Two oxygen atoms of the carboxyl of each C₁₀H₈N₂O₃^2- acts as a bridge to bond two neighboring copper(Ⅱ) ions, leading to an infinite one-dimensional chainlike coordination polymer. Each chain is linked by coordinated hexamethylenetetramines with its neighbors to form an infinite two-dimensional network structure. CCDC: 255347.     

二维层状铜配位聚合物[Cu2(3-PyOH)2(EDTA)]n的合成与结构研究

A 2D copper coordination polymer of [Cu₂(3-PyOH)₂(EDTA)]_n (EDTA^4-=ethylenediaminetetraacetate quadrivalent anion C₁₀H₁₂N₂O₈, 3-PyOH=3-hydroxypyridine) was synthesized and characterized by the element analysis, IR and single crystal X-ray diffraction. The title complex crystallizes in monoclinic system with space group P2₁/c, a=1.327 5(3) nm, b=0.930 39(19) nm, c=0.948 44(19) nm, β=108.21(3)°, and V=1.112 8(4) nm³, Z=2, R=0.025 2, wR=0.066 1. Each copper(Ⅱ) atom is five-coordinated by three O atoms and one N atom from two different EDTA^4- groups and one N atom from 3-PyOH ligand, forming a distorted square-pyramidal coordination geometry. Two adjacent copper(Ⅱ) atoms are bridged by the bis-tetradentate EDTA^4- groups, constructing a two-dimensional layer structure along bc plane. The adjacent Cu…Cu distances are 0.502 5(3) and 0.611 3(3) nm. CCDC: 618806.     

Heterobimetallic thiocyanato-bridged coordination polymers based on [Hg(SCN)4]: Synthesis, crystal structure, magnetic properties and ESR studies

Three new M/Hg bimetallic thiocyanato-bridged coordination polymers; [Hg(SCN)₄Ni(Im)₃]_∞1, [Hg(SCN)₄Mn(Im)₂]_∞2, and [Hg(SCN)₄Cu(Me-Im)₂ Hg(SCN)₄Cu(Me-Im)₄]_∞3, (Im=imidazole, Me-Im=N-methyl-imidazole), have been synthesized and characterized by means of elemental analysis, ESR, and single-crystal X-ray. X-ray diffraction analysis reveals that these three complexes all form 3D network structure, and their structures all contain a thiocyanato-bridged Hg?M?Hg chain (M=Mn, Ni, Cu) in which the metal and mercury centers exhibit different coordination environments. In complex 1, the [Hg(SCN)₄]²⁻ anion connects three [Ni(Im)₃]²⁺ using three SCN ligands giving rise to a 3D structure, and in complex 2, four SCN ligands bridge [Hg(SCN)₄]²⁻ and [Mn(Im)₂]²⁺ to form a 3D structure. The structure of 3 contains two copper atoms with distinct coordination environment; one is coordinated by four N-methyl-imidazole ligands and two axially elongated SCN groups, and another by four SCN groups (two elongated) and two N-methyl-imidazole ligands. The magnetic property of complex 1 has been investigated. The spin state structure in hetermetallic NiHgNi systems of complex 1 is irregular. The ESR spectra results of complex 3 demonstrate Cu²⁺ ion lie on octahedral environment.     

Eu2+掺杂KCaCl3晶体的生长及发光性能

通过坩埚下降法生长出不同物质的量分数Eu²⁺掺杂的KCa_1-xEu_xCl₃(x=0.005、0.01、0.02、0.03、0.05)单晶,并对晶体进行了X射线粉末衍射、热重、透过率、光致发光光谱、衰减时间、X射线激发发射光谱等测定。通过相图及结构分析,判断出该晶体为一致熔融化合物,并得出其为正交结构,晶胞参数为a=0.75604 nm,b=1.04823 nm,c=0.72657 nm,空间群为Pnma(62)。在紫外光的激发下,晶体在434 nm左右有一个宽的发射峰,对应于Eu²⁺的4f⁶5d¹→4f⁷跃迁;光致衰减时间1.473μs,晶体在X射线激发下的发光强度随Eu²⁺离子浓度增加而增强。     

Sol-gel synthesis of K3InF6 and structural characterization of K2InC10O10H6F9, K3InC12O14H4F18 and K3InC12O12F18

K₃InF₆ is synthesized by a sol-gel route starting from indium and potassium acetates dissolved in isopropanol in the stoichiometry 1:3, with trifluoroacetic acid as fluorinating agent. The crystal structures of the organic precursors were solved by X-ray diffraction methods on single crystals. Three organic compounds were isolated and identified: K₂InC₁₀O₁₀H₆F₉, K₃InC₁₂O₁₄H₄F₁₈ and K₃InC₁₂O₁₂F₁₈. The first one, deficient in potassium in comparison with the initial stoichiometry, is unstable. In its crystal structure, acetate as well as trifluoroacetate anions are coordinated to the indium atom. The two other precursors are obtained, respectively, by quick and slow evaporation of the solution. They correspond to the final organic compounds, which give K₃InF₆ by decomposition at high temperature. The crystal structure of K₃InC₁₂O₁₄H₄F₁₈ is characterized by complex anions [In(CF₃COO)₄(OH_x)₂]^(5−2x)− and isolated [CF₃COOH_2−x]^(x−1)− molecules with x=2 or 1, surrounded by K⁺ cations. The crystal structure of K₃InC₁₂O₁₂F₁₈ is only constituted by complex anions [In(CF₃COO)₆]³⁻ and K⁺ cations. For all these compounds, potassium cations ensure only the electroneutrality of the structure. IR spectra of K₂InC₁₀O₁₀H₆F₉ and K₃InC₁₂O₁₂F₁₈ were also performed at room temperature on pulverized crystals.     

Multianvil high-pressure/high-temperature preparation, crystal structure, and properties of the new oxoborates Dy4B6O14(OH)2 and Ho4B6O14(OH)2

This paper reports about two new hydrogen-containing rare-earth oxoborates RE₄B₆O₁₄(OH)₂ (RE=Dy, Ho) synthesized under high-pressure/high-temperature conditions from the corresponding rare-earth oxides, boron oxide, and water using a Walker-type multianvil equipment at 8 GPa and 880 °C. The single crystal structure determination of Dy₄B₆O₁₄(OH)₂ showed: Pbcn, a=1292.7(2), b=437.1(2), , Z=2, R1=0.0190, and wR2=0.0349 (all data). The isotypic holmium species revealed: Pbcn, a=1292.8(2), b=436.2(2), , Z=2, R1=0.0206, and wR2=0.0406 (all data). The compounds exhibit a new type of structure, which is built up from layers of condensed BO₄-tetrahedra. Between the layers, the rare-earth cations are coordinated by 7+2 oxygen atoms. Furthermore, we report about temperature-resolved in situ powder diffraction measurements, DTA/TG, and IR-spectroscopic investigations into RE₄B₆O₁₄(OH)₂ (RE=Dy, Ho).     

二维网状有机锑对氨基苯乙酸酯的合成、表征及晶体结构研究

The title complex bis(4-aminophenylacetate)triphenylantimony(V) has been synthesized by the reaction of triphenylantimony dibromide with 4-aminophenylacetic acid in 1∶2 molar ratio. The complex was characterized by elemental analysis, IR spectra, NMR ( ¹H, ¹³C) and X-ray diffraction crystal structure analysis. This complex crystallizes in the monoclinic system, space group C2/c with a=2.279 4(2) nm, b=0.957 10(10) nm, c=1.335 49(15) nm, β=93.781(2)°. The molecular structure adopts a distorted trigonal bipyramidal geometry around the antimony atom. In the crystal structure molecules are connected by intermolecular N-H…O hydrogen-bonding interactions forming a two-dimensional network structure. CCDC: 726039.     

高容量锂离子电池正极材料LiNi0.9Co0.05Mn0.025Mg0.025O2的合成及电化学性能

以β-Ni0.9Co0.05Mn0.025Mg0.025(OH)2和LiOH.H2O为原料通过高温固相法合成了球形LiNi0.9Co0.05Mn0.025Mg0.025O2。采用热重-差热分析了反应过程,采用X射线衍射和扫描电镜对粉末的结构和形貌进行了表征。采用充放电测试和循环伏安测试对材料电化学性能进行了研究。结果表明:750℃煅烧12 h合成的LiNi0.9Co0.05Mn0.025Mg0.025O2为Li原子混排较少的良好层状结构,二次颗粒尺寸在15μm左右,且具有最高的放电比容量和良好的循环性能,在0.2C,2.8~4.3 V的条件下,首次放电比容量达207 mAh.g-1,40次循环后容量保持率为92.5%。     

一维链状配位聚合物[Pb_2(C_8H_7O_2)_4(H_2O)_2]_n的合成、晶体结构及荧光性质

<正>近年来,铅的配位聚合物以其丰富的结构与在离子交换和光学等领域中的应用前景[1-3]而引起了广泛关注。由于铅的原子半径较大,可以形成较高的配位数[4-6];另外,二价铅的6s轨道上有一对孤对     

极性金属间化合物LuSn2的合成、晶体结构及能带特征

在惰性气氛氩气保护下,通过高温固相反应合成得到了一个新的二元极性金属间化合物LuSn2。经X-射线单晶衍射与元素分析等方法确定了其晶体结构。LuSn2属正交晶系,空间群为Cmcm,晶体学参数a=0.435 11(10)nm,b=1.601 6(4)nm,c=0.427 80(8)nm,V=0.298 12(11)nm3,Z=4,R1=0.017 0,wR2=0.032 4。LuSn2属于ZrSi2结构类型,其结构中包含有一维"之"字型Sn链与二维四方格子状Sn层,Lu原子排列在Sn链与Sn层的空隙中。能带结构计算表明LuSn2呈金属导电性。     

三维混合价态铜配位聚合物[Cu(Me_2dtc)_2(CuI)_3]_n的合成与晶体结构(英文)

A new three-dimensional copper dithiocarbamate-copper iodide coordination polymer [Cu(Me2dtc)2(CuI)3]n (Me2dtc=N,N-dimethyldithiocarbamate) was synthesized by reactions of Cu(OAc)2,NaI and Na(Me2dtc) in DMF solution,characterized by elemental analysis,IR spectrum,and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system,space group C2/c with a=1.293 89(17) nm,b=1.077 61(11) nm,c=1.456 05(17) nm,β=115.585 (4)°,V=1.831 1 (4) nm3,Z=4,Dc=3.175 g·cm-3,Mr=875.28,λ (Mo Kα)=0.071 073 nm,μ=10.082 mm-1,F(000)=1 604,the final R=0.029 5 and wR=0.081 7. A total of 2 083 unique reflections were collected,of which 1 918 with I2σ(I) were observed. The Cu atoms are Cu(Ⅰ)/Cu(Ⅱ) mixed-valence and they have two different coordinate geometries,namely planar square and tetrahedron. This three-dimensional structure consists of individual Cu(Me2dtc)2 molecules linking together CuI polymeric chains which run parallel to the [001] direction vis Cu-S bonds.