一个新的夹心型杂多钨酸盐Na6(C5N2H7){[Na(H2O)2]3Co(H2O)5-[Co(H2O)]3(AsW9O33)2}•27H2O的晶体结构及性质

在pH＝7.5的水溶液中, Na₂WO₄•2H₂O, NaAsO₂, CoCl₂•6H₂O与对氨基吡啶反应, 得到了一种新的夹心型杂多钨酸盐Na₆(C₅H₇N₂){[Na(H₂O)₂]₃Co(H₂O)₅[Co(H₂O)]₃(AsW₉O₃₃)₂}•27H₂O单晶, 用X射线单晶衍射法及元素分析确定了其结构, 晶体属三斜晶系, P 空间群, 其晶胞参数为: a＝1.3276(8) nm, b＝1.7581(10) nm, c＝2.4381(14) nm, α＝70.954(9)°, β＝86.663(9)°, γ＝72.885(9)°, V＝5.136(5) nm³, Z＝2, R₁＝0.0608, wR₂＝0.0848 [I＞2σ(I)]. 在{[Na(H₂O)₂]₃Co(H₂O)₅[Co(H₂O)]₃(AsW₉O₃₃)₂}^7－阴离子中, 一个Co^2＋与聚阴离子{[Na(H₂O)₂]₃[Co(H₂O)]₃(AsW₉O₃₃)₂}^9－的一个端基氧共价连接, Co^2＋呈现出5和6两种配位数, 质子化的氨基吡啶正离子作为抗衡离子存在于晶体之中. 对标题化合物进行了IR, UV-Vis, TG-DSC表征. 对该化合物、Na₂WO₄•2H₂O及CoCl₂•6H₂O催化H₂O₂氧化乙醛的活性进行了比较研究, 该化合物的催化活性远优于简单化合物Na₂WO₄•2H₂O和CoCl₂•6H₂O.     

Synthesis and structure of [C6H14N2][(UO2)4(HPO4)2(PO4)2(H2O)]·H2O: An expanded open-framework amine-bearing uranyl phosphate

A new open-framework compound, [C₆H₁₄N₂][(UO₂)₄(HPO₄)₂(PO₄)₂(H₂O)]·H₂O, (DUP-1) has been synthesized under mild hydrothermal conditions. The resulting structure consists of diprotonated DABCOH₂²⁺ (C₆H₁₄N₂²⁺) cations and occluded water molecules occupying the channels of a complex uranyl phosphate three-dimensional framework. The anionic lattice contains uranophane-like sheets connected by hydrated pentagonal bipyramidal UO₇ units. [C₆H₁₄N₂][(UO₂)₄(HPO₄)₂(PO₄)₂(H₂O)]·H₂O possesses five crystallographically unique U centers. U(VI) is present here in both six- and seven-coordinate environments. The DABCOH₂²⁺ cations are held within the channels by hydrogen bonds to both two uranyl oxygen atoms and a μ₂-O atom. Crystallographic data (193 K, Mo Kα, λ=0.71073 Å): DUP-1, monoclinic, P2₁/n, a=7.017(1) Å, b=21.966(4) Å, c=17.619(3) Å, β=90.198(3)°, Z=4, R(F)=4.76% for 382 parameters with 6615 reflections with I>2σ(I).     

[Cu(TO)2(H2O)4](PA)2的合成和晶体结构

[Cu(TO)₂(H₂O)₄](PA)₂ was prepared by mixing the aqueous solution of 1,2,4-triazol-5-one(TO) and Cu(PA)₂. The molecular structure and crystal structure of the title complex was determined by X-ray single crystal diffraction method. The crystal is triclinic, space group with a=0.7321(1)nm,b=0.7474(2)nm,c=1.3649(3)nm;α=88.65(2)°,β=85.63(1)°,γ=63.35(1)°;V=0.6655(2)nm³,Z=1. The Cu²⁺ coordinated with two TO molecule through its 2-nitrogen atom and four water molecules and showed an octahedral configuration.     

Combinatorial topology of uranyl molybdate sheets: syntheses and crystal structures of (C6H14N2)3[(UO2)5(MoO4)8](H2O)4 and (C2H10N2)[(UO2)(MoO4)2]

Two new mixed organic-inorganic uranyl molybdates, (C₆H₁₄N₂)₃[(UO₂)₅(MoO₄)₈](H₂O)₄ (1) and (C₂H₁₀N₂)[(UO₂)(MoO₄)₂] (2), have been obtained by hydrothermal methods. The structure of 1 [triclinic, , Z=1, a=11.8557(9), b=11.8702(9), c=12.6746(9) Å, α=96.734(2)°, β=91.107(2)°, γ=110.193(2)°, V=1659.1(2) Å] has been solved by direct methods and refined on the basis of F² for all unique reflections to R1=0.058, which was calculated for the 5642 unique observed reflections (|F_o|?4σ_F). The structure contains topologically novel sheets of uranyl square bipyramids, uranyl pentagonal bipyramids, and MoO₄ tetrahedra, with composition [(UO₂)₅(MoO₄)₈]⁶⁻, that are parallel to (−101). H₂O groups and 1,4-diazabicyclo [2.2.2]-octane (DABCO) molecules are located in the interlayer, where they provide linkage of the sheets. The structure of 2 [triclinic, , Z=2, a=8.4004(4), b=11.2600(5), c=13.1239(6) Å, α=86.112(1)°, β=86.434(1)°, γ=76.544(1)°, V=1203.14(10) Å] has been solved by direct methods and refined on the basis of F² for all unique reflections to R1=0.043, which was calculated for 5491 unique observed reflections (|F_o|?4σ_F). The structure contains topologically novel sheets of uranyl pentagonal bipyramids and MoO₄ tetrahedra, with composition [(UO₂)(MoO₄)₂]²⁻, that are parallel to (110). Ethylenediamine molecules are located in the interlayer, where they provide linkage of the sheets. All known topologies of uranyl molybdate sheets of corner-sharing U and Mo polyhedra can be described by their nodal representations (representations as graphs in which U and Mo polyhedra are given as black and white vertices, respectively). Each topology can be derived from a simple black-and-white graph of six-connected black vertices and three-connected white vertices by deleting some of its segments and white vertices.     

[Gd2(Gly)6(H2O)4](ClO4)6(H2O)5的合成、晶体结构与热化学研究

利用微波技术合成了配合物[Gd₂(Gly)₆(H₂O)₄](ClO₄)₆(H₂O)₅, 进行了化学成分分析、红外表征和热重分析. 应用X衍射仪测定其晶体结构, 该晶体为一维链结构, 属三斜晶系, P 空间群, 晶胞参数: a＝1.1569(17) nm, b＝1.4138(2) nm, c＝1.5642(2) nm, α＝96.910(2)°, β＝102.735(2)°, γ＝105.512(2)°, V＝2.3606(6) nm³, Z＝2, D_c＝2.144 g•cm^－3. 采用精密溶解-反应量热计, 通过设计热化学循环, 计算出了该配合物的标准摩尔生成焓为 －(7960.73±3.23) kJ•mol^－1.     

Hydrothermal synthesis and characterization of layered vanadium phosphite: [HN(C2H4)3N][(VO)2(HPO3)2(OH)(H2O)]·H2O

A novel compound, [HN(C₂H₄)₃N][(VO)₂(HPO₃)₂(OH)(H₂O)]·H₂O, was hydrothermally synthesized and characterized by single crystal X-ray diffraction. This compound crystallizes in the monoclinic system with the space group C2/c and cell parameters a=11.0753(3) Å, b=17.8265(6) Å, c=16.5229(5) Å, and β=92.362(2)°. The structure of the compound consists of vanadium phosphite layers which are built up from the infinite one-dimensional chains of [(VO)(H₂O)(HPO₃)₂]²⁻ of octahedral VO₅(H₂O) and pseudo pyramidal [HPO₃], and bridging binuclear fragments of [VO(OH)]₂. Thermogravimetric analysis and magnetic susceptibility data for this compound are given.     

Single-crystal characterization of Co7(OH)6(H2O)3(C4H4O4)47H2O; A new cobalt succinate identified through high-throughput synthesis

A new form of cobalt succinate has been discovered using high-throughput methods and its structure was solved by single crystal X-ray diffraction. Co₇(C₄H₄O₄)₄(OH)₆(H₂O)₃7H₂O crystallizes in the monoclinic space group P2₁/c with cell parameters: a=7.888(2) Å, b=19.082(6) Å, c=23.630(7) Å, β=91.700(5)°, V=3555(2) Å³, R₁=0.0469. This complex structure, containing 55 crystallographically distinct non-hydrogen atoms, is compared to the previously reported nickel phase, characterized using ab initio structure solution from synchrotron powder diffraction data.     

Hydrothermal synthesis and characterization of a new 3D vanadium(III) phosphite (C4H8N2H4)0.5(C4H8N2H3)[V4(HPO3)7(H2O)3]1.5H2O

A new vanadium(III) phosphite, (C₄H₈N₂H₄)_0.5(C₄H₈N₂H₃)[V₄(HPO₃)₇(H₂O)₃]1.5H₂O, has been synthesized hydrothermally by using V₂O₅, H₃PO₃ as reactants, piperazine as the structure-directing agent. The as-synthesized product was characterized by powder X-ray diffraction, IR spectroscopy, inductively coupled plasma analysis, thermogravimetric analysis, and SQUID magnetometer. Single-crystal X-ray diffraction analysis shows that the title compound crystallized in the trigonal space group (No. 165) with the parameters: , , and Z=4. Its structure is built up by alternation of octahedral VO₆ or VO₅(H₂O) and pseudo-pyramidal HPO₃ units to form infinite 2D layers, and these layers are interconnected by sharing vertex-oxygen with octahedral VO₆ units to generate a 3D open-framework structure with 12-membered ring channels in a and b directions, respectively, where there exist entrapped diprotonated and mono-protonated piperazine cations, and water molecules. Magnetic measurement indicates that paramagnetic behavior is observed down to 4 K.     

Calorimetric study and thermal analysis of [Gd4/3Y2/3(Gly)6(H2O)4](ClO4)6·5H2O and [ErY(Gly)6(H2O)4](ClO4)6·5H2O (Gly: glycin)

Two solid-state coordination compounds of rare earth metals with glycin, [Gd_4/3Y_2/3(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O and [ErY(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O were synthesized. The low-temperature heat capacities of the two coordination compounds were measured with an adiabatic calorimeter over the temperature range from 78 to 376 K. [Gd_4/3Y_2/3(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O melted at 342.90 K, while [ErY(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O melted at 328.79 K. The molar enthalpy and entropy of fusion for the two coordination compounds were determined to be 18.48 kJ mol⁻¹ and 53.9 J K⁻¹ mol⁻¹ for [Gd_4/3Y_2/3(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O, 1.82 kJ mol⁻¹ and 5.5 J K⁻¹ mol⁻¹ for [ErY(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O, respectively. Thermal decompositions of the two coordination compounds were studied through the thermogravimetry (TG). Possible mechanisms of the decompositions are discussed.     

[Pb2(TNR)2(CHZ)2(H2O)2]4H2O的结构及热分解机理

The coordination compound of [Pb 2(TNR) 2(CHZ) 2(H 2O) 2]•4H 2O was prepared by using the aqueous solution of carbohydrazide, lead nitrate and sodium styphnate. The molecular structure of [Pb 2(TNR) 2(CHZ) 2(H 2O) 2]•4H 2O(C 7H 13 N 7O 12 Pb, Mr=594.43) was determined by using a single crystal diffraction analysis .The thermal decomposition mechanism of the title compound was studied by TGDTG, DSC and IR techniques. The crystal belongs to monoclinic with space group P2 1/n.The unit cell parameters are as follows: a=0.64700(10)nm, b=1.6074(3)nm, c=1.4883(3)nm,β=97.42(2)°,V=1.5349(5)nm3, Z=2, DC=2.572g•cm -3 ,μ(Mo, Kα)=11.080cm -1 , F(000)=1128. R=0.0422, Rw=0.0735. The binuclear lead coordination compound is bridged by two carbohydrazide molecules. The molecule has a symmetrical center. TNR 2- ,CHZ and H 2O coordinate with the central ions simultaneously.     

[C4N2H12]1.5[Zn2(PO4)(HPO4)2]·H2O晶体的合成与表征

由于在电学、磁学、光学、吸附、离子交换和催化等领域具有潜在的应用价值,具有开放骨架结构的金属磷酸盐的合成一直受到人们的广泛关注.在这些磷酸盐微孔化合物中,磷酸锌晶体是拓扑结构最为丰富的一种.     

二维网状配合物[Co(dimb)2(MeOH)2](ClO4)2的合成及晶体结构

设计并合成了一个含咪唑基团的柔性双齿配体:1,3-二(咪唑基-1′-甲基)-5-甲基苯(dimb)(1),并进行了 ¹H NMR和结构表征。通过dimb与高氯酸钴的反应,得到了一个新型的具有二维网状结构的配合物:[Co(dimb)₂(MeOH)₂](ClO₄)₂(2)。X-射线晶体结构测定表明,这两个化合物的晶体学参数分别为:配体(1)属单斜晶系, 空间群     

四水合均苯三甲酸二氢钴的合成、结构和磁性

利用水热法在均苯三甲酸、六水氯化钴、甲酸铵和水的体系中合成了四水合均苯三甲酸二氢钴。该化合物晶体属于单斜晶系,对应的空间群为P2₁/c。磁性测量表明该化合物的钴离子之间存在反铁磁的相互作用,但直至2 K时也没有观察到磁有序。     

[Co(HOC10H6COO)2(H2O)4]配合物的合成、晶体结构和性质研究

Complex [Co(HOC₁₀H₆COO)₂(H₂O)₄] was synthesized by reaction of hydroxy-2-naphthoic acid with CoCl₂·6H₂O. The compound was characterized by elemental analysis, IR and the structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P2₁/n with a=0.675 8(2) nm, b=0.518 15(14) nm, c=2.962 9(9) nm, β=94.925(8)°. V=1.033 6(5) nm³, Z=2, D=1.624 Mg·m^-3, F(000)=522. The Co atom has an octahedron coordination geometry and was six-coordinated with two oxygen atoms from two carboxylate ligands and four oxygen atoms from four water molecules. The complex molecules were linked by different hydrogen bonds to form a 2D network. The complex has thermal stability and shows a strong fluorescent emission at 421 nm (λ_ex=342 nm). CCDC: 250903.     

[C2N2H10]1.5[Nd(SO4)3(H2O)]·2H2O: The first organically templated neodymium sulfate with a layer structure

The first organically templated neodymium sulfate has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction analysis. [C₂N₂H₁₀]_1.5[Nd(SO₄)₃(H₂O)]·2H₂O crystallizes in the monoclinic space group P2₁/c with crystal data , , , β=104.399(5)°, , Z=4. Refinement gave R₁[I>2σ(I)]=0.0471, and wR₂[I>2σ(I)]=0.0899. The compound exhibits an infinite zigzag anionic layer structure, which consists of {Nd(SO₄)₃(H₂O)}³⁻ structural units connected together to form interesting eight-membered rings via corner-sharing and edge-sharing modes. The compound has the antiferromagnetic behavior and exhibits intense photoluminescence upon photo-excitation at 450 nm.     

配合物Fe(pda)2(H2O)4和[FeCo(pda)4(H2O)4]n的合成与晶体结构

采用水热法合成了2个3-(3-吡啶基)丙烯酸的配合物:Fe(pda)2(H2O)4(1)和[FeCo(pda)4(H2O)4]n(2)(pda=3-(3-吡啶基)丙烯酸),用红外光谱、元素分析、热重-差热以及X-射线衍射单晶结构分析进行了表征.2个配合物都属于单斜晶系,配合物1的空间群为P21/n,配合物2的为P21/c.配合物1是一个pda配体中仅吡啶基氮原子参与配位、而羧基上的氧原子未参与配位的单核结构,通过大量的氢键作用形成三维超分子体系.2是pda配体桥联Fe和Co的异核二维层状配位聚合物;配体吡啶基上的氮原子和羧基上的氧原子都参与了配位,其中羧基采用单齿配位模式.     

Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]•0.5bipy•3H2O配合物的合成、晶体结构及荧光性质

在水-乙醇混合体系中, 以2-羰基丙酸水杨酰腙(C₁₀H₁₀N₂O₄)、2,2-联吡啶(C₁₀H₈N₂, 简写bipy)与Eu(NO₃)₃•4H₂O反应, 首次培养出黄色单晶[Eu(C₁₀H₉N₂O₄)(C₁₀H₈N₂O₄)(H₂O)₃]•0.5bipy•3H₂O. 该晶体属三斜晶系, 空间群为P-1, 晶胞参数a＝0.93392(16) nm, b＝1.3100(2) nm, c＝1.3895(2) nm, α＝97.205(3)°, β＝105.411(2)°, γ＝106.364(2)°, V＝15.35(2) nm³, Z＝2, μ＝2.118 mm^－1, D_c＝1.686 Mg/m³, F(000)＝786, R＝0.0116, wR＝0.0507, GOF＝0.995. 晶体测试结果表明, 该单晶结构为铕的9配位配合物, 两个2-羰基丙酸水杨酰腙分别以负一价和负二价酮式和三个水分子同时参与配位; 每个2-羰基丙酸水杨酰腙中的羧基氧、酰胺基中的羰基氧和C＝N中的氮与Eu^3＋配位, 形成两个共边的稳定五元环, 另三个配位原子则分别来自三个水分子中的氧原子, 该配合物在空间呈扭曲的单帽四方反棱柱, 而在不对称单位中还有游离的一个2,2-联吡啶分子和三个水分子, 这些游离分子与配位分子之间存在大量分子内和分子间氢键, 整个分子在空间呈三维网状结构. 发光性能测试表明该配合物具有很好的荧光性质.     

Synthesis and Structure of a New Layered Zincophosphate Zn6(PO4)5(HPO4)·C8N5H28·5H2O, Intercalated with Quintuply Protonated Tetraethylenepentamine

A new two-dimensional zinc phosphate Zn₆(PO₄)₅(HPO₄)·C₈N₅H₂₈·5H₂O has been synthesized hydrothermally using tetraethylenepentamine (TEPA) as structure-directing agent and its structure was determined by means of single-crystal X-ray diffraction. The title compound crystallizes in the orthorhombic system, space group Pca2₁ (No.29) with lattice parameters a=18.6286(12) Å, b=8.0804(5) Å, c=22.5019(15) Å, V= 3387.1(4) ų, Z=4, R₁=0.0389 and wR₂=0.0862 [4042 observed reflections with I>2σ(I)]. The structure involves a network of ZnO₄, PO₄, and PO₃(OH) tetrahedra forming macroanionic inorganic layers with eight-membered apertures. The charge compensation is achieved by the quintuply protonated TEPA molecule in interlamellar space, which interact with the inorganic layers via hydrogen bonding.     

三维钴基MOF[KCo7(OH)3(ip)6(H2O)4]·12H2O作为超级电容器的高容量电极材料

为了开发较高能量密度的超级电容器,我们通过简单的溶剂热反应合成了一种三维的钴基金属有机框架(MOF)化合物([KCo7(OH)3(ip)6(H2O)4]·12H2O,Co?ip;ip=间苯二甲酸根),并考察了其作为超级电容器电极材料的性能。Co?ip电极显示出高比电容、良好的循环稳定性和优良的倍率性能。在1 mol·L^-1 KOH溶液中,电流密度为1 A·g^-1时,其最大比电容为1660 F·g^-1。在电流密度为2 A·g^-1条件下,循环3000次后,其比电容的保持率为82.7%。优异的超级电容性能可归因于Co?ip具有纳米尺寸颗粒和三维的多孔结构。