Na6In4[P7O24(OH)5]·4H2O的水热合成与表征

具有开放骨架结构的金属酸盐在作为微孔材料、非线性光学材料、催化剂载体和离子交换剂等方面具有应用前景 [1] .自从报道第一个具有微孔结构的磷酸铝 [2 ]以来 ,许多其它具有开放骨架结构的金属磷酸盐被合成出来 ,它们的性质和潜在的应用研究也备受关注 [3～ 8] .本文采用温和条件下的水热法 ,合成得到了具有螺旋链状结构的磷酸铟钠盐 [Na6 In4 [P7O2 4 ( OH) 5]· 4H2 O,并采用 X射线单晶衍射方法进行结构测定 ,其结构中包含了共顶角的多面体连接成的螺旋链 ,链间的连接形成多面体四元环和八元环 ,3个四元环围成了一个三配位氧为中心…     

多钼氧簇合物(H3O)6[MnMo9O32]·3H2O2的合成及其晶体结构

通过向钼酸、醋酸锰和冰乙酸的混合溶液中滴加30%过氧化氢,合成了一个未见报道的具有Waugh结构的多钼氧簇合物(H₃O)₆[MnMo₉O₃₂]·3H₂O₂(1),其结构和性能经X-射线单晶衍射,IR和FL表征。1属三方晶系,R₃₂空间群,晶胞参数a=b=15.936 8(6) , c=12.406 7(7) , γ=120.0°, V=2 728.9(2) ³, Z=3, Dc=3.006 g·cm^-3, Mr=1 646.59, μ(MoKα)=3.459 mm^-1, F(000)=2 337,R=0.026 2, wR=0.068 1。晶体结构分析表明：化合物阴离子包含9个MoO₆八面体单元和1个MnO₆八面体单元,其中在MnMo₃单元的上下各有三个MoO₆八面体。荧光性能研究表明:在波长300 nm光激发下,1在410 nm处有强的荧光发射。     

β-K4H3[SiW9O37(CpTi)3]·11H2O环戊二烯钛多酸衍生物与DNA作用研究

某些过渡金属配合物具有特异性催化DNA和RNA断裂的功能, 因而研究过渡金属配合物对DNA和RNA的断链反应对新型抗肿瘤、抗艾滋病化学药物的定向设计及其基因治疗和分子生物学中DNA和RNA的高度专一性定点断裂、 DNA定位诱变和构象识别具有重要意义和应用前景[1,2]. 我们对二茂钛多酸有机金属衍生物合成及抗肿瘤活性研究表明, 环戊二烯钛多氧金属酸盐衍生物具有很高的抗肿瘤活性和较好的水溶性及稳定性, 有潜在的抗肿瘤药用价值[3].     

[CH3NH3][NH3(CH2)6NH3]H3[P2Mo2W16O62]·H2O的水热合成与表征

首次合成了[CH3NH3][NH3(CH2)6NH3]H3[P2Mo2W16O62]·H2O,通过元素分析、红外光谱和X射线单晶衍射对合成产物进行了表征,并用TGA-DSC研究了化合物的热稳定性.晶体属单斜晶系,P21/m空间群,a=1.2596(3)nm,b=1.8715(4)nm,c=1.9816(4)nm,α=γ=90°,β=90.16(3)°,V=4.671(2)nm3,Z=2,Mr=4358.66,Dc=3.100g·cm-3,μ=19.978mm-1,F(000)=3792,R=0.0835,Rw=0.2026.结果表明,在晶体结构内形成了0.7364nm×0.8354nm的微孔.     

[C6N2H18]2[Mo5O15(HPO4)2]·H2O的水热合成与结构表征

通过水热法合成了一个新化合物[C6N2H18]2[Mo5O15(HPO4)2]·H2O,并通过IR光谱、ICP、元素分析、差热与热重分析和X射线单晶衍射分析等手段进行了表征.结果表明,晶体属三方晶系,P3(2)21空间群,a=1.1231(1)nm,c=2.2802(5)nm,V=2.4911(7)nm3,Dx=2.835Mg/m3,Z=6,最后的一致性因子R=0.0227,wR=0.0675.阴离子中Mo5O15构成一环状结构,2个HPO4一个连在环的下方,一个连在环的上方,形成类似于“飞碟”状的结构,阳离子为2个质子化的四甲基乙二胺.     

有机-无机杂化材料[Na2(H2O)4]2[γ-Mo8O26·(Gly-Gly)2]·4H2O的合成及晶体结构

多金属氧酸盐因其独特的结构而具有较高的抗肿瘤及抗病毒活性,蛋白质和肽是氨基酸的聚合体,氨基酸侧链官能团能与多金属氧酸盐形成新型配合物.了解氨基酸和肽与多金属氧酸盐的相互作用对于深入研究多金属氧酸盐抗肿瘤及抗病毒机理很有意义.我们曾报道了赖氨酸、丙氨酸及甘氨酸二肽与钼磷酸所形成化合物的晶体结构.     

Synthesis and crystal structure of sodium isopolyvanadate [Na2(H2O)8]2H2[V10O28] · 4H2O

The sodium hydrogen oxovanadate [Na₂(H₂O)₈] ₂H₂[V₁₀O₂₈] · 4H₂O was synthesized and studied by TGA, X-ray diffraction, and NMR and IR spectroscopy. The crystals are triclinic, space group P $ \bar 1 $ \bar 1 , a = 8.545(7) ?, b = 10.827(2) ?, c = 11.627(2) ?, α = 105.48(3)°, β = 99.38(3)°, γ = 101.29(3)°, V = 989.9(3) ?³, ρ(calcd) = 2,381 g/cm³, Z= 1.     

Synthesis, thermogravimetric analysis, IR spectrum, and the crystal structure of sodium hexatunstomanganate [Na2(H2O)10][Na(H2O)3]2[MnW6O18(OH)6] · 6H2O

The complex [Na₂(H₂O)₁₀][Na(H₂O)₃]₂[MnW₆O₁₈(OH)₆] · 6H₂O was synthesized and studied by mass spectrometry, thermogravimetry, IR spectroscopy, X-ray diffraction. The crystals are monoclinic, space group P2₁/n, a = 11.698(2), b = 11.670(2), c = 14.652(3) ?, β = 102.52(3)°, V = 1952.7(7) ?³, ρ(calcd.)= 3.45 g/cm³, Z = 2.     

Acid nickel oxovanadate [Ni(H2O)6]2[H2V10O28] · 6H2O: Synthesis, IR spectra, thermal analysis, and crystal structure

Acid nickel oxovanadate, [Ni(H₂O)₆]₂[H₂V₁₀O₂₈] · 6H₂O (I) was synthesized and studied by X-ray diffraction analysis, thermogravimetry, powder X-ray diffraction, and IR spectroscopy. The crystals are triclinic: space group , a = 8.869(2) ?, b = 10.869(2) ?, c = 11.116(2) ?, α = 65.14(3)°, β = 74.11(3)°, γ = 70.47(3)°, V = 907.41 ?³, ρ(calcd.) = 2.56 g/cm³, Z = 1. Original Russian Text ? G.Z. Kaziev, A.V. Oreshkina, S.H. Quinones, D.A. Alekseev, V.E. Zavodnik, T.Yu. Glazunova, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 8, pp. 593–598.     

Isomerization of [In(H2O)3Cl3] · 18C6. Crystal structure of [ mer -In(H2O)3Cl3] · 18C6 and [ fac -In(H2O)3Cl3] · 18C6 · 2H2O

The complex [mer-In(H₂O)₃Cl₃] · 18C6 (I) was isolated from the InCl₃-H₂O-Solv-18C6 solutions (Solv = MeOH, EtOH, THF). The second crystallization from mother solutions resulted in [fac-In(H₂O)₃Cl₃] · 18C6 · 2H₂O (II). The crystal and molecular structures of isomers I, II were identified by the powder X-ray diffraction, IR, and X-ray diffraction methods. Although complexes I, II have different compositions, they have the chain structure. The thermal decomposition of complexes I, II was studied. Original Russian Text ? A.B. Ilykhin, Zh.V. Dobrokhotova, S.P. Petrosyants, 2008, published in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 9, pp. 651–656.     

New polyoxotantalate salt Na8[Ta6O19]·24.5H2O and its properties

The interaction of Ta₂O₅ with sodium hydroxide at 400°C yields Na₈[Ta₆O₁₉], which can be recrystallized from an aqueous solution in the form of Na₈[Ta₆O₁₉]·24.5H₂O. The complex is characterized by IR spectroscopy, thermogravimetry, powder XRD, and single crystal XRD: hexagonal system, P6₃ space group, a = 12.3622(2) ?, c = 31.4305(7) ?, V = 4159.81(13) ?³, d _x = 3.217 g/cm³, R = 0.0195.     

Synthesis, structure, and thermal decomposition of [H2(4,4′-Bipy)][In(H2O)2(NCS)4]2 and [HUr]2[In(H2O)(NCS)5] · 2H2O

The reaction of indium thiocyanate with bipyridine (4,4-Bipy) and urotropine (Ur) gave [H₂(4,4′-Bipy)][In(H₂O)₂(NCS)₄]₂ (I) and [HUr]₂[In(H₂O)(NCS)₅] · 2H₂O (II), which were identified using elemental analysis, IR spectra, and thermogravimetric analysis. The thermal decomposition of compound I and II ends at 650 and 640°C, respectively, and gives In₂O₃. X-Ray diffraction analysis of compound I showed that complex anions in the crystal form chains through O-H…S hydrogen bonds. The anion chains form a close packing of columns with bipyridine cations located in the voids. Original Russian Text ? S.P. Petrosyants, A.B. Ilyukhin, V.A. Ketsko, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 6, pp. 951–955.     

Synthesis and structures of nine-coordinate K[SmIII (Edta)(H2O)3] · 2H2O and Ten-Coordinate K2[SmIII(Pdta)(H2O)2]2 · 4.5H2O complexes

The title complexes, K[Sm^III(Edta)(H₂O)₃] · 2H₂O(I)(H₄Edta = ethylenediamine-N,N,N′,N′-tetraacetic acid) and K₂[Sm^III(Pdta)(H₂O)₂]₂ · 4.5H₂O (II) (H₄Pdta = propylenediamine-N,N,N′,N′-tetraacetic acid), were prepared and their compositions and structures were determined by elemental analyses and single-crystal X-ray diffraction techniques, respectively. Complex I has a mononuclear structure, and the Sm³⁺ ion is nine-coordinated by an Edta ligand and three water molecules, yielding a pseudo-monocapped square antiprismatic conformation, and the complex crystallizes in the orthorhombic crystal system with space group Fdd2. The crystal data are as follows: a = 19.84(5), b = 35.58(9), c = 12.15(3) ?, V = 8580(38) ?³, Z = 16, ρ _c = 1.925 g/cm³, μ = 3.010 mm⁻¹, F(000) = 4976, R = 0.0252, and wR = 0.0560 for 3510 observed reflections with I ≥ 2σ(I). Complex II has a binuclear structure and the Sm³⁺ ion is ten-coordinated by a Pdta ligand, two oxygen atoms from a carboxylic group of adjacent Pdta ligand and two water molecules, yielding a distorted bicapped square antiprismatic prism. The complex crystallizes in the triclinic crystal system with space group P $ \bar 1 $ \bar 1 . The crystal data are as follows: a = 8.9523(15), b = 10.7106(15), c = 11.6900(19) ?, α = 80.613(5)°, β = 80.397(5)°, γ = 76.530(4)°, V = 1065.7(3) ?³, Z = 1, ρc = 1.970 g/cm³, μ = 2.532 mm⁻¹, F(000) = 1620, R = 0.0332 and wR = 0.0924 for 5390 observed reflections with I ≥ 2σ(I).     

Highly efficient utilization of H2O2 for oxygenation of organic sulfides catalyzed by [γ-SiW10O34(H2O)2]

Remarkable efficiency of hydrogen peroxide utilization is reported for oxygenation of four organic sulfides catalyzed by a divacant lacunary silicotungstate, (Bu₄N)₄[γ-SiW₁₀O₃₄(H₂O)₂] (1), under mild conditions. The addition of imidazole, phosphate, or carboxylates significantly enhances the rate of organic sulfide oxygenation. Most notably, use of 1 and imidazole, both at 1% molar concentration, resulted in the quantitative conversion of phenylsulfide to sulfoxide with 1 equiv of H₂O₂ in 3 h, and to sulfone with 2 equiv of H₂O₂ in 6 h.     

Synthesis and characterization of two new photochromic organic-inorganic hybrid materials based on isopolyoxomolybdate: (HDBU)3(NH4)[β-Mo8O26]·H2O and (HDBU)4[δ-Mo8O26]

Two new organic-inorganic hybrid compounds of molybdenum(VI) (HDBU)₃(NH₄)[β-Mo₈O₂₆]·H₂O 1 and (HDBU)₄[δ-Mo₈O₂₆] 2 have been synthesized and characterized by elemental analyses, FT-IR and UV-vis spectroscopies, and single-crystal X-ray diffraction (at 293 and 100 K, respectively). Compound 1 is obtained at room temperature by adding 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) on aqueous molybdate solution at pH=5.7. Compound 2 is obtained hydrothermally from 1 (110 °C, 24 h, autogenous pressure). Compound 1 crystallizes in the triclinic crystal system, space group , with a=11.2492(9), b=14.1907(10), c=16.7498(10) Å, α=80.993(4), β=72.272(6), γ=71.696(7)°, V=2412.5(3) Å³ at T=20 °C and Z=2. The refinement of the structure leads to a residual factor R=0.0697 for 10234 independent observed reflections [I/σ(I)?2] and 623 parameters. Compound 2 crystallizes in the triclinic crystal system, space group , with a=11.3158(9), b=11.3773(8), c=13.2884(17) Å, α=92.110(8), β=112.127(9), γ=117.581(7)°, V=1357.4(3) Å³ at T=−173 °C and Z=2. The refinement of the structure leads to a residual factor R=0.0226 for 11812 independent observed reflections [I/σ(I)?2] and 354 parameters. The structure of 1 consists of β-[Mo₈O₂₆]⁴⁻ anions with HDBU⁺ and NH₄⁺ cations connected to the mineral parts by hydrogen bonds and the structure of 2 contains δ-[Mo₈O₂₆]⁴⁻ anions with HDBU⁺ counter-cations. Both the thermal and chemical isomerizations of the two [Mo₈O₂₆]⁴⁻ isomers are highlighted and discussed. Photochromic behaviors of compounds 1 and 2 are also reported.     

二维层状水合酸式硫酸铈H3O[Ce(SO4)2·(H2O)3]·H2O的水热合成与结构表征

镧系金属硫酸盐由于在稀土分离等方面具有重要的应用而受到广泛关注。但是，因其适于结构测定的单晶相对难以得到，迄今，关于稀土硫酸盐的结构报道仍然较少，且主要局限于水合硫酸盐和三元硫酸盐．近几年中，基于硫酸根与磷酸根在结构上的相似性，借鉴在水热／溶剂热体系中采用有机胺作模板剂大量合成具有空旷骨架结构的微孔磷酸盐的成功经验，以有机胺为模板剂合成具有空旷骨架结构的镧系金属硫酸盐的工作也已见诸报道．在这些化合物中，由于硫酸根配位方式的多样性和稀土元素配位数和配位构型的可调变性，展现出了一些有趣的结构特征．     

以[α-P2W18O62]6-阴离子为构筑块的一维链状稀土配位聚合物[Nd(DMF)6(H2O)2][Nd(DMF)6(H2O)]P2W18O62的合成﹑结构及性质研究

以Nd2O3,DMF和α-H6P2W18O62·nH2O等为原料合成了Dawson结构杂多阴离子有机-无机配位聚合物[Nd(DMF)6(H2O)2][Nd(DMF)6(H2O)]P2W18O62,并对其进行了IR,UV光谱表征及电化学性质研究.X-射线衍射单晶结构分析结果表明,晶体属单斜晶系,Cc空间群,晶胞参数a1.8991(3)nm,b=2.2047(3)nm,c=2.6448(4)nm,β=102.272(3)°,并有Z=4,R1=0.043 8,wR2=0.1107.聚合物中存在2种构型的Nd配离子,Nd(1)以九配位的三加冠三棱柱结构通过端氧与[P2W18O62]6-阴离子赤道位的W相连,Nd(2)以九配位畸变的单加冠四方反棱柱结构通过端氧与[P2W18O62]6-阴离子极位的W相连,从而构成分子结构单元[{Nd(DMF)6(H2O)2}{Nd(DMF)6(H2O)}(P2W18O62)],毗邻的结构单元又通过W-O-Nd(1)-O-W桥联形成一维锯齿无限链状结构.     

K3H3[As2W21O69（H2O）]·19H2O的合成及晶体结构（英文）

利用二缺位K14[As2W19O67]·nH2O前驱体在酸性条件下的结构转变得到了饱和的砷钨酸盐K3H3[As2W21O69(H2O)]·19H2O(1),借助傅立叶变换红外光谱和X射线单晶衍射对其结构进行了表征.结果表明,化合物1的多阴离子骨架由两个相同的三缺位[α-AsW9O33]9-片段通过三个W=O基团连接而成.值得提及的是,在化合物1的阴离子骨架中心空腔中存在一个游离的水分子.     

Hydrothermal Syntheses and Structural Characterization of Two Novel Arsenic–Vanadium Clusters: [Co(2,2′-bpy)3]2[As8V14O42(H2O)]·3H2O and [2,2′-bpy][Ni(2,2′-bpy)3]2[As8V14O42(H2O)]·3H2O

Two new arsenic–vanadium clusters, [Co(2,2- bpy)₃]₂[As₈V₁₄O₄₂(H₂O)] · 3H₂O (1), [2,2-bpy][Ni(2,2-bpy)₃]₂[As₈V₁₄O₄₂(H₂O)] · 3H₂O (2) (2,2-bpy=2,2-bipyridine), have been hydrothermally synthesized and characterized by IR, elemental analysis, UV–VIS, EPR, TGA, XPS, and single crystal X-ray diffraction analysis. Crystal data: 1, triclinic, P1, a=14.368(3) Å, b=16.753(3) Å, c=24.632(5) Å, =94.15(3)°, =93.16(3)°, =113.05(3)°, Z=2; 2, monoclinic, P2₁/c, a= 30.2150(4) Å, b=14.0690(3) Å, c=26.0536(3) Å, =106.8960(10)°, Z=4. X-ray crystallographic studies showed that crystals 1 and 2 are both composed of discrete cluster anion [As₈V₁₄O₄₂(H₂O)]^4– and transition metal coordination complexes [M(2,2-bpy)₃]²⁺ (M=Co or Ni). Interestingly, compound 2 contains another neutral organic space filler of 2,2-bpy. To the best of our knowledge, compounds 1 and 2 are the first examples of structurally characterized vanadium/2,2-bpy/arsenate polyoxometallates.     

A novel hybrid crystal of chiral racemic complexes coexisting with two kinds of polyoxomolybdates: synthesis and structure of [Co(bpy)3]2[Mo6O19] [β-(H2Mo8O26)]·4H2O

A novel polyoxometalate-based organic-inorganic hybrid compound, [Co(bpy)₃]₂ [Mo₆O₁₉] [β-(H₂Mo₈O₂₆)]·4H₂O (1), have been hydrothermally synthesized and structurally characterized by elemental analysis, single-crystal X-ray diffraction, IR and X-ray photoelectron spectra. Compound 1 represents the first example that racemic complexes coexisting with two kinds of polyoxomolybdate anions in the same crystal architecture, which should be of rare chance that four kinds of complexes crystallizes into a compound.