Synthesis and X-ray diffraction study of cs3[UO2(CH3COO)3]2[UO2(CH3COO)(NCS)2(H2O)] and Cs5[UO2(CH3COO)3]3[UO2(NCS)4(H2O)] · 2H2O

Cs₃[UO₂(CH₃COO)₃]₂[UO₂(CH₃COO)(NCS)₂(H₂O)] (I) and Cs₅[UO₂(CH₃COO)₃]₃[UO₂ (NCS)₄(H₂O)] · 2H₂O (II) have been synthesized via the reaction between uranyl acetate and cesium thiocyanate in aqueous solution. According to single-crystal X-ray diffraction data, both compounds crystallize in monoclinic system with the unit cell parameters a = 18.7036(5) Å, b = 16.7787(3) Å, c = 12.9636(3) Å, β = 92.532(1)°, space group C2/c, Z = 4, R = 0.0434 (I); and a = 21.7843(3) Å, b = 24.6436(5) Å, c = 13.1942(2) Å, β = 126.482(1)°, space group Cc, Z = 4, R = 0.0273 (II). Uranium-containing structural units of compound (I) are mononuclear [UO₂(CH₃COO)₃]^? and [UO₂(CH₃COO)(NCS)₂(H₂O)]^? moieties, which correspond to the AB ₃ ⁰¹ and AB⁰¹M ₃ ¹ crystallochemical groups (A = UO ₂ ²⁺ , B⁰¹ = CH₃COO^?, M¹ = NCS^? and H₂O). The structure of compound II is built of [UO₂(CH₃COO)₃]^? and [UO₂(NCS)₄(H₂O)]^2? complexes, which belong to the AB ₃ ⁰¹ and AM ₅ ¹ crystallochemical groups, respectively. Uranium-containing complexes in both structures are linked into a framework by hydrogen bonds and electrostatic interactions with cesium cations. The IR spectra of compounds I and II agree well with X-ray diffraction data.     

Rare-Earth Substituted Polyoxoanions: [{La(CH3COO)(H2O)2(α2-P2W17O61)}2]16− and [{Nd(H2O)3(α2-P2W17O61)}2]14−

The lanthanum-substituted polyoxometalate [{La(CH₃COO)(H₂O)₂( ₂-P₂W₁₇O₆₁)}₂]^16– (1) and the neodymium-substituted species [{Nd(H₂O)₃( ₂ -P₂W₁₇O₆₁)}₂]^14– (2) have been synthesized and characterized by IR spectroscopy and elemental analysis. Single-crystal X-ray analysis was carried out on K₁₆[{La(CH₃COO)(H₂O)₂( ₂ -P₂W₁₇O₆₁)}₂]36H₂O, which crystallizes in the triclinic system, space group P¯1, with a=12.3863(6) Å, b=12.8934(6) Å, c=31.7285(14) Å, =84.2000(10)°, =81.2300(10)°, =61.6500(10)°, and Z=1; K_6.5Nd_2.5[{Nd(H₂O)₃( ₂-P₂W₁₇O₆₁)}₂]55H₂O, which crystallizes in the monoclinic system, space group P2 ₁ /n, with a=17.5030(9) Å, b=23.7842(12) Å, c=19.1869(10) Å, =100.6610(10)°, and Z=1. The head-on, trans-oid dimer 1 consists of two ( ₂ -P₂W₁₇O₆₁)^10– fragments connected by a lanthanum-acetate dimer, (La₂(CH₃COO)₂(H₂O)₄)⁴⁺. Each La³⁺ ion is nine-coordinated in a monocapped, square-antiprismatic fashion. The neodymium-derivative 2 is also a trans-oid dimer, but the mode of binding is different from 1 and is best described as side-on. Each Nd³⁺ ion is eight-coordinated in a square-antiprismatic fashion with three terminal water molecules.     

Theoretical study for the CH3C(O)(CH2)2OH + OH reaction

The mechanisms and the kinetics of the OH radical reaction with 4-hydroxy-2-butanone (4H2B) are investigated theoretically. Five hydrogen-abstraction channels are identified for the title reaction. The first potential energy profile of the title reaction is presented. The rate constants for each reaction channel are evaluated using transition state theory method in the temperature range of 200–1,000 K. Branching ratio of the title reaction is calculated and plotted. It is shown that the “in-plane hydrogen abstraction” from the methoxy end is the dominant channel, and the other hydrogen-abstraction channels play the minor role. The comparison between theoretical and experimental results is discussed. The three-parameter Arrhenius expression for the rate constants is also provided.     

新型环形聚阴离子[{WO(H_2O)}_3(AsW_8O31)_3]~21-的结构及表征

在pH=3.0的水溶液中，Na_2WO_4·2H_2O与NaAsO_2·6H_2O和NH_4Cl反应，得 到了新的杂多钨酸盐(MH_4)_19Na_2[{WO(H_2O)}_3(AsW_8O31)_3]·45H_2O单晶， 用X射线单晶衍射法及元素分析确定了其结构，晶体属单斜晶系，空间群C2/c，晶 胞参数为：a=3.1165(11)nm, b=1.7388(7)nm, c=2.2789(9)nm, β=97.342(6)°, V=12.248(8)nm~3, Z=4, R_1=0.0571,wR_2=0.0741[I＞2σ(I)]. 环型聚阴离子 [{WO(H_2O)}_3(AsW_8O31)_3]~21-是由三个{WO(H_2O)}桥连三个新发现的 {AsW_8O31}单元构成的，环聚离子[{WO(H_2O)}_3(AsW_8O31)_3]~21-具有近似D_ (3h)对称性。对该化合物还进行了~183W NMR, IR和TG表征。     

镧系四元混合阴离子配合物[Ln(CCl3COO)2(CH3COO)(Phen)(H2O)]2的合成与晶体结构

在水乙醇溶液中合成了３ 种四元混合阴离子配合物， 用元素分析、ＩＲ、ＵＶ 及单晶Ｘ射线衍射进行了表征。［Ｌａ（ＣＣｌ３ＣＯＯ）２（ＣＨ３ＣＯＯ）（Ｐｈｅｎ）（Ｈ２Ｏ）］２·２ＤＭＦ 晶体属三斜晶系， Ｐ１ 空间群， 晶胞参数：ａ＝ １－２５１０（４） ｎｍ ， ｂ＝ １－３４６０（５） ｎｍ ， ｃ ＝ １－０３４３（３） ｎｍ ， α＝ １０２－４７（３）°， β＝ １０２－３４（２）°， γ＝ １１３－８２（２）°， μ（ＭｏＫα） ＝ ２０．４７ ｃｍ －１ ， Ｚ＝ １， Ｄｃ＝ １－８００ ｇ·ｃｍ － ３ ， Ｆ（０００） ＝ ７８０－００。稀土配合物中醋酸根以桥联方式配位， 三氯醋酸根则有２ 种配位方式， 在二者共同参与配位的体系中呈现出丰富的配位模式。     

Synthesis and structure of (NH4)2[(UO2)2(C2O4)(CH3COO)4] · 2H2O

Single crystals of (NH₄)₂[(UO₂)₂C₂O₄(CH₃COO)₄] · 2H₂O have been synthesized and studied. The compound crystallizes in the orthorhombic system with the unit cell parameters a = 6.9225(14) Å, b = 12.327(3) Å, c = 14.619(3) Å, space group Immm, Z = 2, and V = 1247.6(5) ų. The main structural units of the crystals are the isle binuclear groups [(UO₂)₂C₂O₄(CH₃COO)₄]^2? belonging to the crystal-chemical group A₂K⁰²B ₄ ⁰¹ (A = UO ₂ ²⁺ , K⁰² = C₂O ₄ ^2? , B⁰¹ = CH₃COO^?) of the uranyl complexes. The uranium-containing groups are linked into a three-dimensional framework due to electrostatic interaction with the ammonium cations and through a system of hydrogen bonds involving atoms of the water molecules, oxalate and acetate ions, and ammonium and uranyl cations.     

配合物[Ln(CH3COO)2(NO3)(bipy)]2的合成与晶体结构

合成了５种新型镧系四元混合阴离子配合物,用Ｘ射线四圆衍射仪测定了［Ｐｒ（ＣＨ３ＣＯＯ）２（ＮＯ３）（ｂｉｐｙ）］２的晶体结构,四个醋酸根呈两种配位方式,测定了铕和钆配合物的荧光和ＥＳＲ谱．     

Synthesis and structure of [Cr3O(CH3COO)6(H2O)3][UO2 (CH3COO)3] · 3H2O

Crystals of [Cr₃O(CH₃COO)₆(H₂O)₃][UO₂(CH₃COO)₃]·3H₂O (I) were synthesized for the first time and studied by X-ray crystallography. The crystals of I are orthorhombic: a = 8.3561(3) ?, b = 16.8421(5) ?, c = 25.7448(9) ?, V = 3623.2(2) ?³, space group P2₁2₁2₁, Z = 4, R = 0.0409. The structure is composed of trinuclear [Cr₃O(CH₃COO)₆(H₂O)₃]⁺ complexes and mononuclear [UO₂(CH₃COO)₃]^? complexes classified with crystal-chemical groups A₃M³B ₆ ² M ₃ ¹ (A = Cr³⁺, M³ = O^2?, B² = CH₃COO^?, M¹ = H₂O) and AB ₃ ⁰¹ (A = UO ₂ ²⁺ , B⁰¹ = CH₃COO^?), respectively. The complexes are bound to each other by electrostatic interactions and hydrogen bonds involving outer-sphere water molecules. The results of IR spectroscopic study of I are in good agreement with the structural data for the crystal.     

Acetate-Functionalized Zirconium-Substituted Tungstogermanate, [Zr4O2(OH)2(CH3COO)2(α-GeW10O37)2]12−

The two acetate-functionalized zirconium(IV)-substituted tungstogermanates, Na₈K₄[Zr₄O₂(OH)₂(CH₃COO)₂(α-GeW₁₀O₃₇)₂] · 33H₂O and Na₈Cs₄[Zr₄O₂(OH)₂(CH₃COO)₂(α-GeW₁₀O₃₇)₂] · 32H₂O, were synthesized by the reaction of ZrOCl₂ with [A-α-GeW₉O₃₄]¹⁰⁻ in pH = 4.8 buffer and their structures were determined by single-crystal X-ray analysis. Both of them contain a centrosymmetric polyanion [Zr₄O₂(OH)₂(CH₃COO)₂(α-GeW₁₀O₃₇)₂]¹²⁻ consisting of two {α-GeW₁₀O₃₇} units sandwiching an inorganic–organic hybrid {Zr₄O₂(OH)₂(CH₃COO)₂} cluster. The polyanion contains a mixing of seven- and eight-coordinate Zr centres. The two compounds were also characterized by elemental analysis, IR spectroscopy, UV–vis and TG–DSC analysis.     

The complexation of cadmium acetate and propionate by phenanthroline. Structure and properties of [Cd(CH3COO)2(C12H8N2)(H2O)] · H2O and [Cd(CH3CH2COO)2(C12H8N2)]2 · 2CH3CH2COOH

The coordination compounds [Cd(CH₃COO-κO ¹,O ²)₂(phenanthroline-kN ¹ N ²)(H₂O)] · H₂O (1) and [Cd{μ-(CH₃CH₂COO-κO ¹,O ²)}₂(phenanthroline-κN ¹,N ²)]₂ · 2CH₃CH₂COOH (2) were synthesized and characterized by elemental and thermal analysis and IR spectroscopy. Crystal and molecular structures of both compounds were determined. The complexes are air stable and fairly soluble in water. In both compounds the cadmium is seven-coordinate and contains chelating phenanthroline and two chelating carboxylate groups in the inner coordination sphere. The seventh coordinating oxygen belongs to water in 1 and to bridging carboxylate in 2. All carboxylate groups are bonded unsymmetrically to the central atom. The coordination polyhedra can be described as distorted pentagonal bipyramid (compound 1) and distorted capped tetragonal bipyramid (compound 2). In the structure of 1 intermolecular O(water)–H ··· O (water/carboxylate) hydrogen bonds create a two-dimensional net along the crystallographic a0c plane. Each molecule of 2 is connected to two propionic acid molecules via hydrogen bonds. In both compounds exist π-stacking interactions.     

Synthesis and crystal structures of yttrium sulfates Y(OH)(SO4), Y(SO4)F,YNi(OH)3(SO4)-II and Y2Cu(OH)3(SO4)2F·H2O

Y(OH)(SO₄), Y(SO₄)F, YNi(OH)₃(SO₄)-II and Y₂Cu(OH)₃(SO₄)₂F·H₂O are obtained from hydrothermal reactions at 380°C under a pressure of 210 MPa. Their crystal structures were refined from single-crystal X-ray diffraction data. The four compounds have the following space groups and unit cells: Y(OH)(SO₄), P2₁/n, a=7.9498(6), b=10.9530(9), c=8.1447(6) Å, β=93.764(1)°; Y(SO₄)F, Pnma, a=8.3128(9), b=6.9255(7), c=6.3905(7) Å; YNi(OH)₃(SO₄)-II, Pnma, a=6.9695(8), b=7.2615(8), c=10.292(1) Å; Y₂Cu(OH)₃(SO₄)₂F·H₂O, P2₁/n, a=11.6889(7), b=6.8660(4), c=12.5280(8) Å, β=97.092(1)°. The coordination environments of the yttrium atoms in the four structures vary from highly irregular 6+2, 6+3, 7+1 coordination polyhedra to relatively regular dodecahedra.     

Hydrothermal Synthesis,Crystal Structure and Thermal Stability Properties of the Complex [Cd2(phen)2(C14HuO3)4(CH3CH2OH)]·(CH3OH)·(H2O)

T A dinuclear cadmium complex[Cd2(phen)2(C14H11O3)4(CH3CH2OH)]·(CH3OH)·(H2O)has been synthesized with benzilic acid and 1,10-phenanthroline by hydrothermal method.The crystal structure was determined bv X-ray diffraction with crystal parameters as follows:triclinic system with space group P-1,α=1.21298(10),b=1.32586(1 1),c=2.4815(2)nm,α=76.2630(10),β=81.4500(10),γ=69.1700(10)°V=3.6143(5)nm3,Dc=1.438g/cm3,Z=1,F(000)=1600,the final GOOF=0.937,R=0.0521 and wR=0.1328.In the title complex,the dinuclear structure is defined by carboxyl oxygen atoms adopting a monodentate bridged coordination mode.The coordination environment of Cd(Ⅱ)ion is CdO4N2,giving a distorted octahedral coordination geometry.TG analysis shows that the title complex is stable under 140℃.     

Synthesis and characterization of hybrid organic-inorganic, dimeric tungstoantimonate, {[Cu(En)2(H2O)]2[Cu4Na2(H2O)2(OH)2](α-SbW9O33)2}6?1

The copper-substituted tungstoantimonate(III) [Cu(En)₂(H₂O)₂]₂[Cu(En)₂(H₂O)]{[Cu(En)₂ (H₂O)]₂[Cu₄Na₂(H₂O)₂(OH)₂][(??-SbW₉O₃₃)₂]} · 3H₂O (I) (En = ethylenediamine) has been synthesized and characterized by IR spectrum, elemental analysis, and XPS. X-ray single-crystal analyses were carried out on I, which crystallizes in the triclinic system, space group P-1, with a = 13.071(2) ?, b = 14.434(2) ?, c = 15.729(2) ?, ?? = 83.004(3)°, ?? = 71.237(2)°, ?? = 74.787(2)°, and Z = 1. The title polyanion consists of two [??-SbW₉O₃₃]^9? trivacant moieties joined together by an annular [Cu₄Na₂(H₂O)₂(OH)₂]^8? unit leading to a sandwich-type structural framework. The central belt of I contains two crystallography unique Cu²⁺ and four disordered Cu²⁺/Na⁺ ions which reduce the symmetry of the polyanion to C _2??.     

Bis[tetraruthenium(IV)]-containing polyoxometalates: [{Ru(IV)4O6(H2O)9}2Sb2W20O68(OH)2]4- and [{Ru(IV)4O6(H2O)9}2{Fe(H2O)2}2{β-TeW9O33}2H]-

The reaction of [Sb(2)W(22)O(74)(OH)(2)](12-) and [Fe(4)(H(2)O)(10)(β-TeW(9)O(33))(2)](4-) with (NH(4))(2)[RuCl(6)] in aqueous solution resulted in the novel ruthenium(IV)-containing polyanions [{Ru(IV)(4)O(6)(H(2)O)(9)}(2)Sb(2)W(20)O(68)(OH)(2)](4-) and [{Ru(IV)(4)O(6)(H(2)O)(9)}(2){Fe(H(2)O)(2)}(2){β-TeW(9)O(33)}(2)H](-), exhibiting two cationic, adamantane-like, tetraruthenium(IV) units {Ru(4)O(6)(H(2)O)(9)}(4+) bound to the respective polyanion in an external, highly accessible fashion.     

Intramolecular Rearrangements of >Si(O–C·=O)(CH2–CH3) and >Si(CH2–CH·–CH3)(CH2–CH3) Radicals

Using ESR and IR spectroscopy, the structures of >Si(O–C^·=O)(CH₂–CH₃) (1) and >Si(CH₂–CH^·–CH₃)(CH₂–CH₃) (2) radicals were deciphered. The directions and kinetic parameters of reactions of intramolecular rearrangements in these radicals were determined. The reactions of hydrogen atom abstraction in radical (1) from the CH₂ and CH₃ groups were studied. It was found that the endothermic reaction of hydrogen atom abstraction from the methyl group occurs at a higher rate than the exothermic reaction with the methylene group. The differences are determined by changes in the size of a cyclic transition state. Based on the experimental data, the strengths of separate C–H bonds in surface fragments are compared. The rearrangement >Si(CH₂–CH^·–CH₃)(CH₂–CH₃) >Si(C^·(CH₃)₂)(CH₂–CH₃) was discovered and its mechanism was determined. One of its steps is the skeletal isomerization Si- (2)- _. (1)Si- (1)- _. (2). Experimental data are analyzed using the results of quantum-chemical calculations of model systems.     

Synthesis and Crystal Structure of [{Mn(IBG)(2,2'-bipy)(H_2O)}·4H_2O]_n

A novel MnⅡ complex [{Mn(IBG)(2,2'-bipy)(H2O)}·4H2O]n 1(H2IBG=isophtha-loylbisglycine and 2,2'-bipy = 2,2'-bipyridine) has been synthesized and characterized by singlecrystal X-ray diffraction,elemental analysis,IR spectra and thermogravimetric analysis.It crystallizes in monoclinic,space group P21/n,with a=13.667(2),b=14.045(2),c=14.195(2),β=101.483(3)°,V=2670.1(7)3,Z=4,C22H26N4O11Mn,Mr=577.41,Dc=1.436 g/cm3,F(000)=1196.0,μ(MoKα)=0.558 mm-1,the final R=0.0578 and wR=0.1460 for 2974 observed reflections with I2σ(I).In the structure,the MnⅡ atom is coordinated in a distorted octahedral environment arranged by one water molecule,one 2,2'-bipy ligand and two IBG ligands.     

Conductivity of Al2(WO4)3–WO3 and Al2(WO4)3–Al2O3 Composites

Russian Journal of Electrochemistry - Composites of (1 – x)Al2(WO4)3–xWO3 and (1 – x)Al2(WO4)3–xAl2O3 are synthesized and their conductivity is studied as dependent on the...     

Crystal Structure of [CH_3CH(OH)COO]_2Fe(H_2O)_2·H_2O

<正> The title compound C6H16O9Fe, Mr = 288. 13, was synthesized and crystallized in monoclinic space group P21/c, a = 9. 409(4), b = 5. 812(4), c= 22. 122(7)(?) , β=90. 80(3)°. V = 1209. 6(?)3, Z = 4, Dc=1. 572g/cm3, F(000) = 592, μ = 12. 73cm-1, R = 0. 063, Rw= 0. 068 for 1191 observed reflections. The iron atom is surrounded by O(1 - 6) in a distorted octahedron.     

CRYSTAL STRUCTURE OF [Eu(μ-CH_3COC-O)(CH3COO)_2(H_2O)_2]_2·4H_2O

<正> C12H34O20Eu2,Mr=802.30 triclinic, space group P1, a= 8.955(2), b=9.328(1), c=10.536(2) A,α= 91.74(2),β=113.87(2),γ=118.23(2), V=681.7(2)A,Dm(flotation in CC14/ BrCH2CH2Br)=1.95,DX(Z=1) =1.954g cm-3,λ(MoKα)=0.71069 A,μ=6.41 cm-1,F(OOO)=391.92, T =. 295°K,final RF= 0.032 for 7483 observed reflections with |F0|>3a(|Fo|). The compound is isostructural with the known erbium complex,the basic unit being a centrosymmetric dimer composed of two nine-coordinate polyhedra sharing a common edge. An O atom in one or the three bidentate acetato groups about each europium atom serves as a bridge between the metal centars. The dimeric units are linked by hydrogen bonds involving both ligand and lattice water molecules to form a three-dimensional network.