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1.
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 = O2?, 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.  相似文献   

2.
The heteronuclear-oxoacetate with the composition [Fe2NiO(CH2COO)6(H2O)3]·2H2O decomposed on heating, forming nickel ferrite NiFe2O4 and (depending on the decomposition conditions) in part other solid phases. H2O, CH3COOH, acetone and CO2 were also formed in the decomposition. A reaction scheme is given for the decomposition. The products were porous powders with grain diameters between 3 and 10m. On increase of the temperature of decomposition from 300 to 800 C, the BET surface area and the surface area of the pores decreased, but only a small alteration in grain size was observed. As a result of thermal treatment in the temperature region abone 800C, larger aggregates of grains were formed in sintering processes.
Zusammenfassung Heteronukleare-Oxoazetate der Zusammensetzung [Fe2NiO(CH3COO)6(H2O)3]·2H2O werden durch Erhitzen zersetzt, wobei Nickelferrite NiFe2O4 und — in AbhÄngigkeit von den Bedingungen der Zersetzung — mit einem Teil anderer fester Phasen gebildet wird. In der Zersetzungsreaktion werden auch H2O, CH3COOH, Azeton und CO2 gebildet. Es wird ein Reaktionsschema für die Zersetzung angegeben. Die Produkte sind poröse Pulver mit einem Korndurchmesser zwischen 3 und 10 m. Wird die Zersetzungstemperatur von 300 auf 800C erhöht, nimmt die BET-OberflÄche und die PorenoberflÄche ab, wobei sich die Korngrö\e aber nur wenig verÄndert. Im Ergebnis der WÄrmebehandlung im Temperaturbereich oberhalb 800C werden durch Sinterprozesse grö\ere Partikelaggregate gebildet.
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3.
Synthesis and X-ray study of the polyanion [AsIII 4Mo6W14O72(H2O)2]12 isomorphous of [AsIII 4W20O72(H2O)2]12. The addition of an excess of MoO42– to a solution of [AsIII2W8O30(OH)]7– led at pH=4 to a new polyanion [AsIII 4Mo6W14O72(H2O)2]12– isostructural of [AsIII 4W20O72(H2O)2]12–. The structure of this compound was determined by X-ray diffraction: a=11.183(4) Å, b=13.432(3) Å, c=19.626(5) Å, α=77.87(2), β=73.57(3), γ=67.44(3)°, V=2 594(1) Å3, P1̄. Reliability factors are R=7.89 and Rw=9.97. The starting compound underwent an isomerisation β→α and one tungsten was formally substituted by one molybdenum atom; two other molybdenum atoms were incorporated. The polyanion is formed of two units αB–AsIIIMo2W7O33 connected by a double chain AsIIIOMo2O2(H2O). Arsenic and molybdenum are both bound to two octahedrons WO6 of one unit AsIIIOMoO2W7O33, both molybdenum atoms of which are contiguous. © 2000 Académie des sciences / Éditions scientifiques et médicales Elsevier SASpolymolybdotungstate / arsenomolybdotungstate / crystal structure / (hexamolybdenumtetradecatungsten)ate / synthesis of a new mixed polytungstate  相似文献   

4.
《Solid State Sciences》2012,14(5):611-615
Three new ionic crystals based on Keggin anion and mixed-valent diruthenium tetracetate, [Ru2(CH3CO2)4(H2O)2]2[HnXW12O40]·[Ru2(CH3CO2)4(H2O)Cl]·12H2O {X = B, n = 3 (1); X = Si, n = 2 (2); X = Ge, n = 2 (3)}, have been prepared in acidic aqueous solution at about pH 3.0 by reaction of K4BW12O40·mH2O, K8SiW11O39·mH2O and K8GeW11O39·mH2O with diruthenium tetracetate Ru2(CH3COO)4Cl, respectively, and their structures were determined by X-Ray diffraction analysis. They are isostructural structure with the ratio of heteropolytungstate anion, Ru2(CH3CO2)4+ cation and neutral molecular Ru2(CH3CO2)4Cl of 1:2:1. The cyclic voltammetry in 0.5 M KNO3 aqueous solution at pH 3.0 show the respective electrochemical behaviors of the W-centers and Ru2-centers for these three complexes. Magnetic data analysis shows that diruthenium units display the ground state electronic configuration π*2δ* with large positive D value.  相似文献   

5.
The oxalato-titanium(IV)-containing, dimeric 18-tungsto-2-phosphate [Ti8(C2O4)8P2W18O76(H2O)4]18? (1) and the 32-tungsto-4-phosphate [Ti6(C2O4)4P4W32O124]20? (2) are formed upon reaction of the oxalato-titanium complex [TiO(C2O4)2]2? with the trilacunary Keggin precursor [A-α-PW9O34]9? and the hexalacunary Wells–Dawson precursor [H2P2W12O48]12?, respectively. Polyanion 1 consists of two {PW9} units encapsulating eight titanium centers and connected to each other via two Ti–O–Ti bridges, and crystallizes as a mixed potassium-sodium-lithium salt in the triclinic space group $P{\bar{1}}$ . Polyanion 2 comprises two {P2W16} units containing each two titanium atoms, and the two half-units are connected via two titanium atoms decorated by two oxalate groups each, and crystallizes as a mixed potassium-lithium salt in the rhombohedral space group $R{\bar{3}}c$ . Polyanions 1 and 2 were characterized in the solid state by single-crystal XRD, FT-IR, and TGA, whereas polyanion 2 was also investigated by 31P and 183W NMR.  相似文献   

6.
One novel polyoxometalate compound connected via trivalent cerium cation as bridge H2{[K(H2O)2]2[Ce(H2O)5]2(H2Mo1.16W10.84O42)}·8H2O 1 was designed and synthesized in aqueous solution. X-ray diffraction analysis reveals that the structure of 1 is a three-dimensional framework assembled from the arrangement of H2Mo1.16W10.84O42 (named paradodecmetalate-B) and Ce(H2O)53 containing two planes, which are constructed through the unification of H2Mo1.16W10.84O4210- and Ce(H2O)53 along the [100] and [001] directions. Crystal data H96Ce4K4Mo2.32O128W21.68, Mr = 7074.89, monoclinic, P21/n, a = 12.5037(17), b = 17.002(2), c = 12.7473(17) (A), β = 105.966(2)°, V = 2605.4(6) (A)3, Z = 1, Dc = 4.509 g/cm3, F(000) = 3132, μ = 26.098 mm(1, R = 0.0377 and wR = 0.0789 (I > 2σ(I)).  相似文献   

7.
One novel polyoxometalate compound connected via trivalent cerium cation as bridge H2{[K(H2O)2]2[Ce(H2O)5]2(H2Mo1.16W10.84O42)}·8H2O 1 was designed and synthesized in aqueous solution. X-ray diffraction analysis reveals that the structure of 1 is a three-dimensional framework assembled from the arrangement of H2Mo1.16W10.84O42 (named paradodecmetalate-B) and Ce(H2O)53 containing two planes, which are constructed through the unification of H2Mo1.16W10.84O4210- and Ce(H2O)53 along the [100] and [001] directions. Crystal data: H96Ce4K4Mo2.32O128W21.68, Mr = 7074.89, monoclinic, P21/n, a = 12.5037(17), b = 17.002(2), c = 12.7473(17) (A), β = 105.966(2)°, V = 2605.4(6) (A)3, Z = 1, Dc = 4.509 g/cm3, F(000) = 3132, μ = 26.098 mm(1, R = 0.0377 and wR = 0.0789 (I > 2σ(I)).  相似文献   

8.
以MoO3和C6H5CH2N(CH3)2为原料,制得[C6H5CH2NH(CH3)2]4[Mo8O26]·4H2O,并通过扩散法得到无色透明晶体.X射线单晶衍射表明,晶体属三斜晶系,空间群为P墿,晶胞参数a=1.0685(2)nm,b=1.4050(3)nm,c=1.0643(2)nm,α=93.12(3)°,β=110.26(3)°,γ=71.41(3)°,V=1.4179(5)nm3,R=0.0383.  相似文献   

9.
One new polyoxometalate compound connected via nickel/potassium cations, H8K{[Ni(H2O)5]2(H2Mo1.80W10.20O42)}Cl3·16H2O 1, was prepared and characterized by elemental analysis and IR spectroscopy. Single-crystal X-ray diffraction analysis results reveal that clusters of [Ni(H2O)5]2(H2Mo1.80W10.20O42)}6-in compound 1 are linked by potassium cations to form one- dimiensional chains, based on which a three-dimensional network is further constructed via the hydrogen bonds of O…O and O…Cl. Magnetic measurements show that compound 1 has para- magnetic properties. Crystal data: H62Cl3KMo1.80Ni2O68W10.20, Mr = 3461.33, monoclinic, space group C2/c, a = 18.9291(19), b = 16.6758(17), c = 19.1064(19)(A), β = 106.6880(10)(, V = 5777.1(10) (A)3, Z = 4, Dc = 3.980 g/cm3, F(000) = 6250, μ = 21.574 mm(1, R = 0.0579 and wR = 0.1623 (Ⅰ > 2σ(I)).  相似文献   

10.
Zusammenfassung Die Absorptions- und Reflexionsspektren der Oktocyanokomplexe desMo(IV) undW(IV) sowie die Absorptionsspektren der Oktocyanotomplexe desMo(V) undW(V) werden mitgeteilt. Die Spektren werden unter Zugrundelegung der durch Raman- und IR-spektroskopische Untersuchungen gefordertenD 4d-Symmetrie dieser Verbindungen interpretiert. Die beobachteten Banden niedriger Intensität (log<3) werden Übergängen in einem Termsystem zugeordnet, das für die Konfigurationend 2 undd 1 und die SymmetrieD 4d berechnet worden ist. Banden hoher Intensität (log>3) werden auf Übergänge in antibindende Zustände zurückgeführt, an denen höherep-Zustände des Zentralions sowie Ligandenzustände beteiligt sind. Die erhaltenen Werte des Feldparameters stimmen mit ligandenfeldtheoretischen Erwartungen überein.
Absorption and reflection spectra of the octacyanides ofMo(IV) andW(IV) and the absorption spectra of the octacyanides ofMo(V) andW(V) are presented. The spectra are interpreted in terms of theD 4d symmetry of the compounds supported by investigations of Raman and infrared spectra. Bands of low intensity (log<3) correspond to transitions between levels obtained in the case of the configurationsd 2 andd 1 respectively, in a field ofD 4d symmetry. Bands of high intensity (log>3) are attributed to transitions into antibonding levels in which p-orbitals of the central ion and ligand orbitals participate. The values of the field parameter obtained are in accord with ligand field theory.

Résumé Les spectres d'absorption et de réflexion des complexes octocyanurés duMo(IV) et duW(IV) ainsi que les spectres d'absorption des mêmes complexes deMo(V) et de W(V) sont présentés. Les spectres sont interprétés en supposant la symétrieD 4d des molécules indiquée par des analyses des spectres Raman et infrarouges. Les bandes de faible intensité (log<3) sont attribuées à des transitions dans un système de niveaux, calculé pour les configurationsd 2 etd 1, respectivement, en symétrieD 4d. Des bandes de forte intensité (log>3) sont attribuées à des transitions vers des niveaux antiliants auxquels participent des fonctions élevéesp de l'ion central et des fonctions des groupes liés. Les valeurs obtenues pour le paramètre de champ sont en accord avec les prévisions de la théorie.
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11.
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.  相似文献   

12.
Research on Chemical Intermediates - Using the heterometallic oxo-centered trinuclear [ZnFe2O(CH3COO)6(H2O)3]·2H2O complex as a novel precursor, pure and single-phase ZnFe2O4 nanostructure was...  相似文献   

13.
<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.  相似文献   

14.
The title complex[NH3CH2CH(NH2)CH3]2[M(Ⅵ)O2(OC6H4O)2](M=Mo0.6W0.4)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 [MO6] coordination geometry and is ges show that the title complex is comprised of nano-particles with diameters ranging from 20 to 50 nm. The NMR study shows the 1 H downfield chemical shifts of [NH3CHaHbCH(NH2)CH3] 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 Na2MoO4 which possesses antitumor property, but higher than that by Na2WO4.  相似文献   

15.
Results of X-ray structural analysis, IR spectroscopy, and quantum chemical study of the [Fe3O(CH3COO)6(H2O)3]NO3·4H2O complex are reported. The crystal belongs to the monoclinic system with a=15.688(3), b=11.767(2), c=15.318(4) Å, γ=92.54(3)o, space group P21/a, R=0.078. The molecule has a trinuclear structure: three iron atoms occupy the vertices of an equilateral, triangle with an Fe−Fe distance of 3.29 Å and are bonded by the μ3-oxo and μ-CH3COO (O,O′) ligands. To each iron atom, one water molecule is coordinated. Using the obtained values of populations on 3d AO of Fe (d xy 1.34 ; d xz 1.39 ; d yz 1.46 ; ; ) and charges on oxygen atoms (O c −0.5 ; O ac −0.31 ; O w −0.31 ), we estimated the values of isomeric shift and quadrupole splitting (0.75 and 0.70 mm/sec, respectively; these are close to the experimental values of 0.75 and 0.58 mm/sec, (300 K)). Institute of Chemistry, Moldovian Academy of Sciences. Moldovian State University. Institute of Applied Physics, Moldovian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii., Vol. 35, No. 2, pp. 112–120, March–April, 1994. Translated by T. Yudanova  相似文献   

16.
Cu(CH3COO)2·H2O脱水反应动力学探讨   总被引:6,自引:1,他引:6  
唐定兴  赵芸 《应用化学》2003,20(8):760-0
水合乙酸铜;;脱水动力学;热分析;等温等转化率法;Cu(CH3COO)2·H2O脱水反应动力学探讨  相似文献   

17.
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.  相似文献   

18.
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; K6.5Nd2.5[{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.  相似文献   

19.
K4H2[SiW5Mo6Mn(H2O)O39]·22H2O的晶体结构   总被引:1,自引:0,他引:1  
合成了一个锰硅钼钨四元取代含氧簇合物,用单晶X射线衍射方法测定了结构,该晶体属于四方晶系,空间群P4/mnc,a=14.119(3),c=12.496(4),V=2490.9(12)3,Mr=2862.70,z=2,Dc=3.817g*cm-3,μ=15.922mm-1,R=0.0462,wR=0.1232.锰硅钼钨阴离子中,中心SiO4四面体在C4轴的两个位置上是无序的.  相似文献   

20.
标题配合物M=1892.01,单斜晶系,空间群P21/c,a=1.2975(3)nm,b=2.6591(9)nm,c=1.2118(3)nm,β=96.95(1)°,Z=2,Dc=1.577g/cm3,T=293(2)K。最终的偏离因子R=0.0583。该配合物以二聚体形式存在,通过其中的桥联羧基形成了双核分子。该分子中羧基具有桥联双齿、桥联三齿和单齿三种配位模式,Eu-Eu之间的距离为0.4019(1)nm。在77K下测得配合物中Eu(Ⅲ)离子仅有一种格位。5D0→7FJ(J=0~2)跃迁光谱说明Eu(Ⅲ)离子格位具有C2对称性。  相似文献   

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