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1.
Reaction of BaO, Nb2O5, and Nb in mole ratios of 2.4:1.6:1 in an evacuated silica capsule at 1250°C produces a mixture of at least two products, one of which has the probable composition Ba6+xNb14Si4O47 (x ? 0.23). This compound has an hexagonal unit cell of dimensions a = 9,034 ± 0.004 Å, c = 27.81 ± 0.02 Å, probable space group P63mcm, Z = 2. Its structure has been determined from 942 independent reflections collected by a counter technique and refined by least squares methods to a conventional R value of 0.062. The basic structure consists of strings of four NbO6 octahedra sharing opposite corners, each string joined to the next by edge sharing of the end octahedra, so that the c axis corresponds to the length of a strand of seven corner-linked octahedra. Chains of three such strands are formed by corner sharing between the strands. The chains in turn are joined by NbO6 octahedra and Si2O7 groups in which the SiOSi linkage is linear. Barium atoms are in sites between the chains coordinated by 13 oxygen atoms. A second site, 15 coordinated, probably has a small amount of barium as well; the fractional occupancy for barium in this site is 0.076.  相似文献   

2.
A new hydrate of tungsten trioxide, WO3 · 13H2O has been obtained by hydrothermal treatment at 120°C of an aqueous suspension of either tungstic acid gel or crystallized dihydrate. This hydrate has been characterized by different methods. A crystallographic study was carried out from X-ray powder diffraction. The hydrate crystallizes in the orthorhombic system: a = 7.359(3) Å, b = 12.513(6) Å, c = 7.704(5) Å, Z = 12. The existence of structural relationships between the hydrate, WO3 · 13H2O, and the product of dehydration, hexagonal WO3, has permitted us to propose a structural model in agreement with the experimental data. WO3 · 13H2O must be regarded as an interesting compound because its dehydration leads to a new anhydrous tungsten trioxide, hexagonal WO3.  相似文献   

3.
Crystal structures for the fluorite-related phases CaHf4O9ф1) and Ca6Hf19O44 (ф2) have been determined from X-ray powder diffraction data. qf1 is monoclinic, C2c, with a = 17.698 Å, b = 14.500Å, c = 12.021 Å, β = 119.47° and Z = 16. qf2 is rhombohedral, R3c, with a = 12.058 Å, α = 98.31° and Z = 2.Both phases are superstructures derived from the defect fluorite structure by ordering of the cations and of the anion vacancies. The ordering is such that the calcium ions are always 8-coordinated by oxygen ions, while the hafnium ions may be 6-, 7-, or 8-coordinated. The closest approach of anion vacancies is a 12〈111〉 fluorite subcell vector, and in each structure vacancies with this separation form strings.  相似文献   

4.
The new compound BaSb2S4 crystallizes in the monoclinic system (space group: P21c, No. 14) with a = 8.985(2) Å, b = 8.203(3) Å, c = 20.602(5) Å, β = 101.36(3)°. SbS3 ψ tetrahedra and ψ-trigonal SbS4 bipyramids are connected by common corners and edgers to infinite strings. These are arraged cross-wise in sheets perpendicular to the c axis.  相似文献   

5.
Three anhydrous polymorphs of cupric iodate, two hydrates, and the basic iodate salesite have been investigated. α-Cu(IO3)2 is monoclinic, space group P21, with a = 5.551 ± 0.008, b = 5.101 ± 0.004, c = 9.226 ± 0.010 Å and β = 95°4′ ± 11′, with two formulas in the unit cell. Below ΘN = 8.5 K, α-Cu(IO3)2 is antiferromagnetic and also pyroelectric. β-Cu(IO3)2 is triclinic, space group P1, with a = 11.230 ± 0.006, b = 11.368 ± 0.009, c = 10.630 ± 0.009 Å, α = 99°18.3′ ± 0.3′, β = 107°0.4′ ± 0.2′ and γ = 114°23.8′ ± 0.2′ and eight formulas per unit cell: the crystal is paramagnetic to 1.4K. γ-Cu(IO3)2 is monoclinic, space group P21m, with a = 4.977 ± 0.004, b = 6.350 ± 0.004, c = 8.160 ± 0.004 Å and β = 92°20′ ± 4′, with two formulas per unit cell; γ-Cu(IO3)2 becomes antiferromagnetic below ΘN = 5 K. Cu(IO3)2·2H2O is monoclinic, space group P21c, with a = 6.725 ± 0.005, b = 4.770 ± 0.007, c = 11.131 ± 0.013 Å and β = 103°1′ ± 4′, with two formulas per unit cell; Cu(IO3)2·2H2O is paramagnetic to 1.4 K. Cu(IO3)2·23H2O (mineral bellingerite) is triclinic, space group P1, with a = 7.197 ± 0.005, b = 7.824 ± 0.004, c = 7.904 ± 0.004 Å, α = 105°2′ ± 2′, β = 97°7′ ± 2′ and γ = 92°54′ ± 2′ with three formulas per unit cell; this crystal is paramagnetic to 1.4 K, with a moderate antiferromagnetic Cu-Cu interaction. Cu(OH)IO3 (mineral salesite) is orthorhombic, with a = 10.772 ± 0.004, b = 6.702 ± 0.002 and c = 4.769 ± 0.002 Å and four formulas per unit cell. The magnetic susceptibility indicates the possibility of antiferromagnetic ordering at 162 K; strong antiferromagnetic interactions give Θp = ?340 K. The only copper iodate studied that generates second harmonics is α-Cu(IO3)2. Indexed powder patterns are given for all six compounds.  相似文献   

6.
The rz structure of 1,1-dichloroethylene has been determined by a joint analysis of the electron diffraction intensity and the rotational constants as follows: rz(CH) = 1.088 ± 0.011, rz(CC) = 1.329 ± 0.003, rz(CCl) = 1.725 ± 0.002 A?, ∠zHCH = 121.4 ± 0.7 andzClCCl = 114.1 ± 0.2°. The uncertainties represent estimated limits of error. The observed structural parameters are compared with those for related compounds and the systematic trends in the bond lengths and bond angles are discussed. The effective constants representing anharmonicity have been obtained from an analysis of the isotopic differences in the rz structure. By using the rz parameters and the effective constants, the equilibrium structure has been estimated as follows: re(CH) = 1.079 ± 0.012, re(CC) = 1.324 ± 0.005, re(CCl) = 1.721 ± 0.003 A?, ∠eHCH = 120.5 ± 0.8 andeClCCl = 114.0 ± 0.3°.  相似文献   

7.
The crystal structure of SrFeF5 has been determined by single crystal X-ray diffraction methods.The unit cell is monoclinic (space group P21c) with a = 7.062 ± 0.001 Å, b = 7.289 ± 0.001 Å, c = 14.704 ± 0.001 Å, β = 95.40 ± 0.01° and Z = 8.The lattice is built up of spiral chains of octahedra parallel to the Oy axis. These chains are formed by (FeF6)3? octahedra sharing corners of the same edge. The strontium atoms bridge three neighbouring chains. The SrTiF5, SrVF5, SrCoF5, and BaInF5 phases are isostructural with SrFeF5.  相似文献   

8.
Single crystals of a new oxide “FeV3O8” (FexV1?xO2: x ? 0.25) have been synthesized by slowly cooling a melted mixture with the composition, 8VO2, 3V2O5, Fe2O3. The chemical formula has been determined by electron microprobe analysis. The compound, isostructural with AlNbO4 and VO2(B), has a monoclinic symmetry, space group C2m; the unit cell dimensions are a = 12.13Å, b = 3.679 Å, c = 6.547 Å, β = 106.85°. A structural refinement based on single crystal data has been carried out. It gave an R-factor of 1.9%. This refinement indicated that the iron and vanadium cations are partially ordered, although the average cation-oxygen distances for the two six-coordinated cations were exactly the same (1.961 Å). This conjecture was supported by the calculation of the cation valences.  相似文献   

9.
Photon-correlation spectroscopy has been used to measure the diffusion coefficient D and first-mode intramolecular relaxation time τ1 of polystyrene in a theta solvent, cyclohexane at 34.5°C. Measurements were made on five narrow fractions (Mw = 2.88 × 106 to 9.35 × 106) as a function of concentration c, in the dilute regime. D varied linearly with c, D = Do (I + kDc), with Do = (1.4 ± 0.2) × 10?4Mw?(0.508±0.007) cm2 s?1. Although the values obtained for τ1 were reproducible to within 5%, no systematic variation with c was detected. The results are fitted by the relation τ1 = (7.7 ? 0.3) × 10?8Mw(1.42±0.05) μs, which agrees well with the theoretical expression of Zimm for the non-draining bead-and-spring model, modified for the light-scattering case.  相似文献   

10.
The system MgOSiO2H2O was investigated at pressures between 40 and 95 kbar and at temperatures between 500 and 1400°C. The reaction products were examined by X-ray, optical and thermal analysis techniques and the density of phase A discovered by Ringwood and Major was also measured. It was found that phase A was hydrated and its chemical formula was H6Mg7Si2O14. When the MgSi ratio of the system is 2, phase A + clinoenstatite, and forsterite are stable at temperatures lower and higher than a boundary curve T (°C) = 10P (kbar), respectively. When the MgSi ratio of the system is 3, phase A + phase D (which is completely different from the phases, A, B and C discovered by Ringwood and Major, and any other known phases of magnesium silicate) and phase D + brucite are stable at temperatures lower and higher than a boundary curve T(°C) = 10P (kbar) + 200. Phase A has approximately an hexagonal symmetry and the space group and the lattice parameters are determined as P63 or P63m and a = 7.866(2) Å and c = 9.600(3) Å, respectively. The measured density is 2.96 ± 0.02 g/cm3. The optical observations show that phase A is biaxial positive crystal with refractive indices α = 1.638 ± 0.001, β = 1.640 ± 0.002, and γ = 1.649 ± 0.001. Some interpretation is given on the inconsistency between the symmetry determined by the X-ray diffraction and the optical observation. The new phase D belongs to the space group P21c with lattice parameters a = 7.914(2)Å, b = 4.752(1) Å, c = 10.350(2) Å and β = 108.71(5)° and is a biaxial crystal with refractive indices α = 1.630 ± 0.002, β = 1.642 ± 0.002 and γ = 1.658 ± 0.001.  相似文献   

11.
A single-crystal study of a sample of Ba4Nb3LiO12 provided by Dr. T. Negas has been carried out and confirms the |(4)|(4)| layer stacking scheme (Zhdanov notation) for the eight BaO3 layers per unit cell. Of the eight MO6 octahedra per cell (M = Nb or Li), four share faces in pairs, and these pairs are linked by pairs of corner-sharing MO6 octahedra. The compound has an hexagonal cell of dimensions a = 5.777 ± 0.006 Å and c = 18.95 ± 0.03 Å, probable space group P63mmc, Z = 2. The theoretical density is 6.22 g/cm3; within the limit of error of the pycnometrically measured density, 6.08 ± 0.06 g/cm3. The study was carried out with 620 independent reflections, of which 437 were considered observed, collected by automated counter methods and refined by least-squares to a conventional R value of 0.076.  相似文献   

12.
A single-crystal study of a sample of barium tungsten lithium oxide, supplied by Dr. T. Negas and identified as Ba5W3Li2O15, confirms the |(5)|(5)| layer stacking scheme (Zhdanov notation) for the ten BaO3 layers per unit cell. Pairs of face-sharing MO6 octahedra (MW or Li) are linked through corner sharing by strings of three corner-sharing octahedra. In these strings of three, the two outer octahedra are occupied by W; but no X-ray evidence was found for the existence of Li in the middle one. The compound has an hexagonal cell of dimensions a = 5.7614 ± 0.0008 Å and c = 23.719 ± 0.007 Å, probable space group P63mmc, Z = 2. Its structure was determined from 757 independent reflections, of which 426 were considered observed, collected by automated counter methods, and refined by least-squares methods to a conventional R of 0.064. The X-ray refinement based on the assumption that two octahedral sites in the unit cell are empty suggests formulas such as Ba5W3.2Li0.8O15 or Ba5W3LiO14.5 rather than the “ideal” formula Ba5W3Li2O15.  相似文献   

13.
The structure of a KxP2W4O16 (x ? 0.4) crystal was established by X-ray analysis. The solution in the cell of symmetry P21m, with a = 6.6702(5), b = 5.3228(8), c = 8.9091(8) Å, β = 100.546(7)°, Z = 1, has led to R = 0.033 and Rw = 0.036 for 2155 reflections with σ(I)I ≤ 0.333. This structure can be described as two octahedra-wide ReO3-type slabs connected through “planes” of PO4 tetrahedra. A new structural family KxP2W2nO6n+4 can be foreseen which is closely related to the orthorhombic P4W8O32 and the monoclinic RbxP8W8nO24n+16 series.  相似文献   

14.
Reactions between MX(PPh3)2(η-C5H5) (M = Ru, X = Cl; M = Os, X = Br) and 2-CH2CHC6H4PPh2 afford MX(η2-CH2CHC6H4PPh2)(η-C5H5); the Os complex is obtained in two isomeric forms. The X-ray structure of the major isomer shows the CC double bond (OsC, 2.214, 2.195 Å; CC, 1.57 Å) is almost coplanar with the OsBr vector, with the terminal C cis to Br; the minor isomer is assumed to have the alternative, more sterically congested conformation, with the β-C cis to Br. The chlororuthenium complex reacts with NaOMe/MeOH to give the corresponding hydrido complex, which also exists as two isomers in solution; reaction of this complex with CS2 gives the expected dithio acid derivative Ru(S2CCHMeC6H4PPh2)(η-C5H5), together with small amounts of a complex assumed to be Ru[S2C(CH2)2C6H4PPh2](η-C5H5). The X-ray structure of the major product reveals an unusual η3-S2C mode of coordination of the dithio acid fragment (RuS, 2.418, 2.426(1) Å; RuC 2.175(4) Å). Crystals of OsBr(η2-CH2CHC6H4P)Ph2)( η-C5H5) are monoclinic, space group P21/n, with a 12.696(2), b 21.719(6), c 15.929(3) Å, β 79.77(2)°, Z = 8; 2867 data (I > 2.5σ(I)) were refined to R = 0.040, Rw = 0.044. Crystals of Ru(η3-S2CCHMeC6H4PPh2)(η-C5H5) are orthorhombic, space group Pbca, with a 8.921(2), b 15.982(9), c 32.216(5) Å, Z = 8; 1685 data (I > 2.5σ(I)) were refined to R = 0.027, Rw = 0.030.  相似文献   

15.
The mutual solubilities of {xCH3CH2CH2CH2OH+(1-x)H2O} have been determined over the temperature range 302.95 to 397.75 K at pressures up to 2450 atm. An increase in temperature and pressure results in a contraction of the immiscibility region. The results obtained for the critical solution properties are: To(U.C.S.T.) = 397.85 K and xo = 0.110 at 1 atm; (dTodp) = ?(12.0±0.5)×10?3K atm?1 at p < 400 atm and (dTodp) = ?(7.0±0.7)×10?3K atm?1 at 800 atm < p < 2500 atm; (dxodT) = ?(4.0±0.5)×10?4K?1.  相似文献   

16.
The standard enthalpy of formation of γ-UO3 has been critically assessed; the value ?(292.5 ± 0.2) kcalth mol?1 is suggested.The enthalpies of solution of β-UO3 and γ-UO3 in 3 M H2SO4 have been measured and used to derive:
ΔHf°(β?UO3, 298.15 K) = ?(291.6 ± 0.2) kcalth mol?
  相似文献   

17.
Linear and branched bisphenol A polycarbonate (PC) samples were characterized by their average molecular weights, Mn and Mw, polydispersity degree q = Mw/Mn, and branching degree gv. The weight fraction of microgel was also determined for branched samples. The samples were amorphized and densities were measured at 23°C to obtain the values of specific volume, vsp. The dependence of vsp on molecular characteristics is described by the multivariable power function Δvsp = AspMxaqapx gvab, where Δvsp = vsp ? vsp,∞, and Asp, a, apx and ab are constants. It has been confirmed that a = ?1, apn = 0 and apw = 1. It has also been found that the branching exponent ab significantly depends on microgel content. The relationships found for PC should, in principle, be valid for other polymers. Examples based on literature data are given for linear polyethylene and polydimethylsiloxane.  相似文献   

18.
The compound Th0.25 NbO3 melts congruently at 1390°C. Single crystals obtained by slow cooling from the melt are transparent and show uniaxial optical properties. A single-crystal X-ray analysis confirms the tetragonal cell found by Kovba and Trunov from a powder data and gives a = 3.90 Å and c = 7.85 Å. No systematic absence of the hkl reflections is observed on precession films. The relative intensities of the main reflections are characteristic of a perovskite-like arrangement ABO3 whose large dodecahedral A sites are only partly occupied. Several domains have been found in the perovskite-type solid solution (1 ? x) Th0.25NbO3-x NaNbO3. For 0 ? x ? 0.5 the phases have a tetragonal cell with a ? a0 and c ? 2a0 as in pure Th0.25 NbO3. When 0.6 ? x ? 0.8 the corresponding phases crystallize with a small cubic cell (a0 ? 3.9Å), while phases with 0.9 ? x ? 1 have an orthorhombic cell (a ? 212a0, b ? 212a0, c ? a0).  相似文献   

19.
A new form of tungsten trioxide WO3 has been obtained by dehydration of WO3·13H2O hydrate. The structural study was carried out from X-ray powder diffraction and selected area electron diffraction data. The crystallographic characteristics are: the hexagonal system; a = 7.298(2) Å, c = 7.798(3) Å; Z = 6. This hexagonal WO3 is built up of slightly distorted (WO6) octahedra sharing their corners arranged in six-membered rings in layers normal to the hexagonal axis; stacking of such layers leads to formation of large hexagonal tunnels. Some confirmations of this structure were made by high-resolution electron microscopy. Powder X-ray diffraction allowed us to determine an average structure. Absence of suitable single crystals has not permitted us to perform a complete structural determination. Although the existence of such a hexagonal structure for pure WO3 had been considered as likely, it had not been hitherto observed.  相似文献   

20.
The lanthanum β-alumina phase doped with europium was investigated by X-ray diffraction and fluorescence. This nonstoichiometric phase exists over the composition range: 11Al2O31La2O3 to 14Al2O31La2O3. The unit cell is hexagonal hexagonal with a = 5.560 ± 0.003 Å, c = 22.001 ± 0.003 Å and belongs to the P63mmc space group. X-ray diffraction patterns do not vary between both boundary compositions, but fluorescence spectra show that the structure of the mirror plane in which the lanthanide ions are located is deeply modified. The atomic structure of the mirror plane is of “β-type” (like β(Na) or β(Ag)) for the lower alumina contents; it gradually changes to a “magnetoplumbite type” for higher alumina contents.  相似文献   

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