Crystal Structure of Benzene II at 25 Kilobars

Crystals of a high-pressure form of benzene (benzene 11) were grown in the diamond-anvil pressure cell at elevated temperature and pressure from the transition of solid I to solid II. X-ray precession data were obtained from a single-crystal in the high-pressure cell. At 21 degrees C and about 25 kilobars, benzene II crystallizes in the monoclinic system with a = 5.417 +/- 0.005 angstroms (S.D.), b = 5.376 +/- 0.019 angstroms, c = 7.532 +/- 0.007 angstroms, beta = 110.00 degrees +/- 0.08 degrees , space group P2(1)/ c, Pc= 1.26 grams per cubic centimeter. The crystal structure was solved by generating all possible molecular packing configurations and calculating structure factors, reliability factors, and packing energies for each configuration. This procedure produced a unique solution for the molecular packing of benzene II.     

Precision Lattice-Parameter Determination of (Mg,Fe)SiO3 Tetragonal Garnets

The tetragonal garnet (Mg,Fe)SiO(3) is a high-pressure phase of pyroxene that is thought to be a major constituent of the earth's upper mantle. Its crystal structure is similar to that of cubic garnet, but it is slightly distorted to tetragonal symmetry so that its x-ray powder diffraction pattern shows a very small line splitting. A suite of tetragonal garnets with different compositions in the MgSiO(3)-rich portion of the MgSiO(3)-FeSiO(3) system was synthesized at about 20 gigapascals and 2000 degrees C. The lattice parameters a and c of quenched samples were determined by whole-powder-pattern decomposition analysis of Fe Kalpha x-ray powder diffraction data, which has the capacity to resolve to a high degree heavily overlapping reflections. It was found that the lattice parameters can be obtained from the following equations; a (in angstroms) = 11.516 + 0.088x and c (in angstroms) = 11.428 + 0.157x, where x, teh mole fraction of FeSiO(3), is 0.0 相似文献   

Natural NaAlSi(3)O(8)-hollandite in the shocked sixiangkou meteorite

The hollandite high-pressure polymorph of plagioclase has been identified in shock-induced melt veins of the Sixiangkou L6 chondrite. It is intimately intergrown with feldspathic glass within grains previously thought to be "maskelynite." The crystallographic nature of the mineral was established by laser micro-Raman spectroscopy and x-ray diffraction. The mineral is tetragonal with the unit cell parameters a = 9.263 +/- 0.003 angstroms and c = 2.706 +/- 0.003 angstroms. Its occurrence with the liquidus pair majorite-pyrope solid solution plus magnesiowustite sets constraints on the peak pressures that prevailed in the shock-induced melt veins. The absence of a calcium ferrite-structured phase sets an upper bound for the crystallization of the hollandite polymorph near 23 gigapascals.     

Structural studies on transfer RNA: preliminary crystallographic analysis

Single-crystal diffraction patterns from Escherichia coli leucine tRNA and yeast formylmethionine tRNA show a tetragonal lattice for the former, with a = 46 angstroms and c = 137 angstroms, and a hexagonal lattice for the latter, with a = 115 angstroms and c = 137 angstroms. Initial analysis suggests a molecule with a long, double helix parallel to the c-axis for both crystals.     

High-Pressure Polymorph of Thulium: An X-ray Diffraction Study

An x-ray diffractiotn study of thulium at room temperature and high pressure by means of a diamond-anvil press has shown that thulium transforms from a hexagonal close-packed structure to the samarium type, as other rareearth elements (gadolinium, terbium, dysprosium, and holmium) do. Unlike the other rare-earth elements, thulium (hexagonal close-packed) has an axial ratio (c/a) that is independent of pressure within experimental error and the transition is reversible. The transition occurs with increasing pressure in the range of 60 to 116 kilobars. The lattice paralieters of the samarium-type phase of thulium at about 116 kilobars are a = 3.327 +/- 0.005 angstroms and c = 23.48 +/- 0.04 angstroms, and the volume change at the transition is estimated to be - 0.5 percent of the volume of the hexagonal close-packed phase at the transition.     

Structural aspects of reversible molecular oxygen uptake

The system IrX(CO)[P(C(6)H(5))(3)](2) in benzene solution adds mo lecular oxygen reversibly if X is chlorine and irreversibly if X is iodine. The crystal structure of the complex IrIO(2)(CO)[P(C(6)H(5))(3)](2) * CH(2)Cl(2) is reported here and compared with a previous study of the structure of IrClO(2)(CO)[P(C(6)H(5))(3)](2). The O-O bond length is 1.47 +/- 0.02 angstroms in the irreversibly oxygenated iodo-compound and 1.30 +/- 0.03 angstroms in the reversibly oxygenated chloro compound.     

A Fluorite Isotype of SnO2 and a New Modification of TiO2: Implications for the Earth's Lower Mantle

The existence of a cubic fluorite-type SnO(2) and a hexagonal TiO(2) (which may be related to the fluorite structure) have been demonstrated by an in situ x-ray diffraction study in which a diamond-anvil pressure cell was used after the samples had been heated by a continuous yttrium-aluminum-garnet laser. At room temperature, the lattice parameter for SnO(2) (fluorite) is a = 4.925 +/- 0.005 angstroms and those for TiO(2) (fluorite-related) are a = 9.22 +/- 0.01 angstroms and c = 5.685 +/- 0.006 angstroms at about 250 kilobars. The volume change associated with the transition from rutile to fluorite (or related structure) is about -8 percent for SnO(2) and -10.5 percent for TiO(2) at transition. Upon release of pressure, both the fluorite-type SnO(2) and the TiO(2) reverted to the alpha-PbO(2) structure at room temperature. The hypothesis that the earth's lower mantle is composed of oxide phases might be feasible if it were possible for SiO(2) to possess the fluorite structure or its related forms at high pressure, as shown for SnO(2) and TiO(2) in this study. The oxide hypothesis proposed here differs from that postulated by Birch in that the primary coordination of silicon is 6 for Birch's hypothesis and 8 for the hypothesis presented here.     

Crystal Structure of the High-Pressure Phase of Solid CO2

X-ray diffraction study of solid CO(2) at room temperature has shown that the powder pattern of the high-pressure phase, which supersedes the low-pressure cubic Pa3 phase at about 10 gigapascals, is consistently interpreted in terms of an orthorhombic Cmca structure. The orthorhombic cell at 11.8 gigapascals has dimensions of 4.330 +/- 0.015, 4.657 +/- 0.005, 5.963 +/- 0.009 angstroms for its a, b, and c faces, respectively, and a volume of 120.3 +/- 0.5 cubic angstroms. Four molecules contained in the unit cell are located at the base-centered positions with their molecular axes inclined at about 52 degrees with respect to the crystallographic c axis. The volume change associated with the Pa3-Cmca transition is close to zero. The structural dimensions obtained for the high-pressure crystalline phase of CO(2) are of great importance for a theoretical understanding of the role of intermolecular interactions, including quadrupole-quadrupole interactions, in molecular condensation.     

First occurrence of the garnet-ilmenite transition in silicates

Pyrope garnet (Mg(3)Al(2)Si(3)O(12)) has been found to transform to an ilmenite-type phase at a loading pressure between 240 and 250 kilobars and at about 1000 degrees to 1400 degrees C in a diamond-anvil press coupled with laser heating. The lattice parameters for the ilmenite-type phase of (Mg(.75) Al(.25))(Si(.75) Al(.25))O(3) are a(0) = 4.755 +/- 0.002 and c(0) = 13.360 +/- 0.005 angstroms. The zero-pressure volume change associated with the garnet-ilmenite transition is calculated to be -7.1 percent. This result verifies the prediction that pyrope garnet would transform to the ilmenite structure at high pressure first suggested in 1962 by Clark et al. and Ringwood.     

Phosphide from metorites: barringerite, a new iron-nickel mineral

Schreibersite, (Fe,Ni)(3)P, and a higher phosphide, barringerite, occur in the Ollague pallasite. The composition of the higher phosphide, determined by electron probe microanalysis, is (Fe(0.58)Ni(0.42)Co(0.003))(1.95)P. It is hexagonal, with space group P62m and a = 5.87 +/- 0.07 angstroms and c = 3.44 +/- 0.04 angstroms. If we assume a primary origin, the new mineral indicates that troilite and schreibersite crystallized at high temperatures. The occurrence of a higher phosphide in a pallasite indicates local nonequilibria within a group of meteorites that are remarkable for their overall degree of equilibrium crystallization.     

Ammonioborite: new borate polyion and its structure

The mineral ammonioborite is monoclinic with unit cell dimensions (in angstroms): a = 25.27, b = 9.65, and c = 11.56; beta = 94 degrees 17', and the space group is C 2/c. Analysis of the crystal structure revealed the crystallo-chemical formula (NH(4))(3)B(15)O(20)(OH)(8).4H(2)O, with four such formula units in the unit cell. The basic structural unit is the double ring consisting of one BO(4) tetrahedron and four BO(3) triangles: in ammonioborite three of these units are connected to give trimeric ions [B(15)O(20)(OH)(8)](3-).     

A New Dense Form of Solid Germanium

A new form of solid germanium, of greater density than ordinary cubic germanium, can be formed by compressing cubic germanium at pressures exceeding 120 kilobars and reducing the pressure back to that of the atmosphere. The crystal structure is tetragonal, with a equal to 5.93 angstroms and c, to 6.98; 12 atoms per unit cell; and theoretical density, 5.91 grams per cubic centimeter. Electrically it behaves like a semiconductor. At temperatures above 200 degrees C it reverts rather rapidly to the cubic form.     

Djurleite (Cu1.94S) and Low Chalcocite (Cu2S): New Crystal Structure Studies

Additional x-ray structure studies on low chalcocite generally confirm the previously reported structure but show that either disorder is present or the true space group is not P2(1)/c but Pc, four of the 96 copper atoms in the monoclinic unit cell taking on twofold (linear) coordination. The crystal structure of djurleite has been solved in space group P2(1)/n, the monoclinic cell having parameters a = 26.897, b = 15.745, and c = 13.565 angstroms; beta = 90.13 degrees ; and a content of 248 copper and 128 sulfur atoms. Of the 62 different copper atoms in the structure, 52 are in threefold, triangular coordination with sulfur, nine in tetrahedral, and one in linear coordination.     

An octahedral coordination complex of iron(VI)

The hexavalent state, considered to be the highest oxidation level accessible for iron, has previously been found only in the tetrahedral ferrate dianion, FeO4(2-). We report the photochemical synthesis of another Fe(VI) compound, an octahedrally coordinated dication bearing a terminal nitrido ligand. M?ssbauer and x-ray absorption spectra, supported by density functional theory, are consistent with the octahedral structure having an FeN triple bond of 1.57 angstroms and a singlet d2(xy) ground electronic configuration. The compound is stable at 77 kelvin and yields a high-spin Fe(III) species upon warming.     

A chromium terephthalate-based solid with unusually large pore volumes and surface area

We combined targeted chemistry and computational design to create a crystal structure for porous chromium terephthalate, MIL-101, with very large pore sizes and surface area. Its zeotype cubic structure has a giant cell volume (approximately 702,000 cubic angstroms), a hierarchy of extra-large pore sizes (approximately 30 to 34 angstroms), and a Langmuir surface area for N2 of approximately 5900 +/- 300 square meters per gram. Beside the usual properties of porous compounds, this solid has potential as a nanomold for monodisperse nanomaterials, as illustrated here by the incorporation of Keggin polyanions within the cages.     

Monoclinic hydroxyapatite

The existence of a monoclinic phase of hydroxyapatite, Ca(2)(PO(4))(4)OH, has been confirmed, by single-crystal structure analysis (weighted "reliability" factor = 3.9 percent on |F|(2)). The structure has space group P21/b, a = 9.4214(8) angstroms, b = 2a, c = 6.8814(7) angstroms, and gamma = 120 degrees , and is analogous to that of chlorapatite. The distortions from the hexagonal structure with which the monoclinic structure is pseudosymmetric are similar to those in chlorapatite, including enlargement of that triangular array of oxygen atoms in which the chlorine ion or, in hydroxyapatite, the hydroxyl hydrogen ion is approximately centered. The hydroxyapatite specimen was prepared by the conversion of a single crystal of chlorapatite in steam at 1200 degrees C, was mimetically twinned, and was approximately 37 percent monoclinic.     

Manganese oxide octahedral molecular sieves: preparation, characterization, and applications

A thermally stable 3 x 3 octahedral molecular sieve corresponding to natural todorokite (OMS-1) has been synthesized by autoclaving layer-structure manganese oxides, which are prepared by reactions of MnO(4)(-) and Mn(2+) under markedly alkaline conditions. The nature and thermal stability of products depend strongly on preparation parameters, such as the MnO(4)(-)/Mn(2+) ratio, pH, aging, and autoclave conditions. The purest and the most thermally stable todorokite is obtained at a ratio of 0.30 to 0.40. Autoclave treatments at about 150 degrees to 180 degrees C for more than 2 days yield OMS-1, which is as thermally stable (500 degrees C) as natural todorokite minerals. Adsorption data give a tunnel size of 6.9 angstroms and an increase of cyclohexane or carbon tetrachloride uptake with dehydration temperature up to 500 degrees C. At 600 degrees C, the tunnel structure collapses. Both Lewis and Br?nsted acid sites have been observed in OMS-1. Particular applications of these materials include adsorption, electrochemical sensors, and oxidation catalysis.     

Crystal Structure of Krypton Difluoride at -80{degrees}C

Krypton difluoride is tetragonal, space group P4(2)/ mnm, with two linear molecules per unit cell aligned in planes perpendicular to the tetrad axes. The alignment alternates by 90 degrees between successive planes. The kryptonfluorine bond distance is 1.89 +/- 0.02 angstroms.     

Structure of a dinucleotide: thymidylyl-(5'-3')-thymidylate-5' (pTpT)

The crystal and molecular structure of the naturally occurring deoxyribose dinucleotide sodium thymidylyl-(5'-->3')-thymidylate-5' has been determined by x-ray diffraction. There are four molecules of dinucleotide and 52 water molecules in an orthorhombic unit cell of dimensions (in angstroms) a = 16.06, b = 15.13, c = 15.65, space group P2(1)2(1)2. There is a very high degree of conformational consistency between the two halves of the molecule when the dinucleotide is viewed as the combination of two 5'-mononucleotides. The planes of the two thymines are not parallel, but are tilted 38 degrees with respect to each other. An extensive system of hydrogen bonding exists involving the bases, waters, phosphates, and sodiums; no base-base hydrogen bonding occurs. The dinucleotide structural parameters should be of assistance in interpreting DNA fiber diagrams in terms of possible structures.     

An ultradense polymorph of rutile with seven-coordinated titanium from the Ries crater

We report the discovery of an ultradense post-rutile polymorph of titanium dioxide in shocked gneisses of the Ries crater in Germany. The microscopic diagnostic feature is intense blue internal reflections in crossed polarizers in reflected light. X-ray diffraction studies revealed a monoclinic lattice, isostructural with the baddeleyite ZrO2 polymorph, and the titanium cation is coordinated with seven oxygen anions. The cell parameters are as follows: a = 4.606(2) angstroms, b = 4.986(3) angstroms, c = 4.933(3) angstroms, beta (angle between c and a axes) = 99.17(6) degrees; space group P2(1)/c; density = 4.72 grams per cubic centimeter, where the numbers in parentheses are standard deviations in the last significant digits. This phase is 11% denser than rutile. The mineral is sensitive to x-ray irradiation and tends to invert to rutile. The presence of baddeleyite-type TiO2 in the shocked rocks indicates that the peak shock pressure was between 16 and 20 gigapascals, and the post-shock temperature was much lower than 500 degrees C.