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1.
New high-pressure orthorhombic (GdFeO3-type) perovskite polymorphs of MnSnO3 and FeTiO3 have been observed using in situ powder X-ray diffraction in a diamond-anvil cell with synchrotron radiation. The materials are produced by the compression of the lithium niobate polymorphs of MnSnO3 and FeTiO3 at room temperature. The lithium niobate to perovskite transition occurs reversibly at 7 GPa in MnSnO3, with a volume change of -1.5%, and at 16 GPa in FeTiO3, with a volume change of -2.8%. Both transitions show hysteresis at room temperature. For MnSnO3 perovskite at 7.35 (8) GPa, the orthorhombic cell parameters are a=5.301 (2) A, b=5.445 (2) Å, c=7.690 (8) Å and V= 221.99 (15) Å3. Volume compression data were collected between 7 and 20 GPa. The bulk modulus calculated from the compression data is 257 (18) GPa in this pressure region. For FeTiO3 perovskite at 18.0 (5) GPa, cell parameters are a=5.022 (6) Å, b=5.169 (5) Å, c=7.239 (9) Å and V= 187.94 (36) Å3. Based on published data on the quench phases, the FeTiO3 perovskite breaks down to a rocksalt + baddelyite mixture of FeO and TiO2 at 23 GPa. This is the first experimental verification of the pressure-induced breakdown of a perovskite to simple oxides.  相似文献   

2.
A simulated annealing technique was used to search for global and local minimum energy structures of a potential energy model for silica. The model is based on ab initio SCF MO calculations on the disilicic acid molecule, H6Si2O7. Starting with 4 SiO2 units, with the atoms randomly distributed in the unit cell, 23 distinct silica tetrahedral framework structures were found, with a variety of space group symmetries and cell dimensions. Despite the assumption of P 1 space group symmetry for the starting structure, only 7 of the local minimum energy structures were found to possess triclinic symmetry with the remainder exhibiting symmetries ranging from P c to to within 0.001 Å. Although the interaction potential for the disilicic acid molecule has a single minimum energy SiO bond length and SiOSi angle, the local minimum energy structures exhibit angles that range between 105° and 180° and bond lengths that range between 1.55 and 1.68 Å. The correlation observed for coesite and the other silica polymorphs between SiO bond length and fs(O) is reproduced. The generated structures show a wide variety of coordination sequences, ring sizes and framework densities, the later ranging from 19.8 to 35.5 Si/1000 Å3. The energies of these structures correlate with their framework densities, particularly for higher energy structures.  相似文献   

3.
Summary The synthetic TlPbSbS3 represents a rare example of a sulphosalt with statistical distribution of Tl, Pb and Sb in the structure. Within the TlSbS2-PbS system, TlPbSbS3 is the end member of the solid solution series with TlSbS2, but no solubility with PbS is detected. The high temperature-TlPbSbS3 is orthorhombic and inverts at about 620 K to the low-temperature phase. The low-temperature modification of TlPbSbS3 was structurally investigated by X-ray powder diffraction and by the Rietveld analysis of the data. The structure is monoclinic, with a = 4.1707(4) Å, b = 4.2856(4) Å, c = 12.157(1) Å, = 105.49(1)°, space group P21/c. Like in the high-temperature form, there is a cation disorder over the equivalent positions in the structure. The interatomic distances of (Tl, Ph, Sb) to S are 2.71, 2.72, 2.88, 3.15, 3.29, 3.51 (Å). There is a close similarity between the TlPbSbS3 polymorphs and the and forms of SnS, as regards the atomic coordinations and the general structure types and the same type of phase transformation is supposed for both cases. The small differences in the structure type and symmetry, between the low temperature forms of SnS and TlPbSbS3, result probably from stronger metal-metal interactions in the latter. A substitution-derivative relation to SnS type is established owing to the strong structural effect of the lone electron pairs of Tl and Sb. The substitution of Ag for Tl and Bi for Sb in ABCS3 type compounds diminishes this effect and PbS type structures are produced.
Die zwei Polymorphen von TlPbSbS3 und die Strukturellen Beziehungen von Phasen in System TlSbS2-PbS
Zusammenfassung Die synthetische Phase TlPbSbS3 ist ein seltenes Beispiel von einem Sulfosalz mit der statistischen Verteilung von TI, Pb und Sb in der Struktur. In der TlSbS2-PbS Phasensystem, ist TlPbSbS3 das Endmitglied der Mischkristallreihe, die sich im Richtung TlSbS2 ausstreckt. Weitere Ausdehnung der Mischkristallreihe in der Richtung SbS konnte nicht bewiesen werden. Die Hochtemperatur-TlPbSbS3 ist rhombisch und wird beim 620 K in die Tieftemperatur Modifikation umgewandelt. Die Tieftemperaturphase ist mit der Röntgenpulverdiffraktion und Rietveld Methode strukturell untersucht worden. Die ist monoklin, mit den Gitterkonstanten: a = 4.1707(4) Å, b = 4.2856(4) Å, c = 12.157(1) Å, = 105.49(1)°, Raumgruppe P21/c. Die statistische Verteilung von Kationen ist auch hier vorhanden. Die zwischenatomare Abstande (Tl, Pb, Sb)-S sind: 2.71, 2.72, 2.88, 3.14, 3.28, 3.51 (Å). Es besteht eine enge Verwandschaft zwischen den polymorphen Modifikationen von TlPbSbS3 und den und Polymorphen von SnS, was die atomare Koordinationen und den generellen Strukturtypus betrifft, wobei ein ähnlicher Mechanismus der Phasenumwandlung für die beiden Fälle vermutet werden könnte. Die Differenzen in der Struktur und Symmetrie zwischen der Tieftemperaturmodifikationen von SnS und TlPbSbS3 sind wahrscheinlich durch die bedeutende Metall-Metall Wirkungen in der zweiten verursacht. Die Phase TlPbSbS3 ist ein substitution-derivative von der SnS Struktur, was durch die starke lone-electron-pair Aktivität von Kationen zu erklären ist. Die Ersetzung von Tl durch Ag und Sb durch Bi vermindert diese Aktivität und die entstandenen Strukturen sind in dem Fall dem PbS-Typus verwandt.

With 3 Figures  相似文献   

4.
The behaviour of tetrahedrally coordinated and octahedrally coordinated Cr3+ ions in diopside is discussed from the study on the join CaMg-Si2O6-CaCrCrSiO6. The molecule CaCrCrSiO6 decomposes into uvarovite+eskolaite and its maximum solubility in diopside is 6.7 wt percent at 940 ° C. Crystalline phases are diopside ss (ss is abbreviation of solid solution), uvarovite ss, wollastonite ss, spinel and eskolaite. The diopside ss is blue in colour. Its optical spectra were measured in the wavelenght range of 325–2600 nm, and assigned after tetrahedral configuration Td and octahedral configuration Oh. It is estimated that octahedral Cr3+ ions are in high spin state, while tetrahedral Cr3+ ions may be probably in low spin state. The t and B are 10,300–10,370 cm–1 and 429–432 cm–1. The CFSE for tetrahedral low spin Cr3+ ions is nearly the same as that for octahedral high spin Cr3+ ions. The ionic radii of tetrahedral low spin Cr3+ ions calculated are 0.47–0.53 Å, shrinked from the radius of octahedral high spin Cr3+ ion (0.615 Å) as much as 14–24 percent. Petrologic implications of the result are also discussed.The first half of the D. Sc. dissertation of K. Ikeda presented to Hokkaido University in June, 1976  相似文献   

5.
The space group and hydrogen positions of -(Al0.84Mg0.07Si0.09)OOH are investigated using a single crystal synthesized using a multi-anvil apparatus under conditions of 1000 °C and 21 GPa. The space group determined by single-crystal X-ray diffraction is to Pnn2, with unit-cell parameters of a=4.6975(8) Å, b= 4.2060(6) Å, c=2.8327(4) Å, and V=55.97(1) Å3. Partial occupancy of the Al site by Mg and Si suggests the possibility of a limited solid solution between -AlOOH, stishovite, and a hypothetical CaCl2-type Mg(OH)2 that is 16% denser than brucite. Difference-Fourier maps reveal two small but significant Fourier peaks attributable to hydrogen atoms. Atomic distances and angles around the first peak indicate a hydrogen bond with O···O distances of 2.511 Å, while those around the second peak are suggestive of a bifurcated hydrogen bond with O···O distances of 2.743 and 2.743 Å.  相似文献   

6.
Chlorite and berthierine occur through alteration of cordierite within enclaves of metamorphic rocks transformed by the Sierra Albarrana pegmatites. The coexistence of both phyllosilicates allows us to study their stability relationships and to compare their chemical compositions. Samples showing incipient replacement of cordierite by small cryptocrystalline aggregates can be identified by X-ray diffraction (XRD) as berthierine with small quantities of chlorite. Electron Microprobe (EMP) analyses give mixed compositions of berthierine and cordierite. Samples with extensive replacement of cordierite by aggregates show similar characteristics to those with incipient replacement, but some small crystals are present. The last type of sample shows complete replacement of cordierite by crystals showing optical properties of chlorite and EMPA compositions coherent with chlorite or berthierine. Their XRD pattern corresponds to chlorite and their high resolution transmission electron microscopy (HRTEM) images only show perfect sequences of 14 Å lattice fringes. The cryptocrystalline aggregates of the samples with incipient and extensive replacement present coexistent areas of 14 Å and 7 Å lattice fringes that are intergrown at different levels: (1) large areas (> 1 m) of 7 Å layers; (2) packets of 7 Å layers between 14 Å layer areas, with visible 7 Å to 14 Å lateral changes; (3) random mixed-layers 7 Å/14 Å. Chlorite is the final stable product of alteration of cordierite, with berthierine as an intermediate metastable phase. Energy dispersive X-ray spectrometry microanalyses of 14 Å, 7 Å and (14+7) Å areas show lack of systematic differences in chemical compositions between both phyllosilicates which may be considered as true polymorphs.  相似文献   

7.
Summary A crystal structure determination of the mineral nealite, Pb4Fe(AsO3)2Cl4 . 2H2O, (a = 6.548(4), b = 10.243(8), c = 5.587(3) [Å]; = 96.2(1), = 89.6(1), = 97.7(1) [°]; Z = 1; space group ) was performed using single crystal X-ray data and a direct method strategy; the structural parameters were fitted by least squares techniques. The structure is characterized by isolated FeO2Cl2(H2O)2 octahedra (Fe-O: 2.08 Å, 2x, and 2.12 Å, 2x, Fe-Cl: 2.60 Å, 2x) and AsO3 pyramids (As-O from 1.79 to 1.89 Å) which are connected by PbO4Cl4 and PbO5Cl4 polyhedra to a framework (with Pb-O distances from 2.22 to 3.34 Å, Pb-Cl distances from 3.10 to 3.54 Å). Oscillation photographs, exposed for 20 h, show very faint streaks indicating a doubling of c, probably caused by a partial ordering of a split lead atom position. Nealite is the first mineral found to contain a divalent iron atom coordinated to oxygen and chlorine atoms simultaneously.
Änderung der chemischen Formel des Nealits, Pb4Fe(AsO3)2Cl4 . 2H2O, basierend auf der Kristallstrukturbestimmung
Zusammenfassung Die Kristallstrukturbestimmung des Minerals Nealit, Pb4Fe(AsO3)2Cl4 . 2H2O, a = 6.548(4), b = 10.243(8), c = 5.587(3) [Å]; = 96.2(1), = 89.6(1), = 97.7(1) [°]; Z = 1; Raumgruppe ) wurde anhand von röntgenographischen Einkristalldaten mit direkten Methoden durchgeführt und die Strukturparameter nach der Methode der kleinsten Quadrate verfeinert. Die Kristallstruktur ist charakterisiert durch isolierte FeO2Cl2(H2O)2-Oktaeder (Fe-O: 2.08 Å, 2x, und 2.12 Å, 2x, Fe-Cl: 2.60 Å, 2x) und AsO3-Pyramiden (As-O von 1.79 Å bis 1.89 Å), welche durch PbO4Cl4 und PbO5Cl4-Polyeder zu einem Gerüst verknüpft sind (Pb-O von 2.22 bis 3.34 Å und Pb-Cl von 3.10 bis 3.54 Å). Schwenkaufnahmen, etwa 20 h belichtet, zeigen sehr feine Schwärzungsstreifen, die auf eine Verdopplung von c hinweisen, möglicherweise durch eine teilweise Ordnung einer aufgespaltenen Position eines Bleiatoms hervorgerufen. Nealit ist das erste Mineral, in dem ein zweiwertiges Eisenatom gleichzeitig an Sauerstoff- und Chloratome gebunden ist.

Dedicated to Prof. Dr. Josef Zemann (Vienna) on the occasion of his 70th birthday

With 1 Figure  相似文献   

8.
Giester  G. 《Mineralogy and Petrology》1995,53(1-3):165-171
Summary The crystal structure of synthetic KMn[SeO4]2 was determined by single crystal X-ray diffraction methods in space group , a = 4.827(2) Å, b = 4.988(2) Å, c = 7.981(3) Å, = 83.18(1)°, = 85.32(2)°, = 67.92(1)°, V = 176.66 Å3, Z = 1; 1564 unique data, measured up to 2 = 70° (MoK-radiation); R, R(I)w = 0.034, 0.074.KMn[SeO4]2 is closely related to monoclinic yavapaiite, KFe[SO4]2, and isotypic compounds. Jahn-Teller distorted MnO6 octahedra are alternately linked with KO10 polyhedra along [001]. The mean values of the Mn-O and Se-O distances are 2.007 Å and 1.637 Å, respectively.
Die Kristallstruktur vonKMn 3+[SeO4]-einem triklin verzerrten Vertreter der Yavapaiite-Familie
Zusammenfassung Die Kristallstruktur von synthetisch dargestelltem KMn[SeO4]2 wurde mittels Einkristallröntgenmethoden in der Raumgruppe bestimmt: a = 4.827(2) Å, b = 4.988(2) Å, c = 7.981(3) Å, = 83.18(1)°, = 85.32(2)°, = 67.92(1)°, V = 176.66 Å3, Z = 1; 1564 unabhängige Daten bis 2 = 70° (MoK-Strahlung); R, R(I)w = 0.034, 0.074.KMn[SeO4]2 ist eng mit dem monoklinen Mineral Yavapaiit, KFe[SO4]2 und einer Reihe damit isotyper Verbindungen verwandt. Jahn-Teller verzerrte MnO6 Oktaeder sind alternierend mit KO10 Polyedern parallel [001] verbunden. Die Mittelwerte der Mn-O und Se-O Abstände sind 2.007 Å bzw. 1.637 Å.

With 1 Figure  相似文献   

9.
Summary Based on a X-ray structure analysis it was proved that the mineral schmiederite contains both selenite and selenate groups [a = 9.922(3)Å,b = 5.712(2)Å,c = 9.396(3)Å, = 101.96(3)°, space group P21/m,Z = 2 {Pb2Cu2(OH)4(SeO3)(SeO4)},R w = 0.055 for 1131 reflections up to sin / = 0.65 Å–1]. The crystal structure is closely related to that of linarite [a = 9.701(2) Å,b = 5.650(2) Å,c= 4.690(2)Å, = 102.65(2)°, space group P21/m,Z = 2 {PbCu(OH)2(SO4)},R w = 0.034 for 1991 reflections up to sin / = 1.0 Å–1].The Pb atom in linarite and the Pb(1) atom in schmiederite have each three Pb-O bonds < 2.45 Å with trigonal pyramidal arranged ligands; the Pb(2) atom in schmiederite has only one such near O atom. The Cu atoms are approximately square planar coordinated by hydroxil groups. In addition two further O atoms complete the coordination figure to a strongly distorted octahedron. All the anion groups have the usual geometry.
Kristallstruktur und chemische Formel von Schmiederit, Pb2Cu2(OH)4(SeO3)(SeO4), mit einem Vergleich zu Linarit, PbCu(OH)2(SO4)
Zusammenfassung Basierend auf einer Röntgen-Strukturuntersuchung konnte das Vorliegen von Selenit-und Selenatgruppen im Mineral Schmiederit belegt werden [a=9,922(3) Å,b = 5,712(2) Å,c = 9,396(3) Å, = 101,96(3)°, Raumgruppe P21/m,Z=2 {Pb2Cu2(OH)4(SeO3)(SeO4)},R w = 0,055 für 1131 Reflexe bis sin /, = 0,65 Å–1]. Die Kristallstruktur weist enge Beziehungen zu jener des Linarits auf [a = 9,701(2) Å,b = 5,650(2) Å,c = 4,690(2) Å, = 102,65(2)°, Raumgruppe P21/m,Z=2 {PbCu(OH)2(SO4)},R w = 0,034 für 1991 Reflexe bis sin / = 1,0 Å–1].Das Pb-Atom im Linarit sowie das Pb(1)-Atom im Schmiederit haben jeweils drei Pb-O-Bindungen <,45 Å, wobei die Liganden trigonal pyramidal angeordnet sind; das Pb(2)-Atom im Schmiederit hat hingegen nur ein derart nahes O-Atom. Die Cu-Atome sind etwa quatratisch planar von Hydroxilgruppen koordiniert; zwei weitere O-Atome ergänzen die Koordinationsfigur zur einem stark verzerrten Oktaeder. Die Aniongruppen haben die üblichen Dimensionen.
  相似文献   

10.
Zusammenfassung Schultenit, PbHAsO4 [a=4,859(1) Å,b=6,756(1) Å,c=5,843(1) Å, =95,40(1)°] und PbHPO4 [a=4,6838(3) Å,b=6,6451(2) Å,c=5,7817(3) Å, =97,138(4)°] sind isotyp und kristallisieren monoklin. Für beide Verbindungen war bei einer Temperatur vonT c312 K der Übergang von RaumgruppeP c nachP2/c bekannt. Der Strukturtyp von Schultenit ist durch das Vorliegen einer kurzen Wasserstoffbrückenbindung zwischen zwei in RaumgruppeP2/c über ein Symmetriezentrum ineinander überführbarer XO4-Tetraeder charakterisiert. Die O–H...O-Bindungslänge beträgt in beiden Verbindungen übereinstimmend 2,46 Å. Mit Hilfe von Röntgen-Einkristallstrukturuntersuchungen konnte gezeigt werden, daß dieser Übergang vonPc nachP2/c offensichtlich nur auf einer Ordnung des H-Atoms beruht, während alle anderen Atome auch bei Zimmertemperatur innerhalb des Fehlers eine zentrosymmetrische Atomanordnung aufweisen.
Schultenite, PbHAsO4, and PbHOP4: Syntheses and crystal structures with a discussion on their symmetry
Summary Schultenite PbHAsO4 [a=4.859(1) Å,b=6.756(1) Å,c=5,843(1) Å, =95.40(1)°] and PbHPO4 [a=4,6838(3) Å,b=6,6451(2) Å,c=5.7817(3) Å =97.138(4)°] are isotypic and crystallize monoclinic. For both compounds a transition from space groupPc toP2/c has been described atT c312 K. The structure type of schultenite is characterized, by a short hydrogen bond between two XO4 tetrahedra which are combined by a center of symmetry in space groupP2/c. The O–H...O bond length is for both these compounds 2.46 Å. Based on X-ray single crystal structure refinements it has been shown, that the transition fromPc toP2/c is obviously caused only by an ordering of the H atom; all the other atoms are also at room temperature centrosymmetrically arranged within limits of error.

Hern Prof.Dr.K.Komarek zum 60.Geburtstag gewidmet

Mit 1 Abbildung  相似文献   

11.
Kokchetavite, a new polymorph of K-feldspar (KAlSi3O8), has been identified as micrometer-size inclusions in clinopyroxene and garnet in a garnet-pyroxene rock from the Kokchetav ultrahigh-pressure terrane, Kazakhstan. Kokchetavite has a hexagonal structure with a =5.27(1) Å, c=7.82(1) Å, V=188.09 Å3, Z=1, and is found to be associated with phengite + /-cristobalite (or quartz) + siliceous glass ± phlogopite/titanite/calcite/zircon, occurring as multi-phase inclusions in clinopyroxene and garnet. It is concluded that kokchetavite could not be an exsolution phase in host minerals. Instead, it might be metastably precipitated from an infiltrated K-rich melt during rock exhumation. Alternatively, although less likely, kokchetavite might be derived from dehydration of K-cymrite, which, in turn, was formed at high pressures. In either case, kokchetavite is a metastable polymorph of K-feldspar.  相似文献   

12.
Zusammenfassung Wasserfreies Eisen(III)sulfat, Fe2(SO4)3, existiert in zwei Modifikationen. Nach Einkristallaufnahmen kristallisiert die eine wahrscheinlich in Raumgruppe (arh=8,791±0,004 Å, =55°52±2; Z=2), die andere in Raumgruppe C 2h 5 –P21/n (a=8,296±0,002 Å, b=8,515±0,002 Å, c=11,60±0,002 Å, =90°30; Z=4). Von Cr2(SO4)3 und Ga2(SO4)3 konnten für die rhomboedrischen Modifikationen, die isotyp zu jener von Fe2(SO4)3 sind, aus Pulveraufnahmen die Gitterkonstanten bestimmt werden.
Summary Anhydrous iron(III)sulfate exists in two modifications. From single-crystal work, one of the modifications crystallizes probably in space group (arh=8.791±0.004 Å, =55°52±2; Z=2), whereas the other in space group C 2h 5 –P21/n (a=8.296±0.002 Å, b=8.515±0.002 Å, c=11.60±0,002 Å, =90°30; Z=4). The lattice constants of the rhombohedral modifications of Cr2(SO4)3 and Ga2(SO4)3, which are isomorphous with rhombohedral Fe2(SO4)3, have been determined from powder photographs.

Herrn Professor Dr.F. Machatschki zum 70. Geburtstag gewidmet.  相似文献   

13.
Zusammenfassung Prehnitkristalle vom Radautal, Harzburg, besitzen die Gitterkonstanten a=4,627 Å, b=5,490 Å, c=18,48 Å, die Raumgruppe P2cm–C 2v 4 , Z=2 für die Formel Ca2Al(OH)2[Si3AlO10]. Es wird gezeigt, daß im Prehnit ein neuer Schichtsilikattyp verwirklicht ist, der einer Vierereinfachschicht [Si3AlO10] 2 entspricht. Die Lage der Schicht, senkrecht zur c-Achse, spiegelt die Spaltbarkeit in dieser Ebene gut wider. Ferner wird ausgeführt, daß in der Struktur des Prehnits vom Radautal die Si/Al-Verteilung einen hohen Ordnungsgrad besitzt.
Summary Prehnite crystals from Radautal, Harzburg, have the lattice parameters a=4.627 Å, b=5.490 Å, c=18,48 Å, the space group P2cm–C 2v 4 , Z=2 for the formula Ca2Al(OH)2[Si3AlO10]. It is proved that in prehnite a new type of layer silicate is realized, in this case a Vierer-single layer [Si3AlO10] 2 . This layer which is perpenticular to the c-axis reflects the cleavage in this plane. It is shown further that in the prehnite structure from Radautal the Si/Al-distribution has a high degree of order.

Mit 4 Textabbildungen  相似文献   

14.
Summary The crystal structure of hydrothermally grown NaFe[SeO4]2 was determined by single crystal X-ray diffraction methods: space group C2/m, a = 8.231(1)Å b = 5.425(1)Å, c = 7.176(1)Å, = 92.44(1)°, V = 320.14Å3, Z = 2; 767 unique data, measured up to 20 = 70° (Mo Kx radiation); R,RW= 0.042, 0.055.NaFe[SeO4]2 is isotypic with yavapaiite, KFe[SO4]2. FeO6 and NaO6 form chains of edge-sharing distorted octahedra with mean Me-O bond lengths of 2.001Å and 2.496Å, respectively, linked via tetrahedral SeO4 groups [
Die Kristallstruktur von NaFe[SeO4]2, einer Verbindung des Yavapaiit-Typsre]19921030
Zusammenfassung Die Kristallstruktur von hydrothermal gezüchtetem NaFe[SeO4]2 wurde mittels Einkristallröntgenmethoden bestimmt: Raumgruppe C2/m, a = 8.231(1)Å, b = 5.425(1)Å, c = 7.176(1)Å, = 92.44(1)°, V = 320.14Å3, Z = 2; 767 unabhängige Intensitätsdaten, Meßbereich bis 20 = 70° (Mo K-Strahlung); R,RW = 0.042, 0.055.NaFe[SeO4]2 ist isotyp mit Yavapaiit, KFe[SO4]2. FeO6 und NaO6 bilden Ketten von kantenverknüpften, verzerrten Oktaedern mit mittleren Me-O Bindungslängen von 2.001Å bzw. 2.496Å, die über tetraedrische SeO4 Gruppen verbunden sind [ = 1.639Å].

Dedicated to Prof. Josef Zemann on the occasion of his 70th birthday

With 3 Figures  相似文献   

15.
Summary The crystal structure of scotlandite —a=4.505(2),b=5.333(2),c=6.405(6) Å, =106.24(3)o; space groupP21/m; cell content 2 {PbSO3} — was determined from singlecrystal X-ray diffractometer data. Scotlandite is isotypic with molybdomenite, PbSeO3. Lead is coordinated to nine oxygen atoms with Pb-Oav=2.75 Å, and possibly further to one sulphur atom with Pb–S=3.46 Å. The average S–O distance in the pyramidal SO3 group is 1.52 Å. The structural relationships to cerussite, PbCO3, are discussed.
Die Kristallstruktur des Scotlandits, PbSO3
Zusammenfassung Die Kristallstruktur des Scotlandits —a=4,505(2),b=5,333(2),c=6,405(6) Å, =106,24(3)o; RaumgruppeP21/m; Zellinhalt 2 {PbSO3} — wurde aus Einkristall-Röntgendiffraktometerdaten bestimmt. Scotlandit ist mit Molybdomenit, PbSeO3, isotyp. Blei wird von neun Sauerstoffatomen mit Pb–Oav=2,75 Å und möglicherweise zusätzlich von einem Schwefelatom mit Pb–S=3,46 Å koordiniert. Der durchschnittliche S–O-Abstand in der pyramidalen SO3-Gruppe mißt 1,52 Å. Die strukturellen Beziehungen zu Cerussit, PbCO3, werden diskutiert.

With 2 Figures  相似文献   

16.
Formation of todorokite from vernadite in Ni-rich hemipelagic sediments   总被引：1，自引：0，他引：1  
Todorokite is considered to form from vernadite in nature and commonly concentrates nickel. However, this mineralogical transformation has never been imaged nor explained mechanistically, and its effect on the uptake of nickel has never been quantified at the molecular-level. We have characterized these reactions at the macroscopic, microscopic, nanoscopic and atomic scales in a marine manganese concretion by combining transmission electron microscopy, electron and X-ray microprobe analysis, powder and micro X-ray diffraction, and Mn and Ni K-edge EXAFS spectroscopy. The concretion was collected during the Ticoflux II expedition near the Nicoya Peninsula, Costa Rica, and is representative of Mn deposits in hemipelagic sediments. It consists of 5 to 25 μm aggregates, shaped like sea-urchins, with a core of 7Å-vernadite (1.0 wt% Ni), a rim of 10Å-vernadite (3.8 wt% Ni), and an outermost region of todorokite fibers (1.9 wt% Ni) that extend outwards. The crystallites of 7Å-vernadite are single- to bi-layered, with hexagonal layer symmetry (a = b = 2.83 Å), and an average structural formula of . The crystallites of 10Å-vernadite contain 10 to 20 layers semi-coherently stacked in the ab plane and uniformly separated in the [0 0 1] direction by ∼9 Å due to the intercalation of hydrated Mg2+ cations. The average structural formula of 10Å-vernadite is if the layers contain vacancy sites, or alternately , if they contain Mn3+. The average formula of todorokite is .A genetic model is proposed based on combining these new data with previously published results. The thermodynamically unstable 7Å-vernadite transforms via dissolution-recrystallization to semi-ordered Mg-rich 10Å-vernadite. Nickel is released from dissolved biogenic silica or reduced organic matter, and taken up mainly in the Mn layer of 10Å-vernadite. Interlayer magnesium serves as a template to the further topotactic transformation of 10Å-vernadite to todorokite. The dimension of the todorokite tunnels in the [0 0 1] direction is uniform and determined by the size of the hydrated Mg2+ ion (8.6 Å). The tunnel dimension in the [1 0 0] direction depends on the density of Mg2+ in the interlayer and the superstructure of the phyllomanganate layer. If the parent phyllomanganate contains high amounts of Mg2+ (i.e., high layer charge), or Mn3+ and Mn4+ cations ordered following the Mn3+-Mn4+-Mn4+ sequence as in synthetic triclinic birnessite, then the tunnel dimension is ideally 3 × 3 octahedral chain widths in both crystallographic directions. Otherwise, the tunnel dimension is incoherent in the [1 0 0] direction (i.e., T(3,n) tunnel structure), as has been observed in all natural todorokites. Natural todorokite is defective because the precursor natural phyllomanganates either have a layer charge deficit below 0.33e per octahedral site, or rarely are triclinic birnessite. The abundance of Mg in seawater and its key role in converting phyllomanganate to tectomanganate with T(3,n) tunnel structure explain why todorokite is common in marine ferromanganese oxides, and seldom present in terrestrial environments. The topotactic phase transformation described here is the only known route to todorokite crystallization. This implies that all natural todorokites may be authigenic because they are formed in situ from a phyllomanganate precursor.  相似文献   

17.
Zusammenfassung Emmonsit kristallisiert triklin, RaumgruppeP , Gitterkonstanten:a 0=7,90 Å,b 0=8,00 Å,c 0=7,62 Å, =96o44, =95o 0, =84o 28,Z=2. Der Strukturtyp wurde aus 3-dimensionalen photographischen Röntgendaten ermittelt. Die Eisenatome werden je von 6 Sauerstoffen verzerrt oktaedrisch koordiniert. Jedes Telluratom wird von 3 Sauerstoffen in einem Abstand <2,0 Å umgeben. Ein vierter Sauerstoff hat bezüglich dieser drei einen um etwa 25–35% größeren Abstand, so daß jedes Telluratom im weiteren Sinne eine (3+1)-Koordination aufweist.
The structure type of emmonsite, {Fe2[TeO3]3·H2O}·xxH2O (x=0–1)
Summary Emmonsite is triclinic with space groupP , and lattice constantsa 0=7.90 Å,b 0=8.00 Å,c 0=7.62 Å, =96o 44, =95o 0, =840 28,Z=2. The structure type is derived from 3-dimensional photographic X-ray data. The iron atoms are coordinated by six oxygens in the form of a distorted octahedron. Each tellurium atom is coordinated to 3 oxygens at a distance <2.0 Å. Compared with these 3 Te–O distance the distance of a fourth oxygen is only 25 to 35% greater; therefore each tellurium atom has a (3+1)-coordination of oxygens.

Mit 2 Abbildungen  相似文献   

18.
Zusammenfassung Die Kristallstruktur des Johannits wurde anhand eines verzwillingten Kristalls von Joachimsthal, Böhmen, mit dreidimensionalen Röntgendaten bestimmt und für 2005 unabhängige Reflexe aufR=0,039 verfeinert. Johannit kristallisiert triklin, RaumgruppeP1, mita=8,903 (2),b=9,499 (2),c=6,812 (2) Å, =109,87 (1) =112,01 (1), =100,40 (1)° undV=469,9 Å3. Chemische Formel und Zellinhalt lauten Cu(UO2)2(OH)2(SO4)2·8H2O, das ist um zwei H2O-Moleküle mehr als bisher angenommen. In der Struktur sind pentagonal dipyramidale (UO2)(OH)2O3-Polyeder paarweise über eine von zwei OH-Gruppen gebildete Kante zu Doppelpolyedern und diese wiederum durch SO4-Gruppen zu (UO2)2(OH)2(SO4)2-Schichten parallel (100) verknüpft. Die Schichten sind parallel über gestreckte Cu(H2O)4O2-Oktaeder und Wassermoleküle miteinander verbunden. Folgende Bindungslängen wurden gefunden: U–O=1,78 Å (2x) und 2,34–2,39 Å (5x); Cu–O=1,97 Å (4x) und 2,40 Å (2x); =1,47 Å; O–O in Wasserstoffbrücken 2,71–2,91 Å (8x) und 3,30 Å.
The crystal structure of johannite, Cu(UO2)2(OH)2(SO4)2·8H2O
Summary The crystal structure of johannite has been determined from threedimensional X-ray data measured on a twinned crystal from Joachimsthal, Böhmen, and has been refined toR=0.039 for 2005 independent reflections. Johannite crystallizes triclinic, space groupP1, witha=8.903 (2),b=9.499 (2),c=6.812 (2) Å, =109.87(1), =112.01(1), =100.40 (1)° andV=469.9 Å3. Chemical formula and cell content are Cu(UO2)2(OH)2(SO4)2·8H2O, by two H2O molecules more than previously assumed. Pairs of pentagonal dipyramidal (UO2) (OH)2O3 polyhedra form double polyhedra by edgesharing via two OH groups. The double polyhedra are linked by the SO4 tetrahedra to form layers (UO2)2(OH)2(SO4)2 parallel zu (100). These layers are interconnected parallel toa by elongated Cu(H2O)4O2 octahedra and water molecules. Following bond lengths have been observed: U–O=1.78 Å (2x) and 2.34–2.39 Å (5x); Cu–O=1.97 Å (4x) and 2.40 Å (2x); =1.47 Å; O–O for hydrogen bonds 2.71–2.91 Å (8x) and 3.30 Å.

Mit 2 Abbildungen  相似文献   

19.
A new high pressure phase with the composition Ca2AlSiO5.5 has been synthesized using an MA-8 apparatus operating at 1700° C and 16 GPa. The phase possesses a structure analagous to CaSiO3 perovskite but with half the Si atoms replaced by Al, and charge balance provided by vacancies in the oxygen sub-lattice. The unit cell possesses a lattice parameter, ao = 3.706 ± 0.003 Å (room P and T value), based on a simple cubic perovskite structure. However, electron diffraction shows that a superstructure has developed parallel to one of the {111} cubic planes with a wavelength of 10.70 Å (equals 5 × ¦d111¦), so that the Ca2AlSiO5.5 cell must be described formally as rhombohedral with a = 11.12 Å and = 27.27 degrees. This rhombohedral cell is metrically cubic, since the distortion of the cubic cell is not determinable from X-ray diffraction patterns obtained so far. The calculated density of this high pressure phase Ca2AlSiO5.5 is 3.64 gm·cm-3. This low density is related in part to the large proportion of oxygen vacancies present in the structure. Because of the low density, this phase is unlikely to be a significant mineralogical constituent of the lower mantle, unless the phase is characterized by extreme compressibility. However, the identification of the phase may be of significance in showing how A12O3 can be accommodated in silicate perovskite via replacement of SiVI in octahedral sites accompanied by production of one oxygen defect for every 2 Al atoms substituted. The possibility that this mode of substitution might be relevant to the incorporation of Al2O3 in MgSiO3 perovskite warrants further study.  相似文献   

20.
Zusammenfassung Die Verbindung Fe2 3+Te4O11 kristallisiert monoklin, RaumgruppeC 2h 5 –P 21/c, sowie den Gitterkonstantena 0=11,88 Å,b 0=6,95 Å,c 0=14,13 Å, =123°44, Z=4. Die Struktur wurde an dreidimensionalen photographischen Röntgendaten ermittelt.R=0,08 für 1365 beobachtete Reflexe. In der Atomanordnung ist ein Eisenatom verzerrt oktaedrisch von sechs, das zweite Eisenatom von fünf Sauerstoffen umgeben. Jedes Telluratom wird von drei Sauerstoffen in einem Abstand 2,10 Å umgeben. Ein vierter Sauerstoff hat bezüglich dieser drei einen um 10 bis 25% größeren Abstand. Der Übergang von einer (3+1)-zu einer 4-Koordination um vierwertiges Tellur wird aufgezeigt.
The crystal structure of Fe2Te4O11
Summary The compound Fe2 3+Te4O11 crystallizes monoclinic, space groupC 2h 5 –P 21/c, with lattice constantsa 0=11.88 Å,b 0=6.95 Å,c 0=14.13 Å, =123°44, Z=4. The crystal structure is derived from 3-dimensional photographic X-ray data.R=0.08 for 1365 observed reflections. In the atomic arrangement one iron is coordinated octahedrally by six oxygens, the other one by five oxygens. Each tellurium atom is coordinated by 3 oxygens with Te–O2.10 Å. Comparable with these 3 Te–O distances the distance of a fourth one is 10 to 25% greater. A transition from (3+1) to 4 in the coordination number around tetravalent tellurium is shown.

Mit 6 Abbildungen  相似文献   

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