Crystal structure of daqingshanite

Daqinshanite, a new mineral recently discovered in China, is a kind of strontium-rare earth-bearing phosphate-carbonate. The ideal formula is: (Sr, Ca, Ba), RF(PO₄)(CO₃)₃. The mineral belongs to the trigonal system. The intensity data were collected with a single-crystal four-circle diffractometer. The lattice parameters are given as:a=10.058(±0.002) Å;c=9.225(±0.003) Å. Space group=R3m,Z=3. The crystal structure was solved by Patterson and electron density synthesis methods. The least-squares refinement led to a final conventional factorR=0.079. Crystal structural analysis shows that daqingshanite is of calcite-type structure and the ordered model of cations is similar to that of huntite (Mg₃Ca(CO₃)₄).     

Crystal structure of xinganite

Xinganite is a new REE-Be-rich silicate discovered in China. Its ideal formula is: (Y, Ce)Be SiO₄ OH. The mineral is of monoclinic system. The intensity data were collected with a single-crystal four-circle diffractometer. The lattice parameters are: a=4.7681 (± 0.00263) Å,b=7.7657 (± 0.00686) Å, c=9.9301 (± 0.00639) Å; α =90°, β=90.171° (±0.0053°), γ=90° space group p2¹/c;,Z=4. The crystal structure has been determined by direct methods and electron density synthesis methods. The least squares refinement gave a final discrepancy indexR=0.086. The crystal structural analysis shows that xinganite is of datolite-type structure.     

Crystal structure of magnetite under pressure

The crystal structure and the unit-cell parameters of magnetite have been studied at room temperature up to a pressure of 4.5 GPa using a diamond anvil cell and a four-circle X-ray diffractometer. The isothermal bulk modulus (K _T ) and its pressure derivative (K' _T ) determined by fitting the pressure-volume data to the Murnaghan equation of state are 181(2) GPa and 5.5(15), respectively. The positional parameter u does not vary significantly over the pressure range of this study. The linear compressibilities of the interatomic distances and the bulk moduli of the polyhedra have been calculated from the pressure dependences of the unit-cell edge a and the u parameter. The Bloch equation has been modified to derive a relationship between the Néel temperature and the parameter u. The modified Bloch equation gives a closer agreement with the experimental results than the Weisz equation.     

Crystal structure of meteoritic schreibersites: determination of absolute structure

Minerals of the schreibersite–nickelphosphide series (Fe,Ni)₃P crystallize in the non-centrosymmetric space group . As a consequence, they can possess two different spatial arrangements of the constituting atoms within the unit cell, related by the inversion symmetry operation. Here, we present the crystal structure refinements from single crystal X-ray diffraction data for schreibersite grains from iron meteorites Acuña, Carlton, Hex River Mts. (three different crystals), Odessa (two different crystals), Sikhote Alin, and Toluca aiming for the determination of the absolute structure of the examined crystals. The crystals studied cover the composition range from ~58 mol% to ~80 mol% Fe₃P end-member. Unit-cell parameter a and volume of the unit cell V, as well as certain topological structural parameters tightly correlate with Fe₃P content. Unit-cell parameter c, on the other hand, does not show such strong correlation. Eight of the nine crystal structure refinements allowed unambiguous absolute structure assignment. The single crystal extracted from Toluca is, however, of poor quality and consequently the structure refinement did not provide as good results as the rest of the materials. Also, this crystal has only weak inversion distinguishing power to provide unequivocal absolute structure determination. Six of the eight unambiguous absolute structure determinations indicated inverted atomic arrangement compared to that reported in earlier structure refinements (here called standard). Only two grains, one taken from Odessa iron and the other from the Hex River Mts. meteorite, reveal the dominance of standard crystal structure setting.     

Crystal structure of columbite under high pressure

The structural evolution of two columbites under pressure, one ferrocolumbite from Raode (Africa) and one manganocolumbite from Kragero (Norway), has been determined by single-crystal X-ray diffraction. Structural investigations at high pressure have been carried out on samples which were preliminarily annealed to attain the complete cation-ordered state. For each crystal, five complete datasets have been collected from room pressure up to ca. 7 GPa. Structure refinements converged to final discrepancy factors R ranging between 5.2 and 5.8% for both the crystals. Structure refinements of X-ray diffraction data at different pressures allowed characterisation of the mechanisms by which the columbite structure accommodates variations in pressure. A and B octahedral volumes in both samples decrease linearly as pressure increases, with a larger compression of the larger A site. The difference in polyhedral bulk moduli of the A sites for the two samples does not appear to relate directly to the octahedral sizes, the A site being more compressible in the Fe-rich sample than in the Mn-rich one. By far the most compressible direction in both the analysed samples is along b. The cations are in fact free to move along this direction, thus allowing the octahedral chains to slide over each other; this effect is particularly evident in the manganocolumbite sample which shows a steep shortening of interchain A–B distances along b.     

Crystal structure and growth fabric of length-fast chalcedony

Chalcedony from Brazilian agates, has been investigated by using transmission-electron microscopy, X-ray-diffraction, thermogravimetry and optical techniques. The quartz fibers of length-fast chalcedony are composed of submicroscopical polysynthetic, lamellar-twinned right- and lefthanded crystals, according to the Brazil law. This very narrow twinning causes 3 systems of diffuse diffraction streaks (corresponding to the three-fold symmetry) parallel to 〈10.1〉, very frequently possessing an intensity maximum at h±1/2, k, l±1/2. These extra reflections were detected both in electron- and X-ray-diffraction patterns. Wall-lining chalcedony is parallel fibrous consisting of smaller crystallites with a higher total water content (0.06±0.01 μm and 1.2±0.1 wt %) than spherulitic chalcedony in horizontal agate bands (ca. 0.1 μm and 0.7±0.1 wt%).     

Crystal structure model for metavoltine from Sierra Gorda

Summary The crystal structure of metavoltine from Sierra Gorda, Chile, has been solved from photographic X-ray data by the heavy atom method. The space group used wasP3 witha=9.575(5) andc=18.17(1)Å; cell content: K₂Na₆ (Fe ²⁺, Cu, Zn)Fe ₆ ³⁺ (SO₄)₁₂O₂·18H₂O. From the relatively small number and the somewhat poor quality of the X-ray data, the least squares refinement did not give very satisfactory results-especially so for the light atoms. Therefore, steric considerations and information from the Fourier maps were also used when choosing the final atomic coordinates. The salient features of the structure are clusters of Fe ₃ ³⁺ O(H₂O)₃(SO₄)₆ with Fe³⁺ in octahedral coordination, and Fe²⁺(H₂O)₆ octahedra. The Na⁺ ions show octahedral coordination, the K⁺ ions irregular nine coordination.

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Ein Kristallstrukturmodell für den Metavoltin von Sierra Gorda

Zusammenfassung Die Kristallstruktur des Metavoltins von Sierra Gorda (Chile) wurde aus photographischen Röntgendaten mit der Schweratommethode gelöst. Als Raumgruppe wurdeP3 mita ₀9,575(5) undc ₀=18,17(1) Å verwendet; Zellinhalt K₂Na₆ (Fe ²⁺, Cu, Zn) Fe ₆ ³⁺ (SO₄)₁₂O₂·18H₂O.Wegen der relativ kleinen Zahl und der nicht sehr guten Qualität der Röntgendaten gab die Verfeinerung nach der Methode der kleinsten Quadrate keine sehr guten Ergebnissebesonders nicht für die leichten Atome. Deshalb wurden zur Festlegung der endgültigen Atomkoordinaten auch sterische Überlegungen und Informationen aus Fouriersynthesen herangezogen. Hervorstechende Züge der Struktur sind Gruppen Fe ₃ ³⁺ O(H₂O)₃(SO₄)₆ mit Fe³⁺ in oktaedrischer Koordination sowie Fe²⁺(H₂O)₆-Oktaeder. Die Na⁺-Ionen zeigen oktaedrische Koordination, die K⁺-Ionen unregelmäßige 9-Koordination.

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With 4 Figures     

Crystal structure of nitrate cancrinite synthesized under low-temperature hydrothermal conditions

Doklady Earth Sciences -     

Machatschkiite: Crystal structure and revision of the chemical formula

Summary Single crystal X-ray investigation shows that machatschkiite crystallizes in space groupR3c witha _hex =15.127(2) Å andc _hex =22.471(3) Å. The crystal structure was determined by direct methods and Fourier syntheses; the refinement by least squares methods led toR=0.04 for 645 independent reflections. Our X-ray results, supplemented by a partial electron microprobe analysis, indicate that the chemical formula of machatschkiite is close to Ca_6–x Na _x (AsO₄)(AsO₃OH)₃(PO₄)_1–x (SO₄) _x ·15H₂O (x0.3) withZ _hex =6. The atomic arrangement of machatschkiite represents a new structure type and seems to be the first example of a crystal structure in which three oxygens of an AsO₄ group are acceptors of each one hydrogen bond from three surrounding AsO₃(OH) groups.

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Machatschkiit: Kristallstruktur und Revision der chemischen Formel

Zusammenfassung Röntgenographische Einkristalluntersuchungen zeigten, daß Machatschkiit in der RaumgruppeR3c mita _hex =15,127(2) Å undc _hex =22,471(3) Å kristallisiert. Die Kristallstruktur wurde mit direkten Methoden und mit Fourier-Synthesen bestimmt; die Verfeinerung nach der Methode der kleinsten Quadrate führte für 645 Reflexe aufR=0.04. Unser Röntgenbefund, der durch eine partielle Elektronenstrahlmikroanalyse ergänzt wird, weist darauf hin, daß die chemische Formel des Machatschkiites mit guter Näherung Ca_6–x Na _x (AsO₄)(AsO₃OH)₃ (PO₄)_1–x (SO₄) _x ·15H₂O (x0,3) mitZ _hex =6 lautet. Die Atomanordnung des Machatschkiites stellt einen neuen Strukturtyp dar und ist anscheinend das erste Beispiel, in welcher drei Sauerstoffe einer AsO₄-Gruppe Akzeptoren von je einer Wasserstoffbindung dreier benachbarter AsO₃OH-Gruppen sind.

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With 4 Figures

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Dedicated to the memory of Prof. Dr.F. Machatschki, Editor of Tschermaks Mineralogische und Petrographische Mitteilungen 1948–1968.     

Crystal structure refinement and electron density distribution in diaspore

Diaspore from Dilln, Hungary, AlOOH, is orthorhombic with space group Pbnm, a=4.4007(6), b=9.4253(13), c=2.8452(3) Å, and Z=4. The crystal structure and electron distribution have been refined from 791 graphite-monochromatized MoKα data (maximum 2θ=130°) to R=0.035 (R _w =0.029). Difference maps show substantial electron density ascribed to covalent bonding in the hydroxyl group, O(2)-H, but no residual density is observed along the Al-O(1,2) bonds. An analysis of the charge distribution implies net charges of +1.47(26), ?1.08(16), ?0.59(13) and +0.20(5) for Al, O(1), O(2) and H respectively. Semi-empirical molecular orbital calculations of the Hückel type agree with the experimentally determined atomic charge distribution and also allow a rationalization of the observed bond length variations.     

Crystal structure and cation distribution in some natural magnetites

Summary The crystal structures of two natural magnetites were refined. Both turned out to have equipoints 8a and 16d (Fd3m) fully occupied and hence different from type I and type II defect structures investigated by Fleet (1981, 1982). It was possible to improve the cation radii for Fe²⁺ ad Fe³⁺ in octahedral and tetrahedral coordinations for pure and almost pure magnetites obtaining very good agreement between observed and calculated values of the two independent geometric structure parameters, i.e. cell edge and oxygen coordinate. The present results lead to an estimate of inversion parameter i in (Fe _1–i ²⁺ Fe _i ³⁺ )(Fe _i ²⁺ Fe _2t-i ³⁺ )O₄, of about 0.90, equal for all the four pure magnetites, independently of type of structure and also of cooling history.

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Kristallstruktur und kationverteilung von einigen natürlichen magnetiten

Zusammenfassung Die Kristallstrukturen von zwei natürlichen Magnetiten wurden verfeinert. Es stellte sich heraus, daß ihre Gitterplätze 8 a und 16d (Fd 3 m) voll besetzt sind, und sich somit von den von Fleet (1981, 1982) bestimmten Defektstrukturen unterscheiden. Die Kationradien für Fe²⁺ und Fe³⁺ in Oktaeder- und Tetraeder-Koordinationen wurden für reine und fast reine Magnetite verbessert. Dabei wurde eine gute Korrelation zwischen beobachteten und berechneten Werten der beiden unabhängigen Parameter in der Struktur, d.h. Gitterkonstante und Sauerstoff-Ortsparameter gefunden. Die vorliegenden Ergebnisse bringen einen Umkehrparameter i in (Fe _1–i ²⁺ Fe _i ³⁺ )(Fe _i ²⁺ Fe _2–i ³⁺ )O₄ von ungefähr 0.90, der in allen reinen Magnetiten gleich und unabhängig von dem Strukturtyp sowie dem Abkühlverhalten ist.

     

白钨矿晶体结构及微量元素替代机理

白钨矿是钨矿床中主要的载钨矿物,其独特的晶体结构使其富含微量元素,被广泛用于示踪钨成矿过程与流体源区。本文对南岭地区氧化型矽卡岩、还原型矽卡岩、黑钨矿-石英脉型、白钨矿-石英脉型、(矽卡岩-)云英岩型、(石英脉-)云英岩型钨矿床中白钨矿开展矿物组合和X-射线单晶衍射分析,实验结果显示：(1)白钨矿晶体结构存在一定差异,矽卡岩型钨矿中白钨矿Ca-O键长变化较大(0.0043 nm),石英脉型钨矿中白钨矿次之(0.0035 nm),云英岩型钨矿中白钨矿最小(0.0034 nm);(2) Ca-O键长的差异对最优替代稀土元素影响较大,氧化型矽卡岩钨矿中白钨矿从成矿早期到晚期,最优替代稀土元素从Pr-Nd(进变质阶段)、Pr-Sm(退变质阶段)转变为Nd-Sm(石英-方解石-萤石阶段),而(石英脉-)云英岩型钨矿中白钨矿呈现以Sm³⁺为中心(Nd-Gd)的最优替代元素;(3)矽卡岩型和云英岩型钨矿中白钨矿,稀土元素主要通过Nb⁵⁺耦合替代和空位替代进入白钨矿晶格,石英脉型钨矿的白钨矿中,稀土元素主要通过空位替代和Na⁺耦合替代进...     

Crystal structure and crystallographic properties of a Schröckingerite from Joachimsthal

Summary The crystal structure of a schröckingerite from Joachimsthal, NaCa₃[UO₂(CO₃)₃](SO₄) F·10H₂O, triclinic, space groupP1,a=9.634(1),b=9.635(1),c=14.391(2) Å, -91.41(1), =92.33(1), =120.26(1)°,V=1151 ų,Z=2, has been determined by X-ray diffraction and refined toR=0.026 for 5451 reflections. The structure contains NaCa₃[UO₂(CO₃)₃] (SO₄) F·6H₂O layers built up from UO₂(CO₃) ₃ ^4– anions, NaO₃(H₂O)₃ octahedra, three kinds of CaO₅F(H₂O)₂ polyhedra, Ca₃F pyramids and Ca-bonded SO₄ tetrahedra. These layers extend atz1/5 andz4/5 parallel to (001). They are linked parallel to c exclusively by hydrogen bonds, both directly as well as via interlayer H₂O molecules. The structure shows a striking trigonal pseudosymmetry within the range 0.04<z<0.96. Atz0 these parts of the structure are dislocated relative to each other by a step of 1 Å parallel to [110]. Morphologic and optical properties of schröckingerite have been investigated in the light of the known crystal structure.

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Kristallstruktur und kristallographische Eigenschaften eines Schröckingerits von Joachimsthal

Zusammenfassung Die Kristallstruktur eines Schröckingerits von Joachimsthal, NaCa₃[UO₂(CO₃)₃](SO₄) F·10H₂O, triklin, RaumgruppeP1,a=9,634(1),b=9,635(1),c=14,391(2) Å, =91,41(1), =92,33(1), =120,26(1)°,V=1151 ų,Z=2, wurde mit Röntgenbeugung bestimmt und für 5451 Reflexe aufR=0.026 verfeinert. Die Kristallstruktur enthält NaCa₃[UO₂(CO₃)₃] (SO₄)I·6H₂O Schichten, die aus UO₂(CO₃) ₃ ^4– . Anionen, NaO₃(H₂O)₃-Oktaedern, drei Arten von CaO₅F(H₂O)₂-Polyedern, Ca₃ F-Pyramiden und an Ca gebundenen SO₄-Tetraedern aufgebaut sind. Diese Schichten erstrecken sich inz1/5 undz4/5 parallel zu (001). Sie sind parallel zuc ausschließlich durch Wasserstoffbrücken verknüpft, und zwar sowohl direkt als auch indirekt durch zwischen den Schichten gelegene Wassermoleküle. Die Struktur zeigt im Bereich 0,04<z<0,96 eine ausgeprägte trigonale Pseudosymmetrie. Derartige Bereiche sind inz0 um etwa 1 Å parallel zu [110] stufenartig gegeneinander versetzt. Morphologische und optische Eigenschaften von Schröckingerit wurden im Licht der bekannten Kristallstruktur untersucht.

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With 6 Figures     

Crystal structure of the yavapaiite type compound NaFe[SeO4]2

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 = 320.14ų, Z = 2; 767 unique data, measured up to 20 = 70° (Mo Kx radiation); R,R_W= 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 = 320.14ų, Z = 2; 767 unabhängige Intensitätsdaten, Meßbereich bis 20 = 70° (Mo K-Strahlung); R,R_W = 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].

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

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With 3 Figures     

Crystal structure refinement and reflectance measurements of hausmannite,Mn3O4

Summary The crystal structure of hausmannite from Langbån, Sweden, was refined with 462 independent X-ray diffraction data toR = 0.036 (R_W = 0.034). The Jahn-Teller distortion of the Mn³⁺O6 octahedron is relatively strong: Mn³⁺ -O = 1.930 (1) Å (4 x), 2.282 (1) Å (2 x), and the anisotropies of the thermal vibrations of Mn^3- and O differ clearly from those of the corresponding atoms in cubic spinels. It is shown that, from a stereochemical point of view, the hausmannite structure-type is not the only geometrically possible Jahn-Teller distortion of the spinel-type. The reflectance of hausmannite was measured on an oriented cut plate with polarized light (k = 400–700 nm) in air and in oil immersion, and the refractive indices and absorption coefficients were derived.

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Kristallstrukturverfeinerung und reflexionsmessungen am Hausmannit, Mn₃O₄

Zusammenfassung Die Kristallstruktur eines Hausmannits von Langbån, Schweden, wurde an Hand von 462 unabhängigen Einkristall-Röntgendiffraktometerdaten zu einemR = 0.036 (R _w = 0.034) verfeinert. Die Jahn-Teller-Verzerrung des Mn3+O_6-Oktaeders ist relativ stark: Mn^3--O = 1.930 (1) Å (4 x); 2.282 (1) Å (2 x), und die Anisotropien der thermischen Schwingungen von Mn3 und O unterscheiden sich deutlich von denen analoger Atome in kubischen Spinellen. Es wird gezeigt, daß aus einer stereochemischen Sicht der Strukturtyp des Hausmannits nicht die einzig geometrisch mögliche JahnTeller-Verzerrung des Spinell-Typs ist. Das Reflexionsvermögen des Hausmannits wurde an einer orientiert geschnittenen Platte mit polarisiertem Licht ( = 400–700 nm) in Luft und in Ölimmersion gemessen und Brechungsindizes und Absorptionskoeffizienten wurden bestimmt.

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With 2 Figures