Refinement of the mangan-neptunite crystal structure

The crystal structure of mangan-neptunite, a manganese analogue of neptunite, has been refined in two space groups (Cc and C2/c). The mineral is monoclinic, with the correct space group Cc; the unit-cell dimensions are: a = 16.4821(6), b = 12.5195(4), c = 10.0292(3) Å, β = 115.474(1)°, and V = 1868.31 ų. The crystal structure has been refined to R ₁ = 0.0307 (wR ₂ = 0.0901) on the basis of 4892 observed reflections with |F _hkl | ≥ 4σ|F _hkl |. The most plausible acentric model is caused by the Ti- and (Fe, Mn, Mg)-ordering in the structure. Ti-octahedrons are strongly distorted and consist of short bond Ti-O (1.7 Å), one long bond (2.2 Å), and four equal bonds (2.0 Å). Fe-octahedrons are regularly shaped, with all Fe-O bonds being approximately identical.     

Refinement of the crystal structure of wöhlerite

Summary The crystal structure of wöhlerite (monoclinicP2₁,a=10.823(3,b=10.244(3),c=7.290(2) Å, =109.00(4)^o) was refined using 2343 independent diffractions toR ₁=0.019 andR ₂=0.025.The refinement confirms the main features of the structure model proposed byShibayeva andBelov (1962), namely the walls of large cation polyhedra interconnected as in cuspidine, with Si₂O₇ groups linked to the polyhedra. At difference from the structure proposed by the quoted authors, both the Si₂O₇ groups are clinging to edges of calcium polyhedra.The cation distribution in the polyhedral walls and the location of fluorine anions are clarified and discussed, resulting in the following crystal chemical formula Na₄(Ca_7.48Mn_0.20Fe_0.32)Zr₂(Nb_1.6Ti_0.4) (Si₂O₇)₄O₄F₂(O_1.6F_0.4).

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Verfeinerung der Kristallstruktur des Wöhlerits

Zusammenfassung Die Kristallstruktur des Wöhlerits (monoklinP2₁,a ₀=10,823(3),b ₀=10,244(3),c ₀=7,290(2) Å, =109,00(4)^o) wurde mit 2343 unabhängigen Reflexen aufR ₁=0,019 undR ₂=0,025 verfeinert.Die Verfeinerung bestätigt im wesentlichen Züge des vonShibayeva undBelov (1962) vorgeschlagenen Strukturmodells, nämlich Bänder aus den Polyedern um die großen Kationen, die — wie im Cuspidin — durch an den Polyedern hängenden Si₂O₇-Gruppen verknüpft sind.Die Kationenverteilung in den Polyederbändern und die Lokalisation der Fluor-Anionen wurden aufgeklärt und werden diskutiert; es ergibt sich folgende kristallchemische Formel Na₄(Ca_7,48 Mn_0,20Fe_0,32)(Zr₂(Nb_1,6 Ti_0,4) (Si₂O₇)₄O₄F₂(O_1,6F_0,4).

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With 3 Figures     

Refinement of the crystal structure of låvenite

Summary The crystal structure of låvenite (monoclinicP2 ₁ /a,a=10.83(1),b=9.98(1),c=7.174(5) Å, =108.1(1)^o), was refined using 1743 independent reflections toR=0.032 andR _w=0.036. The refined structure is in agreement with the structure model proposed bySimonov andBelov (1960), characterized by the presence of walls of large cation polyhedra. These walls are four columns large, linked together by both direct connection as well as by Si₂O₇ groups. The cation distribution inside the wall is explained and compared with that found in other phase of the cuspidine group. The crystal chemical formula resulting from structural and chemical analyses on låvenite from Langesund (Norway) is (Na_6.50Ca_1.47Y_0.03) (Ca_0.93 Mn_1.26Fe _0.87 ²⁺ Ti_0.65Zr_0.18Mg_0.05) (Zr_3.42Nb_0.58) (Si₂O₇)₄O_3.82F_3.98.

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Verfeinerung der Kristallstruktur des Låvenits

Zusammenfassung Die Kristallstruktur des Låvenits (monoklinP2 ₁ /a,a=10,83(1),b=9,98(1),c=7,174(5) Å. =108,1(1)^o) wurde mit 1743 unabhängigen Reflexen aufR=0,032 undR _w=0,036 verfeinert.Die Verfeinerung bestätigt in wesentlichen Zügen das vonSimonov undBelov (1960) vorgeschlagene Strukturmodell, nämlich Bänder aus den Polyedern um die großen Kationen, die sowohl direkt als auch durch an den Polyedern hängende Si₂O₇-Gruppen miteinander verknüpft sind.Die Kationenverteilung in den Polyederbändern wurde aufgeklärt; es ergibt sich folgende kristallchemische Formel: (Na_6,50Ca_1,47Y_0,03) (Ca_0.93Mn_1,26Fe _0,87 ²⁺ Ti_0,65Zr_0,18Mg_0,05) (Zr_3,42Nb_0,58) (Si₂O₇)₄O_3,82F_3,98.

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With 3 Figures     

Lunar ilmenite (Refinement of the crystal structure)

The crystal structure of ilmenites from Mare Tranquillitatis and terrestrial basaltic rocks have been refined from X-ray data using least squares methods. The two structures are virtuallly identical both in structural parameters and relative degree of order. Occupation of Fe and Ti sites is highly ordered. The metal ions have low apparent charges (near 0.3) and formal oxidation states of Fe (II) and Ti (IV).     

Refinement of the crystal structure of beryllonite,NaBePO4

Summary The refined lattice parameters of beryllonite are:a=8.178 (3) Å,b=7.818 (2) Å,c=14.114 (6) Å, =90.00° (2); space groupP2₁/n,Z=12. Integrated Weissenberg photographs were taken by using CuK radiation and multiple film packs. The anisotropic refinement of the crystal structure by means of least-square methods gave a finalR value of 0.063 for the 1388 observed reflections. In the crystal structure PO₄ and BeO₄ tetrahedra, linked by shared oxygen atoms in a three-dimensional network, form pseudo-ditrigonal rings perpendicular to theb axis. The independent Na atoms lying in the channels formed by the rings are coordinated as an irregular nine-cornered polyhedron and as distorted octahedra.

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Verfeinerung der Kristallstruktur des Beryllonits,NaBePO ₄

Zusammenfassung Verfeinerte Gitterkonstanten des Beryllonits lauten:a=8,178 (3) Å,b=7,818 (2) Å,c=14,114 (6) Å, =90,00 (2)°; Raumgruppe:P2₁/n,Z=12. Integrierte Weissenbergaufnahmen wurden mit CuK-Strahlung und multiplen Filmpaketen aufgenommen. Die anisotrope Verfeinerung der Kristallstruktur nach der Methode der kleinsten Quadrate ergab für 1388 beob. Reflexe einen abschließendenR-Wert von 0,063. In der Kristallstruktur bilden PO₄-und BeO₄-Tetraeder, die über gemeinsame Sauerstoffe zu einem dreidimensionalen Gerüst verknüpft sind, pseudo-ditrigonale Ringe senkrecht zurb-Achse. Die kristallographisch unabhängigen Arten von Na-Atomen, welche in den aus Ringen gebildeten Kanälen liegen, sind in der Form eines unregelmäßigen neuneckigen Polyeders bzw. in der Form verzerrter Oktaeder koordiniert.

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With 2 Figures     

Refinement of the crystal structure of papagoite,CaCuAlSi2O6(OH)3

Summary The crystal structure of papagoite, CaCuAlSi₂O₆(OH)₃, monoclinic,a = 2.926 (3),b = 11.496 (3),c = 4.696 (1) Å, = 100.81 (2)°, V = 685.4 (3) ų, space groupC 2/m,Z = 4, has been refined to anR index of 3.4% for 913 observed reflections measured with MoK X-radiation. The single unique Cu cation is surrounded by six anions in a pseudo-octahedral arrangement showing strong Jahn-Teller distortion. Edge-sharing rutile-like chains of pseudo-octahedrally coordinated Cu and Al extend in the Y direction, and are cross-linked into an octahedral sheet by Ca₂Ø₁₀ (O = unspecified ligand, O or OH) dimers. These sheets are linked by (Si₄O₁₂) rings to form a mixed tetrahedral-octahedral framework.

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Verfeinerung der Kristallstruktur von Papagoit, CaCuAlSi₂O₆(OH)₃

Zusammenfassung Die Kristallstruktur von Papagoit, CaCuAlSi₂O₆(OH)₃, monoklina = 12,926 (3),b = 11.496 (3),c = 4.696 (1) Å, = 100.81 (2)°,V = 685.4 (3) ų, RaumgruppeC2/m,Z = 4, wurde für 913 beobachtete, MoK-Röntgenstrahlung gemessene Reflexe aufR = 3,4% verfeinert. Das eine symmetrieunabhängige Kupfer-Kation ist pseudooktaedrisch von sechs Anionen mit einer starken Jahn-Teller-Verzerrung umgeben. Die pseudo-oktaedrisch koordinierten Cu- und Al-Atome werden über Kanten zu parallel zur y-Achse verlaufenden rutil-ähnlichen Ketten verbunden, die zusammen mit den Ca₂Ø₁₀-Gruppen (Ø = nicht spezifsierter Ligand, O bzw. OH) Oktaederschichten bilden. Diese Schichten werden durch (Si₄O₁₂)-Ringe zu einem aus Tetraedern und Oktaedern bestehenden Netzwerk verknüpft.

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With 4 Figures     

Refinement of the crystal structure of bonshtedtite, Na3Fe(PO4)(CO3)

The crystal structure of bonshtedtite, Na₃Fe(PO₄)(CO₃) (monoclinic, P2₁/m, a = 5.137(4), b = 6.644(4), c = 8.908(6) Å, β = 90.554(14)°, V = 304.0(4) ų, Z = 2) has been refined to R ₁ = 0.041 on the basis of 1314 unique reflections. The structure is similar to that of other minerals of the bradleyite group. It is based on the [Fe(PO₄)(CO₃)]^3? layers oriented parallel to (001). The layers are formed by corner-sharing PO₄ tetrahedra and FeO₄(CO₃) complexes, where FeO₆ tetrahedra and CO₃ triangles are edge-shared. The topology of the octa-tetrahedral layer in bonshtedtite is similar to that of the autunite-group minerals, but it differs from the latter in terms of local topological properties.     

In situ determination of crystal structure for high pressure phase of ZrO2 using a diamond anvil and single crystal X-ray diffraction method

Combining a miniature diamond-anvil pressure cell with a single crystal four-circle diffractometer, the crystal structure of a synthetic ZrO₂ has been studied in situ up to 51 kbar at room temperature. The space group of the unquenchable orthorhombic high pressure phase is Pbcm. The directions of the b and c axes are preserved through the transition and the transformation is displacive. The coordination configurations of the Zr atoms and oxygen atoms are the same in the high pressure and low pressure phases. The orthorhombic high pressure phase has a higher entropy than that of low pressure monoclinic phase.     

Refinement of a lunar FeO mapping method

Clementine UVVIS and NIR data from the lunar sampling sites (totaling 46 sampling sites) were processed and used to refine the iron determination method of Le Mouéic et al. (2000, 2002). We found that about 21 sampling sites are unsuitable to Le Mouéic et al's spectral parameters ("slope" and "depth l") because their 1500 nm filter could not be used as spectral parameters' right shoulders and to evaluate the depth of the 1-μm absorption feature accurately. We used the rest 25 sampling sites to refine the method developed by Le Mouéic et al. (2000, 2002 ) and obtained our own equation of FeO content determination. We tested our own equation, and the results are satifactory. In our work we also acquired some useful experiences in scientific applications of our own dataset of the Chang'E-1 mission.     

基于氮吸附法的页岩有机孔隙结构表征

页岩的微观孔隙结构对页岩气的赋存至关重要,气体吸附法可以较好对页岩的微观孔隙结构进行表征。通过测量丁页1井不同深度样品的矿物含量、RO值和TOC含量,结果表明丁页1井龙马溪组页岩样品的矿物含量比较稳定,有机质成熟度变化不大,均为过成熟。通过低温氮吸附法计算样品的比表面积和微、介孔容积和孔径分布,结果表明：（1）样品的平均孔径为2.8 ~ 4.9 nm,10 nm以下的孔隙提供了大部分的微、介孔容积。微、介孔容积为0.00136 ~ 0.0108 cm3/g,平均0.004 cm3/g,比表面积为2.54 ~ 13.69 m2/g,平均6.68 m2/g;（2）微、介孔容积、比表面积和TOC三者之间有很强的正相关性。通过计算TOC含量为0时的微、介孔容积和比表面积推算无机孔和有机孔之间的比例和其对比表面积的影响,发现有机孔提供了大部分的微、介孔容积,有机孔还是比表面积的主要贡献因素;（3）样品的吸附曲线符合IPUAC分类中的第IV型吸附曲线,样品的脱附曲线反映样品孔隙形态随TOC含量的增加,由楔形孔（不定型孔）变为连通的墨水瓶型孔（狭缝型孔）或墨水瓶型孔。     

Refinement and comparison of the crystal structures of a dolomite and of an Fe-rich ankerite

Summary The crystal structures of a dolomite and of an iron rich ankerite were refined from three-dimensional X-ray data by least squares methods toR0.03. The angle of rotation of the CO₃ group is 6.35(5)^o in dolomite but only 5.28(5)^o in ankerite, a consequence of the different sizes of the (Mg, Fe)O₆ octahedra. The carbonate group deviates very slightly from planarity in both minerals. The Ca–O distances are somewhat larger in both minerals than in calcite; the Mg–O distance in dolomite, on the contrary, is somewhat smaller than in magnesite.

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Verfeinerung und Vergleich der Kristallstrukturen eines Dolomits und eines Fe-reichen Ankerits

Zusammenfassung Die Kristallstrukturen eines Dolomits und eines eisenreichen Ankerits wurden aus dreidimensionalen Röntgendaten mittels der Methode der kleinsten Quadrate aufR0,03 verfeinert. Der Verdrehungswinkel der CO₃-Gruppe ist im Dolomit 6,35(5)^o, im Ankerit nur 5,28(5)^o; das ist eine Folge der unterschiedlichen Größen der (Mg, Fe)O₆-Oktaeder. Die Gestalt der Karbonatgruppe weicht in beiden Mineralen ganz leicht von planar ab. Die Ca–O-Abstände sind in beiden Mineralen etwas größer als im Calcit, der Mg–O-Abstand ist hingegen im Dolomit etwas kleiner als im Magnesit.

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With 1 Figure     

Re-examination of the crystal structure of weberite

Summary The crystal structure of weberite, Na₂MgAlF₇, was redetermined from 3-dim. X-ray data and refined by least squares methods in space groupImma to a conventional reliability factorR=0.036. Mg and Al have octahedral 6-coordination. Two crystallographically independent kinds of Na atoms form different NaF₈-polyhedra with the F atoms at the corners of a flattened hexagonal bipyramid and of a square prism, respectively.

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Neubestimmung der Kristallstruktur des Weberits

Zusammenfassung Die Kristallstruktur des Weberits, Na₂MgAlF₇, wurde aus 3-dim. Röntgendaten neu hestimmt und mit der Methode der kleinsten Quadrate in RaumgruppeImma auf den konventionellen ZuverlässigkeitsfaktorR=0,036 verfeinert. Mg und Al haben oktaedrische 6-Koordination. Zwei kristallographisch unabhängige Arten von Na-Atomen bilden mit den F-Atomen zwei verschiedene NaF₈-Polyeder; in einem sitzen die F-Atome an den Ecken einer abgeflachten hexagonalen Bipyramide, im anderen an den Ecken eines quadratischen Prismas.

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With 2 Figures     

Aktashite Cu6Hg3As4S12 from the Aktash deposit, Altai, Russia: Refinement and crystal chemical analysis of the structure

The composition and structure of aktashite from the Aktash deposit, Gorny Altai, Russia, have been studied by electron microprobe and X-ray structural analysis. On the basis of close compositions and crystal structures, the identity of aktashite from the Gal-Khaya and Aktash deposits has been demonstrated. Crystals of aktashite are of trigonal symmetry; the unit-cell dimensions are: a = 13.7500(4), c = 9.3600(3) Å, V = 532.54(8) ų, space group R3, Z = 3 for the composition of Cu₆Hg₃As₄S₁₂, R = 0.043. The structure of aktashite as a framework of vertex-shared HgS_4? and CuS_4? tetrahedrons of the same orientation is intimately related to the sphalerite-type structure. The earlier identified uncommon cluster group [As₄] has been verified and its parameters have been refined. It is shown that the structure may be represented as construction blocks (As₄S₁₂)_12? packed according to the law of the distorted cubic I-cell.     

The crystal structure of sarcolite

Summary The crystal structure of sarcolite from Monte Somma (Vesuvius), Na(Na, K, Fe, Mg)<1 Ca₆[Al₄Si₆O₂₃](OH, H₂O)<2 [(Si,P)O₄]_0.5[(CO₃, Cl)]_0.5, space groupI4/m witha=12,343(5)Å,c=15,463(5)Å andZ=4, has been determined from X-ray data collected on an automatic diffractometer. The 1637 independent reflections withI>2 (I) converged to a conventionalR value of 0.054 with partially anisotropic factors.The tetrahedral framework in sarcolite has a sharing coefficient of 1.85. Mean Si–O and Al–O distances are 1.616 and 1.763 Å, respectively. Isolated (Si, P)O₄, CO₃, OH, H₂O and Cl species occupy cavities in the tetrahedral framework in a partially disordered way. The two crystallographically different Ca atoms coordinate respectively with 5 and 6 framework oxygens; further contacts occur with available anions. Ca–O distances range from 2.34 to 2.69 Å. Na atoms coordinate with 4 oxygens of the tetrahedral frame and one from the CO₃ groups.A structure analysis of a sarcolite crystal baked out at 1100°C confirmed some structural details involving atoms occupying cavities in the tetrahedral framework.

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Die Kristallstruktur des Sarkoliths

Zusammenfassung Die Kristallstruktur des Sarkoliths vom Monte Somma (Vesuv), Na(Na, K, Fe, Mg)<1 Ca₆[Al₄Si₆O₂₃](OH, H₂O)<2[(Si, P)O₄]_0,5[(CO₃, Cl)]_0,5, RaumgruppeI4/m,a ₀=12,343(5)Å,c ₀=15,463(5)Å,Z=4, wurde aus Röntgendaten, die auf einem automatischen Diffraktometer gesammelt worden waren, bestimmt. Der konventionelleR-Wert für 1637 kristallographisch unabhängige Reflexe mitI>2 (I) konvergierte mit partiell anisotropen Temperaturfaktoren auf 0.054.Der Verknüpfungskoeffizient des Tetraedergerüstes in Sarkolith ist 1,85. Die mittleren Si–O-bzw. Al–O-Abstände sind 1,616Å und 1,763 Å. Isolierte Strukturbestandteile (Si, P)O₄, CO₃, OH, H₂O und Cl besetzen zum Teil ungeordnet die Hohlräume des Tetraedergerüstes. Die beiden kristallographisch verschiedenen Ca-Atome werden von funf bzw. sechs Sauerstoffen des Gerüstes koordiniert, weitere Kontakte bestehen zu verfügbaren Anionen. Die Ca–O-Abstände variieren von 2,34 bis 2,69 Å. Die Na–Atome sind von vier Sauerstoffen des Tetraedergerüstes und von einem weiteren der CO₃-Gruppen koordiniert. Die Strukturanalyse eines bei 1100°C getemperten Sarkolithkristalls bestätigte einige Details über die Atome, welche die Hohlräume des Tetraedergerüstes besetzen.

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With 4 Figures