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Dark-green platy crystals of the compound P[b.sub.31][O.sub.22][Br.sub.10][C.sub.l8] is obtained by rapid quenching of a lead oxide halide melt. The structure of P[b.sub.31][O.sub.22][Br.sub.10][C.sub.l8] can be viewed as incorporation of [Pb[X.sub.6]][.sup.4-] halide units (X=Br, Cl) into the defect PbO matrix.

The synthesis and structure of (C4H12N)(sub 14)[(UO2)(sub 10)(SeO4)(sub 17)(H2O)] a first amine-templated uranyl selenate based upon highly porous uranyl selenate nanotubules is described. This finding demonstrates the possibility of nanostructures for actinides in higher oxidation states.

Single crystals of Rb2CaCu6(PO4)4O2 were synthesized by a hydrothermal method in the multicomponent system CuCl2–Ca(OH)2–RbCl–B2O3–Rb3PO4. The synthesis was carried out in the temperature range from 690 to 700 K and at the general pressure of 480–500 atm [1 atm = 101.325 kPa] from the mixture in the molar ratio 2CuO:CaO:Rb2O:B2O3:P2O5. The crystals studied by single‐crystal X‐ray analysis were found to be monoclinic, space group C2, a = 16.8913 (4), b = 5.6406 (1), c = 8.3591 (3) Å, β = 93.919 (3)°, V = 794.57 (4) Å3. The crystal structure of Rb2CaCu6(PO4)4O2 is similar to that of shchurovskyite and dmisokolovite and is based upon a heteropolyhedral open framework formed by polar layers of copper polyhedra linked via isolated PO4 tetrahedra. The presence of well‐isolated 2D heteropolyhedral layers in the title compound suggests low‐dimensional magnetic behavior which is masked, however, by the fierce competition between multiple ferromagnetic and antiferromagnetic exchange interactions. At TC = 25 K, Rb2CaCu6(PO4)4O2 reaches a magnetically ordered state with large residual magnetization. [ABSTRACT FROM AUTHOR]

The high‐temperature (HT) behaviour of lobanovite, K2Na(Fe2+4Mg2Na)Ti2(Si4O12)2O2(OH)4, was studied using in situ powder X‐ray diffraction in the temperature range 25–1000°C and ex situ single‐crystal X‐ray diffraction of 17 crystals quenched from different temperatures. HT iron oxidation associated with dehydroxylation starts at 450°C, similar to other ferrous‐hydroxy‐rich heterophyllosilicates such as astrophyllite and bafertisite. A prominent feature of lobanovite HT crystal chemistry is the redistribution of Fe and Mg+Mn cations over the M(2), M(3), M(4) sites of the octahedral (O) layer that accompanies iron oxidation and dehydroxylation. This HT redistribution of cations has not been observed in titanosilicates until now, and seems to be triggered by the need to maintain bond strengths at the apical oxygen atom of the TiO5 pyramid in the heteropolyhedral (H) layer during oxidation–dehydroxylation. Comparison of the HT behaviour of lobanovite with five‐coordinated Ti and astrophyllite with six‐coordinated Ti shows that the geometry of the Ti polyhedron plays a key role in the HT behaviour of heterophyllosilicates. The thermal expansion, geometrical changes and redistribution of site occupancies which occur in lobanovite under increasing temperature are reported. A brief discussion is given of minerals in which the cation ordering (usually for Fe and Mg) occurs together with iron oxidation–dehydroxylation at elevated temperatures: micas, amphiboles and tourmalines. Now this list is expanded by the inclusion of titanosilicate minerals. [ABSTRACT FROM AUTHOR]

Thermal behavior of three copper molybdates, lindgrenite, Cu3(MoO4)2(OH)2, szenicsite Cu3(MoO4)(OH)4, and cupromolybdite, Cu3O(MoO4)2, has been studied by high-temperature X-ray powder diffraction in the temperature range of 25–900 °C. The decomposition of lindgrenite and formation of cupromolybdite were observed at T > 325 °C according to the reaction: Cu3(MoO4)2(OH)2 → Cu3O(MoO4)2 + H2O. Szenicsite decomposes to cupromolybdite and tenorite at T > 350 °C according to the reaction: 2Cu3(MoO4)(OH)4 → Cu3O(MoO4)2 + 3CuO + 2H2↑. Cupromolybdite is stable up to 825 °C. The thermal expansion of lindgrenite, szenicsite and cupromolybdite is strongly anisotropic; the values of αmax/αmin are 5.6, 11.0 and 4.3, respectively. The maximal/minimal thermal expansion refers to the dominant direction of long/short Cu–O bonds owing to the distortion of CuO6 octahedral geometry due to the Jahn–Teller effect. For all three Cu molybdates, there are more or less aligned orientations of Jahn–Teller-distorted (CuO6) octahedra, which allows calculating the average 〈Cu–O〉 bond lengths along particular crystallographic directions. The 〈Cu–O〉 values observed are found to be in good correlation with the observed anisotropy of thermal expansion. The additional O2− anions in cupromolybdite act as coordination centers that form four strong Cu–O bonds each. These bonds propagate along the direction of the minimal thermal expansion, thus showing that the anion-centered structural motifs in cupromolybdite are the strongest after the Mo6+-centered (MoO4) tetrahedra. [ABSTRACT FROM AUTHOR]

Hydrotalcite, ideally [Mg6Al2(OH)16](CO3)(H2O)4, was studied in samples from Dypingdal, Snarum, Norway (3 R and 2 H), Zelentsovskaya pit (2 H) and Praskovie–Evgenievskaya pit (2 H) (both Southern Urals, Russia), Talnakh, Siberia, Russia (3 R), Khibiny, Kola, Russia (3 R), and St. Lawrence, New York, USA (3 R and 2 H). Two polytypes, 3 R and 2 H (both 'classical'), were confirmed on the basis of single-crystal and powder X-ray diffraction data. Their chemical composition was studied by electron-microprobe analysis, infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. The crystal structure of hydrotalcite-3 R was solved by direct methods in the space group R $ {\bar 3} $ m on three crystals (two data collections at 290 K and one at 120 K). The unit-cell parameters are as follows (290/290/120 K): a = 3.0728(9)/3.0626(3)/3.0617(4), c = 23.326(9)/23.313(3)/23.203(3) Å and V = 190.7(1)/189.37(4)/188.36(4) Å3. The crystal structures were refined on the basis of 304/150/101 reflections to R 1 = 0.075/0.041/0.038. Hydrotalcite-2 H crystallises in the P 63/ mmc space group; unit-cell parameters for two crystals are (data collection at 290 K and 93 K): a = 3.046(1)/3.0521(9), c = 15.447(6)/15.439(4) Å, V = 124.39(8)/124.55(8) Å3. The crystal structures were refined on the basis of 160/142 reflections to R 1 = 0.077/0.059. This paper reports the first single-crystal structure data on hydrotalcite. Hydrotalcite distribution in Nature, diagnostic features, polytypism, interlayer topology and localisation of M 2+– M 3+ cations within metal hydroxide layers are discussed. [ABSTRACT FROM AUTHOR]

Zuktamrurite, FeP2, is a new mineral, a natural iron diphosphide found in the pyrometamorphic rocks of the Hatrurim Formation, in the southern part of the Negev Desert, Israel and on the Transjordan Plateau, Jordan. The mineral occurs as irregular grains up to 50 µm in size associated with murashkoite, FeP, and barringerite, (Fe,Ni)2P. In reflected light, zuktamrurite is white with a distinct bluish tint. It is non-pleochroic but exhibits distinct anisotropy in bluish colours. Reflectance values for the IMA COM recommended wavelengths are [Rmax/Rmin, % (λ, nm)]: 50.40/47.20 (470); 49.16/46.23 (546); 48.97/46.16 (589); 49.40/46.40 (650). It is brittle. Electron microprobe analysis of the holotype specimen gave the following chemical composition (wt%, average of 5 points): Fe 40.23; Ni 7.97; P 51.70; total 99.90. The empirical formula calculated on the basis of 3 apfu is (Fe0.86Ni0.16)1.02P1.98 corresponding to FeP2. Zuktamrurite is orthorhombic, space group Pnnm, unit cell parameters refined from the single-crystal data: a 4.9276(6), b 5.6460(7), c 2.8174(4) Å, V 78.38(1) Å3, Z = 2. Dx = 5.003 g cm−3. The crystal structure was solved and refined to R1 = 0.0121 on the basis of 109 unique reflections with I > 2σ(I). The strongest lines of the powder X-ray diffraction pattern [(d, Å) (I, %) (hkl)]: 3.714 (54) (110); 2.820 (31) (020); 2.451 (100) (120, 101); 2.242 (55) (111); 1.760 (37) (211). The mineral is named for the Zuk-Tamrur cliff (Dead Sea) located nearby the type locality, the Halamish Wadi, southern Negev Desert, Israel. Zuktamrurite is the phosphide analogue of löllingite (loellingite), FeAs2. It is the most phosphorus-rich phosphide ever found in nature. [ABSTRACT FROM AUTHOR]

Single crystals of new Mn2[Bi2O](SeO3)4 (I), MnBi(SeO3)2Cl (II), MnIIMnIII(SeO3)2Cl (III), Mn5(SeO3)2Cl6 (IV), and Mn4(Mn5,Bi)(SeO3)8Cl5 (V) have been synthesized by chemical vapour transport and hydrothermal methods. They have been structurally characterized by single crystal X-ray diffraction analysis. The compounds II–V are the first Mn selenite chlorides, while the I, II and V compounds are the first Bi-containing Mn oxoselenites. Structural relationships of the new phases with other compounds are discussed. An overview of the mixed-ligand MnOmCln polyhedra in inorganic compounds is given. [ABSTRACT FROM AUTHOR]

The crystal structure of thornasite, [Na.sub.12][Th.sub.3][[[Si.sub.8][O.sub.19].sub.4][([H.sub.2]O).sub.18], Z = 6, rhombohedral, a = 29.124(1), c = 17.2602(9) [Angstrom], V = 12,679.2(9) [[Angstrom].sup.3], space group R3c, has been solved by direct methods, and refined to an agreement index (RI) of 5.7% calculated, based on 2266 unique observed reflections collected using MoK[Alpha] X-radiation and a CCD-based detector. The structure consists of a new interrupted silicate framework with composition [[[Si.sub.8][O.sub.19]].sup.6-]. The framework density is 15.4 atoms per 1000 [[Angstrom].sup.3], which is typical for microporous aluminosilicate materials. The framework density, together with the presence of a three-dimensional network of channels in the structure, permit thornasite to be designated as a new member of the zeolite structure family. The framework consists of cubic cages and distorted six-membered rings linked via common edges. The circuit symbol is ([4.sup.3][14.sup.3])[([4.sup.3][6.sup.2]14).sub.3][([6.sub.2]10).sub.6]. Interruptions of the framework are caused by the presence of [Th.sup.4+] cations that are coordinated by eight O atoms. [Na.sup.+] cations and [H.sub.2]O groups are located in channels through the structure. The theoretical parent framework for thornasite may be constructed by the insertion of two additional Si atoms in place of one Th atom. The theoretical framework density is 18.0 atoms per 1000 [[Angstrom].sup.3]; the circuit symbol is [4.sup.3][10.sup.3])[([4.sup.3][6.sup.2]10).sub.6] [([4.sup.3][6.sup.2]8).sub.3][([4.sup.3]6.8.10).sub.3][([4.sup.2][6.s up.2]8.10).sub.3][([4.sup.1][6.sup.3]8.10).sub.3].

Philipsburgite, Cu5Zn((As,P)O4)2(OH)6·H2O, from the Middle Pit, Gold Hill Mine, Tooele Co., Utah, USA, was studied by single-crystal X-ray diffraction and scanning electron microscopy. The empirical formula of the studied sample is (Cu4.69Zn1.23)(As0.86P0.18O4)2(OH)5.61·H2O, which agrees well with the previous reports on the mineral. Philipsburgite is monoclinic, P21/c, a = 12.385(6), b = 9.261(4), c = 10.770(5) Å, β = 97.10(1)o, V = 1225.7(9) Å3 (at 100 K), and Z = 4. The crystal structure was refined to R1 = 0.046 for 2563 unique observed reflections with |Fo| ≥ 4σF. The crystal structure of philipsburgite is isotypic to that of kipushite and can be considered as a complex three-dimensional framework consisting of two types of layers stacked parallel to the a-axis. The A-type layer is formed by the edge-sharing Jahn-Teller-distorted Cuφ6 octahedra [φ = O2−, (OH)−, H2O]. Two adjacent octahedral layers are linked via (As2O4) tetrahedra. The B-type layer is built by corner-sharing (ZnO4) and (As1O4) tetrahedra and is formed by the four- and eight-membered tetrahedral rings. The A:B ratio of the A and B layers is equal to 2:1. The hydrogen bonding network in philipsburgite is rather complex and consists of two- and three-center hydrogen bonds. The As1 site accommodates ca. 18% of P and is a preferable position for the P substitution in philipsburgite. The observed selectivity of the As1 site for P may indicate that, for the intermediate compositions with the P:As ratios close to 1:1, there is a fully ordered species with P prevalent at the As1 site and As prevalent at the As2 site. The intermediate composition would, therefore, be Cu5Zn(AsO4)(PO4)(OH)6·H2O and such a mineral can be considered as a separate species, according to the rules of the International Mineralogical Association (IMA). Philipsburgite should be considered as structurally complex with the Shannon information contents of 4.954 bits/atom and 614.320 bits/cell. The obvious reason for the structural complexity of the mineral is its modularity, i.e., the presence of two structurally distinct modules, the octahedral-tetrahedral (A) and tetrahedral (B) layers. [ABSTRACT FROM AUTHOR]