Uranyl interactions: The title compound is the first example of an actinide compound that contains three different actinyl‐ion coordination geometries, namely, octahedral, pentagonal bipyramidal, and hexagonal bipyramidal. Strong cation–cation interactions between the uranyl ions lead to pentamers with a rather unusual configuration (see picture; U dark gray, O light gray).
The new mineral saranchinaite, ideally Na2Cu(SO4)2, was found in sublimates of the Saranchinaitovaya fumarole, Naboko Scoria Cone, Tolbachik volcano, Kamchatka, Russia. Its discovery and study has enabled the characterization of the thermal decomposition of kröhnkite and provided an insight into the high-temperature behaviour of other kröhnkite-type materials. Saranchinaite is monoclinic, P21, a = 9.0109(5), b = 15.6355(8), c = 10.1507(5) Å, β = 107.079(2)°, V = 1367.06(12) Å3, Z = 8 and R1 = 0.03. Saranchinaite is a unique mineral in that two of its four independent Cu sites display a very unusual Cu2+ coordination environment with two weak Cu–O bonds of ~2.9–3.0 Å, resulting in [4+1+2] CuO7 polyhedra. Each of the Cu-centred polyhedra shares common corners with SO4 tetrahedra resulting in a [Cu4(SO4)8]8– framework with a complex channel system occupied by Na atoms. Saranchinaite is sensitive to moisture and transforms into kröhnkite within one week when exposed to open air at 87% relative humidity and 25°C. High-temperature X-ray diffraction studies were performed for both kröhnkite (from La Vendida mine, Antofagasta Region, Chile) and saranchinaite. During thermal expansion kröhnkite retains its strongly anisotropic character up to its full dehydration and the formation of saranchinaite at ~200°C, which then transforms back into kröhnkite after exposure to open air. The thermal expansion of saranchinaite is more complex than that of kröhnkite. Saranchinaite is stable up to 475°C with subsequent decomposition into tenorite CuO, thénardite Na2SO4 and unidentified phases.
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Cerianite-(Ce), ideally CeO2, occurs as rounded grains up to 5 μm across in a block of highly altered calcite carbonatite lava from the Kerimasi volcano, and as euhedral crystals up to 200 μm across in carbonatite-derived eluvial deposits in the Kisete and Loluni explosion craters in the Gregory Rift, northern Tanzania. X-ray powder diffraction data (a = 5.434(5) Å) and Raman spectroscopy (minor vibration modes at 184 and 571 cm—1 in addition to a strong signal at 449 cm—1) suggest the presence of essential amounts of large cations and oxygen vacancies in the Kisete material. Microprobe analyses reveal that the mineral contains both light and heavy trivalent rare earth elements (REE) (7.9-15.5 wt.% LREE2O3 and 4.9-9.7 wt.% HREE2O3), and that it is enriched in yttrium (7.1 — 14.5 wt.% Y2O3) and fluorine (2.2—3.5 wt.%). Single-crystal structure refinement of the mineral confirms a fluorite-type structure with a cation—anion distance of 2.3471(6) Å. The cerianite-(Ce) is considered to be a late-stage secondary mineral in the carbonatitic rocks.
White lead or basic lead carbonate, 2PbCO·Pb(OH), the synthetic analogue of hydrocerussite Pb(OH)(CO), has been known since antiquity as the most frequently used white paint. A number of different minerals and synthetic materials compositionally and structurally related to hydrocerussite have been described within the last two decades. Herein, a review is given of general structural principles, chemical variations and IR spectra of the rapidly growing family of hydrocerussite-related minerals and synthetic materials. Only structures containing a hydroxo- and/or oxo-component, i.e. which are compositionally directly related with hydrocerussite and `white lead', are reviewed in detail. An essential structural feature of all the considered phases is the presence of electroneutral [PbCO] cerussite-type layers or sheets. Various interleaved sheets can be incorporated between the cerussite-type sheets. Different sheets are stacked into two-dimensional blocks separated by the stereochemically active 6s lone electron pairs on Pb cations. Minerals and synthetic materials described herein, together with a number of still hypothetical members, constitute a family of modular structures. Hydrocerussite, abellaite and grootfonteinite can be considered to constitute a merotype family of structures. The remaining hydrocerussite-related structures discussed are built on similar principles, but are more complex. Structural architectures of somersetite and slag phase from Lavrion, Attica, Greece, are unique for oxysalt mineral structures in general. Thus, the whole family of hydrocerussite-related phases can be denoted as a plesiotype family of modular structures. The crystal structures of hydrocerussite from Merehead quarry, Somerset, England, and of its synthetic analogue, both determined from single crystals, are reported here for the first time. The results of the infrared (IR) spectroscopy show that this method is useful for distinguishing several different minerals related to hydrocerussite and their synthetic analogues.
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