Karlditmarite (IMA 2021-003), Cu9O4(PO4)2(SO4)2, is a new mineral species from an active Arsenatnaya fumarole, Tolbachik volcano, Kamchatka peninsula, Russia.Karlditmarite occurs as green prismatic crystals. The mineral is biaxial (-), with alpha = 1.872(2)degrees, beta = 1.835(3)degrees, and gamma = 1.810(3)degrees (589 nm). Under the microscope, karlditmarite is green with weak pleochroism. Electron microprobe analysis provided the empirical formula (Cu8.614Zn0.175Al0.053Ca0.019Fe0.157)(P1.574S1.814As0.444V0.109Si0.059)O20. Karlditmarite is triclinic, P1: a = 6.1256(7) & Aring;, b = 7.9192(8) & Aring;, c = 7.9866(8) & Aring;, alpha = 75.173(2)degrees, beta = 86.639(2)degrees, gamma = 88.660(2)degrees, V = 373.87(7) & Aring;3. The crystal structure (R1 = 0.039) is unique. The infinity 2Cu9O410+ ${ }_{\infty}<^>{2}\left[\mathrm{Cu}_{9} \mathrm{O}_{4} ight]<^>{10+}$ layer in karlditmarite can be described as composed of six-membered rings, in which two of the six OCu4 tetrahedra share a common edge. The interlayer space between the bends of the highly corrugated infinity 2Cu9O410+ ${ }_{\infty}<^>{2}\left[\mathrm{Cu}_{9} \mathrm{O}_{4} ight]<^>{10+}$ layers hosts phosphate tetrahedra, whereas sulfate tetrahedra are situated above the centers of the rings. Karlditmarite is the first anhydrous Cu phosphate-sulfate mineral among more than 100 copper oxysalt mineral species known from the active fumaroles. In addition, phosphorus geochemistry in fumarolic environments is discussed here.

Thermal expansion of the mineral soddyite, (UO2)2SiO4(H2O)2, and structurally related synthetic compound Na2(UO2)2SiO4F2 ( NAUSIF ) has been studied by means of high-temperature single-crystal and powder X-ray diffraction. The mineral is orthorhombic, Fddd, while NAUSIF is tetragonal, I41/amd. The framework structures of both compounds are comprised of either neutral [(UO2)2(SiO4)(H2O)2] or negatively charged [(UO2)2(SiO4)F2]2- chains of similar topology. In the structure of soddyite, the chains cross at the angle of 72 degrees, while in NAUSIF of 90 degrees. Upon increasing temperature, the acute inter-chain angles in soddyite increase due to hinge deformations, the overall symmetry approaching tetragonal. The mineral is stable below 325 +/- 25 degrees & Scy;; between 325 and 640 degrees & Scy;, the decomposition products cannot be identified unambiguously and contain significant amount of amorphous phases; at higher temperatures, a mixture of U3O8 polymorphs is formed. NAUSIF is stable until its melting point of 625 +/- 25 degrees & Scy;. The thermal expansion of both compounds is strongly anisotropic; for NAUSIF , it is due to difference in bond strength in the uranium and sodium polyhedra. Anisotropic thermal expansion of soddyite is controlled by shear deformations of the structure upon the temperature rise.

Single crystals of two new calcium perrhenates, anhydrous Ca(ReO 4 ) 2 ( 1 ) and K 2 Ca 3 (ReO 4 ) 8 ·4H 2 O ( 2 ), were prepared during solid-state and solution attempts to prepare the potassium analog of NaCa(ReO 4 ) 3 . Both structures can be regarded as frameworks comprised of vertex-sharing CaO 8 and ReO 4 polyhedra. 1 is a complete structural analog of Sr(ReO 4 ) 2 while 2 corresponds to its own structure type. It is also the first hydrated binary perrhenate to date. We discuss the similarities and differences in the structures of alkaline earth perrhenates and pertechnetates; existence of more complex and elegant metal-perrhenate architectures is predicted.

We investigated crystal structures and the mechanism of thermal expansion of weeksite and its synthetic analogues (K-, Rb-, Cs-) using a combination of geometrical-topological analysis and empirical methods (powder X-ray diffraction, infrared spectroscopy, scanning electron microscopy, single-crystal and powder X-ray variable-temperature diffraction). The weeksite sample studied herein was collected at the Anderson mine, Yavapai County, Arizona, USA. Its synthetic analogues were prepared using high-temperature approaches in sealed silica tubes. Natural weeksite is stable up to 860 +/- 10 degrees C; it dehydrates between 100-200 degrees C. Its synthetic analogues with Rb and Cs are stable at least until 1000 degrees C. Their thermal expansion is strongly anisotropic due to shear deformations of the crystal structure. The framework in the structure of weeksite can be regarded as a sequence of uranyl silicate layers linked by SiO4 tetrahedra. With increasing temperature, the angles at the Si-O-Si 'hinges' change, which causes the shear deformations. The differences in the thermal behaviour, including expansion anisotropy, are probably due to the nature (size) of the alkali cations occupying the cavities in the framework. The partial or complete replacement of Rb+ by Cs+ illustrates the zeolite-like nature of the uranyl silicate framework in weeksite. Therefore, its structure can be considered a possible candidate for the selective immobilization of 137Cs+ upon storing nuclear waste with little interference from the more abundant Na+ and K+.

Новый уранил силикат калия и рубидия (K0.67Rb0.33)2[(UO2)2(Si5O13)](H2O) (1) получен методом синтеза из расплава в вакуумированной кварцевой ампуле. Соединение кристаллизуется в ромбической сингонии, Pbca, a = 14.1909(4), b = 14.0406(5), c = 17.9151(7) Å, V = 3569.6(2) Å3, R1 = 0.03. В кристаллической структуре нового соединения слои [Si5O13]6- объединяются с цепочками из урановых полиэдров с образованием микропористого гетерополиэдрического каркаса, содержащего каналы размером 9.63×3.34 Å, в которых располагаются смешанно-заселенные позиции катионов щелочных металлов. В статье приводится кристаллохимическое сравнение нового соединения со структурами родственных соединений и минералов.

A synthetic analog of mourite (SM), (UO2)Mo5O14(OH)4(H2O)2, has been hydrothermally synthesized at 220 degrees & Scy; and characterized using single-crystal X-ray diffraction, single-crystal and powder X-ray diffraction studies at non-ambient temperatures, X-ray photoelectron spectroscopy, infrared spectroscopy, thermal, and chemical analyses. SM is monoclinic, P2/c, a = 9.9063(6), b = 7.1756(4), c = 12.2105(7) & Aring;, beta = 102.496(6)degrees, V = 847.41(9) & Aring;3; the crystal structure has been refined to R1 = 0.043. The chemical composition of the SM is (the Mo2O5:MoO3 ratio obtained from X-ray photoelectron spectroscopy, H2O by stoichiometry; wt.%): Mo2O5 = 4.61, MoO3 = 61.06, UO3 = 26.95, H2O = 6.76, total 99.38. The empirical formula calculated on the basis of 22 oxygen atoms per formula unit with MoV + MoVI = 5 is (UVI1.03O2)[(MoVI4.63MoV0.37)Sigma 5.00O13.81(OH)0.19] (OH)4(H2O)2. The crystal structure of SM contains UO8, Mo1O6, Mo2O5(H2O), and Mo3O4(OH)2 polyhedra that share vertices and edges to form layers linked by hydrogen bonds only. SM is stable up to 250 +/- 10 degrees & Scy;. Upon heating, continuous dehydration occurs between 160-250 degrees & Scy; until the formation of amorphous products; crystallization above 450 degrees & Scy; produces UO2MoO4, MoO3, and UMo10O32. Below 250 degrees & Scy;, thermal expansion of the compound is strongly anisotropic, with the maximal direction perpendicular to the plane of the layers.

Structures of a family of new hydrated and anhydrous perrhenates of lead and strontium have been determined. Sr(ReO4)2·H2O is isostructural to Ce(CrO4)2·H2O and Th(CrO4)2·H2O; Pb(ReO4)2·2H2O is analogous to Sr(ReO4)2·2H2O and Pb(TcO4)2·2H2O. The compounds Sr(ReO4)2·6H2O, Pb(ReO4)Cl·2H2O, and Pb4(OH)4(ReO4)4·H2O correspond to new structural architectures. We discuss the similarities and differences in the crystal structures of relatively simple inorganic salts containing tetrahedral oxoanions based on d-elements (MnO4−, TcO4−, ReO4−, CrO42−, and MoO42−); the analogies to tetrahedral p-based hydrido- or fluoroanions (BF4− and AlH4−) exist but are as yet rare.

A new uranyl silicate [(K,Na) 4 Cl 2 ][(UO 2 ) 6 (Si 2 O 7 ) 2 F 2 ] ( 1 ) was obtained from melt in evacuated silica tubes. The crystal structure of 1 is orthorhombic, Pnma , a = 36.8677(7), b = 7.7946(2), c = 19.1931(4) Å, V = 5,515.5(2) Å 3 . It represents a microporous framework comprised of Ur O 5 and Ur O 4 F pentagonal bipyramids and Si 2 O 7 disilicate groups. The framework contains two types of channels with the size of 8.14 × 8.66 and 6.38 × 4.42 Å 2 ; the smaller ones host the potassium cations while the larger ones contain more complex alkali-chloride species.

A new uranyl silicate Cs-4[(UO2)(5)(SiO3OH)(2)O2F4] (1), was obtained via a hydrothermal route. The new compound is monoclinic, P2(1)/n, a = 8.3870(2), b = 13.4612(2), c = 10.9503(2) & Aring;, beta = 91.223(2)degrees, V = 1236.00(4) & Aring;(3); the structure has been solved and refined down to R-1 = 0.022. Therein, the phosphouranylite units (PUs) associate into a new type of uranyl-silicate layers, [(UO2)(5)(SiO3OH)(2)O2F4](4-), which interleave with the Cs+ cations. Topological analysis of PU based structures indicates that these layers in 1 provide a unique example of complexes constructed only via association of the PU and not involving other building units.

We report synthesis and crystal structure of a new copper molybdate oxosulfate Cu6O2(MoO4)3(SO4). The new compound is obtained in evacuated silica ampoules at 675-725 °C. Cu6O2(MoO4)3(SO4) is monoclinic, space group P21/m, a = 7.5208(4) Å, b = 6.8602(3) Å, c = 14.0019(7) Å, β = 93.471(5)°, V = 721.09(6) Å3, R1 = 0.051. The 3D framework of the new compound consists of oxo-centered [OCu3]4+ chains and MoO4 and SO4 tetrahedra. The structural motif of the new compound is related to the previously described fumarole minerals, glikinite Zn3O(SO4)2 and vergasovaite Cu3O(MoO4)(SO4). The crystal chemical peculiarities of this group of synthetic compounds and minerals are discussed.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Polythermic single-crystal X-ray studies of chalcocyanite CuSO 4 , dolerophanite Cu 2 OSO 4 , and kamchatkite KCu 3 O(SO 4 ) 2 Cl have established their melting points as well as peculiarities of their thermal expansion. Association of oxocentered and sulfate tetrahedra in dolerophanite and kamchatkite leads to the formation of rigid tetrahedral “backbones” only slightly sensitive to thermal variations. Rigid complexes can also be distinguished in the structure of chalcocyanite, if we consider only the system of the shortest and strongest Cu–O and S–O bonds. The anisotropy of the thermal expansion can be explained by either rigid complexes drifting parallel to each other (as in dolerophanite and chalcocyanite), or radial and angular distortions in the polyhedra of alkali cations. The presence of a tetrahedrally coordinated additional oxygen atom in the structure of dolerophanite and kamchatkite leads to an increase in the principal eigenvalues. The demonstrated rigidity of the sulfate tetrahedra in studied anhydrous copper sulfate minerals explains the absence of phase transitions up to the melting temperatures. The variation of chemical composition leads to changes in their thermal decomposition points. Chlorine-containing kamchatkite decomposes at the lowest temperature of 590(5) K, next are chalcocyanite 675(10) K, and dolerophanite 925(10) K.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Systematic studies of crystalline compounds formed in aqueous systems containing aliphatic diamines, divalent transition metal halides, and selenious acid resulted in the discovery of a large family of new complex species corresponding to several new structure types. With ethylenediamine (en), layered (enH2)[M(HSeO3)2X2] compounds are the most commonly formed species which constitute a significant contribution to the family of layered hydrogen selenites containing neutral [M(HSeO3)2] (M = Mg, Mn, Co, Ni, Cu, Zn, Cd) 2D building blocks. In contrast to some previous suggestions, piperazine (pip), as well as its homologue N-methylpiperazine, mostly give rise to quite different, sometimes more complex, structures of varied dimensionality while the (pipH2)[M(HSeO3)2X2] compounds are formed only with M = Cu and Cd. In addition, metal-, halide-, or selenium-free by-product species are observed. The SeIV can be present in a multitude of forms, including H2SeO3, HSeO3−, SeO32−, and Se2O52−, reflecting amazing adaptability to the shape of the templating cations.

To date, uranyl silicates are mostly represented by minerals in nature. However, their synthetic counterparts can be used as ion exchange materials. A new approach for the synthesis of framework uranyl silicates is reported. The new compounds Rb2[(UO2)2(Si8O19)](H2O)2.5 (1), (K,Rb)2[(UO2)(Si10O22)] (2), [Rb3Cl][(UO2)(Si4O10)] (3) and [Cs3Cl][(UO2)(Si4O10)] (4) were prepared at harsh conditions in “activated” silica tubes at 900 °C. The activation of silica was performed using 40% hydrofluoric acid and lead oxide. Crystal structures of new uranyl silicates were solved by direct methods and refined: 1 is orthorhombic, Cmce, a = 14.5795(2) Å, b = 14.2083(2) Å, c = 23.1412(4) Å, V = 4793.70(13) Å3, R1 = 0.023; 2 is monoclinic, C2/m, a = 23.0027(8) Å, b = 8.0983(3) Å, c = 11.9736(4) Å, β = 90.372(3) °, V = 2230.43(14) Å3, R1 = 0.034; 3 is orthorhombic, Imma, a = 15.2712(12) Å, b = 7.9647(8) Å, c = 12.4607(9) Å, V = 1515.6(2) Å3, R1 = 0.035, 4 is orthorhombic, Imma, a = 15.4148(8) Å, b = 7.9229(4) Å, c = 13.0214(7) Å, V = 1590.30(14) Å3, R1 = 0.020. Their framework crystal structures contain channels up to 11.62 × 10.54 Å filled by various alkali metals.

Thermal expansion of metatorbernite, Cu(UO2)2(PO4)2(H2O)8 (1), and metazeunerite, Cu(UO2)2(AsO4)2(H2O)8 (2), has been investigated using single-crystal and powder X-ray diffraction. Both minerals are prone to dehydration, which proceeds already at ambient conditions. According to the single-crystal XRD data, 1 is stable up to 300(50) K, while 2 is stable up to 250(50) K. Powder XRD studies at various temperatures suggest that 1 dehydrates in three stages at ca. 353, 373, and 483 K, while 2 in two stages at ca. 283 and 543 K. Calculation of the main coefficients of thermal expansion reveals strong anisotropy. The expansion is maximal in the direction normal to the autunite-type layers. This correlates with the anisotropy in thermal evolution of Cu–O bond lengths and differences in the thermal behavior of PO4 and AsO4 tetrahedra.

An entry from the Inorganic Crystal Structure Database, the world’s repository for inorganic crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the joint CCDC and FIZ Karlsruhe Access Structures service and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Abstract A new rubidium uranyl silicate, Rb2(UO2)2O(Si3O8) (1), was obtained using high-temperature approach from the melt in silica tubes. Its crystal structure was solved by direct methods: hexagonal, P6/m, a = 27.7992(7), c = 7.2346(2) Å, V = 4841.8(3) Å3, R1 = 0.033. The structure of 1 represents a new structure type with unprecedented topology not observed before among U(VI) oxides and oxysalts. It is comprised of layers with large voids derived from the U3O8 structure formed exclusively by pentagonal UrO5 bipyramids. The low-occupied Rb sites are located in the interlayer space. The SiO4 silicate tetrahedra in the structure of 1 share vertices to form rolled [Si6O16]8− chains. The nanotubules [(UO2)(Si6O16)]6− penetrate through both U3O8-derived layers and Rb interlayer. These tubules are attached to the U3O8 derived sheets via uranyl-uranyl interactions and edge-sharing between silicate tetrahedra and UrO5 bipyramids.

AbstractNapoliite, ideally Pb2OFCl, is a new fluoroxychloride mineral found in a specimen from a fumarole formed subsequent to the 1944 eruption of Vesuvius volcano, Naples Province, Italy. It occurs as well-shaped lamellar crystals up to 0.25 × 0.25 × 0.01 mm typically forming clusters up to 0.4 × 0.4 mm on the surface of volcanic scoria in association with anglesite, artroeite, atacamite, calcioaravaipaite, cerussite, challacolloite, cotunnite, hephaistosite, manuelarossiite, matlockite and susannite. Napoliite is colourless with white streak and adamantine lustre. It is brittle and has a laminated fracture. Cleavage is perfect on {001}. Dcalc = 7.797 g cm–3. The calculated mean refractive index is 2.10. Chemical composition (wt.%, electron microprobe) is: PbO 91.71, F 3.89, Cl 7.34, –O=(F+Cl) –3.30, total 99.64. The empirical formula calculated on the basis of 3 anions is Pb1.999O0.997F0.996Cl1.007. Raman spectroscopy confirms the absence of OH– groups and H2O molecules in the mineral. Napoliite is tetragonal, space group P42/mcm, a = 5.7418(11), c = 12.524(4) Å, V = 412.9(2) Å3 and Z = 4. The strongest lines of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are: 3.860 (85) (111); 3.139 (20) (004); 2.914 (100) (113); 2.866 (63) (200); 2.118 (19) (204); 2.027 (19) (220); 1.665 (20) (313); and 1.642 (23) (117). The crystal structure was refined to R1 = 0.024 for 222 reflections with F > 4σ(F). It is based on lead oxide blocks derived from that of litharge PbO, which alternate with layers of chloride ions. Napoliite represents a new structure type with a unique order/disorder pattern of fluorine and oxygen atoms. The new mineral is dimorphous with rumseyite. It is named after the city of Naples (Napoli in Italian).

Studies of the oxygen-rich part of the PbO-PbI2 system revealed existence of a novel Pb8O7I2 which can be prepared via both solid-state and hydrothermal routes. The new compound exhibits a new and complex structure type formed by [Pb8O7](2+) rod-like chains formed by OPb4 tetrahedra and OPb3 pyramids. Pb8O7I2 exhibits high transparency in the 550-2000 nm range; experimental and quantum chemical data indicate that it is a semiconductor with E-g approximate to 2.6 eV consistent with the intense yellow color.