Crystal Chemistry and Structural Complexity of the Uranyl Vanadate Minerals and Synthetic Compounds

Tschauner O., Bermanec M.

Rules that control the arrangement of chemical species within crystalline arrays of different symmetry and structural complexity are of fundamental importance in geoscience, material science, physics, and chemistry. Here, the volume of crystal phases is normalized by their ionic volume and an algebraic index that is based on their space-group and crystal site symmetries. In correlation with the number of chemical formula units Z, the normalized volumes exhibit upper and lower limits of possible structures. A bottleneck of narrowing limits occurs for Z around 80 to 100, but the field of allowed crystalline configurations widens above 100 due to a change in the slope of the lower limit. For small Z, the highest count of structures is closer to the upper limit, but at large Z, most materials assume structures close to the lower limit. In particular, for large Z, the normalized volume provides rather narrow constraints for the prediction of novel crystalline phases. In addition, an index of higher and lower complexity of crystalline phases is derived from the normalized volume and tested against key criteria.

Faudoa-Gómez F.G., Fuentes-Cobas L.E., Esparza-Ponce H.E., Canche-Tello J.G., Reyes-Cortés I.A., Fuentes-Montero M.E., Eichert D.M., Rodríguez-Guerra Y., Montero-Cabrera M.

Margaritasite is a mineral compound discovered in the early 1980s in Chihuahua, Mexico. It is a natural cesium uranyl vanadate found only, so far, in the Margaritas mine of the Peña Blanca highlands. In this work, a thorough characterization of the aforementioned mineral is presented. The portfolio of the techniques employed includes high-resolution X-ray diffraction, scanning electron microscopy with energy dispersive X-ray spectroscopy, transmission electron microscopy in selected area electron diffraction (SAED) mode, and X-ray absorption spectroscopy (XAS). After extensive data analysis and modeling, new information on the mineral has been retrieved. Its phase composition is margaritasite–carnotite: a solid solution of cesium and potassium uranyl vanadate [(Cs,K)2(UO2)2(VO4)2·nH2O], and margaritasite, which is practically pure cesium uranyl vanadate [Cs2(UO2)2(VO4)2·nH2O]. The crystal structure of both components presents the space group P 1 21/c 1. Yet, each phase has similar, but appreciably different, lattice parameters. The mineral has a lamellar tabular and prismatic morphology. SAED patterns confirm the crystal structure of margaritasite. XAS spectra of Cs, V, and U confirm the elemental composition, oxidation states, and interatomic distances of this structure. These findings are consistent with the presence of cesium in this unique mineral from the paragenesis point of view.

Kuporev I.V., Kalashnikova S.A., Gurzhiy V.V.

This paper reviews not the largest, but at the same time quite an interesting, group of natural and synthetic uranyl molybdate compounds. Nowadays, nine minerals of U and Mo are known, but the crystal structures have only been reported for five of them. Almost an order of magnitude more (69) synthetic compounds are known. A significant discrepancy in the topological types for natural and synthetic phases is shown, which is most likely due to elevated temperatures of laboratory experiments (up to 1000 °C), while natural phases apparently grow at significantly lower temperatures. At the same time, the prevalence of dense topologies (with edge-sharing interpolyhedral linkage) among natural phases can be noted, which is fully consistent with other recently considered mineral groups. Uranyl molybdates demonstrate several similarities with compounds of other U-bearing groups; however, even topological matches do not lead to the appearance of completely isotypic compounds. Structural complexity calculations confirm, in general, crystal chemical observations. Considering the prevalence of dense structures in which coordination polyhedra of uranium and molybdenum are connected through common edges as well as framework architectures, one can expect a less significant influence of interlayer species on the formation of the crystal structure than the main U-bearing complexes. The more structural complexity of the uranyl molybdate units, the more complex of the entire crystal structure is. In addition, there is a tendency for complexity to increase with increasing density of the complex; the simplest structures are vertex-shared, while the complexity increases with the appearance of common edges.

Durova E.V., Kuporev I.V., Gurzhiy V.V.

This paper reviews the state of the art in the structural chemistry of organically templated uranyl sulfates and selenates, which are considered as the most representative groups of U-bearing synthetic compounds. In total, there are 194 compounds known for both groups, the crystal structures of which include 84 various organic molecules. Structural studies and topological analysis clearly indicate complex crystal chemical limitations in terms of the isomorphic substitution implementation, since the existence of isotypic phases has to date been confirmed only for 24 compounds out of 194, which is slightly above 12%. The structural architecture of the entire compound depends on the combination of the organic and oxyanion parts, changes in which are sometimes realized even while maintaining the topology of the U-bearing complex. An increase in the size of the hydrocarbon part and number of charge functional groups of the organic cation leads to the formation of rare and more complex topologies. In addition, the crystal structures of two novel uranyl sulfates and one uranyl selenate, templated by isopropylammonium cations, are reported.

Spano T.L., Olds T.A., Hall S.M., Van Gosen B.S., Kampf A.R., Burns P.C., Marty J.

Abstract Finchite (IMA2017-052), Sr(UO2)2(V2O8)·5H2O, is the first uranium mineral known to contain essential Sr. The new mineral occurs as yellow-green blades up to ~10 µm in length in surface outcrops of the calcrete-type uranium deposit at Sulfur Springs Draw, Martin County, Texas, U.S.A. Crystals of finchite were subsequently discovered underground in the Pandora mine, La Sal, San Juan County, Utah, U.S.A., as diamond-shaped golden-yellow crystals reaching up to 1 mm. The crystal structure of finchite from both localities was determined using single-crystal X-ray diffraction and is orthorhombic, Pcan, with a = 10.363(6) Å, b = 8.498(5) Å, c = 16.250(9) Å, V = 1431.0(13) Å3, Z = 4 (R1 = 0.0555) from Sulfur Springs Draw; and a = 10.3898(16), b = 8.5326(14), c = 16.3765(3) Å, V = 1451.8(4) Å3, Z = 4 (R1 = 0.0600) from the Pandora mine. Electron-probe microanalysis provided the empirical formula (Sr0.88K0.17Ca0.10Mg0.07Al0.03Fe0.02)Σ1.20(UO2)2(V2.08O8)·5H2O for crystals from Sulfur Springs Draw, and (Sr0.50Ca0.28Ba0.22K0.05)Σ0.94(U0.99O2)2(V2.01O8)·5H2O for crystals from the Pandora mine, based on 17 O atoms per formula unit. The structure of finchite contains uranyl vanadate sheets based upon the francevillite topology. Finchite is a possible immobilization species for both uranium and the dangerous radionuclide 90Sr because of the relative insolubility of uranyl vanadate minerals in water.

Chukanov N.V., Aksenov S.M., Rastsvetaeva R.K.

This paper is an overview of available data on crystal structures, crystal chemical features, physical and chemical properties, and genesis of multilayer microporous compounds related to cancrinite and sodalite (CRCs). These compounds meet the criteria for considering them as zeolite-type materials and molecular sieves. Ten types of the CRCs’ frameworks ( AFG , CAN , FAR , FRA , GIU , LIO , LOS , MAR , TOL , SOD ) have been included into the Database of Zeolite Structures. Since the overwhelming majority of such materials are known only as phases of natural origin, a significant part of the review refers to multilayer mineral species belonging to the cancrinite group. Separate sections of the review contain data on various topological types of aluminosilicate frameworks, crystal chemistry of extra-framework components, isomorphism, IR spectroscopy, and genesis of multilayer CRCs as well as physical and chemical properties of two- and three-layer representatives of this group of microporous materials ( i.e . materials with cancrinite- and sodalite-type frameworks, respectively). • This paper is an overview of available data on crystal chemistry, physical and chemical properties, and genesis of microporous compounds related to cancrinite and sodalite. • AFG , CAN , FAR , FRA , GIU , LIO , LOS , MAR , TOL , and SOD types frameworks are included into the Database of Zeolite Structures.

Gurzhiy V.V., Kalashnikova S.A., Kuporev I.V., Plášil J.

Uranyl carbonates are one of the largest groups of secondary uranium(VI)-bearing natural phases being represented by 40 minerals approved by the International Mineralogical Association, overtaken only by uranyl phosphates and uranyl sulfates. Uranyl carbonate phases form during the direct alteration of primary U ores on contact with groundwaters enriched by CO2, thus playing an important role in the release of U to the environment. The presence of uranyl carbonate phases has also been detected on the surface of “lavas” that were formed during the Chernobyl accident. It is of interest that with all the importance and prevalence of these phases, about a quarter of approved minerals still have undetermined crystal structures, and the number of synthetic phases for which the structures were determined is significantly inferior to structurally characterized natural uranyl carbonates. In this work, we review the crystal chemistry of natural and synthetic uranyl carbonate phases. The majority of synthetic analogs of minerals were obtained from aqueous solutions at room temperature, which directly points to the absence of specific environmental conditions (increased P or T) for the formation of natural uranyl carbonates. Uranyl carbonates do not have excellent topological diversity and are mainly composed of finite clusters with rigid structures. Thus the structural architecture of uranyl carbonates is largely governed by the interstitial cations and the hydration state of the compounds. The information content is usually higher for minerals than for synthetic compounds of similar or close chemical composition, which likely points to the higher stability and preferred architectures of natural compounds.

Kornyakov I.V., Tyumentseva O.S., Krivovichev S.V., Gurzhiy V.V.

Six new uranyl compounds were synthesized within the K+-bearing uranyl sulfate system. An unexpected example of dimensional evolution is demonstrated.

Kornyakov I.V., Kalashnikova S.A., Gurzhiy V.V., Britvin S.N., Belova E.V., Krivovichev S.V.

Abstract Experimental investigations of crystallization in a family of uranyl triacetate compounds with Na, K, Rb and Cs were performed. The crystal structures of two novel Cs- and Rb-bearing tri(acetato)uranylates were solved, and the content of H2O molecules in the crystal structure of K-bearing uranyl triacetate was refined. Synthesized compounds were analyzed using IR spectroscopy and single-crystal X-ray diffraction. Crystal chemical analysis of the M[(UO2)(CH3COO)3](H2O) n family (M = Na, K, Rb, Cs; n = 0–1.0) reveals the sequence of structural transformations depending on the size of alkali cation resulting in the symmetry reduction from cubic P 213 (for Na), through tetragonal I 41/a (for K and Rb) to triclinic P 1̅ space groups (for Cs), which is in accordance with the principle of morphotropism, suggested by Paul von Groth, founder of the Zeitschrift für Krystallographie journal, in 1870.

Tyumentseva O.S., Kornyakov I.V., Britvin S.N., Zolotarev A.A., Gurzhiy V.V.

An alteration of the uranyl oxide hydroxy-hydrate mineral schoepite [(UO2)8O2(OH)12](H2O)12 at mild hydrothermal conditions was studied. As the result, four different crystalline phases Cs[(UO2)(SO4)(OH)](H2O)0.25 (1), Cs3[(UO2)4(SO4)2O3(OH)](H2O)3 (2), Cs6[(UO2)2(SO4)5](H2O)3 (3), and Cs2[(UO2)(SO4)2] (4) were obtained, including three novel compounds. The obtained Cs uranyl sulfate compounds 1, 3, and 4 were analyzed using single-crystal XRD, EDX, as well as topological analysis and information-based structural complexity measures. The crystal structure of 3 was based on the 1D complex, the topology of which was unprecedented for the structural chemistry of inorganic oxysalts. Crystal chemical analysis performed herein suggested that the majority of the uranyl sulfates minerals were grown from heated solutions, and the temperature range could be assumed from the manner of interpolyhedral linkage. The presence of edge-sharing uranyl bipyramids most likely pointed to the temperatures of higher than 100 °C. The linkage of sulfate tetrahedra with uranyl polyhedra through the common edges involved elevated temperatures but of lower values (~70–100 °C). Complexity parameters of the synthetic compounds were generally lower than that of uranyl sulfate minerals, whose structures were based on the complexes with the same or genetically similar topologies. The topological complexity of the uranyl sulfate structural units contributed the major portion to the overall complexity of the synthesized compounds, while the complexity of the respective minerals was largely governed by the interstitial structure and H-bonding system.

Gurzhiy V.V., Kuporev I.V., Kovrugin V.M., Murashko M.N., Kasatkin A.V., Plášil J.

Comparison of the natural and synthetic phases allows an overview to be made and even an understanding of the crystal growth processes and mechanisms of the particular crystal structure formation. Thus, in this work, we review the crystal chemistry of the family of uranyl selenite compounds, paying special attention to the pathways of synthesis and topological analysis of the known crystal structures. Comparison of the isotypic natural and synthetic uranyl-bearing compounds suggests that uranyl selenite mineral formation requires heating, which most likely can be attributed to the radioactive decay. Structural complexity studies revealed that the majority of synthetic compounds have the topological symmetry of uranyl selenite building blocks equal to the structural symmetry, which means that the highest symmetry of uranyl complexes is preserved regardless of the interstitial filling of the structures. Whereas the real symmetry of U-Se complexes in the structures of minerals is lower than their topological symmetry, which means that interstitial cations and H2O molecules significantly affect the structural architecture of natural compounds. At the same time, structural complexity parameters for the whole structure are usually higher for the minerals than those for the synthetic compounds of a similar or close organization, which probably indicates the preferred existence of such natural-born architectures. In addition, the reexamination of the crystal structures of two uranyl selenite minerals guilleminite and demesmaekerite is reported. As a result of the single crystal X-ray diffraction analysis of demesmaekerite, Pb2Cu5[(UO2)2(SeO3)6(OH)6](H2O)2, the H atoms positions belonging to the interstitial H2O molecules were assigned. The refinement of the guilleminite crystal structure allowed the determination of an additional site arranged within the void of the interlayer space and occupied by an H2O molecule, which suggests the formula of guilleminite to be written as Ba[(UO2)3(SeO3)2O2](H2O)4 instead of Ba[(UO2)3(SeO3)2O2](H2O)3.

Gurzhiy V.V., Tyumentseva O.S., Izatulina A.R., Krivovichev S.V., Tananaev I.G.

Chemically induced polytypic phase transitions have been observed during experimental investigations of crystallization in the mixed uranyl sulfate-selenate Mg[(UO2)(TO4)2(H2O)](H2O)4 (T = S, Se) system. Three different structure types form in the system, depending upon the Se:S ratio in the initial aqueous solution. The phases with the Se/(Se + S) ratios (in mol %) in the ranges 0-9, 16-47, and 58-100 crystallize in the space groups P21, Pmn21, and P21/c, respectively. The structures of the phases are based upon the same type of uranyl-based sulfate/selenate chains that, through hydrogen bonds, are linked into pseudolayers of the same topological type. The layers are linked into three-dimensional structures via interlayer Mg-centered octahedra. The three structure types contain the same layers but with different stacking sequences that can be conveniently described as belonging to the 1M, 2O, and 2M polytypic modifications. The Se-for-S substitution demonstrates a strong selectivity with preferential incorporation of Se into less tightly bonded T1 site. The larger ionic radius of Se6+ relative to S6+ induces rotation of (T1O4) tetrahedra in the adjacent layers and reconstruction of the structure types. From the information-theoretic viewpoint, the intermediate Pmn21 structure type is more complex than the monoclinic end-member structure types.

Aksenov S.M., Mackley S.A., Deyneko D.V., Taroev V.K., Tauson V.L., Rastsvetaeva R.K., Burns P.C.

Single crystals of compounds based on novel microporous heteropolyhedral frameworks containing Ce and Er were synthesized hydrothermally and their structures were determined. The triclinic unit cell parameters of K 7 [Ce 3 (Si 12 O 32 )]⋅2H 2 O and K 7 [Er 3 (Si 12 O 32 )]⋅2H 2 O, respectively, are as follows: a = 6.9833(2), 6.8334(3) Å, b = 11.4171(3), 11.4474(3) Å, c = 11.6988(4), 11.4792(3) Å, α = 87.632(2), 88.501(2)°, β = 87.546(3), 89.086(3)°, γ = 78.732(2), 79.711(3)°; V = 913.40(5), 883.16(5) Å 3 , space group P -1. Structural models were refined to R = 6.52 and 4.74%, respectively. The crystal structures are similar to reported compounds with the general formula K 7+ x [ Ln 3 (Si 12 O 32 )]Ø x ⋅ n H 2 O and are based on (Si 12 O 32 ) layers of silicate tetrahedra that are one tetrahedron wide linked by Ln O 6 octahedra and Ln 2 O 10 dimers of octahedra into a heteropolyhedral framework. The structures contain two systems of parallel channels that contain potassium cations and water molecules. Topological analysis indicates the frameworks are formed by condensation of the sequence of tiles [4 6 ][3 4 .4 3 .6 3 ] 2 [3 4 .4 8 .6 8 .8 2 ]. Bond valence sums show partial oxidation of Ce 3+ to Ce 4+ , as previously observed by XANES. Luminescence spectra for K 7 [Er 3 (Si 12 O 32 )]⋅2H 2 O indicate emission bands are related to the transitions from the 2 H 11/2 and 4 S 3/2 exited states to the 4 I 15/2 ground state. A short review of all potassium containing lanthanide silicate compounds, most of which have heteropolyhedral frameworks, is provided in which twenty-four chemical families of isostructural compounds are grouped according to the type of silicate anion. • Cerium and erbium compounds of K 7+ x [ Ln 3 (Si 12 O 32 )]Ø x ⋅ n H 2 O family with microporous heteropolyhedral frameworks were synthesized. • Luminescence spectroscopy data for the Er-containing compound were measured. • Crystal chemical comparison for all potassium containing lanthanide silicate compounds was provided.

Krivovichev V.G., Krivovichev S.V., Charykova M.V.

Chemical diversity of minerals containing selenium as an essential element has been analyzed in terms of the concept of mineral systems and the information-based structural and chemical complexity parameters. The study employs data for 123 Se mineral species approved by the International Mineralogical Association as of 25 May 2019. All known selenium minerals belong to seven mineral systems with the number of essential components ranging from one to seven. According to their chemical features, the minerals are subdivided into five groups: Native selenium, oxides, selenides, selenites, and selenates. Statistical analysis shows that there are strong and positive correlations between the chemical and structural complexities (measured as amounts of Shannon information per atom and per formula or unit cell) and the number of different chemical elements in a mineral. Analysis of relations between chemical and structural complexities provides strong evidence that there is an overall trend of increasing structural complexity with the increasing chemical complexity. The average structural complexity for Se minerals is equal to 2.4(1) bits per atom and 101(17) bits per unit cell. The chemical and structural complexities of O-free and O-bearing Se minerals are drastically different with the first group being simpler and the second group more complex. The O-free Se minerals (selenides and native Se) are primary minerals; their formation requires reducing conditions and is due to hydrothermal activity. The O-bearing Se minerals (oxides and oxysalts) form in near-surface environment, including oxidation zones of mineral deposits, evaporites and volcanic fumaroles. From the structural viewpoint, the five most complex Se minerals are marthozite, Cu(UO2)3(SeO3)2O2·8H2O (744.5 bits/cell); mandarinoite, Fe2(SeO3)3·6H2O (640.000 bits/cell); carlosruizite, K6Na4Na6Mg10(SeO4)12(IO3)12·12H2O (629.273 bits/cell); prewittite, KPb1.5ZnCu6O2(SeO3)2Cl10 (498.1 bits/cell); and nicksobolevite, Cu7(SeO3)2O2Cl6 (420.168 bits/cell). The mechanisms responsible for the high structural complexity of these minerals are high hydration states (marthozite and mandarinoite), high topological complexity (marthozite, mandarinoite, carlosruizite, nicksobolevite), high chemical complexity (prewittite and carlosruizite), and the presence of relatively large clusters of atoms (carlosruizite and nicksobolevite). In most cases, selenium itself does not play the crucial role in determining structural complexity (there are structural analogues or close species of marthozite, mandarinoite, and carlosruizite that do not contain Se), except for selenite chlorides, where stability of crystal structures is adjusted by the existence of attractive Se–Cl closed-shell interactions impossible for sulfates or phosphates. Most structurally complex Se minerals originate either from relatively low-temperature hydrothermal environments (as marthozite, mandarinoite, and carlosruizite) or from mild (500–700 °C) anhydrous gaseous environments of volcanic fumaroles (prewittite, nicksobolevite).

Chong S., Aksenov S.M., Dal Bo F., Perry S.N., Dimakopoulou F., Burns P.C.