Displacement Of Oxygen Atoms Research Articles

Atomistic simulation study of influence of Al2O3–Al interface on dislocation interaction and prismatic loop formation during nano-indentation on Al2O3-coated aluminum

A large-scale molecular dynamics (MD) simulation of nano-indentation was carried out to provide insight into the influence of the Al-Al2O3 interface on dislocation evolution and deformation behavior of Al substrate coated with Al2O3 thin film. Adaptive common neighbor analysis (a-CNA), centro-symmetry parameter (CSP) estimation, and dislocation extraction algorithm (DXA) were implemented to represent structural evolution during nano-indentation deformation. The absence of elastic regime was observed in the P-h curve for this simulated nano-indentation test of Al2O3 thin film coated Al specimen. The displacement of oxygen atoms from Al2O3 to Al partly through the interface greatly influences the plastic deformation behavior of the specimen during nano-indentation. Prismatic dislocation loops, which are formed due to pinning of Shockley partials (1/6 < 112>) by Stair-rod (1/6 < 110>) and Hirth dislocation (1/3 < 001>), were observed in all cases studied in this work. Pile-up of atoms was also observed and the extent of the pile-up was found to vary with the test temperature. A distorted stacking fault tetrahedron (SFT) is formed when a nano-indentation test is carried out at 100K. The presence of a prismatic dislocation loop, SFT and dislocation forest caused strain hardening and, consequently, there is an increase in hardness as indentation depth increases. Graphical abstract Figure illustrates nano-indentation model set up along with load vs. depth curve and distorted stacking fault tetrahedron.

Structures and thermodynamic stability of cobalt molybdenum oxide (CoMoO4-II)

This contribution reports density functional theory (DFT) calculations on structural and electronic properties of bulk and surfaces of cobalt molybdenum oxide CoMoO4-II; i.e., a material that enjoys a wide array of chemical catalytic and optical applications. Estimated lattice constants and atomic charges for bulk CoMoO4-II reproduce limited analogous experimental measurements. Bader's charges confirm the ionic nature for metal-O bonds in bulk and surfaces of CoMoO4-II. Plotted partial density of states reveal a narrow band gap of 1.8 eV for bulk CoMoO4-II. We found that cleaving bulk of CoMoO4-II along the low-Miller indices afford twelve distinct surfaces. Upward displacement of oxygen atom becomes evident when contrasting bulk positioning of atoms with relaxed surfaces. The two mixed Mo/O- and Co/O–terminated surfaces dominate the thermodynamic stability diagram at 1 atm and 300 – 1400 K, and across a wide range of oxygen chemical potential. The presence of surface oxygen atoms in these stable surfaces is expected to facilitate the occurrence of oxygen reduction reactions as experimentally demonstrated. Likewise, the adjacent surface cations (Mo4+/Co2+) and anions (O2−) serve as Lewis-acid pairs; i.e., very potent active sites in prominent catalysis reactions.

Measurement of O and Ti atom displacements in TiO2 during flash sintering experiments

AbstractIn‐situ flash experiments on rutile TiO2 were performed at the synchrotron at the Brookhaven National Laboratory. Pair distribution function analysis of total X‐ray scattering measurements yielded mean‐square atomic displacements of oxygen and titanium atoms during the progression of the 3 stages of flash. The displacements are measured to be far greater for oxygen atoms than for titanium atoms. These large displacements may signal an “elastic softening” of the lattice, which, recently, has been predicted as a precursor to the onset of flash.

Structure, dielectric and electric properties of diisobutylammonium hydrogen sulfate crystal

Diisobutylammonium hydrogen sulfate, a new organic-inorganic hybrid compound, was successfully synthesized and three structural phases in 298–433K temperature range were revealed by differential scanning calorimetry and X-ray powder diffraction studies. Single crystal X-ray diffraction data were used to describe the crystal structures in each particular case. In phase III (below 336/319K on heating/cooling) the crystal arrangement appears to be within the triclinic symmetry with P-1 space group. During heating in the 336–339K region (and 319–337K on cooling) the crystal exists in the phase II, characterized by monoclinic symmetry with P21/c space group. Consequently, above 339K (during heating, and 337K during cooling temperature sequences), i.e. in phase I the crystal exhibits orthorhombic symmetry (Cmce space group). Ferroelastic domain structure was observed in phase III. These phase boundaries (III→II and II→I) were accompanied by the presence of small anomalies, apparent in the dielectric permittivity and electric conductivity experimental data. Fast proton transport with activation energy of 0.23eV was observed in the high temperature phase I and related to phonon assisted proton diffusion conditioned by disorder of diisobutylammonium (diba) cations, as well as by high thermal displacements of oxygen and sulfur atoms of hydrogen sulfate anion (hs).

Directional dependence of the threshold displacement energies in metal oxides

Molecular dynamics (MD) simulations are performed to investigate the directional dependence and the values of the threshold energies (TDEs) for the displacements of the oxygen and metal atoms and for producing stable Frenkel pairs in five metal oxides of Cr2O3, Al2O3, TiO2, SiO2, and MgO. The TDEs for the Frenkel pairs and atoms displacement are calculated in 66 crystallographic directions, on both the anion and cation sublattices. The performed simulations are for metal and oxygen PKA energies up to 350 and 400 eV, respectively. The calculated probability distributions for the atoms displacement and average number of Frenkel pairs produced in the different oxides are compared. The results revealed unique symmetrical patterns of the TDEs for the displacement of the atoms and the formation of stable Frenkel pairs, confirming the strong dependence on the direction and the crystalline structure of the oxides. Results also showed that the formation of stable Frenkel pairs is associated with the displacements of the PKAs and/or of the SKAs. The probabilities of the TDEs for the displacement of the oxygen and metal PKAs are consistently lower than those of the atoms in the crystal. In SiO2, TDEs for the displacement of oxygen and metal atoms and those for the formation of stable Frenkel pairs are the lowest, while those in TiO2 are among the highest. The results for Cr2O3 and Al2O3, which have the same crystal structure, are similar. The calculated TDEs for MgO, Al2O3 and TiO2 are generally in good agreement with the experimental values and the probability distributions of the TDEs for the PKAs in TiO2 are in good agreement with reported MD simulation results.

In situ disordering of monoclinic titanium monoxide Ti5O5 studied by transmission electron microscope TEM

The superlattice and domain structures exhibited by ordered titanium monoxide Ti5O5 are disrupted by low energy electron beam irradiation. The effect is attributed to the disordering of the oxygen and titanium sublattices. This disordering is caused by the displacement of both oxygen and titanium atoms by the incident electrons and results in a phase transformation of the monoclinic phase Ti5O5 into cubic B1 titanium monoxide. In order to determine the energies required for the displacement of titanium or oxygen atoms, i.e. threshold displacement energies, a systematic study of the disappearance of superstructure reflections with increasing electron energy and electron bombardment dose has been performed in situ in a transmission electron microscope (TEM). An incident electron energy threshold between 120 and 140 keV has been observed. This threshold can be ascribed to the displacements of titanium atoms with 4 as well as with 5 oxygen atoms as nearest neighbors. The displacement threshold energy of titanium atoms in Ti5O5 corresponding with the observed incident electron threshold energy lies between 6.0 and 7.5 eV. This surprisingly low value can be explained by the presence of either one or two vacant oxygen lattice sites in the nearest neighbors of all titanium atoms.

On relaxation nature of glass transition in amorphous materials

A short review on relaxation theories of glass transition is presented. The main attention is paid to modern aspects of the glass transition equation qτg = C, suggested by Bartenev in 1951 (q – cooling rate of the melt, τg – structural relaxation time at the glass transition temperature Tg). This equation represents a criterion of structural relaxation at transition from liquid to glass at T = Tg (analogous to the condition of mechanical relaxation ωτ = 1, where the maximum of mechanical loss is observed). The empirical parameter С = δTg has the meaning of temperature range δTg that characterizes the liquid-glass transition. Different approaches of δTg calculation are reviewed. In the framework of the model of delocalized atoms a modified kinetic criterion of glass transition is proposed (q/Tg)τg = Cg, where Cg ≅ 7·10−3 is a practically universal dimensionless constant. It depends on fraction of fluctuation volume fg, which is frozen at the glass transition temperature Cg = fg/ln(1/fg). The value of fg is approximately constant fg ≅ 0.025. At Tg the process of atom delocalization, i.e. its displacement from the equilibrium position, is frozen. In silicate glasses atom delocalization is reduced to critical displacement of bridge oxygen atom in Si-O-Si bridge necessary to switch a valence bond according to Muller and Nemilov.An equation is derived for the temperature dependence of viscosity of glass-forming liquids in the wide temperature range, including the liquid-glass transition and the region of higher temperatures. Notion of (bridge) atom delocalization is developed, which is related to necessity of local low activation deformation of structural network for realization of elementary act of viscous flow – activated switch of a valence (bridge) bond. Without atom delocalization (“trigger mechanism”) a switch of the valence bond is impossible and, consequently, the viscous flow. Thus the freezing of atom delocalization process at low temperatures, around Tg, leads to the cease of the viscous flow and transition of a melt to a glassy state. This occurs when the energy of disordered lattice thermal vibrations averaged to one atom becomes equal or less than the energy of atom delocalization.The Bartenev equation for cooling rate dependence of glass transition temperature Tg = Tg(q) is discussed. The value of fg calculated from the data on the Tg(q) dependence coincides with result of the fg calculation using the data on viscosity near the glass transition. Derivation of the Bartenev equation with the account of temperature dependence of activation energy of glass transition process is considered. The obtained generalized relation describes the Tg(q) dependence in a wider interval of the cooling rate compared Bartenev equation. Experimental data related to standard cooling rate q = 3K/min were used in this work.

Structural transitions in iron-based Ba3NbFe3Si2O14 langasite at high pressures

Synchrotron X-ray diffraction studies of the structural characteristics of Ba3NbFe3Si2O14 langasite were performed at high hydrostatic pressures (up to 60 GPa) created in a diamond anvil cell. The Mössbauer absorption spectra of 57Fe nuclei and optical absorption spectra were recorded at pressures up to 10 and 54 GPa, respectively. The cascade of structural phase transitions at pressures of about ∼ 3, ∼ 20, and ∼ 41 GPa was discovered. The first transition corresponds to the displacements of light oxygen atoms and associated with an increase in the local symmetry of oxygen 3f tetrahedra surrounding iron ions. The volume drop at the first transition is about 1.5%. The second transition at ∼ 20 GPa is accompanied by a pronounced change in the lattice parameters a and c, while the unit cell volume undergoes a stepwise drop by 7%. Significant decrease in the parameter c at the structural transition should result in a strong increase of the exchange coupling constants between iron ions in neighboring ab planes, which may lead to a giant increase in the Néel temperature in this crystal at pressures above ∼ 20 GPa. At the third transition at about 38–44 GPa, only a small anomaly in the relation is observed, but this anomaly is accompanied by substantial changes in the optical gap and in the quadruple splitting parameter.

Oxygen-storage behavior and local structure in Ti-substituted YMnO3

Hexagonal manganates RMnO3 (R=Y, Ho, Dy) have been recently shown to exhibit oxygen-storage capacities promising for three-way catalysts, air-separation, and related technologies. Here, we demonstrate that Ti substitution for Mn can be used to chemically tune the oxygen-breathing properties of these materials towards practical applications. Specifically, Y(Mn1−xTix)O3 solid solutions exhibit facile oxygen absorption/desorption via reversible Ti3+↔Ti4+ and Mn3+↔Mn4+ reactions already in ambient air at ≈400°C and ≈250°C, respectively. On cooling, the oxidation of both cations is accompanied by oxygen uptake yielding a formula YMn3+1−x-yMn4+yTi4+xO3+δ. The presence of Ti promotes the oxidation of Mn3+ to Mn4+, which is almost negligible for YMnO3 in air, thereby increasing the uptake of oxygen beyond that required for a given Ti4+ concentration. The reversibility of the redox reactions is limited by sluggish kinetics; however, the oxidation process continues, if slowly, even at room temperature. The extra oxygen atoms are accommodated by the large interstices within a triangular lattice formed by the [MnO5] trigonal bipyramids. According to bond distances from Rietveld refinements using the neutron diffraction data, the YMnO3 structure features under-bonded Mn and even more severely under-bonded oxygen atoms that form the trigonal bases of the [MnO5] bipyramids. The tensile bond strain around the 5-fold coordinated Mn site and the strong preference of Ti4+(and Mn4+) for higher coordination numbers likely provide driving forces for the oxidation reaction. Reverse Monte Carlo refinements of the local atomic displacements using neutron total scattering revealed how the excess oxygen atoms are accommodated in the structure by correlated local displacements of the host atoms. Large displacements of the under-bonded host oxygen atoms play a key part in this lattice-relaxation process, facilitating reversible exchange of significant amounts of oxygen with atmosphere.

Oxygen Displacement in Cuprates under Ionic Liquid Field-Effect Gating

We studied structural changes in a 5 unit cell thick La1.96Sr0.04CuO4 film, epitaxially grown on a LaSrAlO4 substrate with a single unit cell buffer layer, when ultra-high electric fields were induced in the film by applying a gate voltage between the film (ground) and an ionic liquid in contact with it. Measuring the diffraction intensity along the substrate-defined Bragg rods and analyzing the results using a phase retrieval method we obtained the three-dimensional electron density in the film, buffer layer, and topmost atomic layers of the substrate under different applied gate voltages. The main structural observations were: (i) there were no structural changes when the voltage was negative, holes were injected into the film making it more metallic and screening the electric field; (ii) when the voltage was positive, the film was depleted of holes becoming more insulating, the electric field extended throughout the film, the partial surface monolayer became disordered, and equatorial oxygen atoms were displaced towards the surface; (iii) the changes in surface disorder and the oxygen displacements were both reversed when a negative voltage was applied; and (iv) the c-axis lattice constant of the film did not change in spite of the displacement of equatorial oxygen atoms.

Time-resolved crystal structure analysis of resonantly vibrating langasite oscillator

The momentary crystal structure of a Y-cut langasite oscillator resonantly vibrating under an alternating electric field is revealed by time-resolved crystal structure analysis to understand the microscopic mechanism of piezoelectricity. The thickness-shear lattice strain under an electric field is amplified ∼103 times by the resonant effect. The lattice vibration involves the deformation of GaO4 and Ga0.5Si0.5O4 tetrahedra accompanied by atomic displacements of specific oxygen atoms along the electric field. The deformation of GaO4 and Ga0.5Si0.5O4 tetrahedra enhances the piezoelectricity of langasite.

Gamma induced atom displacements in LYSO and LuYAP crystals as used in medical imaging applications

The radiation damage, in terms of atom displacements, induced by gamma irradiation in LYSO and LuYAP crystals is presented. 44Sc, 22Na and 48V are used as gamma sources for this study. The energy of gammas from the electron–positron annihilation processes (511keV) is also included in the study. The atom displacements distributions inside each material are calculated following the Monte Carlo assisted Classical Method introduced by the authors. This procedure also allows to study the atom displacements in-depth distributions inside each crystal. The atom displacements damage in LYSO crystals is found to be higher than in LuYAP crystals, mainly provoked by the displacements of silicon and oxygen atoms. But the difference between atom displacements produced in LYSO and LuYAP decreases when more energetic sources are used. On the other hand, the correlation between the atom displacements and energy deposition in-depth distributions is excellent. The atom displacements to energy deposition ratio is found to increases with more energetic photon sources. LYSO crystals are then more liable to the atom displacements damage than LuYAP crystals.

Equation of state and structural phase transitions in iron-based Ba3TaFe3Si2O14 langasite at high hydrostatic pressures

Synchrotron X-ray diffraction studies of the structural characteristics of Ba3TaFe3Si2O14 langasite are performed at high hydrostatic pressures (up to 60 GPa) created in a diamond anvil cell. At pressures up to 20 GPa, the Mossbauer absorption spectra for 57Fe nuclei and the Raman spectra are recorded. Two structural phase transitions at P ≈ 5.5 and 20 GPa are observed. The first transition corresponds to the displacements of light oxygen atoms and to an increase in the local symmetry of 3f oxygen tetrahedra surrounding iron ions. The second one is accompanied by a pronounced change in the lattice parameter c, and the unit cell volume undergoes a stepwise drop as large as 8.6%. An appreciable decrease in the parameter c at the structural transition should result in a significant increase in the exchange coupling constants between iron ions in neighboring ab planes underlying the giant increase in the Neel temperature in this crystal at pressures exceeding 20 GPa.

Combined experimental and theoretical investigation of interactions between kaolinite inner surface and intercalated dimethyl sulfoxide

Kaolinite intercalation complex with dimethyl sulfoxide (DMSO) was investigated by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and thermogravimetry–differential scanning calorimetry (TG–DSC) combined with molecular dynamics simulation. The bands assigned to the OH stretching of inner surface of kaolinite were significantly perturbed after intercalation of DMSO into kaolinite. Additionally, the bands attributed to the vibration of gibbsite-like layers of kaolinite shifted to the lower wave number, indicating that the intercalated DMSO were strongly hydrogen bonded to the alumina octahedral surface of kaolinite. The slightly decreased intensity of 1031cm−1 and 1016cm−1 band due to the in-plane vibration of SiO of kaolinite revealed that some DMSO molecules formed weak hydrogen bonds with the silicon tetrahedral surface of kaolinite. Based on the TG result of kaolinite–DMSO intercalation complex, the formula of A12Si2O5(OH)4(DMSO)0.7 was obtained, with which the kaolinite–DMSO complex model was constructed. The molecular dynamics simulation of kaolinite–DMSO complex directly confirmed the monolayer structure of DMSO in interlayer space of kaolinite, where the DMSO arranged almost parallel with kaolinite basal surface with all methyl groups being distributed near the interlayer midplane and oxygen atoms orienting toward to the alumina octahedral surface. The radial distribution function between kaolinite and intercalated DMSO verified the strong hydrogen bonds forming between hydroxyl hydrogen atoms of alumina octahedral surface and oxygen atoms of DMSO. Moreover, some methyl groups of DMSO were weakly hydrogen bonded to the oxygen atoms of silicon tetrahedral surface through the hydrogen atoms. The mean square displacement of DMSO oxygen atoms and hydrogen atoms in z direction kept unchanged during the simulation time because of the hydrogen-bond interaction between inner surface of kaolinite and DMSO, which constrained the mobility of intercalated DMSO in the direction normal to the kaolinite basal surface.

Theory of structural phase transition in MgTi2O4

A theory of phase transition in MgTi2O4 is proposed based on a study of the order-parameter symmetry, thermodynamics, and mechanisms of formation of the atomic and orbital structure of the low-symmetry MgTi2O4 phase. The critical order parameter (which induces a phase transition) is determined. It is shown that the calculated MgTi2O4 tetragonal structure is a result of displacements of magnesium, titanium, and oxygen atoms; ordering of oxygen atoms; and the participation of dxy, dxz, and dyz orbitals. The contribution of noncritical representations to ion displacements is proven to be insignificant. The existence of various metal clusters in the tetragonal phase has been established by calculation in correspondence with experimental data. It is shown (within the Landau theory of phase transitions) that phase states can be changed as a result of both first- and second-order phase transitions: the high-symmetry phase borders two low-symmetry phases by second-order transition lines, while the border between low-symmetry phases is a first-order transition line.

Structure, phase transition, and controllable thermal expansion behaviors of Sc(2-x)Fe(x)Mo₃O₁₂.

The crystal structures, phase transition, and thermal expansion behaviors of solid solutions of Sc(2-x)Fe(x)Mo3O12 (0 ≤ x ≤ 2) have been examined using X-ray diffraction (XRD), neutron powder diffraction (NPD), and differential scanning calorimetry (DSC). At room temperature, samples crystallize in a single orthorhombic structure for the compositions of x < 0.6 and monoclinic for x ≥ 0.6, respectively. DSC results indicate that the phase transition temperature from monoclinic to orthorhombic structure is enhanced by increasing the Fe(3+) content. High-temperature XRD and NPD results show that Sc(1.3)Fe(0.7)Mo3O12 exhibits near zero thermal expansion, and the volumetric coefficients of thermal expansion derived from XRD and NPD are 0.28 × 10(-6) °C(-1) (250-800 °C) and 0.65 × 10(-6) °C(-1) (227-427 °C), respectively. NPD results of Sc2Mo3O12 (x = 0) and Sc(1.3)Fe(0.7)Mo3O12 (x = 0.7) indicate that Fe substitution for Sc induces reduction of the mean Sc(Fe)-Mo nonbond distance and the different thermal variations of Sc(Fe)-O5-Mo2 and Sc(Fe)-O3-Mo2 bond angles. The correlation between the displacements of oxygen atoms and the variation of unit cell parameters was investigated in detail for Sc2Mo3O12.

Measuring the sense of the Dzyaloshinskii–Moriya interaction

The spin-orbit Dzyaloshinskii–Moriya (DM) interaction EDM=D·[s1×s2] can induce small canting of neighboring magnetic moments s1 and s2. It is also very important for multiferroics and helimagnetic MnSi-type crystals with the spiral or Skyrmionic structures. The sense of the DM vector D has been experimentally determined for the first time in canted antiferromagnetic FeBO3 crystal [1]. The technique of interference between magnetic and resonant channels in synchrotron x-ray scattering was exploited. The phase of antiferromagnetic ordering (and scattering) was fixed by external magnetic field and the phase of resonant scattering was calculated with FDMNES program. Similar experiments have been also performed for MnCO3 and CoCO3 crystals. For Fe2O3 hematite crystal, the technique of interference between magnetic and multiple diffraction channels has been used. The experimental measurements are supported by ab initio calculations of the DM interaction. The first-principles calculations have been performed with Local Density Approximation incorporating the on-site Coulomb interaction U and the Spin-Orbit coupling (LDA+U+SO) [2,3]. It was found how DM interaction depends on displacements of oxygen atoms. These experimental and theoretical approaches open up new possibilities for exploring, modeling and exploiting novel magnetic and multiferroic materials. VED and ENO are grateful to the RFBR research project No. 13-02-00760 and to the project of Presidium of Russian Academy of Sciences No. 24. The work of VVM is supported by the grant program of President of Russian Federation MK-5565.2013.2, the contracts of the Ministry of education and science of Russia N 14.A18.21.0076 and 14.A18.21.0889. MIK acknowledges a financial support by FOM (The Netherlands).

Structural Evolution according to the temperature of the Compound LiNbO3

Structural evolution of LiNbO3 with temperature. A comparative study was made by X-ray diffraction on a single crystal of lithium niobate (LiNbO3) at low temperature (120K) and room temperature (293K). LiNbO3 is a ferroelectric compound particularly interesting for applications in the nonlinear optics field. After a recording of high resolution X-ray diffraction data, we used Blessing formalism for the reduction and the processing of the raw data. Structure refinement was carried out by program SHELXL. The results of the refinement led to a reliability factor of about 6% at T = 293K and of 3% at T = 120K. The structure evolution study of lithium niobate with temperature made it possible to highlight the compound stability in the investigated temperature range. Results show a light displacement (about 0.01Å) of oxygen atoms around the Li - Nb bond.

Control of Structural Distortions in Transition‐Metal Oxide Films through Oxygen Displacement at the Heterointerface

Structural distortions in the oxygen octahedral network in transition‐metal oxides play crucial roles in yielding a broad spectrum of functional properties, and precise control of such distortions is a key for developing future oxide‐based electronics. Here, it is shown that the displacement of apical oxygen atom shared between the octahedra at the heterointerface is a determining parameter for these distortions and consequently for control of structural and electronic phases of a strained oxide film. The present analysis by complementary annular dark‐ and bright‐field imaging in aberration‐corrected scanning transmission electron microscopy reveals that structural phase differences in strained monoclinic and tetragonal SrRuO3 films grown on GdScO3 substrates result from relaxation of the octahedral tilt, associated with changes in the in‐plane displacement of the apical oxygen atom at the heterointerface. It is further demonstrated that octahedral distortions and magnetrotransport properties of the SrRuO3 films can be controlled by interface engineering of the oxygen displacement. This provides a further degree of freedom for manipulating structural and electronic properties in strained films, allowing the design of novel oxide‐based heterostructures.

Symmetry reduction in uranyl compounds with [(UO2)2(TO4)3]2- (T = Se, S, Mo) layers: crystal structures of the new guanidinium uranyl selenate and methylammonium uranyl sulfate

Abstract Single crystals of the new guanidinium uranyl selenate, [CH6N3]2[(UO2)2(SeO4)3] (1), and methylammonium uranyl sulfate, [CH3NH3]2[(UO2)2(SO4)3] (2) have been prepared by isothermal evaporation from aqueous solutions under room-temperature conditions. The crystal structure of 1 has been solved by direct methods [monoclinic, P2, a = 9.9448(15), b = 9.727(2), c = 10.1508(15) Å, β = 90.213(12)°, V = 981.9(3) Å3, Z = 2] and refined to R1 = 0.0696 (wR2 = 0.1611) for 2511 reflections with |F0| ≥ 4σF using least square techniques. The crystal structure of 2 has been solved by direct methods [triclinic, P1, a = 8.4784(6), b = 9.7873(8), c = 9.8121(7) Å, α = 90.170(2), β = 95.744(2), γ = 90.136(2)°, V = 810.12(10) Å3, Z = 1] and refined to R1 = 0.0146 (wR2 = 0.0336) for 5378 reflections with |F0| ≥ 4σF using least square techniques. The structures of 1 and 2 are based upon the [(UO2)2(TO4)3]2- (T = Se, S) twodimensional uranyl layers formed by linkage of U pentagonal bipyramids and TO4 tetrahedra via common O atoms. The layers consist of two types of 4-membered rings; this topology has previously been observed in the structures of several actinyl compounds that crystallize in tetragonal or orthorhombic space groups. Violation of the higher symmetry is caused by tiltings of the TO4 tetrahedra, associated with displacement of bridging oxygen atoms from their ideal position induced by the formation of moderate hydrogen bonds with the organic cations.