High-resolution X-ray Powder Diffraction Data Research Articles

ISODISTROTLaMTeO6 (M = Ga3+ and Mn3+): the critical role of electronic configuration and cation ordering in crystal structures.

In this work, PbSb2O6-type oxides LaMTeO6 (M = Ga3+ and Mn3+) were synthesized and structurally characterized by Rietveld refinements against high-resolution X-ray powder diffraction data. The Ga3+/Te6+ partial ordering within the honeycomb-like two-dimensional [GaTeO6]3- anionic layer leads to the loss of the inversion center between Ga3+ and Te6+; however the inversion center on the 3̄-roto-inversion axis is preserved, thereby resulting in a 2-fold PbSb2O6-type superstructure by doubling the c-axis associated with a structural symmetry descending from the original P3̄1m to P3̄1c symmetry. In contrast, LaMnTeO6 (P21/c) adopts a monoclinically distorted 4-fold superstructure with lattice dimensions of a ≈ aH, b ≈ √3aH, c ≈ 2cH, where aH and cH represent the lattice parameters of trigonal PbSb2O6. The formation of this P21/c-superstructure is attributed to the combination of complete Mn3+/Te6+ ordering and the first-order Jahn-Teller distortion of Mn3+ with the electronic configuration of d4. Such a monoclinic distortion can effectively lift the Mn3+ spin moments arranged on the triangular sublattice, resulting in a sharp peak for antiferromagnetic transition, which is in stark contrast to subtle magnetic transitions for PbSb2O6-type tellurates AMn(VI)TeO6 (A = alkaline earth and Pb2+) and LnCrTeO6 (Ln = rare earth) with higher structural symmetry. Our findings highlight that the electronic configuration effects of M-cations play a critical role in controlling the structure symmetry of LaMTeO6, providing a strategy to fine-tune the crystal structures and physical properties.

Structural effects of Mn-substitution in β-FeSe

In the present work the structural and microstructural properties of Mn substituted β-FeSe are inspected by using high-resolution synchrotron X-ray powder diffraction data collected between 10 K and 150 K. It is demonstrated that the thermal increase of the structural strain in the tetragonal phase progressively breaks the 4-fold symmetry at the local scale, qualitatively tracing the development of anisotropy measured in some physical properties, generally ascribed to nematicity. This result points to a close relationship and interplay between structural strain and physical properties; with this notion, the structural strain can be considered as the origin of the unexpected anisotropy observed in some physical properties. Remarkably, incommensurate satellite peaks are observed in the diffraction pattern collected in the low-temperature orthorhombic phase field, likely related to the occurrence of a charge-density-wave instability.

Cation Disorder and Large Tetragonal Supercell Ordering in the Li-Rich Argyrodite Li7Zn0.5SiS6.

A tetragonal argyrodite with >7 mobile cations, Li7Zn0.5SiS6, is experimentally realized for the first time through solid state synthesis and exploration of the Li–Zn–Si–S phase diagram. The crystal structure of Li7Zn0.5SiS6 was solved ab initio from high-resolution X-ray and neutron powder diffraction data and supported by solid-state NMR. Li7Zn0.5SiS6 adopts a tetragonal I4 structure at room temperature with ordered Li and Zn positions and undergoes a transition above 411.1 K to a higher symmetry disordered F43m structure more typical of Li-containing argyrodites. Simultaneous occupation of four types of Li site (T5, T5a, T2, T4) at high temperature and five types of Li site (T5, T2, T4, T1, and a new trigonal planar T2a position) at room temperature is observed. This combination of sites forms interconnected Li pathways driven by the incorporation of Zn2+ into the Li sublattice and enables a range of possible jump processes. Zn2+ occupies the 48h T5 site in the high-temperature F43m structure, and a unique ordering pattern emerges in which only a subset of these T5 sites are occupied at room temperature in I4 Li7Zn0.5SiS6. The ionic conductivity, examined via AC impedance spectroscopy and VT-NMR, is 1.0(2) × 10–7 S cm–1 at room temperature and 4.3(4) × 10–4 S cm–1 at 503 K. The transition between the ordered I4 and disordered F43m structures is associated with a dramatic decrease in activation energy to 0.34(1) eV above 411 K. The incorporation of a small amount of Zn2+ exercises dramatic control of Li order in Li7Zn0.5SiS6 yielding a previously unseen distribution of Li sites, expanding our understanding of structure–property relationships in argyrodite materials.

Magnetic ground state and crystal structure of the giant dielectric constant material Ba(Fe1/2Nb1/2)O3

The room temperature crystal structure as well as the magnetic ground state of Ba(Fe1/2Nb1/2)O3 (BFN) are controversial. The results of Rietveld refinements using high-resolution synchrotron x-ray powder diffraction (SXRPD) data are presented to show that BFN belongs to cubic perovskite structure in the Pm3¯m space group and not in the cubic Fm3¯m or monoclinic symmetries, proposed by some earlier workers based on the analysis of the laboratory source XRD data. The temperature dependent specific heat measurements in the 1.8 to 300 K range on well characterized BFN samples are presented to show the absence of any long-range ordered (LRO) antiferromagnetic (AFM) transition, proposed by some earlier workers based on the observation of a peak in the temperature dependence of zero-field cooled (ZFC) DC magnetization around 25 to 32 K. Results of temperature dependent magnetization measurements during warming cycle on ZFC and field cooled (FC) BFN samples reveal history dependent bifurcation with a peak in the ZFC M (T) curve at Tf ~ 29 K, in agreement with some previous results where it was attributed to a spin-glass transition even though such an irreversibility can result from superparamagnetic (SPM) blocking as well. The appearance of a short plateau in our FC M (T) curve below Tf suggests a cluster spin-glass phase of BFN below Tf. This was confirmed by us through the ac susceptibility χ' (T, ω) studies which reveal divergence of spin dynamics at the spin-glass transition temperature TSG ~ (28 ± 1) K with a large characteristic spin relaxation time τ0 ~ 10−6 s following Vogel-Fulcher as well as power-law type critical dynamics. The existence of the magnetic glassy state in BFN is further supported by the observation of (1) magnetic field dependent shift of Tf with increasing magnetic field along the de Almeida-Thouless line in the T-H plane with a characteristic exponent of m = 2/3, (2) weak remanent magnetization Mr below Tf with exponentially decreasing Mr on approaching Tf, (3) extremely slow decay of the thermoremanent magnetization below Tf with time as per a stretched exponential function, and (4) characteristic aging, rejuvenation and memory effects below Tf. These results provide the first unambiguous confirmation of the cluster spin-glass state of BFN and settle the existing controversies related to its magnetic ground state.

Lab Case Study of Microbiologically Influenced Corrosion and Rietveld Quantitative Phase Analysis of X-ray Powder Diffraction Data of Deposits from a Refinery.

This paper reports a laboratory-based case study for the characterization of deposits from a crude cooler and reboilers in a Saudi Aramco refinery by microbiologically influenced corrosion (MIC) using microbial, metallurgic, and special analyses and correlates the Rietveld quantitative phase analysis of high-resolution X-ray powder diffraction (XRD) data of scale deposits with microbe compositions. Therefore, rapid in-field microbiological assays could be carried out to assess the potential of MIC. Based on the results, it can be highlighted that the MIC investigation showed that total bacteria and sulfate-reducing bacteria (SRB) were detected in all sampling locations. Methanogens, acid-producing bacteria, and sulfate-reducing archaea were not detected in all samples. Iron-oxidizing bacteria (IOB) were detected in the solid samples from reboilers C and D. Low loads of general bacteria and low levels of microbes with MIC potential were detected in both C and D samples. The trace amount of corrosion products in one sample and the low level of MIC microbes cannot justify the contribution of MIC microbes in the formation of accumulated solids in the system. The findings recommend conducting frequent sampling and analysis including water, oil, and solid from upstream locations to have more decisive evidence of the likelihood of the scale formation and possible contribution of MIC in the formation of deposits in the plant. Subsequently, quantitative phase analysis of XRD data of scale deposits by the Rietveld method revealed that the major phase is calcium sulfate in the form of anhydrate and the minor phases are calcium carbonate in the form of calcite and aragonite, silicon oxide in the form of quartz, and iron oxide corrosion product in the form of magnetite. The results are supported by high-resolution wavelength-dispersive X-ray fluorescence (WDXRF) results. These accurate and reproducible X-ray crystallography findings obtained from Rietveld quantitative phase analysis can guide the field engineers at the refineries and gas plants to overcome the problems of the affected equipment by drawing up the right procedures and taking preventive actions to stop the generation of these particular deposits.

Synthesis and structural analysis of nonstoichiometric ternary fulleride K 1.5 Ba 0.25 CsC 60.

The existence of cation-vacancy sites in fullerides might lead to long-range ordering and generate a new vacancy-ordered superstructure. The purpose of this work is to search whether or not long-range ordering of vacant tetrahedral sites, namely superstructure emerges in nonstoichiometric K 1.5 Ba 0.25 CsC 60 fulleride. Therefore, K 1.5 Ba 0.25 CsC 60 with cation-vacancy sites is synthesized using a precursor method to avoid inadequate stoichiometry control and formation of impurity phases within the target composition. For this purpose, first, phase-pure K 6 C 60 , Ba 6 C 60 and Cs 6 C 60 precursors are synthesized. Stoichiometric quantities of these precursors are used for further reaction with C 60 to afford K 1.5 Ba 0.25 CsC 60 . Rietveld analysis of the high-resolution synchrotron X-ray powder diffraction data of the precursors and K 1.5 Ba 0.25 CsC 60 confirms that K 6 C 60 , Ba 6 C 60 and Cs 6 C 60 are single-phase and they crystallize in a body-centered-cubic structure ( Im 3) as reported in the literature. The analysis also shows that K 1.5 Ba 0.25 CsC 60 phase can be perfectly modeled using a face-centered cubic structure. No new peaks appear which could have implied the appearance of a superstructure. This suggests that there is no long-range ordered arrangement of vacant tetrahedral sites in K 1.5 Ba 0.25 CsC 60 .

Insulin polymorphism induced by two polyphenols: new crystal forms and advances in macromolecular powder diffraction.

This study focuses on the polymorphism of human insulin (HI) upon the binding of the phenolic derivatives p-coumaric acid or trans-resveratrol over a wide pH range. The determination of the structural behaviour of HI via X-ray powder diffraction (XRPD) and single-crystal X-ray diffraction (SCXRD) is reported. Four distinct polymorphs were identified, two of which have not been reported previously. The intermediate phase transitions are discussed. One of the novel monoclinic polymorphs displays the highest molecular packing among insulin polymorphs of the same space group to date; its structure was elucidated by SCXRD. XRPD data collection was performed using a variety of instrumental setups and a systematic comparison of the acquired data is presented. A laboratory diffractometer was used for screening prior to high-resolution XRPD data collection on the ID22 beamline at the European Synchrotron Radiation Facility. Additional measurements for the most representative samples were performed on the X04SA beamline at the Swiss Light Source (SLS) using the MYTHEN II detector, which allowed the detection of minor previously untraceable impurities and dramatically improved the d-spacing resolution even for poorly diffracting samples.

Propyne Gas Adsorption in a Cyclic Hexapeptoid: A Combined In Situ XRPD and DFTB Study*.

Cyclic peptoids are macrocyclic N-substituted oligoglycines, with remarkable structural, chemical and physical properties. The gas adsorption properties of a permanently porous hexameric cyclopeptoid decorated with four propargyl and two methoxyethyl side chains were monitored by in situ X-ray powder diffraction (XRPD). High-resolution XRPD data together with Rietveld and density functional based tight binding (DFTB) method allowed us to locate propyne guest molecules inside the host channels, even though the powder sample contains more than one phase. We were able to characterize the host-guest interactions, providing useful information on the host recognition sites and discuss host adaptiveness and host-guest chemical affinity in comparison with analogous compounds.

Variation of cation distribution with temperature and its consequences on thermal expansion for Ca3Eu2(BO3)4.

The structure of calcium europium orthoborate, Ca3Eu2(BO3)4, was determined using high-resolution powder X-ray diffraction data collected at the ID22 beamline (ESRF) under ambient conditions, as well as at high temperature. Rietveld refinement allowed determination of the lattice constants and structural details, including the Ca/Eu ratios at the three cationic sites and their evolution with temperature. Clear thermal expansion anisotropy was found, and slope changes of lattice-constant dependencies on temperature were observed at 923 K. Above this temperature the changes in occupation of the Ca/Eu sites occur, exhibiting a tendency towards a more uniform Eu distribution over the three Ca/Eu sites. Possible structural origins of the observed thermal expansion anisotropy are discussed.

Differential Adsorption of l- and d-Lysine on Achiral MFI Zeolites as Determined by Synchrotron X-Ray Powder Diffraction and Thermogravimetric Analysis.

Reported here is the first crystallographic observation of stereospecific bindings of l- and d-lysine (Lys) in achiral MFI zeolites. The MFI structure offers inherent geometric and internal confinement effects for the enantiomeric difference in l- and d-Lys adsorption. Notable differences have been observed by circular dichroism (CD) spectroscopy and thermogravimetric analysis (TGA). Distinct l- and d-Lys adsorption behaviours on the H-ZSM-5 framework have been revealed by the Rietveld refinement of high-resolution synchrotron X-ray powder diffraction (SXRD) data and the density-functional theory (DFT) calculations. Despite demonstrating the approach for l- and d-Lys over MFI zeolites at an atomistic resolution, the differential adsorption study sheds light on the rational engineering of molecular interaction(s) with achiral microporous materials for chiral separation purposes.

Structural and electronic properties of the overexpanded quaternary superconducting fulleride K0.25Rb0.25Cs2.5C60

The structural and magnetic properties of the overexpanded quaternary K0.25Rb0.25Cs2.5C60 fulleride are investigated. Rietveld analysis of the high-resolution synchrotron X-ray powder diffraction data shows that K0.25Rb0.25Cs2.5C60 adopts a cubic structure with face-centered (fcc) symmetry. Magnetization measurements at ambient pressure reveal that the material is a superconductor with a transition temperature, Tc, of 29.4 K. Temperature dependence of the magnetic susceptibility does not show a simple temperature-independent Pauli susceptibility term – instead, it shows a cusp at a certain temperature implying an insulator-to-metal crossover on cooling. Complementary high-pressure magnetization measurements to a pressure of 10.2 kbar show a non-monotonic response of Tc with a dome-shaped scaling with pressure and a maximum value of 32.4 K at 3.9 kbar. The experimental results are consistent with quaternary K0.25Rb0.25Cs2.5C60 following the established unconventional behavior of overexpanded fullerides. However, our results also unveil well-defined detrimental cation specific effects on the electronic properties associated with the introduction of increased disorder in the tetrahedral interstices of the fcc fulleride structure.

Interstitial nitrides revisited – A simple synthesis of MxMo3N (M = Fe, Co, Ni)

The efficient synthesis of polycrystalline filled beta-Mn structured Ni2Mo3N, and the eta-carbides Fe3Mo3N and Co3Mo3N, by a single heating of metal powders at 975 °C under a hydrogen-nitrogen mixture is reported. Rietveld analysis of high-resolution X-ray powder diffraction data shows that the reduction-nitridation of NiMoO4 produces Ni2Mo3N and nickel; Ni3Mo3N is not obtained in this way and its existence is disproved.

Doped Sr2FeIrO6-Phase Separation and a Jeff ≠ 0 State for Ir5.

High-resolution synchrotron X-ray and neutron powder diffraction data demonstrate that, in contrast to recent reports, Sr2FeIrO6 adopts an I1̅ symmetry double perovskite structure with an a-b-c- tilting distortion. This distorted structure does not tolerate cation substitution, with low levels of A-site (Ca, Ba, La) or Fe-site (Ga) substitution leading to separation into two phases: a stoichiometric I1̅ phase and a cation-substituted, P21/ n symmetry, a-a-c+ distorted double perovskite phase. Magnetization, neutron diffraction, and 57Fe Mössbauer data show that, in common with Sr2FeIrO6, the cation substituted Sr2- xA xFe1- yGa yIrO6 phases undergo transitions to type-II antiferromagnetically ordered states at TN ∼ 120 K. However, in contrast to stoichiometric Sr2FeIrO6, cation substituted samples exhibit a further magnetic transition at TA ∼ 220 K, which corresponds to the ordering of Jeff ≠ 0 Ir5+ centers in the cation-substituted, P21/ n symmetry, double perovskite phases.

Lead apatites: structural variations among Pb5(BO4)3Cl with B = P (pyromorphite), As (mimetite) and V (vanadinite).

The crystal structure of four Pb apatite samples, Pb5(BO4)3Cl, was refined with synchrotron high-resolution powder X-ray diffraction data, Rietveld refinements, space group P63/m and Z = 2. For this isotypic series, B = P5+ is pyromorphite, B = As5+ is mimetite and B = V5+ is vanadinite. The ionic radius for As5+ (0.355 Å) is similar to that of V5+ (0.335 Å), and this is twice as large as that for P5+ (0.170 Å). However, the c unit-cell parameter for mimetite is surprisingly different from that of vanadinite, although their unit-cell volumes, V, are almost equal to each other. No explanation was available for this peculiar c-axis value for mimetite. Structural parameters such as average 〈B-O〉 [4], 〈Pb1-O9〉 [9] and 〈Pb2-O6Cl2〉 [8] distances increase linearly with V (the coordination numbers for the cations are given in square brackets). Mimetite has a short Pb2-O1 distance, so the O1 oxygen atom interacts with the 6s2 lone-pair electrons of the Pb2+ cation that causes the Cl-Cl distance (= c/2) to increase to the largest value in the series because of repulsion, which causes the c-axis to increase anomalously. Although Pb apatite minerals occur naturally in ore deposits, they are also formed as scaly deposits in lead water pipes that give rise to lead in tap water, as was found recently in Flint, Michigan, USA. It is important to identify Pb-containing phases in water-pipe deposits.

Rational Design of a Commensurate (3 + 3)-D Modulated Structure within the Fast-Ion Conducting Stabilized δ-Bi2O3 Series

We report the systematic design, preparation, and characterization of the first commensurate member of the oxide-ionic conducting, (3 + 3)-D modulated, Type II phases of doped δ-Bi2O3. The incommensurate Type II modulation vector e was previously described as continuously variable, but high-resolution synchrotron X-ray powder diffraction data show that close to the composition Bi23CrNb3O45, it “locks in” to e = 1/3. The space group of the resulting 3 × 3 × 3 fluorite-type supercell was found to be F43m by selected-area electron diffraction, and the structure was solved and Rietveld-refined against neutron powder diffraction data in conjunction with local structural information from X-ray absorption spectroscopy, high-resolution transmission electron microscopy, and ab initio geometry optimization calculations. The result unambiguously validates the crystal-chemical model of the Type II phases as being based on the local ordering of oxygen around transition metals M into tetrahedral clusters of MO6 octahe...

Phase identification and structure investigation of novel quaternary rare-earth substituted titanates

Novel quaternary lanthanide-substituted oxides of stoichiometry LnxY2−xTi2O7 (where Ln is lanthanum, neodymium, samarium, gadolinium, or ytterbium) were prepared by traditional high-temperature, solid-state techniques and characterized by X-ray powder diffraction. Samples with nominal values of x up to 1.0 were attempted. The well-studied ternary cubic pyrochlore compound yttrium titanium oxide (Y2Ti2O7, space group Fd-3m, Z = 8), served as a parent structural framework in which Ln3+ cations were substituted on the Y3+ site. Laboratory-grade X-ray powder diffraction data revealed pure quaternary pyrochlore phases for LnxY2−xTi2O7 with x ≤ 0.2. Pyrochlore phase purity was verified by Rietveld analysis using high-resolution synchrotron X-ray powder diffraction data when x ≤ 0.2, however, for La3+ substitution specifically, pure quaternary pyrochlore formed at x<0.1. Band gap energies on selected samples were determined using optical diffuse reflectance spectroscopy and showed that these materials can be classified as electrical insulators with indirect band gap energies around 3.7eV.

Accurate unrestrained DDM refinement of crystal structures from highly distorted and low-resolution powder diffraction data.

The structure of benzene:ethane co-crystal at 90 K is refined with anisotropic displacement parameters without geometric restraints from high-resolution synchrotron X-ray powder diffraction (XRPD) data using the derivative difference method (DDM) with properly chosen weighting schemes. The average C-C bond precision achieved is 0.005 Å and the H-atom positions in ethane are refined independently. A new DDM weighting scheme is introduced that compensates for big distortions of experimental data. The results are compared with density functional theory (DFT) calculations reported by Maynard-Casely et al. [(2016). IUCrJ, 3, 192-199] where a rigid-body Rietveld refinement was also applied to the same dataset due to severe distortions of the powder pattern attributable to experimental peculiarities. For the crystal structure of 2-aminopyridinium fumarate-fumaric acid formerly refined applying 77 geometric restraints by Dong et al. [(2013). Acta Cryst. C69, 896-900], an unrestrained DDM refinement using the same XRPD pattern surprisingly gave two times narrower dispersion of interatomic distances.

Ab Initio Structure Determination and Photoluminescent Properties of an Efficient, Thermally Stable Blue Phosphor, Ba2Y5B5O17:Ce3+

The crystal structure of a novel barium yttrium borate, Ba2Y5B5O17, was determined using a combination of ab initio global optimization algorithms and density functional theory calculations along with Rietveld refinement of high-resolution synchrotron X-ray powder diffraction data. Synthesized using a high-temperature solid-state route, the structure consists of edge- and corner-sharing Y- and Ba-centered polyhedra along with BO3 trigonal planes. Ba and Y occupy four crystallographically independent sites with two fully occupied by Y and two having a statistical mixture of Y and Ba. Substituting Ce3+ into the structure for Y3+ yields blue photoluminescence (λem = 443 nm) upon excitation with UV (λem = 365 nm) light. The emission of this new compound is efficient with an external quantum yield of 70% and is stable as a function of temperature with a quenching temperature of ≈400 K.

Structural and spectroscopic studies of alkali-metal exchanged stilbites

The structural, infrared (IR) and Raman spectroscopic properties of alkali-metal exchanged (Na+, K+, Rb+, Cs+) zeolites with the stilbite (STI) framework have been studied by Rietveld analysis of high-resolution synchrotron X-ray powder diffraction data, micro-Raman and synchrotron IR spectroscopy at ambient conditions. Ordered arrangements of the extra-framework cations (EFCs) and H2O molecules were found at the intersection of the 10- and 8-ring channels as well as framework distortions and deformations of the channel system caused by the EFCs distributions. The T(5)–T(5) distances along the chains of the structural building units range from 8.921(1) to 8.979(5) Å and scale with the size of EFCs in Na-, K-, Rb-, Cs-STI. Furthermore, our spectroscopic studies show a systematic increase of characteristic band frequencies for the 4- and 5-ring breathing vibration modes in the far-IR spectral region with the size of the EFCs. The frequencies of the ring vibrational bands in the IR and Raman spectra are very sensitive to the presence of specific EFCS, and framework distortion.

Chabazite structures with Li+, Na+, Ag+, K+, NH4+, Rb+ and Cs+ as extra-framework cations

Chabazites with Li+, Na+, Ag+, K+, NH4+, Rb+, Cs+ as monovalent extra-framework cations have been prepared from natural chabazite (ORI-CHA, Ca1.6Na0.5Si8.4Al3.6O24·14.3H2O) and characterized using a combination of Rietveld analyses of high-resolution synchrotron X-ray powder diffraction data and synchrotron infrared (IR) spectroscopy. All monovalent cation-exchanged chabazites crystallize in the rhombohedral space group R3¯m; Li-CHA (Li2.9Si8.6Al3.4O24·13.2H2O), a = 9.4068(6), α = 94.9156(9); Na-CHA (Na3.4Si8.6Al3.4O24·11.4H2O), a = 9.4216(3), α = 94.0773(6); Ag-CHA (Ag3.5Si8.5Al3.5O24·15.9H2O), a = 9.4402(4), α = 94.1354(9); K-CHA (K3.2Si8.7Al3.3O24·10.7H2O), a = 9.4420(1), α = 94.2540(3); NH4-CHA ((NH4)2.1Si8.4Al3.6O24·11.6H2O), a = 9.4378(9), α = 94.6101(1); Rb-CHA (Rb4.1Si7.9Al4.1O24·6.5H2O), a = 9.4318(4), α = 94.533(1); Cs-CHA (Cs3.4Si8.6Al3.4O24·6.4H2O), a = 9.4447(4), α = 94.2604(8). We establish correlations between the unit-cell volume, extra-framework cation distribution, and cation selectivity in chabazites. We establish that the unit cell volume of monovalent-cation exchanged chabazites decreases in the order of decreasing ion selectivity, based on the standard free hydration energies of exchange i.e., Cs+ > K+ > Ag+ > Rb+ > Na+ > Li+ and not the cation size.