Maximum filling principle and sublattices of actinide atoms in crystal structures

The most important characteristics of the Voronoi-Dirichlet polyhedra (VDP) of A atoms (A is actinide) in chemically homogeneous sublattices in the crystal structures of 3479 inorganic, coordination, and organometallic compounds are determined. The effect of the actinide nature on the A-A interatomic distances in the crystal structures is considered. In the Th, U, Np, or Pu sublattices, VDP have most often 14 faces and the Fedorov cuboctahedron is the most abundant type of VDP, whereas in Ac, Pa, Am, Cm, Bk, or Cf sublattices, the VDP have mainly 12 faces and are shaped like rhomobododecahedra. In A sublattices that typically form VDP with 14 faces, the actinide atoms occupy, most often, sites with C ₁ symmetry (47 to 59% of the sample size). In the case of actinides whose A sublattices tend to form VDP with 12 faces, the C ₁ site symmetry is found either very rarely (Pa, Am, Cf) or not at all (Ac, Cm, Bk).     

N-(1-萘基)-琥珀酰亚胺化合物晶体结构的理论预测

用Materials Studio软件对N-(1-萘基)-琥珀酰亚胺多晶粉末的X射线衍射数据进行衍射峰指标化、晶胞参数优化和空间群搜索等理论计算, 可以确定晶体结构所属的晶系和空间群, 并初步给出和多晶粉末衍射数据相近的晶胞参数; 在已确定空间群范围内, 以密度泛函理论计算得到的最低能量构象作为初始分子结构, 对N-(1-萘基)-琥珀酰亚胺多晶进行晶体结构理论预测, 给出一系列假定的晶胞参数, 从中可以找到和经上述计算给出的晶胞参数一致的晶体结构；对其进行晶胞参数优化后, 得到晶体结构具有和多晶粉末X射线衍射数据相近的衍射曲线, 并与已有的单晶数据相吻合.     

Neutron powder diffraction study of A2BeF4 (A=K, Rb, Cs): Structure refinement and analysis of background

The crystal structure of potassium, rubidium and caesium fluoroberyllates have been re-examined by neutron powder diffraction at room temperature and at 1.5 K. Previously, their structures, obtained from X-ray data, were described in the Pn2₁a space group. However, the results obtained from Rietveld refinements, using powder neutron diffraction, at both temperatures, indicated that all structures are orthorhombic with space group Pnma. The known phase transition at high temperature is probably related to the appearance of a hexagonal pseudo-symmetry instead of the elimination of the mirror plane between the above mentioned orthorhombic space groups. A possible phase transition, at very low temperature, was discarded considering the stereochemical criteria concerning the structural stability of A₂BX₄ compounds. This was confirmed by thermal analysis. On the other hand, a modulated background has been detected in all samples during the refinements. This is compatible with the presence of an amorphous phase, coexisting with the crystalline phase, or with a disordered component within the main crystalline phase. Instead of using a polynomial function, the background was modelled by Fourier filtering improving the fit for all patterns. The radial distribution function (RDF) was obtained from the analysis of the calculated background and compared with the RDF from the average crystal structure. The advantages of neutron with respect to X-ray diffraction were evidenced for this type of compound with β-K₂SO₄-type structure.     

Short-Chain Mono-Alkyl β-D-Glucoside Crystals—Do They Form a Cubic Crystal Structure?

Three-dimensional liquid crystal (LC) phases, cubic LC phases, have been extensively studied as fascinating molecular assembled systems formed by amphiphilic compounds. However, similar structures have only been seen in rare instances in lipid crystal states in glycolipid crystal studies. In this study, we prepared short-chain n-alkyl β-D-glucosides (CnG) with an alkyl chain length n ranging from 4 to 6 and investigated their crystal structures. First, differential thermal analysis (DTA) and thermogravimetric analysis (TG) measurements showed the formation of hydrated crystals for C4G and C5G, respectively. Second, the crystal structures of CnG (n = 4, 5, 6) in both anhydrous and hydrated states were examined using a temperature-controlled powder X-ray diffraction (PXRD) measurement. Both hydrate and anhydrous crystals of C4G and C5G with critical packing parameters (CPPs) less than 0.33 formed cubic crystal phases. Bilayer lengths, calculated from the main diffraction peaks in each PXRD profile, depended on crystalline moisture for C5G, but no significant change was confirmed for C4G, indicating that the properties of each hydrophilic layer differ. However, C6G with a CPP of 0.42 formed a crystal structure with a modulated lamellar structure similar to C7G and C8G with similar CPP values. Thus, a glycolipid motif concept with a cubic crystal structure was demonstrated.     

A Comparative Analysis of Crystal Lattice Topology in Molybdates and Binary Compounds

A method for topological analysis of crystal structures using graph theory and the IsoTest program is described. Topological analysis and comparison of crystal structures for 34 ordinary and 62 binary molybdates, 2486 compounds A_yX_z, and previously studied anhydrous sulfates using the structural topological program complex TOPOS are reported. Topological relationships between the above classes of compounds are revealed and discussed. The topology of ion sublattices in molybdates is analyzed. Ion sublattices constructed according to the closest-packing motifs may be isolated in 34 of 96 compounds.     

Crystal and molecular structure of nitrophenyl 2,3,4-tri-O-acetyl-β-d-xylopyranosides

Comprehensive structural analyses were performed for o-, m-, and p-nitrophenyl 2,3,4-tri-O-acetyl-β-d-xylopyranosides. Single-crystal X-ray diffraction data were collected and revealed that meta isomer undergoes temperature-dependent polymorph transition (crystal structures of two polymorphs were obtained). This transition was verified by differential scanning calorimetry. The number of molecules in the independent part of the crystal unit cells of the compounds under investigation was in agreement with the number of resonances in solid-state ¹³C and ¹⁵N NMR spectra. The o- and p-nitrophenyl 2,3,4-tri-O-acetyl-β-d-xylopyranosides exist as single polymorph at room temperature, as confirmed by powder X-ray diffraction measurements.     

Magnetic properties and structures of equiatomic rare earth-platinum compounds RPt (R = Gd,Tb, Dy,Ho, Er,Tm)

The magnetic properties and structures of RPt compounds (R = Gd, Tb, Dy, Ho, Er, and Tm) are presented. Below their Curie temperature the compounds exhibit ferromagnetic behavior. In GdPt, the spontaneous magnetization at 4.2°K ($\text{6.7 μ}{}_{\mathrm{<mtext>B</mtext>}}\text{Gd}$) and the small superimposed susceptibility suggest that the gadolinium moments are parallel and the exchange interactions are positive. In the three types of noncollinear magnetic structures observed in the other compounds the rare earth atoms are divided into two sublattices with different magnetization directions. They give rise to a ferromagnetic component associated with an antiferromagnetic component. These structures, which are analyzed in terms of crystal field effects, result from a competition between a magnetocrystalline anisotropy and positive exchange interactions of Heisenberg type.     

Maximum filling principle and sublattice characteristics for the atoms of period 2 elements

The most important characteristics of the Voronoi-Dirichlet polyhedra (VDP) of 7195542 atoms A (A = Li, Be, B, C, N, O, or F) in sublattices containing only chemically identical A atoms in the crystal structures of inorganic, coordination, and organoelement compounds were determined. The VDP of Li, Be, B, N, O, or F atoms in these sublattices have most often 14 faces and those of C atoms, 16 faces. The Fedorov cuboctahedron is the most abundant combinatorial topologic type of VDP in all cases. The effect of the nature of the A atoms on the A-A interatomic distances in the homoatomic sublattices of the crystal structures was considered.     

A green route for microwave synthesis of sodium tungsten bronzes NaxWO3 (0<x<1)

A green route has been developed for microwave synthesis of sodium tungsten bronzes Na_xWO₃ (0<x<1) from Na₂WO₄, WO₃ and tungsten powder. The hybrid microwave synthesis was carried out in argon atmosphere using CuO powder as the heating medium. Tungsten powder is used as the reducing agent instead of the alkali metal iodides previously used for the microwave synthesis of oxide bronzes. The prepared samples were characterized by powder X-ray diffraction, energy-dispersive X-ray analysis and scanning electron microscopy, and their phase constitutions, crystal structures and morphologies are in consistence with that in the literature. This synthesis method is simple, green and atom economic, and promising for preparation of other oxide bronzes and related compounds.     

Synthesis, characterization and thermal properties of small R2R2NX-type quaternary ammonium halides

Twenty-one R₂R^′₂N⁺X⁻ -type (R=methyl or ethyl, R^′=alkyl, X=Br or I) quaternary ammonium (QA) halides have been prepared by using a novel one-pot synthetic route in which a formamide (dimethyl-, diethylformamide, etc.) is treated with alkyl halide in the presence of sodium or potassium carbonate. The formation of QA halides was verified with ¹H-NMR, ¹³C-NMR, MS and elemental analysis. The crystal structures of four QA halides (two bromide and two iodide) were determined using X-ray single crystal diffraction, and the powder diffraction method was used to study the structural similarities between the single crystal and microcrystalline bulk material. The thermal properties of all compounds were studied using TG/DTA and DSC methods. The smallest compounds decomposed during or before melting. The decreasing trend of melting points was observed when the alkyl chain length was increased. The liquid ranges of 120-180 °C were observed for compounds with 5-6 carbon atoms in the alkyl chain. The low melting points and wide liquid ranges suggest potential applicability of these compounds for example as ionic liquids precursors.     

Maximum filling principle and sublattice characteristics for the atoms of period 3 elements

The most important characteristics of the Voronoi-Dirichlet polyhedra (VDP) of A atoms (A = Na, Mg, Al, Si, P, S, Cl, or Ar) were determined. The sublattices contain chemically identical A atoms in the crystal structures of 232006 inorganic, coordination, and organoelement compounds. The VDP of A atoms have most often 14 faces, the Fedorov cuboctahedron being the most abundant VDP type. The effect of the nature of the A atoms on the characteristic A-A interatomic distances in the homoatomic sublattices of the crystal structures was considered.     

RuGavSnw Nowotny Chimney Ladder Phases and the 14-Electron Rule

A series of ruthenium gallium stannides have been prepared with stoichiometry RuGa_vSn_w, where 8+3v+4w=14 and 0<v<0.70. These samples have been analyzed by X-ray powder diffraction and transmission electron microscopy (TEM). The data show that these compounds are Nowotny chimney ladder phases with both commensurate and incommensurate structures. We show that there are special characteristics in chimney ladder powder diffraction patterns that allow one to determine the ratio of main group atom-sites to transition metal atom-sites to high accuracy. Our results confirm earlier work which suggest that both the stoichiometry and the structure of chimney ladder phases are dominated by electronic factors. The structures reported in this paper adhere to the 14-electron rule, i.e., there are 14 valence electrons per transition metal ion. The interplay of main group and transition metal structures leads to a pseudo c-axis, the presence of which is confirmed by the TEM data. We discuss the relation between these phases and the Fibonacci sequence.     

Structure determination from powder diffraction

The review surveys modern methods for the determination of unknown crystal structures of organic and inorganic compounds from powder diffraction data. The main stages of this process, from the preparation of the specimen to a search for the structural motif followed by the Rietveld refinement, are considered. The results obtained on different diffractometers using X-ray, synchrotron, and neutron radiations are demonstrated to be well reproducible. Examples of successful structure solution are cited, which provide evidence that powder diffraction is a reliable tool in establishing structures of a wide range of compounds for which single crystals are unavailable.     

Structural phase transition and magnetic properties of the Sr2FeRe1−xBx′O6 (B′=Nb, Ta; x=0, 0.1) double perovskites

The double perovskites, Sr₂FeReO₆ and Sr₂FeRe_0.9M_0.1O₆ (M=Nb, Ta) have been obtained by soft synthesis methods which yield homogeneous particles of micrometric grain size. The materials have been studied by X-ray and neutron powder diffraction, scanning electron microscopy and magnetic measurements. Rietveld refinements show that the compounds adopt a tetragonal I4/mmm structure at high temperatures and monoclinic P2₁/n below the transition temperature. The magnetic structures were determined by neutron powder diffraction at 100 and 300 K for the Sr₂FeReO₆, Sr₂FeRe_0.9Nb_0.1O₆ and Sr₂FeRe_0.9Ta_0.1O₆ phases, respectively. Evidence for a ferrimagnetic coupling between the Fe³⁺ and Re⁵⁺ sublattices has been observed. Magnetic measurements yield magnetic moments lower than the theoretical ones being in accord with the antisite disorder of 25% in the B-B′ positions.     

Spectral thermal and X-ray diffraction studies of La(III) and Sm(III) complexes of nitrogen and sulphur donor ligands

Some interesting lanthanide metal chelates of nitrogen and sulphur donor ligands, e.g. salicylalidinethiosemicarbazone, 2 - hydroxy - 1 - naphthalidinethiosemicarbazone and 2 - hydroxyacetophenoneiminethiosemicarbazone (TSCH₂) have been prepared by 1:1, 2:3 and 1:2 (M:L) molar reactions of tris-(isopropoxyl)lanthanum or samarium under anhydrous conditions. The elemental analysis, molecular weight determinations, conductance measurements and IR, proton magnetic resonance and electronic spectral studies along with magnetic measurements are discussed in relation to the characteristics and proposed structures for these newly synthesized compounds. The thermolytic decomposition of a few chelates has also been studied and the data have been used for evaluating the kinetic parameters along with thermal stabilities. The X-ray powder diffraction patterns of the representative compounds have been used for determining the crystal symmetry of the proposed structures and the cell parameters along with the number of molecules per unit cell.     

Palladium site ordering and the occurrence of superconductivity in Bi2Pd3Se2−xSx

The crystallographic and electronic structures of compounds related to parkerite (Bi₂Ni₃S₂) are investigated with respect to the recently reported occurrence (Bi₂Pd₃Se₂) and absence (Bi₂Pd₃S₂) of superconductivity. Similarities and differences of the crystal structures are discussed within the series of solid solutions Bi₂Pd₃S_2−xSe_x from powder and single crystal diffraction data. From crystal structure refinements, the question of different structures and settings of parkerite is discussed. Similar and different 2D and 3D partial Pd-Ch (Ch=S, Se) structures are related to half antiperovskite ordering schemes. To investigate the relation of low dimensional structures and the occurrence of superconductivity, electronic structures are analyzed by scalar-relativistic DFT calculations, including site projected DOS, ECOV and Fermi surfaces.     

Effect of microfibril twisting on theoretical powder diffraction patterns of cellulose Iβ

Previous studies of calculated diffraction patterns for cellulose crystallites suggest that distortions that arise once models have been subjected to molecular dynamics (MD) simulation are the result of both microfibril twisting and changes in unit cell dimensions induced by the empirical force field; to date, it has not been possible to separate the individual contributions of these effects. To provide a better understanding of how twisting manifests in diffraction data, the present study demonstrates a method for generating twisted and linear cellulose structures that can be compared without the bias of dimensional changes, allowing assessment of the impact of twisting alone. Analysis of unit cell dimensions, microfibril volume, hydrogen bond patterns, glycosidic torsion angles, and hydroxymethyl group orientations confirmed that the twisted and linear structures collected with this method were internally consistent, and theoretical powder diffraction patterns for the two were shown to be effectively indistinguishable. These results indicate that differences between calculated patterns for the crystal coordinates and twisted structures from MD simulation can result entirely from changes in unit cell dimensions, and not from microfibril twisting. Although powder diffraction patterns for models in the 81-chain size regime were shown to be unaffected by twisting, suggesting that a modest degree of twist is not inconsistent with available crystallographic data, it may be that other diffraction techniques are capable of detecting this structural difference. Until such time as definitive experimental evidence comes to light, the results of this study suggest that both twisted and linear microfibrils may represent an appropriate model for cellulose Iβ.     

A computational,X-ray crystallographic and thermal stability analysis of TETROL and its pyridine and methylpyridine inclusion complexes

The identification and application of (+)-(2R,3R)-1,1,4,4-tetraphenylbutane-1,2,3,4-tetrol (TETROL) as an efficient and selective host compound is described. Computational and single crystal X-ray diffraction analyses revealed that the butane backbone of TETROL adopts a relatively rigid anti-conformation, with the hydroxy groups oriented syn and connected through a cyclic, homodromic arrangement of their O–H bonds. This structure is stabilised through a pair of 1,3-hydrogen bonding interactions. TETROL forms inclusion complexes with pyridine and 3- and 4-methylpyridine, and does so selectively from mixtures of the pyridines. X-ray diffraction (single crystal and powder) and thermal analyses of the inclusion compounds are described.     

Single-crystal structures of uranium and neptunium oxychalcogenides AnOQ (An=U, Np; Q=S, Se)

The compounds UOS, UOSe, NpOS, and NpOSe have been synthesized and their structures determined by means of single-crystal X-ray diffraction methods. The results provide more detailed crystallographic information, including more precise interatomic distances, than earlier determinations from powder diffraction data. These isostructural compounds adopt the PbFCl structure type. Each An atom is surrounded by four O and five Q atoms in a distorted monocapped square-antiprismatic arrangement.