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Determination of the crystal system and space group is the first step of crystal structure analysis. Often this turns out to be a bottleneck in the material characterization workflow for polycrystalline compounds, thus requiring manual interventions. This work proposes a new machine-learning (ML)-based web platform, CrystalMELA (Crystallography MachinE LeArning), for crystal systems classification. Two different ML models, random forest and convolutional neural network, are available through the platform, as well as the extremely randomized trees algorithm, available from the literature. The ML models learned from simulated powder X-ray diffraction patterns of more than 280 000 published crystal structures from organic, inorganic and metal–organic compounds and minerals which were collected from the POW_COD database. A crystal system classification accuracy of 70%, which improved to more than 90% when considering the Top-2 classification accuracy, was obtained in tenfold cross-validation. The validity of the trained models has also been tested against independent experimental data of published compounds. The classification options in the CrystalMELA platform are powerful, easy to use and supported by a user-friendly graphic interface. They can be extended over time with contributions from the community. The tool is freely available at https://www.ba.ic.cnr.it/softwareic/crystalmela/ following registration.

The solid-state chemistry of inclusions in Al2O3 is of high relevance in several applications, spanning from photonics to materials engineering and gemology. Be-thermodiffusion is a common treatment of corundum crystals to improve their optical properties. The chemistry of such a high-temperature process is still unclear. Particularly, the interconversion between corundum host and guest inclusion species involves many chemical species and several steps, whose knowledge would guide the tuning of corundum chemical preparation. Herein, 43 thermodiffusion-treated sapphires are investigated, with a focus on 14 samples endowed with blue halos, via optical microscopy, scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDS) quantitative chemical analyses, Raman microspectroscopy, and X-ray powder diffraction. This study searches for the snapshots of the chemical path and then recomposes them to propose a novel chemical mechanism in which Be reduces TiO2 inclusion, which is then converted, mediated by iron ions, to several titanates. The chemical mechanism is discussed in terms of applications not limited to only gemology but to any derivative corundum crystal preparation.

Innovative computational and graphical tools have been implemented for advancing the crystal structure solution process from powder diffraction data using the EXPO software. These improve the capacity of EXPO to tackle challenging solution cases and make the structural study of microcrystalline materials more user friendly. The novel features concern the structure solution both in reciprocal space and in direct space. For reciprocal-space solution, the new capability to solve an unknown structure from a mixture composed of one unknown structure and one or more phases with known structures is particularly valuable. For direct-space structure solution, EXPO has been enhanced by parallelized simulated annealing with the aim of both reducing the execution time of the solution process and providing a successful result when several degrees of freedom must be varied. Many other new tools, functional for overcoming practical difficulties usually encountered during the solution process, have also been completed. In particular, a new tool for searching and importing structures from the Crystallography Open Database is effective for supporting the solution process in direct space. The advances in EXPO aim to provide software with improved reliability, expanded operation and greater speed.

The scientific interest toward the structural, luminescence, and dielectric properties of tricalcium phosphate (TCP) materials, in particular, the doped TCP-based compounds, is mainly due to their biocompatibility and bioactivity behavior and the increasing number of their applications. In the literature, structural investigations of a doped ?-TCP compound are usually carried out by powder diffraction data under the assumption that it has a centrosymmetric whitlockite structure. Recent studies have shown that this assumption is not always fulfilled. For this reason, it is necessary to use methods of nonlinear and dielectric spectroscopy to prove the true symmetry of whitlockite-like phases. This work provides a detailed and comprehensive study on the structural, dielectric, and nonlinear properties of the polycrystalline Tb- and Ho-doped tricalcium phosphates, chemically Ca9Tb(PO4)7 and Ca9Ho(PO4)7. Their crystal structure was explored using powder X-ray diffraction, adopting an ab initio approach for the structure solution followed by the Rietveld refinement. For Ca9Tb(PO4)7, the qualitative analysis of the experimental powder X-ray diffraction pattern revealed that the sample was not a single phase. Nevertheless, its crystal structure has been determined by Direct Methods. The presence of the dopant cation was omitted in the solution process by Direct Methods and considered in the successive Rietveld refinement step. The analysis of the occupancies has clarified the Tb3+ cation distribution in its preferential sites. The same pathway has been followed for the Ca9Ho(PO4)7 sample, which corresponded to a single-phase structure. The dielectric properties of the two doped compounds (Tb3+ and Ho3+) were also examined, and reversible ferroelectric-paraelectric phase transitions were found at 862 and 872 K, respectively.

Niclosamide (NCS) is a drug that has been used as an anthelmintic and anti-parasitic drug for about 40 years. Recently, some studies have highlighted its potential in treating various tumors, allowing a repositioning of this drug. Despite its potential, NCS is a Biopharmaceutical Classification System (BCS) Class II drug and is consequently characterized by low aqueous solubility, poor dissolution rate and reduced bioavailability, which limits its applicability. In this work, we utilize a very novel technique, direct powder extrusion (DPE) 3D printing, which overcomes the limitations of previously used techniques (fused deposition modelling, FDM) to achieve direct extrusion of powder mixtures consisting of NCS, hydroxypropyl methylcellulose (HPMC, Affinisol 15 LV), hydroxypropyl-β-cyclodextrin (HP-β-CD) and polyethylene glycol (PEG) 6000. For the first time, direct printing of powder blends containing HP-β-CD was conducted. For all tablets, in vitro dissolution studies showed sustained drug release over 48 h, but for tablets containing HP-β-CD, the release was faster. Solid-state characterization studies showed that during extrusion, the drug lost its crystal structure and was evenly distributed within the polymer matrix. All printed tablets have exhibited good mechanical and physical features and a stability of the drug content for up to 3 months. This innovative printing technique has demonstrated the possibility to produce personalized pharmaceutical forms directly from powders, avoiding the use of filament used by FDM. Graphical abstract

Niclosamide (NCS) is a drug that has been used as an anthelmintic and anti-parasitic active principle for about 40 years. Recently, some studies have highlighted its potential in treating various tumors, allowing a repositioning of this drug. Despite its potential, NCS is a Biopharmaceutical Classification System (BCS) Class II drug, and is consequently characterised by low aqueous solubility, poor dissolution rate and reduced bioavailability, which limits its applicability. In this work, we utilize a very novel technique, Direct Powder Extrusion (DPE) 3D printing, which overcomes the limitations of previously used techniques (Fused Deposition Modelling, FDM) to achieve direct extrusion of pharmaceutical grade powder mixtures consisting of NCS, hydroxypropyl methylcellulose (HPMC, Affinisol 15 LV), hydroxypropyl-b-cyclodextrin (HP-β-CD) and polyethylene glycol (PEG) 6000. For the first time, direct printing of powder blends containing HP-β-CD was explored. For all tablets, in vitro dissolution studies showed sustained drug release over 48 hours, but for tablets containing HP-β-CD, the release was faster. Solid-state characterisation studies showed that during extrusion, the drug lost its crystal structure and was evenly distributed within the polymer matrix. All printed tablets exhibited good mechanical and physical features and guarantee stability of the drug content for up to 3 months. This innovative printing technique has demonstrated the possibility to produce personalised pharmaceutical dosage forms starting directly from powders, avoiding the use of filament used by FDM.

The title compound, 3N-ethyl-2N’-(2-ethylphenylimino)thiazolidin-4-one (C13H16N2OS), was synthesized and structurally studied by IR and (1H, 13C) NMR spectroscopy. The crystal structure of the title compound was investigated using powder X-ray diffraction (PXRD) data via Direct Methods and refined by the Rietveld method. The compound crystallizes in the tetragonal system, space group I−4 with cell constants: a = 16.99742(15) A, b = 16.99742(15) A, c = 9.2663(2) A, V = 2677.15(7) A3, Z = 8. The molecular geometry was optimized using the density functional theory (DFT/B3LYP) method with the 6-311G(d,p) basis set and compared to the experimental data. The experimental and theoretical structures are found to be consistent. The molecular packing of the title compound exhibits C H⋅⋅⋅O and O H⋅⋅⋅N hydrogen bonds forming supramolecular network. The details of the intermolecular interactions were studied through the Hirshfeld surface map and two-dimensional fingerprint plot. Detailed vibrational assignments and NMR chemical shifts were explored by DFT computation, showing good agreement with the experimental results. All the vibrational modes were assigned using the potential energy distribution (PED). UV–Visible spectrum in chloroform solvent was analyzed and electronic transitions involved in the title compound were predicted using the TD-DFT method. The direct and indirect band gaps were estimated using Tauc Plots via UV–Vis spectroscopy. Furthermore, the values of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy were calculated by the DFT method and their distribution was confirmed by the determination of DOS spectra. The global reactivity descriptors and the Fukui functions were evaluated. Mulliken population analysis and natural bond orbital (NBO) theory were used to compute atomic charges and the outcomes are consistent with the MEP map distribution.

Despite the increasing incidence of hepatocellular carcinoma (HCC) worldwide, current pharmacological treatments are still unsatisfactory. We have previously shown that lysophosphatidic acid receptor 6 (LPAR6) supports HCC growth and that 9-xanthenylacetic acid (XAA) acts as an LPAR6 antagonist inhibiting HCC growth without toxicity. Here, we synthesized four novel XAA derivatives, (±)-2-(9H-xanthen-9-yl)propanoic acid (compound 4 - MC9), (±)-2-(9H-xanthen-9-yl)butanoic acid (compound 5 - MC6), (±)-2-(9H-xanthen-9-yl)hexanoic acid (compound 7 - MC11), and (±)-2-(9H-xanthen-9-yl)octanoic acid (compound 8 - MC12, sodium salt) by introducing alkyl groups of increasing length at the acetic α-carbon atom. Two of these compounds were characterized by X-ray powder diffraction and quantum mechanical calculations, while molecular docking simulations suggested their enantioselectivity for LPAR6. Biological data showed anti-HCC activity for all XAA derivatives, with the maximum effect observed for MC11. Our findings support the view that increasing the length of the alkyl group improves the inhibitory action of XAA and that enantioselectivity can be exploited for designing novel and more effective XAA-based LPAR6 antagonists.

Pure and Co

Anionic complexes having vapochromic behavior are investigated: [K(H2O)][M(ppy)(CN)2], [K(H2O)][M(bzq)(CN)2], and [Li(H2O)n][Pt(bzq)(CN)2], where ppy = 2-phenylpyridinate, bzq = 7,8-benzoquinolate, and M = Pt(II) or Pd(II). These hydrated potassium/lithium salts exhibit a change in color upon being heated to 380 K, and they transform back into the original color upon absorption of water molecules from the environment. The challenging characterization of their structure in the vapochromic transition has been carried out by combining several experimental techniques, despite the availability of partially ordered and/or impure crystalline material. Room-temperature single-crystal and powder X-ray diffraction investigation revealed that [K(H2O)][Pt(ppy)(CN)2] crystallizes in the Pbca space group and is isostructural to [K(H2O)][Pd(ppy)(CN)2]. Variable-temperature powder X-ray diffraction allowed the color transition to be related to changes in the diffraction pattern and the decrease in sample crystallinity. Water loss, monitored by thermogravimetric analysis, occurs in two stages, well separated for potassium Pt compounds and strongly overlapped for potassium Pd compounds. The local structure of potassium compounds was monitored by in situ pair distribution function (PDF) measurements, which highlighted changes in the intermolecular distances due to a rearrangement of the crystal packing upon vapochromic transition. A reaction coordinate describing the structural changes was extracted for each compound by multivariate analysis applied to PDF data. It contributed to the study of the kinetics of the structural changes related to the vapochromic transition, revealing its dependence on the transition metal ion. Instead, the ligand influences the critical temperature, higher for ppy than for bzq, and the inclination of the molecular planes with respect to the unit cell planes, higher for bzq than for ppy. The first stage of water loss triggers a unit cell contraction, determined by the increase in the b axis length and the decrease in the a (for ppy) or c (for bzq) axis lengths. Consequent interplane distance variations and in-plane roto-translations weaken the π-stacking of the room-temperature structure and modify the distances and angles of Pt(II)/Pd(II) chains. The curve describing the intermolecular Pt(II)/Pd(II) distances as a function of temperature, validated by X-ray absorption spectroscopy, was found to reproduce the coordinate reaction determined by the model-free analysis., This research has been supported by the short-term mobility program of the National Research Council (CNR) of Italy and by the Spanish Ministerio de Economía y Competitividad (Ministerio de Ciencia Innovación y Universidades)/FEDER (Project PGC2018-094749-B-I00).

Pure and Co3+-doped BaAl2O4 [Ba(Al1–xCox)2O4, x = 0, 0.0077, 0.0379] powder samples were prepared by a facile hydrothermal route. Elemental analyses by static secondary ion mass spectrometry (SIMS), X-ray absorption spectroscopy (XAS) measurements at the Co K- edge, and X-ray diffraction studies were fully correlated, thus addressing a complete description of the structural complexity of Co3+- doped BaAl2O4 powder. Powder X-ray diffraction (PXRD) patterns indicated that prepared samples were nanocrystalline with a hexagonal P63 symmetry. The X-ray absorption near-edge structure (XANES) measurements revealed the presence of cobalt in a +3 oxidation state, while the rarely documented, tetrahedral symmetry around Co3+ was extracted from the extended X-ray absorption fine structure (EXAFS) oscillation patterns. Rietveld structure refinements showed that Co3+ preferentially substitutes Al3+ at tetrahedral Al3 sites of the BaAl2O4 host lattice, whereas the (Al3)O4 tetrahedra remain rather regular with Co3+–O distances ranging from 1.73(9) to 1.74(9) Å. The underlying magneto- structural features were unraveled through axial and rhombic zero-field splitting (ZFS) terms. The increased substitution of Al3+ by Co3+ at Al3 sites leads to an increase of the axial ZFS terms in Co3+-doped BaAl2O4 powder from 10.8 to 26.3 K, whereas the rhombic ZFS parameters across the series change in the range from 2.7 to 10.4 K, showing a considerable increase of anisotropy together with the values of the anisotropic g- tensor components flowing from 1.7 to 2.5. We defined the line between the Co3+ doping limit and influenced magneto- structural characteristics, thus enabling the design of strategy to control the ZFS terms’ contributions to magnetic anisotropy within Co3+-doped BaAl2O4 powder.

The important role played by powder diffraction in the last twenty-five years both in its earlier fields of application (e [...]

The solution of crystal structures from X-ray powder diffraction data has undergone intense development in the last 25 years. Overlapping, background estimate, and preferred orientation are the main difficulties in the process of determining a crystal structure from the analysis of the mono-dimensional powder diffraction pattern. EXPO is a well-known computer program that is designed to solve organic, inorganic, and metal&ndash, organic structures by powder diffraction data, employing the two most widely used kinds of solution methods: Direct Methods, working in the reciprocal space, and Simulated Annealing, working in the real space. EXPO also allows the suitable combination of these two approaches to validate the structural solution. In this paper, we give examples of structure characterization by EXPO with the aim of suggesting a solution strategy for the application of reciprocal-space methods or real-space methods, or both.

Luminescence properties of europium-doped Ca10-xEux(PO4)6(OH)2 (xEu = 0, 0.01, 0.02, 0.10 and 0.20) and gadolinium-doped hydroxyapatite Ca9.80Gd0.20(PO4)6(OH)2 (HA), synthesized via solid-state reaction at T = 1300 &deg, C, were investigated using scanning electron microscopy (SEM), powder X-ray diffraction (PXRD), Fourier transform infrared (FTIR), and luminescence spectroscopy. Crystal structure characterization (from unit cell parameters determination to refined atomic positions) was achieved in the P63/m space group. FTIR analyses show only slight band shifts of (PO4) modes as a function of the rare earth concentration. Structural refinement, achieved via the Rietveld method, and luminescence spectroscopy highlighted the presence of dopant at the Ca2 site. Strong luminescence was observed for all Eu- and Gd-doped samples. Our multi-methodological study confirms that rare-earth (RE)-doped synthetic hydroxyapatites are promising materials for bio-imaging applications.

Silver lanthanum diphosphates doped with terbium, AgLa1-xTbxP2O7 (x=0%, 1%, 5%, 10%, 15% and 20%), were prepared by solid state reaction at T=500°. The obtained compounds were investigated by means of a multi-methodological approach, involving the Scanning Electron Microscopy (SEM) equipped with energy dispersive X-Ray spectroscopy (EDS) for morphological investigation and semi-quantitative chemical analysis, respectively; powder X-ray diffraction (PXRD) for structural characterization and Rietveld refinement; Fourier Transform InfraRed (FTIR) and Raman spectroscopies for qualitative study. Finally, emission spectra were collected in order to detect the fluorescence properties of the compounds. The unit cell parameters and the space group of all the family members were determined by PXRD data. The compounds crystallize in the orthorhombic Pnma space group, with the AgLaP2O7 cell constants equal to: a = 8.6706(1) A, b = 5.3218(1) A, c = 12.8839(1) A and cell volume V = 594.51(1) A3. A decreasing trend for unit cell parameters was observed at increase of dopant concentration. For the pure phase, the investigation was completed with the structure solution via Direct Methods and Rietveld refinement. The crystal structure consists of compact layers of LaO9 polyhedra, down the c axis, bridged by P2O7 diphosphate groups and by zig-zag chains of AgO9 polyhedra down b. The FTIR and Raman analysis supports the chemical structure, highlighting the deformation (δPO3) and stretching (νPO3) vibration of PO3 groups, and the characteristic bands of P2O74- groups attributed to the symmetric and asymmetric stretching (νs and νas) of P-O-P bridge, respectively. The luminescence properties of Tb3+ activating ion in AgLa1-xTbxP2O7 (x=1%, 5%, 10%, 15% and 20%) were also examined. No concentration quenching of the main 5D4-→7F5 emission, responsible for the well known green emission of Tb3+ ion, was observed in the studied concentration range, whereas a concentration quenching of the emission from 5D3 level, due to 5D3-→5D4 cross relaxation process, was revealed.

The Shift_and_Fix procedure is a new method which has been developed for improving the quality of a structure model obtained by the ab initio solution process from powder diffraction data. The main features of the new approach, which is fully automatic, are as follows: (a) the structure model usually attained at the end of the phasing process by direct methods is shifted partly and randomly; (b) a combination of Fourier map calculation and least-squares cycles has been designed for relocating the shifted atoms onto positions which can finally be moved onto the true ones by the standard model optimization approaches; (c) the Fourier map is calculated using coefficients which depend on the chemical content of the compound under study. When the figure of merit for selecting the best set of phases derived by direct methods does not work well, the ALLTRIALS strategy can be applied: it aims to investigate, automatically and sequentially, all the stored direct methods phasing sets and pick up the correct solution. The Shift_and_Fix method has been applied for improving the structure model calculated by each one of the phasing sets processed by ALLTRIALS. It has been implemented in the computer program EXPO and proved to be effective in providing a better ALLTRIALS outcome and increasing the probability of succeeding in the ab initio powder solution.

The phase identification of a polycrystalline mixture by X-ray powder diffraction data is often requested for studying materials interesting to different scientific and technological fields: chemistry, pharmaceutics, mineralogy, archeometry, forensic science, etc. The availability of user friendly computer programs, able to carry out qualitative phase analysis in efficient and possibly automatic way, is extremely useful to the scientific community involved in powder diffraction. QUALX2.0, the evolution of QUALX, is a freely distributed software for qualitative phase analysis. Based on the traditional search–match method, it is able to manage both a commercial database (PDF-2 maintained by ICDD), and a freely available database (POW_COD generated by the structure information contained in the Crystallography Open Database). QUALX2.0 is continuously improved in terms of computing and graphic tools. Correspondingly, the database POW_COD is suitably modified to make efficient the operations of search. The search–match approach can be facilitated by the use of restraints, when available, involving the chemical composition, the kind of compound(s) (e.g., organic, inorganic, etc.), the symmetry (space group, crystal system), the unit-cell parameters and/or volume, the crystal properties (measured and/or calculated crystal density, crystal color). An outline of the main features of QUALX2.0 and an example of application is described.

Three hydrated double layered vanadium oxides, namely Na0.35V2O5·0.8(H2O), K0.36(H3O)0.15V2O5 and (NH4)0.37V2O5·0.15(H2O), were obtained by using mild hydrothermal conditions. Their delta type structural frameworks were solved by high-resolution synchrotron X-ray powder diffraction and the interlayer spacings were interpreted from difference Fourier maps. The inter-slab distances are modulated by the water content and the special arrangements of the alkali and ammonium cations. The XPS measurements denote mixed valence systems with high contents of V4+ ions up to 40%. The monitoring of the V4+ EPR signal over time suggests a reduction of the electronic delocalization on account of the partial oxidation to V5+. The electrochemical performance of the active phases is strongly conditioned by the vacuum-drying process of the electrodes, showing better capacity retention when vacuum is not applied. In situ X-ray diffraction shows a structural mechanism of contraction/expansion of the bilayers upon lithium insertion/extraction where the alkali ions behave as structural stabilizers. Galvanostatic cycling at very low current density implies migration of the alkali "pillars" triggering the collapse of the structure.

C a 2.90 M e 0.10 2 + ( P O 4 ) 2 (with Me = Mn, Ni, Cu) &beta, tricalcium phosphate (TCP) powders were synthesized by solid-state reaction at T = 1200 &deg, C and investigated by means of a combination of scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS), powder X-ray diffraction (PXRD), Fourier transform infrared (FTIR) spectroscopy, and luminescence spectroscopy. SEM morphological analysis showed the run products to consist of sub spherical microcrystalline aggregates, while EDS semi-quantitative analysis confirmed the nominal Ca/Me composition. The unit cell and the space group were determined by X-ray powder diffraction data showing that all the compounds crystallize in the rhombohedral R3c whitlockite-type structure, with the following unit cell constants: a = b = 10.41014(19) &Aring, c = 37.2984(13) &Aring, and cell volume V = 3500.53(15) &Aring, 3 (Mn), a = b = 10.39447(10) &Aring, c = 37.2901(8) &Aring, V = 3489.22(9) &Aring, 3 (Ni), a = b = 10.40764(8) &Aring, c = 37.3158(6) &Aring, V = 3500.48(7) &Aring, 3 (Cu). The investigation was completed with the structural refinement by the Rietveld method. The FTIR spectra are similar to those of the end-member Ca &beta, tricalcium phosphate (TCP), in agreement with the structure determination, and show minor band shifts of the (PO4) modes with the increasing size of the replacing Me2+ cation. Luminescence spectra and decay curves revealed significant luminescence properties for Mn and Cu phases.

In this work, a rapid "bottom-up" procedure of the preparation of alcoholic dispersions of calcium hydroxide and strontium hydroxide has been realized. The particles of calcium hydroxide have an average diameter of 360 nm, PdI (Poly dispersion Index) is equal to 0.188 (mono-disperse) and the colloidal particles show a good kinetic stability (600 nm) with a zeta potential of +37mV. The particles of strontium hydroxide show an average diameter of 180nm, PdI is 0.260 and zeta potential of +14mV.

Silver terbium diphosphate AgTbP2O7 was prepared by solid state reaction at T=500° and characterized by combining SEM-EDS morphological investigation and semi-quantitative chemical analysis via Scanning Electron Microscopy (SEM) equipped with energy dispersive X-Ray spectroscopy (EDS), structure solution via Rietveld refinement of powder X-ray diffraction (PXRD) data, and Fourier transform infrared (FTIR) spectroscopy. The synthesized compound is monoclinic, P21/n space group, with cell parameters: a=11.9108(3) Å, b=6.90265(16) Å, c=6.62030(15) Å, β=90.3702(5)° and V=544.28(2) Å3. The crystal structure consists of a network of zig-zag chains of TbO8 polyhedra extending along the b axis, bridged by P2O7 diphosphate groups and by chains of AgO7 polyhedra running along the c crystallographic direction. MIR (medium infrared) spectrum shows bands typical of P–O modes of diphosphate compounds. Observed band multiplicity is in agreement with the symmetry reduction with respect to orthorhombic rare earth diphosphates with similar stoichiometries reported in the literature.

International audience; Oxetanes are key synthons for asymmetric synthesis and also effective in directing ortho‐lithiation. This work first reports the solution and the solid‐state structure of an ortho‐lithiated aryloxetane (1‐Li) in the presence/absence of a bidentate ligand such as N,N,N′,N′‐tetramethylethylenediamine (TMEDA). Single crystal X‐ray diffraction analysis of 1‐Li revealed a singular crystallographic structure in which the asymmetric unit comprises a core where the lithium atom is coordinated to the nitrogen atom of half a molecule of TMEDA and intramolecularly stabilised by the oxetane ring oxygen. This aggregation state is unprecedented in ortho‐lithiated arenes. Variable temperatures multinuclear magnetic resonance (1H, 7Li, 13C) mono‐ and two‐dimensional NMR studies and DFT computations supported the coexistence in solution of three chelated bridged dimeric aggregates, in slow equilibration at 180 K. The major isomer is an heterochiral aggregate on the basis of 1H,7Li‐HOESY and 1H,1H‐NOESY experiments. Conclusions were supported by the preparation of enantiomerically enriched (S)‐1‐Li. The privileged formation of homochiral aggregates from racemic mixtures may also have implications for the development of chiral resolution processes.

Rare earth elements doped (beta-tricalcium phosphates Ca9RE(PO4)(7) (RE = La, Pr, Nd, Eu, Gd, Dy, Tm, Yb) were synthesized by solid-state reaction at T = 1200 degrees C. The obtained RE-doped beta-TCP phases were studied by a combination of Scanning Electron Microscopy (SEM) equipped with energy dispersive X-Ray spectroscopy (EDS), X-ray diffraction (XRD), Fourier Transform Infra Red (FTIR) and Raman spectroscopies. SEM morphological analyses revealed the presence of sub spherical micro crystalline aggregates, while EDS semi quantitative analyses confirmed the nominal RE/Ca composition for all the phases. The unit cell and the space group were determined by X-ray powder diffraction data showing that all phases in the series crystallize in the rhombohedral R3c whitlockite-type structure; the unit cell constants are a linear function of the dimension of the substituting rare-earth element, and range from a = b = 10.4695(3) angstrom, c = 37.500(3) angstrom and V= 3559.7(2) angstrom(3) (La) up to a = b = 10.4073(2) angstrom, c = 37.2725(2) angstrom, V = 3496.2(2) angstrom(3) (Yb). The analysis of each compound was completed with the structure model refinement by the Rietveld method and the distribution of RE within the available structural sites is discussed according to the results of the Rietveld refinement. The FTIR and Raman spectra show slight band shifts of the phosphate modes correlated to the evolving size of the RE element.

The reactivity of 2-(prop-2-ynylthio)-1 H-benzo[d]imidazoles and their corresponding hydrobromide salts under PdI2/KI-catalyzed oxidative aminocarbonylation conditions has been studied. It is found that 2-prop-2-ynylsulfanyl-3 H-benzimidazolium salts, when allowed to react with amines, carbon monoxide, and oxygen, under the catalytic action of PdI2 (1 mol %) in conjunction with KI (1 equiv), under suitable conditions (80 °C and 20 atm of a 4:1 mixture of CO/air, in MeCN, and in the presence of a six-fold excess of amine, for 15 h), could be selectively converted into 2-benzo[4,5]imidazo[2,1-b]thiazol-3-yl-N,N-dialkylacetamides in 60–78 % yields, through an oxidative aminocarbonylation/heterocyclization process. The structure of a representative product, 2-benzo[4,5]imidazo[2,1-b]thiazol-3-yl-1-pyrrolidin-1-ylethanone, was confirmed by X-ray diffraction analysis.

The Rietveld method is the most reliable and powerful tool for refining crystal structure when powder diffraction data are available. It requires that the structure model to be adjusted is as close as possible to the true structure. The Rietveld method usually represents the final step of the powder solution process, in particular when a new structure is going to be determined and published. EXPO is a software able to execute all the steps of the solution process in a mostly automatic way, by starting from the chemical formula and the experimental diffraction pattern, passing through computational methods for locating the structure model and optimizing it, and ending to the Rietveld refinement. In this contribution, we present the most recent solution strategies in EXPO, both in reciprocal and direct space, aiming at obtaining models suitable to be refined by the Rietveld method. Examples of Rietveld refinements are described, whose results are related to different solution procedures and types of compounds (organic and inorganic).

The hybrid big bang–big crunch algorithm is a combination of a global optimization algorithm inspired by one of the theories of the evolution of the universe, named the big bang and big crunch theory, and the simulated annealing method. The procedure was implemented in the latest version of the programEXPOand applied to crystal-structure solution from powder diffraction data. Several aspects of the hybrid big bang–big crunch algorithm can be further optimized with the aim of obtaining good quality solutions in a shorter computation time. In the present study, the hybrid big bang–big crunch procedure has been combined with the greedy randomized adaptive search procedure (GRASP) and some steps of the algorithm have been improved. The new approach, implemented in theEXPOpackage, has been successfully tested on numerous known crystal structures.

The Shift_and_Fix procedure is a new method which has been developed for improving the quality of a structure model obtained by the ab initio solution process from powder diffraction data. The main features of the new approach, which is fully automatic, are as follows: (a) the structure model usually attained at the end of the phasing process by direct methods is shifted partly and randomly; (b) a combination of Fourier map calculation and least-squares cycles has been designed for relocating the shifted atoms onto positions which can finally be moved onto the true ones by the standard model optimization approaches; (c) the Fourier map is calculated using coefficients which depend on the chemical content of the compound under study. When the figure of merit for selecting the best set of phases derived by direct methods does not work well, the ALLTRIALS strategy can be applied: it aims to investigate, automatically and sequentially, all the stored direct methods phasing sets and pick up the correct solution. The Shift_and_Fix method has been applied for improving the structure model calculated by each one of the phasing sets processed by ALLTRIALS. It has been implemented in the computer program EXPO and proved to be effective in providing a better ALLTRIALS outcome and increasing the probability of succeeding in the ab initio powder solution.

The Open Chemistry Database (OChemDb) is a new free online portal which uses an appropriately designed database of already solved crystal structures. It makes freely available computational and graphical tools for searching and analysing crystal-chemical information of organic, metal–organic and inorganic structures, and providing statistics on desired bond distances, bond angles, torsion angles and space groups. Atom types have been classified by an identifier code containing information about the chemical topology and local environment. The crystallographic data used by OChemDb are acquired from the CIFs contained in the free small-molecule Crystallography Open Database (COD). OChemDb offers easy-to-use and intuitive options for searching. It is updated by following the continuous growth of information stored in the COD. It can be of great utility for structural chemistry, in particular in the process of determination of a new crystal structure, and for any discipline involving crystalline structure knowledge. The use of OChemDb requires only a web browser and an internet connection. Every device (mobile or desktop) and every operating system is able to use OChemDb by accessing its web page. Examples of application of OChemDb are reported.

Innovative methodologies, introduced in the software EXPO and working both in the reciprocal and in the direct space, can be successfully adopted for solving crystal structure by X-ray powder diffraction data. The principles underlying these methodologies are summarized. Three representative examples of crystal structure solution of the peptides Z-(Aib)2-OH, Z-(Aib)3-O-t-Bu and Z-(Aib)4-OH are discussed in relation to their different degree of structure complexity.

QUALX2.0is the new version ofQUALX, a computer program for qualitative phase analysis by powder diffraction data. The previous version ofQUALXwas able to carry out phase identification by querying the PDF-2 commercial database. The main novelty ofQUALX2.0is the possibility of querying also a freely available database, POW_COD. POW_COD has been built up by starting from the structure information contained in the Crystallography Open Database (COD). The latter is a growing collection of diffraction data, freely downloadable from the web, corresponding to inorganic, metal–organic, organic and mineral structures.QUALX2.0retains the main capabilities of the previous version: (a) automatically estimating and subtracting the background; (b) locating the experimental diffraction peaks; (c) searching the database for single-phase pattern(s) best matching to the experimental powder diffraction data; (d) taking into account suitable restraints in the search; (e) performing a semi-quantitative analysis; (f) enabling the change of default choices and strategiesviaa user-friendly graphic interface. The advances ofQUALX2.0with respect toQUALXinclude (i) a wider variety of types of importable ASCII file containing the experimental diffraction pattern and (ii) new search–match options. The program, written in Fortran and C++, runs on PCs under the Windows operating system. The POW_COD database is exported in SQLite3 format.

The results from a third structure determination by powder diffractometry (SDPD) round robin are discussed. From the 175 potential participants having downloaded the powder data, nine sent a total of 12 solutions (8 and 4 for samples 1 and 2, respectively, a tetrahydrated calcium tartrate and a lanthanum tungstate). Participants used seven different computer programs for structure solution (ESPOIR,EXPO,FOX,PSSP,SHELXS,SUPERFLIP, andTOPAS), applying Patterson, direct methods, direct space methods, and charge flipping approach. It is concluded that solving a structure from powder data remains a challenge, at least one order of magnitude more difficult than solving a problem with similar complexity from single-crystal data. Nevertheless, a few more steps in the direction of increasing the SDPD rate of success were accomplished since the two previous round robins: this time, not only the computer program developers were successful but also some users. No result was obtained from crystal structure prediction experts.

Silicate materials have been proposed as alternative cathodes for Li-ion battery applications. A novel mixture of silicates, labelled Li6MnSi5, based on the molar ratio among the Li / Mn / Si precursors, with promising electrochemical properties as positive electrode material is synthesized through a solid-state reaction. The results indicate the proposed synthetic method as effective for preparation of nanostructured silicate owders with average particle diameter of 30 nm. Structural morphology of the samples was determined using X-ray powder diffraction (XRPD), XPS and FESEM analysis. A joint analysis by XRPD data and by density unctional theory (DFT) identified LiHMn4Si5O15, Li2Mn4Si5O15, Li2Si2O5 and Li0.125Mn0.875SiO4 as components of Li6MnSi5 mixture. The electrochemical performance of Li6MnSi5 was evaluated by charge/discharge testing at constant current mode. Li6MnSi5 discharge behaviour is characterized by high capacity value of 480 mA h g-1 , although such capacity fades gradually on cycling. Ex situ XPS studies carried out on the electrode in both full charged and discharged states, pointed out that Li2Si2O5 is decisive for achieving such high capacity. The discharge/charge plateau is most probably related to the change in the oxidation state of silicon at the surface of the silica material.

This work is focused on the crystal-chemical characterization of the cationic and anionic components of sodalite-group minerals (SGM) occurring in various igneous-to-metamorphic rocks and ejecta from the alkaline-potassic Somma-Vesuvius volcano (southern Italy). A combination of different analytical techniques, i.e., XRD, SEM, EPMA, SIMS, FTIR, and mu-FTIR-FPA imaging, were used. Minor and trace volatile elements (H, C, and F) have been quantified for the first time (to the authors' knowledge) by SIMS, and in situ ion probe data were integrated with information derived from FTIR spectroscopy. The studied samples correspond to sodalite sensu stricto, nosean, and hauyne. SIMS measurements for H, F, and C (quantified as H2O, F, and CO2 wt.%, respectively) show contents 0.02-5.0 wt.% H2O, 0.01-0.14 wt.% F, and 0.08-2.95 wt.% CO2. Within the single crystals, the F and, to a lesser extent, CO2 concentrations are homogeneous, whereas, in terms of H2O, they range from relatively homogenous to strongly zoned. Single-crystal FTIR spectra of SGM can be grouped into sodalites and noseans/hauynes, according to the occurrence of the (CO2)-C-12 absorption at 2340 cm(-1). The absorption due to H2O or OH groups occurs as a very broad band extending from 3700 to 3000 cm(-1). FTIR data show the presence of CO32- in all samples. The collected data allow us to fully characterize the SGM from Somma-Vesuvius, and also provide some constraints regarding their genesis. These data can contribute to a more detailed understanding of the crystal chemistry of SGM, their geological environments of formation, and possibly of the technological characteristics of their synthetic analogues.

Five turquoise samples, belonging to the XVII century historical collection of the Real Museo Mineralogico (University of Naples Federico II), were investigated by a multi-methodological approach based on powder X-ray diffraction, electron microprobe analysis in wavelength-dispersive spectroscopy mode, backscattered electron images from scanning electron microscopy in energy-dispersive spectroscopy mode, laser ablation inductively coupled plasma mass spectrometry, Fourier transform infrared and Raman spectroscopy.The samples originate from Sinai (Egypt), Santa Fè S. Miguel (New Mexico), Saxony (Germany), Montebras Creuse (France) and Nishapur (Khorassan, Iran) and display different mineralogical compositions and various mineral associations. The study has shown the presence of: (1) four minerals of the turquoise group: turquoise, faustite, chalcosiderite and planerite; (2) other phosphates from different groups: wavellite, crandallite, goyazite, gorceixite, variscite, metavariscite, fluorapatite; and (3) other minerals: voltaite, adularia and quartz.The present investigation is intended to show the mineralogical and geochemical variability of the samples with particular attention to the mineralogical parageneses, textural analyses and trace-element concentrations.

Negli ultimi venticinque anni il metodo della diffrazione da polveri è stato applicato con successo crescente per risolvere strutture cristalline (composti organici, inorganici, metallorganici). Nonostante ciò, la soluzione strutturale da polveri è ancora oggi una sfida perché i problemi del metodo, dovuti principalmente all'interpretazione dei dati sperimentali, devono essere ancora risolti.

The 5-(5-nitro furan-2-ylmethylen), 3-N-(2-methoxy phenyl), 2-N′-(2-methoxyphenyl) imino thiazolidin-4-one compound has been synthesized and fully characterized by FT-IR, 1H and 13C NMR spectroscopy. The crystal structure of the title compound was investigated by X-ray powder diffraction (XRPD). The obtained structure is triclinic, space group P-1, with a = 11.4746(3), b = 10.9106(2), c = 8.8083(2) A, α = 103.6665(9)°β = 91.4910(13)° γ = 84.1433(12)°, V = 1065.93(4)A3 and Z = 2. The XRPD structural investigation has been completed by a theoretical analysis performed using the density functional theory (DFT) via a B3LYP functional at 6-311G(d,p) basis set. To highlight and establish the contribution of the different intermolecular interactions, Hirshfeld surface analysis and fingerprint plots were performed. The solid state molecular structure and packing are discussed.