Single-crystal Structure Refinement Research Articles

Enhancement of superconductivity and phase diagram of Ta-doped Kagome superconductor CsV3Sb5

Kagome superconductors AV3Sb5 (A = K, Rb, and Cs) have attracted enormous interest due to the coexistence of charge density wave (CDW) order, unconventional superconductivity (SC) and anomalous Hall effect (AHE). In this paper, we reported an intensive investigation on Cs(V1−xTax)3Sb5 single crystals with systematic Ta doping. Ta was confirmed to be doped into V-site in the Kagome layer from both single crystal X-ray diffraction structural refinement and scanning transmission electron microscopy observation. The highest Ta doping level was found to be about 16%, which is more than twice as much as 7% in Nb-doped CsV3Sb5. With the increase of Ta doping, CDW order was gradually suppressed and finally vanished when the doping level reached to more than 8%. Meanwhile, superconductivity was enhanced with a maximum critical temperature (Tc) of 5.3 K, which is the highest Tc in the bulk crystal of this Kagome system at ambient pressure so far. The μ0Hc2(T) behavior demonstrates that the system is still a two-band superconductor after Ta doping. Based on the electrical transport measurement, a phase diagram was set up to exhibit the evolution of CDW and SC in the Cs(V1−xTax)3Sb5 system. These findings pave a new way to search for new superconductors with higher Tc in the AV3Sb5 family and establish a new platform for tuning and controlling the multiple orders and superconducting states.

Crystal chemistry, Raman and FTIR spectroscopy, optical absorption, and luminescence study of Fe-dominant sogdianite

Abstract Fe-dominant sogdianite, a cyclosilicate compound with the chemical formula (Fe3+ 0.74Zr0.64Ti0.46 Al0.15)(□1.02Na0.98)K[Li3Si12O30], was studied. The investigation involved a comprehensive analysis of the mineral sample, including crystal-chemical analysis, Raman and FTIR spectroscopy, optical absorption, and luminescence study. Crystallographic site populations were determined through single crystal structure refinement and electron probe microanalysis. The thermoelastic behavior of a powder was studied using in situ high-temperature X-ray diffraction (30–750 °C). Notably, no phase transition was detected; sogdianite exhibited anisotropic thermal expansion. The first time study of vibrational spectra and spectral bands assigning were performed. The electronic transitions in d 5-ion impurities of sogdianite were studied using optical absorption and luminescence spectroscopy. The origin of pink color and luminescence of sogdianite was clarified. The broad spectral bands in the visible UV spectral region are responsible for the pink color exhibited by sogdianite and could be attributed to d–d transitions occurring in Fe3+ ions.

From Cs[C2N3] to Cs3[C6N9] – a thermal and structural investigation

Abstract Cesium dicyanamide Cs[C2N3] (≡ Cs[N(CN)2] or Cs[dca]) was obtained by a metathesis reaction in form of transparent colorless platelets. The results of single-crystal X-ray structure measurements and refinements (C2/c, Z = 8) with the monoclinic cell parameters a = 932.31(8), b = 1274.67(9), c = 824.94(7) pm, β = 110.803(3)° at −70 °C and a = 939.59(7), b = 1281.58(8), c = 827.57(6) pm, β = 110.610(3)° at 20 °C corroborate earlier results for this compound. The Raman and IR spectra of Cs[C2N3] are presented for the first time and the result compares well with those of NaCs2[C2N3]3. The heat-driven cyclotrimerization process of Cs[C2N3] was studied by thermal analyses (DSC) and temperature-dependent X-ray powder diffraction methods. At 370 °C, its trimerization product Cs3[C6N9] is formed, crystallizing in the orthorhombic space group Pbam with the cell parameters a = 3043.0(3), b = 1052.4(1) and c = 415.21(4) pm for Z = 4. The IR spectrum of this cesium tricyanomelaminate (Cs3[C6N9] or Cs3[TCM]) is presented, but a well-resolved Raman spectrum could not be acquired owing to fluorescence phenomena. An overview about the cyclotrimerization reactions of all pseudo-binary alkali-metal dicyanamides (A[C2N3]) to their corresponding tricyanomelaminates (A 3[C6N9]) with A = Li–Cs gives a basis for a discussion of the different thermal and structural characteristics.

Polymorphism and Structural Variety in Sn(II) Carboxylate Coordination Polymers Revealed from Structure Solution of Microcrystals.

The crystal structures of four coordination polymers constructed from Sn(II) and polydentate carboxylate ligands are reported. All are prepared under hydrothermal conditions in KOH or LiOH solutions (either water or methanol-water) at 130-180°C and crystallize as small crystals, microns or less in size. Single-crystal structure solution and refinement are performed using synchrotron X-ray diffraction for two materials and using 3D electron diffraction (3DED) for the others. Sn2 (1,3,5-BTC)(OH), where 1,3,5-BTC is benzene-1,3,5-tricarboxylate, is a new polymorph of this composition and has a three-dimensionally connected structure with potential for porosity. Sn(H-1,3,5-BTC) retains a partially protonated ligand and has a 1D chain structure bound by hydrogen bonding via ─COOH groups. Sn(H-1,2,4-BTC) contains an isomeric ligand, benzene-1,2,4-tricarboxylate, and contains inorganic chains in a layered structure held by hydrogen bonding. Sn2 (DOBDC), where DOBDC is 2,5-dioxido-benzene-1,4-dicarboxylate, is a new polymorph for this composition and has a three-dimensionally connected structure where both carboxylate and oxido groups bind to the tin centers to create a dense network with dimers of tin. In all materials, the Sn centers are found in highly asymmetric coordination, as expected for Sn(II). For all materials phase purity of the bulk is confirmed using powder X-ray diffraction, thermogravimetric analysis, and infrared spectroscopy.

Crystal chemistry of type paulkerrite and establishment of the paulkerrite group nomenclature

Abstract. A single-crystal structure determination and refinement has been conducted for the type specimen of paulkerrite. The structure analysis showed that the mineral has monoclinic symmetry, space group P21/c, not orthorhombic, Pbca, as originally reported. The unit-cell parameters are a=10.569(2), b=20.590(4), c=12.413(2) Å, and β=90.33(3)∘. The results from the structure refinement were combined with electron microprobe analyses to establish the empirical structural formula A1[(H2O)0.98K0.02]Σ1.00 A2K1.00 M1(Mg1.02Mn0.982+)Σ2.00 M2(Fe1.203+Ti0.544+Al0.24Mg0.02)Σ2.00 M3(Ti0.744+ Fe0.263+)Σ1.00 (PO4)4.02 X[O1.21F0.47(OH)0.32]Σ2.00(H2O)10 ⋅ 3.95H2O, which leads to the end-member formula (H2O)KMg2Fe2Ti(PO4)4(OF)(H2O)10 ⋅ 4H2O. A proposal for a paulkerrite group, comprising orthorhombic members benyacarite, mantiennéite, pleysteinite, and hochleitnerite and monoclinic members paulkerrite and rewitzerite, has been approved by the International Mineralogical Association's Commission for New Minerals, Nomenclature and Classification. The general formulae are A2M12M22M3(PO4)4X2(H2O)10 ⋅ 4H2O and A1A2M12M22M3(PO4)4X2(H2O)10 ⋅ 4H2O for orthorhombic and monoclinic species, respectively, where A= K, H2O, □ (= vacancy); M1 = Mn2+, Mg, Fe2+, Zn (rarely Fe3+); M2 and M3 = Fe3+, Al, Ti4+ (and very rarely Mg); X= O, OH, F. In monoclinic species, K and H2O show an ordering at the A1 and A2 sites, whereas O, (OH), and F show a disordering over the two non-equivalent X1 and X2 sites, which were hence merged as X2 in the general formula. In both monoclinic and orthorhombic species, a high degree of mixing of Fe3+, Al, and Ti occurs at the M2 and M3 sites of paulkerrite group members, making it difficult to get unambiguous end-member formulae from the structural determination of the constituents at individual sites. To deal with this problem an approach has been used that involves merging the compositions at the M2 and M3 sites and applying the site-total-charge method. The merged-site approach allows end-member formulae to be obtained directly from the chemical analysis without the need to conduct crystal-structure refinements to obtain the individual site species.

Compositional Variation and Crystal-Chemical Characterization of a Watermelon Variety of Tourmaline from Anjanabonoina, Central Madagascar

A polychrome tourmaline crystal from Anjanabonoina pegmatite (Madagascar) was characterized using a multi-analytical approach. The sample showed a complex concentric zoning and a wide range of colors typical of the variety known as “watermelon”. The sample was cut perpendicularly to the c axis. The basal slice exhibits a rim characterized by narrow, differently colored layers parallel to the prism faces and a relatively homogeneous triangular core. Four main pronounced color zones were identified from the rim to core: a dark green rim (M1RVS); a pale green rim (M1RVC); a pale pink rim (M1CR); and a brownish yellow core (M1CG). Compositional variations in the basal slice were studied by scanning electron microscopy and electron microprobe analyses (WDS mode). The Li content was determined via micro-laser-induced breakdown spectroscopy. To deeply characterize the sample, single crystal structure refinement was also performed on fragments extracted from the four zones. The results show that the polychrome tourmaline sample consists of two different species: the three outer zones are Mn-rich fluor-liddicoatite, whereas the inner zone is Mn-rich fluor-elbaite. The structural and compositional characterization of the color zoning shows that each step of the tourmaline growth is related to a change in the geological environment.

A matrine-based supramolecular ionic salt that enhances the water solubility, transdermal delivery, and bioactivity of salicylic acid

Salicylic acid (H[Sal]) is an attractive bionic acid that is widely used in cosmetics and drugs for the treatment of skin diseases, owing to its excellent anti-acne, anti-inflammatory, antibacterial, oil-control, stratum-corneum-conditioning, and anti-photoaging abilities. However, H[Sal] is a relatively strong irritant and cannot be used on sensitive skin, and its poor water solubility limits the amounts that can be included in formulas, resulting in poor transdermal efficiency and bioavailability. In this study, we develop matrinium salicylate ([Mat][Sal]), a supramolecular ionic salt that is less cytotoxic and irritates the skin less than H[Sal], while exhibiting enhanced water-solubility, transdermal-delivery, and bioactivity properties. The anticancer, antioxidant, anti-inflammatory, and antibacterial properties of [Mat][Sal] are found to be superior or comparable to those of H[Sal]. The molecular structure of [Mat][Sal] is thoroughly investigated, including through single-crystal structure refinement, to gain an in-depth understanding of its properties. Moreover, in-vitro skin penetration experiments show that forming a salt with matrine increase the transdermal efficiency of H[Sal] while not damaging the skin barrier. The transdermal mechanisms of H[Sal] and [Mat][Sal] are studied both experimentally and using molecular dynamics simulations, which show that, compared to H[Sal], [Mat][Sal] reacts more strongly with the skin, and [Sal]− diffuses more rapidly in the skin owing to its higher water solubility and the ion-pair effect. Furthermore, [Mat][Sal] exhibits satisfactory anti-acne capabilities in a clinical-efficacy trial, highlighting its great potential for use in biomedical and cosmetics applications.

Bobtraillite from Gejiu hyperagpaitic nepheline syenite, southwestern China: new occurrence and crystal structure

Abstract. A second occurrence of bobtraillite is described from the Gejiu nepheline syenite, southwestern China. The extremely rare and complex boron-bearing zirconium silicate is associated with albite, orthoclase, jadeite, fluorite, andradite, titanite, as well as other REE and zirconium-bearing minerals, catapleiite, moxuanxueite, låvenite, eudialyte, britholite-(Ce), and calcioancylite-(La). The EMP and LA-ICP-MS analyses of the studied material give an empirical formula: (Na9.70Li0.42K0.08□1.80)Σ12.00(Sr10.61Ca1.14Fe0.07□0.18)Σ12.00(Zr12.87Ti0.53Nb0.31REE0.08Y0.06U0.02Th0.01□0.12)Σ14.00(Si42.41B5.59Al0.02)Σ48.02O132(OH)12 ⚫ 12H2O. Bobtraillite is trigonal, with space group P3¯c1, a=19.6977(6), c=9.9770(3) Å, V=3352.4(2) Å3, Z=1. Single-crystal structure refinement revealed that all sodium occupies the Na(1) and Na(2) sites; the site occupancy of these two positions is 0.835(18) and 0.15(2), respectively, suggesting that Na(1) site is Na dominant, while Na(2) is a vacancy-dominant site. The [8]-coordinated site has been assigned to Sr and Ca, with free occupancy factors, 0.874(10) and 0.126(10), respectively. These new data indicate that the ideal formula of bobtraillite could be written as (Na,□)12(□,Na)12Sr12Zr14(Si3O9)10[Si2BO7(OH)2]6 ⚫ 12H2O.

Crystal chemistry of turkestanite, Dara-i-Pioz massif, Tajikistan

AbstractThe results of combined single-crystal X-ray diffraction, electron probe microanalysis, Fourier microspectroscopy, and photoluminescence spectroscopy study of crystals of turkestanite from the Dara-i-Pioz deposit, Tien-Shan Mountains, Tajikistan are reported. It is a single-layer sheet silicate belonging to the ekanite group with a steacyite structural type. Averaged major-element analysis provided (wt.%): K2O 4.13(6), CaO 8.1(1), Na2O 2.3(1), ThO2 25.8(4), UO2 3.6(4) and SiO2 55.9(1). The averaged crystal-chemical formula for the studied turkestanite is (Th0.84U0.12)Σ0.96(Ca1.24Na0.65)Σ1.89(K0.75☐0.25)Σ1.00Si8O19.72(OH)0.28. Single-crystal structural refinement of turkestanite gave tetragonal, space group P4/mcc, a = 7.5708(3) Å, c = 14.7300(11) Å, V = 844.27(6) Å3 and Z = 2. Luminescence of the uranyl ion (UO2)2+ is observed in turkestanite. In the excitation spectrum, the bands corresponding to a charge transfer transition from the 2p states of the ligand to the 5f state of uranium were found.

Versatility of guanidoacetic acid coordination modes and synthesis of its new zinc complex

Guanidinoacetic acid (GAA) is an amino acid involved in several biological processes including renal activity since it is synthesized mainly in the kidneys, insulin metabolism, creatine/phosphocreatine synthesis and recently as experimental nutrient for multiple sclerosis treatment. Given its biological role, some interactions between GAA and its complexation with essential and toxic metal ions have been previously investigated, both in aqueous medium with Ni(II), Co(II), Cu(II), Zn(II), Cd(II), and Pb(II), as well as in the synthesis of complexes in solid phase. This study presents the versatile coordination modes of GAA and reports its novel solid zinc complex. GAA complexation ranges from the usual α-nitrogen and oxygen bidentate coordination to a paddlewheel monodentate-oxygen mode in a Cu2GAA4 complex. The novel solid GAA zinc complex has only been succeeded to be synthesized in the presence of copper(II) salt, being characterized by single-crystal structure refinement using X-ray diffraction and mid and far-Fourier Transform Infrared spectroscopy. The results showed that the synthesized complex, (HGAA)[Zn(GAA)Cl3].H2O (1) , exhibits a tetrahedral geometry with an oxygen-carboxylate GAA monodentate coordination complemented by three chloride ligands and a water bridge linked to amonoprotonated GAA species. Hydrogen bonds play a crucial role in the stabilization of1, especially between Zn(GAA)Cl3- and its cation ion, HGAA+.Infrared spectroscopy of 1 presented aband at 412 cm-1 and three bands at 291, 273 and 239 cm-1, corresponding to Zn-O and Zn-Cl stretching modes, respectively. The different coordination modes of guanidinoacetate ion and its complexation with zinc and copper(II), as well as the way the hydrogen bonds stabilize their structures may help to further understand the diverse biochemical processes involved in this amino acid.

New secondary phosphate mineral occurrences and their crystal chemistry, at the Hagendorf Süd pegmatite, Bavaria

Abstract. First occurrences from the Hagendorf Süd pegmatite of the secondary phosphate minerals kenngottite, Mn32+Fe43+(PO4)4(OH)6(H2O)2; allanpringite, Fe33+(PO4)2(OH)3 ⚫ 5H2O; iangreyite, Ca2Al7(PO4)2(PO3OH)2(OH,F)15 ⚫ 8H2O; and nizamoffite, MnZn2(PO4)2(H2O)4, are reported with characterisation of their crystal chemistry and phase associations. A synchrotron single-crystal structure refinement for kenngottite shows that it has the same level of disordering (75 %/25 %) of Fe3+ in adjacent octahedra along the 5 Å axis as for type-locality kenngottite from Krásno, Czech Republic. This is explained in terms of 1 : 1 fine-scale mixing of domains of ordered kenngottite-type and souzalite-type structures. Allanpringite occurs in an unusual epitaxial relationship to associated strunzite. The epitaxy is explained by the close metrical and structural match of common planes in the two minerals, (010) for allanpringite and (100) for strunzite. Iangreyite occurs in close association with perhamite in 30 µm spheroids. The characterisation results support a paragenesis of iangreyite from perhamite by selective leaching of silica from the layer structure of perhamite and rejoining of the layers by fusion of AlO4 tetrahedra from adjacent layers into AlO2(OH)3 trigonal bipyramids.

Single-crystal structure refinements and Debye temperatures of Ir2S3 kashinite and Rh2S3 bowieite.

Single crystals of Ir2S3 (diiridium trisulfide) and Rh2S3 (dirhodium trisulfide) were grown in evacuated silica-glass tubes using a chemical transport method and their crystal structures were determined by single-crystal X-ray diffraction analysis. These compounds have a unique sesquisulfide structure in which pairs of face-sharing octahedra are linked into a three-dimensional structure by further edge- and vertex-sharing. Ir2S3 and Rh2S3 had similar unit-cell parameters and bond distances. The atomic displacement parameter (MSD: mean-square displacement) of each atom in Ir2S3 was considerably smaller than that in Rh2S3. The Debye temperatures (ΘD) estimated from the observed MSDs for the Ir, S1 and S2 sites in Ir2S3 were 259, 576 and 546 K, respectively, and those for Rh, S1 and S2 in Rh2S3 were 337, 533 and 530 K, respectively. The bulk Debye temperature for Ir2S3 kashinite (576 K) was found to rank among the higher values reported for many known sulfides. The bulk Debye temperature for Rh2S3 bowieite (533 K) was lower than that for Ir2S3 kashinite, which crystallizes in the early sequences of mineral crystallization differentiation from the primitive magma in the Earth's mantle.

High-pressure phase transition and equation of state of hydrous Al-bearing silica

Abstract Stishovite, a rutile-structured polymorph of SiO2, is a main component of subducted basaltic lithologies in the lower mantle. At mid lower-mantle depths, a second-order ferroelastic transition to orthorhombic CaCl2-type (post-stishovite) structure occurs, causing extensive elastic shear softening. Previous studies showed that Al incorporation can decrease the transition pressure, while it is still debated whether H has a similar effect. Here we report the equations of state, structural evolution, and phase transformation of Si0.948Al0.052O1.983H0.018 (Al5) stishovite and Si0.886Al0.114O1.980H0.074 (Al11) post-stishovite samples using diamond-anvil cells in combination with synchrotron X-ray diffraction and Raman spectroscopy. The Al5 sample transformed to the orthorhombic polymorph upon compression to 16 GPa, displaying a drop of ~12% in its bulk modulus across the transformation. The Al11 sample did not undergo any phase transition in the pressure range investigated. Single-crystal structural refinements and Raman spectroscopy measurements on the Al5 sample show that the soft optic mode B1g is decoupled from the tetragonal-to-orthorhombic structural transformation and shows a plateau in the stability field of post-stishovite, between 20 and 30 GPa. This observation indicates that the transformation is not pseudo-proper ferroelastic as in SiO2 stishovite and that existing Landau expansions are likely not applicable to H-rich Al-bearing silica samples. Using the equation of state parameters of orthorhombic Al5 and Al11 and literature data on SiO2 post-stishovite we then discuss the possibility of non-ideal mixing along the SiO2-AlOOH join.

Crystal Structure and Magnetism of Fe1−xTe (x=0.31)

AbstractReaction of iron‐tellurium mixtures in the composition range from Fe0.41Te0.59 to Fe0.43Te0.57 followed by quenching to ambient temperature yields the high‐temperature δ phase Fe1−xTe (0.25<x<0.31). Single crystals of δ phase Fe1−xTe, with x=0.31(1), are obtained by reacting Fe−Te mixtures with nominal composition Fe0.43Te0.57 in closed ampoules at 973 K for 15 days before quenching to ambient temperature. In accordance with the chemical transport behavior of other phases in the iron‐tellurium system, the refined composition of the single crystals Fe1−xTe with x=0.31(1) suggests that crystallization and growth preferably occur in the tellurium‐rich part of the homogeneity range.The resulting crystals adopt a monoclinic crystal structure with unit cell parameters a=6.645(2) Å, b=3.8409(6) Å, c=11.314(3) Å, β=90.47(1)°, Z=4 (space group I2/m, non‐standard setting of C2/m). Single crystal structure refinement reveals a NiAs motif with partial occupation in every second iron layer along [001]. Magnetic susceptibility measurements indicate antiferromagnetic order below 400 K.

Synthesis and Structure of Pb[C2O5]: An Inorganic Pyrocarbonate Salt.

We have synthesized Pb[C2O5], an inorganic pyrocarbonate salt, in a laser-heated diamond anvil cell (LH-DAC) at 30 GPa by heating a Pb[CO3] + CO2 mixture to ≈2000(200) K. Inorganic pyrocarbonates contain isolated [C2O5]2- groups without functional groups attached. The [C2O5]2- groups consist of two oxygen-sharing [CO3]3- groups. Pb[C2O5] was characterized by synchrotron-based single-crystal structure refinement, Raman spectroscopy, and density functional theory calculations. Pb[C2O5] is isostructural to Sr[C2O5] and crystallizes in the monoclinic space group P21/c with Z = 4. The synthesis of Pb[C2O5] demonstrates that, just like in other carbonates, cation substitution is possible and that therefore inorganic pyrocarbonates are a novel family of carbonates, in addition to the established sp2 and sp3 carbonates.

Elasticity of Nonstoichiometric Alumina-Rich Spinel Determined by Bond Valence Theory and Brillouin Scattering.

An accurate knowledge of the elastic properties of materials is essential for material science and engineering applications. Four single crystals of nonstoichiometric alumina-rich spinel [Mg1-xAl2(1+x/3)O4] were obtained from sintered transparent ceramics for the investigation of its elastic properties. The disordered crystal structures were fully resolved by combining single-crystal structure refinement and a quadratic programming approach for the first time. The bond valence model and Brillouin scattering experiments were used to evaluate the bulk modulus (K), shear modulus (G), Young's modulus (E), and Poisson's ratio. The discrepancy between the theoretical and experimental results is <2.6%. The independent elastic constants (C11, C12, and C44) were determined from Brillouin scattering experiments. A negative Poisson's ratio, υ(110, 11̅0), was found to exist in all alumina-rich spinels, which means it is a partially auxetic material. Blackman diagram analysis was introduced to identify the interrelationships and trends in mechanical and bonding properties in alumina-rich spinels. The bond valence model was suggested to be an effective and accurate approach for predicting the elastic modulus of spinels, which provides a useful tool for the study of the composition-structure-property relationship of materials.

Two new rare-earth borates Sr2Tb3B27-δO46 and Ba2Eu3B27-δO46 (δ = 2/3): syntheses, crystal structures, and luminescence properties.

Two new alkali-earth and rare-earth metal borates, Sr2Tb3B27-δO46 and Ba2Eu3B27-δO46 (δ = 2/3), have been prepared by high-temperature solution reactions at 950 °C. The single-crystal XRD analysis showed that the borates crystallize in the rhombohedral space group R3 with the cell parameters a = 7.7468(1) Å, c = 46.3657(5) Å, V = 2409.75(3) Å3, Z = 3 and a = 7.7964(1) Å, c = 46.5086(6) Å, V = 2448.23(7) Å3, Z = 3, respectively, which further confirms that "LnMB9O16" has the right formula of M2Ln3B27-δO46 (δ = 2/3). Their crystal structures consist of 3D networks constructed by Tb(Eu)O6 trigonal prisms, BO3 planar triangles, and BO4 tetrahedra, with large cavities accommodating Sr2+ (Ba2+) cations. Furthermore, the phase composition, morphology, IR, Raman, and XPS spectra as well as photoluminescence properties of these two compounds were studied. Upon excitation by ultraviolet radiation, Sr2Tb3B27-δO46 exhibits the characteristic emission lines originating from Tb3+ corresponding to 5D4-7F6,5,4,3,2,1,0 transitions, whereas Ba2Eu3B27-δO46 displays bright red emission from Eu3+ with four groups of emission bands associated with 5D0 → 7F1,2,3,4 transitions. Both phosphors show stable luminescence and color purity at elevated temperatures. As it may be expected, Sr2Tb3B27-δO46 and Ba2Eu3B27-δO46 (δ = 2/3) are promising green (Tb) and red (Eu) components for use in WLEDs.

Structural investigations of halogen substituted 1,4-dihydropyridine derivatives: Crystallographic and computational studies

Single crystal structure solution and refinement have been carried out on 1,4-dihydropyridine derivative molecules, namely, 4-(4‑chloro-phenyl)-2,6-dimethyl-1, 4-dihydropyridine-3,5-dicarboxylic acid bis-[(2-chlorophenyl)amide] and 4-(4-fluoro-phenyl)-2,6-dimethyl-1, 4-dihydropyridine-3,5-dicarboxylic acid bis-[(2-chlorophenyl)amide]. Final refinement values, of [I > 2σ(I)] (all data) were refined as 0.0608 (0.0768) and 0.0595 (0.0696) for M-Cl and M-F. Hirshfeld surfaces analysis mapped dnorm surfaces, shape index, curvedness and hydrogen bonding in both the molecules and major relative contributions to the percentage of Hirshfeld surface area for the various intermolecular contacts were calculated. DFT studies using Quantum ESPRESSO were carried out by transformation of the conventional monoclinic unit cell to the primitive unit cell converted back to the original monoclinic cell to compare with the experimental data. The NBO analysis implemented in Gaussian was used to know intermolecular force between two molecular units and to obtain the stabilization energies from donors to acceptors in M-Cl and M-F. The natural localized molecular orbital (NLMO) analysis was also performed to capture the intermolecular delocalization interactions of NBOs.

Potassic-Hastingsite from the Kedrovy District (East Siberia, Russia): Petrographic Description, Crystal Chemistry, Spectroscopy, and Thermal Behavior

In this work we report on a petrographic, crystal-chemical, and optical characterization, obtained from different analytical methods, of amphibole species. Potassic-hastingsite, ideally AKBCa2C(Fe2+4Fe3+)T(Si6Al2)O22W(OH)2, has been found in the Kedrovy district (East Siberia, Russia). The sample occurs as well-formed and large radially radiant aggregates of dark green, almost black crystals. The unit cell dimensions are a = 9.9724(3) Å, b = 18.2968(4) Å, c = 5.3573(1) Å, β = 104.945(3)°, V = 944.44(4) Å3, Z = 2. Site populations were determined by combining single-crystal structure refinement and electron probe microanalysis, and Fe3+/Fe2+ ratio was obtained from X-ray fluorescence analysis. Infrared, diffuse light UV/Vis/NIR absorption, and electron spin resonance spectra are presented and discussed. A thermoelastic behavior of a powder of potassic-hastingsite was studied by in situ high-temperature X-ray diffraction. A thermal expansion and subsequent significant contraction in the unit cell volume during a high-temperature X-ray powder diffraction experiment is observed as a consequence of the deprotonation process, which is locally balanced via oxidation of Fe2+. According to the data obtained for potassic-hastingsite, these processes occur within 400–600 °C. The thermal expansion of the mineral is anisotropic; the thermal expansivity coefficients αa:αb:αc (×10−6) = −18.06:9.59:−1.09 at 400 °C, −26.15:−1.52:2.22 at 600 °C and 23.77:−25.06:42.08 at 750 °C.

Recommended X-ray single-crystal structure refinement and Rietveld refinement procedure for tremolite

A detailed description of the structure of the amphibole-supergroup minerals is very challenging owing to their complex chemical composition that renders the process of cation partition extremely difficult, particularly because of the occurrence of multivalent elements. Since amphiboles naturally occur under a fibrous morphology and have largely been used to produce asbestos, there is a growing demand for detailed and accurate structural data in order to study the relationships between structure, composition and toxicity. The present study proposes a recommended refinement procedure for both X-ray single-crystal structure refinement (SREF) and Rietveld analysis for tremolite, selected as a test case. The corresponding structural results are compared to estimate the `degree of confidence' of the Rietveld refinement with regard to SREF. In particular, it is shown that the interpretation of the electron density of the tremolite structure by SREF is model dependent. By assuming that the site-scattering values from SREF should be as close as possible to those from electron microprobe analysis, as a crucial constraint for the correct description of the final crystal-chemical model, it is found that it is best satisfied by using partially ionized scattering curves (SCs) for O and Si, and neutral SCs (neutral oxygen curves or NOCs) for other atoms. This combination leads to the best fit to the diffraction data. Moreover, it is found that Rietveld refinement using NOCs produces the best structural results, in excellent agreement with SREF. It is worth noting that, due to the complexity of the diffraction pattern and the fairly large number of freely refinable parameters, refinements with different combinations of SCs produce results almost indistinguishable from a statistical point of view, albeit showing significant differences from a structural point of view.