Ac Plane Research Articles

Crystal structure and Hirshfeld surface analysis of 2-{[7-acetyl-4-cyano-6-hy-droxy-8-(4-meth-oxyphen-yl)-1,6-dimethyl-5,6,7,8-tetra-hydro-isoquinolin-3-yl-]sulfan-yl}acetic acid ethyl ester.

In the title mol-ecule, C25H28N2O5S, (alternative name ethyl 2-{[7-acetyl-4-cyano-6-hy-droxy-8-(4-meth-oxy-phen-yl)-1,6-dimethyl-5,6,7,8-tetra-hydro-isoquinolin-3-yl]sulfanyl}-acetate) the 4-meth-oxy-phenyl group is disposed on one side of the bicyclic core and the oxygen atoms of the hydroxyl and acetyl groups are disposed on the other side. In the crystal, a layered structure parallel to the ac plane is generated by O-H⋯O and C-H⋯O hydrogen bonds plus C-H⋯π(ring) inter-actions.

Crystal structure from X-ray powder diffraction data, DFT-D calculation, Hirshfeld surface analysis, and energy frameworks of (RS)-trichlorme-thia-zide.

The structure of racemic (RS)-trichlorme-thia-zide [systematic name: (RS)-6-chloro-3-(di-chloro-meth-yl)-1,1-dioxo-3,4-di-hydro-2H-1λ6,2,4-benzo-thia-di-azine-7-sulfonamide], C8H8Cl3N3O4S2 (RS-TCMZ), a diuretic drug used in the treatment of oedema and hypertension, was determined from laboratory X-ray powder diffraction data using DASH [David et al. (2006 ▸). J. Appl. Cryst. 39, 910-915.], refined by the Rietveld method with TOPAS-Academic [Coelho (2018 ▸). J. Appl. Cryst. 51, 210-218], and optimized using DFT-D calculations. The extended structure consists of head-to-tail dimers connected by π-π inter-actions which, in turn, are connected by C-Cl⋯π inter-actions. They form chains propagating along [101], further connected by N-H⋯O hydrogen bonds to produce layers parallel to the ac plane that stack along the b-axis direction, connected by additional N-H⋯O hydrogen bonds. The Hirshfeld surface analysis indicates a major contribution of H⋯O and H⋯Cl inter-actions (32.2 and 21.7%, respectively). Energy framework calculations confirm the major contribution of electrostatic inter-actions (E elec) to the total energy (E tot). A comparison with the structure of S-TCMZ is also presented.

Electric field induced polarization rotation in squaric acid crystals revisited

Using the previously developed model we revisit the problem of the electric field induced polarization rotation in antiferroelectric crystals of squaric acid. We test an alternative set of the model parameters, according to which the dipole moments associated with the H2C4O4 groups are assumed to be parallel to the diagonals of the ac plane. The T-E phase diagrams and the polarization curves P(E) for the fields directed along the a axis and along one of the diagonals are considered. Comparison of the theoretical results with the newly published experimental data confirm the validity of the model. The calculations reveal no apparent advantage of the new set of the parameters over the previously used set.

Magnetic field effect on topological properties of Dirac semimetals PdTe2/PtTe2/PtSe2

We investigated magnetic field effect on the topological properties of transition metal dichalcogenide Dirac semimetals (DSMs) PdTe2/PtTe2/PtSe2 based on Wannier-function-based tight-binding (WFTB) model obtained from first-principles calculations. The DSMs PdTe2/PtTe2/PtSe2 undergo a transition from DSMs into Weyl semimetals with four pairs of Weyl points (WPs) in the entire Brillouin zone by splitting Dirac points under external magnetic field B . The positions and energies of WPs vary linearly with the strength of the B field under the c -axis magnetic field B . Under the a - and b -axis B field, however, the positions of magnetic-field-inducing WPs deviate slightly from the c axis, and their k z coordinates and energies change in a parabolic-like curve with the increasing B field. However, the system opens an axial gap on the A–Γ axis, and the gap changes with the direction of the B field when the out of c -axis B field is applied. When we further apply the magnetic field in the ac, bc, and ab planes, the results are more diverse compared to the axial magnetic field. Under the ac and bc plane B field, the k z and energies of WPs within angle θ = [0°, 90°] and θ = [90°, 180°] are mirror symmetrically distributed. The distribution of WPs shows broken rotational symmetry under the ab plane B field due to the difference of non-diagonal part of Hamiltonian. Our theoretical findings can provide a useful guideline for the applications of DSM materials under external magnetic field in the future topological electronic devices.

Controlling Spin Orientation and Metamagnetic Transitions in Anisotropic van der Waals Antiferromagnet CrPS4 by Hydrostatic Pressure

AbstractControlling the phases of matter is a central task in condensed matter physics and materials science. In 2D magnets, manipulating spin orientation is of great significance in the context of the Mermin–Wagner theorem. Herein, a systematic study of temperature‐ and pressure‐dependent magnetic properties up to 1 GPa in van der Waals CrPS4 is reported. Owing to the temperature‐dependent change of the magnetic anisotropy energy, the material undergoes a first‐order spin reorientation transition with magnetic moments realigning from being almost parallel with the c axis in the ac plane to the quasi‐1D chains of CrS6 octahedra along the b axis upon heating. The spin reorientation temperature is suppressed after applying pressure, shifting the high‐temperature phase to lower temperatures with the emergence of spin‐flop transitions under magnetic fields applied along the b axis. The saturation field increases with pressure, indicating the enhancement of interlayer antiferromagnetic coupling. However, the Néel temperature is slightly reduced, which is ascribed to the suppression of intralayer ferromagnetic coupling. The work demonstrates the control of spin orientation and metamagnetic transitions in layered antiferromagnets, which may provide new perspectives for exploring 2D magnetism and related spintronic devices.

Giant conventional and rotating magnetocaloric effects in TbScO3 single crystal

Magnetocaloric effect (MCE) shows great potential in refrigeration field and especially fundamental scientific research with cooling requirement. In this work, we studied the anisotropic magnetic and magnetocaloric properties of TbScO3 single crystal, a popular substrate used for depositing epitaxial ferroelectric films. Our results indicate a strong antiferromagnetic ordering below TN ~ 3.1 K in orthorhombic TbScO3 single crystal. Large magnetocrystalline anisotropy exists between the magnetic easy ab plane and the hard c axis, leading to a giant anisotropic MCE. In field changes of 20 and 50 kOe along the a axis, large magnetic entropy changes reach 15.25 and 23.71 J/kg K at 3 K and 7 K, respectively, while the magnetic entropy changes along the c axis are negligible. As a result, large rotating magnetic entropy changes of 15.27 and 23.63 J/kg K are obtained by rotating TbScO3 single crystal with constant fields of 20 and 50 kOe lying in the ac plane. The large anisotropic MCE of TbScO3 single crystal indicates this material as a promise refrigerant candidate for rotating magnetic refrigeration technique near the helium temperature.

Thermal Deformations of Crystal Structures in the L-Aspartic Acid/L-Glutamic Acid System and DL-Aspartic Acid

The method of temperature-resolved powder X-ray diffraction (TRPXRD) was used to determine the elevated temperature behavior of L-aspartic acid (L-asp), DL-aspartic acid (DL-asp), L-glutamic acid (L-glu), and an L-asp0.25,L-glu0.75 solid solution. These amino acids were not found to undergo any solid-phase (polymorph) transformations. When heated, they all experienced only thermal deformations. The corresponding parameters of the monoclinic cells of L-asp and DL-asp, and the orthorhombic cells of L-glu and L-asp0.25,L-glu0.75, were calculated for the entire range of studied temperatures (up to 220 °C). The data obtained were used to calculate the parameters of the thermal deformation tensors, and to plot the figures of their thermal expansion coefficients. A correlation between the maximum and minimum values of thermal expansion coefficients and the length, type, direction, and number of hydrogen bonds in the crystal structures of the investigated amino acids was established. The observed negative thermal expansion (contraction) of crystal structures of L-asp and DL-asp along the ac plane can be explained as a result of shear deformations occurring in monoclinic crystals with a non-fixed angle β. The studies were related to the presence of amino acids in various natural and technological processes occurring at different temperatures.

Withanolides from Physalis angulata L.

The compounds (17S,20R,22R,24R,25S)-5β,6β:20,24-diep-oxy-4β,25-dihy-droxy-1-oxowith-2-en-26,22-olide and (20R,22R)-5α,14α,20-Trihy-droxy-1-oxo-6α,7α-ep-oxy-witha-2-enolide were isolated from a chloro-form extract of the aerial parts of Physalis angulata L. (Solanaceae). Two products were isolated from the chromatographic separation extract. Compound I corresponds to physangulide B chloro-form monosolvate, C28H38O7·CHCl3, while compound II is 14α-hy-droxy-ixocarpanolide, C28H40O7. In the two mol-ecular structures, the conformation of the steroid part (rings A, B, C, D) does not differ. In both crystals, mol-ecules are linked by inter-molecular O-H⋯O hydrogen bonds along the c-axis direction and form a two-dimensional network parallel to the ac plane. The absolute configuration was determined from X-ray diffraction data.

Mn-Doped XAlO3 (X = Y, Tb) Single-Crystalline Films Grown onto YAlO3 Substrates: Raman Spectroscopy Study toward Visualization of Mechanical Stress

Single-crystalline films (SCFs) of perovskites TbAlO3 (TbAP) and YAlO3 (YAP) doped with Mn ions were grown using the liquid-phase epitaxy (LPE) method on YAlO3 single-crystal (SC) substrates and investigated using Raman spectroscopy. The cross-section of the above-mentioned epitaxial structures was probed to obtain Raman signals of TbAP:Mn, YAP:Mn SCFs, and the YAP SC substrate. The undisturbed Raman signals of TbAP:Mn and YAP:Mn were recorded. For the TbAP:Mn sample, due to the difference in lattice constants between the SCF and the substrate, significant changes in the Raman spectra were observed. Over the interface between the SCF and the substrate, called the transition layer, gradual changes in the Raman spectra were observed. The changes are connected with the replacement of Tb3+ ions with Y3+ cations and are manifested as shifts of the modes assigned to translational, librational, and internal vibrations. Angular-dependent measurements of polarized spectra allowed determination of the TbAP:Mn SCF orientation in the ac plane (010). High-resolution luminescence spectra confirmed electronic transition attributed to Tb3+ cations and Nd3+ trace impurities in the YAP substrate. The Raman map recorded for the region close to the transition layer showed a shift of the Raman band at 552 cm–1 (YAP) related to the changes in the lattice constants and mechanical stress.

Crystal structure and Hirshfeld surface analysis of dimethyl 5-[2-(2,4,6-trioxo-1,3-diazinan-5-yl-idene)hydrazin-1-yl]benzene-1,3-di-carboxyl-ate 0.224-hydrate.

In the crystal, the whole mol-ecule of the title compound, C14H12N4O7·0.224H2O, is nearly planar with a maximum deviation from the least-squares plane of 0.352 (1) Å. The mol-ecular conformation is stabilized by an intra-molecular N-H⋯O hydrogen bond, generating an S(6) ring motif. In the crystal, mol-ecules are linked by centrosymmetric pairs of N-H⋯O hydrogen bonds, forming ribbons along the c-axis direction. These ribbons connected by van der Waals contacts, forming sheets parallel to the ac plane. There are also inter-molecular van der Waals contacts and and C-H⋯π inter-actions between the sheets. A Hirshfeld surface analysis indicates that the most prevalent inter-actions are O⋯H/H⋯O (41.2%), H⋯H (19.2%), C⋯H/H⋯C (12.2%) and C⋯O/ O⋯C (8.4%).

Hexanuclear copper(II) complex of 2-hy-droxy-N,N'-bis-[1-(2-hy-droxy-phen-yl)ethyl-idene]propane-1,3-di-amine incorporating an open-cubane core.

The title mol-ecular structure, namely, di-aqua-tris-(μ3-1,3-bis-{[1-(2-oxidophen-yl)ethyl-idene]amino}-propan-2-olato)-μ3-hydroxido-dinitrato-hexa-copper(II) ethanol tris-olvate, [Cu6(C19H19N2O3)3(NO3)2(OH)(H2O)2]·3C2H5OH, corres-ponds to a non-symmetric hexa-nuclear copper complex. The complex exhibits one core in which three CuII metal centres are mutually inter-connected, two by two, via three phenolato oxygen anions acting in a μ2-mode. These three copper cations are inter-connected in a μ3-mode by one hydroxyl group. An open-cube structure is generated in which each of the CuII cations of the three CuO4N units is connected by two μ2-O anions from phenolate groups and one μ3-O atom from a hy-droxy anion. Each of the three penta-coordinated CuII cations situated in the open-cube unit has a distorted NO4 square-pyramidal environment. Each of these three CuII centres is inter-connected with another CuII cation via one enolate O atom in μ2-mode, yielding one CuNO4 unit and two CuNO3 units. The penta-coordinated CuII atom has a distorted square-pyramidal environment while the two tetra-coordinated copper(II) cations are situated in a square-planar environment. A series of intra-molecular O-H⋯O hydrogen bonds are observed. In the crystal, the units are connected two by two by inter-molecular C-H⋯O and O-H⋯O hydrogen bonds, thus forming sheets parallel to the ac plane.

A new organic-inorganic compound, ethyl-enedi-ammonium hexa-chlorido-stannate(IV) p-anisaldehyde disolvate.

The asymmetric unit of the title organic-inorganic hybrid complex [systematic name: ethane-1,2-diaminium hexa-chlorido-stannate(IV)-4-meth-oxy-benz-alde-hyde (1/2)], (C2H10N2)[SnCl6]·2C8H8O2, contains one half of an ethyl-enedi-ammonium cation, one half of an [SnCl6]2- anion and one p-anisaldehyde mol-ecule. Both the organic cation and the quasi-regular octa-hedral inorganic anion are located about inversion centres. The organic cations and [SnCl6]2- anions lie in layers parallel to the ac plane with p-anisaldehyde mol-ecules occupying the space between the layers. A network of classical N-H⋯Cl and N-H⋯O hydrogen bonds exists between the ethyl-enedi-ammonium cations and the [SnCl6]2- anions and p-anisaldehyde mol-ecules. These inter-actions, together with non-classical C-H⋯O inter-actions between the ethyl-enedi-ammonium cations and the p-anisaldehyde mol-ecules, serve to hold the structure together. The crystal studied was refined as a two-component twin.

Synthesis and crystal structures of 3,6-di-hydroxy-picolinic acid and its labile inter-mediate dipotassium 3-hy-droxy-6-(sulfonato-oxy)pyridine-2-carboxyl-ate monohydrate.

A simplified two-step synthesis of 3,6-di-hydroxy-picolinic acid (3-hy-droxy-6-oxo-1,6-di-hydro-pyridine-2-carb-oxy-lic acid), C6H5NO4 (II), an inter-mediate in the metabolism of picolinic acid, is described. The crystal structure of II, along with that of a labile inter-mediate, dipotassium 3-hy-droxy-6-(sulfonato-oxy)pyridine-2-carboxyl-ate monohydrate, 2K+·C6H3NO7S2-·H2O (I), is also described. Compound I comprises a pyridine ring with carboxyl-ate, hydroxyl (connected by an intra-molecular O-H⋯O hydrogen bond), and sulfate groups at the 2-, 3-, and 6-positions, respectively, along with two potassium cations for charge balance and one water mol-ecule of crystallization. These components are connected into a three-dimensional network by O-H⋯O hydrogen bonds arising from the water mol-ecule, C-H⋯O inter-actions and π-π stacking of pyridine rings. In II, the ring nitro-gen atom is protonated, with charge balance provided by the carboxyl-ate group (i.e., a zwitterion). The intra-molecular O-H⋯O hydrogen bond observed in I is preserved in II. Crystals of II have unusual space-group symmetry of type Abm2 in which extended planar networks of O-H⋯O and N-H⋯O hydrogen-bonded mol-ecules form sheets lying parallel to the ac plane, constrained to b = 0.25 (and 0.75). The structure was refined as a 50:50 inversion twin. A minor disorder component was modeled by reflection of the major component across a mirror plane perpendicular to c.

Crystal structure and Hirshfeld surface analysis of N-[(Z)-(2-hy-droxy-phen-yl)methyl-idene]aniline N-oxide.

The conformation of the title compound, C13H11NO2, is partially determined by a strong, intra-molecular O-H⋯O hydrogen bond. The crystal packing consists of strongly corrugated layers parallel to the ac plane and associated through C-H⋯π(ring) inter-actions. A Hirshfeld surface analysis of the crystal structure indicates that the most significant contributions to the crystal packing are from H⋯H (44.1%), C⋯H/H⋯C (29.4%) and O⋯H/H⋯O (17.3%) contacts.

Lithium dipotassium citrate monohydrate, LiK2C6H5O7(H2O).

The crystal structure of dilithium potassium citrate monohydrate, Li+·2K+·C6H5O7 3-·H2O or LiK2C6H5O7·H2O, has been solved by direct methods and refined against laboratory X-ray powder diffraction data, and optimized using density functional techniques. The complete citrate trianion is generated by a crystallographic mirror plane, with two C and three O atoms lying on the reflecting plane, and chelates to three different K cations. The KO8 and LiO4 coordination polyhedra share edges and corners to form layers lying parallel to the ac plane. An intra-molecular O-H⋯O hydrogen bond occurs between the hydroxyl group and the central carboxyl-ate group of the citrate anion as well as a charge-assisted inter-molecular O-H⋯O link between the water mol-ecule and the terminal carboxyl-ate group. There is also a weak C-H⋯O hydrogen bond.

Complete mapping of magnetic anisotropy for prototype Ising van der Waals FePS3

Several Ising-type magnetic van der Waals (vdW) materials exhibit stable magnetic ground states. Despite these clear experimental demonstrations, a complete theoretical and microscopic understanding of their magnetic anisotropy is still lacking. In particular, the validity limit of identifying their one-dimensional Ising nature has remained uninvestigated in a quantitative way. Here we performed the complete mapping of magnetic anisotropy for a prototypical Ising vdW magnet FePS3 for the first time. Combining torque magnetometry measurements with their magnetostatic model analysis and the relativistic density functional total energy calculations, we successfully constructed the three-dimensional mappings of the magnetic anisotropy in terms of magnetic torque and energy. The results not only quantitatively confirm that the easy axis is perpendicular to the ab plane, but also reveal the anisotropies within the ab, ac, and bc planes. Our approach can be applied to the detailed quantitative study of magnetism in vdW materials.

Defects, diffusion and dopants in the ceramic mineral “Lime- Feldspar”

ABSTRACT Calcium aluminosilicate, CaAl2Si2O8, is a promising ceramic material that has found applications in several areas, such as glass production and petrology. Atomistic scale simulation techniques are used to study the intrinsic defects, Ca-ion migration paths and doping behavior in CaAl2Si2O8. The most favorable defect is the Al–Si anti-site in agreement with the experimental observation. The O-Frenkel is the second most favorable defect. The Ca-Frenkel is higher in energy only by 0.62 eV than the O-Frenkel. Long-range Ca-ion migration is observed in the ac plane with the activation energy of 2.84 eV suggesting that Ca-ion diffusion in this material is slow. The prominent isovalent dopant on the Ca site is the Sr, which was experimentally substituted on the Ca site to prevent phase transformation. The formation of Ca interstitials and oxygen vacancies is favored by Fe3+ doping on the Si site. The favorable tetravalent dopant on the Si site and the Al site to form Ca vacancies is the Ge.

Synthesis, crystal structure and thermal properties of poly[bis-[μ2-3-(amino-meth-yl)pyridine]-bis-(thio-cyanato)-cobalt(II)

The reaction of Co(NCS)2 with 3-(amino-meth-yl)pyridine as coligand leads to the formation of crystals of the title compound, [Co(NCS)2(C6H8N2)2] n , that were characterized by single-crystal X-ray analysis. In the crystal structure, the CoII cations are octa-hedrally coordinated by two terminal N-bonded thio-cyanate anions as well as two pyridine and two amino N atoms of four symmetry-equivalent 3-(amino-meth-yl)pyridine coligands with all pairs of equivalent atoms in a trans position. The CoII cations are linked by the 3-(amino-meth-yl)pyridine coligands into layers parallel to the ac plane. These layers are further linked by inter-molecular N-H⋯S hydrogen bonding into a three-dimensional network. The purity of the title compound was determined by X-ray powder diffraction and its thermal behavior was investigated by differential scanning calorimetry and thermogravimetry.

Symmetry analysis of complex magnetic structure in monoclinically distorted Er3Cu4Sn4.

The magnetic structure in Er3Cu4Sn4 has been determined using high-resolution powder neutron diffraction, supported by symmetry analysis. At low temperatures, Er3Cu4Sn4 assumes a crystal structure of the Tm3Cu4Sn4 type (in the monoclinic space group C2/m). The Er atoms occupy two distinct Wyckoff sites: 2c and 4i. It has been found that the Er magnetic moments on the 2c site form a commensurate antiferromagnetic structure (k1 = [0, 0, ½]) below 6 K. The magnetic moments reach 8.91 (8) μB at 1.4 K and are parallel to the b axis. The Er magnetic moments on the 4i site order below 2 K and form an incommensurate antiferromagnetic sine-modulated structure (k2 = [1, 0.4667 (1), ½]), with magnetic moments lying in the ac plane and perpendicular to the a axis. The amplitude of modulation equals 8.7 (1) μB at 1.4 K.

Thermal expansion, shear deformations and electrical conductivity of alluaudite-group minerals (badalovite and calciojohillerite)

Two specimens of alluaudite-group minerals, badalovite NaNaMg(Mg,Fe3+)2(AsO4)3 and calciojohillerite NaCaMgMg2(AsO4)3, were taken on the Second scoria cone of the Great fissure Tolbachik eruption, Kamchatka Peninsula, Russia. The crystal structures of these monoclinic minerals have been refined by single-crystal X-ray diffraction. The thermal expansion of badalovite and calciojohillerite has been studied by high-temperature powder X-ray diffraction. The electrical conductivity was evaluated by impedance spectroscopy. The thermal expansion of these minerals is similar: maximum expansion is close to the longer diagonal of the parallelogram ac, minimum expansion is close to the shorter diagonal of the parallelogram ac. Thermal deformation of the ac plane is described in terms of the theory of shear deformation of monoclinic crystals. The results of shear deformations calculation and its consideration with thermal expansion are given. The shear deformations were calculated using bisectors of the ac parallelogram at different temperatures. The axes of shear deformation are located in the directions of the mutually perpendicular bisectors of ac parallelogram. The electrical conductivity of badalovite is ~ 3–4 times greater than for calciojohillerite in the studied temperature range (350–600 °C).