Low-temperature Crystal Structure Research Articles

Influence of the Rare Earth Cation on the Magnetic Properties of Layered 12R-Ba4M4+Mn3O12 (M = Ce, Pr) Perovskites.

Material design is increasingly used to realize desired functional properties, and the perovskite structure family is one of the richest and most diverse: perovskites are employed in many applications due to their structural flexibility and compositional diversity. Hexagonal, layered perovskite structures with chains of face-sharing transition metal oxide octahedra have attracted great interest as quantum materials due to their magnetic and electronic properties. Ba4MMn3O12, a member of the "12R" class of hexagonal, layered perovskites, contains trimers of face-sharing MnO6 octahedra that are linked by a corner-sharing, bridging MO6 octahedron. Here, we investigate cluster magnetism in the Mn3O12 trimers and the role of this bridging octahedron on the magnetic properties of two isostructural 12R materials by systematically changing the M4+ cation from nonmagnetic Ce4+ (f0) to magnetic Pr4+ (f1). We synthesized 12R-Ba4MMn3O12 (M= Ce, Pr) with high phase purity and characterized their low-temperature crystal structures and magnetic properties. Using substantially higher purity samples than previously reported, we confirm the frustrated antiferromagnetic ground state of 12R-Ba4PrMn3O12 below TN ≈ 7.75 K and explore the cluster magnetism of its Mn3O12 trimers. Despite being atomically isostructural with 12R-Ba4CeMn3O12, the f1 electron associated with Pr4+ causes much more complex magnetic properties in 12R-Ba4PrMn3O12. In 12R-Ba4PrMn3O12, we observe a sharp, likely antiferromagnetic transition at T2 ≈ 12.15 K and an additional transition at T1 ≈ 200 K, likely in canted antiferromagnetic order. These results suggest that careful variation of composition within the family of hexagonal, layered perovskites can be used to tune material properties using the complex role of the Pr4+ ion in magnetism.

Low-Temperature Chiral Crystal Structure and Superconductivity in (Pt0.2Ir0.8)3Zr5.

We report the observation of superconductivity in (Pt0.2Ir0.8)3Zr5 with a chiral space group (P6122) at low temperatures. The bulk nature of the superconductivity at a transition temperature of 2.2 K was confirmed using specific heat measurements. We revealed that (Pt0.2Ir0.8)3Zr5 obeys the weak-coupling Bardeen-Cooper-Schrieffer model, and the dominant mechanism in the upper critical field is the orbital pair-breaking limit rather than the Pauli-Clogston limit. This indicates that the antisymmetric spin-orbit coupling caused by the chiral crystal structure does not significantly affect the superconductivity of (Pt0.2Ir0.8)3Zr5.

Comparison between the intermolecular interactions in the liquid and solid forms of propellant 1,1,1,2 – Tetrafluoroethane

A multitude of metered dose inhaler (MDI) formulation properties, such as permanent particle growth or separation, can affect the device’s drug delivering performance. 1,1,1,2 – Tetrafluoroethane (HFA-134a) is a liquid propellant commonly employed in MDIs. Here molecular modelling approaches are reported to evaluate the effect weak hydrogen bonding and steric repulsions have on its solid and liquid state molecular-scale structure. Molecular dynamics (MD) simulations of pure liquid HFA-134a were completed for a range of temperatures (203 – 323 K) and intermolecular interactions were analysed using the molecular trajectory files generated. Empirical force fields were used to calculate the strength of interactions seen in the low-temperature crystal structure, and these were compared to the liquid.The solid-state intermolecular structure arranges to maximise attractive interactions between permanent dipoles which enables the formation of ‘weak hydrogen bonds’, these were found to guide the transition from body centred cubic to its low temperature, monoclinic phase. Reducing HFA-134a’s liquid phase temperature increases its resemblance to the believed body centred cubic structure, with improved similarity between intermolecular radial distribution functions and vector angles. Weak hydrogen bonds in the liquid occurred more frequently at lower temperatures but the minimisation of steric repulsions is identified as the main cause of structural ordering, this shows liquid propellant is relatively non-polar. Understanding the structure of pure propellant is useful when evaluating the variation in wetting between different formulation materials and has the potential to be a useful resource for digital drug product design.

Order-disorder phase transition driven by interlayer sliding in lead iodides

A variety of phase transitions have been found in two-dimensional layered materials, but some of their atomic-scale mechanisms are hard to clearly understand. Here, we report the discovery of a phase transition whose mechanism is identified as interlayer sliding in lead iodides, a layered material widely used to synthesize lead halide perovskites. The low-temperature crystal structure of lead iodides is found not 2H polytype as known before, but non-centrosymmetric 4H polytype. This undergoes the order-disorder phase transition characterized by the abrupt spectral broadening of valence bands, taken by angle-resolved photoemission, at the critical temperature of 120 K. It is accompanied by drastic changes in simultaneously taken photocurrent and photoluminescence. The transmission electron microscopy is used to reveal that lead iodide layers stacked in the form of 4H polytype at low temperatures irregularly slide over each other above 120 K, which can be explained by the low energy barrier of only 10.6 meV/atom estimated by first principles calculations. Our findings suggest that interlayer sliding is a key mechanism of the phase transitions in layered materials, which can significantly affect optoelectronic and optical characteristics.

Low-temperature crystal structures of the solvent dimethyl carbonate

Dimethyl carbonate (DMC) is an important industrial solvent but is additionally a common component of liquid lithium-ion battery electrolytes. Pure DMC has a melting point of 277 K, so encountering solidification under outdoor climatic conditions is very likely in many locations around the globe. Even eutectic, ethylene carbonate:dimethyl carbonate commercial LiPF6 salt electrolyte formulations can start to solidify at temperatures around 260 K with obvious consequences for their performance. No structures for crystalline DMC are currently available which could be a hindrance for in situ battery studies at reduced temperatures. A time-of-flight neutron powder diffraction study of the phase behavior and crystal structures of deuterated DMC was undertaken to help fill this knowledge gap. Three different orthorhombic crystalline phases were found with a previously unreported low-temperature phase transition around 50–55 K. The progression of Pbca → Pbcm → Ibam space groups follow a sequence of group–subgroup relationships with the final Ibam structure being disordered around the central carbon atom.

The rich structural phase behaviour of 2,2,2-trifluoroethanol

A remarkable degree of polymorphism is exhibited in the high-pressure and low-temperature crystal structures of 2,2,2-trifluoroethanol, with the observation of four ordered phases (forms 1–4) and a cubic rotor phase (form 5).

Synthesis and crystal structure of topiramate azido-sulfate at 90 K and 298 K.

The low (90 K) and room (298 K) temperature crystal structures of topiramate azido-sulfate [systematic name 2,3:4,5-bis-O-(1-methyl-ethyl-idene)-β-d-fructo-pyran-ose azido-sulfate], C12H19N3O8S, an inter-mediate in the synthesis of the anti-convulsant drug topiramate, are described. Topiramate azido-sulfate (I) finds use as a reference impurity standard for topiramate. A modified synthesis and some spectroscopic details are also presented.

Unusual Magnetic Features in Two-Dimensional Fe5GeTe2 Induced by Structural Reconstructions.

Recent experiments on Fe5GeTe2 suggested the presence of a symmetry breaking of its conventional crystal structure. Here, using density functional theory calculations, we elucidate that the stabilization of the (√3 × √3)R30° supercell structure is caused by the swapping of Fe atoms occurring in the monolayer limit. The swapping to the vicinity of Te atoms is facilitated by the spontaneous occurrence of Fe vacancy and its low diffusion barrier. Our calculated magnetic exchange parameters show the simultaneous presence of ferromagnetic and antiferromagnetic exchange among a particular type of Fe atom. The Fe sublattice projected magnetization obtained from Monte Carlo simulations clearly demonstrates an exotic temperature-dependent behavior of this Fe type along with a large canting angle at T = 0 K, indicating the presence of a complex noncollinear magnetic order. We propose that the low-temperature crystal structure results from the swapping between two sublattices of Fe, giving rise to peculiar magnetization obtained in experiments.

Pronounced Magnetic Bistability in Highly Cooperative Mononuclear [Fe(Lnpdtz)2(NCX)2] Complexes.

Molecular materials that exhibit stimuli-responsive bistability are promising candidates for the development of molecular switches and sensors. We herein report on the coexistence of a wide thermal hysteretic spin crossover (SCO) effect and a thermally inducible metastable high-spin state at low temperatures achieved with the two new complexes [FeII(Lnpdtz)2(NCX)2] (X = S; Se), with Lnpdtz being (2-naphthyl-5-pyridyl-1,2,4-thiadiazole) and X = S (1) and Se (2). Pronounced π-π-stacking of the aromatic side residues of the ligands enables strong intermolecular interactions, leading to abrupt SCO properties and broad magnetic hysteresis of 10 K for X = S and 58 K for X = Se. In this paper, we also present the pressure-induced spin-state switching around 0.8 GPa. A pronounced thermally induced excited spin state trapping (TIESST effect) is observed for the highly cooperative SCO compounds, which was experimentally followed by low-temperature single crystal structure analysis (20 K) and temperature-dependent Mössbauer spectroscopy.

A Discrepancy in Thermal Conductivity Measurement Data of Quantum Spin Liquid β′-EtMe3Sb[Pd(dmit)2]2 (dmit = 1,3-Dithiol-2-thione-4,5-dithiolate)

A molecular Mott insulator β′-EtMe3Sb[Pd(dmit)2]2 is a quantum spin liquid candidate. In 2010, it was reported that thermal conductivity of β′-EtMe3Sb[Pd(dmit)2]2 is characterized by its large value and gapless behavior (a finite temperature-linear term). In 2019, however, two other research groups reported opposite data (much smaller value and a vanishingly small temperature-linear term) and the discrepancy in the thermal conductivity measurement data emerges as a serious problem concerning the ground state of the quantum spin liquid. Recently, the cooling rate was proposed to be an origin of the discrepancy. We examined effects of the cooling rate on electrical resistivity, low-temperature crystal structure, and 13C-NMR measurements and could not find any significant cooling rate dependence.

Neutron diffraction of field-induced magnon condensation in the spin-dimerized antiferromagnet Sr3Cr2O8

In this work, we investigate the evolution and settling of magnon condensation in the spin-1/2 dimer system ${\mathrm{Sr}}_{3}{\mathrm{Cr}}_{2}{\mathrm{O}}_{8}$ using a combination of magnetostriction in pulsed fields and inelastic neutron scattering in a continuous magnetic field. The magnetic structure in the Bose-Einstein condensation phase was probed by neutron diffraction in pulsed magnetic fields up to 39 T. The magnetic structure in this phase was confirmed to be an $\mathit{XY}$-antiferromagnetic structure validated by irreducible representational analysis. The magnetic phase diagram as a function of an applied magnetic field for this system is presented. Furthermore, zero-field neutron diffraction results indicate that dimerization plays an important role in stabilizing the low-temperature crystal structure.

Structure driven magnetic correlations and magnetodielectric coupling in 6H-perovskite Ba3DyRu2O9

The 6H-perovskites Ba3(R/M)Ru2O9 (R = rare Earth, M = transition metal) exhibit complex magnetism and have been extensively studied recently for their magnetodielectric (MD) properties. Here, we present a detailed study of structural, magnetic, thermodynamic and MD properties of a 6H-perovskite Ba3DyRu2O9. This compound is found to undergo long range antiferromagnetic ordering below ∼5.8 K (T N), along with the presence of metamagnetic transition at low temperatures. The heat capacity shows two additional anomalies at ∼28 K (T 1) and ∼33 K (T 2), besides the anomaly at T N. Signature of these anomalies is also visible in the derivative of magnetization curve. The dielectric response also shows weak anomalies around T 1 and T 2 at zero field whereas anomaly at T 2 gets suppressed at 80 kOe. The observed MD coupling of ∼2%–4% at 80 kOe field below ∼30 K temperature range, is among the highest values observed for the compounds of this family. Low temperature crystal structures of the compound show sharp distortion of Ru2O9 octahedra near T 2. Our study points toward the emergence of structurally driven spin correlations of Ru moments resulting in the observed MD coupling in this compound.

Rietveld refinement of the low temperature crystal structures of Cs2XSi5O12 (X = Cu, Cd and Zn)

The synthetic leucite silicate framework mineral analogues Cs2XSi5O12 (X = Cu, Cd, Zn) were prepared by high-temperature solid-state synthesis. The results of Rietveld refinement, using 18 keV synchrotron X-ray powder diffraction data collected at low temperatures (8K X = Cu, Zn; 10K X = Cd) show that the title compounds crystallize in the space group Pbca and are isostructural with the ambient temperature structures of these analogues. The structures consist of tetrahedrally coordinated SiO4 and XO4 sharing corners to form a partially substituted silicate framework. Extraframework Cs cations sit in channels in the framework. All atoms occupy the 8c general position for this space group. In these refined structures, silicon and X atoms are ordered onto separate tetrahedrally coordinated sites (T-sites).

Structural, electronic, and magnetic properties of nearly ideal Jeff=12 iridium halides

Heavy transition metal magnets with $J_{\rm eff}$ $=$ 1/2 electronic ground states have attracted recent interest due to their penchant for hosting new classes of quantum spin liquids and superconductors. Unfortunately, model systems with ideal $J_{\rm eff}$ $=$ 1/2 states are scarce due to the importance of non-cubic local distortions in most candidate materials. In this work, we identify a family of iridium halide systems [i.e. K$_2$IrCl$_6$, K$_2$IrBr$_6$, (NH$_4$)$_2$IrCl$_6$, and Na$_2$IrCl$_6 \cdotp $ 6(H$_2$O)] with Ir$^{4+}$ electronic ground states in extremely close proximity to the ideal $J_{\rm eff}$ $=$ 1/2 limit, despite a variation in the low-temperature global crystal structures. We also find ordered magnetic ground states for the three anhydrous systems, with single crystal neutron diffraction on K$_2$IrBr$_6$ revealing Type-I antiferromagnetism. This spin configuration is consistent with expectations for significant Kitaev exchange in a face-centered-cubic magnet.

Low-Temperature Crystal Structure and Mean-Field Modeling of ErxDy1−xAl2 Intermetallics

Low-temperature crystal structure of the ErxDy1−xAl2 alloys with x = 0.45, 0.67, 0.90 was examined using temperature-dependent powder X-ray diffraction. The Er-rich sample, Er0.9Dy0.1Al2, exhibits a rhombohedral distortion associated with the magnetic ordering that occurs around 20 K. The rhombohedral distortion is suppressed in Er0.67Dy0.33Al2, while a weak low-temperature tetragonal distortion is observed in Er0.45Dy0.55Al2. The mean-field theory supports the correlation between the type of structural distortion and the variable easy magnetization axis in ErxDy1−xAl2 intermetallics.

Structural Phase Diagram of LaO1−xFxBiSSe: Suppression of the Structural Phase Transition by Partial F Substitutions

Recently, the anomalous two-fold-symmetric in-plane anisotropy of superconducting states has been observed in a layered superconductor system, LaO1−xFxBiSSe (x = 0.1 and 0.5), with a tetragonal (four-fold symmetric) in-plane structure. To understand the origin of the phenomena observed in LaO1−xFxBiSSe, clarification of the low-temperature structural phase diagram is needed. In this study, we have investigated the low-temperature crystal structure of LaO1−xFxBiSSe (x = 0, 0.01, 0.02, 0.03, and 0.5). From synchrotron X-ray diffraction experiments, a structural transition from tetragonal to monoclinic was observed for x = 0 and 0.01 at 340 and 240 K, respectively. For x = 0.03, a structural transition and broadening of the diffraction peak were not observed down to 100 K. These facts suggest that the structural transition could be suppressed by 3% F substitution in LaO1−xFxBiSSe. Furthermore, the crystal structure for x = 0.5 at 4 K was examined by low-temperature laboratory X-ray diffraction, which confirmed that the tetragonal structure is maintained at 4 K for x = 0.5. Our structural investigation suggests that the two-fold-symmetric in-plane anisotropy of superconducting states observed in LaO1−xFxBiSSe was not originated from structural symmetry lowering in its average structure. To evaluate the possibility of the local structural modification like nanoscale puddles in the average tetragonal structure, further experiments are desired.

Discovery of a low-temperature orthorhombic phase of the Cd2Re2O7 superconductor

Using an {\it ab initio} approach, we report a phonon soft mode in the tetragonal structure described by the space group $I4_{1}22$ of the $1$ K $5d$ superconductor Cd$_2$Re$_2$O$_7$. It induces an orthorhombic distortion to a crystal structure described by the space group $F222$ which hosts the superconducting state. This new phase has a lower total energy than the other known crystal structures of Cd$_2$Re$_2$O$_7$. Comprehensive temperature dependent Raman scattering experiments on isotope enriched samples, $^{116}$Cd$_2$Re$_2{^{18}}$O$_7$, not only confirm the already known structural phase transitions but also allow us to identify a new characteristic temperature regime around $\sim 80$ K, below which the Raman spectra undergo remarkable changes with the development of several sharp modes and mode splitting. Together with the results of the \textit{ab initio} phonon calculations we take these observations as strong evidence for another phase transition to a novel low-temperature crystal structure of Cd$_2$Re$_2$O$_7$.

Cooperative interactions govern the fermiology of the polar metal Ca3Ru2O7

The antiferromagnetic Ruddlesden-Popper ruthenate Ca$_3$Ru$_2$O$_7$ is a model polar metal, combining inversion symmetry breaking with metallic conductivity; however, its low temperature ($T < 48$ K) crystal structure and Fermi surface topology remain ambiguous despite numerous measurements and theoretical studies. Here we perform both first principles calculations with static correlations and angle resolved photoelectron spectroscopy experiments to construct a complete model of Ca$_3$Ru$_2$O$_7$, reconciling inconsistencies among interpretations of electrical transport, thermopower measurements, and momentum- and energy-resolved band dispersions. The solution relies on treating the interplay among Coulomb repulsion, magnetic ordering, spin-orbit interactions, and the RuO$_6$ octahedral degrees-of-freedom on equal footing. For temperatures $30<T < 48$ K, we propose weak electron-electron interactions produce a symmetry-preserving metal-semimetal transition with Weyl nodes in proximity to the Fermi level, whereas a new orthorhombic $Pn2_1a$ structure emerges for $T<30$ K, exhibiting charge and spin density waves from enhanced Coulombic interactions.

Crystal structures of the flavonoid Oroxylin A and the regioisomers Negletein and Wogonin.

The flavonoid Oroxylin A (6-methoxychrysin or 5,7-dihydroxy-6-methoxy-2-phenyl-4H-chromen-4-one, C16H12O5) and its regioisomers are of increasing interest for a variety of bioactive functions and their pharmaceutical formulation is of importance. Previous difficulties in the separation and misidentification of Oroxylin A from its regioisomers Wogonin (8-methoxychrysin or 5,7-dihydroxy-8-methoxy-2-phenyl-4H-chromen-4-one) and Negletein (5,6-dihydroxy-7-methoxyflavone or 5,6-dihydroxy-7-methoxy-2-phenyl-4H-chromen-4-one) render its full structural and powder X-ray characterization highly desirable. The low-temperature (100 K) crystal structures of Oroxylin A, Negletein and Wogonin sesquihydrate are reported for the first time. Wogonin crystallizes in two related but distinct hydrated forms. These have very similar powder diffractograms, indicating that such issues need to be addressed for its pharmaceutical formulation.

Electronic Structure and Magnetic Properties of a Titanium(II) Coordination Complex.

Stable coordination complexes of TiII (3d2) are relatively uncommon, but are of interest as synthons for low oxidation state titanium complexes for application as potential catalysts and reagents for organic synthesis. Specifically, high-spin TiII ions supported by redox-inactive ligands are still quite rare due to the reducing power of this soft ion. Among such TiII complexes is trans-[TiCl2(tmeda)2], where tmeda = N,N,N',N'-tetramethylethane-1,2-diamine. This complex was first reported by Gambarotta and co-workers almost 30 years ago, but it was not spectroscopically characterized and theoretical investigation by quantum chemical theory (QCT) was not feasible at that time. As part of our interest in low oxidation state early transition metal complexes, we have revisited this complex and report a modified synthesis and a low temperature (100 K) crystal structure that differs slightly from that originally reported at ambient temperature. We have used magnetometry, high-frequency and -field EPR (HFEPR), and variable-temperature variable-field magnetic circular dichroism (VTVH-MCD) spectroscopies to characterize trans-[TiCl2(tmeda)2]. These techniques yield the following S = 1 spin Hamiltonian parameters for the complex: D = -5.23(1) cm-1, E = -0.88(1) cm-1, (E/D = 0.17), g = [1.86(1), 1.94(2), 1.77(1)]. This information, in combination with electronic transitions from MCD, was used as input for both classical ligand-field theory (LFT) and detailed QCT studies, the latter including both density functional theory (DFT) and ab initio methods. These computational methods are seldom applied to paramagnetic early transition metal complexes, particularly those with S > 1/2. Our studies provide a complete picture of the electronic structure of this complex that can be put into context with the few other high-spin and mononuclear TiII species characterized to date.