Edge-sharing Octahedra Research Articles

Crystal structure of a sodium, zinc and iron(III)-based non-stoichiometric phosphate with an alluaudite-like structure: Na1.67Zn1.67Fe1.33(PO4)3.

The new title compound, disodium dizinc iron(III) tris-(phosphate), Na1.67Zn1.67Fe1.33(PO4)3, which belongs to the alluaudite family, has been synthesized by solid-state reactions. In this structure, all atoms are in general positions except for four, which are located on special positions of the C2/c space group. This structure is characterized by cation substitutional disorder at two sites, one situated on the special position 4e (2) and the other on the general position 8f. The 4e site is partially occupied by Na(+) [0.332 (3)], whereas the 8f site is entirely filled by a mixture of Fe and Zn. The full-occupancy sodium and zinc atoms are located at the Wyckoff positions on the inversion center 4a (-1) and on the twofold rotation axis 4e, respectively. Refinement of the occupancy ratios, bond-valence analysis and the electrical neutrality requirement of the structure lead to the given composition for the title compound. The three-dimensional framework of this structure consists of kinked chains of edge-sharing octa-hedra stacked parallel to [10-1]. The chains are formed by a succession of trimers based on [ZnO6] octa-hedra and the mixed-cation Fe(III)/Zn(II) [(Fe/Zn)O6] octa-hedra [Fe(III):Zn(III) ratio 0.668 (3)/0.332 (3)]. Continuous chains are held together by PO4 phosphate groups, forming polyhedral sheets perpendicular to [010]. The stacked sheets delimit two types of tunnels parallel to the c axis in which the sodium cations are located. Each Na(+) cation is coordinated by eight O atoms. The disorder of Na in the tunnel might presage ionic mobility for this material.

Crystal structure of di-chlorido-bis-(methyl isonicotinate-κN)copper(II).

In the title compound, [CuCl2(C7H7NO2)2], the square-planar-coordinated CuII ion lies on a centre of symmetry and is bonded to two monodentate methyl­isonicotinate ligands through their N atoms and by two chloride ligands. The mol­ecules pack in a herringbone pattern. Perpendicular to [100] there are weak inter­molecular C—H⋯Cl and C—H⋯O contacts. Along [100] there are infinite chains of edge-sharing octa­hedra linked through the chlorido ligands

Mapping of reciprocal space of La0.30CoO2 in 3D: Analysis of superstructure diffractions and intergrowths with Co3O4

We have used electron diffraction tomography and powder X-ray diffraction to elucidate the structural properties of layered cobaltate γ-La0.30CoO2. The structure consists of hexagonal sheets of edge-sharing CoO6 octahedra interleaved by lanthanum monolayers. The La3+ cations occupy only one third of available P2 sites, forming a 2-dimensional a√3×a√3 superstructure in a–b plane. The results show that there exists no order in the mutual relative shift between the neighbouring La interlayers within the a–b plane. This is manifested in the observed monotonous decrease of the diffracted intensity of the superstructure diffractions along c⁎ in both X-ray and electron diffraction data. The observed lack of stacking order differentiates the LaxCoO2 from its Ca and Sr analogues where at least a partial stacking order of the cationic interlayers is manifested in experimental data published in literature.

Synthesis of sodium nickel phosphate and its crystallographic, spectroscopic, and temperature-controlled X-ray diffraction study

Sodium nickel phosphate NaNiPO4 has been synthesized by crystallization from salt solutions containing corresponding metals and phosphoric acid and subsequent heat treatment. NaNiPO4 with a maricite structure has been studied by a combination of methods. Its structure has been refined by the Rietweld method (space group Pnma, a = 8.7839(2) A, b = 6.7426(2), c = 5.0368(2) A, V = 298.31(2) A3, Z = 4). The structure framework is composed of edge-sharing NiO6 octahedra arranged in columns running along the b axis and linked with each other through PO4 tetrahedra. The cavities in the structure accommodate Na+ ions. No temperature-induced changes in the X-ray diffraction pattern of NaNiPO4 in the temperature range 25–700°C have been observed. The volumetric thermal expansion coefficient of the phosphate, αV = 34 × 10−6 K−1, allows one to classify it as a strongly expanding substance. Maricite structure stabilities are compared for NaEIIPO4 (EII = Mn, Fe, Co, Ni).

Atomic structure and chemistry of dislocation cores at low-angle tilt grain boundary in SrTiO3 bicrystals

Dislocations in perovskite oxides have been found to have important impacts on their electronic and ionic transportation properties, which are believed to be related to the structure and chemistry of dislocation cores. For dislocation cores at a 6° low-angle [001] tilt grain boundary in SrTiO3, an embedded TiOx rocksalt-like structure has been suggested, consistent with a deficiency of Sr. However, direct evidence supporting these suggestions has not been obtained up to now. In this work, we reveal the atomic structure and chemistry of edge dislocation cores at a low-angle [001] symmetric tilt-boundary in SrTiO3 bicrystals by imaging techniques of high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and electron energy loss spectroscopy (EELS) with an FEI Titan cube3 60–300 (PICO) microscope operated at 80kV. The experimental results demonstrate direct evidence for a local coordination of edge-sharing TiO6 octahedra at the dislocation cores, which can be understood as the result of strain. The local coordination of edge-sharing TiO6 octahedra is associated with the face-centered cubic (FCC) NaCl-type TiO phase. The present study therefore provides a solid structural and chemical basis for understanding the properties of dislocations.

Antiferromagnetism ofNi2NbBO6withS=1dimer quasi-one-dimensional armchair chains

Long range antiferromagnetic (AFM) ordering of Ni spins in Ni2NbBO6 has been studied with single crystal from spin susceptibility measurement and comparedwith the ab initio calculation results consistently. Below TN = 23.5 K, the S = 1 spins align along the a direction for edge-shared NiO6 octahedra which form crystallographic armchair chains along the b direction. The isothermal magnetization M(H) below TN shows spin-flop transition for magnetic field above 36 kOe along the a axis,which indicates the spin anisotropy is along the a direction. The electronic and magnetic structures of Ni2NbBO6 have also been explored theoretically using density functional theory with generalized gradient approximation plus on-site Coulomb interaction (U). These calculations support the experimentally observed antiferromagnetism of Ni2NbBO6. In particular, the long range AFM ordering below TN can be dissected into armchair chains which consists of S = 1 dimers of J2 = 2.43 meV with ferromagnetic (FM) intrachain and interchain couplings of size half |J2|.

Crystal structure and ion conductivity of a new mixed-anion phosphate LiMg3(PO4)P2O7

A new lithium-containing phosphate, LiMg3(PO4)P2O7, was prepared by a solid-state reaction, and it was characterized by an ab initio structure determination method on the basis of synchrotron powder X-ray diffraction data. LiMg3(PO4)P2O7 was found to be orthorhombic (space group Pnma) with lattice parameters a=9.0387(1)Å, b=10.6072(1)Å, c=8.3065(1)Å, and V=796.39(1)Å3. The structure features infinite [Mg3O10]∞ layers that are parallel to the bc plane and that are interconnected along the a axis by PO4 and P2O7 groups. The [Mg3O10]∞ layer contains Mg3O14 trimers that are formed by three edge-shared MgO6 octahedra. The PO4 and P2O7 groups are located alternatively between [Mg3O10]∞ layers. This gives rise to a three-dimensional framework that contains large tunnels along the directions [100] and [010]; the Li+ ions are stabilized in these tunnels. AC impedance spectroscopy shows that LiMg3(PO4)P2O7 has an ionic conductivity of 3.40×10−5Scm−1 at 769K, with an activation energy of 1.17eV.

Coexistence of high-T(c) ferromagnetism and n-type electrical conductivity in FeBi2Se4.

The discovery of n-type ferromagnetic semiconductors (n-FMSs) exhibiting high electrical conductivity and Curie temperature (Tc) above 300 K would dramatically improve semiconductor spintronics and pave the way for the fabrication of spin-based semiconducting devices. However, the realization of high-Tc n-FMSs and p-FMSs in conventional high-symmetry semiconductors has proven extremely difficult due to the strongly coupled and interacting magnetic and semiconducting sublattices. Here we show that decoupling the two functional sublattices in the low-symmetry semiconductor FeBi2Se4 enables unprecedented coexistence of high n-type electrical conduction and ferromagnetism with Tc ≈ 450 K. The structure of FeBi2Se4 consists of well-ordered magnetic sublattices built of [FenSe4n+2]∞ single-chain edge-sharing octahedra, coherently embedded within the three-dimensional Bi-rich semiconducting framework. Magnetotransport data reveal a negative magnetoresistance, indicating spin-polarization of itinerant conducting electrons. These findings demonstrate that decoupling magnetic and semiconducting sublattices allows access to high-Tc n- and p-FMSs as well as helps unveil the mechanism of carrier-mediated ferromagnetism in spintronic materials.

New honeycomb iridium(V) oxides: NaIrO3 and Sr3CaIr2O9.

We report the structures and physical properties of two new iridates, NaIrO3 and Sr3CaIr2O9, both of which contain continuous two-dimensional honeycomb connectivity. NaIrO3 is produced by room temperature oxidative deintercalation of sodium from Na2IrO3, and contains edge-sharing IrO6 octahedra that form a planar honeycomb lattice. Sr3CaIr2O9, produced via conventional solid-state synthesis, hosts a buckled honeycomb lattice with novel corner-sharing connectivity between IrO6 octahedra. Both of these new compounds are comprised of Ir(5+) (5d(4)) and exhibit negligible magnetic susceptibility. They are thus platforms to investigate the origin of the nonmagnetic behavior exhibited by Ir(5+) oxides, and provide the first examples of a J = 0 state on a honeycomb lattice.

A frustrated ferrimagnet Cu5(VO4)2(OH)4 with a 1/5 magnetization plateau on a new spin-lattice of alternating triangular and honeycomb strips.

Cu5(VO4)2(OH)4 (turanite) is a layered compound, exhibiting a copper(II) oxide layer in the [0 1 1] plane composed of edge-sharing CuO6 octahedra. Each Cu-O layer is further separated by VO4 tetrahedra. Closer scrutiny found that the copper(II) oxide layer in the compound represents a totally new geometrically-frustrated lattice, a 1/6 depleted triangular lattice. More specifically, the spin network in the [0 1 1] plane is formed by the alternate ranking of triangular and honeycomb strips. Magnetic measurements show that the Cu5(VO4)2(OH)4 behaves as a spin-1/2 ferrimagnet with a Tc = ∼4.5 K. It exhibits an unusual 1/5 magnetization plateau arising from the competition between antiferromagnetic and ferromagnetic interactions caused by the strong frustration. The possible spin-arrangements are also suggested.

A Smart Solution to the Edge-sharing Octahedra Problems

A Smart Solution to the Edge-sharing Octahedra Problems

Topolology-symmetry law of structure of natural titanosilicate micas and related heterophyllosilicates based on the extended OD theory: Structure prediction

A topology-symmetry analysis of the structures in the family of titanosilicate micas and related heterophyllosilicates based on the extended OD theory reveals their kinship with the family of rhodezite, delhayelite, and other minerals that had been analyzed earlier by distinguishing sheets common for all the structures. Like in the family studied earlier, the structural variety of a more complex titanosilicate family is determined by different local symmetries of sheets. Sheets consist of central O layers of edge-sharing octahedra and H layers formed by tetrahedra connected into diortho groups and Ti(Nb,Fe) semioctahedra (octahedra). Three patterns of connection of O and H layers correspond to sheet symmetry P2/m, P21/m, and \(P\bar 1\). Various symmetry modes of sheet connection in the structures are analyzed. Hypothetical structures, including structures with a higher degree of disorder, which can be found in nature or obtained by crystal synthesis, are deduced. Factors responsible for structural variety, including the existence of two main sheet varieties (with P2/m and P21/m symmetry) are considered a consequence of the difference in the chemism of the mineral formation medium.

Antisymmetric Spin-Orbit Coupling in a d-p Model on a Zigzag Chain

We theoretically investigate how an antisymmetric spin-orbit coupling emerges in electrons moving on lattice structures which are centrosymmetric but break the spatial inversion symme- try at atomic positions. We construct an effective d-p model on the simplest lattice structure, a zigzag chain of edge-sharing octahedra, with taking into account the crystalline electric field, the spin-orbit coupling, and on-site and inter-site d-p hybridizations. We show that an effective antisymmetric spin-orbit coupling arises in the sublattice-dependent form, which results in a hidden spin polarization in the band structure. We explicitly derive the effective antisymmetric spin-orbit coupling for d electrons, which not only explains the hidden spin polarization but also indicates how to enhance it.

Synthesis, structure and characterization of two new Zn(II) and Cd(II) complexes with the bidentate ligand 2-[(2-aminoethyl)amino]ethanaminium (AEEA)

Two new Zn(II) and Cd(II) complexes with the bidentate ligand 2-[(2-aminoethyl)amino]ethanaminium (AEEA), [ZnCl2(C4H14N3)]ClO4 (1) and [CdCl2(C4H14N3)]ClO4 (2), have been prepared and were characterized by single crystal X-ray diffraction, elemental analysis, CP–MAS-NMR and IR spectroscopies. The basic coordination patterns of the AEEA coordinated metal cations is highly distorted tetrahedral in (1) and distorted octahedral in (2). The crystal structure of (1) is characterized by ZnCl2N2 tetrahedra interconnected via N–H⋯Cl hydrogen bonds to form layers parallel to the (b, a+c) plane. In (2), the CdN2Cl4 entities form polymeric chains of edge-sharing octahedra extending along the a-axis direction. The crystal structures are stabilized by sets of hydrogen bonds, some of which are bi or trifurcated. The 13C and 15N CP–MAS NMR spectra are discussed and the vibrational absorption bands were identified by infrared spectroscopy.

First-principles investigation of exchange interactions in quasi-one-dimensional antiferromagnet CaV2O4

The effects of orbital degrees of freedom on the exchange interactions in a quasi-one-dimensional spin-1 antiferromagnet CaV2O4 are systematically studied. For this purpose a realistic low-energy electron model with the parameters derived from the first-principles calculations is constructed in the Wannier basis for the t2g bands. The exchange interactions are calculated using both the theory of infinitesimal spin rotations near the mean-field ground state and the superexchange model, which provide a consistent description. The obtained behaviour of exchange interactions differs substantially from the previously proposed phenomenological picture based on magnetic measurements and structural considerations, namely: (i) despite the quasi-one-dimensional character of the crystal structure, consisting of the zigzag chains of the edge-sharing VO6 octahedra, the electronic structure is essentially three-dimensional, that leads to finite interactions between the chains; (ii) the exchange interactions along the legs of the chains appear to dominate; and (iii) there is a substantial difference in exchange interactions in two crystallographically inequivalent chains. The combination of these three factors successfully reproduces the behaviour of experimental magnetic susceptibility.

Bismuth zinc vanadate, BiZn2VO6: New crystal structure type and electronic structure

We report a combined experimental and computational study of the crystal structure and electronic properties of bismuth zinc vanadate, BiZn2VO6, known for its visible light photocatalytic activity. The crystal structure has been solved from laboratory powder X-ray diffraction data using the repeated minimisations from random starting values method. BiZn2VO6 adopts a new structure type, based on the following building blocks: corner- and edge-sharing ZnO4 tetrahedra, ZnO6 octahedra and VO4 tetrahedra, and Bi2O12 dimers. It is the only known member of the BiM2AO6 (M=Pb, Ca, Cd, Mn, Zn, Mg, Cu; A=V, P, As) family which does not appear to be structurally closely related to others. The electronic structure of BiZn2VO6, calculated by DFT methods, shows that it is an indirect gap semiconductor with a calculated band gap of 1.6eV, which compares favourably to the experimentally measured value of 2.4eV.

Single crystal and magnetic structures of maricite-type AgMnVO4

Single crystals of the ternary manganese vanadate AgMnVO4, were grown using AgVO3 flux. The structure was determined from single crystal X-ray diffraction data. The magnetic structure and properties of AgMnVO4 were characterized by magnetic susceptibility, specific heat, and low-temperature neutron powder diffraction measurements. AgMnVO4 crystallizes in the maricite-type structure with space group Pnma, a=9.5393(12), b=6.8132(9), c=5.3315(7)Å and Z=4. AgMnVO4 contains MnO4 chains made up of edge-sharing MnO6 octahedra, and these chains are interlinked by the VO4 and AgO4 tetrahedra. The specific heat measurements indicate a 3D-antiferromagnetic ordering at ~12.1K and the neutron powder diffraction measurements at 5K show that the Mn2+magnetic moments are antiferromagnetically coupled within the chains which are antiferromagnetically coupled to each other.

Perovskite to postperovskite transition in NaFeF3.

The GdFeO3-type perovskite NaFeF3 transforms to CaIrO3-type postperovskite at pressures as low as 9 GPa at room temperature. The details of such a transition were investigated by in situ synchrotron powder diffraction in a multianvil press. Fit of the p-V data showed that the perovskite phase is more compressible than related chemistries with a strongly anisotropic response of the lattice metrics to increasing pressure. The reduction in volume is accommodated by a rapid increase of the octahedral tilting angle, which reaches a critical value of 26° at the transition boundary. The postperovskite form, which is fully recoverable at ambient conditions, shows a regular geometry of the edge-sharing octahedra and its structural properties are comparable to those found in CaIrO3-type MgSiO3 at high pressure and temperature. Theoretical studies using density functional theory at the GGA + U level were also performed and describe a scenario where both perovskite and postperovskite phases can be considered Mott-Hubbard insulators with collinear magnetic G- and C-type antiferromagnetic structures, respectively. Magnetic measurements are in line with the theoretical predictions with both forms showing the typical behavior of canted antiferromagnets.

Direct measurement of the spin gap in a quasi-one-dimensional clinopyroxene:NaTiSi2O6

True inorganic Spin-Peierls materials are extremely rare, but NaTiSi2O6 was at one time considered an ideal candidate due to it having well separated chains of edge-sharing TiO6 octahedra. At low temperatures, this material undergoes a phase transition from C2/c to P$$\bar{1}$$ symmetry, where Ti3+-Ti3+ dimers begin to form within the chains. However, it was quickly realized with magnetic susceptibility that simple spin fluctuations do not progress to the point of enabling such a transition. Since then, considerable experimental and theoretical endeavours have been taken to find the true ground state of this system and explain how it manifests. Here, we employ the use of x-ray diffraction, neutron spectroscopy, and magnetic susceptibility to directly and simultaneously measure the symmetry loss, spin singlet-triplet gap, and phonon modes. Lastly, we observed a gap of 53(3) meV, fit to the magnetic susceptibility, and compared to previous theoretical models to unambiguously assign NaTiSi2O6 as having an orbital-assisted Peierls ground state.

Synthesis, crystal structure and properties of alluaudite-like triple molybdate Na25Cs8Fe5(MoO4)24

A new triple molybdate Na25Cs8Fe5(MoO4)24 was synthesized using solid state reactions and studied with X-ray powder diffraction, second harmonic generation (SHG) technique, differential scanning calorimetry, Mössbauer and dielectric impedance spectroscopy. Single crystals of Na25Cs8Fe5(MoO4)24 were obtained and its structure was solved (the space group P1¯, a=12.5814(5), b=13.8989(5), c=28.4386(9)Å, α=90.108(2), β=90.064(2), γ=90.020(2)°, V=4973.0(3)Å3, Z=2, R=0.0440). Characteristic features of the structure are polyhedral layers composed of pairs of edge-shared FeO6 and (Fe, Na)O6 octahedra, which are connected by bridging МоО4 tetrahedra. The layers share common vertices with bridging МоО4 tetrahedra to form an open 3D framework with the cavities occupied by the Cs+ and Na+ cations. The compound undergoes first-order phase transformation at 642K and above this phase transition, electrical conductivity reaches 10−3–10−2Scm−1. Thus, Na25Cs8Fe5(MoO4)24 may be considered as a promising compound for developing new materials with high ionic conductivity.