Magnetic structure study of the sawtooth chain antiferromagnet $$\hbox {Fe}_2\hbox {Se}_2\hbox {O}_7$$

A magnetic structure of the sawtooth-chain antiferromagnet $$\hbox {Fe}_2\hbox {Se}_2\hbox {O}_7$$ Fe 2 Se 2 O 7 was investigated by magnetization measurements, single crystalline and powder neutron diffraction experiments, and a further analysis on the Mössbauer spectra. These experiments revealed a nearly collinear antiferromagnetic structure with magnetic moments aligned along the b-axis, indicating dominant antiferromagnetic exchanges between Fe(1)–Fe(2) and Fe(2)–Fe(3) sites. The magnon dispersion relation derived from the linear spin wave approximation suggests the possible flat band nature of magnons.

Incommensurately modulated crystal structure of α′ (O′3)-type sodium cobalt oxide Na x CoO2 (x ∼ 0.78)

A single-phase sample of α′ (O′3)-type layered sodium cobalt oxide Na x CoO2 (x ∼ 0.78) was prepared and its incommensurately modulated crystal structure was analyzed using the (3+1)-dimensional superspace approach to the powder neutron diffraction data. The crystal structure of the cobaltate is accurately described based on the superspace group C2/m(α0γ)00, wherein the positions of Na atoms are most significantly modulated in the monoclinic a direction to form an ordered arrangement. Such a displacive modulation causes a quasi-periodic shift of Na atoms from the centers of the NaO6 polyhedra between undulated CoO2 sheets, changing the form of the NaO6 polyhedron from an octahedral coordination (O) to a trigonal prismatic (P) one, via an intermediate capped trigonal prismatic NaO7 coordination (C). At the positions where the Na atoms are most significantly shifted, the neighboring Na atoms are located at almost touching distances. However, the occupation factor of Na atoms becomes zero at such positions, yielding Na-deficient sites V Na, sandwiched either between C and P, or C and C-type polyhedra.

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 (k 1 = [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 (k 2 = [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.

Structural resolution and mechanistic insight into hydrogen adsorption in flexible ZIF-7

Hydrogen induced flexibility in MOFs can be leveraged to increase useable gas storage capacities. Here hydrogen adsorption isothermal and in situ powder neutron diffraction measurements combine to reveal the mechanism driving flexibility in ZIF-7.

Neutron diffraction study of the tetragonal – monoclinic phase transition in NdNbO4 and NdTaO4

Phase transition and high-temperature properties of NdNbO4 and NdTaO4 were studied in situ using powder neutron diffraction methods. Both oxides undergo a reversible phase transition from a monoclinic I2/a phase...

Octahedral tilting in the polar hexagonal tungsten bronzes RbNbW2O9 and KNbW2O9

The ambient-temperature structures (orthorhombic, space group Cmc21) of the polar hexagonal tungsten bronzes RbNbW2O9 and KNbW2O9 have been determined by high-resolution powder neutron diffraction. Displacement of the A-site cation along the polar c axis with concomitant octahedral tilting occurs to optimize the A cation bonding environment, hence reducing the coordination from 18 to 16. This effect is more evident in KNbW2O9 due to decreased A cation size. The octahedral tilting in both compositions results in a doubling of the c axis that has not previously been reported, highlighting the importance of neutron diffraction as a complementary technique for structural determination of such systems.

Strong magnetic exchange and frustrated ferrimagnetic order in a weberite-type inorganic–organic hybrid fluoride

We combine powder neutron diffraction, magnetometry and 57 Fe Mössbauer spectrometry to determine the nuclear and magnetic structures of a strongly interacting weberite-type inorganic–organic hybrid fluoride, Fe 2 F 5 (H taz ). In this structure, Fe 2+ and Fe 3+ cations form magnetically frustrated hexagonal tungsten bronze layers of corner-sharing octahedra. Our powder neutron diffraction data reveal that, unlike its purely inorganic fluoride weberite counterparts which adopt a centrosymmetric Imma structure, the room-temperature nuclear structure of Fe 2 F 5 (H taz ) is best described by a non-centrosymmetric Ima 2 model with refined lattice parameters a = 9.1467(2) Å, b = 9.4641(2) Å and c = 7.4829(2) Å. Magnetic susceptibility and magnetization measurements reveal that strong antiferromagnetic exchange interactions prevail in Fe 2 F 5 (H taz ) leading to a magnetic ordering transition at T N = 93 K. Analysis of low-temperature powder neutron diffraction data indicates that below T N , the Fe 2+ sublattice is ferromagnetic, with a moment of 4.1(1) µ B per Fe 2+ at 2 K, but that an antiferromagnetic component of 0.6(3) µ B cants the main ferromagnetic component of Fe 3+ , which aligns antiferromagnetically to the Fe 2+ sublattice. The zero-field and in-field Mössbauer spectra give clear evidence of an excess of high-spin Fe 3+ species within the structure and a non-collinear magnetic structure. This article is part of the theme issue ‘Mineralomimesis: natural and synthetic frameworks in science and technology’.

Hydrogen-bond-mediated structural variation of metal guanidinium formate hybrid perovskites under pressure

The hybrid perovskites are coordination frameworks with the same topology as the inorganic perovskites, but with properties driven by different chemistry, including host-framework hydrogen bonding. Like the inorganic perovskites, these materials exhibit many different phases, including structures with potentially exploitable functionality. However, their phase transformations under pressure are more complex and less well understood. We have studied the structures of manganese and cobalt guanidinium formate under pressure using single-crystal X-ray and powder neutron diffraction. Under pressure, these materials transform to a rhombohedral phase isostructural to cadmium guanidinium formate. This transformation accommodates the reduced cell volume while preserving the perovskite topology of the framework. Using density-functional theory calculations, we show that this behaviour is a consequence of the hydrogen-bonded network of guanidinium ions, which act as struts protecting the metal formate framework against compression within their plane. Our results demonstrate more generally that identifying suitable host–guest hydrogen-bonding geometries may provide a route to engineering hybrid perovskite phases with desirable crystal structures. This article is part of the theme issue ‘Mineralomimesis: natural and synthetic frameworks in science and technology’.