Acta Crystallographica Section B
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Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials publishes scientific articles related to the structural science of compounds and materials in the widest sense. Knowledge of the arrangements of atoms, including their temporal variations and dependencies on temperature and pressure, is often the key to understanding physical and chemical phenomena and is crucial for the design of new materials and supramolecular devices. Acta Crystallographica B is the forum for the publication of such contributions. Scientific developments based on experimental studies as well as those based on theoretical approaches, including crystal-structure prediction, structure-property relations and the use of databases of crystal structures, are published.enCopyright (c) 2024 International Union of Crystallography2024-03-26International Union of CrystallographyInternational Union of Crystallographyhttp://journals.iucr.orgurn:issn:2052-5206Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials publishes scientific articles related to the structural science of compounds and materials in the widest sense. Knowledge of the arrangements of atoms, including their temporal variations and dependencies on temperature and pressure, is often the key to understanding physical and chemical phenomena and is crucial for the design of new materials and supramolecular devices. Acta Crystallographica B is the forum for the publication of such contributions. Scientific developments based on experimental studies as well as those based on theoretical approaches, including crystal-structure prediction, structure-property relations and the use of databases of crystal structures, are published.text/htmlActa Crystallographica Section B: Structural Science, Crystal Engineering and Materials, Volume 80, Part 2, 2024textweekly62002-02-01T00:00+00:002802024-03-26Copyright (c) 2024 International Union of CrystallographyActa Crystallographica Section B: Structural Science, Crystal Engineering and Materials51urn:issn:2052-5206med@iucr.orgMarch 20242024-03-26Acta Crystallographica Section Bhttp://journals.iucr.org/logos/rss10b.gif
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Still imageElastic and piezoelectric properties of β-glycine – a quantum crystallography view on intermolecular interactions and a high-pressure phase transition
http://scripts.iucr.org/cgi-bin/paper?px5058
The effect of hydrostatic compression on the elastic and electronic properties of β-glycine was studied using a quantum crystallography approach. The interrelations between the changes in the microscopic quantum pressure in the electronic continuum, macroscopic compressibility and piezoelectricity were considered. The geometries and energies of hydrogen bonds in the crystal structure of β-glycine were considered as functions of pressure before and after a phase transition into the β′-phase in relation to the mechanism of this phase transition.Copyright (c) 2024 International Union of Crystallographyurn:issn:2052-5206Khainovsky, M.A.Boldyreva, E.Tsirelson, V.2024-02-10doi:10.1107/S2052520624000428International Union of CrystallographyElastic and piezoelectric properties of β-glycine were studied in relation to the electron density distribution in the crystal structure. Structural strain of β-glycine crystals under high external pressure was interpreted. The mechanism of a high-pressure phase transition is discussed.ENquantum crystallographystructures under extreme conditionsfunctional materialsphase transitions in materialshydrogen bondsThe effect of hydrostatic compression on the elastic and electronic properties of β-glycine was studied using a quantum crystallography approach. The interrelations between the changes in the microscopic quantum pressure in the electronic continuum, macroscopic compressibility and piezoelectricity were considered. The geometries and energies of hydrogen bonds in the crystal structure of β-glycine were considered as functions of pressure before and after a phase transition into the β′-phase in relation to the mechanism of this phase transition.text/htmlElastic and piezoelectric properties of β-glycine – a quantum crystallography view on intermolecular interactions and a high-pressure phase transitiontext2802024-02-10Copyright (c) 2024 International Union of CrystallographyActa Crystallographica Section Bresearch papers00Study on the vertical Bridgman method of melt-grown CsPbBr3 single crystals for nuclear radiation detection
http://scripts.iucr.org/cgi-bin/paper?tq5014
As an excellent representative of all-inorganic perovskite materials, CsPbBr3 has been widely used in high-energy rays or high-energy particles detection for its outstanding high carrier mobility and long diffusion length. The great challenges and opportunities in these fields are crystal growth technology, especially the high-quality and large-sized CsPbBr3 single crystals. In this work, the influences of growth parameters (temperature gradient, growth rate, cooling rate) and thermal stress by the vertical Bridgman method on the quality and performance of CsPbBr3 crystals are systematically studied. The final results show that 10°C cm−1 is the optimized temperature gradient and 0.5 mm h−1 is the suitable growth rate for CsPbBr3 crystal growth. The study also shows that a cooling rate of 10°C h−1 for the general temperature interval and 1°C h−1 for the phase transition temperature interval is helpful to balance crystal growth efficiency as well as crystal quality. Crystal cracks caused by thermal stress as well as crystal adhesion on the ampoule can be effectively solved by depositing a uniform carbon film on the ampoule in advance. The optical, electrical and detection performance are also investigated. The optical characterization in the wavelength region ranging from ultraviolet to infrared indicates the crystal has a low density of deep-level defects and good crystal quality. The resistivity over 109 Ω cm and μτ of electrons over 10−2 cm−2 V−1 proves that the electrical performance of the crystal has met the basic requirement for nuclear radiation detection. The metal–semiconductor–metal structure Ti/Ni/CsPbBr3/Ni/Ti detector fabricated from the optimized CsPbBr3 single crystal has an energy resolution of 12.85% (137Cs, 662 keV). The purpose of this work is to provide a useful guide and reference for the future exploration of repeatable and improvable CsPbBr3 crystal growth technology.Copyright (c) 2024 International Union of Crystallographyurn:issn:2052-5206Zhang, M.Huang, C.Xia, G.Liu, J.Tian, F.Zou, J.Tang, B.2024-02-10doi:10.1107/S2052520624000398International Union of CrystallographyHigh quality CsPbBr3 single crystals suitable for use in γ-ray detection are grown by the vertical Bridgman method and an optimized single crystal is proved to meet the basic requirement for high-energy nuclear radiation detection.ENCsPbBr3 single crystalcrystal growthvertical Bridgman methodcrystal qualitycrystal performanceAs an excellent representative of all-inorganic perovskite materials, CsPbBr3 has been widely used in high-energy rays or high-energy particles detection for its outstanding high carrier mobility and long diffusion length. The great challenges and opportunities in these fields are crystal growth technology, especially the high-quality and large-sized CsPbBr3 single crystals. In this work, the influences of growth parameters (temperature gradient, growth rate, cooling rate) and thermal stress by the vertical Bridgman method on the quality and performance of CsPbBr3 crystals are systematically studied. The final results show that 10°C cm−1 is the optimized temperature gradient and 0.5 mm h−1 is the suitable growth rate for CsPbBr3 crystal growth. The study also shows that a cooling rate of 10°C h−1 for the general temperature interval and 1°C h−1 for the phase transition temperature interval is helpful to balance crystal growth efficiency as well as crystal quality. Crystal cracks caused by thermal stress as well as crystal adhesion on the ampoule can be effectively solved by depositing a uniform carbon film on the ampoule in advance. The optical, electrical and detection performance are also investigated. The optical characterization in the wavelength region ranging from ultraviolet to infrared indicates the crystal has a low density of deep-level defects and good crystal quality. The resistivity over 109 Ω cm and μτ of electrons over 10−2 cm−2 V−1 proves that the electrical performance of the crystal has met the basic requirement for nuclear radiation detection. The metal–semiconductor–metal structure Ti/Ni/CsPbBr3/Ni/Ti detector fabricated from the optimized CsPbBr3 single crystal has an energy resolution of 12.85% (137Cs, 662 keV). The purpose of this work is to provide a useful guide and reference for the future exploration of repeatable and improvable CsPbBr3 crystal growth technology.text/htmlStudy on the vertical Bridgman method of melt-grown CsPbBr3 single crystals for nuclear radiation detectiontext2802024-02-10Copyright (c) 2024 International Union of CrystallographyActa Crystallographica Section Bresearch papers00Elastic and inelastic strain in submicron-thick ZnO epilayers grown on r-sapphire substrates by metal–organic vapour phase deposition
http://scripts.iucr.org/cgi-bin/paper?yh5029
A significant part of the present and future of optoelectronic devices lies on thin multilayer heterostructures. Their optical properties depend strongly on strain, being essential to the knowledge of the stress level to optimize the growth process. Here the structural and microstructural characteristics of sub-micron a-ZnO epilayers (12 to 770 nm) grown on r-sapphire by metal–organic chemical vapour deposition are studied. Morphological and structural studies have been made using scanning electron microscopy and high-resolution X-ray diffraction. Plastic unit-cell distortion and corresponding strain have been determined as a function of film thickness. A critical thickness has been observed as separating the non-elastic/elastic states with an experimental value of 150–200 nm. This behaviour has been confirmed from ultraviolet photoelectron spectroscopy, X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy measurements. An equation that gives the balance of strains is proposed as an interesting method to experimentally determine this critical thickness. It is concluded that in the thinnest films an elongation of the Zn—O bond takes place and that the plastic strained ZnO films relax through nucleation of misfit dislocations, which is a consequence of three-dimensional surface morphology.Copyright (c) 2024 International Union of Crystallographyurn:issn:2052-5206Martinez-Tomas, M.C.Klymov, O.Shimazoe, K.Sánchez-Royo, J.-F.Changarath, M. E.Agouram, S.Muñoz-Sanjosé, V.2024-02-13doi:10.1107/S2052520624000441International Union of CrystallographySub-micron a-ZnO epilayers (12 to 770 nm) grown on r-sapphire by MOCVD have been analysed using SEM, HRXRD, UPS, XPS and HRTEM. The distortion of the unit cell has been determined and the consequent strain shows a transition from an inelastic to an elastic state, separated by a critical thickness; a method to experimentally determine this critical thickness is given.ENhigh-resolution X-ray diffraction (HRXRD)thin filmsunit-cell parameterselastic straininelastic straincritical thicknessA significant part of the present and future of optoelectronic devices lies on thin multilayer heterostructures. Their optical properties depend strongly on strain, being essential to the knowledge of the stress level to optimize the growth process. Here the structural and microstructural characteristics of sub-micron a-ZnO epilayers (12 to 770 nm) grown on r-sapphire by metal–organic chemical vapour deposition are studied. Morphological and structural studies have been made using scanning electron microscopy and high-resolution X-ray diffraction. Plastic unit-cell distortion and corresponding strain have been determined as a function of film thickness. A critical thickness has been observed as separating the non-elastic/elastic states with an experimental value of 150–200 nm. This behaviour has been confirmed from ultraviolet photoelectron spectroscopy, X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy measurements. An equation that gives the balance of strains is proposed as an interesting method to experimentally determine this critical thickness. It is concluded that in the thinnest films an elongation of the Zn—O bond takes place and that the plastic strained ZnO films relax through nucleation of misfit dislocations, which is a consequence of three-dimensional surface morphology.text/htmlElastic and inelastic strain in submicron-thick ZnO epilayers grown on r-sapphire substrates by metal–organic vapour phase depositiontext2802024-02-13Copyright (c) 2024 International Union of CrystallographyActa Crystallographica Section Bresearch papers00The physical space model of the Tsai-type quasicrystal
http://scripts.iucr.org/cgi-bin/paper?dk5124
The binary Cd5.7Yb phase representing the Tsai-type category of the icosahedral quasicrystals is solved by the assignment of a unique atomic decoration to rhombohedral units in the Ammann–Kramer–Neri tiling. The unique decoration is found for units with an edge length of 24.1 Å and 3m internal point symmetry. The structural refinement was carried out for two underlying tilings generated by the projection method for 6D space. The difference lies in the location of the origin point which for one tiling is in the vertex and for the second one in the center of the 6D unit cell. The two tilings exhibit mutual duality. The choice of the tiling has a minor effect on the final structural model as both converge to an R factor of ∼11.5%. The main difference is related to the treatment of the Cd4 tetrahedral motif which is either orientationally ordered and aligned with the threefold axis or disordered and modeled as a partially occupied icosahedron. Both models can be presented as a covering by rhombic triacontahedral clusters with identical positions of clusters within rhombohedral units. The shell structure is Tsai-type in the case of the first tiling and Bergman-type for the other.Copyright (c) 2024 International Union of Crystallographyurn:issn:2052-5206Buganski, I.Strzalka, R.Wolny, J.2024-03-01doi:10.1107/S2052520624000763International Union of CrystallographyThe structural modeling of the CdYb quasicrystal was carried out in real space with the Ammann–Kramer–Neri tiling. The structural refinement is performed for two independent models where the origin of the tiling obtained by the projection method is set in the vertex or the body center of the 6D unit cell.ENquasicrystalstructure refinementicosahedral symmetryTsai clusterBergman clusterThe binary Cd5.7Yb phase representing the Tsai-type category of the icosahedral quasicrystals is solved by the assignment of a unique atomic decoration to rhombohedral units in the Ammann–Kramer–Neri tiling. The unique decoration is found for units with an edge length of 24.1 Å and 3m internal point symmetry. The structural refinement was carried out for two underlying tilings generated by the projection method for 6D space. The difference lies in the location of the origin point which for one tiling is in the vertex and for the second one in the center of the 6D unit cell. The two tilings exhibit mutual duality. The choice of the tiling has a minor effect on the final structural model as both converge to an R factor of ∼11.5%. The main difference is related to the treatment of the Cd4 tetrahedral motif which is either orientationally ordered and aligned with the threefold axis or disordered and modeled as a partially occupied icosahedron. Both models can be presented as a covering by rhombic triacontahedral clusters with identical positions of clusters within rhombohedral units. The shell structure is Tsai-type in the case of the first tiling and Bergman-type for the other.text/htmlThe physical space model of the Tsai-type quasicrystaltext2802024-03-01Copyright (c) 2024 International Union of CrystallographyActa Crystallographica Section Bresearch papers002327383232738423273852327386Structural changes in Rochelle salt on phase transitions revisited in a multi-temperature single-crystal X-ray diffraction study
http://scripts.iucr.org/cgi-bin/paper?xk5105
Phase transitions in Rochelle salt [sodium potassium l(+)-tartrate tetrahydrate] are revisited in a single-crystal X-ray diffraction multi-temperature study on cooling from 308 to 100 K across the high-temperature paraelectric (PE) ↔ ferroelectric ↔ low-temperature PE phase transition points. The results of structure refinement using three different models (a harmonic with and without disorder, and an anharmonic) were compared. The temperature dependencies of anisotropic displacement parameters (ADPs) and Ueq, which can be calculated directly from ADPs, for the low-temperature PE phase indicate clearly the dynamic nature of disorder of the K1 atoms. The structures of the low-temperature and the high-temperature PE phases are compared for the first time at multiple temperatures for each phase based on diffraction data collected from the same single crystal. The data indicate that the high-temperature and the low-temperature paraelectric phases are probably not two different phases, as was assumed in earlier works, but are structurally the same phase at different temperatures.Copyright (c) 2024 International Union of Crystallographyurn:issn:2052-5206Sharaya, S.S.Zakharov, B.A.Boldyreva, E.V.2024-03-04doi:10.1107/S205252062400115XInternational Union of CrystallographyAnisotropic displacement parameters for K1 atoms and the interatomic distances in the crystal structure of Rochelle salt were refined based on single-crystal X-ray diffraction at multiple temperatures on cooling from 308 to 100 K across the high-temperature paraelectric ↔ ferroelectric ↔ low-temperature paraelectric phase transitions points. Data add to the understanding of the structural distortions and disorder accompanying these transitions and suggest that the high-temperature and the low-temperature paraelectric phases are probably the same phase.ENmolecular ferroelectricsRochelle saltvariable-temperature X-ray diffractionanisotropic displacement parameter analysisparaelectric phasesdisorder modelsPhase transitions in Rochelle salt [sodium potassium l(+)-tartrate tetrahydrate] are revisited in a single-crystal X-ray diffraction multi-temperature study on cooling from 308 to 100 K across the high-temperature paraelectric (PE) ↔ ferroelectric ↔ low-temperature PE phase transition points. The results of structure refinement using three different models (a harmonic with and without disorder, and an anharmonic) were compared. The temperature dependencies of anisotropic displacement parameters (ADPs) and Ueq, which can be calculated directly from ADPs, for the low-temperature PE phase indicate clearly the dynamic nature of disorder of the K1 atoms. The structures of the low-temperature and the high-temperature PE phases are compared for the first time at multiple temperatures for each phase based on diffraction data collected from the same single crystal. The data indicate that the high-temperature and the low-temperature paraelectric phases are probably not two different phases, as was assumed in earlier works, but are structurally the same phase at different temperatures.text/htmlStructural changes in Rochelle salt on phase transitions revisited in a multi-temperature single-crystal X-ray diffraction studytext2802024-03-04Copyright (c) 2024 International Union of CrystallographyActa Crystallographica Section Bresearch papers00233058723305882330589233059023305912330592233059323305942330595233059623305972330598233059923306002330601Three-dimensional electron diffraction on clinkers: the belite α′H incommensurate modulated structure
http://scripts.iucr.org/cgi-bin/paper?je5054
Traditional X-ray methods are extensively applied to commercial cement samples in order to determine their physical and chemical properties. Powder patterns are routinely used to quantify the composition of these phase mixtures, but structure determination becomes difficult because of reflection overlapping caused by the high number of different crystal structures. The fast-growing 3D electron diffraction technique and its related automated acquisition protocols arise as a potentially very interesting tool for the cement industry, since they enable the fast and systematic acquisition of diffraction data from individual particles. In this context, electron diffraction has been used in the investigation of the different crystalline phases present in various commercial clinkers for cement. Automated data collection procedures and subsequent data processing have enabled the structural characterization of the different crystal structures from which the α′H polymorph of Ca2SiO4 (belite) exhibited satellite reflections. Its average crystal structure has been known since 1971 and satellite reflections have been reported previously, yet the modulation was never fully described by means of the superspace formalism. Here, the incommensurately modulated structure is solved and refined using harmonic and crenel functions in the superspace group Pnma(α00)0ss, showing the potential of 3D electron diffraction for systematic crystallographic characterizations of cement. A full description of the different belite polymorphs is provided considering this modulated structure.Copyright (c) 2024 International Union of Crystallographyurn:issn:2052-5206Plana-Ruiz, S.Götz, E.Neumann, T.Schwesig, P.Kolb, U.2024-03-06doi:10.1107/S205252062400146XInternational Union of CrystallographyThree-dimensional electron diffraction is comprehensively used to characterize different specimens of commercial clinkers for cement. The crystallographic analysis has enabled the crystal structure determination of belite α′H as an incommensurate modulated structure with q ≃ 0.376a* and superspace group Pnma(α00)0ss.ENthree-dimensional electron diffraction3D EDelectron microscopymodulated structurescementTraditional X-ray methods are extensively applied to commercial cement samples in order to determine their physical and chemical properties. Powder patterns are routinely used to quantify the composition of these phase mixtures, but structure determination becomes difficult because of reflection overlapping caused by the high number of different crystal structures. The fast-growing 3D electron diffraction technique and its related automated acquisition protocols arise as a potentially very interesting tool for the cement industry, since they enable the fast and systematic acquisition of diffraction data from individual particles. In this context, electron diffraction has been used in the investigation of the different crystalline phases present in various commercial clinkers for cement. Automated data collection procedures and subsequent data processing have enabled the structural characterization of the different crystal structures from which the α′H polymorph of Ca2SiO4 (belite) exhibited satellite reflections. Its average crystal structure has been known since 1971 and satellite reflections have been reported previously, yet the modulation was never fully described by means of the superspace formalism. Here, the incommensurately modulated structure is solved and refined using harmonic and crenel functions in the superspace group Pnma(α00)0ss, showing the potential of 3D electron diffraction for systematic crystallographic characterizations of cement. A full description of the different belite polymorphs is provided considering this modulated structure.text/htmlThree-dimensional electron diffraction on clinkers: the belite α′H incommensurate modulated structuretext2802024-03-06Copyright (c) 2024 International Union of CrystallographyActa Crystallographica Section Bresearch papers002338192233274923381932338194Effect of a halogen bond on the crystal structure of terphenyldicarboxylic acid derivatives
http://scripts.iucr.org/cgi-bin/paper?aw5083
The syntheses and structures of dimethyl [11,21:24,31-terphenyl]-14,34-dicarboxylate (1), dimethyl 22,25-diiodo[11,21:24,31-terphenyl]-14,34-dicarboxylate (2), potassium [11,21:24,31-terphenyl]-14,34-dicarboxylate (3) and dimethyl [1,1′-biphenyl]-4,4′-dicarboxylate (4) are reported. Neighboring phenyl rings in compounds 1, 3 and 4 have a planar structure (torsion angles are 0.6–4.1°) and the molecules are packed into regular layers. In the structure of the iodinated derivative of terphenyldicarboxylic acid (2), the middle benzene ring of the terphenyl fragment is rotated relative to the other rings by 64° due to the repulsion between the protons and the iodine atoms of neighboring rings. The formation of halogen bonds between iodine and oxygen atoms of the carbonyl group leads to the movement of molecules of one layer into another layer and the loss of layered structure. Potassium [11,21:24,31-terphenyl]-14,34-dicarboxylate (3) forms crystals with an ionic structure. The coordination number of the potassium cation is eight and the resulting coordination polyhedron is a distorted square antiprism. Dianions in the potassium salt crystal are packed in layers similar to the layers in the dimethyl ethers 1 and 4. Salt 3 has high thermal stability to 500°C.Copyright (c) 2024 International Union of Crystallographyurn:issn:2052-5206Osipov, A.A.Nayfert, S.A.Sobalev, S.A.Rajakumar, K.Zherebtsov, D.A.Spiridonova, D.V.Vinnik, D.A.2024-03-19doi:10.1107/S2052520624001318International Union of CrystallographyThe methods of synthesis and structures of the derivatives of terphenyl dicarboxylic acid are described. These compounds are promising ligands for metal–organic frameworks.ENterphenyldicarboxylic acidbiphenyldicarboxylic acidhalogen bondsThe syntheses and structures of dimethyl [11,21:24,31-terphenyl]-14,34-dicarboxylate (1), dimethyl 22,25-diiodo[11,21:24,31-terphenyl]-14,34-dicarboxylate (2), potassium [11,21:24,31-terphenyl]-14,34-dicarboxylate (3) and dimethyl [1,1′-biphenyl]-4,4′-dicarboxylate (4) are reported. Neighboring phenyl rings in compounds 1, 3 and 4 have a planar structure (torsion angles are 0.6–4.1°) and the molecules are packed into regular layers. In the structure of the iodinated derivative of terphenyldicarboxylic acid (2), the middle benzene ring of the terphenyl fragment is rotated relative to the other rings by 64° due to the repulsion between the protons and the iodine atoms of neighboring rings. The formation of halogen bonds between iodine and oxygen atoms of the carbonyl group leads to the movement of molecules of one layer into another layer and the loss of layered structure. Potassium [11,21:24,31-terphenyl]-14,34-dicarboxylate (3) forms crystals with an ionic structure. The coordination number of the potassium cation is eight and the resulting coordination polyhedron is a distorted square antiprism. Dianions in the potassium salt crystal are packed in layers similar to the layers in the dimethyl ethers 1 and 4. Salt 3 has high thermal stability to 500°C.text/htmlEffect of a halogen bond on the crystal structure of terphenyldicarboxylic acid derivativestext2802024-03-19Copyright (c) 2024 International Union of CrystallographyActa Crystallographica Section Bresearch papers002204949225478822547892240217Growth, crystal structure and IR luminescence of KSrY1–xErx(BO3)2
http://scripts.iucr.org/cgi-bin/paper?yh5030
A series of novel KSrY1–xErx(BO3)2 (x = 0–1) phosphors that emit near-infrared radiation was synthesized using solid-state methods. Pure Y and Er crystals were grown using a KF flux via the top-seeded solution growth technique. In situ high-temperature single crystal X-ray diffraction, Raman spectroscopy and DFT calculations were used for characterization. Within the series, a polymorphic phase transition from space group P21/m to R3m was discovered between 550 and 600°C. The concentration dependence of the luminescence intensity was measured for the samples. A strong emission of Er3+ electron transition 4I13/2 → 4I15/2 was detected within the 1529–1549 nm range, with the maximum observed for the KSrY0.4Er0.6(BO3)2 composition.Copyright (c) 2024 International Union of Crystallographyurn:issn:2052-5206Kuznetsov, A.B.Kokh, K.A.Gorelova, L.A.Sofich, D.O.Sagatov, N.Gavryushkin, P.N.Vereshchagin, O.S.Bocharov, V.N.Shevchenko, V.S.Kokh, A.E.2024-03-20doi:10.1107/S205252062400177XInternational Union of CrystallographyA series of novel KSrY1–xErx(BO3)2 (x = 0–1) phosphors, emitting near-infrared radiation, was synthesized by solid-state methods. A strong emission of Er3+ electron transition 4I13/2 → 4I15/2 was detected within the 1529–1549 nm range.ENcrystal growthRamanHT-SCXRDDFTluminescenceA series of novel KSrY1–xErx(BO3)2 (x = 0–1) phosphors that emit near-infrared radiation was synthesized using solid-state methods. Pure Y and Er crystals were grown using a KF flux via the top-seeded solution growth technique. In situ high-temperature single crystal X-ray diffraction, Raman spectroscopy and DFT calculations were used for characterization. Within the series, a polymorphic phase transition from space group P21/m to R3m was discovered between 550 and 600°C. The concentration dependence of the luminescence intensity was measured for the samples. A strong emission of Er3+ electron transition 4I13/2 → 4I15/2 was detected within the 1529–1549 nm range, with the maximum observed for the KSrY0.4Er0.6(BO3)2 composition.text/htmlGrowth, crystal structure and IR luminescence of KSrY1–xErx(BO3)2text2802024-03-20Copyright (c) 2024 International Union of CrystallographyActa Crystallographica Section Bresearch papers00230186922975512297553Attractive and repulsive forces in a crystal of [Rb(18-crown-6)][SbCl6] under high pressure
http://scripts.iucr.org/cgi-bin/paper?px5059
The compression behavior of [Rb(18-crown-6)][SbCl6] crystal under pressure up to 2.16 (3) GPa was investigated in a diamond anvil cell (DAC) using a mixture of pentane–isopentane (1:4) as the pressure-transmitting fluid. The compound crystallizes in trigonal space group R3 and no phase transition was observed in the indicated pressure range. The low value of pressure bulk modulus [9.1 (5) GPa] found in this crystal is a characteristic of soft materials with predominant dispersive and electrostatic interaction forces. The nonlinear relationship between unit-cell parameters under high pressure is attributed to the influence of reduced intermolecular H...Cl contacts under pressure over 0.73 GPa. It also explains the high compression efficiency of [Rb(18-crown-6)][SbCl6] crystals at relatively low pressures, resulting in a significant shift of the Rb atom to the center of the crown ether cavity. At pressures above 0.9 GPa, steric repulsion forces begin to play a remarkable role, since an increasing number of interatomic H...Cl and H...H contacts become shorter than the sum of their van der Waals (vdW) radii. Below 0.9 GPa, both unit-cell parameter dependences (P–a and P–c) exhibit hysteresis upon pressure release, demonstrating their influence on the disordered model of Rb atoms. The void reduction under pressure also demonstrates two linear sections with the inflection point at 0.9 GPa. Compression of the crystal is accompanied by a significant decrease in the volume of the voids, leading to the rapid approach of Rb atoms to the center of the crown ether cavity. For the Rb atom to penetrate into the center of the crown ether cavity in [Rb(18-crown-6)][SbCl6], it is necessary to apply a pressure of about 2.5 GPa to disrupt the balance of atomic forces in the crystal. This sample serves as a compression model demonstrating the influence of both attractive and repulsive forces on the change in unit-cell parameters under pressure.Copyright (c) 2024 International Union of Crystallographyurn:issn:2052-5206Rusanov, E.B.Wörle, M.D.Kovalenko, M.V.Domasevitch, K.V.Rusanova, J.A.2024-03-20doi:10.1107/S2052520624001586International Union of CrystallographyThe structure of [Rb(18-crown-6)][SbCl6] is studied under high pressure. This sample serves as a compression model, demonstrating the influence of both attractive London dispersion forces and repulsive forces in the crystal affecting its behavior under extreme pressure.ENX-ray diffractionhigh pressurecrown etherattractive and repulsive forcesalkali metal complexesThe compression behavior of [Rb(18-crown-6)][SbCl6] crystal under pressure up to 2.16 (3) GPa was investigated in a diamond anvil cell (DAC) using a mixture of pentane–isopentane (1:4) as the pressure-transmitting fluid. The compound crystallizes in trigonal space group R3 and no phase transition was observed in the indicated pressure range. The low value of pressure bulk modulus [9.1 (5) GPa] found in this crystal is a characteristic of soft materials with predominant dispersive and electrostatic interaction forces. The nonlinear relationship between unit-cell parameters under high pressure is attributed to the influence of reduced intermolecular H...Cl contacts under pressure over 0.73 GPa. It also explains the high compression efficiency of [Rb(18-crown-6)][SbCl6] crystals at relatively low pressures, resulting in a significant shift of the Rb atom to the center of the crown ether cavity. At pressures above 0.9 GPa, steric repulsion forces begin to play a remarkable role, since an increasing number of interatomic H...Cl and H...H contacts become shorter than the sum of their van der Waals (vdW) radii. Below 0.9 GPa, both unit-cell parameter dependences (P–a and P–c) exhibit hysteresis upon pressure release, demonstrating their influence on the disordered model of Rb atoms. The void reduction under pressure also demonstrates two linear sections with the inflection point at 0.9 GPa. Compression of the crystal is accompanied by a significant decrease in the volume of the voids, leading to the rapid approach of Rb atoms to the center of the crown ether cavity. For the Rb atom to penetrate into the center of the crown ether cavity in [Rb(18-crown-6)][SbCl6], it is necessary to apply a pressure of about 2.5 GPa to disrupt the balance of atomic forces in the crystal. This sample serves as a compression model demonstrating the influence of both attractive and repulsive forces on the change in unit-cell parameters under pressure.text/htmlAttractive and repulsive forces in a crystal of [Rb(18-crown-6)][SbCl6] under high pressuretext2802024-03-20Copyright (c) 2024 International Union of CrystallographyActa Crystallographica Section Bresearch papers0023336362333637233363823336392333640233364123336422333643233364423336452333646233364723336482333649233365023336512333652233365323336542333655Crystal structure solution and high-temperature thermal expansion in NaZr2(PO4)3-type materials
http://scripts.iucr.org/cgi-bin/paper?yh5031
The NaZr2P3O12 family of materials have shown low and tailorable thermal expansion properties. In this study, SrZr4P6O24 (SrO·4ZrO2·3P2O5), CaZr4P6O24 (CaO·4ZrO2·3P2O5), MgZr4P6O24 (MgO·4ZrO2·3P2O5), NaTi2P3O12 [½(Na2O·4TiO2·3P2O5)], NaZr2P3O12 [½(Na2O·4ZrO2·3P2O5)], and related solid solutions were synthesized using the organic–inorganic steric entrapment method. The samples were characterized by in-situ high-temperature X-ray diffraction from 25 to 1500°C at the Advanced Photon Source and National Synchrotron Light Source II. The average linear thermal expansion of SrZr4P6O24 and CaZr4P6O24 was between −1 × 10−6 per °C and 6 × 10−6 per °C from 25 to 1500°C. The crystal structures of the high-temperature polymorphs of CaZr4P6O24 and SrZr4P6O24 with R3c symmetry were solved by Fourier difference mapping and Rietveld refinement. This polymorph is present above ∼1250°C. This work measured thermal expansion coefficients to 1500°C for all samples and investigated the differences in thermal expansion mechanisms between polymorphs and between compositions.Copyright (c) 2024 International Union of Crystallographyurn:issn:2052-5206Hulbert, B.S.Brodecki, J.E.Kriven, W.M.2024-03-22doi:10.1107/S2052520624001598International Union of CrystallographyThe crystal structure in space group R3c in a high-temperature polymorph of SrZr4P6O24 and CaZr4P6O24 was solved with Fourier difference mapping. The thermal expansion tensors for several NaZr2P3O12-type materials were measured from 25 to 1500°C and crystallographic thermal expansion mechanisms investigated.ENNZP-type materialsCaZr4(PO4)6SrZr4(PO4)6phase transformationthermal expansionstructure solutionFourier difference mappowder diffractionThe NaZr2P3O12 family of materials have shown low and tailorable thermal expansion properties. In this study, SrZr4P6O24 (SrO·4ZrO2·3P2O5), CaZr4P6O24 (CaO·4ZrO2·3P2O5), MgZr4P6O24 (MgO·4ZrO2·3P2O5), NaTi2P3O12 [½(Na2O·4TiO2·3P2O5)], NaZr2P3O12 [½(Na2O·4ZrO2·3P2O5)], and related solid solutions were synthesized using the organic–inorganic steric entrapment method. The samples were characterized by in-situ high-temperature X-ray diffraction from 25 to 1500°C at the Advanced Photon Source and National Synchrotron Light Source II. The average linear thermal expansion of SrZr4P6O24 and CaZr4P6O24 was between −1 × 10−6 per °C and 6 × 10−6 per °C from 25 to 1500°C. The crystal structures of the high-temperature polymorphs of CaZr4P6O24 and SrZr4P6O24 with R3c symmetry were solved by Fourier difference mapping and Rietveld refinement. This polymorph is present above ∼1250°C. This work measured thermal expansion coefficients to 1500°C for all samples and investigated the differences in thermal expansion mechanisms between polymorphs and between compositions.text/htmlCrystal structure solution and high-temperature thermal expansion in NaZr2(PO4)3-type materialstext2802024-03-22Copyright (c) 2024 International Union of CrystallographyActa Crystallographica Section Bresearch papers0023336342333635Solid State Materials Chemistry. By Patrick M. Woodward, Pavel Karen, John S. O. Evans and Thomas Vogt. Cambridge University Press, 2021. Hardcover. Pp. 708. Price EUR 81.69. ISBN 9780521873253
http://scripts.iucr.org/cgi-bin/paper?xo0190
Copyright (c) 2024 International Union of Crystallographyurn:issn:2052-5206Suescun, L.2024-03-27doi:10.1107/S2052520624002166International Union of CrystallographyENbook reviewsolid-state chemistrymaterials chemistrytext/htmlSolid State Materials Chemistry. By Patrick M. Woodward, Pavel Karen, John S. O. Evans and Thomas Vogt. Cambridge University Press, 2021. Hardcover. Pp. 708. Price EUR 81.69. ISBN 9780521873253text2802024-03-27Copyright (c) 2024 International Union of CrystallographyActa Crystallographica Section Bbook reviews00