Zeitschrift für Kristallographie - Crystalline Materials

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Volume 237 Issue 4-5 - “Spotlight on Germany’s Young Crystallographers”

Issue of Zeitschrift für Kristallographie - Crystalline Materials

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Contents
Journal Overview

Publicly Available May 10, 2022

Frontmatter

Page range: i-ii

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Publicly Available May 10, 2022

Preface

April 11, 2022

Crystallography in Germany rejuvenated

Matthias Zschornak, Dirk C. Meyer, Peter Paufler

Page range: 83-84

Abstract

This article briefly reflects the history and development of the Young Crystallographers as work group of the German Crystallographic Society within the last decade. It presents the preface to this special issue Spotlight on Germany’s Young Crystallographers.

Original Papers

November 1, 2021

CalcOPP: a program for the calculation of one-particle potentials (OPPs)

Dennis Wiedemann

Page range: 85-92

Abstract

In recent years, one-particle potentials (OPPs) derived from neutron-diffraction data have become a popular means to estimate activation energies of ion migration in solids. Computer programs for their calculation, however, have mostly been private in-house solutions. The software CalcOPP presented herein permits calculating two- or three-dimensional OPPs either from probability density functions put out by the crystallographic suite Jana 2006 / Jana 2020 (including error maps) or from scattering-density maps reconstructed using the maximum entropy method (MEM) implementation Dysnomia . The title program is open-source, written in modern free-form Fortran and Python 3, and available free of charge under the permissive MIT License. Executables are published for 64-bit Microsoft Windows and Linux platforms and can be controlled via an intuitive graphical user interface or via command-line interface. Depending on the kind of input, CalcOPP ’s output is readily visualized with standard crystallographic software or plotting applications. The release of the program not only makes the rather powerful OPP method more transparent, but it also opens it up to a broader, less programming-oriented public.

November 29, 2021

Synthesis and coordination to the coinage metals of a trimethylpyrazolyl substituted 3-arylacetylacetone

Steven van Terwingen, Noah Nachtigall, Ulli Englert

Page range: 93-99

Abstract

The ligand 3-(4-(1,3,5-trimethyl-1 H -pyrazol-4-yl)phenyl)acetylacetone ( 1 ) combines a Pearson hard O,O′ chelating acetylacetone donor with a softer pyrazole N donor bridged by a phenylene spacer. Deprotonation and coordination to Cu II leads to a square planar bis-acetylacetonato complex; interpreting the close proximity of an adjacent complex’s pyrazole moiety as an η 2 ${{\eta}}^{2}$ coordination to the axial Cu II position leads to a two dimensional extended structure. The N donor capabilities are proven by coordination to AgPF 6 and AuCl; for Ag I a cationic linear bis-pyrazole complex as a toluene solvate is obtained with toluene-pyrazole π-interactions and an essentially uncoordinated PF 6 - ${{\mathrm{PF}}_{6}}^{-}$ anion. In the case of AuCl a neutral linear coordination compound with one chlorido and one pyrazole ligand 1 is obtained. Comparing the dihedral angles with a closely related but shorter ligand reveals a larger rotational degree of freedom in 1 , allowing for richer architectures in emerging coordination polymers.

Open Access December 28, 2021

Occupancy disorder in the magnetic topological insulator candidate Mn_1−xSb_2+xTe₄

Laura C. Folkers, Laura Teresa Corredor, Fabian Lukas, Manaswini Sahoo, Anja U. B. Wolter, Anna Isaeva

Page range: 101-108

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Abstract

MnSb 2 Te 4 is a candidate magnetic topological insulator exhibiting more pronounced cation intermixing than its predecessor MnBi 2 Te 4 . Investigating the cation intermixing and its possible implications on the magnetic order in MnSb 2 Te 4 are currently hot topics in research on quantum materials for spintronics and energy-saving applications. Two single-crystal X-ray diffraction measurements of Mn 1− x Sb 2+ x Te 4 ( x = 0.06 and x = −0.1) are presented alongside a detailed discussion of its crystal structure with a spotlight on the apparent occupancy disorder between the two cations. This disorder has been noted by other groups as well, yet never been analyzed in-depth with single-crystal X-ray diffraction. The latter is the tool of choice to receive a meaningful quantification of antisite disorder. Between the two synthesis procedures we find subtle differences in phases and/or alternation of the cation content which has implications on the magnetic order, as illustrated by bulk magnetometry. Understanding and assessing this disorder in magnetic topological insulators of the MnX 2 Te 4 (X = Bi, Sb) type is crucial to gauge their applicability for modern spintronics. Furthermore, it opens new ways to tune the “chemical composition – physical property” relationship in these compounds, creating an alluring aspect also for fundamental science.

December 28, 2021

Structural study of anhydrous and hydrated 5-fluorouracil co-crystals with nicotinamide and isonicotinamide

Tobias Heinen, Sandra Hoelscher, Vera Vasylyeva

Page range: 109-116

Abstract

5-Fluorouracil is a widely used anti-cancer drug which exhibits diverse polymorphic and co-crystalline behavior. Here we report two new solvent-free co-crystals of 5-fluorouracil with model co-formers nicotinamide and isonicotinamide, along with the redetermination of their hydrated analogues. Selected co-formers are categorized as safe and therefore suitable for pharmaceutical applications. Differences and similarities in supramolecular topology of the given structures are discussed. A special emphasis is set on the influence of fluorine moieties on the overall packing and synthetic accessibility of the presented multi-component systems.

January 13, 2022

Synthesis, crystal-structure refinement and properties of bastnaesite-type PrF[CO₃], SmF[CO₃] and EuF[CO₃]

Constantin Buyer, Samira A. Schumacher, Thomas Schleid

Page range: 117-125

Abstract

By adding a hot aqueous solution containing KF and K 2 [CO 3 ] to another hot aquatic brine of Pr[NO 3 ] 3 ⋅ 5 H 2 O, Sm[NO 3 ] 3 ⋅ 5 H 2 O or Eu[NO 3 ] 3 ⋅ 5 H 2 O with a 1.3 times excess of the anion-providing solution, amorphous water-insoluble powders of PrF[CO 3 ], SmF[CO 3 ] and EuF[CO 3 ] can be obtained. Through hydrothermal treatment at 210 °C for five days crystalline powders could be synthesized and their crystal structure was refined with Rietveld methods based on PXRD data. The named compounds crystallize in the bastnaesite-type structure with a = 710.912(12) pm, c = 976.811(6) pm for the praseodymium, a = 704.77(2) pm, c = 971.83(4) pm for the samarium and a = 700.734(6) pm, c = 969.066(8) pm for the europium compound, all hexagonal with Z = 6. Upon heating them, the compounds lose CO 2 and fluoride oxides RE FO emerge. Thermogravimetric experiments with crystalline samples show thermal stability up to 420 °C for PrF[CO 3 ], 400 °C for SmF[CO 3 ] and 340 °C for EuF[CO 3 ], but decomposition below 200 °C for the amorphous ones. Infrared spectroscopy confirms only marginal portions of [OH] − instead of F − anions in all cases. The RE 3+ cations are coordinated by 9 + 2 anions at distances between 236 and 254 pm plus 326 pm to F − anions and oxygen atoms bonded to carbon as oxocarbonate anions [CO 3 ] 2− . Triggered by ultraviolet radiation, the bulk sample of EuF[CO 3 ] shows a poor red luminescence.

January 13, 2022

Crystallographic complexity partition analysis

Wolfgang Hornfeck

Page range: 127-134

Abstract

We present an illustrative analysis of the complexity of a crystal structure based on the application of Shannon’s entropy formula in the form of Krivovichev’s complexity measures and extended according to the contributions of distinct discrete probability distributions derived from the atomic numbers and the Wyckoff multiplicities and arities of the atoms and sites constituting the crystal structure, respectively. The results of a full crystallographic complexity partition analysis for the intermetallic phase Mo 3 Al 2 C, a compound of intermediate structural complexity, are presented, with all calculations performed in detail. In addition, a partial analysis is discussed for the crystal structures of α - and β -quartz.

January 20, 2022

The “ferros” of MAPbI₃: ferroelectricity, ferroelasticity and its crystallographic foundations in hybrid halide perovskites

Joachim Breternitz

Page range: 135-140

Abstract

Hybrid halide perovskites have been identified as an important novel class of photovoltaic absorbers and have proven their great potential with ever record-breaking efficiencies. Some of the more fundamental properties of halide perovskites, however, still are to be properly understood. The ongoing debate as to whether ferroelectricity and/or ferroelasticity play a role in these materials is just one example for this. Herein, I aim to make these phenomena more approachable to the wider research community and elucidate the foundations and consequences of these phenomena.

February 7, 2022

Structure relations in the family of the solid solution Hf_xZr_1−xO₂

Melanie Nentwich

Page range: 141-157

Abstract

Hafnium Zirconium Oxide Hf x Zr 1− x O 2 is a potentially ferroelectric material with great perspectives in semiconductor applications, due to its compatibility with silicon technologies and its low toxicity. Despite its chemical simplicity, the solid solution Hf x Zr 1− x O 2 comprises a large variety of different phases. We compiled a complete list of experimentally and theoretically reported Hf x Zr 1− x O 2 structures. All of them are symmetrically related to the common aristotype with Fluorite type structure. The symmetry relationships between those structures have been determined and are presented in a Bärnighausen-like tree. Interestingly, not all symmetry reductions follow the conventional group-subgroup relations and involve severe atomic shifts. Further, the structures were compared to each other in detail regarding the dimensionality of atomic shifts and the accompanied lattice distortions. Finally, the information provided by the Bärnighausen-like tree was used to transform the indices of a reflection before and after a phase transition. This conversion allows the study of (dis)appearing reflections during phase transitions.

February 16, 2022

The crystal structure of single crystalline PrCa₄O[BO₃]₃

Tina Weigel, Juliane Hanzig, Erik Mehner

Page range: 159-166

Abstract

PrCa 4 O[BO 3 ] 3 was grown as a single crystal by the Czochralski method. The precursor material was synthesized by solid state reaction under O 2 atmosphere and sintered after grinding under N 2 atmosphere with a content of 20% H 2 . The Czochralski crystal growth proceeded under N 2 atmosphere with an <010> oriented GdCa 4 O[BO 3 ] 3 crystal seed. A PrCa 4 O[BO 3 ] 3 crystal with a cylinder length of 20 mm, a diameter of 15 mm, and weight of 23.1 g was obtained. The crystal structure was solved from single crystal X-ray diffraction data in the monoclinic crystal system with space group C 1 m 1 (No. 8), the lattice parameters a = 8.1293(6) Å, b = 16.062(1) Å, c = 3.6023(2) Å, β = 101.371(2)°, formula units of 2 and final R - and w R 2-values below 3.8%. A mixed occupancy between Pr and Ca of 6.0% was found.

February 23, 2022

Crystal structure of a hexacationic Ag(I)-pillarplex-dodecyl-diammonium pseudo-rotaxane as terephthalate salt

Alexandra A. Heidecker, Moritz Bohn, Alexander Pöthig

Page range: 167-177

Abstract

A new pseudo-rotaxane, consisting of a tubular, organometallic Ag-pillarplex ring and dodecyldiammonium axle component, is introduced and investigated towards potential non-covalent interactions by Full Interaction Maps (FIMs). FIMs predict regions of probable supramolecular interactions solely at the organic ligands, namely the rim and the aromatic rings of the pillarplex. The results were compared to structural parameters experimentally obtained by single-crystal X-ray diffraction. The pseudo-rotaxane was crystallized as a hydrated terephthalate salt, and the molecular and the crystal structure are discussed. The experimentally observed interactions are quantified using Hirshfeld surface analysis. In contrast to the FIMs prediction, four different interaction modes can be experimentally observed in the solid-state: encapsulation of a guest molecule, hydrogen bonding, π- and metal interactions.

March 24, 2022

Quantum transport and microwave scattering on fractal lattices

Krishnasamy Subramaniam, Matthias Zschornak, Sibylle Gemming

Page range: 179-190

Abstract

Studying the wave-particle nature of electrons in different ways has lead to many fundamental discoveries. Particularly, the dimensionality dependent electronic behavior in the Luttinger Liquid (1D), Quantum Hall (2D) and non-interacting Fermi Liquid (3D) regimes have already revolutionized our understanding of the mechanisms behind quantum electronics. In this work, the theoretical and experimental studies focus on the non-integer dimension represented by an sp 2 -carbon-based Sierpinski triangular structure with a 1.58D space occupancy. In the tight-binding approach, the spectral distribution of electronic states of such a structure exhibits distinct peak patterns, which are well-separated by gaps. Through quantum transport simulation, the conductance of electrons in 1.58D was studied. Both delocalized, conducting and localized, non-conducting states identified, which differ from the established features of both the fully 2D graphene sheet and 1D carbon nanotubes. In microwave scattering measurements on an adequate experimental setting and the respective simulations on the Sierpinski triangle, the obtained diffraction patterns showed interesting peculiarities such as a reduced number of minima and magic angle, next to diffraction regions of high and low intensity, as well as forbidden regions. The fractal geometry of the structure affects the propagation of waves by manipulating the way they interact with each other which results in structural metamaterial-like interference characteristics, decreasing or amplifying the transmitted or reflected signals, or blocking the transport completely.

March 7, 2022

Leveraging dewetting models rather than nucleation models: current crystallographic challenges in interfacial and nanomaterials research

Contemporary and prospective opportunities to exploit dewetting theory for energy conversion devices and quantum computing

Owen C. Ernst, Yujia Liu, Torsten Boeck

Page range: 191-200

Abstract

No scientific model has shaped crystallography as much as the classical nucleation theory (CNT). The majority of all growth processes and particle formation processes are attributed to the CNT. However, alternative descriptions exist that may be better suited to explain material formation under certain conditions. One of these alternatives is the dewetting theory (DWT). To describe the possibilities of DWT in more detail, we selected three material systems for three current application areas: Gold particles on silicon as catalysts for nanowire growth, indium particles on molybdenum as precursor material in novel solar cell concepts, and silicon layers on silicon germanium as potential wells in semiconductor quantum computers. Each of these material systems showed particular advantages of DWT over CNT. For example, the properties of surface particles with high atomic mobility could be described more realistically using DWT. Yet, there were clear indications that the DWT is not yet complete and that further research is needed to complete it. In particular, modern crystallographic challenges could serve this purpose, for example the development of semiconductor quantum computers, in order to re-evaluate known models such as the CNT and DWT and adapt them to the latest state of science and technology. For the time being, this article will give an outlook on the advantages of the DWT today and its potential for future research in crystallography.

April 25, 2022

Electronic structure of the homologous series of Ruddlesden–Popper phases SrO(SrTiO₃)_n, (n = 0–3, ∞)

Christian Ludt, Matthias Zschornak

Page range: 201-214

Abstract

The system SrO(SrTiO 3 ) n contains promising compounds for several applications, whose functionalities all depend in particular on the band structure of the respective crystal. While the electronic structure of SrO and SrTiO 3 is sufficiently clarified in literature, there is a lack of information concerning the Ruddlesden–Popper (RP) phases. In this work, density functional theory is used to compute the electronic structure for the homologous series with n = 0–3, ∞. The according band structures are presented and effective masses are given for the complete system. In addition, the calculations are consulted to discuss the thermodynamical stability of the RP phases, confirming the gain of formation energy up to n = 3, as reported in recent literature. A promising possibility for applications has been found, analyzing theses band structures: As the optical gaps at distinct high-symmetry points of the Brillouin zone show different dependencies on the lattice parameters, as it is reported for SrO in literature, a similar behavior could be expected in particular for the RP phase with n = 1.

About this journal

Objective
Zeitschrift für Kristallographie – Crystalline Materials was founded in 1877 by Paul von Groth and is today one of the world’s oldest scientific journals. It offers a place for researchers to present results of their theoretical experimental crystallographic studies. The journal presents significant results on structures and on properties of organic/inorganic substances with crystalline character, periodically ordered, modulated or quasicrystalline on static and dynamic phenomena applying the various methods of diffraction, spectroscopy and microscopy.

Topics

General Aspects
Inorganic Crystal Structures
Organic and Metalorganic (including Biological)
Crystal Structures
Technological Aspects
Computer Programs
Instrumentation
Material Properties

Article formats
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Volume 237 Issue 4-5 - “Spotlight on Germany’s Young Crystallographers”

Issue of Zeitschrift für Kristallographie - Crystalline Materials

Frontmatter

In this issue

Crystallography in Germany rejuvenated

Abstract

CalcOPP: a program for the calculation of one-particle potentials (OPPs)

Abstract

Synthesis and coordination to the coinage metals of a trimethylpyrazolyl substituted 3-arylacetylacetone

Abstract

Occupancy disorder in the magnetic topological insulator candidate Mn1−x Sb2+x Te4

Abstract

Structural study of anhydrous and hydrated 5-fluorouracil co-crystals with nicotinamide and isonicotinamide

Abstract

Synthesis, crystal-structure refinement and properties of bastnaesite-type PrF[CO3], SmF[CO3] and EuF[CO3]

Abstract

Crystallographic complexity partition analysis

Abstract

The “ferros” of MAPbI3: ferroelectricity, ferroelasticity and its crystallographic foundations in hybrid halide perovskites

Abstract

Structure relations in the family of the solid solution Hf x Zr1−x O2

Abstract

The crystal structure of single crystalline PrCa4O[BO3]3

Abstract

Crystal structure of a hexacationic Ag(I)-pillarplex-dodecyl-diammonium pseudo-rotaxane as terephthalate salt

Abstract

Quantum transport and microwave scattering on fractal lattices

Abstract

Leveraging dewetting models rather than nucleation models: current crystallographic challenges in interfacial and nanomaterials research

Contemporary and prospective opportunities to exploit dewetting theory for energy conversion devices and quantum computing

Abstract

Electronic structure of the homologous series of Ruddlesden–Popper phases SrO(SrTiO3) n , (n = 0–3, ∞)

Abstract

Occupancy disorder in the magnetic topological insulator candidate Mn_1−xSb_2+xTe₄

Synthesis, crystal-structure refinement and properties of bastnaesite-type PrF[CO₃], SmF[CO₃] and EuF[CO₃]

The “ferros” of MAPbI₃: ferroelectricity, ferroelasticity and its crystallographic foundations in hybrid halide perovskites

Structure relations in the family of the solid solution Hf_xZr_1−xO₂

The crystal structure of single crystalline PrCa₄O[BO₃]₃

Electronic structure of the homologous series of Ruddlesden–Popper phases SrO(SrTiO₃)_n, (n = 0–3, ∞)