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

By adding a hot aqueous solution containing KF and K2[CO3] to another hot aquatic brine of Pr[NO3]3 ⋅ 5 H2O, Sm[NO3]3 ⋅ 5 H2O or Eu[NO3]3 ⋅ 5 H2O with a 1.3 times excess of the anion-providing solution, amorphous water-insoluble powders of PrF[CO3], SmF[CO3] and EuF[CO3] 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 CO2 and fluoride oxides REFO emerge. Thermogravimetric experiments with crystalline samples show thermal stability up to 420 °C for PrF[CO3], 400 °C for SmF[CO3] and 340 °C for EuF[CO3], 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 [CO3]2−. Triggered by ultraviolet radiation, the bulk sample of EuF[CO3] shows a poor red luminescence.

Crystallographic complexity partition analysis

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 Mo3Al2C, 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.

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

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.

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

MnSb2Te4 is a candidate magnetic topological insulator exhibiting more pronounced cation intermixing than its predecessor MnBi2Te4. Investigating the cation intermixing and its possible implications on the magnetic order in MnSb2Te4 are currently hot topics in research on quantum materials for spintronics and energy-saving applications. Two single-crystal X-ray diffraction measurements of Mn1−x Sb2+x Te4 (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 MnX2Te4 (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.

The orthorhombic-to-monoclinic phase transition in NbCrP – Peierls distortion of the chromium chain

The equiatomic metal-rich phosphide NbCrP shows a structural phase transition around 125 K. The structures of the high- and low-temperature modifications were refined from single crystal X-ray diffractometer data of an un-twinned crystal: TiNiSi type, Pnma, a = 619.80(2), b = 353.74(4), c = 735.24(6) pm, wR = 0.0706, 288 F 2 values, 20 variables at 240 K and P121/c1, a = 630.59(3), b = 739.64(4), c = 933.09(5) pm, β = 132.491(6)°, wR = 0.0531, 1007 F 2 values, 57 variables at 90 K. The structural phase transition is of a classical Peierls type. The equidistant chromium chain in HT-NbCrP (353.7 pm Cr–Cr) splits pairwise into shorter (315.2 pm) and longer (373.2 pm) Cr–Cr distances. This goes along with a strengthening of Cr–P bonding. The superstructure formation is discussed on the basis of a group–subgroup scheme. Electronic structure calculations show a lifting of band degeneracy. Protection of the non-symmorphic symmetry of space group Pnma is crucial for the phase transition. The estimated charge modulation is consistent with the interpretation as Peierls transition.

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

The ligand 3-(4-(1,3,5-trimethyl-1H-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 CuII 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 CuII position leads to a two dimensional extended structure. The N donor capabilities are proven by coordination to AgPF6 and AuCl; for AgI 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.

Simultaneous neutron powder diffraction and Raman spectroscopy – an approach of combining two complementary techniques

Diffraction techniques are well-established methods for crystal structure determination as well as phase identification and quantification. Raman spectroscopy can be a valuable complementary characterization technique, because in contrast to the former it yields also information on amorphous materials and it is a probe for short-range structural effects. The herein presented setup allows for simultaneous neutron diffraction and Raman spectroscopy, shown with a sample of lead sulfate under ambient conditions as a proof of principle. In order to fulfil requirements of both methods, a sapphire single-crystal is used as a sample holder. Practical considerations for successful simultaneous in situ neutron diffraction and Raman spectroscopic measurements are given.