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As part of a much larger study on non-covalent interactions in binary adducts, we have explored the solid-state structures of bromopentafluorobenzene (C 6 F 5 Br) using differential scanning calorimetry (DSC), variable-temperature powder X-ray diffraction (VT-PXRD), and single-crystal X-ray diffraction (SXD). DSC data initially indicated a single solid-state phase below the freezing point, but revealed additional weak transitions upon heating. The crystal structures of three solid-state phases have been solved. The SXD data showed that phases I and IV are centrosymmetric, whilst phase II is polar. However, the structure of phase III remains elusive due to the changing phase behaviour of C 6 F 5 Br that is determined as much as by kinetics as thermodynamics. The results underline the need for multiple analytical techniques to study non-covalent interactions and offer valuable data for refining computational models in crystal structure prediction and machine learning. A comparison with the iodinated counterpart is also made., (© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)

Multi-grain crystallography, traditionally performed at synchrotron sources in association with high-pressure studies, has new relevance with respect to laboratory single-crystal X-ray diffraction, in which crystals can be grown rapidly in situ, and a preliminary dataset analysed and solved in a matter of minutes. Subsequently, a full-sphere of IUCr-quality data can then be collected in a few hours. To demonstrate the applicability of laboratory multi-grain crystallography with Cu Kα X-rays, co-crystals of hexafluorobenzene and pyrrole were grown rapidly by cooling a 1:1 liquid mixture in an X-ray capillary on the diffractometer. The software is able to identify a single unit cell from as few as 10% of the diffraction spots from a small number of diffraction frames. Once a unit cell is identified, a full crystal structure solution is rapidly obtained by collecting a small amount of data to a resolution of ca 1 Å. The co-crystal obtained from the 1:1 mixture showed that hexafluorobenzene and pyrrole crystallize in a 3:4 ratio, in contrast to the columnar 1:1 adduct structures typified by hexafluorobenzene and benzene. The generality of our multi-grain approach for samples that are liquid at room temperature (and form a polycrystalline solid mass on cooling) is further demonstrated by investigating and solving the 1:1 co-crystal formed between hexafluorobenzene and pyridine., (open access.)

The prospect of eradicating malaria continues to be challenging in the face of increasing parasite resistance to antimalarial drugs so that novel antimalarials active against asexual, sexual, and liver-stage malaria parasites are urgently needed. In addition, new antimalarials need to be affordable and available to those most in need and, bearing in mind climate change, should ideally be sustainable. The West African climbing shrub Cryptolepis sanguinolenta is used traditionally for the treatment of malaria; its principal alkaloid, cryptolepine ( 1 ), has been shown to have antimalarial properties, and the synthetic analogue 2,7-dibromocryptolepine ( 2 ) is of interest as a lead toward new antimalarial agents. Cryptolepine ( 1 ) was isolated using a two-step Soxhlet extraction of C. sanguinolenta roots, followed by crystallization (yield 0.8% calculated as a base with respect to the dried roots). Semi-synthetic 7-bromo- ( 3 ), 7, 9-dibromo- ( 4 ), 7-iodo- ( 5 ), and 7, 9-dibromocryptolepine ( 6 ) were obtained in excellent yields by reaction of 1 with N -bromo- or N -iodosuccinimide in trifluoroacetic acid as a solvent. All compounds were active against Plasmodia in vitro , but 6 showed the most selective profile with respect to Hep G2 cells: P. falciparum (chloroquine-resistant strain K1), IC 50 = 0.25 µM, SI = 113; late stage, gametocytes, IC 50 = 2.2 µM, SI = 13; liver stage, P. berghei sporozoites IC 50 = 6.13 µM, SI = 4.6. Compounds 3 - 6 were also active against the emerging zoonotic species P. knowlesi with 5 being the most potent (IC 50 = 0.11 µM). In addition, 3 - 6 potently inhibited T. brucei in vitro at nM concentrations and good selectivity with 6 again being the most selective (IC 50 = 59 nM, SI = 478). These compounds were also cytotoxic to wild-type ovarian cancer cells as well as adriamycin-resistant and, except for 5 , cisplatin-resistant ovarian cancer cells. In an acute oral toxicity test in mice, 3 - 6 did not exhibit toxic effects at doses of up to 100 mg/kg/dose × 3 consecutive days. This study demonstrates that C. sanguinolenta may be utilized as a sustainable source of novel compounds that may lead to the development of novel agents for the treatment of malaria, African trypanosomiasis, and cancer., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Abacha, Forkuo, Gbedema, Mittal, Ottilie, Rocamora, Winzeler, van Schalkwyk, Kelly, Taylor, Reader, Birkholtz, Lisgarten, Cockcroft, Lisgarten, Palmer, Talbert, Shnyder and Wright.)

Ring-fused benzimidazolequinones are well-known anti-tumour agents, but dimeric ring-fused adducts are new. The alicyclic [1,2-a] ring-fused dimethoxybenzimidazole-benzimidazolequinone (DMBBQ) intermediate allows late-stage functionalization of bis-p-benzimidazolequinones. DMBBQs are chlorinated and brominated at the p-dimethoxybenzene site using nontoxic sodium halide and Oxone in HFIP/water. X-ray crystallography is used to rationalize site preference in terms of the discontinuity in conjugation in the DMBBQ system. Quinone formation occurs by increasing in situ halogen generation and water. Conversely, radical trifluoromethylation occurs at the quinone of the DMBBQ.

The covalent attachment of molecules to 2D materials is an emerging area as strong covalent chemistry offers new hybrid properties and greater mechanical stability compared with nanoparticles. A nickel bis-aminothiophenol catalyst was grafted onto a range of 2D carbon nitrides (C 3 N x H y ) to form noble metal-free photocatalysts for H 2 production. The hybrids produce H 2 beyond 8 days with turnover numbers reaching 1360 based on nickel, a more than 3 fold higher durability than reported molecular catalyst-carbon nitride mixtures, and under longer wavelengths (>475 nm). Time-resolved spectroscopy reveals sub-microsecond electron transfer to the grafted catalyst, six orders of magnitude faster compared with similar reports of non-grafted catalysts. The photoelectrons on the catalyst have a ca. 1000 times longer half-time (7 ms) compared with bare carbon nitride (10 μs). The grafting strategy operates across a range of molecular catalyst-carbon nitride combinations, thus paving the way for robust efficient photocatalysts based on low-cost tunable components., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

While commercial Li-ion batteries offer the highest energy densities of current rechargeable battery technologies, their energy storage limit has almost been achieved. Therefore, there is considerable interest in Mg batteries, which could offer increased energy densities in comparison to Li-ion batteries if a high-voltage electrode material, such as a transition-metal oxide, can be developed. However, there are currently very few oxide materials which have demonstrated reversible and efficient Mg 2+ insertion and extraction at high voltages; this is thought to be due to poor Mg 2+ diffusion kinetics within the oxide structural framework. Herein, the authors provide conclusive evidence of electrochemical insertion of Mg 2+ into the tetragonal tungsten bronze V 4 Nb 18 O 55 , with a maximum reversible electrochemical capacity of 75 mA h g -1 , which corresponds to a magnesiated composition of Mg 4 V 4 Nb 18 O 55 . Experimental electrochemical magnesiation/demagnesiation revealed a large voltage hysteresis with charge/discharge (1.12 V vs Mg/Mg 2+ ); when magnesiation is limited to a composition of Mg 2 V 4 Nb 18 O 55 , this hysteresis can be reduced to only 0.5 V. Hybrid-exchange density functional theory (DFT) calculations suggest that a limited number of Mg sites are accessible via low-energy diffusion pathways, but that larger kinetic barriers need to be overcome to access the entire structure. The reversible Mg 2+ intercalation involved concurrent V and Nb redox activity and changes in crystal structure, as confirmed by an array of complementary methods, including powder X-ray diffraction, X-ray absorption spectroscopy, and energy-dispersive X-ray spectroscopy. Consequently, it can be concluded that the tetragonal tungsten bronzes show promise as intercalation electrode materials for Mg batteries.

We present the structure of a novel solvate adduct formed by dissolving ferrocene, FeCp 2 , in hexafluorobenzene, C 6 F 6 . This adduct demonstrates the remarkably strong interactions between the five-membered aromatic rings of FeCp 2 and the six-membered aromatic ring of C 6 F 6 . These molecular interactions are sufficiently strong and anisotropic to change the temperature of the order-disorder transition of the ferrocene molecule from below ca. 164 K to RT. No solvate adduct could be formed between benzene and FeCp 2 . These observations will be of particular relevance to the crystal engineering community, whose goal is the design of solids with bespoke properties.

A homologous series of n-alkyl trimethylammonium bromide surfactants, H(CH2)nN+(CH3)3 Br-, from C10TAB to C18TAB have been studied systematically in the bulk over a wide range of temperatures. Common features in the structures are identified, with packing dominated by the co-ordination of the cationic head groups with bromide anions and interdigitation of the hydrocarbon chains. This arrangement provides an explanation for the thin adsorbed bilayers that have been observed at various hydrophilic surfaces from aqueous solutions in previous studies. The molecular volumes and arrangement are comparable with structures of a number of different self-assembled amphiphiles. For these surfactants with bromide counter-ions, formation of crystal hydrates was not observed. The alkyl chains are highly mobile and at high temperatures a plastic phase is found for all materials with a transition enthalpy that is similar to the melting enthalpy of many long alkyl chains. Other unexpected phase transitions depend more markedly on the hydrocarbon chain length and evidently depend on delicate balances of the various contributions to the free energy.

A new hydrogen-bonded supramolecular framework is reported, consisting of ammonium pentaborate, containing poly(ethylene-glycol) chains extending down tubular cavities in the structure. The crystal architecture is templated by the presence of the polyether chains, analogous to template synthesis of zeolites and metal organic frameworks. The ammonium pentaborate is formed by the thermolysis of ammonia borane, followed by hydrolysis of the dehydrogenation products by ambient water. This structure represents the first known example of a borate-based polymer inclusion compound.

Cristobalite, a crystalline form of silica, is shown to be formed within an amorphous titanosilicate, at previously unknown conditions. Mesoporous titanosilicate microspheres (MTSM) were synthesized as efficient catalysts for the epoxidation of cyclohexene with tert -butyl hydroperoxide. High-resolution transmission electron microscopy revealed the presence of crystals in this predominantly amorphous material, after calcination at 750 °C. When calcined at 800 °C, the crystals were identified via PXRD as predominantly cristobalite, which possibly marks its first observation in titanosilicates at such a low temperature, without adding any alkali metals during synthesis. Catalytic experiments conducted with MTSM materials calcined at temperatures varying from 650 to 950 °C, reveal that the amount of cristobalite formed increases with temperature, and that it has a significant impact on the pore structure, and, remarkably, correlates with the catalytic activity of titanosilicates., Competing Interests: Compliance with ethical standardsThe authors declare that they have no conflict of interest.

The development of processes to tune the properties of materials is essential for the progression of next-generation technologies for catalysis, optoelectronics and sustainability including energy harvesting and conversion. Layered carbon nitrides have also been identified as of significant interest within these fields of application. However, most carbon nitride materials studied to date have poor crystallinity and therefore their properties cannot be readily controlled or easily related to their molecular level or nanoscale structures. Here we report a process for forming a range of crystalline layered carbon nitrides with polytriazine imide (PTI) structures that can be interconverted by simple ion exchange processes, permitting the tunability of their optoelectronic and chemical properties. Notable outcomes of our work are (a) the creation of a crystalline, guest-ion-free PTI compound that (b) can be re-intercalated with ions or molecules using "soft chemistry" approaches. This includes the intercalation of HCl, demonstrating a new ambient pressure route to the layered PTI· x HCl material that was previously only available by a high-pressure-high-temperature route (c). Our work also shows (d) that the intercalant-free (IF-) PTI material spontaneously absorbs up to 10 weight% H 2 O from the ambient atmosphere and that this process is reversible, leading to potential applications for membranes and water capture in dry environments.

Gelation processes grant access to a wealth of soft materials with tailorable properties, in applications as diverse as environmental remediation, biomedicine and electronics. Several classes of self-assembling gelators have been studied and employ non-covalent bonds to direct assembly, but recently attention has come to focus on how the overall shape of the gelator molecule impacts its gelation. Here we study a new sub-family of low molecular weight organogelators and explore how steric rearrangement influences their gelation. The gels produced are characterised with X-ray diffraction and small-angle neutron scattering (SANS) to probe their ex situ and in situ gelation mechanisms. The best examples were then tested for environmental remediation applications, gelling petrol and oils in the presence of water and salts.

The cobalt carbonate hydroxide Co 2 CO 3 (OH) 2 is a technologically important solid which is used as a precursor for the synthesis of cobalt oxides in a wide range of applications. It also has relevance as a potential immobilizer of the toxic element cobalt in the natural environment, but its detailed crystal structure is so far unknown. The structure of Co 2 CO 3 (OH) 2 has now been investigated using density functional theory (DFT) simulations and powder X-ray diffraction (PXRD) measurements on samples synthesized via deposition from aqueous solution. Two possible monoclinic phases are considered, with closely related but symmetrically different crystal structures, based on those of the minerals malachite [Cu 2 CO 3 (OH) 2 ] and rosasite [Cu 1.5 Zn 0.5 CO 3 (OH) 2 ], as well as an orthorhombic phase that can be seen as a common parent structure for the two monoclinic phases, and a triclinic phase with the structure of the mineral kolwezite [Cu 1.34 Co 0.66 CO 3 (OH) 2 ]. The DFT simulations predict that the rosasite-like and malachite-like phases are two different local minima of the potential energy landscape for Co 2 CO 3 (OH) 2 and are practically degenerate in energy, while the orthorhombic and triclinic structures are unstable and experience barrierless transformations to the malachite phase upon relaxation. The best fit to the PXRD data is obtained using a rosasite model [monoclinic with space group P112 1 /n and cell parameters a = 3.1408 (4) Å, b = 12.2914 (17) Å, c = 9.3311 (16) Å and γ = 82.299 (16)°]. However, some features of the PXRD pattern are still not well accounted for by this refinement and the residual parameters are relatively poor. The relationship between the rosasite and malachite phases of Co 2 CO 3 (OH) 2 is discussed and it is shown that they can be seen as polytypes. Based on the similar calculated stabilities of these two polytypes, it is speculated that some level of stacking disorder could account for the poor fit of the PXRD data. The possibility that Co 2 CO 3 (OH) 2 could crystallize, under different growth conditions, as either rosasite or malachite, or even as a stacking-disordered phase intermediate between the two, requires further investigation.

Novel lead and bismuth dipyrido complexes have been synthesized and characterized by single-crystal X-ray diffraction, which shows their structures to be directed by highly oriented π-stacking of planar fully conjugated organic ligands. Optical band gaps are influenced by the identity of both the organic and inorganic component. Density functional theory calculations show optical excitation leads to exciton separation between inorganic and organic components. Using UV-vis, photoluminescence, and X-ray photoemission spectroscopies, we have determined the materials' frontier energy levels and show their suitability for photovoltaic device fabrication by use of electron- and hole-transport materials such as TiO2 and spiro-OMeTAD respectively. Such organic/inorganic hybrid materials promise greater electronic tunability than the inflexible methylammonium lead iodide structure through variation of both the metal and organic components.

Ultrasound-assisted crystallization (sonocrystallization) was used to prepare a mixture of nano- and micrometer-sized crystals of the monoclinic form of paracetamol-a widely used analgesic known for its particularly problematic mechanical behavior under compression (i.e. poor tabletability). The nano- and micrometer-sized crystals yielded a powder which exhibits elastic moduli and bulk cohesions that are significantly higher than those observed in samples consisting of macrometer-sized crystals, thus leading to enhanced tabletability without the use of excipients, particle coating, salt, or cocrystal formation. Experimental compaction and finite element analysis were utilized to rationalize the significantly improved compaction behavior of the monoclinic form of paracetamol., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Orientational alignment in a dilute dispersion of kaolinite particles has been investigated in a flow pattern that combines both shear and elongational stress, namely flow at a jet created by a 2 mm diameter nozzle inserted in a 6 mm diameter pipe. Spatially-resolved X-ray diffraction with synchrotron radiation permits detailed maps of the alignment to be deduced and compared with fluid mechanics calculations of the flow. The angular distribution of diffracted intensity from a given position in the pipe provides information about the orientation distribution of the particles. This is quantified and presented in terms of order parameters. The cone-shaped nozzle provides a jet of liquid giving a high degree of alignment of the particles that is uniform along lines across the conical section and constant in the small straight-sided region at the exit of the nozzle. The vortex motion that arises from the flow with a modest Reynolds number could be determined as well as the tendency for some particles to align with their large faces perpendicular to the overall flow direction at the flat surface of the nozzle outlet., (© 2012 American Chemical Society)

High-energy angle-dispersive X-ray diffraction has been used to study the alignment of colloidal suspension of kaolinite particles in water as they flow along a pipe. X-rays with energies above 25 keV have a major advantage, as they can penetrate through thick samples and walls of containers and permit investigation of samples under realistic flow conditions. As an example of the method, flow through a circular cross-section pipe with an internal diameter of 5 mm has been studied: this is typical of industrial applications. The angular distribution of intensities of peaks in the diffraction pattern as a function of the location of the pipe in the X-ray beam provides information about the alignment of particles under flow. Order parameters have been calculated to describe the alignment and direction of orientation. It is observed that the particles align in the direction of flow with their flat faces parallel to the flow. The experimental results are compared with the calculations of the local strain rate that help to explain the onset of alignment of the particles.

High-throughput continuous hydrothermal flow synthesis has been used as a rapid and efficient synthetic route to produce a range of crystalline nanopowders in the Ce-Zn oxide binary system. High-resolution powder X-ray diffraction data were obtained for both as-prepared and heat-treated (850 degrees C for 10 h in air) samples using the new robotic beamline I11, located at Diamond Light Source. The influence of the sample composition on the crystal structure and on the optical and physical properties was studied. All the nanomaterials were characterized using Raman spectroscopy, UV-visible spectrophotometry, Brunauer-Emmett-Teller surface area and elemental analysis (via energy-dispersive X-ray spectroscopy). Initially, for 'as-prepared' Ce(1-x)Zn(x)O(y), a phase-pure cerium oxide (fluorite) structure was obtained for nominal values of x=0.1 and 0.2. Biphasic mixtures were obtained for nominal values of x in the range of 0.3-0.9 (inclusive). High-resolution transmission electron microscopy images revealed that the phase-pure nano-CeO(2) (x=0) consisted of ca 3.7 nm well-defined nanoparticles. The nanomaterials produced herein generally had high surface areas (greater than 150 m(2) g(-1)) and possessed combinations of particle properties (e.g. bandgap, crystallinity, size, etc.) that were unobtainable or difficult to achieve by other more conventional synthetic methods.

Laboratory X-ray diffraction is used to investigate the size and shape of dispersed plate-like and spherical colloidal particles. Analysis of the wide-angle diffraction data provides information about the size and shape of crystals from the width of the Bragg peaks according to the Debye-Scherrer formula. The measurements, data analysis, and evaluation are discussed. It is shown that X-ray diffraction with conventional laboratory equipment on dispersed particles is feasible as a tool to determine both particle size and shape. Data for two samples--gold colloids and nickel (II) hydroxide particles are presented. The advantages and limitations of the method are discussed. X-ray diffraction measurements that are made in combination with dynamic light scattering can be used to estimate the thickness of stabilizing layers of polymers.

A novel High-Throughput Continuous Hydrothermal (HiTCH) flow synthesis reactor was used to make directly and rapidly a 66-sample nanoparticle library (entire phase diagram) of nanocrystalline Ce(x)Zr(y)Y(z)O(2-delta) in less than 12 h. High resolution PXRD data were obtained for the entire heat-treated library (at 1000 degrees C/1 h) in less than a day using the new robotic beamline I11, located at Diamond Light Source (DLS). This allowed Rietveld-quality powder X-ray diffraction (PXRD) data collection of the entire 66-sample library in <1 day. Consequently, the authors rapidly mapped out phase behavior and sintering behaviors for the entire library. Out of the entire 66-sample heat-treated library, the PXRD data suggests that 43 possess the fluorite structure, of which 30 (out of 36) are ternary compositions. The speed, quantity and quality of data obtained by our new approach, offers an exciting new development which will allow structure-property relationships to be accessed for nanoceramics in much shorter time periods.

Crystallographic Nexus CD-ROMs, containing a range of free crystallographic software for single-crystal and powder diffraction available on the Internet, have been distributed on request since 1996. The free CD is made in the form of a ;virtual Internet' with the main intent of benefiting crystallographers with inadequate Internet access. The IUCr funds an annual/biennial update which is distributed to known previous recipients. Feedback from current recipients indicates the CD is still useful. The most current IUCr-funded CD is being produced by the CCP14 project at University College London and The Royal Institution UK for distribution to the ECM 2007 and AsCA 2007 conferences.

The technique of energy-dispersive X-ray diffraction to study the orientation of microscopic crystalline particles dispersed in a liquid has been described recently. This complements previous neutron diffraction studies by permitting measurements at higher spatial resolution. Work with synchrotron radiation and high-energy X-rays has allowed studies on liquid dispersions flowing in pipes with a thickness of about 1 cm and a spatial resolution of 100 mum. Kaolinite is often found as a dispersion of monocrystalline, microscopic plates. The crystallographic layer structure is commensurate with the particle shape: the 00l direction is normal to the plane of the plates. Measurements of diffraction of the flowing liquid dispersion in a pipe oriented in various directions to the incident beam can be used to deduce the average orientation and order parameters of the particles. The competing effects of alignment with walls and in flow fields were observed. Further work has measured the orientation near a bend in a pipe.

The x-ray diffraction of the nonsuperconducting ternary fulleride Li(2)CsC(60) reveals at room temperature a face-centered-cubic (Fm3m) disordered structure that persists to a temperature of 13 Kelvin. The crystal structure is best modeled as containing quasispherical [radius of 3.556(4) angstroms] C(60)(3-) ions, in sharp contrast to their orientational state in superconducting face-centered-cubic K(3)C(60) (merohedral disorder) and primitive cubic Na(2)CsC(60) (orientational order). The orientational disorder of the carbon atoms on the C(60)(3-) sphere was analyzed with symmetry-adapted spherical-harmonic functions. Excess atomic density is evident in the <111> directions, indicating strong bonding Li(+)-C interactions, not encountered before in any of the superconducting alkali fullerides. The intercalate-carbon interactions and the orientational state of the fullerenes have evidently affected the superconducting pair-binding mechanism in this material.

Rhenium heptafluoride, ReF(7), is one of only two stable binary compounds MX(7) with a heptacoordinated metal atom M and halide atom X. Its low-temperature crystal structure, as determined by high-resolution powder neutron diffraction, reveals the molecular structure, which has been the subject of speculation and debate for many years. Here it is shown within experimental error that at 1.5 kelvin the lowest energy configuration of ReF(7) has symmetry Cs (m) and is a distorted pentagonal bipyramid. The deviation of the two axial Re-F bonds from collinear and the puckering of the ring of equatorial fluorine atoms are similar to what has been postulated as one of the conformations of the pseudorotational motion observed at higher temperatures.