Precise control over the crystalline phase and crystallographic orientation within thin films of metal-organic frameworks (MOFs) is highly desirable. Here, we report a comparison of the liquid- and vapour-phase film deposition of two copper-dicarboxylate MOFs starting from an oriented metal hydroxide precursor. X-ray diffraction revealed that the vapour- or liquid-phase reaction of the linker with this precursor results in different crystalline phases, morphologies, and orientations. Pole figure analysis showed that solution-based growth of the MOFs follows the axial texture of the metal hydroxide precursor, resulting in heteroepitaxy. In contrast, the vapour-phase method results in non-epitaxial growth with uniplanar texture only.

This study describes the discovery of a unique ionic cocrystal of the active pharmaceutical ingredient (API) ponatinib hydrochloride (), and characterization using single-crystal X-ray diffraction (SCXRD) and solid-state NMR (SSNMR) spectroscopy. is a multicomponent crystal that features an unusual stoichiometry, with an asymmetric unit containing both monocations and dications of the ponatinib molecule, three water molecules, and three chloride ions. Structural features include (i) a charged imidazopyridazine moiety that forms a hydrogen bond between the ponatinib monocations and dications and (ii) a chloride ion that does not feature hydrogen bonds involving any organic moiety, instead being situated in a "square" arrangement with three water molecules. Multinuclear SSNMR, featuring high and ultra-high fields up to 35.2 T, provides the groundwork for structural interpretation of complex multicomponent crystals in the absence of diffraction data. A C CP/MAS spectrum confirms the presence of two crystallographically distinct ponatinib molecules, whereas 1D H and 2D H-H DQ-SQ spectra identify and assign the unusually deshielded imidazopyridazine proton. 1D Cl spectra obtained at multiple fields confirm the presence of three distinct chloride ions, with density functional theory calculations providing key relationships between the SSNMR spectra and H⋯Cl hydrogen bonding arrangements. A 2D Cl → H D-RINEPT spectrum confirms the spatial proximities between the chloride ions, water molecules, and amine moieties. This all suggests future application of multinuclear SSNMR at high and ultra-high fields to the study of complex API solid forms for which SCXRD data are unavailable, with potential application to heterogeneous mixtures or amorphous solid dispersions.

We explore the role and nature of torsional flexibility of carboxylate-benzene links in the structural chemistry of metal-organic frameworks (MOFs) based on Zn and benzenedicarboxlyate (bdc) linkers. A particular motivation is to understand the extent to which such flexibility is important in stabilising the unusual topologically aperiodic phase known as TRUMOF-1. We compare the torsion angle distributions of TRUMOF-1 models with those for crystalline Zn/1,3-bdc MOFs, including a number of new materials whose structures we report here. We find that both periodic and aperiodic Zn/1,3-bdc MOFs sample a similar range of torsion angles, and hence the formation of TRUMOF-1 does not require any additional flexibility beyond that already evident in chemically-related crystalline phases. Comparison with Zn/1,4-bdc MOFs does show, however, that the lower symmetry of the 1,3-bdc linker allows access to a broader range of torsion angles, reflecting a greater flexibility of this linker.

Self-assembling peptides are of huge interest for biological, medical and nanotechnological applications. The enormous chemical variety that is available from the 20 amino acids offers potentially unlimited peptide sequences, but it is currently an issue to predict their supramolecular behavior in a reliable and cheap way. Herein we report a computational method to screen and forecast the aqueous self-assembly propensity of amyloidogenic pentapeptides. This method was found also as an interesting tool to predict peptide crystallinity, which may be of interest for the development of peptide based drugs.

Bifunctional N-donor carboxylate linkers generally afford and topology coordination networks of general formula ML that are based upon the MN(CO) molecular building block (MBB). Herein, we report on a new N-donor carboxylate linker, β-(3,4-pyridinedicarboximido)propionate (PyImPr), which afforded Cd(PyImPr) reaction of PyImPrH with Cd(acetate)·2HO. We observed that, depending upon whether Cd(PyImPr) was prepared by layering or solvothermal methods, 2D or 3D supramolecular isomers, respectively, of Cd(PyImPr) were isolated. Single crystal X-ray diffraction studies revealed that both supramolecular isomers are comprised of the same carboxylate bridged rod building block, RBB. We were interested to determine if the ethylene moiety of PyImPr could enable structural flexibility. Indeed, open-to-closed structural transformations occurred upon solvent removal for both phases, but they were found to be irreversible. A survey of the Cambridge Structural Database (CSD) was conducted to analyse the relative frequency of RBB topologies in related ML coordination networks in order to provide insight from a crystal engineering perspective.

Metal-organic frameworks bearing coordinatively unsaturated Mg(II) sites are promising materials for gas storage, chemical separations, and drug delivery due to their low molecular weights and lack of toxicity. However, there remains a limited number of such MOFs reported in the literature. Herein, we investigate the gas sorption properties of the understudied framework Mg(-dobdc) (dobdc = 4,6-dioxido-1,3-benzenedicarboxylate) synthesized under both solvothermal and mechanochemical conditions. Both materials are found to be permanently porous, as confirmed by 77 K N adsorption measurements. In particular, Mg(-dobdc) synthesized under mechanochemical conditions using exogenous organic base displays one of the highest capacities reported to date (6.14 mmol/g) for CO capture in a porous solid under simulated coal flue gas conditions (150 mbar, 40 °C). As such, mechanochemically synthesized Mg(-dobdc) represents a promising new framework for applications requiring high gas adsorption capacities in a porous solid.

The tetratopic 1,4-bis(2-phenylethoxy)-2,5-bis(3,2':6',3''-terpyridin-4'-yl)benzene (1) and 1,4-bis(3-phenylpropoxy)-2,5-bis(3,2':6',3''-terpyridin-4'-yl)benzene (2) ligands have been prepared and fully characterised. Combination of ligand 1 or 2 and [M(hfacac)]·HO (M = Cu, = 1; M = Zn, = 2) under conditions of crystal growth by layering led to the formation of [Cu(hfacac)(1)] ·3.6(1,2-ClCH)·2CHCl, [Zn(hfacac)(1)] ·MeCH·1.8CHCl, [Cu(hfacac)(2)] ·MeCH·2HO, [Cu(hfacac)(2)] ·2.8CHCl and [Cu(hfacac)(2)] ·2(1,2-ClCH)·0.4CHCl·0.5HO. For each compound, single-crystal X-ray analysis revealed the assembly of a planar (4,4)-net in which the tetratopic ligands 1 or 2 define the nodes. The metal centres link two different bis(3,2':6',3''-tpy) ligands the outer pyridine rings; whereas copper(ii) has N-donors in a -arrangement, zinc(ii) has them in . This difference between the copper(ii) and zinc(ii) coordination polymers modifies the architecture of the assembly without changing the underlying (4,4)-network.

The performance of zeolitic imidazolate frameworks (ZIFs) as protective hosts for proteins in drug delivery or biocatalysis strongly depends on the type of crystalline phase used for the encapsulation of the biomacromolecule (biomacromolecule@ZIF). Therefore, quantifying the different crystal phases and the amount of amorphous content of ZIFs is becoming increasingly important for a better understanding of the structure-property relationship. Typically, crystalline ZIF phases are qualitatively identified from diffraction patterns. However, accurate phase examinations are time-consuming and require specialized expertise. Here, we propose a calibration procedure (internal standard ZrO) for the rapid and quantitative analysis of crystalline and amorphous ZIF phases from diffraction patterns. We integrated the procedure into a user-friendly web application, named ZIF Phase Analysis, which facilitates ZIF-based data analysis. As a result, it is now possible to quantify i) the relative amount of various common crystal phases (sodalite, diamondoid, ZIF-CO-1, ZIF-EC-1, U12 and ZIF-L) in biomacromolecule@ZIF biocomposites based on Zn and 2-methylimidazole (HmIM) and ii) the crystalline-to-amorphous ratio. This new analysis tool will advance the research on ZIF biocomposites for drug delivery and biocatalysis.

The rapid increase in the number and variety of metal organic frameworks (MOFs) and covalent organic frameworks (COFs) has led to groundbreaking applications in the field of materials science and engineering. New MOF/COF hybrids combine the outstanding features of MOF and COF structures, such as high crystallinities, large surface areas, high porosities, the ability to decorate the structures with functional groups, and improved chemical and mechanical stabilities. These new hybrid materials offer promising performances for a wide range of applications including catalysis, energy storage, gas separation, and nanomedicine. In this highlight, we discuss the recent advancements of MOF/COF hybrids as next generation materials for energy and biomedical applications with a special focus on the use of computational tools to address the opportunities and challenges of using MOF/COF hybrids for various applications.

This paper details the first dedicated production of homogeneous nanocrystalline particles of mixed actinide oxide solid solutions containing americium. The target compositions were UPuAmO, UAmO and UAmO. After successful hydrothermal synthesis and chemical characterisation, the nanocrystals were sintered and their structure and behaviour under self-irradiation were studied by powder XRD. Cationic charge distribution of the as-prepared nanocrystalline and sintered UAmO materials was investigated applying U M and Am M edge high energy resolution XANES (HR-XANES). Typical oxidation states detected for the cations are U(iv)/U(v) and Am(iii)/Am(iv). The measured crystallographic swelling was systematically smaller for the as-synthesised nanoparticles than the sintered products. For sintered pellets, the maximal volumetric swelling was about 0.8% at saturation, in line with literature data for PuO, AmO, (U,Pu)O or (U,Am)O.

[This corrects the article DOI: 10.1039/C4CE02347A.].

The synthesis and X-ray structural study of the new family of compounds BaFeClO with tunable structural modulation are reported. The framework of the structure has the BaFeO composition, with open hexagonal channels extending along the -axis. The channels are filled with linear [Ba-Cl-Ba] triplets. The oxygen stoichiometry and the oxidation state of iron both are controlled by the redox conditions during crystal preparation. The modulation of the crystal structure arises from the distribution of the oxygen atoms in the framework and iron coordination polyhedra are a combination of FeO-tetrahedra, FeO-bipyramids, and FeO-octahedra. The structure modulation also originates from the ordered or disordered distribution of the [Ba-Cl-Ba] triplets filling the channels which is also affected by the conditions of the thermal treatment of the crystals. The structure investigation reveals a composition variation from BaFeClO ( = 0), in which Fe exhibits a 3+ oxidation state, to BaFeClO ( = 1.5) with the framework built exclusively of FeO tetrahedra.

The mineralization of collagen has been extensively investigated for hydroxyapatite, silica, calcium carbonate and lepidocrocite (γ-FeOOH). Henceforth, it is interesting to investigate whether collagen also could serve as a generic mineralization template for other minerals, like magnetite. To this end, and inspired by the partial oxidation approach, first a ferrous hydroxide (Fe(OH)) intermediate is synthesized the titration of base to a solution of Fe. Subsequently, the Fe(OH) is mixed with collagen fibrils and poly(aspartic acid) is added to promote the formation of intrafibrillar crystals. Platelet-shaped lepidocrocite crystals being present throughout the entire thickness of the collagen fibrils can be realized, as was confirmed with electron tomography. The formation of lepidocrocite, which is an Fe compound, is hypothesized to be induced oxidation of the Fe species and, therefore, the oxygen concentration during titration, TEM sample preparation and drying of TEM samples are investigated. Although the reaction is sensitive to small changes in experimental conditions, highly mineralized collagen fibers can be realized.

Corrosion is a major concern for many industries, as corrosive environments can induce structural and morphological changes that lead to material dissolution and accelerate material failure. The progression of corrosion depends on nanoscale morphology, stress, and defects present. Experimentally monitoring this complex interplay is challenging. Here we implement Bragg coherent X-ray diffraction imaging (BCDI) to probe the dissolution of a Co-Fe alloy microcrystal exposed to hydrochloric acid (HCl). By measuring five Bragg reflections from a single isolated microcrystal at ambient conditions, we compare the full three-dimensional (3D) strain state before corrosion and the strain along the [111] direction throughout the corrosion process. We find that the strained surface layer of the crystal dissolves to leave a progressively less strained surface. Interestingly, the average strain closer to the centre of the crystal increases during the corrosion process. We determine the localised corrosion rate from BCDI data, revealing the preferential dissolution of facets more exposed to the acid stream, highlighting an experimental geometry effect. These results bring new perspectives to understanding the interplay between crystal strain, morphology, and corrosion; a prerequisite for the design of more corrosion-resistant materials.

The hexatopic ligands 1,3,5-tris(4,2':6',4''-terpyridin-4'-yl)benzene (1), 1,3,5-tris(3,2':6',3''-terpyridin-4'-yl)benzene (2), 1,3,5-tris{4-(4,2':6',4''-terpyridin-4'-yl)phenyl}benzene (3), 1,3,5-tris{4-(3,2':6',3''-terpyridin-4'-yl)phenyl}benzene (4) and 1,3,5-trimethyl-2,4,6-tris{4-(3,2':6',3''-terpyridin-4'-yl)phenyl}benzene (5) have been prepared and characterized. The single crystal structure of 1·1.75DMF was determined; 1 exhibits a propeller-shaped geometry with each of the three 4,2':6',4''-tpy domains being crystallographically independent. Packing of molecules of 1 is dominated by face-to-face π-stacking interactions which is consistent with the low solubility of 1 in common organic solvents. Reaction of 5 with [Cu(hfacac)]·HO (Hhfacac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione) under conditions of crystal growth by layering resulted in the formation of [Cu(hfacac)(5)] ·2.8CH·0.4CHCl. Single-crystal X-ray diffraction reveals an unusual 1D-coordination polymer consisting of a series of alternating single and double loops. Each of the three crystallographically independent Cu atoms is octahedrally sited with -arrangements two N-donors from two different ligands 1 and, therefore, -arrangements of coordinated [hfacac] ligands; this observation is unusual among compounds in the Cambridge Structural Database containing {Cu(hfacac)N} coordination units in which the two N-donors are in a non-chelating ligand.

In this work we use high-resolution synchrotron X-ray diffraction for electron density mapping, in conjunction with modelling, to study short O-H⋯O and O-H⋯O hydrogen bonds whose behaviour is known to be tuneable by temperature. The short hydrogen bonds have donor-acceptor distances in the region of 2.45 Å and are formed in substituted urea and organic acid molecular complexes of ,'-dimethylurea oxalic acid 2 : 1 (), ,-dimethylurea 2,4-dinitrobenzoate 1 : 1 () and ,-dimethylurea 3,5-dinitrobenzoic acid 2 : 2 (). From the combined analyses, these complexes are found to fall within the salt-cocrystal continuum and exhibit short hydrogen bonds that can be characterised as both strong and electrostatic (, ) or very strong with a significant covalent contribution (). An additional charge assisted component is found to be important in distinguishing the relatively uncommon O-H⋯O pseudo-covalent interaction from a typical strong hydrogen bond. The electron density is found to be sensitive to the extent of static proton transfer, presenting it as a useful parameter in the study of the salt-cocrystal continuum. From complementary calculated hydrogen atom potentials, we attribute changes in proton position to the molecular environment. Calculated potentials also show zero barrier to proton migration, forming an 'energy slide' between the donor and acceptor atoms. The better fundamental understanding of the short hydrogen bond in the 'zone of fluctuation' presented in a salt-cocrystal continuum, enabled by studies like this, provide greater insight into their related properties and can have implications in the regulation of pharmaceutical materials.

The present Highlight article shows the importance of the monitoring of bulk crystalline compounds for a more thorough understanding of heterogeneous catalysts at the intersection of catalysis, materials science, crystallography and inorganic chemistry. Although catalytic action is widely regarded as a purely surface-bound phenomenon, there is increasing evidence that bulk processes can detrimentally or beneficially influence the catalytic properties of various material classes. Such bulk processes include polymorphic transformations, formation of oxygen-deficient structures, transient phases and the formation of a metal-oxide composite. The monitoring of these processes and the subsequent establishment of structure-property relationships are most effective if carried out under real operation conditions. By focusing on synchrotron-based X-ray diffraction as the perfect tool to follow the evolution of crystalline species, we exemplify the strength of the concept with five examples from various areas of catalytic research. As catalyst activation studies are increasingly becoming a hot topic in heterogeneous catalysis, the (self-)activation of oxide- and intermetallic compound-based materials during methanol steam and methane dry reforming is highlighted. The perovskite LaNiO is selected as an example to show the complex structural dynamics before and during methane dry reforming, which is only revealed upon monitoring all intermediate crystalline species in the transformation from LaNiO into Ni/LaO/LaOCO. ZrO-based materials form the second group, indicating the decomposition of the intermetallic compound CuZr into an epitaxially stabilized Cu/tetragonal ZrO composite during methanol steam reforming, the stability of a ZrOC oxycarbide and the gas-phase dependence of the tetragonal-to-monoclinic ZrO polymorphic transformation. The latter is the key parameter to the catalytic understanding of ZrO and is only appreciated in full detail once it is possible to follow the individual steps of the transformation between the crystalline polymorphic structures. A selected example is devoted to how the monitoring of crystalline reactive carbon during methane dry reforming operation aids in the mechanistic understanding of a Ni/MnO catalyst. The most important aspect is the strict use of monitoring of the structural changes occurring during (self-)activation to establish meaningful structure-property relationships allowing conclusions beyond isolated surface chemical aspects.

There is currently an emerging drive towards computational materials design and fabrication of predicted novel materials. One of the keys to developing appropriate fabrication methods is determination of the composition and phase. Here we explore the FeGe system and establish reference Raman signatures for the distinction between FeGe hexagonal and cubic structures, as well as FeGe and FeGe phases. The experimental results are substantiated by first principles lattice dynamics calculations as well as by complementary structural characterization such as transmission electron microscopy and X-ray diffraction, along with magnetic measurements.

Hexamethylenetetramine (HMTA) is commonly used as a base releasing agent for the synthesis of ZnO under mild aqueous conditions. HMTA hydrolysis leads to gradual formation of a base during the reaction. Use of HMTA, however, does have limitations: HMTA hydrolysis yields both formaldehyde and ammonia, it provides no direct control over the ammonia addition rate or the total amount of ammonia added during the reaction, it results in a limited applicable pH range and it dictates the accessible reaction temperatures. To overcome these restrictions, this work presents a direct base titration strategy for ZnO synthesis in which a continuous base addition rate is maintained. Using this highly flexible strategy, wurtzite ZnO can be synthesized at a pH >5.5 using either KOH or ammonia as a base source at various addition rates and reaction pH values. pH measurements suggest a similar reaction mechanism to HMTA-based synthesis, independent of the varied conditions. The type and concentration of the base used for titration affect the reaction product, with ammonia showing evidence of capping behaviour. Optimizing this strategy, we are able to influence and direct the crystal shape and significantly increase the product yield to 74% compared to the ∼13% obtained by the reference HMTA reaction.

Natural products are precious feedstock in drug discovery and sustainable materials. This work using crystal engineering strategy, visible light, and solvent-free cycloaddition successfully constructed two caffeic acid derivatives, -(1,2,3,4)-2,4-bis(3,4-dihydroxyphenyl)cyclobutane-1,3-dicarboxylate and -(1,2,3,4)-2,4-bis(3,4-dihydroxyphenyl)cyclobutane-1,3-dicarboxylic acid. Because of the multiple stereocenters, it is challenging to prepare those compounds using traditional organic synthesis methods. The crystal engineering Hirshfeld surface analysis and 2D intermolecular interaction fingerprints were applied to synthetic route design. The light resources used in this work was visible LED or free, clean, and renewable sunlight. The evidence suggested that pure stereoisomer was obtained demonstrating the stereospecificity and efficiency of the topochemical cycloaddition reaction. The derivatives exhibited free radical scavenging and antioxidant biological activities, as well as the potential inhibitory activity of fatty acid binding proteins. One of the derivatives is the precursor of the natural product Shimobashiric acid C which paves the way for the total synthesis and further study of Shimobashiric acid C. In addition, the derivatives possess photodegradability at a specific wavelength, which is very attractive for "green" degradable polymeric materials.

A significant portion of the population suffers from idipoathic calcium oxalate (CaOx) kidney stones, and current clinical treatments of stones have limited lasting success with a high rate of patients suffering from reoccurring stones. Understanding the role of physiologically relevant urinary species on the formation, aggregation, and growth of CaOx crystals can allow for better understanding of this complex biomineralization process and lead to more effective clinical treatments. Our prior work has focused on developing a two-stage model system, where the first stage emulates the formation of Randall's plaque, and the second stage examines the influence of the plaque on overgrowth of CaOx into a stone. Herein, we report on the development of an easy-to-use flow-cell platform that utilizes basement membrane extract (BME) as a biologically relevant crystallization substrate to study the influence of urinary 'inhibitors' on the formation and growth of CaOx on BME under flow conditions. Magnesium, citrate, and osteopontin were studied because of their known ability to inhibit CaOx formation, but their influence also led to interesting modifications to the terminal crystal habit. Magnesium had little to no effect on the CaOx crystallization, but both citrate and osteopontin resulted in significant changes to the crystallization kinetics and the terminal crystal habits. Triply inhibited artificial urine solutions resulted in CaOx monohydrate formations that resembled physiological stones, and the platform allowed for morphogenesis to be dynamically monitored. The BME was also used in a two-stage model system to first grow CaP that mimicked Randall's plaques, whereby the impact of the CaP crystallizing surface on CaOx formation could be studied. It was found that the CaP surface did not result in any significant changes in CaOx crystal formation or growth indicating that the urinary inhibitors and the basement membrane substrate were the dominant factors in modulating CaOx crystallization. It was also found that the basement membrane surface promoted the attachment and/or nucleation and growth of both CaOx and CaP crystals compared to bare glass surfaces, thereby enabling easy study of the urinary inhibitors. The work presented here has elucidated the terminal growth habit of different COM structures and has provided an easy to use platform that can be widely adopted by the kidney stone and other crystallization communities.