Crystal structures, Hirshfeld analysis, and energy framework analysis of two differently 3'-substituted 4-methylchalcones: 3'-(N=CHC6H4-p-CH3)-4-methylchalcone and 3'-(NHCOCH3)-4-methylchalcone.

Two crystal structures of chalcones, or 1,3-diarylprop-2-en-1-ones, are presented; both contain a p-methyl substitution on the 3-Ring, but differ with respect to the m-substitution on the 1-Ring. Their systematic names are (2E)-3-(4-methylphenyl)-1-(3-{[(4-methylphenyl)methylidene]amino}phenyl)prop-2-en-1-one (C24H21NO) and N-{3-[(2E)-3-(4-methylphenyl)prop-2-enoyl]phenyl}acetamide (C18H17NO2), which are abbreviated as 3'-(N=CHC6H4-p-CH3)-4-methylchalcone and 3'-(NHCOCH3)-4-methylchalcone, respectively. Both chalcones represent the first reported acetamide-substituted and imino-substituted chalcone crystal structures, adding to the robust library of chalcone structures within the Cambridge Structural Database. The crystal structure of 3'-(N=CHC6H4-p-CH3)-4-methylchalcone exhibits close contacts between the enone O atom and the substituent arene ring, in addition to C...C interactions between the substituent arene rings. The structure of 3'-(NHCOCH3)-4-methylchalcone exhibits a unique interaction between the enone O atom and the 1-Ring substituent, contributing to its antiparallel crystal packing. In addition, both structures exhibit π-stacking, which occurs between the 1-Ring and R-Ring for 3'-(N=CHC6H4-p-CH3)-4-methylchalcone, and between the 1-Ring and 3-Ring for 3'-(NHCOCH3)-4-methylchalcone.

Rapid sol-gel synthesis of honeycomb-layered Na3Ni2BiO6 and orthorhombic Na3Ca2BiO6.

The A3M2M'O6 type materials Na3Ca2BiO6 and Na3Ni2BiO6 were successfully synthesised through two sol-gel techniques - a method based on a natural deep eutectic solvent, and a biopolymer-mediated synthesis. The materials were analysed using Scanning Electron Microscopy to determine if there was a difference in final morphology between the two methods, and it was found that the natural deep eutectic solvent method resulted in a more porous morphology. For both materials, the optimum dwell temperature was found to be 800 °C, which in the case of Na3Ca2BiO6 was a much less energy-intensive synthesis process than its seminal solid-state synthesis. Magnetic susceptibility measurements were undertaken on both materials. It was found that Na3Ca2BiO6 exhibits only weak, temperature independent paramagnetism. Na3Ni2BiO6 was found to be antiferromagnetic, with a Néel temperature of 12 K, in line with previously reported results.

True molecular conformation and structure determination by three-dimensional electron diffraction of PAH by-products potentially useful for electronic applications.

The true molecular conformation and the crystal structure of benzo[e]dinaphtho[2,3-a;1',2',3',4'-ghi]fluoranthene, 7,14-diphenylnaphtho[1,2,3,4-cde]bisanthene and 7,16-diphenylnaphtho[1,2,3,4-cde]helianthrene were determined ab initio by 3D electron diffraction. All three molecules are remarkable polycyclic aromatic hydrocarbons. The molecular conformation of two of these compounds could not be determined via classical spectroscopic methods due to the large size of the molecule and the occurrence of multiple and reciprocally connected aromatic rings. The molecular structure of the third molecule was previously considered provisional. These compounds were isolated as by-products in the synthesis of similar products and were at the same time nanocrystalline and available only in very limited amounts. 3D electron diffraction data, taken from submicrometric single crystals, allowed for direct ab initio structure solution and the unbiased determination of the internal molecular conformation. Detailed synthetic routes and spectroscopic analyses are also discussed. Based on many-body perturbation theory simulations, benzo[e]dinaphtho[2,3-a;1',2',3',4'-ghi]fluoranthene may be a promising candidate for triplet-triplet annihilation and 7,14-diphenylnaphtho[1,2,3,4-cde]bisanthene may be a promising candidate for intermolecular singlet fission in the solid state.

Synthesis of porous high-temperature superconductors via a melamine formaldehyde sacrificial template.

Nanostructured high-temperature superconductors YBa2Cu3O6+δ and Bi2Sr2CaCu2O8+δ were synthesised using a melamine formaldehyde sponge as a sacrificial template, via three solution-based approaches. In the case of YBa2Cu3O6+δ , a modified Pechini method produced a material with a superconducting transition at 92 K and a specific surface area of 4.22 m2 g-1. Further analysis with Hg porosimetry determined that the sponge exhibited a porosity of 82%. In the case of Bi2Sr2CaCu2O8+δ , this method produced a material that exhibited superconductivity at 86 K with a specific surface area of 9.62 m2 g-1. Hg-porosimetry determined that the BSCCO sponge exhibited a porosity of 78%.

Structure determination, thermal stability and dissolution rate of δ-indomethacin.

The structure solution of the δ-polymorph of indomethacin was obtained using three-dimensional electron diffraction. This form shows a significantly enhanced dissolution rate compared with the more common and better studied α- and γ-polymorphs, indicating better biopharmaceutical properties for medicinal applications. The structure was solved in non-centrosymmetric space group P21 and comprises two molecules in the asymmetric unit. Packing and molecule conformation closely resemble indomethacin methyl ester and indomethacin methanol solvate. Knowledge of the structure allowed the rational interpretation of spectroscopic IR and Raman data for δ-polymorph and a tentative interpretation for still unsolved indomethacin polymorphs. Finally, we observed a solid-solid transition from δ-polymorph to α-polymorph that can be driven by similarities in molecular conformation.

Structural effects of halogen bonding in iodochalcones.

The structures of three iodochalcones, functionalized with fluorine or a nitro group, have been investigated to explore the impact of different molecular electrostatic distributions on the halogen bonding within each crystal structure. The strongly withdrawing nitro group presented a switch of the halogen bond from a lateral to a linear motif. Surprisingly, this appears to be influenced by a net positive shift in charge distribution around the lateral edges of the σ-hole, making the lateral I...I bonding motif less preferable. A channel of amphoteric I...I type II halogen bonds is observed for a chalcone molecule, which was not previously reported in chalcones, alongside an example of the common synthon involving extended linear chains of I...O2N donor-acceptor halogen bonds. This work shows that halogenated chalcones may be an interesting target for developing halogen bonding as a significant tool within crystal engineering, a thus far underexplored area for this common structural motif.

3D Electron Diffraction Structure Determination of Terrylene, a Promising Candidate for Intermolecular Singlet Fission.

Herein we demonstrate the prowess of the 3D electron diffraction approach by unveiling the structure of terrylene, the third member in the series of peri-condensed naphthalene analogues, which has eluded structure determination for 65 years. The structure was determined by direct methods using electron diffraction data and corroborated by dispersion-inclusive density functional theory optimizations. Terrylene crystalizes in the monoclinic space group P21 /a, arranging in a sandwich-herringbone packing motif, similar to analogous compounds. Having solved the crystal structure, we use many-body perturbation theory to evaluate the excited-state properties of terrylene in the solid-state. We find that terrylene is a promising candidate for intermolecular singlet fission, comparable to tetracene and rubrene.

A new olanzapine cocrystal obtained from volatile deep eutectic solvents and determined by 3D electron diffraction.

A previously unknown cocrystal of olanzapine and phenol was identified from a volatile deep eutectic solvent as the intermediate species in the crystallization of olanzapine. This new nanocrystalline phase was investigated by electron diffraction, powder X-ray diffraction and differential scanning calorimetry. The structure was determined by simulated annealing using 3D electron diffraction data and confirmed using DFT-D optimizations. Olanzapine and phenol cocrystallize in the triclinic space group P1, supporting the hypothesis of a dimeric growth unit, where a centrosymmetric dimer is stabilized by multiple weak C-H...π interactions and forms double N-H...N hydrogen bonding with adjacent dimers.

Crystal structures of three functionalized chalcones: 4'-di-methyl-amino-3-nitro-chalcone, 3-di-methyl-amino-3'-nitrochalcone and 3'-nitro-chalcone.

The structure of three functionalized chalcones (1,3-di-aryl-prop-2-en-1-ones), containing combinations of nitro and di-methyl-amino functional groups, are presented, namely, 1-[4-(di-methyl-amino)-phen-yl]-3-(3-nitro-phen-yl)prop-2-en-1-one, C17H16N2O3, Gp8m, 3-[3-(di-methyl-amino)-phen-yl]-1-(3-nitro-phen-yl)prop-2-en-1-one, C17H16N2O3, Hm7m and 1-(3-nitro-phen-yl)-3-phenyl-prop-2-en-1-one, C15H11NO3, Hm1-. Each of the mol-ecules contains bonding motifs seen in previously solved crystal structures of functionalized chalcones, adding to the large dataset available for these small organic mol-ecules. The structures of all three of the title compounds contain similar bonding motifs, resulting in two-dimensional planes of mol-ecules formed via C-H⋯O hydrogen-bonding inter-actions involving the nitro- and ketone groups. The structure of Hm1- is very similar to the crystal structure of a previously solved isomer [Jing (2009 ▸). Acta Cryst. E65, o2510].

Crystal structure and Hirshfeld analysis of 3'-bromo-4-methyl-chalcone and 3'-cyano-4-methyl-chalcone.

Two crystal structures of chalcones, or 1,3-di-aryl-prop-2-en-1-ones, are presented; both contain a methyl substitution on the 3-Ring, but differ on the 1-Ring, bromo versus cyano. The compounds are 3'-bromo-4-methyl-chalcone [systematic name: 1-(2-bromo-phen-yl)-3-(4-methyl-phen-yl)prop-2-en-1-one], C16H13BrO, and 3'-cyano-4-methyl-chalcone {systematic name: 2-[3-(4-methyl-phen-yl)prop-2-eno-yl]benzo-nitrile}, C17H13NO. Both chalcones meaningfully add to the large dataset of chalcone structures. The crystal structure of 3'-cyano-4-methyl-chalcone exhibits close contacts with the cyano nitro-gen that do not appear in previously reported disubstituted cyano-chalcones, namely inter-actions between the cyano nitro-gen atom and a ring hydrogen atom as well as a methyl hydrogen atom. The structure of 3'-bromo-4-methyl-chalcone exhibits a type I halogen bond, similar to that found in a previously reported structure for 4-bromo-3'-methyl-chalcone.

Metastable crystalline phase formation in deep eutectic systems revealed by simultaneous synchrotron XRD and DSC.

The phase behaviour of various deep eutectic systems was analysed using concurrent synchrotron powder X-ray diffraction and differential scanning calorimetry. Deep eutectic systems containing the pharmaceuticals metacetamol, 2-ethoxybenzamide or benzamide as binary mixtures with phenol revealed new crystalline phases melting either before or with crystals of phenol, highlighting their lower stabilities. Furthermore, in the phenol : 2-ethoxybenzamide system it was shown that multiple metastable phases can form, highlighting the potential for the separation of a hierarchy of crystal structures with differing stabilities from eutectic systems. Through these experiments, we strengthen the idea that eutectic systems can be described by understanding the formation and stabilities of metastable co-crystalline structures. These novel results lead to a deeper understanding of the structure and thermodynamics of deep eutectic solvents, with relevance for analagous systems across materials science.

The solubility and stability of heterocyclic chalcones compared with trans-chalcone.

Heterocyclic chalcones are a recently explored subgroup of chalcones that have sparked interest due to their significant antibacterial and antifungal capabilities. Herein, the structure and solubility of two such compounds, (E)-1-(1H-pyrrol-2-yl)-3-(thiophen-2-yl)prop-2-en-1-one and (E)-3-phenyl-1-(1H-pyrrol-2-yl)prop-2-en-1-one, are assessed. Single crystals of (E)-1-(1H-pyrrol-2-yl)-3-(thiophen-2-yl)prop-2-en-1-one were grown, allowing structural comparisons between the heterocyclic chalcones and (2E)-1,3-diphenylprop-2-en-1-one, trivially known as trans-chalcone. The two heterocyclic chalcones were found to be less soluble in all solvents tested and to have higher melting points than trans-chalcone, probably due to their stronger intermolecular interactions arising from the functionalized rings. Interestingly, however, it was found that the addition of the thiophene ring in (E)-1-(1H-pyrrol-2-yl)-3-(thiophen-2-yl)prop-2-en-1-one increased both the melting point and solubility of the sample compared with (E)-3-phenyl-1-(1H-pyrrol-2-yl)prop-2-en-1-one. This observation may be key for the future crystal engineering of heterocyclic chalcones for pharmaceutical applications.

Crystal structure and Hirshfeld surface analysis of (E)-3-(3-iodo-phen-yl)-1-(4-iodo-phen-yl)prop-2-en-1-one.

The title compound, C15H10I2O, is a halogenated chalcone formed from two iodine substituted rings, one para-substituted and the other meta-substituted, linked through a prop-2-en-1-one spacer. In the mol-ecule, the mean planes of the 3-iodo-phenyl and the 4-iodo-phenyl groups are twisted by 46.51 (15)°. The calculated electrostatic potential surfaces show the presence of σ-holes on both substituted iodines. In the crystal, the mol-ecules are linked through type II halogen bonds, forming a sheet structure parallel to the bc plane. Between the sheets, weak inter-molecular C-H⋯π inter-actions are observed. Hirshfeld surface analysis showed that the most significant contacts in the structure are C⋯H/H⋯C (31.9%), followed by H⋯H (21.4%), I⋯H/H⋯I (18.4%). I⋯I (14.5%) and O⋯H/H⋯O (8.1%).

An experimental and computational study into the crystallisation propensity of 2nd generation sulflower.

The crystallisation propensity of the newly synthesised molecule persulfurated coronene has been investigated through a number of experimental methods. Electrostatic potential calculations and multi-molecular optimisations show that face-face interactions are far more favorable than edge-face interactions, severely restricting the ability of the molecule to crystallise.

The Crystal Structure of Orthocetamol Solved by 3D Electron Diffraction.

Orthocetamol is a regioisomer of the well-known pain medication paracetamol and a promising analgesic and an anti-arthritic medicament itself. However, orthocetamol cannot be grown as single crystals suitable for X-ray diffraction, so its crystal structure has remained a mystery for more than a century. Here, we report the ab-initio structure determination of orthocetamol obtained by 3D electron diffraction, combining a low-dose acquisition method and a dedicated single-electron detector for recording the diffracted intensities. The structure is monoclinic, with a pseudo-tetragonal cell that favors multiple twinning on a scale of a few tens of nanometers. The successful application of 3D electron diffraction to orthocetamol introduces a new gold standard of total structure solution in all cases where X-ray diffraction and electron-microscope imaging methods fail.

Lamotrigine ethanol monosolvate.

Lamotrigine is an active pharmaceutical ingredient used as a treatment for epilepsy and psychiatric disorders. Single crystals of an ethano-late solvate, C9H7Cl2N5·C2H5OH, were produced by slow evaporation of a saturated solution from anhydrous ethanol. Within the crystal structure, the lamotrigine mol-ecules form dimers through N-H⋯N hydrogen bonds involving the amine N atoms in the ortho position of the triazine group. These dimers are linked into a tape motif through hydrogen bonds involving the amine N atoms in the para position. The ethanol and lamotrigine are present in a 1:1 ratio in the lattice with the ethyl group of the ethanol mol-ecule exhibiting disorder with an occupancy ratio of 0.516 (14):0.484 (14).

Thermal Expansion of Carbamazepine: Systematic Crystallographic Measurements Challenge Quantum Chemical Calculations.

We report systematic temperature-dependent X-ray measurements on the most stable carbamazepine polymorph. This active pharmaceutical ingredient is used to demonstrate how the thermal expansion can probe certain intermolecular interactions resulting in anisotropic expansion behavior. We show that most structural features can be captured by electronic structure calculations at the quasi-harmonic approximation (QHA) provided a dispersion-corrected density functional based method is employed. The impact of thermal expansion on the phonon modes and hence free energy contributions is large enough to impact the relative stability of different polymorphs.

Nanostructural origin of blue fluorescence in the mineral karpatite.

The colour of crystals is a function of their atomic structure. In the case of organic crystals, it is the spatial relationships between molecules that determine the colour, so the same molecules in the same arrangement should produce crystals of the same colour, regardless of whether they arise geologically or synthetically. There is a naturally-occurring organic crystal known as karpatite which is prized for its beautiful blue fluorescence under ultra-violet illumination. When grown under laboratory conditions however, the crystals fluoresce with an intense green colour. For 20 years, this difference has been thought to be due to chemical impurities in the laboratory-grown material. Using electron microscopy coupled with fluorescence spectroscopy and X-Ray diffraction, we report here that this disparity is instead due to differences in the structure of the crystals at the nanoscale. The results show that in nature, karpatite has a nanotexture that is not present in the synthetic crystals, which enables different photonic pathways and therefore a blue, rather than green colour whilst undergoing fluorescence.

Low temperature magneto-morphological characterisation of coronene and the resolution of previously observed unexplained phenomena.

The polyaromatic hydrocarbon coronene has been the molecule of choice for understanding the physical properties of graphene for over a decade. The modelling of the latter by the former was considered to be valid, as since it was first synthesised in 1932, the physical behaviour of coronene has been determined extremely accurately. We recently discovered however, an unforeseen polymorph of coronene, which exists as an enantiotrope with the previously observed crystal structure. Using low-temperature magnetisation and crystallographic measurements, we show here for the first time that the electronic and magnetic properties of coronene depend directly on the temperature at which it is observed, with hysteretic behaviour exhibited between 300 K and 100 K. Furthermore we determine that this behaviour is a direct result of the appearance and disappearance of the newly-discovered polymorph during thermal cycling. Our results not only highlight the need for theoretical models of graphene to take into account this anomalous behaviour at low temperatures, but also explain puzzling experimental observations of coronene dating back over 40 years.

An unforeseen polymorph of coronene by the application of magnetic fields during crystal growth.

The continued development of novel drugs, proteins, and advanced materials strongly rely on our ability to self-assemble molecules in solids with the most suitable structure (polymorph) in order to exhibit desired functionalities. The search for new polymorphs remains a scientific challenge, that is at the core of crystal engineering and there has been a lack of effective solutions to this problem. Here we show that by crystallizing the polyaromatic hydrocarbon coronene in the presence of a magnetic field, a polymorph is formed in a ß-herringbone structure instead of the ubiquitous γ-herringbone structure, with a decrease of 35° in the herringbone nearest neighbour angle. The ß-herringbone polymorph is stable, preserves its structure under ambient conditions and as a result of the altered molecular packing of the crystals, exhibits significant changes to the optical and mechanical properties of the crystal.