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This study describes the discovery of a unique ionic cocrystal of the active pharmaceutical ingredient (API) ponatinib hydrochloride (pon·HCl), and characterization using single-crystal X-ray diffraction (SCXRD) and solid-state NMR (SSNMR) spectroscopy. Pon·HCl 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 13C CP/MAS spectrum confirms the presence of two crystallographically distinct ponatinib molecules, whereas 1D 1H and 2D 1H–1H DQ–SQ spectra identify and assign the unusually deshielded imidazopyridazine proton. 1D 35Cl 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 35Cl → 1H 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. [ABSTRACT FROM AUTHOR]

Reactions of trans-[(dmpe)2MnH(C2H4)] (1) with BH3(NMe3), 9-BBN, and HBMes2 yielded the manganese(I) borohydride complexes [(dmpe)2Mn(μ-H)2BR2] (3: R = H, 4: R2 = C8H14, 5: R = Mes). The reaction of 1 with BH3(NMe3) proceeds via ethylene substitution. By contrast, a detuerium labelling study indicates that the reaction of 1 with HBMes2 involves initial isomerization of 1 to an unobserved 5-coordinate ethyl intermediate, [(dmpe)2MnEt], which reacts with the hydroborane to afford EtBR2 and [(dmpe)2MnH], followed by reaction with a second equivalent of hydroborane to generate 5 (an analogous pathway is likely followed for other base-free hydroboranes such as 9-BBN). Identification of 3–5 as κ2-borohydride complexes, as opposed to boryl dihydride or hydroborane hydride isomers, is supported by 11B NMR spectroscopy, X-ray diffraction, and Atoms in Molecules calculations. Two byproducts were observed in the syntheses of 3–5: [{(dmpe)2MnH}2(μ-dmpe)] (6) and [(dmpe)2MnH(κ1-dmpe)] (7). These complexes were independently prepared by exposure of 1 to free dmpe under an atmosphere of Ar or H2, and the generality of this synthetic route was demonstrated by the reaction of 1 with PMe3 (under H2) to form [(dmpe)2MnH(PMe3)] (8). Complexes 6–8 can exist as isomers with either a trans or a cis relationship between the hydride and κ1-coordinated phosphine ligands on manganese. trans to cis isomerization of 6–8 is photochemically induced, whereas the reverse reaction occurs under thermal conditions. X-ray crystal structures were obtained for 3–5, trans,trans-6 , cis,cis-6 , trans-7 , and trans-8. [ABSTRACT FROM AUTHOR]

Reaction of NacNacAl (NacNac=[DippNC(Me)CHC(Me)NDipp]−) with one equivalent of benzophenone affords a ketylate species NacNacAl(η2(C,O)‐OCPh2) that undergoes easy cyclization reactions with unsaturated substrates. The scope of substrates included benzophenone, aldimine (PhNC(Ph)H), quinoline, phenyl nitrile, trimethylsilyl azide, and a saturated cyclic thiourea. The latter substrate reacted by an unusual C−N cleavage that left the C=S functionality intact. The new products were characterized by NMR spectroscopy and X‐ray diffraction analysis. [ABSTRACT FROM AUTHOR]

The protonation of 2,3,4,5-tetraphenylcyclopentadienone (tetracyclone) yields 6,11-diphenyl-5H-benzo[a]fluoren5-one (17) and 2,3,4,5-tetraphenylcyclopent-2-en-1-one (18)as the major products. This contrasts with the pyrolysis of tetracyclone, which yields 5,6-diphenyl-11H-benzo[a]fluoren-11-one (22), a structural isomer of 17. Mechanisms are presented that rationalize these observations. The protonation of 4-hydroxy-2,3,4-triphenylcyclopent-2-en-1-none, the precursor to 2,3,4-triphenylcyclopentadienone, generates 2-(2'-oxo-3',4',5'-triphenylcyclopent-3'-enyl)-3,4,5-triphenylcyclopenta-2,4-dienone (30), which has been unequivocally characterized by X-ray crystallography. The establishment of the conformation of molecule 30 in the solid state, which correlates with the conformation in solution, provides a rationale for the subsequent formation of the tetrahydro-pentaphenyl-as-indacene-3,4-dione (32) upon further protonation. [ABSTRACT FROM AUTHOR]

The use of high-strength polymer in automotive structural components is limited by insufficient understanding of microscopic aspects of deformation for accurate numerical predictions of the mechanical behavior during forming processes. One approach to meeting these critical data needs is a careful examination of the structure property relationships that directly influence formability. Different hot forming processes (solid-state extrusion, axial feed hot oil tube forming, and biaxial ball stretching test) are utilized in this work for investigating the effect of process conditions on the molecular orientation of polypropylene (PP) tubes. White-Spruiell representation of orientation factors based on the results form X-ray diffraction (XRD) patterns is utilized to analyze the development of orientation under extrusion and various forming conditions. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers [ABSTRACT FROM AUTHOR]

Abstract: Two-dimensional X-ray diffraction was employed, to provide a complete understanding of the energy efficiency improvement of organic photovoltaics by AC electric field alignment. Two distinguishable poly (3-hexylthiophene) (P3HT) nanostructures were found in the form of two separated layers, one of which is highly oriented and the other randomly distributed. The finding helps to analyze the crystallite arrangements not only in the interface in the bulk heterojunction, but also those closer to the substrate. The highly oriented P3HT layer, although located near the substrate, was found to enhance the device efficiency, by increasing the short circuit current and decreasing the series resistance. [Copyright &y& Elsevier]

The synthesis, crystal, and magnetic structures and the bulk magnetic properties of Ca2FeCoO5, a brownmillerite type oxide, are presented. The crystal structure, solved and refined from single crystal X-ray and powder neutron diffraction data, is described in Pbcmwith cell parameters, a= 5.3652(3) Å, b= 11.0995(5) Å, c= 14.7982(7) Å. Thus, one axis, bin this setting, is doubled in comparison with the standard brownmillerite structure description giving rise to two sets of octahedral and tetrahedral sites. Aided by the strong scattering contrast between Fe and Co for neutrons, a nearly perfect intralayer cation site ordering, not observed for any brownmillerite before, is detected in the tetrahedral layers. There is a lesser degree of cation site ordering in the octahedral sites. Overall, the Fe/Co site ordering is of the NaCl type both within and between the tetrahedral and octahedral layers. There are also both intra- and interlayer ordering of tetrahedral chain orientations. The left- and right-handed orientations alternate within each tetrahedral layer as well as between the closest tetrahedral layers. The occurrence of the rare Pbcmspace group in Ca2FeCoO5is not consistent with a recently proposed structure-field map for brownmillerite oxides. The magnetic structure is G-type antiferromagnetic, with preferred orientation of magnetic moments parallel to the longest axis between 3.8 K to 100 K which switches to the shortest axis between 225 K and 550 K. The neutron diffraction data indicate different site specific ordering temperatures at about 450(5) K and 555(5) K. The refined ordered moments at 3.8 K are somewhat smaller than expected for Fe3橷 Co3(high spin) but are similar to those found in Sr2FeCoO5. There is evidence for spin canting from isothermal magnetization data that shows well pronounced hystereses and remnant magnetizations at 5 K and 200 K. [ABSTRACT FROM AUTHOR]