Mthphn⋯OMthphn (Mthphn = methoxyphenyl) hydrogen bonds form corrugated layers parallel to (100) that are connected along the a axis by C—H⋯π(ring) and π–π stacking interactions.In the crystal structure, C—H 20H21N3O3, the allyl substituent is rotated out of the plane of its attached phenyl ring [torsion angle 100.66 (15)°]. In the crystal, C—HMthphn⋯OMthphn (Mthphn = methoxyphenyl) hydrogen bonds lead to the formation of (100) layers that are connected into a three-dimensional network by C—H⋯π(ring) interactions, together with π–π stacking interactions [centroid-to-centroid distance = 3.7318 (10) Å] between parallel phenyl rings. Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H⋯H (48.7%) and H⋯C/C⋯H (23.3%) interactions. Computational chemistry reveals that the C—HMthphn⋯OMthphn hydrogen bond energy is 47.1 kJ mol−1. The theoretical structure, optimized by density functional theory (DFT) at the B3LYP/ 6–311 G level, is compared with the experimentally determined molecular structure. The HOMO–LUMO behaviour was elucidated to determine the energy gap.In the title molecule, C The allyl group is rotated out of the plane of the A ring as indicated by the C3—C4—C7—C8 torsion angle of 100.66 (15)°. Both methoxy groups are virtually coplanar with their attached rings with C3—C2—O2—C20 and C17—C16—O3—C19 torsion angles, respectively, of 5.04 (16) and 3.73 (16)°. There are no unusual bond lengths or bond angles in the molecule.The title molecule is non-planar Fig. 1, with thMthphn⋯OMthphn (Mthphn = methoxyphenyl) hydrogen bonds  interactions  Å  layers are formed by C—Hs Table 1. These as Table 1 as well  Å Fig. 3.Crystal Explorer 17.5 , and near O3 indicate their roles in hydrogen bonding; they also appear as blue and red regions corresponding to positive (hydrogen-bond donors) and negative (hydrogen-bond acceptors) potentials on the HS mapped over electrostatic potential rm Fig. 4, the whia, and those delineated into H⋯H, H⋯C/C⋯H, H⋯N/N⋯H, H⋯O/O⋯H, C⋯C, N⋯C/C⋯N, O⋯C/C⋯O and O⋯N/N⋯O contacts  has the tips at de + di = 2.68 Å. The pair of scattered points of spikes in the fingerprint plot delineated into H⋯N/N⋯H contacts  has a distribution of points with small and slightly larger tips at de + di = 2.72 and 2.70 Å, respectively. The H⋯O/O⋯H contacts  have a symmetric distribution of points with the tips at de + di = 2.48 Å. The C⋯C contacts, Fig. 7f, have an arrow-shaped distribution of points with the tip at de = di = 1.68 Å. Finally, N⋯C/C⋯N , O⋯C/C⋯O  and O⋯N/N⋯O  interactions contribute only 1.0%, 0.9% and 0.6%, respectively, to the overall HS and thus have minor significance.The overall two-dimensional fingerprint plot, Fig. 7⋯N Fig. 7g, O⋯C/C⋯O Fig. 7h and O⋯⋯O Fig. 7i interet al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H⋯H and H⋯C/C⋯H interactions suggest that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing  is the sum of electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) energies  were calculated as −20.6 (Eele), −5.7 (Epol), −49.3 (Edis), 35.4 (Erep) and −47.1 (Etot).The intermolecular interaction energies were calculated using a CE–B3LYP/6–31G energy model available in GAUSSIAN 09  using standard B3LYP functional and 6–311 G basis-set calculations  are shown in Fig. 8EHOMO and ELUMO, electronegativity (χ), hardness (η), potential (μ), electrophilicity (ω) and softness (σ).The highest-occupied molecular orbital (HOMO) and the lowest-unoccupied molecular orbital (LUMO) together with the energy gap between them . Colourless crystals were isolated when the solvent was allowed to evaporate (yield: 88%).To a solution of 4-allyl-2-methoxy-1-(prop-2-ynyloxy) benzene  in anhydrous acetonitrile, 1-azido-4-methoxybenzene  and 10 mg copper (I)Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S2056989020006994/wm5559sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020006994/wm5559Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020006994/wm5559Isup3.cdxSupporting information file. DOI: 2005277CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Scientific Reports 10.1038/s41598-017-04775-6, published online 03 July 2017Correction to: This Article contains errors in Table 1, where the mean hatching dates and corresponding standard deviations (SD) have been incorrectly listed.The ‘Mean (SD)’ reported for Species ‘Little auk’, Colony ‘Bjørndalen (Isfjorden)’ change for the date ‘2007, jul-10’,“(4.3)”should read:“(5.6)”The ‘Mean (SD)’ for Species ‘Little auk’, Colony ‘Bjørndalen (Isfjorden)’ change for the date ‘2008, jul-09’,“(3.2)”should read:“(4.5)”The ‘Mean (SD)’ for Species ‘Little auk’, Colony ‘Bjørndalen (Isfjorden)’ change for the date ‘2009, jul-12’,“(2)”should read:“(3.5)”In the same Table 1, the ‘Hatching Dates’ and their associated ‘Mean (SD)’ Species ‘Brünnich’s guillemot’, Colony ‘Diabasodden (Isfjorden)’ change for the year ‘2014′,“jul-01 (7.9)”should read:“jul-07 (3.7)”The ‘Hatching Dates’ and their associated ‘Mean (SD)’ Species ‘Brünnich’s guillemot’, Colony ‘Diabasodden (Isfjorden)’ change for the year ‘2015′,“jun-22 (10.7)”should read:“jul-03 (5.9)”Lastly, in the same Table 1, the ‘Hatching Dates’ and their associated ‘Mean (SD)’ Species ‘Brünnich’s guillemot’, Colony ‘Ossian sarsfjellet (Kongsfjorden)’ change for the year 2014.“jun-29 (6.3)”should read:“jul-06 (5.4)”The ‘Hatching Dates’ and their associated ‘Mean (SD)’ Species ‘Brünnich’s guillemot’, Colony ‘Ossian sarsfjellet (Kongsfjorden)’ change for the year 2015,“jun-23 (9.2)”should read:“jul-02 (7.1)”The correct Table


The title compound, 2-(2-(methoxycarbonyl)-3,6-bis(methoxymethoxy)phenyl)acetic acid, was synthesized as an intermediate for a possible total synthesis of the isocoumarin 3-methyl-3,5,8-trihydroxy-3,4-dihydroisocoumarin. 14H18O8, (I), the methoxycarbonyl [–C(=O)OCH3] and the acetic acid [–CH2C(=O)OH] groups are inclined to the benzene ring by 79.24 (11) and 76.71 (13)°, respectively, and are normal to each other with a dihedral angle of 90.00 (13)°. In the crystal, molecules are linked by a pair of O—H⋯O hydrogen bonds forming the familiar acetic acid inversion dimer. The dimers are linked by two C—H⋯O hydrogen bonds and an offset π–π interaction [intercentroid distance = 3.6405 (14) Å], forming layers lying parallel to the (10In the title compound, C Ceratocystis fimbriata species. The latter are pathogenic agents responsible for the infections of coffee and plane trees , is a key intermediate for the proposed total synthesis of 3-methyl-3,5,8-trihydroxy-3,4-dihydroisocoumarin, and its synthesis is illustrated in Fig. 11), which was first brominated to give compound 2. The latter was then reacted with NaH and ClCH2OCH3 to give compound 3, so protecting the hydroxyl groups. Reacting 3 with tetramethylpiperidene with n-butyllithium and CH2(CO2CH3)2 resulted in the formation of compound 4. Finally 4 was reacted with various quantities of KOH in methanol/water (2:1) to give the title compound, I. The highest yield (81%) was obtained by reacting 20 equivalents of KOH in methanol/water (2:1) at 298 K under stirring for 16 h. Interestingly, the same reaction with reflux for 30 minutes yielded the diacid, 2-(carboxymethyl)-3,6-dihydroxybenzoic acid (5), with a yield of 82%  forming an inversion dimer with an B⋯O6ii and C11—H11A⋯O1iii) and offset π–π interactions between inversion-related benzene rings, so forming layers lying parallel to (10B⋯O4iv) and a C—H⋯π interaction to form a supramolecular framework (Table 1Cg⋯Cgiii = 3.6405 (14) Å, where Cg is the centroid of the C1–C6 benzene ring; interplanar distance = 3.5911 (9) Å; offset = 0.597 Å; symmetry code: (iii) −x, −y + 1, −z.In the crystal of if Fig. 3. The dimk Table 1. Detailset al., 2007CrystalExplorer17.5  through white to blue . The energy frameworks , dispersion (Edis) and total energy (Etot) components, respectively. The radius of the cylinder is proportional to the magnitude of the interaction energy.The Hirshfeld surface analysis  , O⋯H/H⋯O (41.1%) , C⋯H/H⋯C (7.2%)  and C⋯C (2.7%)  contacts. The intermolecular contacts are therefore almost equally distributed between electrostatic and dispersion forces, as shown in Fig. 7a and 7b. The energy frameworks  Fig. 6b, O⋯H/H%) Fig. 6c, C⋯H/H%) Fig. 6d and C⋯%) Fig. 6e contacks Fig. 7 were adja. The individual energy components, electrostatic (Eele), polarization (Epol), dispersion (Edis) and repulsion (Erep) energies and the sum of these components (Etot) for the interactions relative to a reference molecule (*) are shown in Fig. 8b.The calculation of the energy framework results in a colour-coded molecular cluster related to the specific interaction energy, see Fig. 8et al., 2016et al., 2018H-2-benzopyran-1-one phenyl)acetic acid gave zero hits.I is illustrated in Fig. 12–5 and I are available in the PhD thesis of Tiouabi (2005I were obtained by slow evaporation of a solution in acetone-d6.The synthesis of compound uabi 2005. It can Uiso(H) = 1.5Ueq(OH and C-methyl) and 1.2Ueq(C) for other H-atoms.Crystal data, data collection and structure refinement details are summarized in Table 4Intensity data were measured using a Stoe IPDS I, a one-circle diffractometer. For the triclinic system often only 93% of the Ewald sphere is accessible, which explains why the alert diffrn_reflns_laue_measured_fraction_full value (0.942) below minimum (0.95) is given. This involves 155 random reflections out of the expected 2692 for the IUCr cutoff limit of sin θ/λ = 0.60.10.1107/S2056989020007987/ex2033sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989020007987/ex2033Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020007987/ex2033Isup3.cmlSupporting information file. DOI: 2009890CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The title compound comprises two molecules in the asymmetric unit. Intermolecular C—H⋯O and N—H⋯O hydrogen bonds lead to a three-dimensional network structure. 10H15NO2S, comprises two molecules in the asymmetric unit. The S=O bond lengths of the sulfonamide functional group range from 1.428 (2) to 1.441 (2) Å, with S—C bond lengths of 1.766 (3) Å (for both molecules in the asymmetric unit), and S—N bond lengths of 1.618 (2) and 1.622 (3) Å, respectively. When both molecules are viewed down the N—S bond, the propyl group is gauche to the toluene moiety. In the crystal structure, molecules of the title compound are arranged in an intricate three-dimensional network that is formed via intermolecular C—H⋯O and N—H⋯O hydrogen bonds. The crystal structure was refined from a crystal twinned by inversion.The crystal structure of the title sulfonamide, C Commonly referred to as ‘sulfa drugs’, these molecules have been in clinical use since 1968  and butyrylcholinesterase (BChE) inhibitors . The S=O bond lengths of the sulfonamide functional group range from 1.428 (2) to 1.441 (2) Å, which fall within expected values. The S—C bond lengths are 1.766 (3) Å for both molecules, and the S—N bond lengths are 1.618 (2) and 1.622 (3) Å. The O—S—O bond angles are 119.49 (13) and 118.26 (13)°, with N—S—C bond angles of 106.86 (13) and 108.27 (13)°. The two independent molecules differ in the orientation of the propyl chain and the H atom attached to the N atom, however, in each case with the propyl chain being gauche to a sulfonamide oxygen atom and to the toluene moiety when the molecules are viewed down the N1—S1 bond  and the sulfonamide oxygen atom O1 or O1A are 60.5 (3) and 57.3 (2)°, respectively. The groups bonded to the sulfur atom of both sulfonamide groups adopt slightly distorted tetrahedral environments with fourfold coordination τ4 descriptors of 0.94 for both S1 and S1A  atoms of a nearby molecule. These classic hydrogen-bonding interactions form ribbons of the title compound that lie parallel to the ab plane. These interactions have D⋯A distances of 2.925 (3) and 2.968 (3) Å, with D—H⋯A angles of 161 (3) and 172 (3)°. The intermolecular C—H⋯O hydrogen bonding interactions  to 3.594 (4) Å, and D—H⋯A angles ranging from 152.8 to 170.2°. Specifically, the C8(H8B)⋯O2A, C8A(H8AA)⋯O2 and C6(H6)⋯O1A interactions contribute to the stabilization of the supramolecular ribbons. The interaction between C3A(H3A) and O2A links the supramolecular ribbons into an intricate three-dimensional network  to a stirring mixture of propylamine  and p-toluenesulfonyl chloride  in 10 ml of tetrahydrofuran. The reaction mixture was stirred at room temperate for 24 h under a nitrogen atmosphere. After acidification with 5 M HCl and dilution with 15 ml of dichloromethane, the organic layer was washed with water and brine. The aqueous layers were back extracted with 10 ml of dichloromethane. The combined organic layers were then combined, dried over anhydrous sodium sulfate, and evaporated to dryness. The liquid residue was triturated with diethyl ether, placed in a freezer for 48 h and, after isolation via vacuum filtration, the product was obtained as colorless crystals .The title compound was prepared by the dropwise addition of 0.59 et al., 2013Uiso(H) = 1.2Ueq(C) for methylene groups and aromatic hydrogen atoms, and Uiso(H) = 1.5Ueq(C) for methyl groups. Hydrogen atoms bonded to nitrogen atoms were located using electron density difference maps, and were refined freely.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989020007756/wm5567sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020007756/wm5567Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020007756/wm5567Isup3.cmlSupporting information file. DOI: 2008411CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, the molecules are stacked along the b axis via a π–π interaction between the benzene rings.The title compound, [Na 6F5BH3)(C4H8O)2]2, represents a dimeric structure of sodium and organoborohydride, located about a centre of inversion. The Na⋯B distances of 2.7845 (19) and 2.7494 (18) Å were apparently longer than the Li⋯B distances (2.403–2.537 Å) of the lithium organotrihydroborates in the previous reports. Moreover, an interaction between the sodium atom and one fluorine atom on the 2-position of the benzene ring is observed [Na—F = 2.6373 (12) Å]. In the crystal, the dimeric molecules are stacked along the b-axis via a π–π interaction between the benzene rings.The title compound, [Na(μ-C Such a chelation mode was also observed in the previously reported dimeric structure of lithium trihydroborates.The title compound Fig. 1 represeni—F5 = 2.6373 (12) Å] is much shorter than the sum of van der Waals radii (3.74 Å), indicating the presence of a sodium–halogen interaction. Such a halogen–metal interaction is also observed in bromoaryl-substituted lithium trihydroborate  Å; symmetry code: (ii) −x + 1, −y − 1, −z] is slightly longer than the sum of van der Waals radii (3.39 Å), suggesting that the B⋯F interaction is weak. The distance between the closest hydrogen atom (H4) and centroid of the C6F5 ring is 3.343 Å, indicating the absence of C—H⋯π interactions.In the crystal, the dimeric molecules are stacked along the et al., 2019et al., 2010et al., 1998As described above, there is only one example of structural analysis on a sodium alkyltrisboronate complex BH2·S(CH3)2  in THF (20 mL) at 333 K for 5 h. The supernatant solution of the reaction mixture was separated and dried under vacuum. The obtained colourless solid was redissolved into 1 mL of THF, and 10 mL of hexane was layered on it. This solution was stored at 243 K overnight and 1.55 g (51%) of colourless crystals were obtained. 19F NMR : δ −134.72 , −162.85 , −165.17 ; 11B NMR : δ −36.71 .The title compound was prepared by the reaction of NaH  and (CUiso(H) = 1.2Ueq(C), while the H atoms on boron were refined isotropically [refined B—H = 1.08 (3)–1.13 (2) Å].Crystal data, data collection and structure refinement details are summarized in Table 110.1107/S2056989019017201/is5529sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989019017201/is5529Isup3.hklStructure factors: contains datablock(s) I. DOI: 1973896CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


CPNC crystallizes in the monoclinic non-centrosymmetric space group Cc and adopts an s-cis conformation with respect to the ethylenic double bonds (C=O and C=C). The crystal packing features C—H⋯O and C—H⋯π interactions whose percentage contribution was quantified by Hirshfeld surface analysis. Quantum chemistry calculations including geometrical optimization and molecular electrostatic potential (MEP) were analysed by density functional theory (DFT) with a B3LYP/6–311 G++ basis set.A new conjugated carbazole chalcone compound, ( The experimental and theoretical studies and chemical reactivity analysis are discussed.In a continuation of our studies  Å , 1.223 Å (DFT)] and carbon–carbon double bond  Å , 1.348 Å (DFT)]. The CPNC molecule is twisted slightly at the C21—C22 bond, with a C20—C21—C22—C27 torsion angle of −10.4 (3)° . The experimental and theoretical C15—C16—C19—C20 torsion angles are 158.6 (3) and 178.8°, respectively. The 9-phenylcarbazole C13—N1 bond is also observed to be twisted .There is also a twist [dihedral angle = 25.30 (17)°] between the mean planes of the nitrophenyl group  and the enone unit . Meanwhile, the enone bridge forms dihedral angles of 31.52 (18) and 21.77 (16)°, respectively, with the C13–C18 phenyl ring and the 9H-carbazole unit and the C13–C18 phenyl ring subtend a dihedral angle of 53.26 (10)°, which is similar to the dihedral angle of 53.8 (3) between the bridge aromatic ring and the 9H-carbazole unit in the related compound 2-[4-(9H-carbazol-9-yl)benzylidene]-2,3-dihydroinden-1-one ° . This planar nature is possibly due to steric repulsion by the hydrogen atoms of the aromatic rings, leading to a small π-electron delocalization. However, the phenyl ring of the 9-phenylcarbazole moiety subtends a large dihedral angle to the nitrobenzene group of 56.74 (10)° , which tends to suppress the extension of the conjugation effect through the enone moiety.The 9)° Fig. 1c. This )° Fig. 1d, whichb-axis direction via C15—H15A⋯O1 interactions  sites in the red-coloured region, while the blue colour indicates the electrophilic (electron-deficient) site localized on the hydrogen atom. These reactive sites are responsible for intermolecular interactions where the red and blue spots suggest the strongest repulsion site (electrophilic attack) and strongest attraction site (nucleophilic attack), respectively. The MEP results are further supported by the electrostatic potential contour map showing the iso-surface lines shown in Fig. 6b where the red lines refer to the strong electron-withdrawing atoms such as in carbonyl and nitro substituents.The reactive sites of a molecule can be investigated using molecular electrostatic potential (MEP) analysis phenyl]prop-2-en-1-one benzylidene]indan-1-one °] indicates a slight twist, which is which comparable to that in ISADOW [C8—C10—C11—C12 = 178.6 (2)°].A search of the Cambridge Structural Database carbazole (5 mmol) were dissolved in 20 mL of methanol and then a catalytic amount of sodium hydroxide solution  was added dropwise under continuous stirring for about 5–6 h at room temperature until a precipitate formed. This was filtered off, washed successively with distilled water and recrystallized from acetone solution, yielding orange block-shaped crystals suitable for X-ray diffraction analysis.4′-Nitroacetophenone (5 mmol) and Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989020002054/ex2028sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020002054/ex2028Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020002054/ex2028Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989020002054/ex2028sup3.docxSI Comparison between the calculated optimized and X-ray geometrical parameters for the CPNC compound. DOI: 1967669CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Trypanosoma brucei has been greatly facilitated by using CRISPR/Cas9 as a genome editing tool. To date, this has entailed using a limited number of cell lines that are stably transformed to express Cas9 and T7 RNA polymerase (T7RNAP). It would be desirable, however, to be able to use CRISPR/Cas9 for any trypanosome cell line.Generation of knockouts and in situ tagging of genes in We describe a sequential transfection expression system that enables transient expression of the two proteins, followed by delivery of PCR products for gRNAs and repair templates. This procedure can be used for genome editing without the need for stable integration of the Cas9 and T7RNAP genes. Trypanosoma brucei entails creating cell lines which express (either constitutively or inducibly) both Cas9 to generate a DNA double-strand break and T7RNAP for the transcription of guide RNAs from a DNA template [T. brucei [The establishment of genome editing by CRISPR/Cas9 in trypanosomatids has greatly increased the ease with which knockouts can be generated, as two copies of a non-essential gene can often be deleted in a single round of transfection. The system most widely used for template –4. The o. brucei . FurtherT. brucei. The plasmid All-in-one-Cas9  in T. brucei Lister 427 procyclic forms that already expresses Cas9 and T7RNAP constitutively (Lister 427/Cas9) [To test the functionality of the plasmid, we used the LeishGEdit software  to desig27/Cas9) . This gaFor genome editing by transient expression of Cas9 and T7RNAP, we tested two different transfection schemes. Initially, all components were transfected simultaneously: the circular plasmid pAi1C9 encoding Cas9 and T7RNAP, the DNA template for in vivo transcription of a guide RNA, and the DNA repair template harbouring mNG for C-terminal tagging and a hygromycin resistance gene. This procedure gave few hygromycin-resistant clones, only 10 clones in total, from 4 separate transfections. These clones either did not express mNG (4 clones), or expressed it as a cytoplasmic protein 2 clones) or expressed it correctly localised to the flagellum (4 clones). Examples are shown in Fig.  clones oWe therefore tested sequential transfections in which we first used pAi1C9 to enable expression of Cas9 and T7RNAP. A second transfection 20 h later provided the templates for the gRNA and the mNG repair construct. The same electroporation conditions were used for the plasmid and the templates , which are non-essential genes in cultured procyclic form . brucei . Genotyp7T. b. brucei 427 procyclic forms were transfected with 10 µg pAi1C9 dissolved in 100 µl TbBSF transfection buffer [2 for 20 h.4 × 10n buffer . Cells wn buffer  supplemeThe entire culture from the first transfection was centrifuged at 1700 g for 5 min, the supernatant discarded and the cells resuspended in 100 µl TbBSF transfection buffer containing the pooled PCR products (see protocol for PCRs below). For tagging, one sgRNA template (targeted to the 3′ end of the ORF) and one repair template (hygromycin resistance) were provided; to generate the knockouts, we provided two sgRNA templates (targeted to the 5′ and 3′ ends of the ORF) and two repair templates (hygromycin and neomycin resistance genes).−1 Hygromycin B and/or 15  µg  ml−1 Geneticin; stable clones were obtained 2 weeks post selection.Transfection was performed as described above and the cells were transferred to 10 ml SDM79 supplemented with 10% FBS. The cells were diluted 1:5, 1:50 and 1:500 in conditioned medium (fresh medium + 20% supernatant of a log-phase culture) and distributed into 24-well plates (1 ml in each well). Transformants were selected using 25  µg  ml1 μl G00 primer (0.5 μM)4 μl 5 x Phusion HF buffer0.5 μl dNTP mix (250 μM)1 μl sgRNA primer (0.5 μM)0.2 μl Phusion High-Fidelity DNA polymerase (0.4U)2O13.3 μl H1st PCR: template for sgRNAs; two 20 µl reactions per target.30′′, 98 °C10′′, 98 °C30′′, 60 °C15′′, 72 °Cgo to step 2, 35 cycles in total10′, 72 °Chold at 10 °CProgram:2 μl 60 ng pPOTv7 mNG (hygro or G418) plasmid8 μl 5 x Phusion HF buffer1 μl dNTP mix (250 μM)2 μl Upstream forward primer (0.5 μM)2 μl Downstream reverse KO/TAG primer (0.5 μM)0.4 μl Phusion High-Fidelity DNA polymerase (0.4U)2O24.6 μl H2nd PCR: template for resistance gene; two 40 µl reactions per resistance gene5′, 94 °C30′′, 94 °C30′′, 65 °C2′30′′, 72 °Cgo to step 2, 40 cycles in total10′, 72 °Chold at 10 °CProgram:Reactions were performed with reagents from New England Biolabs: Phusion High-Fidelity DNA polymerase (M0530S), 5 x  Phusion HF buffer (B0519S) and dNTP mix N0447S). Cycling conditions are identical to those previously published 47S. Cycl.1st PCR:PCR reactions were pooled and extracted with 1 volume water-saturated phenol (pH 8), followed by extraction with 1 volume chloroform. DNA was precipitated from the aqueous phase by addition of 0.1 volume 3 M sodium acetate, pH 5.2, and 3 volumes ice-cold ethanol. The DNA was pelleted by centrifugation, washed twice with 1 ml 80% ethanol, air-dried at room temperature, dissolved in 40 μl Milli-Q-water and stored at − 20 °C until transfection.G00: aaaagcaccgactcggtgccactttttcaagttgataacggactagccttattttaacttgctatttctagctctaaaacPDEB1 3′ sgRNA primer:gaaattaatacgactcactataggTGAAGAAGTCAGTTGACCGGgttttagagctagaaatagcTrypanin 5′ sgRNA primer:gaaattaatacgactcactataggCAAAAACGAGAAGAGCCTACgttttagagctagaaatagcTrypanin 3′ sgRNA primer:gaaattaatacgactcactataggAGGTGTTGTGGTTCACACGTgttttagagctagaaatagcGPI8 5′ sgRNA primer:gaaattaatacgactcactataggCGGTTGCAAAAAACGAATGCgttttagagctagaaatagcGPI8 3′ sgRNA primer:gaaattaatacgactcactataggGGTATGTCCCATCAGTTGGAgttttagagctagaaatagcTrypanin upstream forward primer:TACTTTTCAGACTGCATCGTGGCGTACCCCgtataatgcagacctgctgcTrypanin downstream reverse KO primer:CTGCAACAAAGCCGTAACTTGGAACAACCAccggaaccactaccagaaccPDEB1 downstream forward primer:ACGAGTTCTGGCAACAACAGCAGTACTCGTggttctggtagtggttccggPDEB1 downstream reverse TAG:ATCACCATTGACAAGAACGTACATCTACCAccaatttgagagacctgtgcGPI8 upstream forward primer:TTGGATCAGGCGCTTGCATATTTATTTCCAgtataatgcagacctgctgcGPI8 downstream reverse KO primer:AGTTTCAGGAAGGAAGTTCGTTTTTCTCCTccggaaccactaccagaaccT. brucei cell line. Moreover, in contrast to stable integration of the CRISPR/Cas9 machinery, transient transfection does not require additional selectable markers and it has the added advantage that it circumvents possible Cas9 toxicity. In addition to using Cas9 for deletion, mutation, tagging or integration of ectopic copies, this procedure could also be adapted for nuclease inactive Cas9 variants for targeting RNAs or epigenetic modifications [Transient transfection with pAi1C9 gives rise to fewer clones than cell lines that are stably transformed with the T7RNAP and Cas9 genes. It has the advantage, however, that it can be applied to any ications , 15.Additional file 1: Validation of knockout (KO) clones. A+B Trypanin-KO (Tb427.10.6350). A Clonal selection of stable transformants in 24-well plates. Dilutions from transfected pool cultures and number of cells seeded are indicated. Circles depict wells containing cells with successful (green filled circle) or unsuccessful (○) genome editing. B Assessment of editing by genotyping PCR and agarose gel electrophoresis. Genes amplified from genomic DNA and target loci are indicated. Lanes corresponding to validated KO clones are marked with green circles. C+D GPI8-KO (Tb427.10.13860) in a cell line allowing inducible expression of an ectopic copy of GPI8. C as in A. D as in B. E List of primers used for genotyping PCRs of Trypanin-KO (left panels) and GPI8-KO (right panels).


The heterocyclic portion of the tetrahydroisoquinoline unit is planar and an intramolecular N—H⋯N hydrogen bond and a C—H⋯π(ring) interaction help to determine the overall conformation. In the crystal, O—H⋯O hydrogen bonds form inversion dimers, which are connected by C—H⋯O hydrogen bonds, forming layers parallel to  interaction help to determine the overall conformation. In the crystal, a layer structure with the layers parallel to (10In the title molecule, C A puckering analysis  Å, θ = 128.52 (14)° and φ = 286.46 (18)°. The conformation of this ring approximates an envelope with C3 as the flap.The title compound crystallizes in space group it Fig. 1. The C5/g Table 1 and placts Fig. 1. AlthougA⋯O1 hydrogen bonds (Table 1i and O1⋯O2i  contacts of 2.8774 (16) and 2.8674 (14) Å , respectively. The dimers are connected by C13—H13⋯O2 hydrogen bonds  Figs. 2 and 3 ▸.et al., 2016et al., 2010et al., 2017a2CO2CH3 group on sulfur , the sites of the intermolecular O—H⋯O and C—H⋯O hydrogen bonds can be seen on the left side near the bottom and at the top, respectively. A weaker point of interaction is at O3 on the lower right of the diagram, which might indicate a weak, intermolecular C4—H4B⋯O3 hydrogen bond since the O⋯H distance is 2.605 (15) Å. The surfaces mapped over shape-index  and curvedness  show a relatively flat region over the C23–C28 benzene ring in the latter and a red triangular area over the edge of the ring in the former. This is suggestive of a C—H⋯π(ring) interaction and can be identified with the C20—H20A⋯Cg3 interaction noted in Section 2. The fingerprint plots derived from the Hirshfeld surface enable the apportionment of the intermolecular interactions into specific sets. Fig. 5a displays the plot for all interactions while Fig. 5b–5d show those delineated into H⋯H, H⋯O/O⋯H and H⋯N/N⋯H interactions, which constitute 47.3%, 11.8% and 10.6% of the total interactions, respectively.Hirshfeld surface analysis is an effective means of probing intermolecular interactions -thione (10 mmol), N-phenyl-2-chloroacetamide (10 mmol) and sodium acetate trihydrate  in ethanol (100 mL) was heated under reflux for one hour. The precipitate that formed after standing at room temperature overnight was collected, washed with water, dried in air and then recrystallized from ethanol to afford the title compound in the form of colorless crystals. Yield: 4.00 g, 82%; m. p.: 470-472 K.A mixture of 7-acetyl-4-cyano-1,5-dimethyl-6-hydroxy-8-phenyl-5,6,7,8-tetrahydroisoquinoline-3 and 7.02–7.04 (J = 8 Hz) can be attributed to the aromatic protons.With regard to the −1): 3522 (OH); 3277 (NH); 3058 ; 2920, 2970, 2991 ; 2217 (C≡N); 1694 ; 1667 .IR : 10.22 ; 7.53–7.55 ; 7.23–7.29 ; 7.17–7.20 ; 7.02–7.04 ; 4.84 ; 4.52–4.54 ; 4.09–4.19 ; 3.25–3.29 ; 2.94–2.96 ; 2.89–2.94 , 2.11 ; 1.92 ; 1.28 .Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989021000372/vm2243sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989021000372/vm2243Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021000372/vm2243Isup3.cmlSupporting information file. DOI: 2055318CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Scientific Reports 10.1038/s41598-019-48199-w, published online 23 August 2019Correction to: The original version of this Article contained errors.In Table 1, in the penultimate column the incorrect symbol for Chi-square was used in the column heading.2 (df)c”“xnow reads:2 (df)c”“χ15 and LC30 were incorrectly reported, due to mistranscription of the exponent values. As a result, the originally reported values were three orders of magnitude too high.Further, Table 3 contained an error. The standard errors for the control, LCr, the values for ‘Control (Mean ± SE)’, ‘LC15 (Mean ± SE)’ and ‘LC30 (Mean ± SE)’,For the parameter “0.302 ± 5.413a, 0.275 ± 5.022b and 0.196 ± 3.035b”now read:“0.302 ± 0.0054a, 0.275 ± 0.0050b and 0.196 ± 0.0030b”λ, the values for ‘Control (Mean ± SE)’, ‘LC15 (Mean ± SE)’ and ‘LC30 (Mean ± SE)’,For the parameter “1.353 ± 7.325a, 1.317 ± 6.617b and 1.217 ± 3.695b”now read:“1.353 ± 0.0073a, 1.317 ± 0.0066b and 1.217 ± 0.0037b”.1, but although the correct Equations were used for calculations, the incorrect Equations were included in the original version of the Article.In the Materials and Methods section under subsection ‘Data Analysis’, Equations (8) and (9) were incorrectly reported. The authors used the notation provided in the original study describing these Equations. This study was subsequently correctedTherefore, Equation (8),In addition, Equation (9),now reads:In the same subsection, under Equation (9):81 using TWOSEX-MS Chart with 100,000 replicates53,82.”“Population growth (mean and standard error) was calculated through paired bootstrap testnow reads:81 using TWOSEX-MSChart with 100,000 replicates53,82.”“Population parameters were calculated and compared through paired bootstrap testReferences 78 and 79 were incomplete and were incorrectly listed as ‘Finney, D. ’ and ‘Huang, Y. B. & Chi, H. The age-stage, two-sex life table with an offspring sex ratio dependent on female age (2011)’ respectively. The correct references are given below.Finney, D. J. Probit Analysis. Cambridge University Press, Cambridge (1971).Journal of Agriculture and Forestry60(4), 337–345 (2011).Huang, Y. B. & Hsin Chi. The age-stage, two-sex life table with an offspring sex ratio dependent on female age. Furthermore, in the Supplementary Materials file, the title,CHS1) in melon aphid, Aphis gossypii”“Impact of low-dose buprofezin on the biological traits and expression profile of chitin synthase 1 gene (now reads:CHS1) in melon aphid, Aphis gossypii”“Impact of low lethal concentrations of buprofezin on biological traits and expression profile of chitin synthase 1 gene (These errors have now been corrected in the HTML and PDF versions of this Article, and in the accompanying Supplementary Materials.Supplementary file1


H-pyrrol-2-yl]acetate dihydrate, Na+·C15H14NO3−·2H2O, contains two sodium cations, two organic anions and two water molecules. The title compound exhibits analgesic, anti-inflammatory and antipyretic activities.The asymmetric unit of the title two-dimensional polymer, sodium 2-[1-methyl-5-(4-methylbenzoyl)-1 H-pyrrol-2-yl]acetate dihydrate, Na+·C15H14NO3−·2H2O, contains two sodium cations, two organic anions (A and B) and two water molecules. The coordination geometry around the sodium cations corresponds to a distorted octahedron. Each pair of sodium cations (A–A or B–B) is chelated by two bridging anions coordinated by the O atoms of the deprotonated carboxylic groups, and each sodium atom is coordinated by an O atom of a third anion, which connects pairs of sodium atoms, and a water molecule. As a result, a two-dimensional polymer is formed in the crystal. Hirshfeld surface analysis and two-dimensional fingerprint plots were used to analyze the intermolecular contacts present in the crystal.The asymmetric unit of the title compound, sodium 2-[1-methyl-5-(4-methylbenzoyl)-1 The coordination geometry around the sodium cations corresponds to a distorted octahedron. Each pair of sodium cations (A–A or B–B) is chelated by two bridging anions coordinated by the O atoms of the deprotonated carboxylic groups, and each sodium atom is coordinated by an O atom of a third anion, which connects pairs of sodium atoms, and a water molecule. As a result, a two-dimensional polymer is formed in the crystal , 2.416 (2) and 2.441 (2) Å while the Na—Owater distances are on average slightly longer, being in the range 2.364 (2)–2.607 (3) Å. It is worth noting that the terminal atom O2B does not interact with a sodium cation.The sodium salt of the Cte Fig. 1. The asyal Fig. 2. The Na—A, 1.243 (3) and 1.250 (3) Å in anion B] are very similar to each other and are slightly elongated in comparison with the standard value of 1.210 Å of a carbonyl group  and 1.250 (3) Å in anion A and −29.0 (4)° in molecule B. The relative orientation of the toluene ring with respect to the pyrrole ring, neither planar nor perpendicular, is given by the the C6—C8—C9—C10 torsion angle: 41.3 (4)° in molecule A and −38.2 (4)° in molecule B. Such an orientation mainly minimizes the intermolecular H⋯H repulsions.The toluene substituent is in a synperiplanar conformation with respect to the C5—C6 bond of the pyrrole ring: the C5—C6—C8—C9 torsion angle is 26.9 (4)° in molecule In the crystal, O—H⋯O hydrogen bonds Table 1 are formCrystal Explorer 17.5  to 1.384 (blue). The areas colored red on the dnorm-mapped Hirshfeld surfaces acetate skeleton yielded only two hits, 2-methoxyphenyl 2-{2-[1-methyl-5-(4-methylbenzoyl)pyrrol-2-yl]acetamido}acetate tetrakisdicopper(II)  or 1.5Ueq.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989021000414/zq2259sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021000414/zq2259Isup2.hklStructure factors: contains datablock(s) I. DOI: 2055407CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Oxm⋯NOxm, O—HHydr⋯OHydr, O—H′Hydr⋯OHydr and O—HOxm⋯OHydr hydrogen bonds link the molecules into infinite chains along the c-axis direction.The phenyl rings are almost oriented perpendicularly. In the crystal, intermolecular O—H N-hydroxyimino)-1,2-diphenylethanol], C14H13NO2, consists of hydroxy phenylacetophenone and oxime units, in which the phenyl rings are oriented at a dihedral angle of 80.54 (7)°. In the crystal, intermolecular O—HOxm⋯NOxm, O—HHydr⋯OHydr, O—H′Hydr⋯OHydr and O—HOxm⋯OHydr hydrogen bonds link the molecules into infinite chains along the c-axis direction. π–π contacts between inversion-related of the phenyl ring adjacent to the oxime group have a centroid–centroid separation of 3.904 (3) Å and a weak C—H⋯π(ring) interaction is also observed. A Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (58.4%) and H⋯C/C⋯H (26.4%) contacts. Hydrogen bonding and van der Waals contacts are the dominant interactions in the crystal packing.The title compound [systematic name: 2-( The dihedral angle between the oxime plane C (O1/N1/C7) and phenyl rings A and B are 39.48 (9) and 80.11 (14)°, respectively. The base of the oxime moiety is approximately coplanar with the A phenyl ring plane, as indicated by the O1—N1—C7—C1 torsion angle of 1.0 (3)°. In the oxime moiety, the O1—N1 [1.4026 (18) Å] bond length and the O1—N1—C7 [115.36 (14)°] bond angle may be compared with the corresponding values of O1—N2 [1.423 (3) Å], O2—N3 [1.396 (3) Å], O2—N3—C10 [111.5 (2)°] and O1—N2—C9 [109.4 (2)°] in the glyoxime moiety reported in 1-propane-1,2-dione dioxime  and a weak C—H⋯π(ring) interaction  powder was purchased from Merck, and crystallized by slow evaporation from a concentrated solution in ethanol as colourless crystals at room temperature.The alpha-benzoinoxime [ABO (CUiso(H) = 1.2Ueq(C). The hydrogen attached to O2 is disordered over two sites (H2 and H2′) in a 0.5:0.5 ratio and was refined with restraints.Experimental details including the crystal data, data collection and refinement are summarized in Table 310.1107/S2056989020016163/pk2654sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020016163/pk2654Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020016163/pk2654Isup3.cmlSupporting information file. DOI: 2049764CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The quinoline moiety of the title quinoline carboxamide derivative is not planar as a result of a slight puckering of the pyridine ring. The secondary amine has a slightly pyramidal geometry. 26H25N3O, is described. The quinoline moiety is not planar as a result of a slight puckering of the pyridine ring. The secondary amine has a slightly pyramidal geometry, certainly not planar. Both intra- and intermolecular hydrogen bonds are present. Hirshfeld surface analysis and lattice energies were used to investigate the intermolecular interactions.The structure of the title quinoline carboxamide derivative, C The mean plane of this ring makes a dihedral angle of 7.49 (13)° with the mean plane of the benzene ring of the quinoline moiety. The angles between the mean planes of the quinoline ring and the benzene rings with pivot atoms C321 and C411 are 28.99 (11) and 59.16 (11)° respectively. The dihedral angle between the mean plane of these benzene rings is 64.71 (14)°.An ellipsoid plot for compound anti conformation placing the quinoline ring trans in relation to the ring with pivot atom C321. The amide group atoms are essentially coplanar with the quinoline ring with deviations of −0.034 (3), (C31), −0.009 (2) (O31), 0.009 (2), (N32) and 0.145 (3) Å (C321). The geometric arrangement of the amide permits the formation of an intramolecular hydrogen bond between the amine hydrogen atom and the carboxyl group of the amide, N41—H41⋯O31; geometric parameters are given in Table 1The amide group attached to C3 is coplanar with the quinoline ring system. The C—N rotamer of the amide has an sp3 hybridization of N41. An inspection of the amine bond lengths shows that there is a slight asymmetry of the electronic distribution around it: C4—N41 = 1.364 (3) Å while N41—C411 = 1.437 (4) Å, suggesting there is higher density between the nitrogen and the carbon atom of the quinoline ring system. However, these bonds and angles are typical for a Cquinoline–NH–C–R group, see the Database Survey below. As a consequence of the screw-boat pucker of the pyridine ring, the C4—N41 bond is displaced from the pyridine mean plane with a deviation of 0.159 (2) Å for N41; atom C411 is displaced by 0.965 (3) Å and consequently, the N41—C411 bond lies further from the mean plane.The secondary amine has a slightly pyramidal geometry, certainly not planar. The angles C411—N41—C4, C41—N41—H41 and C411—N41—H41 are 125.7 (2), 112 (2) and 115 (2)°, respectively, the sum of which (352.7°) is less than 360°; in addition, atom H41 lies 0.41 (3) Å out of the C4/N41/C411 mean plane, confirming the x + y + z + 1), hydrogen bonds, forming C6 chains which run parallel to the a-axis formed by the action of the 21 screw axis at (x + y + z + 1) hydrogen bond, Table 1B⋯O31, both involve atom O31 as an acceptor and link the chains described above to form a sheet which extends along the b-axis direction.In the crystal, the molecules are linked by N32—H32⋯N1, polarization (Epol = −52.8 kJ mol−1), dispersion (Edisp = −251.6 kJ mol−1) and repulsion (Erep = 210.4 kJ mol−1). The dispersive energy contributes the most to the total stabilization energy of the lattice, in addition to the C—H⋯O hydrogen bonds, and to the C—H⋯π interaction. The stabilization energy comes from six sub-structural motifs made by the molecule pairs I to VI that are shown in Figs. 3−1 for the lattice, half of it, −184.7 kJ mol−1 attributed to the  molecule. That energy corresponds approximately to 88% of the total stabilization energy of the network.Hirshfeld surfaces , there are high percentages of C⋯H/H⋯C close contacts (27.0%) and of N⋯H/H⋯N close contacts (6.5%), see Table 2The percentages of atom⋯atom close contacts taken from the FP plot , as can be identified by the red spots in the Hirshfeld Surface  hydrogen bonds, forming C6 chains which run parallel to the a-axis direction, formed by the action of the 21 screw axis at (x + y + z + 1) hydrogen bond, Figs. 3The nitrogen atom N32 acts as a donor for N1 (N32—H32⋯N1). N1 also acts as an acceptor for C6, making a C6—H6⋯N1 hydrogen bond, seen as a red spot in Fig. 9c-axis direction, as a result of the propagation of the molecule pairs IVa/IVb depicted in Fig. 6In addition, the C—H⋯π interaction can also be identified in the HS of the molecule, Fig. 9Va/Vb and VIa/VIb, which are also illustrated in Figs. 7x, y, z (green-coloured molecule) and −x + y + 1, z − x + y + 1, z + Va/Vb and x − y + z + 1/x − y + z + 1 for VIa/VIb. Although these molecules do not exhibit atom⋯atom close contacts, each pair provides a significant contribution to the overall lattice stabilization energy of −14.5 and −11.3 kJ mol−1, respectively for V and VI. The grey molecules drawn in this figure indicate a possible pathway for electronic delocalization within the network of molecules.Apart from the sub-structural motifs described, there are two extra molecule pairs, identified as et al., 2016et al., 2007N,N-dimethylamino)propylamino]-3-nitroquinoline; Boyd et al., 19921, viz. 1.325 and 1.335 Å for the two molecules in the asymmetric unit of SEZJIR and 1.320 Å in PABPUD. The corresponding value in 1 is 1.364 (3) Å.A search of the Cambridge Structural Database -N-(5-fluoro-1H-indazol-3-yl)quinolin-4-amine methanol solvate; Haile et al., 2016aryl—N distances lie in the range 1.396 to 1.438 Å with an average value of 1.418 Å and an average Cquinoline—N—Csp3aryl/ angle of 126.105°. In the second case, the Csp3aryl/—N distances lie in the range 1.439 to 1.478 Å with an average value of 1.458 Å, with an average Cquinoline—N—Csp3aryl/ angle of 123.98°.The situation is more complex for the N—Cet al. sulfanyl]-N-phenylquinolin-4-amine; Florke & Egold, 2016et al., 2000N-[2-(2-phenylvinyl)phenyl]quinolin-4-amine; Mphahlele & Mphahlele, 2011As noted above, the conformation around the amino N atom is slightly pyramidal. In their paper on bond lengths in organic compounds, Allen  al. 2006 discuss N-(4-fluorophenyl)-6-methylquinoline-3-carboxamide; Govender et al., 2018N-isopropyl-6-methyl-2-phenylquinoline-3-carboxamide; Benzerka et al., 20101.There are two compounds in the database which have an amide group attached to C3, GICGIL  were refined. The latter was refined since it is involved in a short contact with H32, which is attached to N32. Although in the riding model for H2 the H-atom position is within the highest contour on the difference map, it is not at the centre. In the refined model it is. The H⋯H distances are 1.87 and 1.93 Å for the riding and refined models, respectively. The angles around C2 are N1—C2—C3 = 125.9 (3) and 125.9°(3); N—C2—H2 = 117 and 111.9 (17)° and C3—C2—H2 = 117 and 122.2 (17)° for riding and refined H atoms, respectively. In the case of H32, the N32—H32 distance changes from 0.89 (3) to 0.90 (4) Å and the angle C31—N32—H32 changes from 120 (2) to 119 (2)° for riding to refined, respectively, which are really insignificant shifts. Hence, in this case the short contact does induce a shift in the angular position of H2 from its calculated position.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989020000298/zl2767sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020000298/zl2767Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020000298/zl2767sup3.tifSpectra. DOI: 1879928CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


After annealing 52Rh/48Fe(001) bilayers above 600 °C the αlʹ phase increases in grain size and either develops into αhʹ with high magnetization  or remains in the αlʹ phase. In contrast to αlʹ, the αhʹ ↔ αʺ transition in the αhʹ films is completely suppressed. When the annealing temperature of the 45Rh/55Fe(001) samples is increased from 450 to 800 °C the low-magnetization nanocrystalline αlʹ films develop into high crystalline perfection epitaxial αhʹ(001) layers, which have a high magnetization of ~ 1,275 emu/cm3. αhʹ(001) films do not undergo a transition to an antiferromagnetic αʺ phase. In 68Rh/32Fe(001) samples above 500 °C non-magnetic epitaxial γ(001) layers grow on the Fe(001) interface as a result of the solid-state reaction between the epitaxial αlʹ(001) and polycrystalline Rh films. Our results demonstrate not only the complex nature of chemical interactions at the low-temperature synthesis of the nfm-B2 and αlʹ phases in Rh/Fe(001) bilayers, but also establish their continuous link with chemical mechanisms underlying reversible αlʹ ↔ αʺ transitions.Here we first report results of the start of the solid-state reaction at the Rh/Fe(001) interface and the structural and magnetic phase transformations in 52Rh/48Fe(001), 45Rh/55Fe(001), 68Rh/32Fe(001) bilayers from room temperature to 800 °C. For all bilayers the non-magnetic nanocrystalline phase with a B2 structure (nfm-B2) is the first phase that is formed on the Rh/Fe(001) interface near 100 °C. Above 300 °C, without changing the nanocrystalline B2 structure, the phase grows into the low-magnetization modification α Kαʺ→αʹ ~ 100 °C between antiferromagnetic (AFM) αʺ and ferromagnetic (FM) αʹ phases in a narrow (0.48 < xRh < 056) concentration interval in chemically ordered B2-FeRh alloys1. This transition is accompanied by an isotropic volume expansion of ~ 1% of the B2-FeRh unit cell, which not only radically changes the magnetic properties, but also changes the entropy3 and resistivity4. The magnetostructural αʺ → αʹ (AFM-FM) transition gives existence to the giant magnetostriction5 large magnetoresistance7 and magnetocaloric effects8 in B2-FeRh alloys. Numerous studies of bulk samples indicate that the starting temperature TKαʺ→αʹ and characteristics of the αʺ → αʹ transition may be modified by variations the magnetic field10, microstructure11, thermal treatment12, energetic ion irradiation13, stress14 and hydrostatic pressure17 and can also be tuned over a wide temperature range (100–600 K) by chemical substitution18. Although bulk B2-FeRh samples exhibit a sharp transition with a small thermal hysteresis, thin films and nanoparticles often have an incomplete and broad asymmetrical hysteresis AFM-FM transition34. The starting transition temperature TKαʺ→αʹ and magnetic properties in B2-FeRh films depend not only on compositional variations34, but are also highly sensitive to the type of substrate35, the thickness of the thin film samples30, the nature underlayers36 and the capping layers31. Significant stresses arise at the film/substrate interface24, which makes it possible to control the magnetic and electrical transport properties of B2-FeRh films on ferroelectric substrates40 by varying the external electric field. Many groups using magnetron sputtering or molecular beam epitaxy achieved epitaxial B2-FeRh(001) films grown on MgO(001) crystalline substrates. In most studies high-temperature heat treatments above 600 °C were used to obtain the high crystalline quality of chemically B2-ordered phase33. However, chemical interactions of Rh with Fe and solid-state synthesis of the Rh-Fe phases at the Rh/Fe interface remain completely uninvestigated.An intriguing feature of the equilibrium diagram of the Fe-Rh system is the existence of the low-temperature transition at TRh < 056) concentration interval and the reaction products for 45Rh/55Fe(001) and 68Rh/32Fe(001) samples lie in Fe-rich and Rh-rich regions of the Fe–Rh system. The main purpose of this article is to show the complex and intricate nature of the B2-FeRh phases synthesis, which begins to form on the Rh/Fe interface at ~ 100 °C.In this work, we describe the solid-state reactions between polycrystalline Rh with epitaxial Fe(001) films in 52Rh/48Fe(001), 45Rh/55Fe(001) and 68Rh/32Fe(001) bilayers with 52Rh:48Fe, 45Rh:55Fe and 68Rh:32Fe atomic ratios, respectively. Under these conditions, the reaction products of 52Rh/48Fe(001) fall into the  transition and a high-ferromagnetic αhʹ with a magnetization ~ 1,220 emu/cm3 and with a completely depressed αhʹ → αʺ transition. As the annealing temperature increases above 600 °C the reaction products contain a mixture of epitaxial αlʹ(001) and αhʹ(001) grains. Figure 4(Ta)/K40 and the MS(Ta)/MS0 relative magnetization as a function of the annealing temperature Ta {where for 52Rh/48Fe(001) samples K40 = 2.4∙105 erg cm3 and MS0 = 825 emu/cm3, see “a the constant K4(Ta) monotonically decreases and becomes zero within experimental accuracy after annealing at 800 °C. This means that the first magnetic anisotropy constant K1 of the B2—ordered FeRh phase is zero or less than the measurement error (0.2 × 104 erg/cm3). A value of K1 ~ 0 is consistent with the FeRh single films exhibiting an in-plane easy axis of magnetization with no measurable magnetocrystalline anisotropy41. Therefore, the K4(Ta)/K40 dependence can be used to find the thickness, magnetization and magnetic moment of the reacted Fe(001) layer after annealing at Ta /K40 and the relative magnetization MS(Ta)/MS0 decrease identically as the annealing temperature increases up 300 °C. The synchronous decrease of the K4(Ta)/K40 and MS(Ta)/MS0 values clearly proves the onset of the slow mixing of the Rh and Fe layers and the synthesis of the nonferromagnetic B2-FeRh(001) phase (nfm-B2) on the Rh/Fe(001) interface, whose volume increases with an increase in annealing temperature to 300 °C. Above 300 °C the magnetization increases to MS/MS0 ~ 1, which indicates a phase transformation of the nfm-B2 to the ferromagnetic αlʹ phase. From Fig. lʹ/Fe (001) has the magnetization of the initial sample MS0 = 825 emu/cm3 (MS/MS0 ~ 1) in the temperature range (350–500 °C), which means that only the Fe atoms contribute to the saturation magnetization of αlʹ-FeRh. Surprisingly, after annealing at 550 °C, the saturation magnetization decreases to 660 emu/cm3 (~ 20%), but the reaction product layer participates completely in the reversible αlʹ ↔ αʺ transition  film at the αlʹ-FeRh(001)/Fe(001) interface. Therefore, a possible explanation is the deformation of some αlʹ-grains with a loss of ferromagnetic order. However, the question about the exact origin of the decrease of MS/MS0 at 550 °C remains open. All of the 52Rh/48Fe (001) samples had the same temperature dependencies of the magnetization MS (Ta) up to 600 °C. However, after annealing above 600 °C the magnetizations of MS sharply increased and assumed values that centered either around MS1 ~ 1,220 emu/cm3  or MS2 ~ 940 emu/cm3   of the synthesized layer B2-FeRh in the Rh/B2-FeRh/Fe (001) trilayer by the torque method at room temperature, after annealing at temperature Ta and after cooling in liquid nitrogen mN(Ta). To characterize the reversible αʹ ↔ αʺ transition, we introduce the value η = 1 − mN(Ta)/m(Ta) for which η = 0 is absence of transition and η = 1 is perfect transition (see “a) of the αʹ ↔ αʺ transition which has values (200–300 °C) η = 0, (400–600 °C) η > 0.95 and (700–800 °C) η = 0 for the (B) samples and η = 0.95–0.8 for the (A) samples in the specified temperature ranges. In the temperature interval 200–300 °C, the equality η = 0 is determined by the formation of a non-magnetic nfm-B2 phase. Although the αlʹ (001) layer is located between the Rh and Fe (001) layers and grows epitaxial on the surface of Fe (001) in the (400–600 °C) interval it has a reversible αlʹ ↔ αʺ transition with a low residual magnetization  samples. We hypothesize that the αʹ phase has two B2-ordered polymorphic modifications having similar lattice parameters, but different magnetic properties. In the first modification the αlʹ phase has a low magnetization about 825 emu/cm3, which is defined only by the Fe atoms with the Rh atoms not contributing to the magnetization, and the αlʹ undergoes a complete reversible αlʹ ↔ αʺ transition  samples, the Fe atoms supposedly polarize the Rh and the Rh atoms make the contribution to the saturation magnetization 1,220 emu/cm3 and in the αhʹ phase the αhʹ ↔ αʺ transition is completely suppressed  and with an increase in annealing temperature the phase sequence 52Rh/48Fe → (~ 100 °C) nfm-B2 → (300 °C) αlʹ → (600 °C) αlʹ or αhʹ is formed as shown in Fig. In experiments, all 52Rh/48Fe001) samples, after annealing each in a temperature range of 100–800 °C, were subjected to an investigation of the αʹ ↔ αʺ transition, consisting of measurements of the magnetic moment m layers on the MgO(001) surface. The K4(Ta)/K40 and MS/MS0 dependencies (where for 45Rh/55Fe(001) samples K40 = 2.5 × 105 erg cm3 and MS0 = 875 emu/cm3, see “lʹ(001) with low magnetization (MS/MS0 ~ 1.0) grows into the high quality epitaxial phase αhʹ(001) with high magnetization (MS/MS0 ~ 1.47) above 450 °C. The high quality of the chemical ordering of the αhʹ(001) films after annealing at 500 °C and 800 °C supports the order parameter S = 0.96 ± 0.02, which is more than the S = 0.90 ± 0.02 for αlʹ in 52Rh/48Fe films. This result is unexpected, since the αlʹ exists in a narrow composition range of nearly equiatomic concentration and must have a more complete B2 order than the Fe-rich αhʹ phase. The αhʹ(001) and αlʹ(001) films have the same orientation relationship with the substrate MgO(001) /K40 dependence  and the AFM-FM transition has a relatively low residual magnetization  αhʹ. Finally, we proved that even a slight Fe doping of αlʹ causes a chemical reaction between Fe and αlʹ and the start of the synthesis of the αhʹ phase. This suggests that the high magnetization αhʹ phase occurring in the 52Rh/48Fe(001) bilayer (B samples) also has more Fe content than αlʹ and explains the compositional heterogeneity arising as a result of the nonequilibrium reaction processes. Thus, we show the phase evolution 45Rh/55Fe → (~ 100 °C) nfm-B2 → (300 °C) αlʹ → (450 °C) αhʹ is induced by the solid-state-reaction method and the final reaction product is a highly B2-ordered phase αhʹ, which has a high magnetization of 1,270 emu/cm3 and in which the reversible αhʹ ↔ αʺ transition is completely suppressed.The schematic diagram in Fig. Fig. hʹ00 layers olʹ phases during annealing up to 500 °C in the 68Rh/32Fe, 52Rh/48Fe  interface  layer in the Rh/αlʹ(001) bilayer system  surface originating from the solid-state reaction Rh + αlʹ → (500 °C) γ. As shown in Fig. S(Ta)/MS0, and the K4(Ta)/K40 dependence presented in Fig. lʹ above 300 °C and the paramagnetic γ phases above 500 °C. As follows from Fig. lʹ phase exists and undergoes a reversible AFM-FM transition (η ~ 0.9) in the 300–500 °C temperature range  nfm-B2 → (300 °C) αlʹ → (500 °C)γ during thermal annealing up to 800 °C and the final reaction product contains only an epitaxial γ(001) layer on the MgO(001) surface.Figure 8Fe Fig. a and 55Rlʹ → αʺ transition, the synthesis kinetics of the nfm-B2 layer during isothermal aging at 110 °C was investigated. As stated above, deposition of Rh on Fe(001) at room temperature at any ratio of thicknesses between Rh and Fe leads to the formation of a thin interfacial nanocrystalline nfm-B2 layer. However, slight heating to 100 °C during sputtering cannot be excluded, therefore, aging of as-deposited samples was investigated at 110 °C. XRD data from the as-deposited Rh/Fe(001) bilayer and after aging up to 360 h shows a small broadened (001) superlattice and the fundamental (002) peaks of the nfm-B2 phase which did not change from aging time to 360 h  layer, which entered into a reaction with Rh at 110 °C, as a function of aging time. There is a large experimental error in the thickness dFe measurements and therefore the dependence dFe(t) is impossible to describe by an unambiguous kinetic equation, which suggests a possible growth mechanism. As shown in Fig. Fe after aging for 360 h at 110 °C is ~ 8 nm, which corresponds to the thickness dnfm-B2 ~ 17 nm of the nfm-B2 layer  interface at the temperature of the α0 h Fig. a. This m nm Fig. b. Figurelʹ around 300 °C, we investigated the evolution of the temperature dependencies of the magnetization and the thickness of the interfacial hB2-FeRh layer in the 52Rh/B2-FeRh/48Fe(001) trilayer after annealing at 280 °C, 300 °C and 350 °C. Figure nfm-B2 interlayer in the 48Rh/nfm-B2/52Fe(001) trilayer increases to a thickness around dnfm-B2 ~ 30 nm after annealing at 280 °C.  ~ 20 nm of the αlʹ layer in the B2-FeRh interlayer. This clearly proves that after annealing at 300 °C the B2-FeRh interlayer contains a mixture of 50% nfm-B2 and 50% αlʹ phases /K40 dependence /K40  < 150 °C49, Tin(Ni/Al) ~ 180 °C50, Tin(Cd/Au) = 67 °C51 in Ti/Ni, Ni/Al, Cd/Au bilayers, respectively. These temperatures are close to or coincide with the reverse martensitic transformation starting temperatures As(B2-TiNi) ~ 100 °C, As(B2-NiAl) ~ 180 °C, As(B2-CdAu) = 67 °C. The reversible αlʹ ↔ αʺ transition in B2-FeRh possesses all the characteristics of a martensitic transformation , because it can pass at high speeds53, has isotropic volume changes at the transition1, can be induced by the application of stress40 and magnetic field10, has martensitic instabilities54 and the αlʹ and αʺ lattices have a cube-on-cube orientation relationship. According to the phase diagram, the transition αlʹ ↔ αʺ has a minimum temperature Tk ~ 100 °C among other structural transformations in the Fe-Rh system. From the above, we have concluded that the initiation temperature of the reaction Tin(Rh/Fe) in the Rh/Fe bilayer coincides with the martensitic-like transition temperature TK ~ 100 °C in B2-FeRh. The coincidence of the starting temperature of the reaction between Fe and Rh and the temperature of the magnetostructural AFM-FM transition suggests common chemical mechanisms behind both phenomena, but that connection remains to be confirmed by additional experimentation.It is well established that ordered B2 alloys, such as NiTi, AuCd, NiAl have reversible low-temperature martensitic transformations, in which the high-temperature austenite B2-phase develops into a low-temperature martensitic phase through a complex process of the55 and found in the experimental study36. Competition between the αlʹ and αʺ phases during the partial crystallization suppresses grain growth and stabilizes the nano-grained B2 structures in an amorphous matrix. The formation of an amorphous phase is a quite common phenomenon in the initial stage of solid-state reactions in bilayers and multilayers, although the nature of this phenomenon is still a subject of dispute58. It is interesting to note the general features of the initial stage of the synthesis of B2 phases in Ti/Ni and Rh/Fe thin films. In Ti/Ni multilayers the amorphous phase starts near the martensitic transition temperature (~ 100 °C), which turns into B2-NiTi60 at annealing temperatures above 350 °C. Similar to Ti/Ni, the reaction in the Rh/Fe(001) bilayer starts at ~ 100 °C with the formation of the interfacial amorphous phase, which partially crystallizes. From this point the as-deposited films consist of nanocrystalline B2 grains dispersed in the amorphous matrix. This strongly suggests that both amorphous phases are amorphous martensite, which may be a universal phenomena of the solid-state synthesis of martensitic phases61. This scenario is different from the synthesis of B2-NiAl and B2-AuCd, which begin to form in Al/Ni50 and Cd/Au51 bilayers at martensitic transformation temperatures without the formation of an intermediate amorphous martensite.As mentioned above, the formation of compounds at the Rh/Fe interface starts in the temperature range 100–300 °C from the synthesis of the non-ferromagnetic nfm-B2 phase. Since this phase has only (001) and (002) B2-FeRh reflections, this means that nfm-B2 is either a martensitic-like antiferromagnetic αʺ-phase or a non-ferromagnetic martensitic variant which is stabilized by strains resulting from the non-equilibrium synthesis of the nfm-B2 phase. B2-FeRh, similar to other B2 phases of NiTi, AuCd, NiAl alloys, experiences premartensitic instabilities with the subsequent formation of the different structural variants of martensite. Our hypothesis is the amorphous phase appears above 100 °C at the Rh/Fe interface, which is then transformed into a nanocrystalline state containing B2 nanograins of martensite variants with lattice parameters close to αʺ martensite. This is consistent with the possible existence of various structural phases of FeRh, predicted by ab initio calculationsin(αhʹ) =  ~ 450 °C and Tin(γ) =  ~ 500 °C of the αhʹ and γ phases coincide with the phase transition temperatures in the Fe-rich and Rh-rich regions of the Fe–Rh system, respectively. Such an approach is justified by us for the well-studied Fe–Ni system62 and made it possible to predict phase transformations in other binary metallic systems48. Therefore, further study of solid-state reactions in Rh/Fe films, depending on the composition, will make it possible to specify the low-temperature part of the Fe–Rh phase diagram, which still remains unknown63.Analysis of the general thermodynamic characteristics and features of B2-FeRh and B2-NiTi suggests the possibility of a fabrication of the B2-FeRh compound by self-propagating synthesis  samples and the αlʹ reacted with Ph and formed the non-ferromagnetic γ phase in the 68Rh/32Fe(001)samples. Magnetic analysis has revealed that only the αlʹ undergoes the complete reversible αlʹ ↔ αʺ transition and there’s no transition in the αhʹ samples. Thus, our work not only provides an idea of how phase sequences start and develop depending on the composition of the Fe/Rh bilayers, but also suggests the interesting possibility that a similar chemical mechanism may be at play behind the low-temperature reaction of Fe and Rh and the AFM-FM transition in B2-FeRh.In conclusion, we have uncovered that regardless of the Rh and Fe thicknesses the thin nonmagnetic nanocrystalline B2-FeRh layer starts to form at ~ 100 °C and grows up to 300 °C on the Rh/Fe interface. Above 300 °C the nonmagnetic phase is converted into a low-ferromagnetic B2 α4, which coincided with the value of bulk iron K1 = 4.9 × 105 erg/cm3. The constant K4 in the (001) plane was determined by a torque magnetometer in a magnetic field H = 12 kOe. The torque curve Lǀǀ(φ) in the (001) plane was determined according to the equation 2Lǀǀ(φ) = K4Vsin4φ + 2 Ku VSin(2φ + γ), in which, in addition to the dominant 4φ-term, there is a minor 2φ-term Ku term due to the surface roughness of the MgO(001) substrate and a slight misorientation of the Fe(001) grains. In the equation Ku is uniaxial anisotropy constant, V is the volume of the film, φ is the angle between the easy axis of fourfold anisotropy and the magnetization MS, γ is the angle between the easy axis of fourfold anisotropy and the axis of the uniaxial anisotropy. The K4V value was calculated from the torque curve Lǀǀ(φ) at the maximum of the 4φ-term: 2Lmax = K4V. High quality epitaxial Fe(001)/MgO(001) films also can be obtained by various other methods as reported in the literature.At first the epitaxial Fe(001)/MgO(001) films were grown on single-crystal MgO(001) substrates by a thermal evaporation method in a vacuum chamber at a pressure of 10–6 mbar. To obtain high-quality Fe(001) films, the substrates was previously outgassed at 300 °C for 1 h and the Fe layers were deposited at 250 °C. Epitaxial Fe (001) films had the orientation ratio Fe(001),[100]||MgO(001),[110] with the MgO(001) substrate and the magnetocrystalline anisotropy constant K–6 mbar, and a working pressure of ~ 1 mTorr Ar was used during sputtering. To prevent a reaction between Rh and Fe, the Rh layer was deposited at room temperature. Under such deposition conditions the polycrystalline Rh layer was formed on the Fe(001) surface. Three different types of samples were prepared for the experiments, namely Rh/Fe (001) bilayers with Rh-rich, approximately 1Fe:1Rh and Fe-rich atomic ratios, each with a total thickness about 300 nm. The elemental chemical composition determined by energy dispersion X-ray (EDX) analysis showed sample compositions of Rh68Fe32, Rh52Fe48 and Rh45Fe55, respectively. The saturation magnetization MS0 and the magnetic fourfold anisotropy constants K40 were determined for the total volume of the 52Rh/48Fe, 45Rh/55Fe and 68Rh/32Fe bilayers, which turned out to be MS0 = 825 emu/cm3, K40 = 2.2 × 105 erg/cm3 for the 52Rh/48Fe bilayers, MS0 = 875 emu/cm3, K40 = 2.4 × 105 erg/cm3 for the 45Rh/55Fe bilayers and MS0 = 450 emu/cm3, K40 = 1.25 × 105 erg/cm3 for the 68Rh/32Fe bilayers.The starting Rh/Fe(001) bilayers were obtained by the evaporation of the Rh layers on Fe(001)/MgO(001) samples using dc sputtering in a magnetron sputtering system. The base pressure of the chamber was less than ~ 1 × 10S and the coercivity HC were measured with a vibration magnetometer in magnetic fields up to 22 kOe. All saturation magnetization measurements were monitored using the torque method64.The reversible AFM-FM phase transitions were checked using a superconducting quantum interference device (SQUID) magnetometer. Magnetic fields of H = 1.0 kOe were applied along the in-plane [100] MgO direction, which coincides with the easy axis of the Rh/Fe (001) bilayers, at all measurements in the 77–400 K temperature interval. The saturation magnetization M001/I002)1/2/1.07, where I001 and I002 are experimental integrated intensities of superstructural (001) and fundamental (002) reflections65.The formed phases were identified with a DRON-4-07 diffractometer (CuKa radiation). The epitaxial relationships between MgO(001) and the B2, γ layers that formed in the reaction products were X-ray studied with a PANalytikal X'Pert PRO diffractometer with a PIXctl detector. CuKa radiation monochromatized by a secondary graphite monochromator was used in the instrument. The order parameter for the synthesized samples at temperatures in the 600–800 °C range was estimated using the equation S =  at 40 kV. In order to protect the surface of interest from milling by the Ga + ion beam during sample preparation, a Ge layer was deposited onto the Fe-Rh film before cross-sectional sample preparation by FIB. TEM studies were carried out using a Hitachi HT7700 TEM  equipped with a STEM system and a Bruker Nano XFlash 6T/60 energy dispersive X-ray (EDX) spectrometer. The imaging and EDX spectroscopy line scans and mapping were carried out in STEM mode with an electron probe of diameter ~ 30 nm.−6 Torr for 1 h. To characterize the phase transformations the crystal structure, the magnetic moments m0(Ta) (where m0(300 K) = MS0V), the magnetic fourfold anisotropy constants K4(Ta) and the degree of the αʹ → αʺ transition η(Ta) were determined for all bilayers after annealing at each temperature Ta. In order to fully characterize the phase transformations, cross-sectional SEM images and an elemental analysis of the phases of several samples using EDX were carried out.The starting 52Rh/48Fe, 45Rh/55Fe and 68Rh/32Fe bilayers were annealed at temperatures ranging from 50 to 800 °C in increments of 50 °C. The samples were held at each temperature at a pressure of 10a) of the FM-AFM phase transition was determined for all 52Rh/48Fe, 45Rh/55Fe and68Rh/32Fe samples after annealing at each temperature in the range of 100–800 °C . The magnetic moments m0(Ta) were measured by the torque method64, after annealing at temperature Ta and cooling in liquid nitrogen mN(Ta), to find the value of the degree η(Ta). The magnetic moment m(Ta) of the synthesized αlʹ—FeRh layer in the Rh/αlʹ—FeRh/Fe(001) trilayer after annealing at temperature Ta is equal to the difference m(Ta) = m0(Ta)—K4(Ta)m0/K40 of the magnetic moments of the m0(Ta) film and the K4(Ta)m0/K40 unreacted layer of the Fe(001) layer, where K4(Ta)m0/K40 is the magnetic moments of the unreacted Fe(001) layer. After placing the sample in liquid nitrogen, only the ferromagnetic αlʹ—FeRh phase in the Rh/αlʹ—FeRh/Fe(001) trilayer is subjected to the transition into the antiferromagnetic αʺ phase and the magnetic moment m(Ta) is reduced to mN(Ta). The quantity η = 1 − mN(Ta)/m(Ta) is a quantitative characteristic of the degree of the αlʹ → αʺ transition, where η = 0 and η = 1 mean the absence of and the complete FM → AFM transition , respectively.In experiments, the degree η(TSupplementary file1 (DOCX 4798 kb)


The crystal packing features N—H⋯N hydrogen bonds, which generate [101] chains.The title structure consists of [Ni(CN) 10H10N3)2[Ni(CN)4], the dihedral angle between the pyridine rings in the cation is 1.92 (13)° and the complete anion is generated by a crystallographic centre of symmetry. An intramolecular N—H⋯N hydrogen bond occurs in the cation, which closes an S(6) ring. In the crystal, the components are linked by N—H⋯N and weak C—H⋯N hydrogen bonds, which generate chains propagating in the [101] direction. Weak aromatic π–π stacking interactions are also observed. A Hirshfeld surface analysis and two-dimensional fingerprint plots indicate that the most important contact types in the crystal packing are N⋯H/H⋯N, C⋯H/H⋯C and H⋯H with contributions of 37.2, 28.3 and 21.9%, respectively.In the title molecular salt, (C The C—Non Fig. 1. The  cyanide ligands, exhibiting a square-planar geometry. The bond lengths and angles in the anion are in good agreement with those found in other [Ni(CN)4]2− salts  −x + 1, −y + 1, −z + 1) link (Table 1H) forms a strong N3—H3A⋯N2 hydrogen bond with a cyano group acceptor and the H3A⋯N2 distance is 2.0 Å. Fig. 3S(6) centroids and pyridyl groups [centroid–centroid distance of 3.487 (2) Å].Fig. 3k Table 1. The secet al., 2007CrystalExplorer 17.5 . Areas on the Hirshfeld surface with high curvedness  can be related to the planar packing arrangement of the cations. The most abundant intermolecular interactions in the crystal packing ·[CuCl4] . The mixture was sealed in a Teflon-lined autoclave and held at 423 K for 3 d, and then cooled to room temperature at a rate of 10 K per hour (yield 27%). Pale-yellow plates of (I)The title compound was synthesized solvothermally under autogenous pressure using a mixture of iron(II) sulfate heptahydrate , 2,2′-dipyridylamine  and potassium tetracyanonickelate(II)  in mixed solvents of water/ethanol (3:1 Uiso(H) = 1.2Ueq.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S205698902001419X/hb7948sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698902001419X/hb7948Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698902001419X/hb7948sup3.tifFigure S1 Hirshfeld surface of (C10H10N3)2[Ni(CN)4] mapped with shape index (a) and curvedness (b). DOI: 2040378CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


S(6) graph-set motif. Intermolecular π–π stacking and C—O⋯π interactions dominate the crystal packing.A short [2.592 (3) Å] intramolecular N—H⋯O hydrogen bond leads to an  13H12N2O2, crystallizes in the orthorhombic space group Pna21 with two very similar molecules in the asymmetric unit. An intramolecular N—H⋯O hydrogen bond leads to an S(6) graph-set motif in each of the molecules. Intermolecular π–π stacking and C=O⋯π interactions involving the aldehyde O atoms link molecules into stacks parallel to [100]. A Hirshfeld surface analysis indicates that the most important contributions to the crystal packing stem from H⋯H (49.4%) and H⋯O/O⋯H (21.5%) interactions. Energy framework calculations reveal a significant contribution of dispersion energy. The crystal studied was refined as a two-component inversion twin.At 100 K, the title compound, C Two major aspects contribute to the interest in modified structural analogues of quinazoline alkaloids. On the one hand, they are attractive targets for the development of methods in organic synthesis; reactions sufficiently general to target a wide range of derivatives of a given lead structure should be easy to carry out and warrant high yields. On the other hand, substituted quinazolines allow the study of structure–property relationships with respect to their biological activities  was first isolated from the plant Mackinlaya subulata Philipson   may be the reason for this selectivity towards primary amines.The title compound, 6-formyl-7,8,9,11-tetrahydro-51) Fig. 1, does re1) Fig. 1, 2016 ▸,1H NMR data and quantum-chemical calculations, Zhurakulov et al. (20161) in the solid state, we studied its molecular and crystal structure. We also report the analysis of the Hirshfeld surface and the energy framework of crystalline (1).Based on  al. 2016 confirmeA and B . In contrast to the quinazolinone moiety, the alkyl ring is not planar. The maximum deviation from the least-squares plane through each of the molecules is encountered for the atoms C2A and C2B and amounts to 0.515 (3) and 0.521 (3) Å, respectively. The almost coplanar arrangement of the aldehyde group and the pyrimidine ring in either molecule A and B enables an intramolecular N—H⋯O interaction (Table 1S(6) graph-set motif.The asymmetric unit of the title compound contains two molecules  B Fig. 2. They ar B Fig. 2; an overn Table 1 and form1) stack into columns parallel to [100] in an equidistant series of coplanar moieties; the independent molecules A and B segregate into different stacks  of 1.5.Molecules of  crystallizes in the non-centrosymmetric achiral space group Pna21, and its absolute structure deserves a comment. The absolute structure is linked to the direction of the polar screw axis along [001]. In the absence of heavy atoms, resonant scattering in (1) is minor, with Friedif  were associated with rather large standard uncertainties: the Flack parameter  and benzene  rings and involve contact distances of Cg1⋯Cg3 = 3.5154 (18) Å (slippage 0.954 Å) and of Cg7⋯Cg9 = 3.5159 (19) Å (slippage 1.054 Å).Consecutive molecules in each column along [100] interact ts Fig. 4. π–π stavia C=O⋯π contacts; they amount to C11A=O2A⋯Cg1(x + y + z) = 3.212 (2) Å and C11B=O2B⋯Cg7(x − y + z) = 3.215 (2) Å. Perpendicular to the stacking direction, non-classical C—H⋯O hydrogen bonds , the Hirshfeld surface (HS)  or longer than the sum of the van der Waals radii, respectively.In order to visualize intermolecular interactions in (a. H⋯H contacts are responsible for the largest contribution (49.4%) to the Hirshfeld surface . Besides these contacts, H⋯O/O⋯H (21.5%), H⋯C/C⋯H (14.9%), C⋯C (6.7%) and N⋯C/C⋯N (4.0%) interactions contribute significantly to the total Hirshfeld surface; their decomposed fingerprint plots are shown in Fig. 6c–f. The contributions of further contacts are only minor and amount to N⋯O/O⋯N (1.4%), C⋯O/O⋯C (1.4%), N⋯H/H⋯N (0.5%) and O⋯O (0.1%).The two-dimensional fingerprint plot for all contacts is depicted in Fig. 6ce Fig. 6b. BesidCrystal Explorer 17  is the sum of electrostatic (Eelec), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) energies -one moiety with a similar planar conformation to that in the title structure: 3-(2-methylphenyl)-2-(2-oxophenylethyl)-4(3H)-quinazolinone -quinazolinone quinazolinone -quinazolinone -quinazolinone -2-[2-oxo-2-(thiophen-2-yl)ethylidene]-3-phenyl-2,3-dihydroquinazolin-4(1H)-one , all compounds mentioned above exist as the enamine tautomer in the crystalline state, and their intramolecular N—H⋯O hydrogen bond between the ethanone and the amine N atom results in an S(6) graph set motif.A search in the Cambridge Structural Database  was synthesized according to the method of Oripov et al. (1979Rf 0.78 (C6H6: MeOH 4:1). A detailed report on the synthesis of (1) and its characterization by 1H NMR is available in Zhurakulov et al.  = 1.2Ueq(C). The enamine H atoms H5A and H5B were refined with a common isotropic displacement parameter; N—H distances were restrained to similarity.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989020016059/wm5590sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020016059/wm5590Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020016059/wm5590sup3.tifFigure S1. DOI: Click here for additional data file.10.1107/S2056989020016059/wm5590Isup4.cmlSupporting information file. DOI: 2049242CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, the molecules are linked by C—H⋯N and weak C—H⋯π hydrogen bonds and very weak π–π stacking interactions. Two-dimensional fingerprint plots show that the largest contributions to the crystal stability come from H⋯H and C⋯H/H⋯C interactions. 17H16N2OS, was synthesized by a condensation reaction between 2-amino benzothiazole and 4-N-propoxybenzaldehyde. The benzo[d]thiazole ring system is nearly planar (r.m.s. deviation 0.0088 Å) and makes a dihedral angle of 3.804 (12)° with the phenyl ring. The configuration about the C=N double bond is E. In the crystal structure, pairs of C—H⋯N hydrogen bonds and C—H⋯π interactions link the molecules into inversion dimers with an R22(16) ring motif. These dimers are additionally linked by weak π–π stacking interactions between the phenyl rings, leading to a layered arrangement parallel to (010). Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the packing arrangement are from H⋯H (47.9%) and C⋯H/H⋯C (25.6%) interactions.The title compound, C Benzothiazole is a weak base, and is widely found in bioorganic and medicinal chemistry with application in drug discovery as a pharmacologically and biologically active compound  Å for atom C4]. The benzo[d]thiazole ring system and the phenyl ring (C9–C14) are slightly twisted with respect to each other, making a dihedral angle of 3.804 (12)°. In the thiazole ring, the C6—N1 [1.379 (3) Å] and C7—N1 [1.288 (3) Å] distances indicate substantial electronic delocalization. The C8=N2 double bond has a length of 1.272 (3) Å, and thus is slightly longer than comparable bonds found in other Schiff base structures  and the centroid of the C1–C6 phenyl ring (Cg2) of an adjacent molecule : −x + 1, −y + 2, −z) where Cg3 is the centroid of the C9–C14 phenyl ring. The resulting supramolecular network is layered and expands parallel to (010).In the crystal structure, molecules are linked by C—H⋯π hydrogen bonds Table 1 between le Fig. 2. Pairs oif Fig. 2. The dimCrystalExplorer -N-benzylidenebenzo[d]thiazol-2-amine skeleton gave 20 hits. Of these 20, the most similar to the title compound are 2-[carbonoimidoyl]phenol -2-[(6-ethoxybenzothiazol-2-yl)iminomethyl]-6-methoxyphenol  was then added dropwise into the mixture under stirring, in the presence of a catalytic amount of glacial acetic acid. The reaction mixture was then placed inside an unmodified household microwave oven and was irradiated for 32 min (eight pulses each of 4 min) at 540 W power, with short interruptions of one minute. The progress of the reaction was monitored by thin-layer chromatography using ethyl acetate and n-hexane (3:7 v:v) as eluent (Rf = 0.69). The formed precipitate was filtered off, washed with 1-propanol, and dried. The resulting solid was further purified by recrystallization from n-hexane to give the pure imine as a crystalline solid .2-Amino benzothiazole  was dissolved in 10 ml of 1-propanol in a 50 ml borosilicate glass beaker. 4-Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other C–bound H atoms.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989020012128/wm5582sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020012128/wm5582Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020012128/wm5582Isup3.cmlSupporting information file. DOI: 1979807CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The Diels–Alder cycloaddition of cycloheptatriene and maleic anhydride produces the title carboxylic anhydride; reaction of this anhydride with 4-bromophenylaniline forms the corresponding tetracyclic imide. The anhydride features C—H⋯O hydrogen bonds in the solid state, while the imide also features C—H⋯O hydrogen bonds as well as C—H⋯π and lone pair–π interactions. 11H10O3 (I) and C17H14BrNO2 (II), both containing the bicyclo[2.2.2]octene ring system, are reported here octene ring system. Non-covalent interactions present in the crystal structure of II include a number of C—H⋯O interactions. The extended structure of II also features C—H⋯O hydrogen bonds as well as C—H⋯π and lone pair–π interactions, which combine together to create supramolecular sheets.The syntheses and crystal structures of the two title compounds, C Goh 2014. Private The bond lengths of the carbonyl groups of the anhydride are shorter than the imide, as expected, with C1=O1 = 1.1943 (18), C2=O2 = 1.1904 (17), C1—O3 = 1.3868 (17) and C2—O3 = 1.3978 (16) Å. The corresponding data for the C1a molecule are 1.1913 (17), 1.1871 (18), 1.3855 (17) and 1.3905 (18) Å, respectively. The configurations of the stereogenic centres in the arbitrarily chosen asymmetric molecules are: C3 S, C4 R, C5 R, C8 S, C9 S, C10 R and C3a R, C4a S, C5a S, C8a R, C9a R, C10a S: crystal symmetry generates a racemic mixture in the bulk.The structure of the title anhydride II was solved in the monoclinic space group P21/n, and its atom labeling scheme is shown in Fig. 4II are C3 R, C4 S, C5 S, C8 R, C9 R and C10 S; again, crystal symmetry generates a racemic mixture.The structure of the imide I is dominated by C—H⋯O hydrogen bonds  to 3.4882 (17) Å with D—H⋯A angles ranging from 119 to 159°; the C9 bond is likely very weak based on its H⋯A distance of 2.73 Å. Combined together, these interactions create supramolecular sheets that lie in the ab plane.The extended structure of the anhydride II, the molecules are linked by C—H⋯O hydrogen bonds as well as C—H⋯π and C—Br⋯π interactions (Table 2D⋯A distance of 3.175 (2) Å with a D—H⋯A angle of 139°. The C—H⋯π interaction is between C3—H3, which is α to the carbonyl group C1(O1), and the aromatic ring C12–C17. This interaction has a H⋯Cg distance of 3.801 (2) Å (where Cg is the centroid of the C12–C17 ring), with a C—H⋯Cg angle of 165°. The aromatic ring C12–C17 bears an electron-withdrawing bromine atom, and accepts a lone pair(LP)–π interaction from the bromine atom of a nearby molecule  Å with a C15—Br1⋯Cg angle of 87.43 (6)°. Dimers of imide II are formed via the Br⋯π interactions, and these dimers are linked into supramolecular sheets that lie along (010) by the C—H⋯O and C—H⋯π interactions via short-path distillation and the reaction mixture was left to cool at room temperature. The round-bottom flask was fitted with a stopper and left to recrystallize for 48 h to afford large, cream-colored needles. The product was recrystallized once more by dissolving in 8 ml of xylene: after a week at room temperature, the pure product I was obtained in the form of large colorless crystals . 1H NMR  δ 5.88 , 3.46 , 3.23 , 1.17–1.04 . 13C NMR  δ 172.45, 128.55, 45.88, 33.65, 9.56, 5.24.Cycloheptatriene  and maleic anhydride  were added to an oven-dried round-bottom flask containing 10 ml of xylene and the mixture was refluxed for 1.5 h. Approximately half of the xylenes were distilled off Synthesis of the imide (II)I  and p-bromoaniline  were added to a vial containing 5 ml of xylene and the mixture was refluxed for 5 min. The mixture was then cooled to room temperature and left for 5 days in a sealed vial. The precipitate was recrystallized from ethanol solution to yield colorless needle-like crystals of II . 1H NMR  δ 7.54 , 7.06 , 5.84 , 3.48 , 3.12 , 1.14 , 0.38–0.21 . 13C NMR  δ 177.42, 132.34, 130.88, 128.11, 127.92, 122.47, 45.40, 33.90, 9.97, 4.80.Compound Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989020009512/hb7931sup1.cifCrystal structure: contains datablock(s) global, II, I. DOI: 10.1107/S2056989020009512/hb7931Isup3.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989020009512/hb7931IIsup4.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989020009512/hb7931Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989020009512/hb7931IIsup5.cmlSupporting information file. DOI: 2015807, 2015806CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


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The title di-substituted thiourea has hydroxylethyl and ethyl benzoate substituents bound to the same amine-N atom; overall the molecule is twisted. Supramolecular layers are formed in the crystal, with the molecules connected by O—H⋯S and N—H⋯O hydrogen bonds. 12H16N2O3S, has the hydroxylethyl and ethyl benzoate substituents bound to the same amine-N atom, and is twisted, having a (+)syn-clinal conformation with the Namine—C—C—O torsion angles of 49.39 (13) and 59.09 (12)°, respectively; the dihedral angle between the almost planar CN2S core and the pendent benzene ring is 69.26 (4)°. In the crystal, supramolecular layers propagating in the ac plane are formed via a combination of hydroxyl-O—H⋯S(thione), amine-N—H⋯O hydrogen-bonds. The layers stack along the b axis with inter-digitation of the benzene rings allowing the formation of π–π stacking [inter-centroid separation = 3.8722 (7) Å] and parallel C=O⋯π interactions. A computational chemistry study shows the conventional hydrogen bonding in the crystal leads to significant electrostatic stabilization but dispersion terms are also apparent, notably through the interactions involving the benzene residue.The title di-substituted thiourea, C In an experiment with R = CH2CH2OH and Ar = C6H5, the solution was also heated resulting in an apparent rearrangement with deprotonation of one hydroxyethyl group followed by nucleophilic attachment at the carbonyl-C atom along with protonation of the primary amine and cleavage of the original N—C(=O) bond to yield (I)2NC(=S)N(CH2CH2OH)CH2CH2OC(=O)C6H5. The molecular structure of (I)The title compound, (I)2S atoms of the thiourea core are almost planar, exhibiting a r.m.s. deviation = 0.0054 Å, with the appended C2 and C4 atoms lying 0.0236 (18) and 0.0216 (16) Å to either side of the plane. The conformation of the C2-hydroxylethyl residue is (+)syn-clinal as indicated by the N2—C2—C3—O1 torsion angle of 49.39 (13)°. The CO2 residue is close to co-planar with the (C7–C12)-benzene ring to which it is connected, forming a dihedral angle of 4.83 (9)°. The dihedral angle between the least-squares planes through the CN2S core and the benzene ring is 69.26 (4)°, indicating the molecule is highly twisted. Finally, the N2—C4—C5—O2 torsion angle of 59.09 (12)° is indicative of a (+)syn-clinal configuration about the C—C bond, thereby confirming the twisted nature of the molecule.The molecule of (I)a-axis direction, Fig. 2a). These hydrogen bonds also lead to the formation of 12-membered {⋯HO⋯HNCS}2 and 14-membered {⋯OC2NCNH}2 synthons, each disposed about a centre of inversion, and linked via the edges defined by the amine-N—H⋯O(hydroxyl) hydrogen bonds. The tape has a step-ladder topology and projecting laterally to either side of the tape are the remaining amine-H and carbonyl-O atoms, which form the donors and acceptors of amine-N—H⋯O(carbonyl) hydrogen bonds to link the tapes into a layer in the ac plane, Fig. 2b). The directional links between layers are twofold, namely π–π stacking between the centrosymmetrically related benzene rings  and parallel C=O⋯π interactions, Table 1c). These interactions are possible owing to the inter-digitation of the benzene rings along the b-axis direction, as highlighted in Fig. 2d).As anticipated, hydrogen bonding plays a key role in the supramolecular assembly of (I)Crystal Explorer 17  hydrogen bond with a dnorm distance of 1.92 Å, which is significantly shorter, by 0.69 Å , the ester-C6⋯π(benzene), benzene-C9—H9⋯S1(thione) and benzene-C9–H9⋯C1(thione) contacts with a combined Eint of −48.3 kJ mol−1 and hydroxyl-O1–H1O⋯S1(thione) [−28.8 kJ mol−1]. Close in energy to latter is that due to π–π [Cg1⋯Cg1 = 3.8722 (7) Å] with Eint = −28.3 kJ mol−1. Next most significant are the pairwise ethylene-C2—H2A⋯S1(thione) interactions (Eint = −23.1 kJ mol−1) then methylene-C3—H3B⋯H8(benzene) (Eint = −4.3 kJ mol−1).Among all the interactions, it is the amine-N1—H2viz. amine-N1—H1N⋯O3(carbonyl) that propagates along the c axis together with amine-N1—H2N⋯O1(hydroxyl) and hydroxyl-O1—H1O⋯S1(thione), which extend along the a axis, thereby forming a step-ladder framework as shown in Fig. 7a). On the other hand, significant dispersion force is also present as evidenced from the wire mesh-like dispersion energy framework predominantly governed by the π–π interactions, with contributions from the interactions involving the benzene-C9 atom, Fig. 7b). Overall, the combination of electrostatic and dispersion forces leads to a cuboid-like framework shown in Fig. 7c).The crystal of (I)R(R′)NC(=S)NH2 are comparatively rare with the simplest derivative being the R = R′ = Me species, the almost planar molecule being first reported in 1994  : 3419 ν(OH), 3323 ν(NH2)asym, 3222 ν(NH2)sym, 3058 ν(CH)arom, 3002–2881 ν(CH), 1706 ν(COO), 1647 ν(C=O), 1600 δ(NH), 1523 ν(C=C), 1270 ν(CN), 1053 ν(C=S), 711 δ(CH).Compound (I)Uiso(H) set to 1.2Ueq(C). The oxygen- and nitrogen-bound H atoms were located from a difference-Fourier map and refined with O—H = 0.84±0.01 Å and N—H = 0.88±0.01 Å, and with Uiso(H) set to 1.5Ueq(O) or 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table 510.1107/S2056989020006829/hb7918sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020006829/hb7918Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020006829/hb7918Isup3.cmlSupporting information file. DOI: 2004940CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: