Speciation, mechanism and polymer chain growth studies support a step‐growth process where reversible chain transfer occurs, i.e. H3B ⋅ PRH2/oligomer/polymer can all coordinate with, and be activated by, the catalyst. Block copolymer [H2BPPhH]110‐b‐[H2BP(n‐hexyl)H]11 can be synthesized and self‐assembles in solution to form either rod‐like micelles or vesicles depending on solvent polarity.An amphiphilic block copolymer of polyphosphinoborane has been prepared by a mechanism‐led strategy of the sequential catalytic dehydropolymerization of precursor monomers, H 2BPPhH]110‐b‐[H2BP(n‐hexyl)H]11, have been prepared by a mechanism‐led strategy of the catalytic reversible chain transfer dehydropolymerization of precursor monomers, H3B ⋅ PRH2 . These self‐assemble in THF:hexane solutions to form nanostructured rod‐like micelles, the morphology of which can be controlled by solvent polarity.Amphiphilic block copolymers of polyphosphinoboranes, [H Organic block copolymers (BCPs), in which chemically‐distinct segments of monomer units are linked together in a polymer chain, have played an important role in the development of macromolecular science.3, 4 T2BPRH]n (ClCH2Cl)][BArF4], I,2OTf, II.[I.II a non‐living chain‐growth mechanism is proposed.2PCH2CH2PPh2)2]Cl, 1, and harnessing a step‐growth like mechanism in which reversible chain transfer also occurs,Polyphosphinoborane homopolymers are generally (η6‐FC6H5)[BArF4] (L1=Ph2PCH2CH2CH2PPh2) will dehydropolymerize H3B ⋅ PPhH2 under melt conditions to form [H2BPPhH]n, while solution conditions produced shorter‐chain oligomers.III complex with a chelating P−H activated diboraphosphine is a plausible intermediate, e.g. [Rh(L1)H][BArF4], III 2C6H3);[F4]− anion we explored the use of air‐stable [Rh(Ph2PCH2CH2PPh2)2]Cl, 1, in the anticipation that the chelating phosphine may become labile under the conditions of catalysis (≈100 °C). Optimization of conditions showed that 1 mol% 1, 1.25 M H3B ⋅ PPhH2, heated at 100 °C in toluene for 19 hours in a sealed thick‐walled NMR tube, followed by precipitation into hexanes, afforded [H2BPPhH]n as a white solid in 86 % isolated yield.Mn=26 500 g mol−1, Ð=1.6 =355 Hz. Under these conditions no significant amounts of shorter chain, or cyclic, oligomers are observed.[1 will also dehydropolymerize relatively electron‐poor H3B ⋅ P2C6H3)H2 to form higher molecular weight polyphosphinoborane [H2BP2C6H3)H]n, Mn=127 500 g mol−1, Ð=1.2 in the same reaction time .31P NMR spectrum by a statistical distribution of proposed rr,  or mm triads, δ(31P{1H}) −45.6, −46.9, −48.3 (1 : 2 : 1 respectively), as noted previously.[1 to form [H2BP(n‐hexyl)H]n as a colorless, hexane‐soluble, oil, Mn=33 000 g mol−1, Ð=1.3;,[2PCH2CH2PPh2)H]Cl, 2, Scheme 2, and a similar mixture of diastereoisomers, can also be formed by direct addition of a slight excess of H3B ⋅ PPhHBH2 ⋅ PPhH22PCH2CH2PPh2)(η6‐C6H5F)][BArF4]8‐toluene. ESI‐MS analysism/z=747.2  with the correct isotopologue pattern. Irrespective of the method of synthesis, accompanying 2 are unidentified minor hydride signals observed between −15 to −16 ppm, that become dominant as catalysis reaches completion. These are currently unidentified,3B ⋅ PPhH2 they are not deactivation products. Complex 2, at least at the early stages of catalysis, is thus identified as a likely resting state.In situ catalyst speciation studies , using the distinctive P−H resonances between 5.5 and 3.5 ppm, reveals a first order decay of H3B ⋅ PPhH2 ×10−4 s−1), linear diboraphosphine H3B ⋅ PPhHBH2 ⋅ PPhH2 as an intermediate and the growth in of oligomeric/polymeric [H2BPPhH]n, Scheme 3B ⋅ PPhH2 restarts catalysis (kobs=1.5(1)×10−4 s−1). In a separate experiment (3 mol% 1) using H3B ⋅ PPhHBH2 ⋅ PPhH2 (0.14 M) as the precursor resulted in its clean first order consumption (kobs=1.0(1)×10−4 s−1) to form [H2BPPhH]n . Combined these observations on the resting state and the temporal evolution of substrates and products lead us to propose a simplified mechanism, Scheme (i) the P/B dehydrocoupling of −PPhH2 and −BH3 end groups at the metal center to form 2 (R′=H), or a close analog thereof, i.e. R′=[PPhHBH2]nPPhH ⋅ BH3; (ii) a reversible chain transfer between bound and free phosphine–boranes; (iii) a turnover limiting step that involves substitution of the newly coupled oligomer with another phosphine–borane (monomer/oligomer/polymer), that leads to the observed first‐order decay of monomers H3B ⋅ PPhH2 or H3B ⋅ PPhHBH2 ⋅ PPhH2; (iv) an overall step‐growth like mechanism that supports the observation of H3B ⋅ PPhHBH2 ⋅ PPhH2 as a persistent intermediate.Following reaction progress by t 100 °C  mol% 1, t 100 °C  mol% 1, Mn of isolated polymer using higher loadings, but incomplete conversions with higher dispersities at lower loadings using the same reaction time  clearly demonstrates step growth propagation (Scheme Mn=77 000 g mol−1) is only formed after 5 days reaction time. In contrast, for a chain growth process, high molecular weight polymer would be expected to be observed at low conversions of monomer.n, Mn(MALS)=7 000 g mol−1, with H3B ⋅ P(n‐hexyl)H2 monomer (1.25 M in toluene), catalyst 1 (3 mol%), and heating for 66 hrs at 100 °C resulted in a mixture of products by 31P{1H} NMR spectroscopy, including homopolymer [H2BP(n‐hexyl)H]n and related short‐chain oligomers. Using the noted solubility difference between Ph‐ and n‐hexyl substituted polyphosphinoboranes, extraction into hexanes selectivity removed polymers/oligomers containing only n‐hexyl groups. Importantly the hexane insoluble portion displayed both phenyl and hexyl resonances in the corresponding 1H and 31P spectra, an initial indication that a block copolymer had been formed, Scheme 31P NMR spectrum a signal at δ −49.5 [J(PH)=350 Hz] is assigned to [H2BPPhH]n segments, while a cluster of signals centered at −63.4 is assigned to [H2BP(n‐hexyl)H]n, interestingly in which the atacticity can now be observed,1H NMR spectrum in the P−H region indicates a similar ratio of Ph to n‐hexyl units. Additional smaller signals are observed in the 31P NMR spectrum at δ −55.8 as an apparent triplet, that simplifies to a singlet on decoupling 1H, and δ −48 . These could reflect connecting units between block segments, P(n‐hexyl)H2 end groups110‐b‐[H2BP(n‐hexyl)H]11, BCP1. A small amount of low molecular weight oligomer (≈500 g mol−1) is also observed in the GPC spectrum. As pre‐formed [H2BPPhH]n contained no such species, we assign this to short oligomers of [H2BP(n‐hexyl)H]n.With this calibration in hand, taking pre‐formed n and [H2BP(n‐hexyl)H]n have very different diffusion coefficients (1.5(2) and 3.9(8) ×10−10 m2 s−1, respectively, Figure S42). However, BCP1 also has a different diffusion coefficient, that is the same for both phenyl and hexyl regions of the 1H NMR spectrum (1.99(3) and 1.95(5) ×10−10 m2 s−1), indicating both segments are in the same macromolecule. A two‐component model is needed to best fit the data in the alkyl region, with a minor, faster diffusing, component required (9.6(2)×10−10 m2 s−1). This is fully consistent with the shorter, oligomeric, material observed by GPC. Dynamic Light Scattering  experiments place the apparent hydrodynamic radius of BCP1 as 2.7±2.0 nm in CHCl3 , a reasonable fit with that from DOSY (2.1±0.2 nm), and supports the formation of non‐aggregated polymer chains in CHCl3 solution.BCP1, the ability to reversibly bind and activate different terminus P−H/B−H groups is no doubt important to the formation of a block copolymer. As it is well established that P−H activation occurs more quickly with PPhH2 than with P(n‐hexyl)H2 H2 or equivalent short chain oligomers.While we currently cannot comment on the precise order of events to form r Scheme , we suggs Scheme C, followBCP1 self‐assembled micellar nanostructures should be formed in solution. Molecularly dissolved BCP unimers were observed in pure THF and CHCl3, or in an equal volume mixture of THF and hexane by dynamic light scattering (DLS) . When the volume fraction of hexane was increased to 37.5 %:62.5 % v/v THF:hexane, to enhance the selectivity for the −[H2BP(n‐hexyl)H]11 segment of BCP1, DLS provided evidence for the formation of self‐assembled aggregates with Rh=132±12 nm . Decreasing the solvent polarity further to 25 %:75 % THF:hexane resulted in larger aggregates being formed . The solvent composition and DLS data indicate that micelles are formed with a core of the more polar −[H2BPPhH]110 block and a corona of the less polar −[H2BP(n‐hexyl)H]11 segment. The core:corona block ratio ca. 10 : 1 classifies these systems as crew‐cut micelles and non‐spherical morphologies, rather than star‐like micelles, would be anticipated based on packing‐parameter considerations.BCP1 in 37.5 %:62.5 % v/v THF:hexane solution revealed the formation of rod‐like micelles  should be addressed to the authors.Supporting InformationClick here for additional data file.


In the crystal structure of the title compound, the packing is driven by C—H⋯F, N—H⋯O and C—H⋯π contacts. Hirshfeld surface analysis showed that the largest contribution to the surface contacts arise from F⋯H/H⋯F interactions. 11H10F4N2O2, the conformation about the N—C—C—O bond is gauche [torsion angle = 61.84 (13)°]. In the crystal, N—H⋯O hydrogen bonds link the molecules into [010] chains, which are cross-linked by C—H⋯F and C—H⋯π contacts. Hirshfeld surface analysis was conducted to aid in the visualization of these various influences on the packing. This analysis showed that the largest contribution to the surface contacts arises from F⋯H/H⋯F interactions (35.6%), followed by O⋯H/H⋯O (17.8%) and H⋯H (12.7%).In the title compound, C The amine nitrogen atom (N2) and ester oxygen atom (O1) are gauche to one another, with N2—C6—C7—O1 = 61.84 (13)°. The C10 methyl group is oriented in such a fashion as to enable a weak C—H⋯π interaction with the aromatic ring of an adjacent molecule  linker unit between the amine nitrogen atom and the ester, and F3 as acceptor. One of these interactions is intramolecular (C6—H6A⋯F3) with the other being intermolecular (C7—H7A⋯F3). A hydrogen-bonding interaction occurs between the secondary amine and the carbonyl oxygen atom (N2—H1N2⋯O2). Finally, a weak C—H⋯π interaction is observed between H7B and the pyridine ring π system.The main directional interactions in the crystal structure of the title compound are of the type C—H⋯F, N—H⋯O and C—H⋯π Table 1. The N—HCrystalExplorer17.5  to 1.38 (blue) a.u.; the pale-red spots symbolize short contacts and negative dnorm values on the corresponding surface plots shown in Fig. 2Hirshfeld surface analysis was used to investigate the presence of hydrogen bonds and intermolecular interactions in the crystal structure. The Hirshfeld surface analysis  < 1.15 Å. The H⋯H and C⋯H/H⋯C contacts have the second and third largest contributions, at 17.8 and 12.7%, respectively. Smaller spikes on the shoulder of the fingerprint plot, appearing at 1.15 Å < (id + ed) < 1.160 Å, correspond to the N⋯H/H⋯N contacts.The largest contribution to the overall crystal packing is from F⋯H/H⋯F interactions (35.6%) Table 2. However4.et al., 2016ConQuest amino]ethan-1-ol was synthesized using a known method and used without further purification : δ 6.01 , 5.61 , 4.90 , 4.38 , 3.86 , 1.93 –, 3H); 19F NMR : δ −93.6 , −163.4 ; 13C NMR : δ 167.8 (C=O), 135.8 (CH2=C(CH3)-), 126.4 [CH2=C(CH3)–], 63.7 (–OCH2CH2NH–), 44.1 (–OCH2CH2NH–), 18.3 [CH2=C(CH3)–].A 500 ml round-bottom flask equipped with an addition funnel was charged with 2-[(perfluoropyridin-4-yl)amino]ethan-1-ol , trimethylamine  and diethyl ether (300 ml). The solution was stirred under nitrogen at 273–278 K for 15 minutes. Next, a solution of methacrylol chloride  in ether (10 ml) was added dropwise to the round-bottom flask using an addition funnel. The solution was allowed to gradually warm to room temperature and was stirred for 96 h under nitrogen. Precipitated salts were removed by vacuum filtration and the filtrate was concentrated under reduced pressure. Crystals of the title compound in the form of colorless needles were obtained by recrystallization from a solution in warm (∼328 K) hexanes : m.p. 335–336 K; 6.Uiso(H) = 1.2–1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989023004334/hb8066sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023004334/hb8066Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023004334/hb8066Isup3.cmlSupporting information file. DOI: 2263932CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Details of correction: correct footnotes to tables 1, 2 and 3; please correct each oneExisting text: in the footnotes of tables 1,2 and 3:µg Vit D31 µg = 40 Corrected text should read:IU Vit D31 µg = 40


The crystal structure of the bromobenzenesulfonamide derivative of the type 2 diabetes drug metformin is presented. 10H14BrN5O2S, is the bromobenzenesulfonamide derivative of the type 2 diabetes drug metformin. The asymmetric unit contains two molecules with almost identical conformations but a different orientation of the bromophenyl moiety. Both molecules exhibit intramolecular N—H⋯N and N—H⋯O hydrogen bonds. The molecular packing features chain formation in the a-axis direction by alternating N—H⋯N and N—H⋯O interactions. In addition, ring motifs consisting of four molecules and π–π interactions between the phenyl rings contribute to the three-dimensional architecture. A Hirshfeld surface analysis shows that the largest contributions to surface contacts arise from contacts in which H atoms are involved.The title compound, C Metformin works by decreasing gluconeogenesis in the liver, increasing insulin sensitivity and preventing insulin resistance  in the asymmetric unit  and N30⋯N34 (molecule B) are shared by the two nitrogen atoms with an occupancy of 0.85 (4) at atoms N15 and N34, and 0.15 (4) at atoms N11 and N30. The dihedral angles between the phenyl ring  and the best plane through the N-containing moiety (N11–C19 in A and N30–C38 in B) are 87.12 (12) and 96.05 (12)° in A and B, respectively. Next to the intramolecular hydrogen bonds N15—H15B⋯N11 and N34—H34B⋯N30, a short interaction is present between atoms H16B and O9 in A, and H35B and O9 in B  interaction, while molecule B forms an N34—H34A⋯O10 hydrogen-bond interaction (Table 1D11(2); Etter & MacDonald, 1990a-axis direction is formed by subsequent N16⋯N32 and N34⋯O10 interactions  distance is 3.686 (3) Å and the slippage is 0.650 Å, while for molecule B the Cg2⋯Cg2 distance is 4.1086 (3) Å and the slippage is 1.936 Å .Further dimer formation is obtained through π–π stacking between the phenyl rings Fig. 6. For molCrystal Explorer21.3 , H16A⋯N32 [2.54 (5) Å] and Br⋯Br [3.4165 (10) Å] interactions present in the crystal packing. The bright-red spots in Fig. 8A and H35B refer to the N16—H16A⋯N32, N34—H34A⋯O10 and N35—H35B⋯O9 hydrogen bonds, while the additional faint-red spots illustrate weaker H15A⋯N30 [2.70 (5) Å] and C14⋯H23 (2.66 Å) interactions present in the crystal packing. The relative distributions from the different interatomic contacts to the Hirshfeld surfaces are presented in Table 2A and B, respectively).A Hirshfeld surface analysis was performed, and two-dimensional fingerprint plots were created with 4.et al., 2016a resulted in 17 hits [DEXBUF and DEXBUF01 . For the title compound, this torsion angle is −177.5 (4) and −171.8 (4)° in A and B, respectively.A search of the Cambridge Structural Database . The mixture was stirred for 30 min at room temperature. After the reaction was complete, water was removed under reduced pressure and the residue was dissolved in cold anhydrous methanol. The sodium chloride was filtered off and the filtrate was evaporated under reduced pressure to obtain basic metformin.Metformin hydrochloride  was dissolved in 12Cl2 = 1:10) to obtain the title compound as a colourless solid.The basic metformin  and 3-bromobenzenesulfonyl chloride  were dissolved in 6 mL of anhydrous dichloromethane and stirred under a nitrogen atmosphere for 3 h at room temperature. The solvent was removed on a rotary evaporator and the residue was purified by column chromatography  and sodium gliclazide  were dissolved in 5 mL of acetone and stirred overnight at room temperature. The solvent was removed under reduced pressure and a light-yellow solid was obtained, which was expected to be the sulfonylurea salt of the title compound.Cuboid-shaped colourless crystals were grown in an NMR tube by slow evaporation over two weeks using deuterated chloroform as solvent. However, the grown crystals consist of the title compound and not of its sulfonylurea salt.1H NMR  δ 8.03 , 7.90–7.76 , 7.64–7.57 , 7.56–7.22 , 7.06 , 5.19 , 2.99 . 13C NMR  δ 160.29 (s), 158.59 (s), 145.65 (s), 134.41 (s), 130.20 (s), 129.13 (s), 124.70 (s), 122.54 (s), 37.00 (s).NMR spectra of the title compound were recorded on a 400 MHz NMR spectrometer: 6.Uiso(H) values assigned as 1.2Ueq or 1.5Ueq (methyl only) of the parent atoms, with C—H distances of 0.93 (aromatic) and 0.96 Å (methyl). The hydrogen atoms bound to nitrogen were located in a difference-Fourier map and refined freely with Uiso(H) values assigned as 1.2Ueq of the parent atoms. The occupancy factors of hydrogen atoms H11 and H15B (molecule A), and H30 and H34B (molecule B) involved in intramolecular hydrogen bonds converged during refinement to 0.85 (4) for H15B and H34B, and 0.15 (4) for H11 and H30.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989023002165/pk2683sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023002165/pk2683Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989023002165/pk2683sup3.pdfCSD survey results. DOI: Click here for additional data file.10.1107/S2056989023002165/pk2683Isup4.cmlSupporting information file. DOI: 2246792CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


II atom is coordinated by the S and N atoms of two N′-[(Z)-(furan-2-yl)methylidene]carbamohydrazonothioic acid ligands in a distorted square-planar geometry.In the title complex, the Ni 6H6N3OS)2]·2CH3OH, the NiII atom is coordinated by the S and N atoms of two N′-[(Z)-(furan-2-yl)methylidene]carbamohydrazonothioic acid ligands in a distorted square-planar geometry. The two mutual ligands bound to NiII are also connected by C—H⋯S interactions, while the H atoms of the NH2 group of the ligands form R44(8) motifs with the O atoms of the solvent ethyl alcohol molecules. At the same time, the OH groups of the solvent ethyl alcohol molecules form parallel layers to the (011) plane by the O—H⋯N interactions with the ligand N atom that is not bonded to the NiII atom.. The layers are connected by van der Waals interactions. A Hirshfeld surface analysis indicates that the most important contacts are H⋯H (37.7%), C⋯H/H⋯C (14.6%), O⋯H/H⋯O (11.5%) and S⋯H/H⋯S (10.6%).In the title complex, [Ni(C The ligands assume a trans arrangement with respect to each other around the NiII ion, which lies on a crystallographic inversion centre at . The Ni—S [2.1818 (6) Å] and Ni—N [1.9055 (17) Å] bond lengths lie within the range of those found in related structures.Fig. 13.II are also linked by C—H⋯S interactions, while the H atoms of the NH2 group of the ligands form et al., 1995II atom  is shown in Fig. 5A Hirshfeld surface analysis was carried out using b; 37.7%) contacts to be the most common, followed by C⋯H/H⋯C , O⋯H/H⋯O  and S⋯H/H⋯S  contacts. The N⋯H/H⋯N (8.5%), O⋯C/C⋯O (4.9%), Ni⋯H/H⋯Ni (3.2%), O⋯N/N⋯O (2.2%), N⋯C/C⋯N (1.9%), C⋯C (1.8%), S⋯C/C⋯S (1.1%), S⋯S (0.7%), O⋯O (0.7%),S⋯O/O⋯S (0.5%) and Ni⋯C/C⋯Ni (0.2%) contacts have little directional influence on the molecular packing.The two-dimensional fingerprint plots show the H⋯H Fig. 6b; 37.7%⋯C Fig. 6c; 14.6%⋯O Fig. 6d; 11.5%⋯S Fig. 6e; 10.6%4.et al., 2016et al., 1987et al., 2009A search of the Cambridge Structural Database  Å and Ni—N(2) = 1.921 (2) Å. The coordination around Ni is trans planar with respect to the two S and two N atoms. The furan ring plane is at an angle of 3(1)° to the coordination plane. In the crystal of NOQCUS, the coordination environment around the nickel(II) ion is totally planar, as the NiN2S2 chromophore lies on its least-squares calculated plane and the four angles formed by the metal centre with the four donor atoms add up to exactly 360°. The Ni—N and Ni—S distances are within the usual range. This plane forms a 18° angle with the uncoordinated furan ring, which is also highly planar.In the crystal of FUTRAN, Ni 5.E)-2-(furan-2-ylmethylene)hydrazine-1-carbothioamide were dissolved in 30 mL of methanol then 13 mg (0.05 mmol) of Ni(OOCCH3)2·4H2O were added. The reaction mixture was kept in air at room temperature for slow evaporation. After ca 2–3 d, orange crystals, suitable for X-ray analysis, were formed.17 mg (0.1 mmol) of (14H20N6NiO4S2 (M = 459.17); C 36.61 ; H 4.35 (4.39); N 18.26 (18.30) %. IR (KBr): 3372 ν(OH), 2965 and 2854 ν(NH), 1643 ν(C=N) cm−1.Yield 81%, soluble in DMSO, ethanol and dimethylformamide and insoluble in non-polar solvents. Elemental analysis: C6.Uiso(H) = 1.2 or 1.5Ueq(C). O- and N-bound H atoms were located in difference Fourier maps  and refined with Uiso(H) = 1.2Ueq(N) and 1.5Ueq(O), with their positions fixed. Two reflections (001) and (010), affected by the beam stop, were omitted in the final cycles of refinement.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989023005182/jy2031sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989023005182/jy2031Isup2.hklStructure factors: contains datablock(s) I. DOI: 2269284CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In all three title crystals, the cations are linked by O—H⋯O and/or C—H⋯O hydrogen bonds. The three-dimensional packing is further consolidated by strong halogen–hydrogen and weak van der Waals interactions. N,N-dimethylacetamide–1-(dimethyl-λ4-azanylidene)ethan-1-ol tribromide (1/1), C4H9NO·C4H10NO+·Br3− or [(C4H9NO)·(C4H10NO)](Br3), (I), N,N-dimethylacetamide–1-(dimethyl-λ4-azanylidene)ethan-1-ol dibromidoiodate (1/1), C4H9NO·C4H10NO+·Br2I− or [(C4H9NO)·(C4H10NO)](Br2I), (II), and N,N-dimethylacetamide–1-(dimethyl-λ4-azanylidene)ethan-1-ol dichloridoiodate (1/1), C4H9NO·C4H10NO+·Cl2I− or [(C4H9NO)·(C4H10NO)]·(Cl2I), (III), all the anions are almost linear in geometry and all the cations, except for the methyl H atoms, are essentially planar. In the crystal structure of (I), the cations are linked by pairs of C—H⋯O hydrogen bonds, forming inversion dimers with an R22(8) ring motif. These dimers also exhibit O—H⋯O hydrogen bonding. Dimerized cation pairs and anions are arranged in columns along the a axis. In the crystal of (II), the cations are linked by pairs of O—H⋯O and C—H⋯O hydrogen bonds, forming an R44(14) ring motif. These groups of cations and the anions form individual columns along the a axis and jointly reside in planes roughly parallel to (011). In the crystal of (III), cations and anions also form columns parallel to the a axis, resulting in layers parallel to the (020) plane. Furthermore, the crystal structures of (I), (II) and (III) are consolidated by strong halogen (Br and/or I and/or Cl)⋯H and weak van der Waals interactions. In addition to the structural evaluation, a Hirshfeld surface analysis was carried out.In the title compounds,  The cations, except for their methyl H atoms, are essentially planar [r.m.s. deviation = 0.041 (1) Å for O1]. For (II), the angles and distances of the anion are Br1—I1—Br2 = 177.942 (5)°, I1—Br1 = 2.7244 (2) Å and I1—Br2 = 2.68597 (19) Å. These values are in agreement with data reported in the literature , I1 resides in the centre of inversion symmetry [Cl1—I1—Cl1 = 180.0°], with distances of I1—Cl1 = 2.53973 (18) Å. The cations, except for their methyl H atoms, are planar and all reside on mirror planes.In the title compounds  Figs. 1 and 3 ▸,I), (II) and (III), the O—C and N—C bond distances of the cation all fall between single and double bond values, with C1—N1 = 1.3134 (17) Å and C1—O1 = 1.2786 (16) Å for (I), C1—N1 = 1.3168 (16) Å, C5—N2 = 1.3121 (16) Å, C1—O1 = 1.2771 (15) Å and C5—O2 = 1.2794 (15) Å for (II), and C1—N1 = 1.3161 (8) Å and C1—O1 = 1.2750 (8) Å for (III). The corresponding bond lengths of the three compounds are in good agreement with each other and with the literature.In (3.I), the cations are linked by pairs of C—H⋯O hydrogen bonds , forming inversion dimers with an et al., 1995x + 2, −y + 1, −z + 2). Dimerized cation pairs and anions are arranged in columns along the a axis , two cations are refined in the asymmetric unit. These cations are linked by pairs of O—H⋯O and C—H⋯O hydrogen bonds, forming an a axis and reside in planes parallel to (011) , cations and anions are arranged in columns parallel to the a axis, forming layers parallel to the (020) plane (Table 3I), (II) and (III) are consolidated by strong halogen (Br and/or I and/or Cl)⋯H bonding interactions, Coulombic attraction and weak van der Waals interactions , (II) and (III) are 2.4224 (15), 2.4278 (14) and 2.4261 (9) Å, respectivly, and are thereby within the range (2.31–2.63 Å) found for short/strong classical hydrogen bonds , (II) and (III) were carried out and created with CrystalExplorer17.5 , (II) and (III) is given in Table 4I), (II) and (III) are shown in Fig. 10b)–(d) and Table 5I); 60.3% for (II); 88.9% for (III)], Br⋯H/H⋯Br , O⋯H/H⋯O [6.5% for (III)] and O⋯H/H⋯O  and C⋯H/H⋯C [2.0% for (III)] contacts.The Hirshfeld surface analysis and the associated two-dimensional fingerprint plots over the cations of (I): space group, monoclinic P21/n, Z = 2; (II): space group, triclinic PZ = 2; (III): space group, monoclinic C2/m, Z = 2], may be the result of small deviations in the interactions arising from the different crystal systems and packing, as well as from the variations in the anions of the compounds.The respective differences in the crystal structures of the three title compounds [aluminium(III)] bisium heptakis(perchlorate)  tetrachlorogold(III) , the Al3+ ion is surrounded by dma molecules (dma = dimethylacetamide) in an octahedral arrangement. The dma molecules are essentially planar. Three Al—O—C—N torsion angles [138.8 (8)–149.3 (4)°] are found to deviate significantly from 180°. The centrosymmetric cation has the bridging H atom at the centre of inversion. The planar structure is essentially the same as those reported for [H(dma)2]+ cations; the O⋯O distance [2.386 (8) Å] is within the range (2.31–2.63 Å) found for short hydrogen bonds , the structure consists of distinct [AuCl4]− anions and [H(dma)2]+ cations, with the gold and the bridging H atoms located at centres of symmetry. The hydrogen bond is ‘symmetrical’ as a result of crystallographic requirements. The O⋯O distance is 2.430 (16) Å. Thermal motion analysis indicates that methyl groups attached to nitrogen have higher rotational amplitudes, resulting in short apparent C—H bond lengths [average 0.96 (4) Å] compared with the methyl group attached to a carbonyl C atom which has an average C—H bond length of 1.02 (2) Å.In the crystal of HDMAAU , two N,N-dimethylacetamide molecules in the asymmetric unit are connected to each other by an O—H⋯O hydrogen bond, essentially sharing the central H atom. These molecules and the Br—Br—Br groups are arranged in columns parallel to the a axis. The arrangement is consolidated in the crystal packing by van der Waals interactions between these columns.In the crystal of SEGMOG , the unit-cell parameters and the arrangement of the molecules are relatively similar to the older structure (SEGMOG), while the H atom bridging the the two acetamides was not refined.In the crystal of SEGMOG01  hydrogen halides as orange colored solids. Single crystals of bis hydrogen halides were obtained by slow crystallization from methanol.To a solution of dimethylacetamide  in 0.09 mol of 38% hydrochloric or 40% hydrobromic acid under stirring and cooling in an ice–water bath, 0.05 mol iodine monochloride , iodine monobromide  or bromine  was added gradually. The mixture was stirred for 1 h and the crystals were filtered off, dried and recrystallized from methanol to give the target bis: 1664 (NCO). 1H NMR : δ  12.51 , 3.28 , 3.19 , 2.45 ; 13C{1H} NMR : δ 174.5, 39.7, 37.5, 19.9.Bright orange crystals (Rodygin 5.3.−1): 1606 (NCO). 1H NMR : δ  10.72 , 3.28 , 3.19 , 2.46 ; 13C{1H} NMR : δ 174.6, 39.6, 37.5, 20.1.Bright-orange crystals, yield 44% (10.2 g), m.p. 343–344 K. IR (KBr), ν (cm5.4.−1): 1611 (NCO). 1H NMR : δ  9.98 , 3.25 , 3.17 , 2.41 ; 13C{1H} NMR : δ 174.2, 39.4, 37.2, 19.8.Bright orange crystals, yield 75% (14 g), m.p. 364–365 K. IR (KBr), ν (cm6.I), (II) and (III), the C-bound H atoms were positioned geometrically, with C—H = 0.98 Å (for methyl H atoms), and constrained to ride on their parent atoms, with Uiso(H) = 1.5Ueq(C). The hydroxy H atoms were found in the difference Fourier maps and their coordinates were refined freely, with Uiso(H) = 1.5Ueq(O). In (I), the H atom of the OH group is located in a special position  with an occupancy of 0.5 for the rrefined atom. In (II), the H atoms of the OH groups are disordered over two positions, with occupancies of 0.49 and 0.51. In (III), the H atom of the OH group was refined with an occupancy of 0.25 for its position close to an inversion centre in between the O atoms of two acetamides and simultaneously residing on a mirror plane.Crystal data, data collection and structure refinement details are summarized in Table 610.1107/S2056989023005509/yz2034sup1.cifCrystal structure: contains datablock(s) I, II, III, global. DOI: 10.1107/S2056989023005509/yz2034Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989023005509/yz2034IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989023005509/yz2034IIIsup4.hklStructure factors: contains datablock(s) III. DOI: 2271693, 2271692, 2271691CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Thus, we highlight thesections where these changes apply.In a recent Letter,Abstract: The DO–Dbond dissociation energy has been reportedto be 5.41 ± 0.10 eV, while considering EA(O) in the originalmanuscript. However, EA(OD) should be used instead, thus leading toa bond dissociation energy of 5.28 ± 0.20 eV.Page 5365,left column, second paragraph; “From the appearance...”is reorganized and reads as follows:Table S4 togetherwith the BDE, the enthalpy of reaction can be obtained from ΔHr(OH–) = D(H–OH) – EA(OH) = 3.34 eV. In the charge transfer process,if we add the potassium ionization energy, OH– isexpected at 7.68 eV. The reactions threshold was obtained assumingno excess energy (E#), yet momentum conservationof the dissociating partners may impact on the lighter fragment kineticenergy, thus shifting the energy to a higher value. We note a differenceof ∼1.1 eV for the energy loss data, which is certainly plausiblegiven the kinetic-energy release distribution of H– in Figure S3. Thus, from the appearanceenergy (AE) in the H2O energy loss spectrum at ΔE ≈ 8.8 eV, one can obtain the HO–Hbond dissociation energy (BDE) by taking the potassium ionizationenergy and the data from Table S4,2 i.e., D(HO–H) = AE(OH–) – IE(K) + EA(OH) – E#, yielding therefore D(HO–H)= 5.19 ± 0.20 eV which is in good agreement with the values 5.15eV 3 and 5.17eV.4 Following the same approach for D2O, the energy loss spectrum shows a threshold feature at ΔE ≈ 9.0 eV. We obtain for the first time the DO–Dbond dissociation energy to be D(DO–D) = 5.28± 0.20 eV. In D2O the DO–D energy value isslightly higher than the O–D bond dissociation energy (5.176eV5), which is in agreement with its analogueH2O.Taking the values in Page 5366, right column, last paragraph; “Electronicstatespectroscopy...” reads as follows:2O/D2O was thoroughly discussedfrom the experimental K+ energyloss spectra obtained, from which the DO–D bond dissociationenergy has been obtained for the first time to be 5.28 ± 0.20eV.The electronic statespectroscopy of HfHg°) in reactions 2a.1–2b.2and 4a.1–4b.2are actually enthalpies of reaction (ΔHr). Table S2 decimal places forO– and OH– from H2Ohave been corrected; they now read 12.08 ± 0.20 and 7.80 ±0.20.Enthalpies of formation (Δ


However, the difficulty in expanding cytotoxic γδT cells to an adequate number has been a major limitation to the efficacy of treatment in most cases. We successfully re-generated γδT cells from γδT cell-derived human induced pluripotent stem cells (iPSCs). The iPSC-derived γδT cells (iγδTs) killed several cancer types in a major histocompatibility complex (MHC)-unrestricted manner. Single-cell RNA sequencing (scRNA-seq) revealed that the iγδTs were identical to a minor subset of PBγδTs. Compared with a major subset of PBγδTs, the iγδTs showed a distinctive gene expression pattern: lower CD2, CD5, and antigen-presenting genes; higher CD7, KIT, and natural killer (NK) cell markers. The iγδTs expressed granzyme B and perforin but not interferon gamma (IFNγ). Our data provide a new source for γδT cell-based immunotherapy without quantitative limitation.For a long time,   •We successfully re-generated γδT cells from γδT cell-derived human iPSCs•The re-generated γδT cells showed cytotoxicity against cancer cell lines•Distinctive signatures of the re-generated γδT cells were identified ex vivo-expanded peripheral-blood-derived γδT cells. Cytotoxicity of iγδTs against several cancer cell lines was exhibited in an MHC-unrestricted manner. The novel cell resource will advance off-the-shelf γδT cell-based immunotherapy.Murai et al. successfully re-generated γδT cells from γδT cell-derived human iPS cells. Molecular signatures of the re-generated γδT cells (iγδTs) were identical to those of a minor subset of  Therefoical use . Howeverical use . Furtherex vivo expansion rate of PBMC-derived γδT cells varies widely from donor individual to individual; thus, ex vivo-expanded autologous PBγδT cell therapy cannot be applied to all patients; (2) patients have to wait for the expansion of autologous cells but not for off-the shelf allogenic cells; and (3) an autologous approach would be associated with high costs. iPSCs have infinite proliferation ability: they show logarithmic growth for at least 100 days and ∼1,028-fold expansion during 100 days  (Induced pluripotent stem cell (iPSC) technology may be able to overcome these limitations and enable us to realize off-the-self allogenic γδT cell-based therapy, which has several advantages over autologous γδT cells therapy: (1) the 2 weeks) . To gene2 weeks) , and re-2 weeks) .bona fide lymphocyte, including γδT cells, and should be categorized as cells resulting from an aberrant characteristic of lymphocytes derived from iPSCs, or abnormal cells. Previous studies have demonstrated that such abnormal cells can be derived from pre-rearranged TCR-carrying pluripotent stem cells or hematopoietic progenitors, and such iPSCs reportedly gave rise to abnormal T cells expressing TCR, an NK cell marker NK1.1, and CD8αα  exhibited cytotoxicity against several cancer cell lines in an MHC-unrestricted manner. We identified distinctive molecular signatures of iγδTs and clarified that the iγδTs were identical to a minor subset of in vitro embryoid body (EB)-mediated differentiation experiment showed that they could differentiate into three germ layers  stimulated with HMBPP for 1 week being composed of both γδTCR-positive and αβTCR-positive cells, CD3-positive iγδTs contained no αβTCR-positive cells A. Genomiin iγδTs B. Furthein iγδTs , whereasin iγδTs ).Figure These data indicated that we successfully re-generated monoclonal γ9δ2 T cells via γδT-iPSCs.A key advantage of γδT cells for cancer immunotherapy is that one type of γδT cell is applicable for various types of cancer in a human leukocyte antigen (HLA)-unrestricted manner . We therFirst, we labeled Jurkat cells with carboxyfluorescein diacetate succinimidyl ester (CFSE) as target cells, co-cultured with the iγδTs as effector cells at an effector (E):target (T) ratio of 2:1 and stained these cells with 7-aminoactinomycin-D (7-AAD) to identify dead cells, followed by flow cytometry (FCM). The no-effector condition showed that only approximately 5% of Jurkat cells were dead B, althouTo assess the cytotoxicity of iγδTs toward solid tumor cells, we observed the co-culture of 62B3 γδT-iPSC line-derived iγδTs with GFP-Huh-7 cells by time-lapse imaging. After 12 h of co-culture, the areas of GFP-Huh-7 cells decreased to 28.7%, 30.1%, and 64.5% of those in no-effector control culture in three independent experiments C and 3D.This video displays the continuous imaging of iγδTs co-cultured with GFP-labeled Huh-7 cells at an E:T ratio of 2:1 from 0 to 6 h. The scale bar (upper left) indicates 100 μm.Next, to confirm the cytotoxicity of purified-iγδTs, we co-cultured CD3-MACS-purified iγδT cells and tumor cells and quantified the tumor toxicity at an E:T ratio of 2:1 at 12 h using xCELLigence. Against Huh-7 cells, the purified iγδT and PBγδT cells showed no significant difference in cytotoxicity G. MoreovThese data demonstrated that the iγδTs have cytotoxicity for at least four different types of cancer cells in an HLA-unrestricted manner. Moreover, we were able to catch iγδTs coming into contact with GFP-Huh-7 cells and peeling off as time went on .We next performed several experiments to obtain insight into the mode of action of the iγδTs. The co-culture of iγδTs and Jurkat cells at various E:T ratios showed the dose-dependent cytotoxic effects of iγδTs A and S3ENext, we investigated the mechanism by which iγδTs exhibit cytotoxicity. Both blocking antibodies for γδTCR and NKG2D reduced the cytotoxicity of the purified iγδTs, suggesting that the iγδTs recognize tumor cells by both γδTCR and NKG2D C. PerforNotably, no iγδTs were positive for IFNγ. In contrast, most granzyme B-positive cells in PBγδT cells were positive for IFNγ D. This fWe compared the cell surface markers of iγδTs with PBγδT cells by FCM E. Both dIn general, T cells are divided into four subsets of naive or memory phenotypes corresponding to the CD45RA and CD27 expression patterns . Despitein vitro for 7 days and CD3(+) γδTCR(+) cells were sorted. (iii) iγδTs; differentiated cells from γδT-iPSC clone 62B3 (according to the protocol shown in γδT cells have been reported to have various subtypes  and it wTRDC(+), CD3E(+), CD4(−), CD8A(+), and CD8B(−) (TRDC(+), CD3E(+), CD4(−) CD8A(−), and CD8B(−)  B and S4A CD8B(−) B and S4Ased SELL B. Cells onocytes C. Cells and CD3E B, but diclusters D. We catThe t-SNE distribution of each sample and the fraction of clusters in each sample are shown in To examine the expression of major immune-related genes in each γδT subset, we created dot plots for T cell-differentiation marker genes , cytokinCTSW, FCER1G, KLRC3, CD244, NKG7, as well as the cytotoxic marker perforin coding gene [PRF1]). Cells in γδT subset 2, the dominant population of in vitro-expanded PBγδTs stimulated with HMBPP, expressed immune checkpoint inhibitory receptors   and IFNγ and IFNγ-inducing genes  . Cells in γδT subset 1, the main population of iγδTs, were enriched for NK cell-related genes  E. The doB, IRF4)  were expδT cells , was notectively C. The ex 1 and 3 A and 6C. 1 and 3 A and 6C.In order to investigate the reproducibility of the iγδT data, the expression of these marker genes in scRNA-seq data of iγδTs prepared three times independently was shown by a heatmap. The similar expression patterns indicated that the gene expression of iγδTs was reproducible E.Taken together, we successfully re-generated MHC-unrestricted cytotoxic γδT cells from iPSCs and clarified the distinctive molecular signatures of iPSC-derived γδT cells.in vivo.In the present study, we successfully re-generated CD3(+)γδTCR(+) cells from γδT cell-derived iPSCs. Although there have been reports of the re-generation of αβT cells from αβT cell-derived iPSCs , it was ex vivo-expanded PBγδTs, indicating that the cells resembling the major population of iγδTs exist in adult PBMCs in nature but are not expandable with HMBPP stimulation, at least under the culture condition used in this study. Previously there have been many studies concerning the classification of human peripheral γδT cells. For example, the functions of γδT cells were reportedly separated into five subsets: IFN-γ-producing, antigen-presenting, follicular B helper, regulatory γδT, and IL-17-producing cells , and CD5(−) γδT cells were reported to be more cytotoxic than CD5(+) γδT cells . In addiNK cell-related markers were expressed in iγδTs. A subset of authentic γδT cells reportedly expressed NK cell-related genes and recognize target cells by a similar mechanism to NK cells. In addition, it is reported that mimetic-γδ NKT cells, which expressed low T cell-related genes and high NK cell-related genes, were induced from iPSCs . The shaWe herein demonstrated that our iγδTs were completely negative for αβTCR and that they killed tumor cells in an MHC-independent manner. The negative expression of αβTCR may reduce the risk of graft-versus-host disease . For thiSeveral limitations of the present study should be addressed in our future studies. First, the induction efficiency of iγδTs was not satisfactory, and we have not clarified what CD3(−) cells existing after iγδTs induction were. Second, it should be evaluated whether or not the iγδTs attack non-cancer cells of KIR-ligand mismatch recipients. Third, the iγδT induction protocol established in this study used xenogenic serum and feeder cells, which are difficult for clinical applications. We are currently trying to generate iγδTs under feeder-free and serum-free conditions (data not shown). Our technologies will advance off-the-shelf γδT cell-based immune therapy.This study did not generate new unique reagents.3 cells and cultured in StemFit medium .Seven days before induction, human γδT-iPSCs were seeded onto a six-well plate at a density of 2.0 × 10On day 0, the medium was completely replaced by StemFit medium supplemented with 4 μM CHIR99021 , 80 ng/mL BMP4 , and 80 ng/mL vascular endothelial growth factor (VEGF) . On day 2, the medium was replaced by Essential 6 medium  supplemented with 2 μM SB431542 , 50 ng/mL bFGF , 50 ng/mL SCF , and 80 ng/mL VEGF. On day 4, the medium was replaced by StemPRO-34 SFM  supplemented with 2 mM L-glutamine, 50 ng/mL IL-3 , 50 ng/mL IL-6 , 50 ng/mL FLT3L , 50 ng/mL SCF, 20 ng/mL VEGF, and 10 IU/mL EPO .On days 6 and 8, the medium was replaced with StemPRO-34 SFM supplemented with 2 mM L-glutamine, 50 ng/mL IL-6, 50 ng/mL SCF, and 10 IU/mL EPO.On day 10, hematopoietic cells were transferred into wells co-cultured with feeder cells. Floating cells and supernatant were collected in the tube. Adhesive cells were dissociated with Accutase , and incubated at 37°C for 10 min. Supernatant was returned to the well, pipetted, and filtered using a 35-μm cell strainer. After centrifugation at 1,200 rpm for 4 min, cells were suspended in OP9 medium supplemented with 10 ng/mL SCF, 10 ng/mL TPO , 5 ng/mL IL-7 , 5 ng/mL FLT3L, and 100 μg/mL L-ascorbic acid . Cells were reseeded to the same well and incubated at 37°C for 30 min. Without pipetting, supernatant and floating cells were transferred into a new well confluent with pre-seeded OP9/N-DLL1 cells.On day 12, half of the medium was changed and cells were transferred into new wells with fresh OP9/N-DLL1 cells by vigorous pipetting. Then, half of the medium was changed every other day and cells were transferred onto fresh OP9/N-DLL1 cells every 6 days.On day 30, we collected cells with Accutase, similarly to day 10. Cells were suspended with RPMI1640 medium supplemented with 10% FBS, 1 nM HMBPP , 100 IU/mL IL-2 , and 10 μM 2-mercaptoethanol and seeded onto new plates in a feeder-free condition. Half of the medium was changed every other day. After more than a week of stimulation, cytotoxicity was analyzed.The day before the targeted scRNA-seq analysis, CD3(+)γδTCR(+) cells were sorted on a BD FACS Aria III from PBγδTs and iγδTs that were stimulated with HMBPP for the indicated days as described above. To infer the origin of the sample, all cells were labeled with multiplex sample tags. Single-cell capture and cDNA library preparation were performed using a BD Rhapsody Single-Cell Analysis System with a BD Human Single-Cell Multiplexing Kit  and BD Human Immune Response Targeted Panel for Human , which contains 399 primer pairs, targeting 397 different genes, according to the manufacturer’s recommendations. The concentration, size, and integrity of the resulting PCR products were assessed using a Qubit High-Sensitivity dsDNA Kit.Sequencing was performed using an Illumina HiSeq X  in Macrogen . Fastq files were uploaded to the Seven Bridges Genomics online platform. The obtained counts were adjusted by distribution-based error correction (DBEC), an error correction algorithm developed by BD Biosciences. DBEC data were then loaded into Seurat (version 4.0.4.). Cells were then clustered using a resolution of 0.03 and visualized by t-SNE. The Seurat functions FeaturePlot, DotPlot, DoHeatmap, and Vlnplot were used to visualize the gene expression with feature plot, dot plot, heatmap, and violin plot, respectively. Markers for a specific cluster against all remaining cells were found by using the Seurat function FindAllMarkers.GSE194072.ScRNA-seq data have been deposited in GEO under accession number Data are expressed as the mean ± SD. Differences between two groups were analyzed using a paired t test. Statistical analyses were performed using Microsoft Excel 2013 and EZR. p values of <0.05 were considered statistically significant.Conceptualization, T.A; methodology, N.M; software, T.A. and M.K.-A; validation, M.K.-A.; formal analysis M.K.-A.; investigation, N.M.; resources, N.M.; writing – original draft, N.M.; writing – review & editing, T.A., M.K.-A.; supervision, T.A. and H.T.; project administration, T.A.


The quinoxaline unit in the title molecule is slightly puckered [dihedral angle between the rings = 2.07 (12)°] while the whole molecule adopts an L-shaped conformation. The packing in the crystal is governed by C—H⋯O hydrogen bonds and slipped π-stacking interactions. 18H16N4O5, is slightly puckered [dihedral angle between the rings = 2.07 (12)°] while the whole molecule adopts an L-shaped conformation. Intramolecular hydrogen bonding determines the orientation of the substituted phenyl ring and the amide nitrogen atom is almost planar. The packing in the crystal is governed by C—H⋯O hydrogen bonds and slipped π-stacking interactions.The quinoxaline unit in the title molecule, C The oris Table 1. H3A mayn Table 1. The quic-axis direction  Å, dihedral angle = 2.07 (10)°, slippage alternates between 1.40 and 1.28 Å along the stack]. The π-stacking is reinforced by C8=O1⋯Cg1 interactions, where Cg1 is the centroid of the C1/C6/N1/C7/C8/N2 ring: O1⋯Cg1 = 3.3333 (16) Å, C8⋯Cg1 = 3.689 (2) Å, C8=O1⋯Cg1 = 96.89 (2)°. The stacks are linked by C10—H10A⋯O2 and C16—H16⋯O4 hydrogen bonds -one was dissolved in 25 ml of dimethylformamide, then 1.53 g (6.24 mmol) of 2-chloro-N-(4-methoxy-2-nitrophenyl)acetamide were added followed by 1.0 g (7.5 mmol) of potassium bicarbonate, and a spatula tip of BTBA [2-benzylsulfanyl-5-(trifluoromethyl)benzoic acid] was used for the phase-transfer catalysis. The reaction was stirred for 2 h under reflux at 80°C. When the starting reagents had completely reacted, 500 ml of distilled water were added and a few minutes later the product precipitated. This was filtered, dried and recrystallized from hot ethanol solution to yield light-yellow plate-like crystals of the title compound.A mass of 1.00 g (6.24 mmol) of 3-methylquinoxalin-2 global, I. DOI: 10.1107/S2414314623001918/hb4426Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314623001918/hb4426Isup3.cmlSupporting information file. DOI: 2245645CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In this DFT mechanistic work, a novel substrate‐dependent catalytic mechanism is disclosed involving cooperative Ca−H−Ca bridges for H2 isotope exchange, competitive Ca−H−Ca bridges and terminal Ca−H bonds for anti‐Markovnikov addition of unactivated 1‐alkenes, and terminal Ca−H bonds for Markovnikov addition of conjugation‐activated styrene. THF‐coordination plays a key role in favoring the anti‐Markovnikov addition while strong cation‐π interactions direct the Markovnikov addition to terminal Ca−H bonds.Recently, it was shown that the double Ca−H−Ca bridged calcium hydride cation dimer complex [LCaH Calcium hydride cation dimer catalysis: Dispersion‐corrected DFT calculations reveal that the same double Ca−H−Ca bridged calcium hydride cation dimer catalyst [LCaH2CaL]2+⋅THF shows a novel substrate‐dependent catalytic activity, involving cooperative Ca−H−Ca bridges for efficient H2 isotope exchange, terminal Ca−H bond for the Markovnikov addition of conjugation‐activated styrene, and competitive Ca−H−Ca bridges and terminal Ca−H bonds for the anti‐Markovnikov addition of unactivated 1‐alkenes. In THF solution, the weakly (or non‐) coordinating counter‐anions BAr4− should be solvated into separated ions, and thus not considered further. Consistent with experiment,2+1 is indeed −2.8 kcal/mol exergonic, with a decisive stabilizing dispersion contribution of −7.6 kcal/mol otherwise the coordination should be 4.8 kcal/mol endergonic and thus thermodynamically unstable. For comparison, the THF coordination to the cation monomer +1 m is only −1.5 kcal/mol exergonic with a smaller dispersion contribution of −4.2 kcal/mol. The formation of double Ca−H−Ca bridged 2+1 from two +1 m monomers is −18.4 kcal/mol exergonic again with a sizable dispersion contribution of −6.2 kcal/mol. The THF coordination to 2+1⋅THF smoothly leads to two +1 m⋅THF cation monomers that is 15.3 kcal/mol endergonic, indicating a rapid dimer‐to‐monomer equilibrium even at room temperature (see Supporting Information Table S1).To gain deep mechanistic insight into the cation dimer 22Ca(BDI)]2 is about 7.7 kcal/mol higher in free energy than two (THF)(BDI)CaH monomers in benzene solution,2Ca(BDI)] is 40.4 kcal/mol lower in enthalpy than two (BDI)CaH monomers in gas‐phase,In two related mechanistic studies on 1‐alkene hydrogenation reactions, the THF‐coordinated [(THF)(BDI)CaH]2+1⋅THF, the anti‐Markovnikov addition of unactivated 1‐alkene CH2=CHR (R=3‐cyclohexenyl) to a Ca−H−Ca bridge of 2+1 after THF‐elimination is 3.6 kcal/mol endergonic over a sizable free energy barrier of 23.8 kcal/mol (via transition state 2+TS1) to selectively form the dinuclear complex 2+A [LCaHR'CaL]2+ containing both a Ca−H−Ca and a Ca−R’−Ca  bridge. The alternative Markovnikov addition with the hydride added to the terminal alkene carbon is kinetically 7.6 kcal/mol less favorable . The subsequent H2 addition over the Ca−R’−Ca bridge of 2+A is highly exergonic and kinetically 5.8 kcal/mol more favorable (via 2+TS2) to form the hydrogenated product CH3CH2R along with regenerated 2+1⋅THF after THF coordination. Such a catalytic 1‐alkene hydrogenation is thus −23.7 kcal/mol exergonic over a sizable barrier of 23.8 kcal/mol involving anti‐Markovnikov alkene addition to cooperative Ca−H−Ca bridges.As shown in Figure +1 m⋅THF that is 7.8 kcal/mol higher in free energy than 2+1⋅THF, the anti‐Markovnikov addition of unactivated CH2=CHR to the terminal Ca−H bond is still 4.0 kcal/mol endergonic but over nearly the same free energy barrier of 23.8 kcal/mol (via +mTS1) to selectively form the calcium alkyl complex +mA [LCaHR’⋅THF]+, with the alternative Markovnikov addition being kinetically 6.0 kcal/mol less favorable . The subsequent hydrogenolysis of the Ca−C bond of +mA with H2 is highly exergonic and kinetically 2.9 kcal/mol more favorable (via +mTS2) to form the hydrogenated product CH3CH2R along with regenerated +1 m⋅THF. When cyclohexene is used as an internal alkene substrate in +1 m⋅THF catalyzed hydrogenation, a 3.3 kcal/mol higher barrier  is found for the anti‐Markovnikov addition to the terminal Ca−H bond, consistent with the experimentally observed selective hydrogenation of terminal alkene.On the other hand, via the THF‐coordinated cation monomer +1 m is kinetically 0.7 kcal/mol less reactive  than that of +1 m⋅THF towards CH2=CHR addition, mainly due to a less Lewis‐basic hydride (Mulliken atomic charges: −0.16 e in +1 m vs. −0.53 e in +1 m⋅THF). Together with the positive THF affinity of +1 m, this leads to a 2.1 kcal/mol higher barrier of 25.9 kcal/mol for CH2=CHR addition without the coordinating THF. Interestingly, despite nearly the same free energy barriers  at 298 K for the competitive mechanisms via 2+TS1 and +mTS1, our DFT calculations show that the former via the solvent‐free dimer 2+1 becomes kinetically 1.4 kcal/mol more favorable than the latter via the THF‐coordinated +1 m⋅THF  upon heating at 60 °C (333 K) in experiment,2+1⋅THF to reach the solvent‐free 2+TS1. In contrary to the usual intuition that the dimer‐to‐monomer conversion should be favored upon heating due to favorable entropy effects, our DFT calculations show that the equilibrium of 2+1⋅THF+THF→+1 m⋅THF++1 m⋅THF in solution is hardly affected by such temperature change due to negligible entropy difference with an unchanged number of molecules on both sides (see Supporting Information Table S1).Interestingly, after THF elimination, the terminal Ca−H bond of solvent‐free 2 isotope exchange may occur via one of two cooperative Ca−H−Ca bridges of the solvent‐free cation dimer 2+1 over a low barrier of 16.9 kcal/mol (via 2+TS3) after THF‐elimination from stable 2+1⋅THF catalyst. Interestingly, three exchanging hydrogen atoms are placed evenly between two calcium ions and perpendicular to the remaining Ca−H−Ca bridge, suggesting potentially strong cooperative effects. With the coordinating THF within 2+1⋅THF, similar H2 isotope exchange (via 2+TS3a) becomes kinetically 4.5 kcal/mol less favorable. On the other hand, facile H2 isotope exchange may also occur via terminal Ca−H bonds that are more reactive but higher in free energy than Ca−H−Ca bridges. Indeed, the THF‐coordinated cation monomer +1 m⋅THF is intrinsically 3.9 kcal/mol (via +mTS3) more reactive than 2+1 for H2 isotope exchange but 7.8 kcal/mol higher in free energy, eventually leading to a 3.9 kcal/mol higher barrier. Interestingly, the solvent‐free cation monomer +1 m with a less Lewis‐basic hydride turns out to be intrinsically 3.9 kcal/mol less reactive than +1 m⋅THF in mediating H2 isotope exchange, which is further disfavored by its positive THF affinity of 1.4 kcal/mol. It is thus clear that very efficient H2 isotope exchange observed at room temperature2+1 over a low barrier of 16.9 kcal/mol (via 2+TS3) rather than recently proposed terminal Ca−H bonds.As seen in Figure 2+1⋅THF, the Markovnikov addition of styrene (CH2=CHPh) as a typical π‐conjugation‐activated 1‐alkene to a cooperative Ca−H−Ca bridge of 2+1 after THF‐elimination is 0.2 kcal/mol endergonic over a sizable barrier of 24.3 kcal/mol (via 2+TS4), selectively leading to the dinuclear calcium‐complex 2+B [LCaHR“CaL]2+ containing both a Ca−H−Ca and a Ca−R”−Ca Ph) bridge. Note that the hydride is now added to the terminal rather than the inner alkene carbon as directed by strong Ca+…Ph cation‐π interactions; the anti‐Markovnikov addition encounters a 2.7 kcal/mol higher barrier  and thus is kinetically disfavored. The subsequent hydrogenolysis of the Ca−R”−Ca bridge of 2+B with H2 is highly exergonic and kinetically 7.7 kcal/mol more favorable (via 2+TS5) to form the hydrogenated product CH3CH2Ph along with regenerated catalyst 2+1⋅THF after THF‐coordination. Such dimeric catalytic mechanism is −22.3 kcal/mol exergonic over a sizable barrier of 24.3 kcal/mol involving Markovnikov 1‐alkene addition to cooperative Ca−H−Ca bridges.As shown in Figure 2+1⋅THF, the Markovnikov styrene addition to the terminal Ca−H bond of the solvent‐free cation monomer +1 m (via +mTS4) is now kinetically very efficient and again directed by strong Ca+…Ph ion‐π interaction, which is now −7.7 kcal/mol exergonic over a moderate barrier of 20.6 kcal/mol to selectively form the calcium benzyl complex +mB LCaR“+. The alternative anti‐Markovnikov styrene addition is 6.4 kcal/mol less favorable  and is kinetically highly disfavored. The subsequent H2 hydrogenolysis of the Ca−C bond of +mB is −14.6 kcal/mol exergonic over a moderate barrier of 19.0 kcal/mol (via +mTS5) to form the hydrogenated product CH3CH2Ph along with regenerated catalyst 2+1⋅THF after +1 m dimerization and THF‐coordination, which is kinetically 1.6 kcal/mol more favorable than the preceding Markovnikov styrene addition. It is thus clear that the catalytic styrene hydrogenation via the terminal Ca−H bond of the solvent‐free cation monomer +1 m encounters only a moderate barrier of 20.6 kcal/mol, which is kinetically 3.7 kcal/mol more favorable than that via cooperative Ca−H−Ca bridges of the solvent‐free cation dimer 2+1 and reasonably accounts for the efficient styrene hydrogenation observed at room temperature.Interestingly, starting from the stable complex 2 isotope exchange reactions with the same calcium hydride cation dimer catalyst 2+1⋅THF. It is shown that cooperative Ca−H−Ca bridges of solvent‐free dimer 2+1 are favored for H2 isotope exchange, competitive Ca−H−Ca bridges of 2+1 and the terminal Ca−H bond of cation monomer +1⋅THF are involved in the anti‐Markovnikov addition of unactivated 1‐alkenes, while the terminal Ca−H bond of solvent‐free monomer +1 is preferred for the Markovnikov addition of conjugation‐activated styrene as directed by strong cation‐π interactions. The novel mechanism can reasonably explain the known experimental observations and may be a useful guide for rational catalyst design.Extensive dispersion‐corrected DFT calculations disclose a novel substrate‐dependent catalytic mechanism of 1‐alkene hydrogenation and Hsolv=3.18 Å). The density‐fitting RI−J approachAll DFT calculations were performed with the TURBOMOLE 7.4 suite of programs.More accurate solvation free energies in THF solution were computed with the COSMO‐RS modelThe authors declare no conflict of interest.1As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re‐organized for online delivery, but are not copy‐edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.Supporting InformationClick here for additional data file.


P21/c symmetry with four molecules in the unit cell. The imidazole ring is rotated 80.7 (1)° relative to the phenyl ring. Intermolecular stabilization primarily results from close contacts between the N-atom at the 3-position on the imidazole ring and the C—H bond at the 4-position on the neighboring DippIm.At 106 (2) K, the title molecule has monoclinic  15H20N2 or DippIm, is reported. At 106 (2) K, the molecule has monoclinic P21/c symmetry with four molecules in the unit cell. The imidazole ring is rotated 80.7 (1)° relative to the phenyl ring. Intermolecular stabilization primarily results from close contacts between the N atom at the 3-position on the imidazole ring and the C—H bond at the 4-position on the neighboring DippIm, with aryl–aryl distances outside of the accepted distance of 5 Å for π-stacking.The crystal structure of the title compound, C They are precursors in many synthetic processes and find use in pharmaceuticals and agrochemicals to create antifungal agents and fungicides  in H2O, followed by addition of H2NCH2CH(OEt2), and acidic workup with HCl and HNO3  ligands, which are a common ligand class for organometallic chemistry and catalysis  or potassium bis(trimethylsilyl)amide (KHMDS) to form the free carbene ligands  reported by our group  is reported.Few arylimidazoles have been structurally characterized, with 1--12.DippIm crystallizes as depicted in Fig. 1MesIm of 106.44 (16), 105.65 (17), 110.89 (18), 104.54 (17), and 112.48 (17)°, respectively  and 1.3759 (16) Å, respectively  Å, C1—N2 = 1.316 (3) Å, C2—C3 = 1.356 (3) Å, N1—C3 = 1.384 (2) Å, and N2—C2 = 1.382 (3) Å  Å between N1—C1 and a longer bond of 1.3153 (16) Å between C1—N2, likely due to steric effects of the aryl group. The backbone imidazole C2—C3 bond distance of 1.3578 (16) Å is consistent with a C3.Mercury program’s centroid algorithm -1H-imidazole. A SciFinder search  of colorless crystals. The product was characterized with 1H NMR and the results were consistent with reported literature values  I. DOI: 10.1107/S2056989023009179/oi2001Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023009179/oi2001Isup3.cmlSupporting information file. DOI: 2302037CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Correction: Neural Dev 18, 1 (2023)10.1186/s13064-022-00169-1The authors would like to correct errors and update two figures in the original publication of the article .1. Page 2, “All mouse lines were backcrossed for at least 6 generations” corrected to “All mouse lines were backcrossed for at least 4 generations”.2. Page 4, “0.1 M boric acid pH 8” corrected to “0.1 M sodium borate pH 8”.3. Page 4, after “RFP goat polyclonal Rockland Immunochemicals 200-101-379 1:500” and before “RFP rabbit polyclonal Rockland Immunochemicals 600-401-379 1:500”, addition of “RFP guinea pig polyclonal Frontier Institute MSFR105900 1:500”.4. Page 4, “To our knowledge, this mouse line was not previously characterized.” corrected to “To our knowledge, this mouse line was not previously characterized in detail.”.2” corrected to “EGFP + KI-67 + ASCL1 + cells, 3373 ± 532 cells per mm2”.5. Page 6, “KI-67 + ASCL1 + EGFP + cells, 3373 ± 532 cells per mm6. Page 6, “Consistent with the notion that the EGFP + KI-67- ASCL1- cells are quiescent B1 type stem cells” corrected to “Consistent with the notion that at least some of the EGFP + KI-67- ASCL1- cells are quiescent B1 type stem cells”.7. Page 12, “all of the RFP + postnatal radial glial cells had cell body under the ventricular wall and contacted the ventricle with an apical extension .” corrected to “almost all of the RFP + postnatal radial glial cells had cell body under the ventricular wall and contacted the ventricle with an apical extension .”8. Figure 9. Figure


This novel combination of a stereochemical probe and isotopic labeling in a silicon‐stereogenic compound opens new analytic possibilities to study stereochemical courses of reactions with the aid of chiral silanols mechanistically.A silicon‐stereogenic aminosilanol was isolated in excellent diastereomeric ratio and the absolute configuration was determined. The silanol is configurative and condensation stable in solution and shows stereoselective transformations with a clean stereospecific pathway in follow‐up reactions, which leads to the isolation of a silicon‐stereogenic zinc complex and siloxane compounds. Investigations with  Silanols are important industrial building blocks for the functionalization of surfaces. In this research, one silicon‐stereogenic silanol was selectively synthesized and analyzed. By using an innovative combination of this stereochemical probe and isotope labeling, a configurationally stable chiral silanol was studied, providing new insights into mechanistic studies. Silanols are a central class of compounds in silicon chemistry and are widely used in synthesis,4, 5 cHowever, the preparation of Si‐chiral compounds has proven challenging in the past due to limited access to suitable prochiral or chiral precursors.24, 25Despite these initial findings on the limited configurational stability of silanols in solution, this aspect was not investigated further. Questions arise here, whose answers are essential in order to maximize the potential applications of chiral silanols. How stable is the configuration of chiral silanols in solution? Which subsequent reactions can be realized without loss of stereo information to make further functional components accessible?1  like siloxides and siloxanes.Thus, it can be used as an efficient mechanistic probe whose potential can be extended by 1 was synthesized by the acid‐catalyzed hydrolysis of the corresponding methoxysilane . Silanol 1 crystallizes in the space group P21. The quality of the crystal structure allowed the localization and free refinement of all protons. Two silanol molecules were observed in the asymmetric unit. These pack with the molecules generated by symmetry operations along the a‐axis to form long, chain‐like structures and are connected by intermolecular hydrogen bonds between the hydroxyl group of silanol 1 and the amine function of the next silanol.After hydrolysis, silanol 1 would be configurationally stable. Moreover, silanol 1 does not show condensation to the siloxane to provide the conditions for clean conversion reactions. For this purpose, the silanol was dissolved in different solvents and 1H‐ and 29Si NMR spectra of the compound were recorded over a period of several days  and THF (8 days) also showed high stability of silanol 1 in the time periods studied.In the following, conditions were sought in which silanol 1 under the conditions was confirmed, it was converted in first transformation reactions. The focus was on the selective synthesis of chiral siloxanes and siloxides. In this case, access to Si‐chiral representatives is of great interest, especially for the development of new materials. In addition, the metallated siloxides often show outstanding catalytic activity and access to Si‐stereogenic ligands could open the development of new components for chiral catalysis. to be able to detect the minor diastereomer as well. To ensure constant experimental conditions, the solution was stored in the refrigerator (T=4 °C) for the duration of the experiment.For this purpose, a THF solution of silanol r Scheme . The comSSi/RSi) were determined after derivatization to siloxane 5. In parallel, the most intense oxygenated molecule fragments were used to determine the respective proportions of 18O in the corresponding diastereomers by GC/EI‐MS. The evaluation of the experiments shows an unexpectedly long stability of the configuration at the silicon center, which at first glance suggests no exchange with water. However, at the same time, the incorporation of large amounts of 18O into the diastereomers of silanol 1 is observed, making the labeled species the major components in solution at the end of the experimental period. Since this exchange occurs without loss of stereochemical information, it can be concluded that the reaction proceeds cleanly with retention of the configuration.During the experiment, samples were taken at regular intervals and the corresponding ratios of the diastereomers ‐isomer exchanges with water faster than the (RSi)‐isomer of 1. It is possible that the amino substituent influences the exchange process through the formation of hydrogen bonds.These show that a stable configuration is not necessarily associated with frozen reactivity, since initial experiments of chiral silanol 1 that proceed in THF with retention of the configuration, thus ensuring long term stability of the configuration in the aqueous environment. The combination of a stereochemical probe and isotopic labeling experiments opens the possibility for large‐scale mechanistic studies of the central processes of silanols, which could provide access to new synthesis opportunities for silanol‐based materials.In summary, we were able to demonstrate access to a Si‐chiral silanol that is stable to configurational changes and to condensation reactions in solution, which can be transformed in clean stereochemical transformations to siloxanes and siloxides. In addition, an isotope labeling experiment revealed hidden exchange processes of water with silanol General remarks: All reactions with oxygen‐ and moisture‐sensitive compounds were performed under an atmosphere of argon with Schlenk‐techniques in dried solvents. The solvents were purified and dried by distillation over sodium and storage under argon atmosphere. Commercially available reagents were used without further purification except for phenylmethyldimethoxysilane, which was distilled and stored over molsieve (4 Å) in argon atmosphere. The NMR spectra were measured on a Bruker Avance III HD NanoBay – 400 MHz, 500 MHz Bruker Avance NEO, 600 MHz Bruker Avance III HD and 500 MHz Agilent Technologies DD2 spectrometer at 25 °C. Chemical shifts (δ in ppm) are referred to tetramethylsilane (TMS), with the deuterium signal of the solvent serving as internal lock and the residual solvent signal as additional reference 1H NMR δ (C6D5H)=7.16 ppm). Signals were assigned with the help of HSQC experiments. For the multiplicities following abbreviations were used: s=singlet, br=broad signal, d=doublet, q=quartet. In diastereomeric associations, diastereomeric signals were assigned to the major diastereomer (Dmaj) and the minor diastereomer (Dmin) if distinguishable. For spectra measured in non‐deutered solvents, a capillary with C6D6 was added and served as an internal standard. 13C NMR Spectra were measured with broadband decoupling and referred to the signal of the solvent [{1H}13C NMR δ (C6D6)=128.39 ppm]. {1H}29Si NMR spectra were as inverted gated with TMS as external standard. Single crystal X‐ray diffraction for compounds 1 and 6 were conducted on a Bruker D8 Venture four‐circle diffractometer by Bruker AXS GmbH using a PHOTON II CPAD detector by Bruker AXS GmbH. X‐ray radiation was generated by a microfocus source IμS Mo by Incoatec GmbH with HELIOS mirror optics and a single‐hole collimator by Bruker AXS GmbH. For the data collection, the programs APEX 4 Suite (v.2020.10‐0) with the integrated programs SAINT (integration) and SADABS (absorption correction) by Bruker AXS GmbH were used.MiTeGen were used for mounting. For mass spectrometric evaluation a GC/EI‐MS system with a nominal‐resolution ISQ mass spectrometer coupled to a Thermo Trace GC Ultra oven and a direct probe controller from Thermo Fischer Scientific was used. The capillary column used was an OPTIMA  from Macherey‐Nagel. Helium was used as the carrier gas. For high resolution mass spectrometry data a LTQ‐Orbitrap (Linear Trap Quadrupole Orbitrap) from Thermo Fischer Scientific coupled to a Shimadzu HPLC consisting of a CBM‐20A communication module, a SPD‐M30A UV detector, a CTO‐20AC column oven, a SIL‐30AC autosampler, a LC‐20ADXR pump system, and a DGU‐20A5R degasser unit were used. Elemental analyses were performed with the elemental analyzer vario MICRO cube from the company Elementar and the weighing of the substance quantities was done with the microbalance Cubis MSE3.6P from the company Sartorius. Optical rotations were measured with an A. Krüss Optical polarimeter operating on the sodium D‐line (589 nm) using a quartz glass cuvette (1 mL) and are reported as: [α]DT. The melting point for compound 1 was obtained using a Büchni M‐560 melting point apparatus and the resulting value is non‐corrected.Using Olex2, the structures were solved with the ShelXT structure solution program using Intrinsic Phasing and refined with the ShelXL refinement package using Least Squares minimization. MicroGrippers from Compound (S)‐2: (S)‐7  was suspended portion wise in 95 % formic acid  under ice cooling and 37 % formaldehyde solution  was subsequently added portion wise. The reaction solution was then stirred for 6 h under reflux and then for 12 h at room temperature. Subsequently, the reaction solution was adjusted to a pH of 13 by adding 2 M sodium hydroxide solution. The aqueous phase was extracted with Et2O (3×50 ml) and the combined organic phases were dried over Na2SO4. After removal of the solvent, the residue was purified by “Kugelrohr”‐distillation . The desired product (S)‐2 was obtained as a colorless oil . 1H NMR : δ=1.23 , 2.08 , 3.07 , 7.08–7.12 , 7.18–7.21 , 7.31–7.33 . 1H}13C NMR{ : δ =21.1 , 43.7 , 66.6 , 127.4 , 128.1 , 128.9 , 145.9 . GC/EI‐MS: tR=6.04 min [80 °C (1 min)–7 °C/min–170 °C (2.5 min)‐50 °C/min–250 °C (1 min)]; m/z (%): 149 (24.5) [M+], 134 (100) [(M−Me)+], 105 (47) [(M−NMe2)+], 91 (23), 77 (36) [(Ph)+], 72 (79) [(M−Ph)+]. Specific rotation: [α]D20=−65.02° mL g−1 dm−1 .Compound ‐3: (S)‐2  was dissolved in Et2O (80 ml). The solution was cooled to 0 °C and t‐Butyllithium  was dropped into solution. The yellowish solution was stirred for 1.5 h at 0 °C. Phenylmethyldimethoxysilane  was then added to the solution and the solution was slowly thawed to room temperature with stirring and stirred for 24 h in total. The solids were separated and the solvent was removed in vacuum. After purification by “Kugelrohr”‐distillation at reduced pressure , the product ‐3 was isolated as a colorless oil . 1H NMR : δ=Dmaj 0.63, Dmin 0.66 , Dmin 1.04, Dmaj 1.08 , Dmaj 1.76, Dmin 1.81 , Dmin 3.34, Dmaj 3.36 , Dmin 3.52, Dmaj 3.57 , 7.16–7.18 , 7.21–7.33 , 7.54–7.59 , 7.63 , 8.04–8.11 . 1H}13C NMR{ : δ=Dmaj −3.0, Dmin −1.9 , Dmin 17.4, Dmaj 18.9 , Dmin 42.5, Dmaj 42.8 , Dmaj 50.8, Dmin 50.9 , Dmin 63.7, Dmaj 64.2 , 126.7 , 128.3 , 129.8 , 130.9 , 134.6 , 136.9 , 138.0 , 138.6 , 153.3 . 1H}29Si NMR{ : δ=Dmin −6.3, Dmaj −5.4 (1Si). GC/EI‐MS: tR=5.99 min [80 °C (1 min)–10 °C min−1–1–250 °C (5.5 min)]; m/z (%): 299 (1) [(M+)], 284 (17) [(M−CH3)+], 268 (3) [(M−OCH3)+], 252 (9) [(M−OCH3−CH3)+], 223 (7) [(M−Ph)+], 206 (100) [(M−Ph−CH3−H)+]. Elemental analysis: Calc.: C: 72.19 %, H: 8.41 %, N: 4.68 %. Found: C: 72.0 %, H: 8.4 %, N: 4.4 %.Compound ‐1: ‐3  was dissolved in Et2O (80 ml). 2 M HCl  was added to the solution and the emulsion was intensively stirred for 2 h. After that the reaction mixture was then cooled to 0 °C and adjusted to pH 13 with KOH. The phases were separated and the aqueous phase was extracted with Et2O (3×15 mL). The combined organic phases were dried with MgSO4 and the volume of the solution was concentrated to 30 ml. After storage at −30 °C for 12 h, the product ‐1 was obtained in the form of colorless crystals . 1H NMR : δ=Dmaj 0.63, Dmin 0.66 , Dmin 1.04, Dmaj 1.08 , Dmaj 1.76, Dmin 1.81 , Dmin 3.34, Dmaj 3.36 , Dmin 3.52, Dmaj 3.57 , 7.16–7.18 , 7.21–7.33 , 7.54–7.59 , 7.63 , 8.04–8.11 . 1H}13C NMR{ : δ=Dmaj −3.0, Dmin −1.9 , Dmin 17.4, Dmaj 18.9 , Dmin 42.5, Dmaj 42.8 , Dmaj 50.8, Dmin 50.9 , Dmin 63.7, Dmaj 64.2 , 126.7 , 128.3 , 129.8 , 130.9 , 134.6 , 136.9 , 138.0 , 138.6 , 153.3 . 1H}29Si NMR{ : δ =Dmin −6.3, Dmaj −5.4 (1Si). GC/EI‐MS: tR=5.99 min [80 °C (1 min)–10 °C min−1‐1–250 °C (5.5 min)]; m/z (%): 299 (1) [(M+)], 284 (17) [(M−CH3)+], 268 (3) [(M−OCH3)+], 252 (9) [(M−OCH3−CH3)+], 223 (7) [(M−Ph)+], 206 (100) [(M−Ph−CH3−H)+].Elemental analysis: Calc.: C: 72.19 %, H: 8.41 %, N: 4.68 %. Found: C: 72.0 %, H: 8.4 %, N: 4.4 %.Compound (S)‐5: ‐1  was dissolved in Et2O (3.0 mL). Hexamethyldisilazane  was then added to the reaction solution. The solution was then stirred for 20 h. The solvent and volatiles were removed under vacuum and the siloxane (S)‐5 was obtained as a colorless oil . 1H NMR : δ=0.13 , 0.69 , 1.14 , 1.86 , 3.50 , 7.15–7.17 , 7.22 , 7.32 , 7.54–7.57 , 7.74 , 7.95 . 1H}13C NMR{ : δ=1.0 , 2.5 , 21.0 , 43.4 , 64.8 , 126.7 , 127.0 , 128.3 , 128.5  129.8 , 130.9 , 134.3 , 136.0 , 136.2 , 140.6 , 153.3 . 1H}29Si NMR{ : δ =Dmin‐14.8, Dmaj −13.6 , Dmin −8.4, Dmaj −8.9 . GC/EI‐MStR=6.00 min [80 °C (1 min)–20 °C/min–290 °C (2 min)]; m/z: 342 (10) [(M−Me)+], 297 (14) {[M−H3CHN(CH3)2]+}, 264 (100) [(M−Ph−Me)+], 209 (21) {[PhMeSiOSi(CH3)3]+}, 72 (41) {[Si(CH3)3]+}, 59 (1) {[CH2N(CH3)2]+}. m/z: 344 (10) [(18M−Me)+], 299 (14) {[18M−H3CHN(CH3)2]+}, 266 (100) [(18M−Ph−Me)+], 211 (4) {[PhMeSi18OSi(CH3)3]+}, 72 (40) {[Si(CH3)3]+}, 59 (1) {[CH2N(CH3)2]+}. LC/HR‐MS: tR=6.23 min [0.3 mL/min H2O/MeCN (+ 0.1 % MeCOOH): 95 : 5 (2 min)–80 : 20 –0 : 100 –95 : 5 ]; 358.20225 m/z {C20H32ONSi2 [M+H]+, (Δ=1.552 ppm)} 360.20618 m/z {C20H3218ONSi2 [M+H]+, (Δ=0.666 ppm)} Specific rotation: [α]D20=+7.338° mL g−1 dm−1 .Elemental analysis: Calc: C: 67.17 %, H: 8.74 %, N: 3.92 %. Found: C: 67.3 %, H: 8.7 %, N: 4.0 %.Compound ‐6: ‐1  was dissolved in 1 mL acetone. ZnBr2  was dissolved in 1 mL acetone and added to the silanol solution. After a few days, the product ‐6 crystallized from acetone in the form of colorless blocks in space group P212121 . Yield: 0.06 g, 0.07 mmol  Elemental analysis: Calc.: C: 52.03 %, H: 6.14 %, N: 3.28 %. Found: C: 52.3 %, H: 6.2 %, N: 3.4 %.The authors declare no conflict of interest.1As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re‐organized for online delivery, but are not copy‐edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.Supporting InformationClick here for additional data file.


The triazole ring in the title molecule is not quite coplanar with the six-membered ring to which it is fused, the dihedral angle between the two least-squares planes being 2.52 (6)°. In the crystal, a layer structure is formed by N—H⋯N and C—H⋯O hydrogen bonds plus slipped π-stacking interactions, with the fused cyclohexene rings projecting to either side. 9H10N4O, is not quite coplanar with the six-membered ring to which it is fused, the dihedral angle between the two least-squares planes being 2.52 (6)°. In the crystal, a layered structure is formed by N—H⋯N and C—H⋯O hydrogen bonds plus slipped π-stacking interactions, with the fused cyclohexene rings projecting to either side.The triazole ring in the title molecule, C Karan et al., 2021e.g. Zhao et al., 2021e.g. El-Shershaby et al., 2021e.g. Zhang et al., 2020e.g. Ibrahim et al., 2021Compounds containing nitrogen heterocycles make up a significant portion (approximately 60%) of small drug molecules that have been approved by the FDA  Å, θ = 129.71 (14)° and φ = 326.36 (18)°. This conformation is quite similar to a half-chair form. The C8/N2/C9/N3/N4 ring is closer to planarity than is the C1/C2/C7/N1/C8/N4 ring  and the dihedral angle between their mean planes is 2.52 (6)°. In the crystal, N1—H1⋯N3 hydrogen bonds  and ethyl 2-oxo-cyclohexanecarboxylate  were combined and heated under reflux in 10 ml of acetic acid for 1 h. The solid product obtained was recrystallized from ethanol solution to afford colorless crystals.1Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2414314623004091/tk4091sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2414314623004091/tk4091Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314623004091/tk4091Isup3.cmlSupporting information file. DOI: 2259950CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The distorted coordination octahedra around Li+ involve four short bonds with two pyrazolate N atoms and two aqua ligands and two longer contacts with nitro-O atoms. When combined with μ4-{TNBPz}2−, this generates a mono-periodic polymeric structure incorporating discrete centrosymmeric [(H2O)2Li–(dinitropyrazolato)2–Li(H2O)2] units. The three-dimensional stack of mutually orthogonal coordination chains is reminiscent of a Lincoln log pattern.In the title salt, the 3,3′,5,5′-tetranitro-4,4′-bipyrazole-1,1′-diide dianion [{TNBPz} 2(C6N8O8)(H2O)4]n, the 3,3′,5,5′-tetranitro-4,4′-bipyrazole-1,1′-diide dianion [{TNBPz}2−] is situated across the twofold axis. The distorted coordination octahedra around Li+ involve four short bonds with two pyrazolate N atoms and two aqua ligands [Li—N(O) = 1.999 (3)–2.090 (2) Å] and two longer contacts with nitro-O atoms . When combined with μ4-{TNBPz}2−, this generates a mono-periodic polymeric structure incorporating discrete centrosymmeric [(H2O)2Li–(dinitropyrazolato)2–Li(H2O)2] units. The three-dimensional stack of mutually orthogonal coordination chains is reminiscent of a Lincoln log pattern. It is influenced by conventional hydrogen bonding [O⋯O = 2.8555 (17)–3.0010 (15) Å] and multiple lone pair–π hole interactions of the nitro groups [N⋯O = 3.0349 (15) and 3.0887 (15) Å]. The Hirshfeld surface and two-dimensional fingerprint plots also support the significance of non-covalent bonding. Coordinative saturation and a favorable geometry at the Li+ ions, dense packing of the polymeric subconnectivities and particularly extensive interanion interactions may be involved in the stabilization of the structure. The title salt is a rare example of an energetic Li nitroazolate, which nicely crystallizes from aqueous solution and is neither hygroscopic nor efflorescent. The TG/DTA data reveal total dehydration in the range of 330–430 K and stability of the anhydrous material up to 633–653 K.In the structure of the title salt, [Li The nitropyrazolates crystallize with difficulty  and 2.090 (2) Å], two aqua-O atoms [1.999 (3) and 2.027 (3) Å] and two elongated bonds with nitro-O atoms [2.550 (2) and 2.636 (2) Å] Li]n–   Å [symmetry code: (ii) −x + y + z], are likely attractive, as a kind of lone pair–π hole bonding  Å vs 1.4644 (15) and 1.462 (2) Å for H2(TNBPz) and Rb{H(TNBPz)}, respectively], which indicates a lack of essential conjugation between two pyrazolate rings. Shortening of the C-NO2 bonds upon deprotonation is also minor [mean 1.4308 (16) Å vs 1.439 (2) Å for H2(TNBPz)], while a certain increase in conjugation is reflected rather by a perceptible flattening of the dinitropyrazole fragments. For the latter, the NO2 groups are nearly coplanar with the ring, the two dihedral angles are 1.35 (8) and 11.66 (8)°, for N4O3O4 and N3O1O2 groups, respectively. In the case of H2(TNBPz), the twist comes to 22.8 (2)°. The most appreciable consequence of the dianionic structure is similarity of bond angles at the ring-N atoms: N2—N1—C1 = 107.11 (9)° and N1—N2—C3 = 106.93 (9)°. For the neutral dinitropyrazole rings, the parameters for N- [103.9 (2)°] and NH-sites [112.0 (2)°] are clearly different 2 cycles (pz is pyrazole).The title compound adopts a mono-periodic polymeric structure with the {TNBPz}rn Fig. 2, which iA⋯O6vii  are important for the connection of the chains into layers, which are parallel to the ab plane, whereas the second aqua/aqua bond O5—H⋯O6v  is readily available by nitration of 4,4′-bipyrazole in mixed acids (yield 92%) and subsequent crystallization from water  of solid H2(TNBPz)·H2O was added with stirring. The mixture was stirred for 30 min and the resulting clear deep-yellow solution was cooled to r.t. Slow evaporation to a minimum volume over 8–10 d led to crystallization of the product as well-developed large lemon-yellow prisms. The crystals were removed and dried on a filter paper in air. The yield was 1.25 g (90%). The material shows neither signs of hygroscopy nor efflorescence when exposed to ambient air for months.For the preparation of the title compound, 0.294 g (7.0 mmol) of LiOH·H6H8Li2N8O12: C 18.10, H 2.03, N 28.15; found: C 18.45, H 1.99, N 28.42. IR : 564 m, 636 m, 698 m, 716 m, 773 w, 853 s, 1006 m, 1021 s, 1189 w, 1284 w, 1308 s, 1321 s, 1353 s, 1381 s, 1410 s, 1484 s, 1540 s, 1641 m, 1658 m, 3460 br, 3580 br.Analysis (%) calculated for C−1 (O—H stretching), 1641, 1658 cm−1 (bend) and 564 cm−1 (libration). The peaks for symmetric and asymmetric NO2 stretching  are very similar to the spectra of comparable 3,5-dinitropyrazole , and its shift, with respect to the band for H2(TNBPz)·H2O . The anhydrous material is stable up to 633 K, with the very minor exothermic event at 597 K possibly indicating a phase transition. Exothermic decomposition proceeds above 653 K, with instantaneous loss of any remaining weight and a sharp exothermic effect at ca 700 K suggesting an explosion. For comparison, typical onset temperatures for decomposition of energetic Li nitropyrazolates are 400–500 K, and only 3,5-dinitropyrazolate is stable up to 600 K . There are two partially separated stages for nearly identical weight losses in the temperature range of 330–430 K Fig. 7, which c6.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989023005339/pk2688sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989023005339/pk2688Isup2.hklStructure factors: contains datablock(s) I. DOI: 2269963CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The caffeinium cations form a double layer via hydrogen bonds and π-stacking interactions. The Hirshfeld surface analysis showed that the largest contribution to the crystal packing is made by H⋯H (31.2%), H⋯Cl/Cl⋯H (22.6%), O⋯H/H⋯O (21.9%) contacts for the cation and H⋯Cl/Cl⋯H (79.3%) contacts for the anion.The molecular and crystal structure of the title compound, (C Studies on the interaction of hexachloroplatinates with various biological organic compounds have been performed before, for example by Novikov et al.  hexachloroplatinum RECJAO  crystallizes in the triclinic space group Pb) contains two caffeinium cations and one centrosymmetric hexachloroplatinate anion with a platinum atom in a special position 1a. In the imidazole ring of the caffeine molecule, the nitrogen N1 atom is protonated. The cation, including the methyl groups, has a flat geometry (maximum deviation for non-hydrogen atoms 0.030 Å). The [PtCl6]2− anion has a slightly distorted octahedral geometry with similar Pt—Cl bond distances  Å .Hydrogen bonds and π-stacking play a significant role in the formation of intermolecular interactions in the crystal structure of  Å Fig. 1b.et al., 2016et al., 2018et al., 2011et al., 2022Cz) and chlorine atoms Cl1 and Cl2, with Cz ⋯ Cl distances of 3.8643 (11) and 3.7170 (11) Å, respectively, and α angles between the ring plane and the Cz⋯Cl vector of 61.82 (7) and 62.28 (7)°, respectively. It is uncertain whether such an interaction exists with Cl3 .Similarly, π–halogen interactions  plane  −x + 1, −y + 1, −z] interaction being the strongest.The crystal packing in ne Fig. 2. The cafne Fig. 2, the N1—4.Crystal Explorer 21 was used to calculate the Hirshfeld surfaces (HS) and two-dimensional fingerprint plots  to 1.063 (blue) for cation and −0.402 to 0.934 a.u. for anion, as illustrated in Fig. 3b).s Figs. 3 and 4 ▸.c,d,i. The structures of II and III show distributions of contacts .Analysis of intermolecular contacts shows that for the caffeinum cation, the largest contributions are made by H⋯H, Cl⋯H/H⋯Cl and O⋯H/H⋯O contacts Fig. 5, and fors Figs. 5 and 6 ▸ 5.et al., 20166 type. The closest analogues of I found were II and III (see above), the former containing N-protonated 3-carboxypyridine (nicotinic acid) as the cation and [PtCl6]2− as the anion, the latter containing a caffeinium cation with a methylated (rather than protonated) N1 atom and a PF6− anion.A search of the Cambridge Structural Database  refined], C4H3 as rotationally disordered between two orientations with occupancies of 0.62 (4) and 0.38 (4) [Uiso(H) = 1.2Ueq(C)], with C—H 0.96 Å in each case. The H atoms at N1 and C3 were refined isotropically.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989023005157/zv2027sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023005157/zv2027Isup2.hklStructure factors: contains datablock(s) I. DOI: 2268577CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


II cinnamaldehyde 4-thiosemicarbazone homoleptic complex is reported. As a result of H⋯S intramolecular interactions, graph-set motif S(5), the coordination sphere resembles a hydrogen-bonded macrocyclic environment-type. In the crystal, the molecules are linked by H⋯S interactions, with graph-set motifs The synthesis, crystal structure and Hirshfeld surface analysis of a new Pd E)-N-phenyl-2-[(2E)-3-phenyl-2-propen-1-ylidene]hydrazinecarbothioamide  deprotonated with NaOH in ethanol with an ethanolic suspension of PdII chloride in a 2:1 molar ratio yielded the title compound, [Pd(C16H14N3S)2]. The anionic ligands act as metal chelators, κ2N1S-donors, forming five-membered rings with a trans-configuration. The PdII ion is fourfold coordinated in a slightly distorted square-planar geometry. For each ligand, one H⋯S and one H⋯N intramolecular interactions are observed, with S(5) and S(6) graph-set motifs. Concerning the H⋯S interactions, the coordination sphere resembles a hydrogen-bonded macrocyclic environment-type. In the crystal, the complexes are linked via pairs of H⋯S interactions, with graph-set motif R22(8), and building a mono-periodic hydrogen-bonded ribbon along [001]. The Hirshfeld surface analysis indicates that the major contributions for the crystal cohesion are: H⋯H (45.3%), H⋯C/C⋯H (28.0%), H⋯S/S⋯H (8.0%) and H⋯N/N⋯H (7.4%).The reaction of (2 It was pointed out that the main product of the characterization reaction was a thiosemicarbazone derivative, R3R4C=N—N(H)C(=S)NR1R2 —C(=S) fragment can be easily deprotonated and the negative charge is then delocalized over the N—N—C—S entity, which enables chemical bonding with many different metal centers, with different Lewis acidity, and a diversity of coordination modes, II heteroleptic complexes with a cinnamaldehyde-thiosemicarbazone derivative turned out to be very active on in vitro Human Topoisomerase IIα inhibition, a biological target of prime importance for cancer research , cervix (HeLa), hepatocellular (HepG2), breast (MCF-7) and prostate (PC-3)  and lung (A549) 2 homo- and heteroleptic complexes results in the formation of ZnS nanocrystallites  2 and CdI2(LH)2 were used as starting materials to obtain CdS nanoparticles 2 homo- and heteroleptic complexes  and 177.57 (2)°, respectively. The metal ion is fourfold coordinated in a slightly distorted square-planar geometry. The maximum deviation from the mean plane through the Pd1/N1/N4/S1/S2 fragment is 0.0227 (5) Å for Pd1 and the r.m.s. for the selected atoms is 0.0151 Å. Concerning the geometry of the N—N—C—S entities, the N1—N2—C10—S1 torsion angle is 0.6 (3)°, while N4—N5—C26—S2 is −0.4 (3)°. Both of the ligands are non-planar, with the angle between the mean planes through the C4–C9 and the C11–C16 aromatic rings being 15.7 (1)°, while that between the C20–C25 and the C27–C32 rings is 45.5 (8)°.The asymmetric unit comprises one molecule of the title compound, with all atoms being located in general positions Fig. 1. The comS(5), and C16—H13⋯N2 and C32—H26⋯N5, with graph-set motif S(6). Considering the S(5) rings, a hydrogen-bonded macrocyclic coordination environment-type can be suggested for the PdII metal center, while the S(6) rings contribute to the stabilization of the molecular structure.Four intramolecular hydrogen-bonding interactions are observed Fig. 2: C1—H1⋯Si.e., non-coordinating thiosemicarbazones, the N—N and C—S bonds have lengths of double-bond character, while the N—C bond shows lengths of single-bond type, which can be written as a N=N(H)—C=S fragment. When the acidic H atom of the hydrazinic fragment is removed, the negative charge is delocalized over the N—N—C—S chain and the bond lengths change to intermediate values. Thus, the N—N and the C—S bond lengths assume single-bond character, being longer, and the N—C bond lengths assume double-bond character, being shorter. Information about the bond lengths of the N—N—C—S entities for the cinnamaldehyde-4-phenylthiosemicarbazone molecule, C16H15N3S, and the Ni(C16H14N3S)2 2 complexes, this work, are summarized in Table 2et al., 2014Finally, the anionic form of the ligands was assigned because of the absence of hydrazinic H atoms and the change in the bond lengths of the N—N—C—S entities. For the neutral or free, 3.via pairs of N—H⋯S interactions with graph-set motif In the crystal, the molecules are connected 1] Fig. 3.Crystal Explorer  x, −y + z + x, −y + z − a) H⋯H (45.3%), (b) H⋯C/C⋯H (28.0%), (c) H⋯S/S⋯H (8.0%) and (d) H⋯N/N⋯H (7.4%). The contributions to the crystal packing are shown as two-dimensional Hirshfeld surface fingerprint plots with cyan dots  and the de (y-axis) values are the closest internal and external distances from given points on the Hirshfeld surface (in Å).The Hirshfeld surface analysis  and as a ligand, viz. in the homoleptic [Ni(C16H14N3S)2] complex  −x + 1, −y + 2, −z + 1]. The negative charge of the ligand was assigned by the absence of a hydrazinic H atom and the bond distances in the N—N—C—S chain , the metal center is fourfold coordinated in a square-planar geometry and the N—N—C—S entity torsion angle is 1.5 (6)°.To the best of our knowledge and using database tools such as ry Fig. 6  Fig. 6. The H⋯C] Fig. 6 and theyII coordination compound was also performed with CrystalExplorer  H⋯H (47.4%), (b) H⋯C/C⋯H (27.6%), (c) H⋯N/N⋯H (7.0%) and (d) H⋯S/S⋯H (6.5%). The di (x-axis) and the de (y-axis) values are the closest internal and external distances from given points on the Hirshfeld surface contacts (in Å). While for the PdII title compound and the NiII reference compound the most important intermolecular contacts are H⋯H and the H⋯C/C⋯H, the order of importance changes for the H⋯S/S⋯H and H⋯N/N⋯H contacts. For the crystal packing of the PdII complex, the H⋯S/S⋯H contacts are more important then H⋯N/N⋯H contacts, while for the NiII complex this order is the opposite.The Hirshfeld surface analysis  = 1.2 Ueq, and with C—H = 0.93 Å and N—H = 0.86 Å.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989023008654/zn2032sup1.cifCrystal structure: contains datablock(s) I, publication_text. DOI: 10.1107/S2056989023008654/zn2032Isup2.hklStructure factors: contains datablock(s) I. DOI: 2163054CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, pairs of molecules are linked by N—H⋯N hydrogen bonds, forming  6H8N2OS, all atoms except for the methyl H atoms are coplanar, with a maximum deviation of 0.026 (4) Å. In the crystal, pairs of molecules are linked by N—H⋯N hydrogen bonds, forming R22(8) ring motifs. Dimers are connected by N—H⋯O hydrogen bonds, forming layers parallel to the (102) plane. Consolidating the molecular packing, these layers are connected by C—H⋯π interactions between the center of the 1,3-thiazole ring and the H atom of the methyl group attached to it, as well as C=O⋯π interactions between the center of the 1,3-thiazole ring and the O atom of the carboxyl group. According to a Hirshfeld surface study, H⋯H (37.6%), O⋯H/H⋯O (16.8%), S⋯H/H⋯S (15.4%), N⋯H/H⋯N (13.0%) and C⋯H/H⋯C (7.6%) interactions are the most significant contributors to the crystal packing.In the title compound, C Other major contributors are O⋯H/H⋯O , S⋯H/H⋯S , N⋯H/H⋯N  and C⋯H/H⋯C  interactions. Other, smaller contributions are made by S⋯C/C⋯S (2.7%), C⋯O/O⋯C (2.6%), C⋯C (1.8%), N⋯C/C⋯N (1.5%), S⋯O/O⋯S (0.8%), S⋯N/N⋯S (0.1%) and O⋯N/N⋯O (0.1%) interactions.u. Fig. 7. The intu. Fig. 7b. Other4.et al., 20161,3-thiazole yielded five compounds related to the title compound, viz. CSD refcodes IXAMAV via weak C—H⋯O hydrogen bonds into a two-dimensional supramolecular framework. The crystal structure of DUTZEY involves intermolecular N—H⋯N hydrogen bonds. In the crystal of LAMQOJ, weak C—H⋯N hydrogen bonds build up a wavy layer of molecules in the (011) plane. The layers are stacked in the [100] direction by weak π–π stacking interactions between the 1,3-thiazole rings.In the crystal of IXAMAV, the supramolecular network is based upon N—H⋯N hydrogen-bonded centrosymmetric dimers linked by N—H⋯O contacts. ABEGAQ forms a supramolecular network based on N—H⋯N hydrogen-bonded centrosymmetric dimers that are linked in turn by N—H⋯O contacts. In the crystal of FEFKUY, an interplay of O—H⋯N and C—H⋯O hydrogen bonds connects the molecules to form 5.et al., 2012The title compound was synthesized using a reported procedure  = 1.2Ueq(N) for the NH2 group and 1.5Ueq(C) for CH3 groups.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989023007181/vm2288sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023007181/vm2288Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023007181/vm2288Isup3.cmlSupporting information file. DOI: 2288949CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: