A stable oxopiperidinium trication salt was synthesized. In the crystal, N—H⋯Cl, C—H⋯Cl and C—H⋯O hydrogen bonds link cations and anions into a three-dimensional network. 28H40N3O3+·3Cl−·2H2O, the central heterocyclic ring adopts a sofa conformation, with the exocyclic N—C bond in an equatorial orientation. The dihedral angles between the planar part of this heterocyclic ring and the two almost flat side-chain fragments, which include the aromatic ring and bridging atoms, are 28.8 (1) and 41.1 (1)°. Both diethylazaniumyl substituents have a tetrahedral geometry, while the dihedral angles between the above-mentioned flat part of the aryl fragments and the imaginary planes drawn through atoms C—N—C of the diethylazaniumyl substituents are 86.3 (2) and 80.4 (1)°, respectively. In the crystal, N—H⋯Cl hydrogen bonds link the cations and anions into [100] chains. The chains are cross-linked by numerous C—H⋯O and C—H⋯Cl interactions, generating a three-dimensional network. One of the chloride ions is disordered over two adjacent positions in a 0.895 (4):0.105 (4) ratio.In the trication of the title hydrated molecular salt, C The dihedral angles between the flat part of the heterocycle  and the two almost planar fragments that include the phenyl-ring and the bridging atoms are 28.7 (1) and 41.1 (1)° for (C7–C13) and (C18–C24), respectively. Such non-planarity might partly be caused by the presence of short intramolecular contacts H2AB⋯H24A and H6AB⋯H13A with distances 2.18 and 2.14 Å, respectively, which are shorter than the doubled van der Waals radius of the H atom -3,5-bis[4-(diethylamino)benzylidene[−1-methyl-4-piperidone was obtained according to a literature procedure  = k × Ueq(C), where k = 1.2 for CH and CH2 and 1.5 for CH3 H atoms. All N-bound H atoms were located using difference Fourier maps, but in the final refinement their distances were constrained at 0.90 Å (DFIX). H atoms of the two water molecules were not localized properly, since they appeared to be disordered over several positions. These H atoms were therefore removed from the refinement, but they were still included in the resulting chemical formula. Atom Cl3 is disordered over two positions in a 0.895 (4):0.105 (4) ratio.Crystal data, data collection, and structure refinement details are summarized in Table 210.1107/S2056989015020952/hb7503sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015020952/hb7503Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015020952/hb7503Isup3.cmlSupporting information file. DOI: 1435161CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The title arylsulfonyl glycinyl hydrazone Schiff base compound crystallizes as a monohydrate. In the crystal, a series of O—H⋯O and N—H⋯O hydrogen bonds leads to the formation of corrugated sheets lying parallel to (100). 16H16ClN3O3S·H2O, is L-shaped being bent at the S atom; the S—N—C—C torsion angle is 132.0 (3)°. The central part of the molecule, C—C—N—N=C, is almost linear, with the C—C—N—N and C—N—N=C torsion angles being −174.1 (2) and 176.0 (2)°, respectively. The dihedral angle between the p-toluenesulfonyl ring and the S—N—C—C(=O) segment is 67.5 (4)°, while that between the two aromatic rings is 52.17 (11)°. In the crystal, the water H atom is involved in O—H⋯O hydrogen bonds with a sulfonamide O atom and the carbonyl O atom. The water O atom is itself hydrogen bonded to both NH hydrogen atoms. These four hydrogen bonds lead to the formation of corrugated sheets lying parallel to (100). There are also weak C—H⋯O contacts present within the sheets.The molecule of the title compound, C N-Acylhydrazones containing a glycine residue have been investigated extensively in recent years for their biological and medical activities -amides  Å indicates that the molecule exists in the keto form in the solid state. The C9—N3 bond length of 1.266 (3) Å confirms its significant double-bond character. The N2—N3 and C8—N2 bond distances are 1.384 (3) and 1.337 (3) Å, respectively, which indicate significant delocalization of the π-electron density over the hydrazone portion of the molecule. The molecule is bent at the S-atom with a S1—N1—C7—C8 torsion angle of 132.0 (2)°. The other central part of the molecule is almost linear with the C7—C8—N2—N3, C8—N2—N3—C9 and N2—N3—C9—C10 torsion angles being −174.1 (2), 176.0 (2) and −176.7 (2)°, respectively. The orientation of the sulfonamide group with respect to the attached p-toluenesulfonyl ring (C1–C6) is given by torsion angles C2—C1—S1—N1 = −99.8 (2)° and C6—C1—S1—N1 = 76.6 (2)°, while that of the hydrazone group with the attached benzene ring (C10-C15) is given by torsion angles C11—C10—C9—N3 = 9.9 (4)° and C15—C10—C9—N3 = −172.1 (2)°. The dihedral angles between the mean plane of the central segment  and the benzene rings (C1–C6 and C10–C15) are 65.22 (15) and 13.06 (14)°, respectively. The two benzene rings are inclined to one another by 52.16 (14)°.The molecular structure of the title compound is illustrated in Fig. 1In the crystal, the water O-atom, O4, shows bifurcated hydrogen bonding with the amino-H atom of the hydrazide segment (N2) and the sulfonamide-H atom (N1); see Table 1viz. –NH–CH2–C(=O)–NH–N=CH–, yielded only one hit, namely N-(2-hydroxy-1-naphthylmethylene)-N′-(N-phenylglycyl)hydrazine  was added to glycine (0.02 mol) dissolved in an aqueous solution of potassium carbonate . The reaction mixture was stirred at 373 K for 6 h, then left overnight at room temperature, filtered and then treated with dilute hydrochloric acid. The solid N-(4-methylbenzenesulfonyl)glycine (L1) obtained was crystallized from aqueous ethanol.The title compound was synthesized in a number of steps. Firstly L1 (0.02 mol) dissolved in ethanol (30 ml) and the mixture was refluxed. The reaction was monitored by TLC at regular intervals. After completion of the reaction, the reaction mixture was concentrated to remove excess ethanol. The product, N-(4-methylbenzenesulfonyl)glycine ethyl ester (L2) obtained was poured into water, neutralized with sodium bicarbonate and recrystallized from acetone.Sulfuric acid (0.5 ml) was added to L2 (0.01 mol) was then added in small portions to a stirred solution of 99% hydrazine hydrate (10 ml) in 30 ml ethanol and the mixture was refluxed for 6 h. After cooling to room temperature, the resulting precipitate was filtered, washed with cold water and dried to obtain N-(4-methylbenzenesulfonyl)glycinyl hydrazide (L3).The pure L3 (0.01 mol) and 3-chlorobenzaldehyde (0.01 mol) in anhydrous methanol (30 ml) and two drops of glacial acetic acid was refluxed for 8 h. After cooling, the precipitate was collected by vacuum filtration, washed with cold methanol and dried. It was recrystallized to constant melting point from methanol (457–458 K). The purity of the title compound was checked and characterized by its IR spectrum. The characteristic absorptions observed are 3253.9, 1680.0, 1597.1, 1334.7 and 1161.2 cm−1 for the stretching bands of N—H, C—O, C—N, S—O asymmetric and S—O symmetric, respectively.A mixture of Prism-like colourless single crystals of the title compound were grown from a DMF solution by slow evaporation of the solvent.Uiso(H) = 1.5Ueq(O). The Ueq of atoms O1 and O2 were restrained to approximate isotropic behaviour. The NH H atoms were also located in a difference Fourier map and refined with Uiso(H) = 1.2Ueq(N). The C-bound H atoms were positioned with idealized geometry and refined using a riding model: C—H = 0.93–0.97 Å with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989015008506/su5128sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015008506/su5128Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015008506/su5128Isup3.cmlSupporting information file. DOI: 1062518CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The title compound exists in the keto–amine tautomeric form. In the crystal, supramolecular layers are formed by O—H⋯O hydrogen bonding. 12H16BrNO5 iminiumyl}methyl)-6-methoxybenzen-1-olate], C12H16BrNO5, is found in the keto–amine tautomeric form, with an intramolecular iminium-N—H⋯O(phenolate) hydrogen bond and an E conformation about the C=N bond. Both gauche (two) and anti relationships are found for the methylhydroxy groups. In the crystal, a supramolecular layer in the bc plane is formed via hydroxy-O—H⋯O(hydroxy) and charge-assisted hydroxy-O—H⋯O(phenolate) hydrogen-bonding interactions; various C—H⋯O interactions provide additional cohesion to the layers, which stack along the a axis with no directional interactions between them. A Hirshfeld surface analysis confirms the lack of specific interactions in the inter-layer region.In the solid state, the title compound, C Thus, various species have been studied for their anticancer potential, Database survey. The conformation about the iminium bond [1.295 (4) Å] is E and this residue is almost coplanar with the benzene ring, forming a C2—C1—C7—N1 torsion angle of 1.9 (4)°. This arrangement allows for the formation of a tight charge-assisted iminium-N—H⋯O(phenolate) hydrogen bond (Table 1gauche relationships about the C8—C9 and C8—C11 bonds , and an anti relationship about the C8—C10 bond . The methoxy group is almost coplanar with the ring it is connected to, as seen in the value of the C12—O5—C3—C2 torsion angle of 177.7 (2)°.The molecular structure of (I)d Table 1. The cona). Within this framework are a number of C—H⋯O interactions, i.e. imine-C7—H⋯O(phenolate), methylene-C11—H⋯O(phenolate) and methylene-C9—H⋯O(hydroxy) . In accord with the distance criteria in PLATON As anticipated from the chemical composition of (I)y) Fig. 2b. In acdnorm contact distance within the range of −0.67 to 1.31 Å through calculation of the internal (di) and external (de) Hirshfeld surface distances to the nearest nucleus  over the range of −0.122 to 0.189 au. All Hirshfeld surface and fingerprints plots were generated using Crystal Explorer a), there are several red spots observed on the Hirshfeld surface of (I)deversus di , with the sum of contact distances being approximately 1.74 Å, signifying a strong intermolecular interaction. Such strong interactions constitute the second major contribution to the Hirshfeld surface, i.e. 25.4%, between the most prominent H⋯H (38.2%) and other major contacts, like C⋯H/H⋯C (15.2%) and Br⋯H/H⋯Br (14.3%)  and 3(d), C⋯H and Br⋯H contacts are at distances greater than their respective van der Waals radii. Fig. 5The Hirshfeld surface map provides a visual summary of any close contacts (shown as red) in contrast to relatively long contacts (shown as white and blue). As displayed in Fig. 3i Fig. 3b, with %) Fig. 4. Their ca), shows that the electronegative sites are predominantly converged on O atoms and that, upon crystallization, the electronegative and electropositive sites are connected . It is noteworthy that despite bromine being an electrophilic element, it did not form a significant non-covalent interaction with neighbouring molecules in the inter-layer region where these atoms are directed. The closest contact in this region occurs with methyl-C⋯H12Ci, at 3.12 Å, i.e beyond the sum of the respective van der Waals radii , exists in the keto–amine tautomeric form and has been the subject of several investigations ° in (I)There are several closely related structures to (I)12H16BrNO5: C 44.48, H 3.70, N 1.99%; found: C 44.81, H 3.42, N 1.64%. IR (cm−1): 3330 (b) ν, 1640 (s) ν(C=N), 1528 (m) ν(—O—C=C—), 1066 (m) ν(C—O—C). 1H NMR : δ 8.35 , 7.01–7.10 , 6.83–6.89 , 5.06 , 3.95 , 3.37–3.75 .A solution of tris(hydroxymethyl)aminomethane  was added to an ethanolic solution of 5-bromo-3-methoxy-2-hydroxybenzaldehyde  and refluxed for 2 h. The solution was allowed to stand at room temperature, during which an orange solid formed. This was recrystallized by slow evaporation of its ethanol solution. Yield: 2.67 (80%). Yellow crystals. M.p. 465–466 K. Analysis calculated for CUiso(H) set at 1.2–1.5Ueq(C). The O- and N-bound H atoms were located from difference Fourier maps and refined with distance restraints O—H = 0.82±0.01 Å and N—H = 0.86±0.01 Å, and with Uiso(H) set at 1.5Ueq(O) and Uiso(H) set at 1.2Ueq(N), respectively. Owing to poor agreement, several reflections, i.e. (−9 7 7), (−12 4 6), (−10 5 6) and (−3 3 2), were omitted from the final cycles of refinement.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016012159/hb7605sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016012159/hb7605Isup2.hklStructure factors: contains datablock(s) I. DOI: 1496206CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The complex exhibits twofold rotation symmetry, with the rotation axis bisecting the zinc cation. The structure is stabilized by weak intermolecular C—H⋯Cl interactions [C⋯Cl = 3.411 (2) and 3.675 (2) Å], connecting neighbouring molecules into layers perpendicular to the c axis.The structure of the title complex, [ZnCl DOI: 10.1107/S2056989015019143/zl2646Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015019143/zl2646fig1.tif11 9 3 2 2 x y -z . DOI: 11H9N3)2Cl2] with thermal ellipsoids plotted at the 30% probability level. Non-labelled atoms are created by the twofold symmetry axis .Molecular structure of [Zn2Cl2] plotted down c, formed through weak C–H⋯Cl interactions.Two–dimensional interaction sheet of [Zn2Cl2] plotted down b axis, formed through weak C–H⋯Cl interactions.Two–dimensional interaction sheet of [Zn. H atoms are omitted for clarity.The arrangement of two-dimensional layers plotted down the 1430587CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Fe—Fe), [Fe2(C8H8O)(CO)6], the diiron hexacarbonyl moiety has a sawhorse arrangement, with the OC—Fe—Fe—CO fragment forming the horizontal bar of the horse, and the other four carbonyl groups the legs. The Fe—Fe distance is 2.795 (2) Å. Each Fe atom is also bonded to three C atoms of the cyclooctatrienone ring. One Fe atom forms a σ-bond with one ring C atom, with Fe—C = 2.109 (2) Å, and also a metal–olefin π-bond with two C atoms on the other side of the ring, with Fe—C distances of 2.238 (2) and 2.236 (3) Å. The second Fe atom forms a η3-allyl bond with three other ring atoms, with Fe—C bond lengths of 2.158 (2), 2.062 (2), and 2.123 (3) Å. Counting the π- and π-allyl interactions as one bond, the coordinations of the Fe atoms can, respectively, be approximated as octahedral and trigonal bipyramidal.In the title compound, bis(tricarbonyliron)( I. DOI: 10.1107/S1600536814012690/pk2527Isup2.hklStructure factors: contains datablock(s) I. DOI: 1006076CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The Ni—N bond lengths to the pyridine rings are 2.1189 (17) and 2.1241 (17) Å, whereas those to the thiocyanate anions are 2.0299 (18) and 2.0359 Å. The Ni—S bond lengths are 2.5357 (6) and 2.5568 (6) Å. The Ni2+ cations are linked by N:S-bridging thiocyanate ligands into chains extending along [010]. The Ni⋯Ni distance within the chains is 5.5820 (5) Å. The asymmetric unit contains two Ni2+ cations of which one is located on a centre of inversion, whereas the second is located on a general position.In the title compound, [Ni(NCS) DOI: 10.1107/S1600536814009611/fk2081Isup2.hklStructure factors: contains datablock(s) I. DOI: 1000026CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


However, their intrinsic differences remain unclear. In this study, we analyzed gene expression profiles of the two subsets using Illumina HiSeq 2000 Sequencer. We identified 1995 transcripts related to the activation of Vγ1+ γδ T cells, and 2158 transcripts related to the activation of Vγ4+ γδ T cells. We identified 24 transcripts differentially expressed between the two subsets in resting condition, and 20 after PMA/Ionomycin treatment. We found that both cell types maintained phenotypes producing IFN-γ, TNF-α, TGF-β and IL-10. However, Vγ1+ γδ T cells produced more Th2 type cytokines, such as IL-4 and IL-5, while Vγ4+ γδ T cells preferentially produced IL-17. Our study provides a comprehensive gene expression profile of mouse peripheral Vγ1+ and Vγ4+ γδ T cells that describes the inherent differences between them.Peripheral γδ T cells in mice are classified into two major subpopulations, Vγ1 Although considerable progress has been made in characterizing their biological significance, much remains unknown. γδ T cells arise earlier than αβ T cells during thymic ontogeny, predominately at the early stage of fetal development + and Vγ4+ γδ T cells, depending on their TCR expression + and Vγ4+ γδ T cells perform distinct functions in many disease models. For example, Vγ1+ γδ T cells produce IL-4 and IFN-γ in the liver + γδ T cells produce IFN-γ or IL-17 depending on the studied models + and Vγ4+ γδ T cells function as oppositional pairs in diseases including coxsackievirus B3 infection + and Vγ4+ γδ T cells remains unresolved, partly due to a lack of comprehensive analysis and comparison of gene expression. Although, gene-expression profiles of emergent γδTCR+ thymocytes have been reported + and Vγ4+ γδ T cells functional differences has not been reported. This is likely due to the limited number of cells that can be obtained from healthy mice.γδ T cells exert diverse functions, however, individual subsets within the population appear to be biased toward specialized functions + and Vγ4+ γδ T cells simultaneously from the same pool of mouse splenocytes. We comprehensively analyzed gene expression profiles using Illumina’s sequencing technology. We identified 1995 transcripts related to the activation of Vγ1+ γδ T cells, and 2158 transcripts were related to the activation of Vγ4+ γδ T cells. Interestingly, only 24 transcripts were differentially expressed between two subsets in resting condition, and 20 transcripts after PMA/Ionomycin-induced activation. Both cells produced high levels of IFN-γ, TNF-α, TGF-β and IL-10. However, Vγ1+ γδ T cells produced more Th2 type cytokines, while Vγ4+ γδ T cells tended to produce more IL-17. These findings describe the inherent differences between Vγ1+ and Vγ4+ γδ T cells.In this study, we expanded Vγ1Male C57BL/6J mice aged 6–8 weeks were purchased from the National Institute for Food and Drug Control. All mice were maintained under specific pathogen-free conditions in the Experimental Animal Center, Institute of Basic Medical Sciences, Chinese Academy of Medical Sciences. All animal experiments were approved by and performed in accordance with the guidelines of the international Agency for Research on Cancer’s Animal Care and Use Committee and IBMS/PUMC’s Animal Care and Use Committee.+ and Vγ4+ γδ T cells were expanded from splenocytes as described previously 7 cells were eluted and added to the Ab-coated wells (4×106 cells/well) and cultured in RPMI 1640 medium (Gibco BRL) supplemented with 10% fetal calf serum and IL-2 (200 IU/ml). After 8 days of expansion, the proportion of γδ T cells reached approximately 80% as determined by Flow Cytometry.Vγ17 Vγ1+ and 1.2×107 Vγ4+ γδ T cells were sorted by Flow Cytometric Cell Sorting (FACS) with PE conjugated anti-mouse TCR Vγ1.1/Cr4 antibody  and APC conjugated anti-mouse TCR Vγ2 antibody . The purity of sorted cells was more than 99%. 5×106 cells per well were seeded into 6-well culture plates at a concentration of 1×106/ml and rested overnight at 37°C in 5% CO2 in RPMI with 10% FCS. Cells were stimulated for 4 h with PBS or 20 ng/ml of PMA (Sigma) and 0.5µg/ml of Ionomycin (Sigma). Cells were washed with PBS and pelleted by centrifugation. Total RNA from each sample was extracted by Trizol reagent (Invitrogen) according to the manufacturer’s instructions. The quality of total RNA from each sample was confirmed and comparable, based on results of Agilent Technologies 2100 Bioanalyzer.1.0×10We prepared the Illumina libraries according to the manufacturer’s instructions. Briefly, mRNAs were extracted from total RNA by mRNA enrichment kit  followed by fragmentation of mRNA into 250–350 bp sizes. The first strand cDNAs were synthesized using reverse transcriptase and random primers. Second strand cDNAs were synthesized using DNA Polymerase I followed by the addition of a single A base at the ends for the ligation to the adapters. After purification, the final cDNA library was created by PCR. Finally, 400–500 bp products were used for cluster generation, 36 bp single-end sequencing was performed using Illumina HiSeq 2000 Sequencer according to the manufacturer’s instructions (Beijing Berry Genomics Co. Ltd. China). The RNA-Seq raw data files have been deposited in NCBI’s Sequence Read Archive (SRA) and are accessible through SRA Series accession number SRP042029.We performed base calling using CASAVA 1.7 software (Illumina). Low quality and polluted adapter reads were filtered; clean reads were stored on fastq files. The sequence reads were aligned to the mouse genome (mm9), and gene expression was calculated by RPKM value. Differentially expressed transcripts were identified using General Chi-square test analysis. Q values were obtained by the “BH” method + and Vγ4+ γδ T cells were selected for verification from biological replicates with real-time quantitative PCR. RNA was extracted as described above. 500 ng of total RNA was reverse transcribed using PrimeScript RT reagent Kit with gDNA Eraser (Takara Bio). Gene-specific primers are listed in  as described previously + and Vγ4+ γδ T cells comprised approximately 35% and 25% respectively . γδ T cells were not screwed to one preferential subset after in vitro expansion, suggesting that in vitro expanded γδ T cells with anti-mouse TCRγδ antibodies plus IL-2 were still representative of in vivo subsets of γδ T cells. Expanded Vγ1+ and Vγ4+ γδ T cells were then sorted by FACS with PE-conjugated anti-mouse TCR Vγ1.1/Cr4 antibody and APC conjugated anti-mouse TCR Vγ2 antibody. We found the purities of sorted Vγ1+ and Vγ4+ γδ T cells were more than 99%  or 20 ng/ml of PMA+0.5 µg/ml of Ionomycin (activated) before mRNA extraction and fragmentation. After cDNA synthesis, adapter ligation and PCR amplification, four cDNA libraries were constructed for the resting and activated γδ T cell subsets. 400–500 bp-sized products were used for cluster generation and 36 bp single-end sequencing was performed by using Illumina HiSeq 2000 Sequencer. Approximately 28 million clean reads were obtained from each sample. More than 88% of reads were mapped to the mouse genome using the default setting in TopHat, suggesting high quality of RNA-seq . Cufflin+ and Vγ4+ γδ T cells share similar transcript profiles in both the resting and activated subsets. We identified 24 transcripts with differential expression between the resting Vγ1+ and Vγ4+ γδ T cells   (PMA/Ionomycin treatment induces a robust non-TCR mediated response in γδ T cells (q<0.05) . 2,158 t(q<0.05) . For a g(q<0.05) .+ γδ T cells were enriched for 32 KEGG pathways (p<0.05) (+ γδ T cells were enriched for 29 KEGG pathways (p<0.05)  . 2,158 t(p<0.05) . Our com+ and Vγ4+ γδ T cells , Itgb2 (Cd18), Itgal (Cd11a), Itgae (Cd103) and Itgb1 (Cd29) (Resting Vγ1 subsets . Interes1 (Cd29) . However+ and Vγ4+ γδ T cells, upregulating T cell activation markers CD25, CD69 and CD44 along with several cytokines. Therefore, we analyzed the expression of these representative markers in activated Vγ1+ and Vγ4+ γδ T cells. As expected, PMA/Ionomycin treatment induced expression of XCL1, CCL3, CCL4, CCL1, IFN-γ, Lta, Csf2, TNF-α, IL-2, Gzmb and Gzmc  technology. They concluded inherent gene expression differences in subsets defined their distinct functional responses Phylogenetic analysis suggests γδ T cells are precursors to modern B and αβ T cells + and Vγ4+ γδ T cells are major subpopulations of peripheral γδ T cells in mice. Although global gene expression profiles of all emergent γδ thymocyte subsets have been reported by the Immunological Genome (ImmGen) Project and much knowledge has been obtained about the early divergence of gene expression programs between different γδ thymocyte subsets + and Vγ4+ γδ T cells isn’t available. A major hurdle has been the limited number of cells that can be obtained from healthy mice.Vγ1+ and Vγ4+ γδ T cells simultaneously from a single pool of mouse splenocytes. Our results proved that in vitro TCR-induced expansion for a week did not significantly change the proportion of Vγ1+ and Vγ4+ γδ T cells. We provide a comprehensive gene expression profile of mouse peripheral Vγ1+ and Vγ4+ γδ T cells in the resting and activated state. Although Vγ1+ and Vγ4+ γδ T cells share similar transcript profiles, we identified subset specific genes defining characteristics of each subset.In this study, we resolved the limited cell count issue by establishing a primary culture method expanding Vγ1+ and Vγ4+ γδ T cells, and 20 transcripts differentially expressed after PMA/Ionomycin treatment. Consistent with γδ thymocytes, expression levels of Rorc, Sox13 and Scart2 were higher in Vγ4+ γδ T cells compared with Vγ1+ γδ T cells Rorc expression is reported in γδ T cells, Th22 cells, NKT cells, CD4+ CD8+ thymocytes, and others that do not belong to the T or B cell lineage Rorc is recognized as a lineage-specific transcription factor of Th17 and is also required for IL-17 production Sox13 serves a general role in the differentiation of γδ T cells Sox13 was indispensable for the maturation of Vγ4+ Th17 cells Scart2 is a marker of γδ T cells prepared to secrete IL-17A + γδ T cells compared with Vγ1+ γδ T cells produce significantly more IL-17A and IL-17F after PMA/Ionomycin treatment are also consistent with findings in γδ thymocytes + γδ T cells produce significantly more IL-4 and IL-5 after PMA/Ionomycin treatment compared with Vγ4+ γδ T cells. This finding is consistent with earlier reports showing Vγ1+ γδ T cells preferentially produce IL-4, and the depletion of Vγ1+ subset cells increases host resistance against Listeria monocytogenes infection + γδ T cells suppress Vγ4+ γδ T cell mediated antitumor function through IL-4 We identified 24 transcripts differentially expressed in resting Vγ1+ and Vγ4+ γδ T cells. We found Bclaf1 and Atf2 were preferentially expressed in Vγ4+ γδ T cells while Hmga1 and Bcl11b were preferentially expressed in Vγ1+ γδ T cells. As a transcriptional repressor, Bclaf1 interacts with several members of the Bcl2 protein family and plays a role in the regulation of apoptosis and DNA repair Bclaf1 also plays an important role in lymphocyte homeostasis and activation Atf2 transcription factor is a member of the leucine zipper family of DNA binding proteins and forms a homodimer or a heterodimer with c-Jun, stimulating cAMP responsive element (CRE) dependent transcription. Atf2 expression is lower in CD8+ T cells compared with CD4+ T cells, a functional explanation to the differential response to glucocorticoids between CD8+ and CD4+ T cells Hmga1 binds preferentially to the minor groove of AT rich regions in double stranded DNA. It is involved in many cellular processes including regulation of inducible gene transcription, insulin resistance, diabetes and malignant transformation Hmga1 in transcriptional silencing in T cell lineages and leukemic cells Bclaf1, Atf2 and Hmga1 in γδ T cells have not been reported. Bcl11b is a T-cell specific gene and required for T-lineage commitment. Aberrant expression of Bcl11b contributes to human T-ALL Bcl11b was preferentially expressed in Vγ4+ γδ thymocytes Bcl11b preferentially expressed in activated Vγ1+ γδ T cells. The role of the transcript isoform of Bcl11b in Vγ1+ γδ T cells needs further study.Alternative splicing plays an important role in increasing functional diversity of eukaryotes. Compared with the ImmGen Project, one of the advantages of RNA-seq is able to quantify individual transcript isoforms and identify differentially expressed transcripts between Vγ1+ and Vγ4+ γδ T cells shared similar signaling pathways. We found higher expression of IL-4 and IL-5 in activated Vγ1+ γδ T cells. This suggests a role in asthma given that Vγ4+ γδ T cells suppress airway hyperresponsiveness, compared with Vγ1+ γδ T cells that enhance airway hyperresponsiveness and raise levels of Th2 cytokines and eosinophils infiltration in the airways Many of the differentially expressed gene transcripts identified in activated Vγ1+ and Vγ4+ γδ T cells exhibited high levels of transcripts for several chemokines and chemokine receptors, including CCL4, CCL5, CCR2, CCR5 and CXCR3. These data highlight the role of Vγ1+ and Vγ4+ γδ T cells in immunoregulatory and inflammatory processes. For example, CCL4 (MIP-1beta) and CCL5 (RANTES) are both Th1-associated chemokines that bind to CCR5. Up-regulation of CCR5 ligands may play a role in the recruitment process of blood monocytes, memory T helper cells and eosinophils. CCR2 is expressed on both Vγ1+ and Vγ4+ γδ T cells, and is necessary for the accumulation of γδ TILs to the tumor bed + and Vγ4+ γδ T cells. CXCR6 plays a critical role in NK cell memory of haptens and viruses + and Vγ4+ γδ T memory cells needs further examination.Both resting Vγ1+ and Vγ4+ γδ T cells. For example, Itgae (Cd103), implicated in epithelial T cell retention, is highly expressed on Vγ1+ and Vγ4+ γδ T cells Itgae contributes to clustering and activation of Vγ 5 TCRs expressed by epidermal T cells Integrins play key roles in immune responses, leukocyte trafficking and many human diseases. Most integrin related research has been focused on αβ T cells, with little published on γδ T cells. Our results show several integrins were highly expressed in Vγ1+ and Vγ4+ γδ T cells. We show after PMA/Ionomycin treatment several activation markers of T cells were upregulated including CD25, CD69 and CD44, along with most cytokine genes in both subsets. In addition, activated Vγ1+ and Vγ4+ γδ T cells produced high levels of XCL1, CCL3, CCL4, CCL1, IFN-γ, TNFα, Lta, Csf2 and IL-10. IFN-γ and TNFα are Th1 type cytokines. Previous reports show Vγ4+ γδ T cells are the major γδ T subset producing IFN-γ, and they steer CD4+ T cells toward a dominant Th1 cell response + γδ T cells produced significantly more IFN-γ compared with Vγ1+ γδ T cells, partly due to the high expression level of eomesodermin + γδ T cells were the major γδ T subset producing IFN-γ in response to L. monocytogenes infection + and Vγ4+ γδ T cells produce high levels of IL-10.PMA/Ionomycin induces a robust non-TCR mediated response in Vγ1+ γδ thymocytes expressed high levels of Stat4, Maf, Gata3 and Eomes compared with Vγ1+ γδ thymocytes + and Vγ4+ γδ T cells expressed high levels of these transcription factors and the levels of Gata3 were slightly higher in Vγ1+ γδ T cells compared with Vγ4+ γδ T cells after PMA/Ionomycin treatment. Gata3 is critical for Th2 cell differentiation and required for IL-4 production. The higher level of Gata3 expression in Vγ1+ γδ T cells is consistent with the phenotype of Vγ1+ γδ T cells producing more IL-4 than Vγ4+ γδ T cells. T-bet is a major factor for Th1 cell differentiation and IFN-γ production Eomes is also involved in Th1 differentiation and IFN-γ production T-bet and Eomes is consistent with the phenotype of both Vγ1+ and Vγ4+ γδ T cells that produce high levels of IFN-γ. The difference between our results with the ImmGen Project may be due to the source of γδ T cells. The cells used in the ImmGen Project are γδ thymocytes, however the cells in our study were peripheral γδ T cells derived from the spleen.Narayan et al. reported that Vγ4+ and Vγ4+ γδ T cells maintain inflammatory and regulatory phenotypes. Both demonstrate an inflammatory cell phenotype via IFN-γ and TNFα expression. And, both display a regulatory cell phenotype via TGF-β and IL-10 production. Vγ1+ γδ T cells produced more Th2 type cytokines, while Vγ4+ γδ T cells tended to produce more IL-17. Thus, Th2 type cytokines may explain how Vγ1+ γδ T cells affect anti-inflammatory functions in different infection models, and describe the enhancing effect on airway hyperresponsiveness (AHR) + γδ T cells in the infection models and the inhibitory effect on airway hyperresponsiveness (AHR). Although this study was performed in Vγ1+ and Vγ4+ γδ T cells expanded in vitro, which may not fully represent the true status of Vγ1+ and Vγ4+ γδ T cells in vivo, our results support the hypothesis that distinct γδ TCR types direct cells to acquire a certain type of functional programming during thymic development Taken together, this study shows both Vγ1+ and Vγ4+ γδ T cells following PMA/Ionomycin treatment. Although both γδ T cell populations have similar transcript profiles, subset-specific transcripts define distinct characteristics and describe the inherent differences between Vγ1+ and Vγ4+ γδ T cells.Complementary to the ImmGen Project, this report provides a comprehensive gene expression profile of mouse peripheral Vγ1Dataset S1Raw data and differential expression analysis in RNA-seq.(XLSX)Click here for additional data file.Dataset S2+ γδ T cells.Differentially expressed genes between the resting and activated Vγ1(XLSX)Click here for additional data file.Dataset S3+ γδ T cells.Differentially expressed genes between the resting and activated Vγ4(XLSX)Click here for additional data file.Dataset S4Transcription factors related to Th cell differentiation and cytokine secretion.(XLSX)Click here for additional data file.


The packing features supramolecular layers sustained by O—H⋯O, O—H⋯N and N—H⋯O hydrogen bonding.A distorted square-pyramidal CdNS 6H12NOS2)2(C4H10N2)], features a distorted square-pyramidal coordination geometry about the central CdII atom. The dithiocarbamate ligands are chelating, forming similar Cd—S bond lengths and define the approximate basal plane. One of the N atoms of the piperazine molecule, which adopts a chair conformation, occupies the apical site. In the crystal, supramolecular layers propagating in the ac plane are formed via hydroxy-O—H⋯O(hydroxy), hydroxy-O—H⋯N and coordinated-piperazine-N—H⋯O(hydroxy) hydrogen bonds; the layers also feature methine-C—H⋯S interactions and S⋯S [3.3714 (10) Å] short contacts. The layers stack along the b-axis direction with very weak terminal-piperazine-N—H⋯O(hydroxy) interactions between them. An evaluation of the Hirshfeld surfaces confirms the importance of intermolecular interactions involving oxygen and sulfur atoms.The title compound, [Cd(C Layers thus formed stack along the b axis, with very weak terminal-piperazine-N4—H⋯O2(hydroxy) interactions between them, Table 2In the extended structure, hydroxy-O1—H⋯O2(hydroxy), hydroxy-O2—H⋯N4 and (coordinated-piperazine)-N3—H⋯O1(hydroxy) hydrogen bonds Table 2 lead to Crystal Explorer , and there is no contribution from C⋯C contacts in the structure as the result of the absence of C—H⋯π and π–π stacking interactions. Finally, the presence of S⋯S contacts can also be viewed in the delineated fingerprint plot, Fig. 7g, by the density of points in the ed, id region around 1.7–2.4 Å as a broken line segment.The overall two-dimensional fingerprint plot, Fig. 72% Fig. 7d, and tet al., 2014The identified intermolecular interactions were further evaluated by an analysis of the enrichment ratios (ER) that give a quantitative measure of the likelihood of specific intermolecular interactions to occur based on a Hirshfeld surface analysis 2]2 compounds are usually binuclear CH2CH2OH]2 CH2CH2OH]2·EtOH]x for x = 2 and, unprecedented, n  form transforming in solution to the thermodynamic, binuclear form (x = 2). Other recrystallization conditions led to decomposition of the dithiocarbamate ligands and subsequent formation of a co-crystal and some salts. This behaviour, along with the unexpected structure of {Cd[S2CN(iPr)CH2CH2OH]22] 2(MeOH)2 CH2CH2OH]2 : ν (O—H) 3281, ν(C—N) 1442, ν (C—O) 1169, ν (C—S) 1029.The reagents Cd[SUiso(H) set to 1.2Ueq(C). The oxygen- and nitrogen-bound H atoms were located in a difference Fourier map but were refined with a distance restraints of O—H = 0.84±0.01 Å and N—H = 0.88±0.01 Å, and with Uiso(H) set to 1.5Ueq(O) and 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table 510.1107/S2056989016000165/hb7558sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016000165/hb7558Isup2.hklStructure factors: contains datablock(s) I. DOI: 1445316CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In three potentially anticonvulsant compounds, of which two are isoindoline derivatives and one an isoquinoline derivative, the central moiety is planar. In the crystals of all three compounds, there are C—H⋯O hydrogen bonds present linking the molecules into two-dimensional slabs for the isoindoline derivatives, and into a three-dimensional framework for the isoquinoline derivative. 9H7NO3, (1), C10H7NO5, (2), and C14H9NO5, (3), are three potentially anticonvulsant compounds. Compounds (1) and (2) are isoindoline derivatives and (3) is an isoquinoline derivative. Compounds (2) and (3) crystallize with two independent molecules (A and B) in their asymmetric units. In all three cases, the isoindoline and benzoisoquinoline moieties are planar . The substituents attached to the N atom are almost perpendicular to the mean planes of the heterocycles, with dihedral angles of 89.7 (3)° for the N—O—Cmethyl group in (1), 71.01 (4) and 80.00 (4)° for the N—O—C(=O)O—Cmethyl groups in (2), and 75.62 (14) and 74.13 (4)° for the same groups in (3). In the crystal of (1), there are unusual intermolecular C=O⋯C contacts of 2.794 (1) and 2.873 (1) Å present in molecules A and B, respectively. There are also C—H⋯O hydrogen bonds and π–π interactions [inter-centroid distance = 3.407 (3) Å] present, forming slabs lying parallel to (001). In the crystal of (2), the A and B molecules are linked by C—H⋯O hydrogen bonds, forming slabs parallel to (10-1), which are in turn linked via a number of π–π interactions [the most significant centroid–centroid distances are 3.4202 (7) and 3.5445 (7) Å], forming a three-dimensional structure. In the crystal of (3), the A and B molecules are linked via C—H⋯O hydrogen bonds, forming a three-dimensional structure, which is consolidated by π–π interactions [the most significant inter-centroid distances are 3.575 (3) and 3.578 (3) Å].The title compounds, C The compound is a dual MES/6Hz active compound. Compounds (2) and (3) showed similar activity.2-Methoxyisoindoline-1,3-dione, (1), studied by X-ray techniques, was inactive in MES and scPTZ in mice, but showed MES protection in rat studies at 50 mg kgThe title compounds, containing either an isoindoline-1,3-dione moiety, (1) Fig. 1 and (2) In compound (1), the isoindoline ring is planar [r.m.s. deviation = 0.017 (4) Å]. The methoxy O atom, O3, deviates from this plane by 0.176 (6) Å while the methyl C atom, C9, is out of the plane by 1.105 (9) Å. The methoxy substituent is oriented almost perpendicular to the indoline ring with the dihedral angle between the mean planes of the indoline ring and the methoxy substituent being 89.7 (3)°.A and B) in the asymmetric unit. The isoindoline ring is planar [r.m.s. deviation = 0.0327 (9) for A and 0.0147 (9) Å for B] with the dione O atoms significantly out of the plane for molecule A but not for molecule B . The carbonato moiety is planar in both molecules  and makes dihedral angles of 71.50 (3) and 80.03 (4)° with the benzoisoquinoline ring in A and B, respectively, indicating that these substituents are oriented almost perpendicular to the benzoisoquinoline ring system.In compound (2), there are two molecules (A and B) in the asymmetric unit. In both molecules, the benzoisoquinoline ring systems are planar . The methoxy O atom deviates from this plane by 0.126 (1) for atom O5A in A and 0.156 (1) Å for atom O5B in B. The methyl carbonate moieties are planar  and these substituents are oriented almost perpendicular to the isoquinoline rings, making dihedral angles of 71.50 (3) and 80.04 (4)° for A and B, respectively. As in (2), these dihedral angles are significantly smaller than that found for (1).In compound (3), there are also two molecules  Å; Cg1 and Cg2 are the centroids of rings N1/C1/C2/C7/C8 and C2–C7, respectively; symmetry codes: (i) x − 1, y, z; (ii) x + 1, y, z].In the crystal of (1), there are C—H⋯O hydrogen bonds Fig. 4 and π–π A and B molecules are linked by C—H⋯O hydrogen bonds  for Cg1⋯Cg5ii and 3.5445 (7) Å for Cg2⋯Cg4ii .In the crystal of (2), the ds Fig. 5, formingA and B molecules are linked by C—H⋯O hydrogen bonds , Cg2⋯Cg3iii = 3.575 (3) Å and Cg9⋯Cg10iv; Cg1, Cg2, Cg3, Cg9 and Cg10 are the centroids of rings N1A/C1A–C5A, C2A/C3A/C6A–C9A, C3A/C4A/C9A–C12A, C2B/C3B/C6B–C9B and C3B/C4B/C9B–C12B, respectively; symmetry codes: (iii) x, −y + z − x, −y + z + In the crystal of (3), the ds Fig. 6, formingA and O1B) has a short intermolecular interactions with the central C atom of the carbonato group , which is perpendicular to the carbonato plane indicating that both atoms, C9A and C9B, must have significant positive character. These interactions link the molecules into dimers as shown in Figs. 6A (but not for molecule B), where a longer intermolecular interaction of 3.060 (3) Å is observed between atoms O2A and C13A, resulting in weakly associated dimers similar to that seen in the case of (2).Interestingly, in the crystal of (2) one of the two dione moieties for each molecule :N-hydroxyphthalimide  in absolute ethanol (350 ml), and the red reaction mixture was stirred at room temperature for 30 min. The brick-red precipitate was collected, washed with water, and dried in the oven at 373 K for 30 min to give 17.45 g (95%) of sodium phthalimide oxide as brick-red crystals; m.p. > 573 K. To the solution of sodium phthalimide oxide  in water (15 ml) was added acetone (10 ml), followed by a solution of bromomethane . The reaction mixture was stirred at room temperature for 16 h, during which the red color disappeared. On standing at room temperature for 48 h, the product solidified in the aqueous mixture and was collected. Recrystallization from 2-propanol gave 0.72 g (78%) of compound (1) as plate-like colorless crystals: m.p. 395–397 K; 1H NMR (CDC13) δ 3.36 , 5.52, s, 1 H,CH, 7.87 .To a freshly prepared solution of sodium  in absolute ethanol (60 ml) was added a solution of Compound (2):1H NMR (CDC13) δ 3.8 , 7.86 .To a solution of sodium phthalimide oxide  in water (15 ml) was added acetone (10 ml), followed by a solution of bromo(methoxy)methanone . The reaction mixture was stirred at room temperature for 16 h, during which the red color disappeared. On standing at room temperature for 48 h, the product solidified in the aqueous mixture and was collected. Recrystallization from ethanol gave 0.82 g (74%) of compound (2) as colorless crystals: m.p. 410–411 K; Compound (3):1H NMR (CDCl3) δ 3.79 , 5.66 , 7.65–8.50 .To a solution of sodium naphthalimide oxide, , in water (50 ml), was added bromo(methoxy)methanone  in acetone (10 ml). The red reaction mixture was stirred at room temperature. The red color disappeared within 5 min and the reaction mixture was filled with a white precipitate. After standing for 4 h, the white precipitate was collected, washed with water, and recrystallized from ethanol to give 1.46 g (89%) of compound (3) as colorless crystals: m.p. 483–485 K; isoU(H) = 1.5Ueq(C) for methyl H atoms and = 1.2eqU(C) for other H atoms.Crystal data, data collection and structure refinement details for (1), (2) and (3) are summarized in Table 410.1107/S1600536814023769/su2795sup1.cifCrystal structure: contains datablock(s) 1, 2, 3. DOI: 10.1107/S1600536814023769/su27951sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S1600536814023769/su27952sup3.hklStructure factors: contains datablock(s) 2. DOI: 10.1107/S1600536814023769/su27953sup4.hklStructure factors: contains datablock(s) 3. DOI: Click here for additional data file.10.1107/S1600536814023769/su27951sup5.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S1600536814023769/su27952sup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S1600536814023769/su27953sup7.cmlSupporting information file. DOI: 1031391, 1031392, 1031393CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The title compound, biscobalt(III) tris(perchlorate) methanol monosolvate monohydrate, is a novel complex in which the metal centre is hexacoordinated. 25H30N4O4)2](ClO4)3·CH3OH·H2O, the metal atom is coordinated by two tridentate crown ether terpyridine ligands, forming a distorted CoN6 octahedron. The three pyridine rings in each crown–terpyridine ligand are approximately coplanar [maximum deviations = 0.088 (12) and 0.102 (15) Å] and the mean planes through the three pyridine rings are perpendicular to each other, making a dihedral angle of 89.95 (17)°. An intramolecular C—H⋯π interaction is observed between the two terpyridine ligands. In the crystal, O—H⋯O and C—H⋯O hydrogen bonds, a π–π stacking interaction [centroid–centroid distance = 3.923 (7) Å] and a C—H⋯π interaction connect the complex cation, the perchlorate anions and the two types of solvent molecules, forming a three-dimensional network.In the title compound, [Co(C M(R-terpy)]X2 , have been investigated because of their interesting properties such as magnetic and photochemical characteristics. Cobalt(II) complexes with R-terpy ligands are known as spin-crossover compounds. Previously, we observed the unique spin-transition behavior in [Co(II)(R-terpy)2](BF4)2 with long-alkylated terpyridine ligands, and showed that the magnetic behaviors are influenced not only by inter-chain interactions between long alkyl chains but also by π–π stacking interactions between terpyridine moieties  compounds. The Co—N distances of the central pyridine in the terpyridine unit [1.844 (9) Å] are shorter than the Co—N distances of the side pyridine in the terpyridine unit [1.910 (10)–1.949 (10) Å], which induces a pronounced distortion of the CoN6 octahedron. The three pyridine rings in each crown–terpy ligand are approximately coplanar [maximum deviations 0.102 (15) and 0.088 (12) Å], and the two mean planes through the three pyridine rings in the complex are nearly perpendicular to each other, making a dihedral angle of 89.95 (17)°.The asymmetric unit of the title compound consists of one [Co(crown–terpy)The overall packing of structure is shown in Fig. 24)3  dissolved in methanol (20 ml) was poured dropwise into a solution of the crown–terpy ligand  in 1:1 methanol–chloroform. The precipitate formed immediately and was filtered. Single crystals of the title compound suitable for X-ray diffraction were obtained from a methanol solution.The crown-terpyridine ligand was prepared by the reaction of 4′-bromo-2,2′:6′,2′′-terpyridine  and 1,4,7,10-tetraoxa-13-azacyclopentadecane  in DMF. The mixed solution was evaporated to give the ligand as a white powder. Co(ClOUiso(H) = 1.2Ueq(C) and 1.5Ueq. The positions of the H atoms of the water molecule were refined with restraints of O—H = 0.85 (2) and H⋯H = 1.38 (2) Å, and with Uiso(H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989015014164/is5400sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015014164/is5400Isup2.hklStructure factors: contains datablock(s) I. DOI: 1415327CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The title complex is a centrosymmetric dimer with a copper–copper distance of 4.0408 (3) Å. The Cu ions in the dimer are bridged by two triazole rings and oxygen donor ligands from water molecules and nitrate anions in a distorted octahedral coordination geometry. 2(C10H8N7)2(NO3)2(H2O)2]·2H2O, consists of centrosymmetric dimeric units with a copper–copper separation of 4.0408 (3) Å. The CuII ions in the dimer display a distorted octahedral coordination geometry and are bridged by two triazole rings, forming an approximately planar Cu2N4 core (r.m.s. deviation = 0.049 Å). In the crystal, O—H⋯O, O—H⋯N and C—H⋯O hydrogen bonds and π–π interactions link the molecules into a three-dimensional network.The structure of the dinuclear title complex, [Cu The study of this type of coordination compound is promising since, as a result, a compound can be obtained with useful physical properties such as optical, magnetic or catalytic  Å for atom N2], with a Cu⋯Cu separation of 4.0408 (3) Å, in good agreement with the values usually observed in μ-triazolyl-bridged complexes  Å; θ2 = 88.62 (16)°], while the five-membered Cu1/N2/C1/C2/N4 chelate ring adopts a flattened envelope conformation with the Cu atom as flap .The structure of the title complex molecule Fig. 1 has a crCg1⋯Cg2ii = 3.8296 (13) Å and Cg3⋯Cg3iii = 3.5372 (10), and perpendicular interplanar distances Cg1⋯Cg2ii = 3.5584 (9) and Cg3⋯Cg3iii = 3.3234 (10) Å .In the crystal, the complex molecules and water molecules of crystallization are linked through O—H⋯O, O—H⋯N and C—H⋯O hydrogen bonds Table 1, forming2–Cu. The most similar are: diaquabis-1,2,4-triazolato-N′,N1,N2,N′′)bis(trifluoromethanesulfonato-O)dicopper(II) -1,2,4-triazolato]diaquadicopper diperchlorate -5-(methyl)-1,2,4-triazol-1-ide]triaquatricopper diperchlorate dihydrate bis(acetonitrile)bis(perchlorato-O)dicopper 2·3H2O  was added to a hot solution of 2-[5--triazol-1-yl-methyl-1H--triazol-3yl]pyridine  in water (7 ml). The transparent blue solution was left to evaporate slowly in the air and after few hours, blue single crystals suitable for X-ray analysis were obtained (yield: 67%).A water solution of Cu(NOUiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016003479/rz5185sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016003479/rz5185Isup2.hklStructure factors: contains datablock(s) I. DOI: 1456451CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The azaadamantane structure in (I) is slightly distorted, with N—CH2—CH2—N torsion angles of 10.4 (3) and −9.0 (3)°. These values differ slightly from the corresponding torsion angles in the free aminal cage (0.0°) and in related co-crystalline adducts, which are not far from a planar geometry and consistent with a Dd2 molecular symmetry in the tetraazatricyclo structure. The structures also differ in that there is a slight elongation of the N—C bond lengths about the N atom that accepts the hydrogen bond in (I) compared with the other N—C bond lengths. In the crystal, the two molecules are not only linked by a classical O—H⋯N hydrogen bond but are further connected by weak C—H⋯π interactions, forming a two-dimensional supramolecular network parallel to the bc plane.In the crystal of the title co-crystalline adduct, C Reaction between TATD with 4-chloro-3,5-dimethylphenol in solution yields symmetrical bis-benzoxazines -1,8,10,12-tetraazatetracyclopentadecane with 4-nitrophenol -4-bromophenol –4-chloro-3,5-dimethylphenol under solvent-free conditions by simply grinding together the components at room temperature. Herein, we describe the synthesis of the title co-crystalline adduct 1,3,6,8-tetraazatricyclododecane (TATD) and a 4-chloro-3,5-dimethylphenol molecule linked via an O—H⋯N hydrogen bond, forming a D motif ; p-bromophenol (pKa = 9.37) and hydroquinone (pKa = 9.85) et al., 2007et al., 2015et al., 1987et al., 20142dD point group, two small differences are noted. The azaadamantane structure in (I)2—CH2—N torsion angles of 10.4 (3)° (N1—C1—C2—N2) and −9.0 (3)° (N3—C7—C8—N4). These values differ slightly from the values of the corresponding torsion angles in the free aminal cage  and 1.480 (2) Å], compared to the the other N—C bond lengths  Å; symmetry operator: (i) x, −y, z − c-axis direction e Table 2. Furtheron Fig. 3.methyl = 1.502 (3), 1.500 (3), 1.514 (3) and 1.505 (3) Å]. For 1,3,6,8-tetraazatricyclododecane, two comparable structures were retrieved from the CSD 3,8]dodecane co-crystallized with hydroquinone 3,8]dodecane is rather limited.The geometric parameters of 4-chloro-3,5-dimethylphenol in (I)3,8]dodecane (TATD)  and 4-chloro-3,5-dimethylphenol  was ground using a mortar and pestle, at room temperature for 15 min., as required to complete the reaction (TLC). The mixture was then dissolved in methanol. Crystals suitable for X-ray diffraction were obtained from a methanol solution upon slow evaporation of the solvent at room temperature.A mixture of 1,3,6,8-tetraazatricyclo[4.4.1.Uiso(H) values set at 1.2Ueq (1.5 for methyl groups) of the parent atom. The methyl groups were allowed to rotate but not to tip.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989015010257/zs2335sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015010257/zs2335Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015010257/zs2335Isup3.cmlSupporting information file. DOI: 1403518CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The Fe—N bond lengths are indicative of a d6 low-spin state for the FeII ion in the complex. The dihedral angle between the phen ligands in the cation is 87.64 (6)°. The Tf2N− counter-anion is non-coordinating, with the –CF3 groups arranged in a trans fashion with respect to each other, leading to an anti,anti conformation of the –CF3 groups and –SO2N– moieties relative to the S—C bonds. The water molecule of crystallization connects two O atoms of the Tf2N− anions through weak hydrogen bonds. C—H⋯O hydrogen-bonding interactions are also observed, consolidating the packing of the molecules into a three-dimensional network structure.The crystal structure of the title complex, [Fe(C DOI: 10.1107/S2056989014026966/wm5100Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989014026966/wm5100fig1.tif3 2+ 2 − 2 x y z . DOI: 3]2+, Tf2N− and H2O molecular units. Displacement ellipsoids are represented at the 30% probability level. Hydrogen atoms were omitted for clarity. [Symmetry code: i) −x + 1,y,-z + View of the [Fe(phen)Click here for additional data file.10.1107/S2056989014026966/wm5100fig2.tif2 2 − x y z x y z . DOI: 2O molecule and Tf2N− anions. [Symmetry codes: ii) x − y − 1/2,z, iii) −x + y − z + Hydrogen bonds between the H1038289CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The cationic NiII center is in a distorted square-planar coordination environment chelated by the imine N and phenolate O donor atoms of the two Schiff base ligands. The N and O donor atoms of the two ligands are mutually trans with Ni—N and Ni—O bond lengths of 1.9242 (10) and 1.8336 (9) Å, respectively. The fluorophenyl ring is almost orthogonal to the coordination plane and makes a dihedral angle of 82.98 (7)° with the phenolate ring. In the crystal, molecules are linked into screw chains by weak C—H⋯F hydrogen bonds. Additional C—H⋯π contacts arrange the molecules into sheets parallel to the ac plane.The asymmetric unit of the title complex, [Ni(C In particular they can be photoluminescent -(4-fluorobenzyl)iminomethyl]-6-methoxyphenolato-κ2N,O1}nickel(II) -(4-methoxybenzyl)iminomethyl]phenolato-κ2N,O1}nickel(II) 2] (1), and its characterization by spectroscopy and elemental analysis. Crystal structure determination confirms the binding mode of the [(4-fluorobenzyl)iminomethyl]phenolate ligand to the NiII cation ° and O1—Ni1—N1i = 87.44 (4)° . As expected under inversion symmetry, the trans angles (N11—Ni1—N1i and O1—Ni1—O1i) are found to be linear. The Ni1—N1 and Ni1—O1 distances in the N2O2 coordination plane are 1.9242 (10) Å and 1.8336 (9) Å, respectively. These compare well with those observed in the two other closely related NiII complexes with N2O2 coordinating Schiff base ligands  Å, θ = 65.3 (3) and ϕ = 4.0 (3)°. Other bond lengths and angles observed in the structure are also normal. The fluorophenyl ring (C9–C14) makes a dihedral angle of 82.98 (7)° with the phenolate ring (C1–C6).The asymmetric unit of (1) contains one-half of the molecule with the Nind Fig. 1. The catA⋯F1 interactions phenolate residues. No corresponding structures with a benzyl or substituted benzyl unit bound to the imino N atom were found. However extending the search to allow additional substitution on the phenolate ring resulted in eight discrete structures including the two closely related structures mentioned previously  revealed a total of 1191 NiE)-2-[(4-fluorobenzylimino)methyl]phenol. Nickel(II) acetate tetrahydrate  was dissolved separately in absolute ethanol (10 ml) and added to a flask containing the cooled ligand solution. The mixture was stirred and refluxed for 3 h upon which a dark-green solid formed. This was filtered off, washed with ice-cold ethanol and air-dried at room temperature. The solid product was recrystallized from chloroform, yielding green crystals. Yield 68.6%; m.p. 471–473 K. Analytical data for C28H22F2N2O2Ni: C, 65.28; H, 4.30; N, 5.44. Found: C, 65.87; H, 4.39; N, 5.55. IR : ν(C=N) 1612 (s), ν(C—N) 1390 (w), ν(C—O) 1221 (s), ν(Ni—N) 597 (w), ν(Ni—O) 451 (w). The infrared spectra of the title complex revealed a strong band of 1612 cm−1 in the spectrum assignable to C=N stretching frequency upon complexation  was added to salicylaldehyde , dissolved in absolute ethanol (2 ml), forming a bright-yellow solution. The mixture was heated under reflux for an hour to produce the ligand,  = 0.95 Å for aromatic and 0.99 Å for CH2 hydrogen atoms. The Uiso values were constrained to be 1.2Ueq of the carrier atoms.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S1600536814020546/sj5425sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814020546/sj5425Isup2.hklStructure factors: contains datablock(s) I. DOI: 1024161CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, N—H⋯O, C—H⋯O and C—H⋯F interactions connect the molecules, forming supramolecular chains propagating along the  22H23F2N3O2, the bicyclic ring system exists in a twin-chair conformation with an equatorial disposition of the 4-fluorophenyl groups on the heterocycle. These aromatic rings are inclined to one another by 19.4 (1)°. In the crystal, molecules are linked by pairs of N—H⋯O and C—H⋯O hydrogen bonds into inversion dimers, incorporating R12(7) and R22(8) ring motifs; the same O atom accepts both hydrogen bonds. These dimers are further linked by a pair of C—H⋯F hydrogen bonds, enclosing R22(28) ring motifs, forming supramolecular chains along [010]. The NH group of the pyridine ring is not involved in hydrogen bonding, probably due to the steric hindrance of the fluorophenyl groups.In the title compound, C The fluorophenyl groups on the heterocycle occupy equatorial positions and are inclined to one another by 19.4 (1)°. The geometric parameters of the title molecule agree well with those reported for similar structures, for example, 2,4-bis(4-fluorophenyl)-3-azabicyclo[3.3.1]nonan-9-one, (II) i and C2—H2⋯O3i .In the crystal, pairs of bifurcated acceptor N3—H3⋯O3i Table 1 hydrogenfs Fig. 2. These di Table 1 hydrogenviz. compound (III)  in the asymmetric unit. In all three compounds, the bicyclo rings have twin-chair conformations with equatorially disposed 4-fluorophenyl groups on the heterocycle. The fluorophenyl rings are oriented at an angle of 28.7 (1)° in (II), and 55.3 (1) (molecule A) and 56.4 (1)° (molecule B) for (III), compared to 19.4 (1)° in the title compound, (I)38 ‘hits’ for crystal structures containing the 3-azabicyclo[3.3.1]nonane subunit were obtained for a search of the Cambridge Structural Database  medium, with the addition of few drops of acetic acid, was stirred for 10–12 h. After completion of the reaction a solid mass was formed. The precipitate was filtered off and washed with an ethanol–water mixture. The crude product was then recrystallized from ethanol–chloroform to obtain colourless diffraction-quality crystals of title compound.A mixture of 2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9-one (0.1 mmol), methyl hydrazinecarboxylate (1.5 mmol) in an ethanol–chloroform (1:1 Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq for all other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S1600536814018935/su2773sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814018935/su2773Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814018935/su2773Isup3.cmlSupporting information file. DOI: 1020373CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the title compound, the planes of the phenoxy and phthalonitrile rings are oriented at a dihedral angle of 60.39 (5)°. In the crystal, molecules are linked by O—H⋯O, O—H⋯N and N—H⋯O hydrogen bonds, forming slabs parallel to (100). The slabs are linked by a pair of inversion-related C—H⋯N hydrogen bonds, forming a three-dimensional structure. 20H20N4O2·H2O, the planes of the phenoxy and phthalonitrile rings are oriented at a dihedral angle of 60.39 (5)°. The 3-(dimethylamino)propyl chain has an extended conformation and is cis with respect to the phthalonitrile ring. In the crystal, O—H⋯O, O—H⋯N and N—H⋯O hydrogen bonds link the molecules to form slabs parallel to (100). There are also C—H⋯O and C—H⋯N hydrogen bonds and C—H⋯π interactions present within the slabs. The slabs are linked by a pair of inversion-related C—H⋯N hydrogen bonds, involving phthalonitrile rings, forming a three-dimensional structure.In the title compound, C Well-known application fields for amino derivatives are their use as synthetic intermediates of anticancer agents, antibiotics and other drugs. They also exhibit exceptionally low ocular irritation and oral toxicity, being well tolerated by human tissue , O—Hw. .Oamd and O—Hw⋯Ndma (dma = dimethylamino) hydrogen bonds , and the O—Hw⋯ Oamd, C—Hphen⋯Oamd and C—Hphen⋯Ow hydrogen bonds form via a pair of inversion-related Cphn—H⋯Nphn  hydrogen bonds, forming a three-dimensional structure phthalonitrile °.A search of the Cambridge Structural Database  = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for the other H atoms.The experimental details including the crystal data, data collection and refinement are summarized in Table 2N,N-dimethylpropane-1,3-diamine  and K2CO3  in dry tetrahydrofuran , stirred in an ice bath for 15 min, was added over a period of 40 min, 4-benzoyl chloride  in dry THF (5 ml). The reaction mixture was then stirred for 5 h at room temperature and monitored by thin-layer chromatography [THF–hexane (3:4 v/v) as a mobile phase on silica-gel plates]. The oily residue obtained was dissolved in MeOH. The solvent was evaporated slowly and colourless block-like crystals appeared in ca 10 d .To a mixture of 10.1107/S2056989015014991/su5187sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015014991/su5187Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015014991/su5187Isup3.cmlSupporting information file. DOI: 1418026CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


P,S-donor set is observed in the title polymorph; an intramolecular Au⋯O interaction is noted. The packing is consolidated by C—H⋯O and C—H⋯π interactions to generate a three-dimensional network.A linear geometry defined by a  8H7ClNOS)(C18H15P)], is a monoclinic  polymorph of the previously reported triclinic form  [Tadbuppa & Tiekink  coordination geometry [P—Au—S = 175.62 (5)° in the title polymorph], being coordinated by thiolate S and phosphane P atoms, a Z conformation about the C=N bond and an intramolecular Au⋯O contact. The major conformational difference relates to the relative orientations of the residues about the Au—S bond: the P—Au—S—C torsion angles are −8.4 (7) and 106.2 (7)° in forms α and β, respectively. The molecular packing of form β features centrosymmetric aggregates sustained by aryl-C—H⋯O interactions, which are connected into a three-dimensional network by aryl-C—H⋯π contacts. The Hirshfeld analysis of forms α and β shows many similarities with the notable exception of the influence of C—H⋯O interactions in form β.The title compound, [Au(Ckink 2010. Acta Cr N-aryl-O-alkylthiocarbamates, i.e. compounds of general formula R3PAu[SC(OR′)=NR′′]  continues owing to their recently disclosed exciting biological activities. Thus, various triphenylphosphane derivatives display excellent cytotoxicity profiles against HT-29 colon cancer cells, a particularly virulent form of cancer, and mechanistic studies have shown these to induce both intrinsic and extrinsic pathways of cell death leading to apoptosis  et al., 2005et al., 2007i.e. 3.052 (3) Å. The pattern of bond angles about the quaternary carbon atom, C1, follow the expected trends with the widest angle involving the sulfur and doubly bonded nitrogen atom and with the narrowest angle involving the single-bonded atoms. The conformation about the formal C1=N1 bond, Table 1Z.The molecular structure of the new monoclinic form of (I)P21/n with Z′ = 1. The earlier polymorph, by contrast, crystallizes in triclinic space group PZ′ = 1. A comparison of the key geometric parameters is given in Table 1Form β crystallizes in the monoclinic space group a and Table 2b and Table 23P ligands align to form a so-called six-fold phenyl embrace (6PE) Supramolecular dimers feature in the molecular packing of form β of (I)i.e. forms α and β, were studied through Hirshfeld surface analysis by mapping on the normalized contact distance (dnorm) upon computation of the inner (di) and outer (de) distances of the Hirshfeld surface to the nearest nucleus Supramolecular features, C—H⋯π interactions feature in both structures. To a first approximation the decomposed fingerprint plots look similar, as seen from Fig. 5b. However, relatively shorter contacts are found in form β cf. form α, i.e. 2.62 vs 2.68 Å. The clear distinction between the two forms is readily noted from the decomposed fingerprint plots for the O⋯H/H⋯O contacts with very distinct spikes evident for form β, Fig. 5c, correlating with the C—H⋯O interactions leading to dimer formation. While beyond the sum of their respective van der Waals radii  and asphericity (Ω) indices. All these indicators suggest that the polymorphs arise as a result of a simple interplay between molecular conformation and crystal-packing effects.In general, the observation of generally shorter contacts in form β may indicate greater crystal-packing efficiency ,  is intermediate between those found in the polymorphic forms of (I)The most closely related structure to (I)Chemical context, biological considerations motivate ongoing investigations into the chemistry of phosphanegold(I) N-aryl-O-alkylthiocarbamates. This notwithstanding, the relative ease of growing crystals have prompted several crystal engineering studies. Thus, correlations between Au⋯Au (aurophilic) and solid-state luminescence responses have been made for the series of compounds, R3PAu[SC(OMe)=NC6H4NO2-p] , and bidentate phosphane analogues, Ph2P–(CH2)n–PPh2 for n = 1–4 and when the bridge is Fc (ferrocenyl) 4PPh2){AuSC(OR′)=NC6H4Y-p}2] for R′ = Me, Et or iPr and Y = H, NO2 or Me was undertaken =NR′′], for R = Ph, o-tol, m-tol or p-tol, and R′’ = Ph, o-tol, m-tol, p-tol or C6H4NO2-p, where it proved possible to induce a conformational change in the molecule so that an intramolecular Au⋯π interaction formed rather than Au⋯O  species yielding binuclear molecules also with intramolecular Au⋯π interactions  in MeOH , followed by addition of the thiocarbamide, MeOC(=S)N(H)C6H4Cl3 , prepared following literature precedents : 1434 (s) ν(C=N), 1180 (s) ν(C—O), 1098 (s) ν(C—S).Preparation of (I)Uiso(H) set to 1.2–1.5Ueq(C). The maximum and minimum residual electron density peaks of 2.04 and 1.06 e Å−3, respectively, were located 1.01 and 0.77 Å from the Au atom.Crystal data, data collection and structure refinement details are summarized in Table 510.1107/S2056989016010781/hb7598sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016010781/hb7598Isup2.hklStructure factors: contains datablock(s) I. DOI: 1489737CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the title compound, the pyrrolidine and cyclohexane rings exhibit envelope and chair conformations, respectively. In the crystal, C—H⋯O interactions connect the molecules into tape structures. 19H25NO2, the pyrrolidine ring adopts an envelope form, with the spiro C atom as the flap, while the cyclohexane ring shows a chair form. A weak intramolecular C—H⋯O interaction supports the molecular conformation, generating an S(6) ring motif. In the crystal, pairs of C—H⋯O interactions connect the molecules into inversion dimers with an R22(16) ring motif. The dimers are linked by a second pair of C—H⋯O interactions, enclosing an R42(12) ring motif, into a tape structure along the b axis.In the title compound, C N-hydroxy or N-alkoxy substituent have been widely explored in organic synthesis. These substances show specific and intriguing reactivity caused by a covalent bond between the electronegative heteroatoms. Among these compounds, for example, the N-alkoxyamines are known to be initiators for stable free radical polymerization  = 0.1965 (16) Å and φ(2) = 151.8 (5)°. The flap atom C5 deviates from the mean plane of other four atoms by 0.314 (2) Å. For the N-alkoxy-N-alkylamide moiety, the geometry around atom N1 is a little deformed from a planar to a pyramidal configuration. The shift of atom N1 from the C2/C5/O14 plane is 0.2163 (13) Å, and the sum of angles for C2—N1—O14, O14—N1—C5 and C5—N1—C2 is 353.0°.The molecular structure of the title compound is shown in Fig. 1Q = 0.5782 (17) Å, θ = 1.82 (17)°, φ = 347 (5)°, Q(2) = 0.0197 (17) Å and Q(3) = 0.5779 (17) Å. The equatorially oriented C10—C11 bond makes an angle of 70.60 (9)° with the normal to the Cremer & Pople plane of the cyclohexane ring, and the vinyl group (C11=C12) is positioned in syn-periplanar geometry to the cyclohexane framework, with a C9—C10—C11=C12 torsion angle of 10.9 (2)°.The cyclohexane ring (C5–C10), which is spiro-fused to the pyrrolidine ring, adopts a chair form with puckering parameters of S(6) graph-set motif. No intramolecular C—H⋯π interaction is observed.An intramolecular C—H⋯O interaction (C15—H15⋯O13) supports the molecular conformation, generating an i; Table 1b axis by weak C—H⋯O interactions , are registered , but no compound with an N-alkoxy substituent, (c).In the Cambridge Structural Database , which is related to the title compound, (e), has also been reported , the pyrrolidine ring adopts a similar conformation to the title compound. The spiro-C atom is at the flap of the envelope, and the geometry around the N atom shows a little deformation to a pyramidal configuration with the sum of the C(carbonyl)—N—O, O—N—C and C—N—C(carbonyl) angles being 345.8 (5)°. No intramolecular C—H⋯O interaction is observed in (d).The structure of an et al., 2015m/z calculated for C19H25NO2Na+ [M + Na]+: 322.1783; found: 322.1779. Analysis calculated for C19H25NO2: C 76.22, H 8.42, N 4.68%; found: C 76.31, H 8.44, N 4.58%.The title compound was synthesized convergently from hex-5-en-1-ol, methyl 4-chloro-4-oxobutyrate and 1-phenylethanol (Yamamoto Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989015021209/is5431sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015021209/is5431Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015021209/is5431Isup3.cmlSupporting information file. DOI: 1435676CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The two tridentate terpyridine ligands define the coordination of the Ni2+ cation, resulting in a nearly octahedral coordination sphere, although there is not any imposed crystallographic symmetry about the Ni2+ site. The two nearly linear dicyanidoaurate(I) anions [C—Au—C = 179.0 (2) and 178.2 (2)°] contain a short aurophilic interaction of 3.1017 (3) Å. The structure does not demonstrate any π–π stacking. Non-classical C—H⋯N interactions between the cations and anions build up a three-dimensional network.The title compound, [Ni(C M(terpy)2](X)  have been known since the 1970′s 2][Au(CN)2]2, (I)Derivatives of the compound 2 was synthesized and analysed ]2+ cation with dicyanidoaurate(I) anions. However, the important difference between the two compounds is that there are no metal–metal interactions in the [Ni(terpy)][Au(Br)2(CN)2]2 structure containing the d8 Au(III) ion, whereas the [Ni(terpy)2][Au(CN)2]2 structure contains a d10 gold(I) dicyanidoaurate(I) anion that has a strong propensity to form aurophilic interactions. This makes the title compound of interest because it contains short aurophilic interactions, contained within dimeric [Au(CN)2]2 moieties, with Au⋯Au distances of 3.1017 (3) Å  Å Fig. 1.D⋯A distance of 3.5 Å as the upper defined limit. Details of the interactions can be found in Table 1Structural commentary above. There are no π–π stacking interactions in the structure.A packing diagram of the title compound is illustrated in Fig. 2M Ni(NO3)2 (1 ml) and 0.1 M 2,2′:6′.2"-terpyridine (1 ml) were mixed together. Following the mixture of these two compounds, 2 ml of 0.05 M KAu(CN)2 (50:50 ethanol/water v/v) was added dropwise. A precipitate formed and the suspension was mixed thoroughly and centrifuged. The brownish-red solution was decanted from the solid precipitate and placed in a test tube to allow for slow evaporation. After approximately one week, the formation of brownish-red crystals had begun. The grown single crystals were then gathered and isolated.Ethanol solutions of 0.1 Uiso(H) = 1.2Ueq(C) and C—H distances of 0.93 Å.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S1600536814024672/wm5063sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814024672/wm5063Isup2.hklStructure factors: contains datablock(s) I. DOI: 1033527CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The asymmetric unit contains a quarter each of two crystallographically independent propane-1,3-diammonium dications, [AlF6]3− and [AlF4(H2O)2]− anions and four water molecules. The cations, anions and three of the independent water molecules are situated on special positions mm, while the fourth water molecule is disordered about a mirror plane. In the crystal, intermolecular N—H⋯F and O—H⋯F hydrogen bonds link the cations and anions into a three-dimensional framework with the voids filled by water molecules, which generate O—H⋯O hydrogen bonds and further consolidate the packing.The title compound, (C The [AlF6] octahedron is regular whereas [AlF4(H2O)2] exhibits a pronounced distortion due to the strong influence of the crystal field created by the heteroligands (F−/H2O). The value of the calculated valences (3.08 for Al1 and 3.01 for Al2) of the individual Al3+ cations 2] octahedron is linked via N—H⋯F or O—H⋯F hydrogen bonds (Table 1a axis. These chains are linked to each other by the AlF63− dications and form infinite (H2dap)[AlF4(H2O)2] layers parallel to the ac plane anions or extended 1D inorganic chains, 2D inorganic layers or 3D networks are mentioned. Eight compounds with AlF63− anions exist 2− anion 2− anions have been reported.In the Cambridge Structural Database  in 40% HF (1.5 ml) and ethanol (5 ml). 1,3-Diaminopropane (0.54 ml) was added and mild hydrothermal conditions (463 K) were applied in a Teflon-lined autoclave (25 ml). The resulting product was washed with ethanol and dried in air giving colourless single crystals.The title compound was prepared from a starting mixture of AlF3 and CH2 groups of the organic molecule were fixed geometrically [N—H = 0.89 (1) and C—H = 0.97 (1) Å with Uiso(H) = 1.2Ueq]. All H atoms of the water molecules were located from a Fourier difference map. The O—H distances and H—O—H angles were fixed [O—H = 0.84 (1) and H⋯H = 1.34 (1) Å with Uiso(H) =1.5Ueq(O)]. The water molecule OW5 is disordered over two positions with the occupanies fixed to 0.5.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S1600536814024155/cv5471sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814024155/cv5471Isup2.hklStructure factors: contains datablock(s) I. DOI: 1032262CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


II atom in the title complex is surrounded by a distorted Cl2N4 coordination set. In the crystal structure, adjacent complex molecules are connected through C—H⋯Cl hydrogen-bonding interactions into a layered arrangement parallel to (100). Additional C—H⋯Br hydrogen-bonding interactions along with π–π stacking interactions complete a three-dimensional supramolecular network.The Ru 2(C12H9BrN2)2] or [RuCl2(PM-BrA)2] (PM-BrA = 4-bromo-N-(2′-pyridylmethylene)aniline), the RuII cation is located on a centre of inversion and is surrounded by four N atoms of two PM-BrA ligands in the equatorial plane and by two Cl atoms in a trans axial arrangement, displaying a distorted octahedral coordination environment. Two C atoms in the benzene ring of the PM-BrA ligand are equally disordered over two sets of sites. The benzene and pyridine rings of the PM-BrA ligand are oriented at dihedral angles of 62.1 (10) and 73.7 (11)° under consideration of the two orientations of the disordered benzene ring. In the crystal, the complex molecules are connected via C—H⋯Cl hydrogen-bonding interactions into a layered arrangement parallel (100). C—H⋯Br hydrogen bonding and weak aromatic π–π stacking interactions complete a three-dimensional supramolecular network.In the title complex, [RuCl Their complexes have found utility in a wide range of applications  Å with an N1—Ru1—N2 bite angle of 76.9 (1)°. The reduced bite angle of the chelating ligand is one of the main factors accounting for the distortion from the ideal octahedral geometry of the coordination polyhedron, with the the largest cis angle being 103.1 (2)°. The Ru—N bond lengths are 2.073 (5) and 2.084 (5) Å, and the Ru—Cl bond length is 2.3908 (14) Å, in agreement with those observed in the structures of similar compounds re Fig. 1. The cooX  interactions are compiled in Table 1In the crystal, weak intermolecular C—H⋯Cl hydrogen-bonding interactions between the C atoms of the benzene ring and the Cl atoms connect the complex molecules into a supramolecular layered arrangement parallel to (100) Fig. 2. As showtrans-[RuCl2(Hpyrimol)2] (Hpyrimol = 4-methyl-2-N-(2-pyridylmethylene)aminophenol) with a closely related Schiff base N2 donor set for each ligand has been reported aniline  in dry methanol (5 ml) was placed in a test tube. A solution of RuCl3  in dry methanol (5 ml) was then carefully layered on the top of a methanolic solution. After slow diffusion at room temperature for three days, pale-green plate- or block-like crystals of complex (I)A solution of the ligand 4-bromo-Uiso(H) = 1.2Ueq(C) using a riding model with C—H = 0.95 Å. C atoms C11 and C12 and attached H atoms in the benzene ring are disordered over two set of sites and were refined using a split model with equal occupancy.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S205698901501556X/wm5204sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901501556X/wm5204Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901501556X/wm5204Isup3.cdxSupporting information file. DOI: 1419653CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


E conformation with respect to the azomethine C=N bond and the aromatic rings are inclined to one another by 3.29 (4)°. In the crystal, molecules are linked via C—H⋯O hydrogen bonds, forming zigzag chains along [10-1].The title compound has an  14H13NO2 {systematic name: (E)-2-[(4-methoxybenzylidene)amino]phenol}, is a product of the condensation reaction between 4-methoxybenzaldehyde and 2-aminophenol. The molecule adopts an E conformation with respect to the azomethine C=N bond and is almost planar, the dihedral angle between the two substituted benzene rings being 3.29 (4)°. The methoxy group is coplanar with the benzene ring to which it is attached, the Cmethyl—O—C—C torsion angle being −1.14 (12)°. There is an intramolecular O—H⋯N hydrogen bond generating an S(5) ring motif. In the crystal, molecules are linked via C—H⋯O hydrogen bonds, forming zigzag chains along [10-1]. The chains are linked via C—H⋯π interactions, forming a three-dimensional structure.The title azastilbene derivative, C The molecule is almost planar with a dihedral angle of 3.29 (4)° between the two substituted benzene rings. The methoxy group is co-planar with the benzene ring to which it is attached, the C14—O1—C4—C5 torsion angle being −1.14 (12)°. There is an intramolecular O—H⋯N hydrogen bond  ring motif. The bond lengths are comparable with those found for some closely related structures . Colourless block-shaped crystals, suitable for X-ray structure analysis, were obtained by recrystallization from methanol by slow evaporation at room temperature after several days (m.p. 388–390 K).A solution of 4-methoxybenzaldehyde  in water (20 ml) and 2-aminophenol  in water (20 ml) were mixed and stirred at room temperature for around 8 h until a white precipitate appeared. The resulting white solid was filtered, washed several times with cold ethanol and then dried 3OH) λmax (log∊): 275 (1.93), 340 (0.61) nm; FT–IR (KBr) ν: 3337, 1595, 1510, 1248, 1027 cm−1.; 1H NMR  δ, p.p.m.: 8.87 , 8.61 , 7.98 , 7.18 , 7.06 , 7.03 , 6.83 , 6.09 , 3.84 . The UV–Vis spectroscopic data showed absorption bands of an azastilbene (275 and 340 nm) while the FT–IR spectrum exhibited the stretching vibrations of O—H (3337 cm−1), C=N (1595 cm−1), C=C (1510 cm−1), C—N (1248 cm−1) and C—O (1027 cm−1). The successful synthesis was also supported by the 1H NMR spectroscopic data, which showed the characteristic signals of an olefinic proton at 8.61  and para-substituted aromatic protons at 7.98  and 7.06 , respectively. Moreover the 1H NMR spectrum also showed typical signals of ortho-substituted aromatic protons at 7.18 , 7.03 , 6.83  and 6.09  and a methoxy proton at 3.84 .UV–Vis  = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989015008348/su5124sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015008348/su5124Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015008348/su5124Isup3.cmlSupporting information file. DOI: 1062128CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


I atom within an S(dithiocarbamate) and P(phosphane) donor set.The centrosymmetric molecule features a linearly coordinated Au 34H28FeP2)[Au(C5H8NS2)]2}, comprises half a molecule, with the full molecule being generated by the application of a centre of inversion. The independent AuI atom is coordinated by thiolate S and phosphane P atoms that define an approximate linear geometry [S—Au—P = 169.35 (3)°]. The deviation from the ideal linear is traced to the close approach of the (intramolecular) non-coordinating thione S atom [Au⋯S = 3.1538 (8) Å]. Supramolecular layers parallel to (100) feature in the crystal packing, being sustained by phenyl–thione C—H⋯S interactions, with the non-coordinating thione S atom in the role of a dual acceptor. Layers stack with no specific interactions between them.The asymmetric unit of the title compound, {(C R3PAu(S2CNR′2), date back over a decade CH2CH2OH], R = Ph and Cy, exhibited specific activity against Gram-positive bacteria while the R = Et derivative displayed broad-range activity against both Gram-positive and Gram-negative bacteria. Motivated by observations that 1,1′-bis(diphenylphosphanyl)ferrocene (dppf) derivatives also possess biological activity 4]}2, (I)Investigations into the potential anti-cancer activity of phosphanegold(I) dithiocarbamates, II atom in dppf{Au[S2CN(CH2)4]}2, (I)I central atom exists in the anticipated linear geometry defined by thiolate-S and phosphane-P atoms. The Au—S1 bond length is considerably longer than the Au—P1 bond, i.e. 2.3378 (8) cf. 2.2580 (8) Å. The dithiocarbamate ligand is orientated to place the S2 atom in close proximity to the AuI atom. However, the resulting intramolecular Au⋯S2 interaction is long at 3.1538 (8) Å, consistent with a monodentate mode of coordination for the dithiocarbamate ligand. The pattern of C1—S1, S2 bond lengths supports this conclusion in that the strongly bound S1 atom forms a longer, i.e. weaker, C1—S1 bond [1.757 (3) Å] cf. with C1—S2 of 1.689 (3) Å. Nevertheless, the close approach of the S2 atom to the AuI central atom is correlated with the deviation from the ideal linear geometry, i.e. S1—Au—P1 is 169.35 (3)°. The FeDatabase survey. The pyrrolidine ring is twisted about the C2—C3 bond. Owing to being located on a centre of inversion, the FeII atom is equidistant from the ring centroids of the Cp rings  and the Cg—Fe—Cgi angle is constrained by symmetry to be 180°; symmetry operation (i): 1 − x, −y, 2 − z. Again, from symmetry, the Cp rings have a staggered relationship.Similar features are noted in related structures as outlined below in the bc plane, Fig. 2a axis, i.e. 10.9635 (4) Å, and the layers stack along this axis with no directional interactions between them, Fig. 3In the crystal packing, the most prominent interactions are of the type C—H⋯S. Data for the phenyl-C—H⋯S(thione) interactions are collected in Table 1i.e. Ph3PAu(S2CNEt2), by Wijnhoven et al. (19723P 2·2CHCl3, bis[chloridogold(I)] (synthesized by the reduction of KAuClUiso(H) set to 1.2Ueq(C). The maximum and minimum residual electron density peaks of 1.57 and 1.11 e Å−3, respectively, were located 0.92 and 0.79 Å from the Au atom.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989015016382/vn2097sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015016382/vn2097Isup2.hklStructure factors: contains datablock(s) I. DOI: 1421954CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Sodium bicarbonate intake has been shown to improve exercise tolerance, but the effects on high-intensity intermittent exercise are less clear. Thus, the aim of the present study was to determine the effect of sodium bicarbonate intake on Yo-Yo intermittent recovery test level 2 performance in trained young men.2max: 61.3 ± 3.3 mlO2 · kg−1 · min−1; means ± SEM) performed the Yo-Yo intermittent recovery test level 2 (Yo-Yo IR2) on two separate occasions in randomized order with (SBC) and without (CON) prior intake of sodium bicarbonate (0.4 g · kg−1 body weight). Heart rate and rating of perceived exertion (RPE) were measured during the test and venous blood samples were taken frequently.Thirteen men aged 23 ± 1 year . Blood lactate was 0.9 ± 0.1 and 0.8 ± 0.1 mmol · l−1 at baseline and increased to 11.3 ± 1.4 and 9.4 ± 0.8 mmol · l−1 at exhaustion in SBC and CON, respectively, being higher (P = 0.03) in SBC. Additionally, peak blood lactate was higher (P = 0.02) in SBC than in CON (11.7 ± 1.2 vs 10.2 ± 0.7 mmol · l−1). Blood glucose, plasma K+ and Na+ were not different between trials. Peak heart rate reached at exhaustion was 197 ± 3 and 195 ± 3 bpm in SBC and CON, respectively, with no difference between conditions. RPE was 7 % lower (P = 0.003) in SBC than in CON after 440 m, but similar at exhaustion (19.3 ± 0.2 and 19.5 ± 0.2).Yo-Yo IR2 performance was 14 % higher (P = 0.04) in SBC than in CON . Blood pH and bicarbonate were similar between trials at baseline, but higher (P = 0.003) immediately prior to the Yo-Yo IR2 test in SBC than in CON (7.44 ± 0.01 vs 7.32 ± 0.01 and 33.7 ± 3.2 vs 27.3 ± 0.6 mmol · lIn conclusion, high-intensity intermittent exercise performance is improved by prior intake of sodium bicarbonate in trained young men, with concomitant elevations in blood alkalosis and peak blood lactate levels, as well as lowered rating of perceived exertion. The remaining whole blood was then centrifuged at 4000 rpm for 3 min  before plasma was extracted and stored on ice for ~30 min prior to being frozen at -80 Denmark) .RPE was assessed at 160, 280, 440 m and exhaustion according to the 20-stage Borg scale .P < 0.05. Results are presented as mean ± SEM unless stated otherwise.Differences between SBC and CON in Yo-Yo IR2 performance were analyzed using a paired-samples t-test. Differences between SBC and CON in blood and plasma variables were analyzed using a two-way ANOVA with repeated measures (supplement x time). If a significant F-value was observed, a Tukey post-hoc test was used to identify the points of difference. Statistical significance was accepted at Yo-Yo IR2 performance was 735 ± 61 m in SBC, which was 14 % higher (P = 0.04) than in CON  to 7.44 ± 0.01 in SBC before the Yo-Yo IR2 test and decreased (P = 0.005) in CON  in SBC before the Yo-Yo IR2 test (33.7 ± 3.2 mmol · l−1) and was unchanged in CON (27.3 ± 0.6 mmol · l−1) compared to baseline. At exhaustion, blood [bicarbonate] declined (P < 0.001) in SBC and CON (25.2 ± 2.6 and 20.2 ± 0.8 mmol · l−1). Pre-exercise and exhaustive blood [bicarbonate] was higher (P = 0.01 and 0.03) in SBC than in CON  11.3 ± 1.4 and 9.4 ± 0.8 mmol · l−1 at exhaustion in SBC and CON, respectively, being higher (P = 0.03) in SBC (Table −1).Blood lactate was 0.9 ± 0.1 and 0.8 ± 0.1 mmol · l−1 at baseline to 5.1 ± 0.5 and 5.2 ± 0.6 mmol · l−1 at exhaustion, with no difference between trials (Table Blood glucose rose (P < 0.05) from 4.2 ± 0.4 and 4.1 ± 0.2 mmol · l+] rose (P < 0.05) from 4.3 ± 0.4 and 4.2 ± 0.4 mmol · l−1 at baseline to 5.7 ± 0.5 and 5.8 ± 0.6 mmol · l−1 at exhaustion in SBC and CON, respectively, with no differences between trials  during the test, reaching 197 ± 3 and 195 ± 3 bpm at exhaustion in SBC and CON, respectively. No difference in heart rate response between conditions was determined during or after the test.RPE was not different between trials after 160 and 280 m , but was 7 % lower (P = 0.003) after 440 m in SBC than in CON (16.8 ± 0.4 vs 17.9 ± 0.3). At exhaustion, RPE was similar in SBC and CON (19.3 ± 0.2 and 19.5 ± 0.2).+ and Na+ as well as cardiovascular loading during high-intensity intermittent exercise were unaffected by sodium bicarbonate intake.In the present study, we observed that prior intake of sodium bicarbonate in capsular form using a protocol with gradual intake enhanced high-intensity intermittent exercise performance in young trained males. The performance improvement after sodium bicarbonate ingestion was accompanied by an elevated blood alkalosis and concentration of bicarbonate. In addition, blood lactate concentrations at exhaustion and peak values reached during the experimental protocol were higher, while the rating of perceived exertion was lower during intense exercise after sodium bicarbonate supplementation. In contrast, blood glucose, plasma KPerformance in the Yo-Yo IR2 test increased by 14 % after sodium bicarbonate intake, which is comparable to a 16 % increase after caffeine intake in a comparable athlete population , but lowIn the present study, we did not apply a placebo, since the gastrointestinal effects of high doses of bicarbonate are usually easy to trace . A poten+ gradient  and [Na+] between the sodium bicarbonate and control trials. However, since the potential fatiguing effect of a homeostatic imbalance in these ions is exerted in the muscle interstitial compared to intracellular environment [+ regulation, Street et al. [+ accumulation rate during intense exercise was attenuated after drug-induced alkalosis.Fatigue development during high-intensity intermittent exercise may be caused by a complex interplay between intra- and extracellular concentrations and gradients of ions such as K− and H+ , 29. In ironment –32, a soironment . In suppt et al.  found, umax and blood lactate and plasma K+ were markedly elevated. Moreover, although further distance was covered before exhaustion, the RPE scores remained the same as in the control trial at the point of fatigue. Thus, a higher performance level was achieved while reporting an equal level of perceived fatigue at exhaustion. Peripheral alterations are likely to lead to modulation of neural strategies, for example via group III and IV muscle afferents, widely distributed through muscle and responsive to a variety of chemical stimuli, including altered H+ [In the present study, RPE was lowered after 440 m of running in the Yo-Yo IR2 test in the sodium bicarbonate trial compared to the control, despite the fact that the heart rate and blood lactate concentration at this time-point were similar between trials. This may suggest that centrally mediated mechanisms were affected. The participants experienced less exertion late in the Yo-Yo IR2 test in the SBC trial when the heart rate was >95 % of HRtered H+ , 34, whitered H+ , 35.−1 body weight) improved high-intensity intermittent exercise performance in trained young men, with concomitant increased blood alkalosis. Sodium bicarbonate supplementation increased blood lactate levels at exhaustion and lowered rating of perceived exertion during intense intermittent exercise. The results indicate a link between improved fatigue resistance during high-intensity intermittent exercise and a sodium-bicarbonate-induced improved buffer capacity that may affect perceived exertion during intense intermittent exhaustive exercise.High-dose sodium bicarbonate intake (0.4 g · kg


Single crystals were obtained from HSO3F by slow cooling in a sealed tube. The molecular structure is characterized by the Xe atom covalently bonded to two O atoms of two fluorosulfate tetrahedra in an almost linear fashion [O—Xe—O = 179.13 (4)°]. The crystal packing is strongly influenced by intermolecular van der Waals forces.Thermally unstable Xe(SO For XeF(OSO2F), partial ionic bonding (XeF+·OSO2F−) was discussed. Obviously, both XeF2 and Xe(SO3F)2 have a higher covalent character. The S—O bonds in Xe(SO3F)2 involving the O atoms that are also bonded to the xenon atom (S1—O1 and S2—O4) are about 0.1 Å longer than the terminal S—O bonds  has fewer contacts  was warmed to 273 K and the PFA tube placed in a dewar filled with 273 K ethanol and cooled slowly to 193 K in a freezer. The light-yellow single crystals of Xe(SO3F)2 that had formed were decanted off and mounted in a cold nitrogen stream. At 100 K, the crystals are colorless. The compound decomposes rapidly in moist air and can ignite organic materials.550 mg fluorosulfuric acid were placed in a 8 mm PFA tube. 170 mg (1 mmol) of XeFCrystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989015004788/wm5134sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015004788/wm5134Isup2.hklStructure factors: contains datablock(s) I. DOI: 1052852CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: