Its reaction with copper chloride lead to the formation of a copper(II) paddle-wheel structure.Tranexamic acid is an antifibrinolytic amino acid that exists as a zwitterion [ trans-4-(aminomethyl)cyclohexane-1-carboxylic acid], is an antifibrinolytic amino acid that exists as a zwitterion [trans-4-(ammoniomethyl)cyclohexane-1-carboxylate] in the solid state. Its reaction with copper chloride leads to the formation of a compound with a copper(II) paddle-wheel structure that crystallizes as a hexahydrate, [Cu2Cl2(C8H15NO2)4]2+·2Cl−·6H2O. The asymmetric unit is composed of a copper(II) cation, two zwitterionic tranexamic acid units, a coordinating Cl− anion and a free Cl− anion, together with three water molecules of crystallization. The whole structure is generated by inversion symmetry, with the Cu⋯Cu axle of the paddle-wheel dication being located about a center of symmetry. The cyclohexane rings of the zwitterionic tranexamic acid units have chair conformations. The carboxylate groups that bridge the two copper(II) cations are inclined to one another by 88.4 (8)°. The copper(II) cation is ligated by four carboxylate O atoms in the equatorial plane and by a Cl− ion in the axial position. Hence, it has a fivefold O4Cl coordination sphere with a perfect square-pyramidal geometry and a τ5 index of zero. In the crystal, the paddle-wheel dications are linked by a series of N—H⋯Cl hydrogen bonds, involving the coordinating and free Cl− ions, forming a three-dimensional network. This network is strengthened by a series of N—H⋯Owater, Owater—H⋯Cl and Owater—H⋯O hydrogen bonds.Tranexamic acid [systematic name:  It has important antifibrinolytic activity and is used extensively in both trauma and normal surgery to prevent excessive blood loss  Å; symmetry code (i): −x + 1, −y + 1, −z + 1] of the paddle-wheel being located about a center of symmetry. Selected bond lengths and angles in the paddle-wheel dication are given in Table 1− ion, Cl1, in the axial position. The Cu—O distances vary from 1.950 (4) to 1.991 (3) Å, with a longer Cu1—Cl1 axial distance of 2.499 (1) Å (Table 1i), has a perfect square-pyramidal coordination sphere with a τ5 index of 0.0  Å, θ = 176.3 (6)°, φ = 358 (13)°, and for ring C10–C15 are Q = 0.568 (6) Å, θ = 6.0 (6)°, φ = 137 (6)°. The carboxylate groups (C1/O1/O2 and C9/O3/O4) are inclined to the mean planes of the four planar atoms of the respective cyclohexane rings (C3/C4/C6/C7 and C11/C12/C14/C15) by 67.5 (6) and 85.8 (7)°, while they are inclined to one another by 88.4 (8)°. The ammoniomethyl units, C5/C8/N1 and C13/C16/N2, are inclined to the mean planes of the four planar atoms of the respective cyclohexane rings (C3/C4/C6/C7 and C11/C12/C14/C15) by 34.9 (6) and 47.5 (6)°.The conformations of the two zwitterionic tranexamic acid units differ slightly. The cyclohexane rings (C2–C7 and C10–C15) have chair conformations; puckering parameters for ring C2–C7 are 3+ groups of the zwitterionic tranexamic acid units and the coordinating and free Cl– ions are linked by a series of N—H⋯Cl hydrogen bonds forming a three-dimensional framework  and the hydrochloride of the cis-isomer (CHCAHC) were reported in 1966 , viz. tranexamic acid  is inclined to the mean plane of the four planar atoms of the cyclohexane ring by 48.9 (2)°, compared to 67.5 (6) and 85.8 (7)° in the title compound. The plane of the ammoniomethyl unit (Car—C—N) is inclined to the same mean plane of the four planar atoms of the cyclohexane ring by 37.4 (2)°, compared to 34.9 (6) and 47.5 (6)° in the title compound. Hence, on complexation the cyclohexane rings are rotated about the Ccarboxylate—Ccyclohexane bonds (C1—C2 and C9—C10), most probably to minimize steric hindrance.A search of the Cambridge Structural Database . The Cu⋯Cu distances vary from ca 2.63 to 2.84 Å, with the carboxylate groups being inclined to one another by ca 84.65–90°, and the Cu—Cl distances varying from ca 2.41 to 2.49 Å. The values observed for the title compound fall within these limits . In all 13 compounds the copper atoms have perfect square-pyramidal geometry, with τ5 = 0.0.In the CSD over 1500 copper(II) paddle-wheel structures have been deposited. There are only 13 compounds in which the axial position is occupied by a Cl2·2H2O  in 20 ml of acetonitrile at ambient temperature and the mixture was stirred for 30 min. The green solution obtained was filtered and the filtrate kept undisturbed at room temperature for slow evaporation. After five days green plate-like crystals of the title compound were obtained.Tranexamic acid  dissolved in 10 ml of deionized water was added dropwise to a transparent blue solution of CuClUiso(H) = 1.5Ueq(O). The ammonium H atoms and the C-bound H atoms were included in calculated positions and treated as riding: N—H = 0.91 Å, C-H = 0.99–1.00 Å with Uiso(H) = 1.5Ueq(N-ammonium) and 1.2Ueq(C) for other H atoms. In the final difference-Fourier map the residual density peaks  are located at a distance of 1.2 and 0.9 Å, respectively, from the copper atoms.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989017012543/wm5416sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989017012543/wm5416Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017012543/wm5416sup3.pdfCSD search of axially Cl- ligated Cu-Cu paddle-wheel structures. DOI: 1571897CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Interleukin 17-producing γδ T (γδT17) cells have unconventional trafficking characteristics, residing in mucocutaneous tissues but also homing into inflamed tissues via circulation. Despite being fundamental to γδT17-driven early protective immunity and exacerbation of autoimmunity and cancer, migratory cues controlling γδT17 cell positioning in barrier tissues and recruitment to inflammatory sites are still unclear. Here we show that γδT17 cells constitutively express chemokine receptors CCR6 and CCR2. While CCR6 recruits resting γδT17 cells to the dermis, CCR2 drives rapid γδT17 cell recruitment to inflamed tissues during autoimmunity, cancer and infection. Downregulation of CCR6 by IRF4 and BATF upon γδT17 activation is required for optimal recruitment of γδT17 cells to inflamed tissue by preventing their sequestration into uninflamed dermis. These findings establish a lymphocyte trafficking model whereby a hierarchy of homing signals is prioritized by dynamic receptor expression to drive both tissue surveillance and rapid recruitment of γδT17 cells to inflammatory lesions. IL-17-producing γδ T (γδT17) cells position in barrier tissues but also home to inflammatory sites. How this trafficking is regulated is unclear. Here the authors show that the dynamic expression of chemokine receptors CCR2 and CCR6 differentiates γδT17 cell trafficking patterns at homeostasis and in inflammatory scenarios. In models of autoimmunity, cancer and infection, activation-induced downregulation of CCR6 releases γδT17 cells from their homeostatic immunosurveillance trafficking circuit through the skin and circulation, which then enhances their CCR2-dependent homing to inflamed tissue. Therefore, the dynamic interplay between CCR6 and CCR2 expression defines γδT17 cell trafficking patterns between resting and activated states.−CCR2+ phenotype marking the encephalitogenic granulocyte–macrophage colony-stimulating factor/interferon-γ-producing population221Il17aCre × Rosa26eYFP mice, where Il17a expression drives permanent marking of cells with eYFP−CD44hi phenotype, characteristic of γδT17 cells (+ and Vγ6+ γδT17 cell subsets as distinguished by both Vγ4 expression and CD3/T-cell receptor (TCR) expression level, as previously reported (‘CD3bright staining')ex vivo chemotaxis (−CCR2+) were prominent in lung and gut-associated tissues  (Ccr2-deficiency inhibited γδT17 cell recruitment to the CNS at both onset and peak disease (Ccr6 and Ccr2 (Ccr6−/−Ccr2−/−) did not further affect γδT17 cell infiltration in either model  . CCR2-dres (LNs) . Similar disease , time po disease . CCR2 aper model .Ccr2−/−Ccr6−/− mice exhibited enhanced tumour growth, while Ccr2−/− and Ccr2−/−Ccr6−/− mice had decreased EAE severity  and Ccr2−/− γδT17 cells were co-transferred into B16 melanoma-bearing recipients. While donor γδT17 cells recovered from spleen retained the input ratio, Ccr2−/− γδT17 cells did not migrate efficiently to tumours. This observation was true for both Vγ4+ and Vγ6+ subsets  than WT at 72 h post-infection , a population previously reported to produce IL-17 and distinct from TCRhi dendritic epidermal T cellslo cells were entirely marked by eYFP in Il17aCre × Rosa26eYFP mice, despite negligible IL-17A production following ex vivo restimulation (Ccr6-deficiency reduced the number of both Vγ4+ and Vγ4− (Vγ6+) γδTlo cells, although the ratio was skewed slightly towards Vγ6+ cells  was highly expressed in resting γδT17 cells but was downregulated by 24 h of activation. Batf and Prdm1 (Blimp1) were rapidly upregulated by 24 h, while Irf8 and Irf4 were upregulated by 48 h, although Irf4 was already present in resting γδT17 cells. Expression of Eomes and Tbx21 (T-bet) at rest or following activation was minimal  mice were bred at the University of Adelaide animal facility. Irf4−/−, Irf8−/−, Batf−/− and LckCrePrdm1fl/fl mice were bred at the WEHI animal facility. Mice were age- and gender-matched and used at 6–14 weeks of age. Experiments were conducted with approval of the University of Adelaide Animal Ethics Committee.C57Bl/6 (WT) and Ly5.1 mice were purchased from Animal Resource Centre  or bred at the University of Adelaide animal facility. 35–55 (GL Biochem) in phosphate-buffered saline (PBS) emulsified 1:1 in complete Freund's adjuvant, coupled with i.p. injection of 300 ng Pertussis toxin (Sapphire Bioscience) on days 0 and 2. Mice were analysed at clinical scores of 0.5 (onset) and 2–3 (peak) in wild type (WT) mice, where scoring criteria were: 0.5 tremor, 1 partially limp tail, 2 fully limp tail, 2.25 unable to right, 2.5 sprawled hindlimbs, 2.75 one hindlimb paralysed, 3 both hindlimbs paralysed, 3.5 one forelimb paralysed. B16.F10 melanoma cells  were cultured in RPMI 1640 containing 10% fetal calf serum (FCS) and 5 × 104 cells were injected subcutaneously into mice at four sites. S. pneumoniae EF3030 was grown to a D600 of 0.18 in nutrient broth with 10% horse serum at 37 °C 5% CO2 and stored at −80 °C. Stocks were defrosted and 1 × 106 colony-forming units were delivered intranasally. Bacterial load was determined by serial dilution of concentrated NW onto blood agar with 5 μg ml−1 gentamicin (Sigma).Mice were immunized for chronic EAE by subcutaneous injection of 100 μg of MOGg. The following digestions were performed at 37 °C with 30U ml−1 DNase (Sigma). Epidermis and dermis from ears or shaved trunk skin were separated by incubation in 0.375% tryspin for 2 h at 37 °C, and then digested separately with 85 μg ml−1 Liberase TM (Roche) for 1 h. Tumours and perfused lungs were digested in 2 mg ml−1 collagenase (Sigma) for 1 h. NP tissue between the nose tip and eyes was dissected following removal of nasal-associated lymphoid tissue, digested with 2 mg ml−1 collagenase for 1.5 h and separated by a 40/80% Percoll gradient at 600g. Livers were pressed through 70 μm filters and then lymphocytes were isolated by a 37.5% Percoll gradient at 850g. Flushed and longitudinally opened small intestine free of Peyer's patches was washed in PBS then incubated in 5 mM EDTA for 40 min at 37 °C to remove epithelium, before remaining lamina propria was digested with 0.5 mg ml−1 collagenase for 1.5 h at 37 °C and separated over a 40/80% Percoll gradient at 1,000g to isolate lamina propria lymphocytes. Peritoneal exudate cells were collected by 3 × 1 ml PBS washes.Single-cell suspensions were prepared from lymphoid organs by pressing through 70 μm filters. Peripheral blood was collected into heparinized Vacutainer tubes (BD). Red blood cells were lysed as required. CNS from PBS-perfused mice was pressed through 70 μm filters and then separated over a 30/70% Percoll (GE) gradient at 5006 lymphocytes per well using antibodies and other reagents detailed in −1 PMA (Life Technologies), 1 nM ionomycin (Life Technologies) and 1/1,500 GolgiStop (BD) for 4 h at 37 °C. Cells were washed in PBS and stained with Near Infrared fixable dye diluted 1/1,000 (Life Technologies) for 15 min at room temperature. Cells were then washed with FACS buffer  and blocked with mouse γ-globulin (mγg) (200 μg ml−1) for 5 min at room temperature. All subsequent steps were incubated at 4 °C. For purified antibodies, cells were stained with purified antibody for 20–60 min, washed in FACS buffer, stained with secondary antibody in mγg (200 μg ml−1) and normal mouse serum (NMS) (1%) for 20 min, washed in FACS buffer and blocked with rat γ-globulin for 15 min. Cells were stained with directly conjugated and biotinylated antibodies for 20 min. In the case of biotinylated antibodies, cells were then washed in FACS buffer and stained with streptavidin for 15 min. Cells were then washed in PBS 0.04% azide. For intracellular cytokine staining, cells were incubated in Cytofix/Cytoperm (BD) for 20 min, washed in Permwash (BD) and stained with intracellular directly conjugated antibodies for 20 min. For transcription factor staining, cells were incubated in Foxp3 kit perm buffer (eBioscience) for 30 min to overnight, and then washed in Foxp3 kit permwash (eBioscience). Cells were then stained with directly conjugated α-transcription factor antibodies in NMS (2%) and normal rat serum (2%), and then washed in PBS 0.04% azide. All stains were washed in PBS 0.04% azide, resuspended in PBS 1% paraformaldehyde and stored at 4 °C in the dark.Single-cell suspensions were stained in 96-well round- or v-bottom plates (Corning) at 2 × 10Ccr2−/− γδT17 cells. CCR2 and CCR6 gating was determined by relevant isotype controls. For measurement of fluorescence intensity, relevant isotype control geometric mean fluorescence intensity was subtracted from raw geometric mean fluorescence intensity value. For in vivo proliferation analysis, mice were given 2 mg BrdU i.p. and then drinking water with 0.8 mg ml−1 BrdU 2% glucose. Following restimulation and surface staining, cells were permeabilized, DNase-treated and stained with α-BrdU (BD) according to the manufacturer's instructions. For in vitro proliferation analysis, cells were labelled with Cell Proliferation Dye (eBioscience) according to the manufacturer's instructions. Flow cytometry was acquired on a BD LSR II or FACSAria and analysed with FlowJo (Treestar). Gating strategies are detailed in Specificity of α-CCR2 was confirmed by negative staining on 6 cells per ml in RPMI 1640 containing 10% FCS, antibiotics, 1 × Glutamax (Gibco), 10 mM HEPES (SA Pathology), 1 mM sodium pyruvate, 54 pM β-mercaptoethanol and 1 × non-essential amino acids (Gibco) with 5 ng ml−1 recombinant (r)IL-23 (eBioscience), 5 ng ml−1 rIL-1β (Miltenyi Biotec) and 10 μg ml−1 α-IFN-γ (BioXCell) in 96-well round-bottom plates coated with 1 μg ml−1 α-TCR-γδ  for 3 days. Cells were washed and re-seeded on fresh plastic at 1 × 106 cells per ml for a further 3 days as above without TCR-γδ stimulation. Cells were then washed and re-seeded in 20 ng ml−1 rIL-7 (Peprotech) and 10 μg ml−1 α-IFN-γ for a further 3 days. pMIG, pMIG-Rorc and pMIG-Ccr6 (cloned from mouse Ccr6 cDNA) were transfected into EcoPack 2 293 cells  with Lipofectamine 2000 (ThermoFisher), and supernatant collected after 48 h. γδT17 cells at days 4 and 5 of culture were centrifuged at 2,500 r.p.m. (30 °C for 1.5 h) in supernatant with 8 μg ml−1 polybrene (Sigma) in flat-bottom 96 well trays before being returned to culture.Pooled spleen and LN cells were cultured at 1 × 10Ccr2−/− and Ccr6tg trafficking experiments, 1–2 × 106 each of in vitro-expanded F1 (CD45.1+CD45.2+) and Ccr2−/−(CD45.2+), or transduced control and Ccr6tg γδT17 cells (F1 or WT), were mixed and transferred i.v. into Ly5.1 (CD45.1+) recipient mice d5 post-challenge with B16 melanoma, d8–10 post EAE induction or 24 h post-S. pneumoniae infection. γδT17 cell infiltration of target organs was analysed 24–48 h post-transfer, and CD45 congenic ratios were normalized to input sample. For S. pneumoniae Tcrd−/− reconstitution, in vitro-expanded WT and Ccr2−/− γδT17 cells were further purified by MACS (Miltenyi Biotec) before 3 × 106 cells were transferred into separate Tcrd−/− hosts 24 h prior to infection. For naïve dermis trafficking experiments, 5–10 × 107 fresh WT or Ccr6−/− lymphocytes or 3 × 107 72 h IL-23/IL-1β-stimulated WT lymphocytes were transferred into separate unimmunized Ly5.1 mice and analysed 36 h later. Number of recovered cells was normalized to number of γδT17 cells transferred.For Tumour and NP supernatants from digested samples and supernatants from filtered CNS were supplemented with protease inhibitors (Sigma) and stored at −80 °C. Mouse CCL2 Duoset ELISA (R&D) was conducted according to the manufacturer's instructions.Il17aCre × Rose26eYFP mice were enriched by MACS using mouse TCRγδ+ isolation kit , and then sorted using a BD FACSAria. Naïve CD4+ T cells were sorted from WT splenocytes, and skin stromal populations were sorted from digested epidermal and dermal suspensions from WT mice. Sorting strategies are detailed in −(CT target–CT reference) where reference was Rplp0.γδ T cells from 6 splenocytes or 2 × 105in vitro-expanded γδT17 cells were loaded into the upper chambers and plates were incubated at 37 °C for 3 h. Lower wells were harvested and stained for flow cytometry. CountBrite beads (Invitrogen) were added to samples prior to acquisition to normalize event counts. Chemotaxis index was calculated as number of gated events divided by number in 0 chemokine control.Splenocytes were rested in complete RPMI for 3–4 h at 37 °C, washed and suspended in chemotaxis buffer . γδT17 cells from culture were washed and suspended in chemotaxis buffer. CCL2 or CCL20 (from the late Prof. Ian Clark-Lewis) were diluted in chemotaxis buffer and loaded into the lower chambers of 96-well 5 μm pore transwell plates (Corning). 2 × 10L-glutamine, β-mercaptoethanol) at 2.5 × 106 cells per ml with 10 ng ml−1 rIL-23 (eBioscience), 10 ng ml−1 rIL-1β (Miltenyi Biotec), 20 ng ml−1 rIL-7 (Peprotech), 10 ng ml−1 rIL-12 (R&D), 10 ng ml−1 rIL-18 (R&D) and/or with pre-coating in 1 μg ml−1 α-TCR-γδ (Biolegend) for up to 72 h at 37 °C. For mitomycin C pre-treatment, cells were first incubated with 10 μg ml−1 mitomycin C (Sigma) in complete IMDM at 2 × 107 cells per ml for 2 h at 37 °C before extensive washing.Splenocytes were cultured in complete IMDM .Publisher's note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.Supplementary Figures and Supplementary Tables


In the crystal, N—H⋯O, O—H⋯O and N—H⋯F hydrogen bonds and weak π–π interactions connect chains of molecules into a three-dimensional network.The title compound {systematic name: 2-[oxy]acetic acid}, C 7H5Cl2FN2O3, the mean plane of the carboxylic acid substituent and the pyridyl ring plane subtend a dihedral angle of 77.5 (1)°. In the crystal, pairs of O—H⋯O hydrogen bonds form inversion dimers with R22(8) ring motifs. These are extended into chains along [011] by N—H⋯F hydrogen bonds. In addition, intermolecular N—H⋯O hydrogen bonds and weak π–π interactions [ring centroid separation = 3.4602 (9) Å] connect these chains into a three-dimensional network.In the title pyridine herbicide {systematic name: 2-[oxy]acetic acid}, C It is widely used on cereal crops, olive trees and fallow croplands to control broad-leaf weeds  Å; symmetry code: (iv) −x, −y + 2, −z], resulting in a three-dimensional network structure  = 0.84 Å, Uiso = 1.5Ueq(C) for the O—H group, d(N—H) = 0.88 Å, Uiso = 1.2Ueq(C) for the amine group, and d(C—H) = 0.99 Å, Uiso = 1.2Ueq(C) for the CH2 group.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016018533/sj5515sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989016018533/sj5515Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016018533/sj5515Isup3.cmlSupporting information file. DOI: 1518035CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystals of both compounds, molecules are linked  30H18N2O5S, (I), and C27H18N2O4S2, (II), are carbazole derivatives with a phenylsulfonyl group and a nitrophenyl group attached to the carbazole moiety in identical positions in both molecules. A benzofuran ring system in (I) and a methylthiophene ring in (II) are fused with the respective carbazole moieties on the same sides. The mean plane of the carbazole ring system makes a dihedral angle of 3.17 (7)° with the benzofuran ring system in (I) and a dihedral angle of 3.39 (11)° with the methylthiophene ring in (II), implying that both fused units are essentially planar. The mean planes of the carbazole ring systems in both the compounds are almost orthogonal to the respective nitro-substituted phenyl rings, making dihedral angles of 75.64 (10) and 77.63 (12)° in compounds (I) and (II), respectively. In (I), the phenylsulfonyl ring system is positionally disordered with a refined occupancy ratio of 0.63 (2):0.37 (2). In both compounds, the molecular structures are stabilized by intramolecular C—H⋯O hydrogen bonds, generating S(6) ring motifs with the sulfone group O atoms. In the crystal of compound (I), molecules are linked by pairs of C—H⋯O hydrogen bonds, which generate R22(18) inversion dimers, and interconnected by C(14) chains running along the c-axis direction, whereas in compound (II), the C—H⋯O hydrogen bonds generate R43(37) ring motifs. In the crystals of both compounds, C—H⋯O hydrogen-bonded sheets are formed lying parallel to (10-1). In addition, C—H⋯π and offset π–π interactions [intercentroid distance = 3.7158 (14) Å in (I) and 3.9040 (15) Å in (II)] are also present in the crystals of both compounds.The title compounds, C Carbazole derivatives exhibit various biological activities such as antitumor 2 groups are inclined to the benzene ring (C19–C24) to which they are attached by 9.8 (4)° in (I)The mean planes of the carbazole ring systems make dihedral angles of 3.17 (7) and 3.39 (11)°, respectively, with the benzofuran ring in (I)sp2 bond lengths are longer than the mean value of 1.355 (14) Å for N—C bond lengths  ring motifs with the sulfone oxygen atoms (Tables 1The sums of the bond angles around atom N1 are 349.58° in (I) Tables 1 and 2 ▸.via pairs of C20—H20⋯O2ii hydrogen bonds  chains. These interactions result in the formation of sheets parallel to  = 3.7158 (14) Å, interplanar distance = 3.472 (1) Å, slippage = 1.324 (11) Å; Cg4 is the centroid of the C7–C12 ring]; see Table 1In the crystal of compound (I)s Table 1, formingi and C14—H14⋯Oii4 hydrogen bonds  = 3.9040 (15) Å, interplanar distance = 3.791 (1) Å, slippage 0.932 Å; Cg4 is the centroid of the C7–C12, ring]; see Table 2In the crystal of compound (II)s Table 2, which rfs Fig. 4. The cryrs Fig. 5, which aet al., 2016H-[1] benzofurancarbazole and 47 hits for 9-(phenylsulfonyl)-9H-carbazole. However, the compound 7-phenylsulfonyl-7H-benzofurancarbazole H-thienocarbazole et al., 2011A search of Cambridge Structural Database : A solution of [3-(4-nitrobenzoyl)-1-(phenylsulfonyl)-1H-indol-2-yl]methyl pivalate , anhydrous SnCl4  and benzofuran  in dry DCE (10 ml) was stirred at room temperature under nitrogen for 3 h. After completion of the reaction (monitored by TLC), it was poured into ice–water (100 ml). The organic layer was separated and the aqueous layer was extracted with DCM (2 × 20 ml). The combined extract was washed with water (3 × 50ml) and dried (Na2SO4). Removal of the solvent by column chromatographic purification  yielded compound (I)Compound (II): A solution of [3-(4-nitrobenzoyl)-1-(phenylsulfonyl)-H-indol-2-yl]methyl pivalate , anhydrous SnCl4  and 2-methylthiophene  in dry DCE (10 ml) was stirred at room temperature under nitrogen atmosphere for 3 h. After the completion of the reaction (monitored by TLC), it was poured into ice–water (100 ml), the organic layer was separated and the aqueous layer was extracted with DCM (2 × 20ml). The combined extract was washed with water (3 × 50 ml) and dried (Na2SO4). Removal of the solvent by column chromatographic purification  yielded compound (II)Uiso(H)= 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms. In compound (I)SHELXL97; Sheldrick, 2008Crystal data, data collection and structure refinement details for compounds (I)10.1107/S2056989016016996/su5333sup1.cifCrystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989016016996/su5333Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016016996/su5333IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989016016996/su5333Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989016016996/su5333IIsup5.cmlSupporting information file. DOI: 1473995CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


II cation displays a distorted octahedral geometry coordinated by four pyridine N atoms from four individual ligands and two O atoms from two monodentate nitrate anions. Two symmetry-related ligands are connected by two symmetry-related CoII cations, forming a 20-membered cyclic dimer. These cyclic dimers are connected to each other by sharing CoII atoms, forming a looped chain. In the crystal, adjacent looped chains are connected by intermolecular π–π stacking interactions and C—H⋯π and C—H⋯O hydrogen bonds, resulting in the formation of a three-dimensional supramolecular architecture.The reaction of cobalt(II) nitrate with bis(pyridin-3-ylmethyl)sulfane ligand, afforded a one-dimensional looped polymeric chain. The Co 3)2(C12H12N2S)2]n, contains a bis(pyridin-3-ylmethyl)sulfane (L) ligand, an NO3− anion and half a CoII cation, which lies on an inversion centre. The CoII cation is six-coordinated, being bound to four pyridine N atoms from four symmetry-related L ligands. The remaining coordination sites are occupied by two O atoms from two symmetry-related nitrate anions in a monodentate manner. Thus, the CoII centre adopts a distorted octahedral geometry. Two symmetry-related L ligands are connected by two symmetry-related CoII cations, forming a 20-membered cyclic dimer, in which the CoII atoms are separated by 10.2922 (7) Å. The cyclic dimers are connected to each other by sharing CoII atoms, giving rise to the formation of an infinite looped chain propagating along the [101] direction. Intermolecular C—H⋯π (H⋯ring centroid = 2.89 Å) interactions between one pair of corresponding L ligands and C—H⋯O hydrogen bonds between the L ligands and the nitrate anions occur in the looped chain. In the crystal, adjacent looped chains are connected by intermolecular π–π stacking interactions [centroid-to-centroid distance = 3.8859 (14) Å] and C—H⋯π hydrogen bonds (H⋯ring centroid = 2.65 Å), leading to the formation of layers parallel to (101). These layers are further connected through C—H⋯O hydrogen bonds between the layers, resulting in the formation of a three-dimensional supramolecular architecture.The asymmetric unit of the title compound, [Co(NO The CoII cation is coordinated by four pyridine N atoms from four symmetry-related L ligands. In addition, the CoII cation binds to two O atoms of two symmetry-related monodentate nitrate anions, forming a distorted octahedral CoN4O2 coordination. Selected bond lengths and angles around the Co1 atom are listed in Table 1II centre are tilted by 70.75 (7)° with respect to each other  Å. The cyclic dimers are connected by sharing CoII atoms, leading to the formation of an infinite looped chain propagating along the [101] direction. An intermolecular C7—H7B⋯ Cg2i interactions  between one pair of corresponding L ligands and several C—H⋯O hydrogen bonds between the L ligands and the NO3− anions (Table 2Two symmetry-related s Table 2 contribuCg1⋯Cg1ii = 3.8859 (14) Å; yellow dashed lines in Fig. 2Cg1 is the centroid of atoms N1/C1–C5; symmetry code: (ii) −x + 1, −y + 2, −z + 1] together with intermolecular C6—H6A⋯Cg2iii hydrogen bonds , generating layers parallel to (101). Neighboring layers are packed by C1—H1⋯O3iv hydrogen bonds  between pyridine H atoms and nitrogen O atoms, resulting in the formation of a three-dimensional supramolecular architecture.Adjacent looped chains in the structure are connected by intermolecular π–π stacking interactions between the N1-pyridine rings [L ligand was synthesized according to a literature method  solution of the L ligand with Co(NO3)2·6H2O in a 2:1 molar ratio.The sp2—H and 0.97 Å for methylene C—H with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989017014980/hg5499sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989017014980/hg5499Isup2.hklStructure factors: contains datablock(s) I. DOI: 1580230CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The title compound consists of an diethylammonium–anilinesulfonate ion pair and a zwitterionic aniliniumsulfonate molecule. 4H12N+·C6H6NO3S−·C6H7NO3S, consists of an ion pair and a zwitterionic neutral molecule. The cation adopts an extended conformation [C—C—N—C torsion angles = 177.1 (3) and −178.4 (3)°]. In the crystal, the components are linked by N—H⋯O and N—H⋯N hydrogen bonds, generating a three-dimensional network, which is consolidated by weak C—H⋯O interactions.The title compound, C The bi-layers are then linked through N1—H1NA⋯O2, N1—H1NB⋯O5 and N1—H1NB⋯O6 hydrogen bonds, yielding a three-dimensional network  interactions consolidate the packing in the crystal . Examination of the packing reveals layers of diethyl ammonium cation sandwiched between bi-layers of aniline sulfate moieties. The key hydrogen bonds establishing the three-dimensional array are the contacts to sulfonate oxygen atoms and the N2⋯N3 aniline interactions. All amine hydrogen atoms form good hydrogen-bond contacts to neighboring hydrogen-bond acceptor atoms.The zwitterionic aniliniumsulfonate and the anilinesulfonate anion are connected through N2—H2s Table 1 giving srk Fig. 2. Some weet al., 2016et al., 2008A search of the Cambridge Structural Database    I. DOI: 10.1107/S2056989016018041/hb7622Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016018041/hb7622Isup3.cmlSupporting information file. DOI: 1515845CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


N-hydroxyquinoline-2-carboxamide molecule has a nearly planar structure [maximum deviation = 0.062 (1) Å] and only the hydroxy H atom deviates from the molecule plane.The  10H8N2O2·H2O, consists of an N-hydroxyquinoline-2-carboxamide molecule in the keto tautomeric form and a water molecule connected through an O—H⋯O hydrogen bond. The N-hydroxyquinoline-2-carboxamide molecule has a nearly planar structure [maximum deviation = 0.062 (1) Å] and only the hydroxy H atom deviates significantly from the molecule plane. In the crystal, π–π stacking between the aromatic rings [intercentroid distance = 3.887 (1) Å] and intermolecular O—H⋯O hydrogen bonds organize the crystal components into columns extending along the b-axis direction.The title compound, C The carbonyl group possesses a Z conformation against the N1 atom of the quinoline moiety and E conformation against the hydroxy oxygen atom [torsion angles O2—N2—C10—O1 = 0.8 (2)° and N1—C9—C10—O1 −177.33 (14)°]. The N-hydroxyquinoline-2-carboxamide molecule has an almost planar structure (non-hydrogen atoms are planar to within 0.03 Å). Only the H atom of the OH group deviates significantly from the molecular plane: the C—N—O—H torsion angle of −75.1 (13)° is defined by the O—H⋯O hydrogen bond between hydroxy group and the water molecule. The C—N and C—C bond lengths in the quinoline moiety are typical for 2-substituted pyridine derivatives  Å, intercentroid distance 3.887 (1) Å, displacement 1.846 (1) Å]. These columns are linked pairwise by the O—H⋯O hydrogen bonds  global, I. DOI: 10.1107/S2056989017005618/xu5902Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017005618/xu5902Isup3.cmlSupporting information file. DOI: 1543825CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The persence of C—H⋯π(phenyl) interactions in the crystals lead to dimeric aggregates in (I) and supramolecular chains (II).The metal coordination geometry in each of the title molecules, [Sn(C viz. [Sn(C6H5)3(C8H16NS2)], (I), and [Sn(C6H5)3(C10H12NS2)], (II), are described. The dithiocarbamate ligand in each molecule coordinates in an asymmetric fashion resulting in heavily distorted tetrahedral C3S coordination geometries for the Sn atoms, with the distortions traced to the close approach of the non-coordinating thione-S atom. The molecular packing in both compounds features C—H⋯π(Sn-phenyl) interactions. In (I), the donors are Sn-phenyl-C—H groups leading to centrosymmetric aggregates, while in (II), the donors are both Sn-phenyl-C—H and methyl-C—H groups leading to supramolecular chains propagating along the b axis. The identified aggregates assemble into their respective crystals with no directional interactions between them. An analysis of the Hirshfeld surfaces show distinctive patterns, but an overwhelming predominance (>99% in each case) of H⋯H, C⋯H/H⋯C and S⋯H/H⋯S contacts on the respective Hirshfeld surface.The crystal and molecular structures of two triphenyltin dithiocarbamate compounds,  A key interest in dithiocarbamate compounds of both transition metals and main-group elements relates to their biological activity 3Sn[S2CN(Me)Hex] (I)6H5)3Sn[S2CN(CH3)CH2CH2Ph] (II)A vast array of different dithiocarbamate anions, a, is coordinated by three ipso-carbon atoms along with a dithiocarbamate ligand. As seen from Table 1long – Sn—Sshort) being 0.64 Å. This asymmetry is confirmed in the differences in the C—S bond lengths with the C1—S1 bond associated with the short Sn—S1 contact, at 1.761 (4) Å, being significantly longer than the C1—S2 bond, i.e. 1.688 (4) Å, involving the weakly bound S2 atom. If the S2 atom is ignored, the coordination geometry about the tin atom is distorted C3S tetrahedral with the range of angles being 90.00 (11)°, for S1—Sn—C31, to 121.53 (10)°, for S1—Sn—C11. The wide angle clearly reflects the influence of the close approach of the S2 atom, Fig. 1a and Table 13S2 donor set is almost perfectly intermediate between ideal square-pyramidal (SP) and trigonal–bipyramidal (TP). This is quantified in the value of τ = 0.52, which compares with the ideal values for SP and TP geometries of τ = 0.0 and 1.0, respectively , 178.5 (4) and 178.9 (5)°, respectively, indicate + anti-periplanar descriptors but, that of C5—C6—C7—C8, i.e. −66.4 (8)°, indicative of a − syn-clinal disposition.The tin atom in (I)b, resembles closely that described for (I)3S2 description pertains, the value of τ = 0.60 indicates a distortion towards TP. The phenylethyl chain is kinked as seen in the N1—C3—C4—C5 and C3—C4—C5—C6 torsion angles of −175.8 (3) and 91.9 (5)°, respectively.The molecular structure of (II)a. Such cooperative C—H⋯π(phenyl) embraces have been described for many phenyl-rich systems and in instances where six phenyl rings of two residues associate by edge-to-face interactions, i.e. a six-fold embrace, the energies of stabilization can resemble or even exceed that provided by strong conventional hydrogen bonding PLATON et al., 2017i.e. n-hexyl in the former and phenylethyl in the latter. These differences are readily discerned from the differently shaped Hirshfeld surfaces mapped over dnorm for (I)The Hirshfeld surface calculations for the triphenyltin dithiocarbamate derivatives (I)a reflect the presence of a weak C—H⋯π interaction, as summarized in Table 4C and n-hexyl atoms C7 and H7B are indicative of the short interatomic H⋯H and C⋯H/H⋯C contacts involving these atoms, as listed in Table 4cf. (I)dnorm in Fig. 5B and phenyl-C11 together with the pair of faint-red spots near the methyl-H2B and phenyl-C16 atoms in Fig. 5a. The influence of other short interatomic C⋯H/H⋯C contacts summarized in Table 4a,b. The involvement of different atoms in the intermolecular interactions in the crystals of (I)The faint-red spots near the phenyl-C33 and H26 atoms in Fig. 4a, also highlight the different molecular environments for the two molecules. The significant contributions from H⋯H, C⋯H/H⋯C and S⋯H/H⋯S contacts to the Hirshfeld surfaces of both (I)C and n-hexyl-H7B atoms in (I)de + di ∼2.0 Å in the delineated plot A and phenyl-H7, H9 and H23 atoms in comparatively weaker short interatomic H⋯H contacts, Table 4de + di ∼2.6 Å in the fingerprint plot delineated into C⋯H/H⋯C contacts for (I)c, is the result of a short interatomic contact between phenyl-C32 and -H23 atoms while the points corresponding to other short interatomic contacts are merged within the plot. The presence of a pair of twin forceps-like tips at de + di ∼ 2.7 Å in the C⋯H/H⋯C delineated plot for (II)c, also indicates the involvement of methyl-H2A and -H2B, and phenyl-C7, -C8, -C11, -C16 and -C35 atoms in short interatomic contacts, Table 4d, that the pair of spikes at de + di ∼ 3.0 Å for (I)de + di > 3.1 Å for (II)The distinct distribution of points in the overall two-dimensional fingerprint plots for (I)et al., 2016N-hexyl-N-methyldithiocarbamate ligand reported in (I)i.e. dtcI, has been reported in the crystal structures of Ph2Sn(dtcI)2  compound, i.e. Hg(dtcII)3  in the Cambridge Structural Database short bond length is 2.47 Å and the average Sn—Slong bond length is 3.04 Å. This gives rise to an average Δ(Sn—S) of 0.57 Å. These values indicate the structures of (I)long are generally longer than usually observed. An analysis of the available crystallographic data showed the shortest Sn—S1 bond length occurred in the structure of Ph3Sn(S2CNEt2) SnPh3  2} ; 26.39 [N—(CH2)3CH2]; 22.6 [N—CH2)4CH2]; 14.06 (hexyl—CH3). 119Sn NMR (CDCl3): −187.56.Synthesis of triphenyltin(IV)N-methyl-N-phenylethyldithiocarbamate (II) compound (II)N-methyl-N-phenylethylamine  in place of N-hexyl-N-methylamine. Recrystallization was achieved by dissolving the compound in a chloroform/ethanol mixture (1:2 v/v). Yield: 67%, m.p. 387.5–388.3 K. Elemental analysis: calculated (%): C 60.0, H 4.9, N 2.5, S 11.4. Found (%): C 57.9, H 5.3, N 2.8, S 11.2. IR (KBr cm−1): 1452 ν(C—N), 977 ν(C—S), 502 ν(Sn—C), 488 ν(Sn—S). 1H NMR (CDCl3): δ 7.43–7.77 ; 7.24–7.35 ; 4.06 ; 3.36 ; 3.09 . 13C NMR (CDCl3): δ 196.61 (NCS2); 126.8–142.3 (C-aromatic); 60.25 (NCH2); 44.59 (NCH2CH2); 33.12 (N—CH3). 119Sn NMR (CDCl3) = −183.84.Uiso(H) set to 1.2–1.5Ueq(C). For (I)−3, respectively, are located 0.95 and 0.86 Å from the Sn atom. For (II)−3, respectively, are located 0.96 and 0.68 Å from the C11 and Sn atoms, respectively.Crystal data, data collection and structure refinement details are summarized in Table 710.1107/S2056989018005133/hb7745sup1.cifCrystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989018005133/hb7745Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989018005133/hb7745IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1833664, 1833663CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The cation and anion of the title salt are linked by an O—H⋯N hydrogen bond and a C—H⋯O interaction, resulting in a high viscosity and a crystallization temperature slightly lower than ambient temperature. 3H8NO+·C2F6NO4S2−, has orthorhombic (P212121) symmetry; the amino H atom of bis(trifluoromethanesulfonyl)amine (HNTf2) was transferred to the basic O atom of dimethylformamide (DMF) when the ionic liquid components were mixed. The structure displays an O—H⋯N hydrogen bond, which links the cation to the anion, which is reinforced by a non-conventional C—H⋯O interaction, generating an R22(7) loop. A further very weak C—H⋯O interaction generates an [001] chain.At 100 K, the title molecular salt, C The N2—C4—O5 angle does not deviate from the expected 120° of an sp2-hybridized carbon atom [120.37 (11)°]. The bis(trifluoromethanesulfonyl)amide anion features S1—N1 and S2—N1 bond distances of 1.6035 (11) and 1.5947 (11) Å, respectively.The asymmetric unit consists of one bis(trifluoromethanesulfonyl)amide anion and one dimethylformamidium cation Fig. 1: when thThe ion pair features two hydrogen bonds Table 1. One is A CSD search  found no structures that have the same ion pairing. Some structures feature the same bis(trifluoromethanesulfonyl)amide anion but different cations, which are usually metal complexes.2 (I)et al., 2014A literature procedure was followed to synthesize [(DMF)H]NTfUiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms. The methyl groups were refined as rotating groups.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016012251/hb7586sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016012251/hb7586Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016012251/hb7586Isup3.cmlSupporting information file. DOI: 1496417CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, dications, anions and solvent water molecules are connected via N/C/O—H⋯Cl and N—H⋯O hydrogen bonds and C—H⋯π interactions, forming a three-dimensional network.In the title salt, C N,N-bis(pyridin-4-ylmethyl)cyclohexane-1,4-diamine with hydrochloric acid in ethanol led to the formation of the title salt, C18H26N42+·2Cl−·2H2O, which lies about a crystallographic inversion center at the center of the cyclohexyl ring. The asymmetric unit therefore comprises one half of the N,N-bis(pyridin-4-ylmethyl)cyclohexane-1,4-diammonium dication, a chloride anion, and a solvent water molecule. In the dication, the two trans-(4-pyridine)–CH2–NH2– moieties occupy equatorial sites at the 1- and 4-positions of the central cyclohexyl ring, which is in a chair conformation. The terminal pyridine ring is tilted by 27.98 (5)° with respect to the mean plane of the central cyclohexyl moiety (r.m.s. deviation = 0.2379 Å). In the crystal, dications, anions, and solvent water molecules are connected via N/C/O—H⋯Cl and N—H⋯O hydrogen bonds together with C—H⋯π interactions, forming a three-dimensional network.Treatment of  The terminal pyridine ring is tilted by 27.98 (5)° with respect to the mean plane through the central cyclohexyl moiety (r.m.s. deviation = 0.2379 Å). The distance between the two terminal pyridine nitrogen atoms in the dication is 15.864 (2) Å. This is slightly shorter than the N⋯N separation [15.970 (3) Å] in the dication ligand of a one-dimensional zigzag-like CoII coordination polymer built up from alternate CoII ions and the dication of the title salt cyclohexane-1,4-diamine, synthesized according to a literature method  = 0.95 Å for Csp2—H, 0.99 Å for methylene, 1.00 Å for methine H atoms, and were refined as riding with Uiso(H) = 1.2Ueq(C). The N- and O-bound H atoms involved in hydrogen bonding were located in difference Fourier maps and refined freely .Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016014626/sj5507sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989016014626/sj5507Isup2.hklStructure factors: contains datablock(s) I. DOI: 1504428CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Both molecules adopt the ladder structure typical for this class of dimeric tetraorganodistannoxane dicarboxylates. A nearly linear very short C—H⋯O contact gives rise to a chain-like arrangement of molecules in the [111] directionThe asymmetric unit of [{Sn(C 4H9)2(C6H5COO)}2O]2, consists of two half molecules, completed by application of inversion symmetry. Both molecules adopt a ladder structure typical for this class of dimeric tetraorganodistannoxane dicarboxylates characterized by a centrosymmetric four-membered (Sn—O)2 ring of rhomboidal shape that is extended on both sides by folded six-membered Sn—O—C rings. To a first approximation, both kinds of Sn atoms (Sni and Sno) are trigonal–bipyramidally coordinated. The bond angles between the n-butyl groups are widened [135.64 (7)–146.20 (7)°] in comparison with an ideal trigonal bipyramid. Sn—O bond lengths within the {R2SnO3} coordination sphere depend strongly on the position of the corresponding O atom – axial (ax) or equatorial (eq) – as well as on the functionality of the carboxylate groups which exhibit μ2 (–COOi) and μ1 (–COOo) coordination modes, respectively. In summary, the following sequence of distances [mean values] is found: d(Sno—Oμ3)eq [2.024 (2) Å] < d(Sni—Oμ3)eq [2.044 (2) Å] < d(Sni—Oμ3)ax [2.158 (6) Å] < d(Sno—Oμ1-carb)ax [2.182 (6) Å] < d(Sni—Oμ2-carb)ax [2.250 (2) Å] ≃ d(Sno—O2-carbμ)ax [2.247 (12) Å]. The n-butyl groups adopt an anti–anti conformation with exception of two disordered outer n-butyl groups of the second molecule which exhibit gauche–anti and anti–gauche conformations. Weak intramolecular Sn⋯O interactions between the different O atoms of the outer carboxyl groups with the inner, as well as outer, Sn atoms give rise to a strongly distorted octahedral coordination at these Sn atoms. Intermolecular interactions between the individual molecules are restricted to van der Waals and O⋯H—C interactions of which a nearly linear very short C—H⋯O contact between the H atom of the phenyl group of one of the molecules with the outer non-coordinating C=O group of the other molecule is the most prominent. It gives rise to a chain-like arrangement of the molecules along [111]. The two n-butyl groups attached to the outer Sn atom of one molecule are disordered over two sets of sites with occupancies of 0.806 (3)/0.194 (3) and 0.702 (3)/0.298 (3).The asymmetric unit of the title compound, [{Sn(C The disorder of the two n-butyl groups was managed by a split model with site occupancies of 0.806 (3)/0.194 (3) and 0.702 (3)/0.298 (3). No further consideration will be made for the structural parameters of those n-butyl groups. It is noteworthy, however, that this disorder is caused by the conformational flexibility of the n-butyl group which adopts – in the case of the major/minor components – a gauche–anti/anti–gauche and anti-gauche/anti–gauche conformation with respect to the Sn—Cα—Cβ—Cγ and Cα—Cβ—Cγ—Cδ torsion angles . This conformation of the disordered n-butyl groups is in contrast to the conformation of all other n-butyl groups of both dimers, which show exclusively an anti–anti conformation . Structural parameters mean = 1.521 (6) Å, 〈(C—Cβ/γ—C)mean = 112.6 (11)° while bond angles at Cα range from 112.5 (1) to 123.1 (1)°. Sn—C distances are in the range of 2.127 (2)–2.134 (2) Å, mean value 2.130 (3) Å.The title compound Fig. 1 crystallry Fig. 1. With thes Fig. 2b,c. Thion Fig. 2a. Strucs Table 1 within tladder structure typical for this class of tetraorganodistannoxane dicarboxylates  and two outer (Sno) tin atoms are – to a first approximation – fivefold, trigonal–bipyramidally coordinated and linked together via two μ2-coordinating oxygen atoms (Oi) and two chelating (–COOi) carboxylate groups. The structure is completed by two monodentate carboxylate groups (–COOo) attached to the outer tin atoms /75.78 (5)°] angles at tin and obtuse ones [104.10 (5)/104.22 (5)°] at oxygen. Its rhomboidal shape with different Sn—O distances results from the position of the μ3-oxygen atom (O1/O3) within the trigonal–bipyramidal coordination sphere of the inner tin atoms (Sn1/Sn3): bonds where the O atom is in an equatorial (eq) position are significantly shorter [2.042 (1)/2.046 (1) Å] than those where the O atom is in an axial (ax) position [2.164 (1)/2.152 (1) Å]. The second axially positioned Sn—O bond at the inner tin atoms is even longer [2.251 (1)/2.248 (1) Å] as it results from a coordinative bond of the oxygen atom (O11/O31) of the μ2-benzoate ligand (–COOi). In contrast to the prediction of the VSEPR concept, the bond angle between both equatorially positioned n-butyl groups is widened to 146.20 (7)/141.73 (7)°.The central, planar and centrosymmetric four-membered (Sn–O)d(Sno—Oμ3)eq [2.027 (1)/2.022 (1) Å] < d(Sno—Oμ1-carb)ax [2.175 (1)/2.188 (1) Å] < d(Sno—Oμ2-carb)ax [2.260 (1)/2.235 (1) Å]. Bond angles between the n-butyl groups at the tin atoms are 142.49 (7) and 135.64 (7)°.The conformation of the outer, six-membered Sn–O–C rings is defined by an angle of 19.9 (1)/23.4 (1)° between the O–C–O plane and the Sn–O–Sn plane Fig. 4. In caseo), the C—O bonds are of different strengths: the short, strong one [1.232 (2)/1.222 (3) Å] indicates a localized C=O double bond whereas the long, weak one [1.307 (2)/1.306 (3) Å] of the Sn-coordinating oxygen atom indicates a localized C—O single bond. In the case of the bridging benzoate groups (–COOi) both C—O bonds are of almost equal lengths , in accordance with a delocalized π-system. In the two benzoate ligands, the carboxylate groups and the phenyl groups are not co-planar, but are inclined to each other at angles of 15.1 (2), 14.8 (3)/3.9 (3) and 17.3 (1)°.The different coordination modes of both benzoate ligands are reflected in different C—O bond lengths: in the case of the monodentate carboxylate group (–COOd(Sn⋯O) = 2.7857 (2)/2.7141 (2) Å] of the μ1-O atoms (O21/O41) of the outer carboxylate groups with the inner tin atoms (Sn1/Sn3), while those of the μ0-O atoms (O22/O42) of the outer carboxylate groups with the outer tin atoms (Sn2/Sn4) are still longer [2.8901 (2)/2.9883 (2) Å]. Taking these weak interactions into account, both kinds of Sn atoms adopt a strongly distorted octahedral coordination. All bonding features (except the last ones) of the two molecules are summarized in Fig. 5n-butyl groups relative to the Sn–O framework.Another characteristic feature of the molecular structure comprises some additional, very weak interactions [d(H⋯O) = 2.487 Å], nearly linear [〈(C—H⋯O) = 172.6°] contact between the hydrogen atom H26 of a phenyl ring of molecule 1 and the non-coordinating oxygen atom O42 of the second molecule attracts attention as it leads to a chain-like arrangement of the two molecules along [111] ]2O, have been extensively structurally characterized. The Cambridge Structural Database  while for the dicarboxylates benzoic acid derivatives (90) are the most studied. Even for the combination of R = nBu and R′ = benzoic acid derivatives not less than 67 structures are described, but from the parent compound with R′ = PhCOO−, only the structure of the methyl compound (R = Me) has been completely characterized }2O]2 was obtained from an equimolar mixture of 0.300 g (1.2 mmol) of n-dibutyltin oxide with 0.147 g (1.2 mmol) of benzoic acid in ethanol under reflux for 3.5 h. After removal of the solvent, single crystals were obtained by recrystallization of the solid from ethanol/n-hexane. and displacement parameters were taken from the chemically equivalent C atoms of the major occupancy component.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989017001505/zl2692sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017001505/zl2692Isup2.hklStructure factors: contains datablock(s) I. DOI: 1530058CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the former, the 4-methylbenzene ring substituent makes a dihedral angle of 71.40 (9)° with the mean plane of the naphthalene ring system, while the phenyl ring substituent in the latter makes a dihedral angle of 67.08 (12)° with the mean plane of the anthracene ring system.The title compounds, 6-, and C26H16S, (II), are benzothiophene derivatives in which the benzothiophene moiety is fused with a naphthalene ring system in (I), and with an anthracene ring system in (II). In (I), the mean plane of the benzothiophene ring system makes a dihedral angle of 2.28 (6)° with the naphthalene ring system, and a dihedral angle of 1.28 (6)° with the anthracene ring system in (II), showing that the fused units are essentially planar. In (I), the 4-methylbenzene ring substituent makes a dihedral angle of 71.40 (9)° with the naphthalene ring system, while the phenyl ring substituent in (II) makes a dihedral angle of 67.08 (12)° with the anthracene ring system. In the crystals of both compounds, molecules are linked by C—H⋯π interactions, leading to the formation of slabs parallel to (001) in (I) and to zigzag chains along [001] in (II). There are also offset π–π interactions present within the slabs in (I). In the crystal of (II), they link the chains, forming sheets parallel to (010). The triclinic polymorph of compound (II) has been reported .The title compounds, Cal., 2012. J. Org. In the crystal of (II)Cg2⋯Cg4iii = 3.711 (2) Å, interplanar distance = 3.479 (1) Å, slippage = 1.21 Å; Cg3⋯Cg4iii = 3.741 (2) Å, interplanar distance = 3.443 (1) Å, slippage = 1.22 Å; Cg2, Cg3 and Cg4 are the centroids of rings C1–C3/C10–C12, C1/C12–C16 and C4–C9, respectively; symmetry code: (iii) −x + 1, −y + 1, −z + 1].In the crystals of both compounds, molecules are linked by C—H⋯π interactions benzo[b]naphthothiophene b]thiophen-3-yl){2-[pivaloyloxy(p-tolyl) methyl]phenyl}methyl pivalate as a viscous liquid. Dipivalate (benzo[b]thiophen-3-yl){2-[pivaloyloxy(p-toyl) methyl]phenyl}methyl pivalate  upon interaction with ZnBr2  followed by removal of solvent and column chromatographic purification  gave 6-(p-tolyl)benzo[b]naphthothiophene as a pale-green solid . Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of (I)The reduction of the diketone (benzothiophen-3-yl)[2-(4-methylbenzoyl)phenyl]methanone  using sodium borohydride  followed by work-up gave the diol. Dipivaloylation of the diol  using pivaloyl chloride  and triethylamine  in the presence of a catalytic amount of DMAP (10 mg) in dry DCM (20 ml) led to the isolation of dipivalate (benzothiophen-2-yl)methanone  using sodium borohydride  followed by work-up gave the diol. Dipivaloylation of the diol  using pivaloyl chloride  and triethylamine  in the presence of a catalytic amount of DMAP (10 mg) in dry DCM (20 ml) led to the isolation of dipivalate {2-[phenylmethyl]phenyl}methyl pivalate as a thick liquid. Dipivalate {2-[phenylmethyl]phenyl}methyl pivalate  upon interaction with ZnBr2  followed by removal of solvent and column chromatographic purification  gave a new orthorhombic polymorph of 7-phenylanthrabenzo[d]thiophene  as a yellow solid. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the compound (II)The reduction of the diketone (2-benzoylphenyl)(dibenzo[Uiso(H) = 1.5Ueq(methyl C) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details for compounds (I)10.1107/S2056989016012937/lh5819sup1.cifCrystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989016012937/lh5819Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016012937/lh5819IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989016012937/lh5819Isup4.cmlSupporting information file. DOI: 1498519, 1498518CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The three molecules have slightly varying overall conformations, all having trans conformations with respect to the C=N bond. In the crystal, the packing features N—H⋯N hydrogen bonds, which connect molecules into chains extending along the c-axis direction, interlinked by C—H⋯π interactions (minimum H⋯Cg = 2.65 Å) into sheets lying parallel to (001).The title compound, C These are close to the literature value of 1.279 Å for Csp2=Nsp2 bonds , 1.472 (3) and 1.476 (3) Å, respectively. The comparative N1—C16 bonds connecting the central benzene ring to the central C=N bond in A, B and C are 1.422 (2), 1.419 (2) and 1.420 (2) Å, respectively. The C14—C15—N1—C16, torsion angles for the –C—C—N—C– bridge groups are −178.47 (17)° (for A), −176.35 (17)° (for B) and 178.31 (17)° (for C). The comparative dihedral angles between the anthracene ring system of the molecule (defined by C1–C14) and the benzene and phenyl rings (defined by C16–C21 and C22–C27) and between the benzene and phenyl rings, respectively, are 82.68 (4), 73.76 (5) and 25.63 (11)° in A, 80.10 (4), 78.82 (5) and 22.56 (11)° (in B) and 85.02 (5), 81.66 (5) and 16.25 (11)° (in C).The title compound, crystallizes with three independent molecules  = 2.65 Å; C—H⋯Cg = 154°], forming layers lying parallel to (001)  Fig. 3.et al., 2016N-phenyl-p-phenylenediamine. Of these three compounds, N1-phenyl-N-4-(quinolin-2-ylmethylene)benzene-1,4-diamine {synonym: N-phenyl-4-[(quinolin-2-ylmethylene)amino]-aniline; WOJJIQ -(pyren-1-yl)-methylidene]benzene-1,4-diamine  of 9-anthracenecarboxaldehyde in 5 ml of absolute ethanol was added dropwise under stirring. The mixture was stirred for 10 min, two drops of glacial acetic acid were then added and the mixture was further refluxed for 2h. The resulting yellow precipitate was recovered by filtration, washed several times with small portions of ice-cold ethanol and then with diethyl ether to give 140 mg (87%) of the title compound. Dark-yellow block-like crystals suitable for X-ray analysis were obtained within 3 days by slow evaporation of a solution in MeOH.80 mg (0.435 mmol) of Uiso(H)= 1.2–1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016020612/zs2373sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016020612/zs2373Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016020612/zs2373Isup3.cmlSupporting information file. DOI: 1524849CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The evolution of T1ρ and of other endogenous contrast methods  in the first month after reperfused myocardial infarction (MI) is uncertain. We conducted a study of reperfused MI in pigs to serially monitor T1ρ, T2 and T1 relaxation, scar size and transmurality at 1 and 4 weeks post-MI.n = 10) and 4 weeks (n = 5). Semi-automatic FWHM  thresholding was used to assess scar size and transmurality and compared to histology. Relaxation times and contrast-to-noise ratio were compared in healthy and remote myocardium at 1 and 4 weeks. Linear regression and Bland-Altman was performed to compare infarct size and transmurality.Ten Yorkshire swine underwent 90 min of occlusion of the circumflex artery and reperfusion. T1ρ, T2 and native T1 maps and late gadolinium enhanced (LGE) cardiovascular magnetic resonance (CMR) data were collected at 1 week (T1 = 7.0 ± 3.5 (1 week) and 6.9 ± 2.4 (4 week), CNRT1ρ = 12.0 ± 6.2 and 12.3 ± 3.2, and CNRT2 = 8.0 ± 3.6 and 10.3 ± 5.8. Infarct size was not significantly different for T1ρ, T1 and T2 compared to LGE (p = 0.14) and significantly decreased from 1 to 4 weeks (p < 0.01). Individual infarct size changes were ∆T1ρ = −3.8%, ∆T1 = −3.5% and ∆LGE = −2.8% from 1 – 4 weeks, but there was no observed change in infarct size for T2 or histologically.Relaxation time differences between infarcted and remote myocardial tissue were ∆T1 (infarct-remote) = 421.3 ± 108.8 (1 week) and 480.0 ± 33.2 ms (4 week), ∆T1ρ = 68.1 ± 11.6 and 74.3 ± 14.2, and ∆T2 = 51.0 ± 10.1 and 59.2 ± 11.4 ms. Contrast-to-noise ratio was CNRT1ρ was highly correlated with alterations left ventricle (LV) pathology at 1 and 4 weeks post-MI and therefore it may be a useful method endogenous contrast imaging of infarction.The online version of this article (doi:10.1186/s12968-017-0332-z) contains supplementary material, which is available to authorized users. Ischemic heart disease is an enormous health and economic burden and the most common cause of death throughout the world . A devasT1ρ (“T-one-rho”) CMR has recently emerged as an endogenous contrast method for quantitative imaging of myocardial injury –13. T1ρ We conducted a serial study of reperfused infarction in pigs to monitor T1ρ at 1 and 4 weeks post-MI. The objectives were to compare T1ρ relaxation time changes in ischemic tissue with native T1, T2 and LGE and associate each with infarct size and transmurality. Finally, imaging results were correlated with fibrosis using histological data.n = 10) were procured for this study. During all procedures, sedation was induced with intramuscular ketamine, endotracheal intubation was performed, and the animal was maintained with a mixture of isoflurane 1-2% and oxygen with a ventilator tidal volume of 20 mL/kg . Anesthesia and animal temperature was closely monitored for the duration of surgical and imaging procedures to maintain a constant physiologic state. Arterial access was obtained at the carotid artery for measurement of intraventricular pressure . Venous access was obtained at the internal jugular veins for administration of medication. After each procedure, the animal was weaned from anesthesia and transported to the recovery room. Upon completion of the terminal CMR study, the animal was returned to the operating room for euthanasia and tissue harvest.Yorkshire swine (n = 5) and II, a 4-week terminal study (n = 5). Furthermore, five animals  underwent a baseline CMR immediately prior to coronary artery occlusion. The experimental model was chosen to emulate human post-percutaneous coronary intervention ischemia injury. All the animals of the 4 week group underwent both 1 and 4 week CMR. Figure Ten pigs underwent 90 min of coronary artery occlusion and were randomized into two groups: group I, a 1-week post-MI terminal study  with 40 mT/m gradient and 12 channel RF receiver arrays. Intraventricular pressure was interfaced to physiological monitoring software and filtered to facilitate dual respiratory and cardiac gating . All 2D images were acquired in the short-axis during breath-holding and 3D with dual cardiac and respiratory gating. Breath-holding was performed by temporarily disabling the animal ventilator.x – SLy - 180y – SL-y - 90-x) [1 = 500 Hz, spatial resolution = 1.4 × 1.4 mm2, slice thickness = 6 mm, flip angle = 70°, TE = 1.45 ms, TR = 2.9 ms, NSeg = 55, bandwidth = 900 Hz/pixel, linear k-space phase encoding ordering, parallel imaging with acceleration factor = 2, 34 reference k-space lines obtained in a separate heartbeat, and four heartbeats for T1 relaxation between shots. The T1ρ amplitude was set at the highest available within scanner specific absorption rate limits (B1 = 500 Hz).2D T1ρ single-shot balanced steady-state free precession (bSSFP) sequences were performed using a spin echo, spin lock (SL) T1ρ pulse cluster (90 - 90-x) , 15. T1ρx – 180y – 90-x) bSSFP sequence and 8 images were acquired with different contrast times TE = 2, 10, 18, 26, 34, 42, 50 ms using the same readout as with the T1ρ images.2D T2 maps were obtained using a single-shot T2 prepared  . Other p2, slice thickness = 6 mm.Retrospective, short axis, multi-slice cine CMR was performed with a temporal resolution = 40 ms, flip angle = 70°, bandwidth = 940 Hz/pixel, spatial resolution = 1.1 × 1.1 mm2, flip angle = 50°, TE = 1.6 ms, TR = 3.2 ms. slice thickness = 2 mm, and parallel imaging acceleration factor = 2 [The animals received a 0.1 mmol/kg intravenous injection of gadolinium contrast for LGE imaging . Imaging was performed 10 minutes after injection of contrast agent using an inversion time (TI) scout sequence to determine the inversion time to null myocardial tissue signal. LGE CMR was obtained using a 3D multishot phase-sensitive inversion recovery (PSIR) bSSFP sequence at spatial resolution = 1.2 × 1.2 mmctor = 2 .After ex vivo CMR, the heart was flash-frozen using liquid nitrogen in a 4.5 L cryogenic container . The heart was sectioned into uniformly thick short axis slices using a commercial-grade prosciutto slicer  obtaining slices of uniform thickness of approximately 2 mm to be matched to CMR studies. Slices were submerged in a PBS solution with 0.1 M triphenyl tetrazolium chloride (TTC) and incubated at 50 ° C for 15 min . Slices Cine CMR image series were used to calculate indexed LV mass (Mass), wall thickness (WT), end-diastolic volume (EDV), end-systolic volume (ESV), ejection fraction (EF) and cardiac output (CO). Epi- and endocardial contours were drawn manually at ED and ES (excluding papillary muscles) using standard techniques  , 20.For all images, scar size was assessed using full width at half maximum (FWHM) thresholding in a mid-LV slice with visible enhancement on LGE (QMass) . FWHM thScar transmurality was computed as the ratio of hyperintense (infarct) to non-enhanced myocardium (%) in a mid-ventricular short axis slice. The myocardium was divided into six circumferential wedges and transmurality was reported for anterolateral and posterolateral segments in which infarction was observed (two of six segments). Scar transmurality <5% in a segment was excluded as noise.Motion correction was used to align T1ρ and T2 images using optical flow estimation of the image deformations . T1 and ∆TX=TXinf–TXrem and TXinf (TXrem) was the mean relaxation time in the infarcted (remote) tissue and σ(TXrem) was the standard deviation of the relaxation times observed in remote myocardium [Contrast-to-noise ratio (CNR) was calculated for T1ρ, T2 and native T1:ocardium .t-test.Descriptive statistics were reported as mean ± standard deviation (SD). Comparison of statistical means was performed using 2-way analysis of variance. Correlations were assessed with Pearson’s r. Bland-Altman testing was performed to test for mean bias and variation between imaging methods . Pairwiss = 10) survived the 90 min ischemia and reperfusion study to their terminal CMR at 1 or 4 weeks. At 4 weeks post-MI, there was a 13.4 ± 5.4% reduction in EF compared to baseline and associated with a 22.7 ± 8.0 mL increase in ESV and a 24.2 ± 14.1 mL increase in EDV. End diastolic wall thickness decreased by 4.0% after 4 weeks (p < 0.05) and ΔWT and ΔLVEDV between baseline and 4 weeks were correlated . Additional details are reported in Table All pigs s = 0 surviveHyperintense regions were observed at the lateral wall on all T1ρ, T2, and T1 maps and in LGE images at 1 and 4 weeks, consistent with ischemic injury to the circumflex coronary circulation  and 12.3 ± 3.2 (4 week), CNRT2 = 8.0 ± 3.6 and 10.3 ± 5.8 and CNRT1 = 7.0 ± 3.5 and 6.9 ± 2.4.As illustrated in Fig. ss = 0.14) and, among animals who underwent both 1 and 4 week CMR, significantly decreased from 1 to 4 weeks (s < 0.01). Individual infarct size changes were ΔT1ρ = −3.8%, ΔT1 = −3.5% and ΔLGE = −2.8% from 1 to 4 weeks , good correlation for T1 and LGE  and poor correlation for T2 and LGE   and was unchanged from 1 to 4 weeks (p = 0.15).Infarct transmurality was not significantly different for T1ρ, T1 and T2 compared to LGE (p < 0.001), T1 and LGE  and moderate correspondence between T2 and LGE   T1ρ values had higher relaxation time-dependent change than T2 and contrast-to-noise ratio compared to T1 and T2 in the infarcted myocardium; (2) there was a decrease in infarct size from 1 to 4 weeks on T1ρ, T1 and LGE CMR; and (3) T1ρ infarct size was better correlated with LGE than T1 or T2 and that T2 in particular was poorly correlated. Improved infarct contrast-to-noise ratio on T1ρ may explain the better correlation with LGE and histological infarct size and transmurality than T1 and T2.T1ρ is increased in acute and chronic myocardial infarction , 11, 13,Furthermore, while T2 and native T1 are believed to be biomarkers for myocardial edema in the area-at-risk after acute MI , recent T2 had reduced correlation with LGE as compared to T1ρ and T1, which may be partly explained by differences in the way post-infarction hemorrhage affects endogenous contrast. Degradation of hemoglobin byproducts in the hemorrhage in T2 and T2* CMR studies in patients and animals contribute to increased magnetic susceptibility-induced dephasing on CMR , 28. Acc1. As the amplitude B1 approaches zero, T1ρ approaches T2 . In our comparison of T1ρ, T2 and T1, we used identical readout sequences to eliminate a major cause of measurement variation. In addition, we matched the time between adjacent T2 or T1ρ preparations (4 heartbeats) and discarded the first scan because of variations in T1 recovery between preparations.Another reason for the poor T2 agreement with LGE is that different methods of preparation may give different T2, e.g. preparations with adiabatic refocusing pulses instead of a non-selective Hahn spin echo . The freInfarct size is expected to decrease from sub-acute to chronic post-infarction times . T1ρ, T1We found that T1ρ and T1 infarct transmurality was correlated with LGE CMR at 1 and 4 week post-MI. However, differences in T1ρ infarct transmurality might be explained by the varying acquisition times in the cardiac cycle. Although infarct size is not influenced by cardiac cycle, scar transmurality (derived from LGE CMR) has shown to vary between end-diastolic and end-systolic assessment . LGE MR T1ρ CMR is increased in myocardial infarction compared to T2 and has improved contrast-to-noise ratio compared to T1 and T2. Infarct size and transmurality on T1ρ and native T1 endogenous contrast was correlated with LGE CMR and thus may be useful as endogenous contrast CMR methods in ischemic patients who cannot receive contrast agents.


The 1:1, 2-methylpyridium and 4-methylpyridinium salts of the chiral 4-methylbenzoyloxy-substituted succinic acid form, respectively one- and two-dimensional hydrogen-bonded crystal structures, 6H8N+·C20H17O8−, comprises a 2-methylpyridinium cation and a 2,3-bis(4-methylbenzoyloxy)succinate mono-anion while the salt (II), 2C6H8N+·2C20H17O8−·5H2O, consists of a pair of 4-methylpyridinium cations and 2,3-bis(4-methylbenzoyloxy)succinate mono-anions and five water molecules of solvation in the asymmetric unit. In (I), the dihedral angle between the aromatic rings of the anion is 40.41 (15)°, comparing with 43.0 (3) and 85.7 (2)° in the conformationally dissimilar anion molecules in (II). The pyridine ring of the cation in (I) is inclined at 23.64 (16) and 42.69 (17)° to the two benzene moieties of the anion. In (II), these comparative values are 4.7 (3), 43.5 (3)° and 43.5 (3), 73.1 (3)° for the two associated cation and anion pairs. The crystal packing of (I) is stabilized by inter-ionic N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds as well as weak C—H⋯π interactions, linking the ions into infinite chains along [100]. In the crystal packing of (II), the anions and cations are also linked by N—H⋯O and O—H⋯O hydrogen bonds involving also the water molecules, giving a two-dimensional network across (001). The crystal structure is also stabilized by weak C—H⋯O and C—H⋯π interactions.The title salt (I), C A white precipitate was formed, which was dissolved in 30 ml of water and then kept at room temperature for slow evaporation. After 2 months, crystals of (I)The title salts (I)Uiso = 1.5Ueq(methyl C or O) and Uiso = 1.2Ueq(aromatic and methylene C). H atoms for NH and OH groups were located in difference-Fourier maps and refined with a distance restraint [N—H = 0.86 (1) Å or O—H = 0.82 (1) Å]. The Flack absolute structure obtained for both structures  [(for (I)] and 0.6 (3) [for (II)], for 1335 and 2690 quotients, respectively.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989017012981/zs2388sup1.cifCrystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989017012981/zs2388Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017012981/zs2388IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989017012981/zs2388Isup4.cmlSupporting information file. DOI: 1573939, 1573938CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal of the methylphenyl compound, the molecules are linked  28H24O6, (I), C34H22O5S, (II), and C27H20O3S2, (III), the cyclohexa-1,3-diene rings of the 1,2-dihydronaphthalene ring systems adopt half-chair, boat and half-chair conformations, respectively. The carbonyl O atoms attached to the dihydronaphthalene ring systems are each significantly deviated from the mean plane of the 1,2-dihydronaphthalene ring system, by 0.6162 (12) Å in (I), 0.6016 (16) Å in (II) and 0.515 (3) Å in (III). The mean planes of the 1,2-dihydronaphthalene ring systems make dihedral angles of 85.83 (3), 88.19 (3) and 81.67 (8)°, respectively, with the methylphenyl ring in (I), the pyrene ring in (II) and the phenyl ring in (III). In (I), the molecular structure is stabilized by an intramolecular C—H⋯O hydrogen bond, generating an S(6) ring motif. In the crystal of (I), molecules are linked by an intermolecular C—H⋯O hydrogen bond, which generates a C(8) zigzag chain running along [100]. Adjacent chains are further connected by C—H⋯π and offset π–π interactions [centroid–centroid distance = 3.6572 (9) Å], forming a double-chain structure. In the crystals of (II) and (III), molecules are linked into chain structures by offset π–π interactions with centroid–centroid distances of 3.5349 (12) and 3.8845 (13) Å for (II) and 3.588 (2) Å for (III). In (II) and (III), the thiophene rings are orientationally disordered over two sites, with occupancy ratios of 0.69:0.31 for (II), and 0.528 (4):0.472 (4) and 0.632 (5):0.368 (5) for (III).In the title 1-oxo-1,2-dihydronaphthalene derivatives, C In (II)via C—H⋯O hydrogen bonds  zigzag chain along to [100]. Adjacent chains are further linked into a double-chain structure  Å, interplanar distance = 3.443 (1) Å, slippage = 1.232 Å; Cg1 and Cg4 are the centroids of the C1–C6 and C22–C27 benzene rings, respectively].In the crystal of compound (I)re Fig. 4 through Cg3⋯Cg6iii = 3.5349 (12) Å, interplanar distance = 3.466 (1) Å; Cg3⋯Cg7iii = 3.8845 (13) Å, interplanar distance = 3.468 (1) Å; Cg3, Cg6 and Cg7 are the centroids of the C1–C6, C22–C25/C33/C34 and C25–C29/C34 benzene rings, respectively; symmetry code: (iii) −x, 1/2-y, −z; Fig. 5Cg5⋯Cg7iv = 3.888 (2) Å, interplanar distance = 3.632 (1) Å; Cg5 and Cg7 are the centroids of the benzene C1–C6 and C22–C27 rings, respectively; symmetry code: (iv) x, 3/2-y, z; Fig. 6In the crystal of (II)Compound (I): To a stirred solution of 1-(4-methoxyphenyl)-3-p-tolylisobenzofuran  in dry dichloromethane (DCM), dimethyl acetylenedicarboxylate (DMAD)  was added and the reaction mixture was stirred at room temperature for 1 h. Removal of the solvent was followed by column chromatographic purification  gave the isobenzofuran–DMAD adduct as a colorless solid . To a stirred solution of isobenzofuran–DMAD adduct  in dry DCM, BF3·OEt2  was added and the reaction mixture was stirred at room temperature for 5 min. Removal of the solvent followed by column chromatographic purification  gave compound (I)Compound (II): To a stirred solution of 1-(pyren-1-yl)-3-(thiophen-2-yl)isobenzofuran  in dry DCM (10 ml), DMAD  was added and the reaction mixture was stirred at room temperature for 1 h. To this, BF3·OEt2  was added and stirred at room temperature for 5 min. Removal of the solvent followed by column chromatographic purification  afforded compound (II)Compound (III): To a solution of 1,3-di(thiophen-2-yl)isobenzo furan  in dry toluene (15 ml), ethyl-3-phenylpropiolate  was added and refluxed till the consumption of 1,3-di(thiophen-2-yl)isobenzofuran (disappearance of fluorescent colour in 8 h). After removal of toluene in vacuo, the crude adduct was dissolved in dry DCM (15 ml), BF3·OEt2  was added and the reaction mixture was stirred for 10 min at room temperature. Removal of the solvent was followed by column chromatographic purification  which afforded compound (III)Uiso(H) values were set to 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms. In compound (II)SIMU and DELU) and bond length restraints (DFIX) with C—S = 1.70 (1) Å, C—C = 1.50 (1) Å and C=C = 1.40 (1) Å were applied to the disordered rings.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989017000469/is5470sup1.cifCrystal structure: contains datablock(s) I, II, III, global. DOI: 10.1107/S2056989017000469/is5470Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017000469/is5470IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989017000469/is5470IIIsup4.hklStructure factors: contains datablock(s) III. DOI: Click here for additional data file.10.1107/S2056989017000469/is5470Isup5.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989017000469/is5470IIsup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989017000469/is5470IIIsup7.cmlSupporting information file. DOI: 997379, 1438209, 1438503CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The asymmetric unit contains two independent molecules, which are linked by an O—H⋯O hydrogen bond. The dimers are further assembled into one-dimensional ladder like structure through O—H⋯F hydrogen bonds and stabilized by π–π interactions. The ladders are further linked by C—H⋯π contacts. 2 complex, C12H12BF2N3O, contains two independent molecules, which are linked by an O—H⋯O hydrogen bond. The dimers are further assembled into a one-dimensional ladder-like structure through O—H⋯F hydrogen bonds and stabilized by π–π interactions. The ladders are further linked by C—H⋯π contacts.The asymmetric unit of the title azopyrrole-BF Li et al. (20092–azopyrrole complexes as sensitizers for dye-sensitized solar cells (DSSCs) have been evaluated  and 1.382 (3) Å, respectively; Table 1pyrrole bonds are shorter than the B—Nazo bonds. The two N—N bonds each adopt a trans conformation and at 1.318 (3) and 1.312 (3) Å are much longer than that in the structure of the free azopyrrole ligand  = 3.544 (1) Å, Cg2⋯Cg3 = 3.617 (1) Å and Cg3⋯Cg4 = 3.664 (13) Å; Cg1, Cg2, Cg3 and Cg4 are the centroids of the N1/C1–C4, C7–C12 and C19–C24 rings, respectively]. The ladders assemble into a layer structure through C—H⋯π contacts  and 1.310 (1) Å] are comparable to those in the title compound.A search in the Cambridge Structural Database  and triethylamine (6 mL) in dry dichloromethane (15 mL) was slowly added boron trifluoride ethyl ether (2 mL). The resulting solution was stirred for 40 min, and then saturated potassium carbonate solution was added and stirred for 30 minutes. The resulting solution was extracted with ethyl acetate (10 mL × 3) and evaporated under vacuum to dryness. The residue was purified by column chromatography, eluting with ethyl acetate and petroleum ether (v/v = 1:14), to give a dark-green product, m.p. = 405 K. Yield 65%. 1H NMR : δ 10.118 , 7.548–7.526 , 6.920–6.897, 6.342 , 2.371, 2.314 . Suitable crystals for X-ray diffraction analysis were obtained by the slow evaporation of an CHCl3/CH3OH solution of the title compound.To a solution of 2-(4-hydroxylphenylazo)-3,5-dimethyl-1-Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C-methyl).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989018006229/ex2007sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018006229/ex2007Isup2.hklStructure factors: contains datablock(s) I. DOI: 1839158CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The two molecules are linked into dimers by a combination of Hg⋯Hg [Hg⋯Hg = 3.6153 (3) Å] and C—H⋯Cl and C—H⋯π interactions.The structure of C 3N,C1,N′}[bromido/chlorido(0.30/0.70)]mercury(II)–{2,6-bis[(dimethylamino)methyl]phenyl-κ3N,C1,N′}[bromido/chlorido(0.24/0.76)]mercury(II) (1/1), [HgBr0.30Cl0.70(C12H19N2)]·[HgBr0.24Cl0.76(C12H19N2)], there are two molecules in the asymmetric unit of formula LHgX {L = 2,6-bis[(dimethylamino)methyl]phenyl and X = Cl/Br}. In each molecule, the halide site is mixed Cl/Br, with occupancies of 0.699 (7):0.301 (7) and 0.763 (7):0.237 (7), respectively. The two molecules are linked into dimers by a combination of Hg⋯Hg [Hg⋯Hg = 3.6153 (3) Å] and C—H⋯Cl and C—H⋯π interactions.In the molecular structure of the title compound, {2,6-bis[(dimethylamino)methyl]phenyl-κ R2Hg and RHgX  have received considerable attention in the last three decades, mainly related to the search for versatile reagents in controlled transmetallation reactions :0.237 (7) in molecule B. In these moieties, there are two coordination spheres around each Hg atom  Å is significantly smaller than the sum of the van der Waals radii for Hg⋯Hg 2 dimer at 3.41 Å methyl]-6-[(dimethylamino)methyl]benzene}, which is a dimer linked by Hg2Br2 units, with one dimethylamino arm of each ligand coordinated to an Hg atom, and where there are no Hg⋯Hg interactions present /2.867 (6) Å] are significantly shorter than the sum of the van der Waals radii for Hg and N [ΣrvdW  = 3.53 Å]. However, these values are slightly longer than related organomercury(II) compounds with one pendant arm of 2.65 (1), 2.725 (4) and 2.647 (2) Å  Å, which is significantly smaller than the sum of the van der Waals radii for Hg⋯Hg 2C6H3Br], 1, was prepared according to the procedure given by van Koten and co-workers  was employed instead of 2.2 equivalents to quench with 2-bromo-1,3-bis(bromomethyl)benzene. This afforded a yellow oil which was purified by vacuum distillation to give a colorless oil in 70% yield. n-BuLi  was added dropwise via syringe to the solution of 1  in dry Et2O (15 ml) under an inert atmosphere at 273 K. After 30 min, the color of the reaction mixture changed from colorless to pale yellow. To this, a solution of HgCl2  in dry THF (10 ml) was added. The whole mixture was stirred for 5 h at 273 K and then allowed to warm slowly to room temperature. Then reaction mixture was filtered and the filtrate evaporated to dryness and the resulting precipitate extracted with hexane. The workup afforded a white precipitate of 2 . Colorless crystals of 2 suitable for single-crystal diffraction analysis were obtained by slow diffusion of hexane into CHCl3 at room temperature.The precursor 1H NMR: δ 7.15 , 7.07 , 3.45 , 2.21 . 13C NMR: δ 144.90, 128.36, 128.10, 66.01, 44.85. 199Hg NMR: δ −930. Analysis calculated for C12H19ClHgN2: C 33.73, H 4.48, N 6.56%; found: C 32.55, H 5.10, N 5.26%. ESI–MS (positive mode): [M + H]+m/z = 429.1005 (observed), 429.1015 .Uiso(H) = xUeq(C), where x = 1.5 for methyl H atoms and 1.2 for all other C-bound H atoms. There are two molecules in the asymmetric unit and in each the halide site is occupied by a mix or Cl and Br, with refined occupancies of 0.699 (7):0.301 (7) and 0.763 (7):0.237 (7), respectively.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989017014682/hg5496sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017014682/hg5496Isup2.hklStructure factors: contains datablock(s) I. DOI: 1510433CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, pairs of molecules are linked by N—H⋯O and C—H⋯O hydrogen bonds, forming inversion dimers with graph-set notation  16H13Cl2N3O3S2, the thiophene ring is disordered in a 0.762 (3):0.238 (3) ratio by an approximate 180° rotation of the ring around the S—C bond linking the ring to the sulfonyl unit. The dichlorobenzene group is also disordered over two sets of sites with the same occupancy ratio. The molecular conformation is stabilized by intramolecular C—H⋯Cl and C—H⋯N hydrogen bonds, forming rings with graph-set notation S(5). In the crystal, pairs of molecules are linked by N—H⋯O and C—H⋯O hydrogen bonds, forming inversion dimers with graph-set notation R22(8) and R12(11), which are connected by C—H⋯O hydrogen-bonding interactions into ribbons parallel to (100). The ribbons are further connected into a three-dimensional network by C—H⋯π interactions and π–π stacking interactions between benzene and thiophene rings, with centroid-to-centroid distances of 3.865 (2), 3.867 (7) and 3.853 (2) Å. Hirshfeld surface analysis has been used to confirm and quantify the supramolecular interactions.In the title compound, C The molecular conformation is stabilized by intramolecular C—H⋯Cl and C—H⋯N hydrogen bonds (Table 1S(5).In the molecule of the title compound Fig. 1, the dihs Table 1, formingCg1⋯Cg1v, 3.867 (7) Å for Cg2⋯Cg2v and 3.853 (2) Å for Cg4⋯Cg4vi where Cg1, Cg2 and Cg4 are the centroids of the thiophene ring B, the thiophene ring B′ and the benzene ring C .In the crystal, pairs of molecules are linked by intermolecular N—H⋯O and C—H⋯O hydrogen bonds Table 1 and 3 ▸,CrystalExplorer17.5  and external (revdw) atom of the surface:The intermolecular distance information on the surface can be condensed into a two-dimensional histogram of dnorm= (di − rivdw)/rivdw + (de − revdw)/ervdw.dnorm surfaces mapped over a fixed colour scale of −1.9033 (red) to 1.1934 (blue). In the fingerprint plots  correspond to C⋯Cl (1.3%), N⋯C (1.3%) and other less important interactions (<1%). C⋯C contacts correspond to intermolecular π–π interactions. The occurrence of non-high interaction rates can be attributed to the fact that the small disordered portion of the molecule is not considered.The molecular Hirshfeld surfaces were obtained using a standard (high) surface resolution with the three-dimentional trans-rac-methyl 4-methylbenzenesulfonate thiophen-2-yl]-1,3,4-oxadiazole  thiophen-2-yl]-1,3,4-oxadiazole  in dichloromethane (DCM) were added 2-thiophenesulfonamide , 1-ethyl-3-(3-dimethylamino-propyl)carbodiimide  and 4-dimethyl-aminopyridine , and the resulting mixture was stirred overnight at room temperature. Upon completion of the reaction, the reaction mixture was partitioned between DCM and water. The collected organic layer was dried over anhydrous Na2SO4, filtered and evaporated to give the crude compound, which was purified with automated-flash chromatography . The obtained product was recrystallized from hexane and ethyl acetate (4:1), m.p. 464.8–465.3 K. 1H NMR (CDCl3): δ 2.24 , 5.33 , 6.64 , 7.12 , 7.21 , 7.45 , 7.69 , 7.97 , 9.29 ; 13C NMR (CDCl3): 11.2, 50.5, 107.6, 127.3, 127.9, 129.1, 129.6, 131.7, 132.9, 133.8, 134.8, 135.1, 139.2, 142.0, 143.5, 158.4. HRMS m/z calculated for C16H13Cl2N3O3S2 [M + H]+ 429.9854; found: 429.9857.To a solution of methyl 1--5-methyl-1Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms. A rotating model was used for the methyl group. The nitrogen-bound H atom (H1N) was located in a difference-Fourier map and refined with the constraint N1—H1N = 0.84 (3) Å and Uiso(H) = 1.2Ueq(N). The thiophene ring is rotationally disordered by approximately 180° over two positions, the ratio of refined occupancies being 0.762 (3):0.238 (3). The dichlorobenzene group of the title compound is also disordered over two sets of sites with the same occupancy ratio. The disordered dicholorobenzene groups (C: C11–C16 and C′: C11A–C16A) were refined as rigid hexagons with bond lengths of 1.39 Å. The displacement ellipsoids for the corresponding carbon atoms in the disordered dicholorobenzene groups were constrained by using the EADP command. Six outliers  global, I. DOI: 10.1107/S2056989018006242/rz5232Isup3.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018006242/rz5232Isup4.cmlSupporting information file. DOI: 10.1107/S2056989018006242/rz5232sup4.pdfCheckcif Report. DOI: 1839201CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The asymmetric unit of the title compound contains two independent molecules with very similar conformations. Each molecule is built up from a ferrocene unit substituted in the 1 and 1′ positions by a protected sulfur diphenylphosphine and by a dimethylhydrazine fragment. 8H11N2)(C17H14PS)], contains two independent molecules (A and B) with very similar conformations. Each molecule is built up from a ferrocene unit substituted in the 1 and 1′ positions by a protected sulfur diphenylphosphine and by a dimethylhydrazine, –C(H)=N—N(CH3)2, fragment. The two independent molecules are linked by a C—H⋯N hydrogen bond. In the crystal, the A–B dimer is linked by a pair of C—H⋯S hydrogen bonds, forming a centrosymmetric four-molecule arrangement. These units are linked by C—H⋯π interactions, forming a supramolecular three-dimensional structure.The asymmetric unit of the title compound, [Fe(C The two independent molecules are linked by a C—H⋯N hydrogen bond (Table 2A view of the molecular structures of the two independent molecules (d Table 2.A and 9.4 (1)° for molecule B. However, the Cp rings are roughly parallel to each other with a dihedral angle of 1.46 (12)° for molecule A and 1.85 (12)° for molecule B. The protected diphenylphosphine and the dimethylhydrazine units are approximately trans with respect to the ferrocenyl moiety: the torsion angle P1—C11—C16—C161 and P2—C21—C26—C261 are ca 140.4° and ca 141.0°, respectively.In both molecules, the two Cp rings are between eclipsed and staggered conformations, with a twist angle τ of 5.2 (2)° for molecule endo towards the FeII ion, by −0.7330 (6) Å (molecule A) and 0.6986 (6) Å (molecule B) from the Cp ring plane, whereas the phosphorus atom lies in this plane, displaced by 0.0114 (5) and −0.0603 (4) Å for molecules A and B, respectively. This arrangement, with the protected sulfur atom endo towards the FeII ion and the P atom roughly coplanar with the Cp ring, is quite common in related compounds . The geometry within the hydrazine moiety =N—N(CH3)2 fragments the C=N bond lengths, which vary from 1.270 (5) to 1.287 (4) Å, and the N—N bond lengths, which vary from 1.367 (4) to 1.382 (5) Å, are similar to those in the title compound  to 0.952 (1) Å. The corresponding distances for compound 3 fall within these ranges .In ZEQSOD and ZEQSOD02, the P atom is roughly in the Cp ring plane, with deviations from the mean plane ranging from 0.009 (1) to 0.035 (1) Å, whereas the S atom is 3, is illustrated in Fig. 12), 200 mg (1.66 mmol) of anhydrous magnesium sulfate MgSO4 and 5 ml of anhydrous dichloromethane. To the red suspension, 100 ml of N,N-dimethylhydrazine  was added using a syringe. The reaction mixture was then stirred at room temperature overnight. The crude material obtained was purified by flash chromatography on silica gel to yield 41 mg of compound 3 as a brown solid (yield = 57%). Orange needle-like crystals of 3 were obtained by slow evaporation of a solution in pentane.The synthesis of the title compound, 1H NMR : δ (p.p.m.): 7.77–7.71 , 7.49–7.41 , 6.93 , 4.57 , 4.49 , 4.36 , 4.20 , 2.79 . 31P NMR : δ (p.p.m.): 41.6.Spectroscopic data: Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989018000440/su5416sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018000440/su5416Isup2.hklStructure factors: contains datablock(s) I. DOI: 1815294CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: