One of the two n-pentyl side chains was refined as disordered over two sets of sites, with occupancies of 0.733 (18) and 0.267 (18). The geometry around the HgII atom in the [HgCl4]2− anion is distorted tetrahedral, with bond angles ranging from 98.16 (3) to 120.68 (3)°. In the [HgCl4]2− anion, there are two short Hg—Cl bonds [2.4120 (9) and 2.4171 (11) Å], one intermediate Hg—Cl bond [2.4716 (12) Å] and one long Hg—Cl bond [2.6579 (13) Å] for the Cl atom involved in a trifurcated hydrogen bond as an acceptor, including two N—H⋯Cl⋯H—N interactions as well as one C—H⋯Cl interaction. There are several C—H⋯Cl interactions, with C⋯Cl distances ranging from 3.492 (3) to 3.796 (3) Å. These link the cations and anions into a zigzag chain along the c-axis direction. In addition, there are Cl⋯Cl halogen bonds, as well as π–π interactions, with centroid-to-centroid distances of 3.4765 (18) Å, which link one of the two benzimidazole moieties into dimeric units.In the title salt, (C H-benzo[d]imidazol-2-yl)benzene have been well explored. This ligand is an ideal candidate for metalation due to the presence of two N atoms and one C atom, which bind tightly with metal atoms . Reports of structurally related complex have been published recently -2-(dichlorostibanyl)-1,3-phenylene)bis(1-pentyl-1H-benzimidazole) (2) from (4-(tert-butyl)-2,6-bis(1-pentyl-1H-benzimidazol-2-yl)phenyl)mercury(II) chloride; [C34H41N4HgCl] (1) using SbCl3 in dry 1,4-dioxane via transmetallation. Related reactions  to 120.68 (3)°. In the [HgCl4]2− anion, there are two short Hg—Cl bonds , one intermediate Hg—Cl bond  and one long Hg—Cl bond  for the Cl atom involved in a trifurcated bond as an acceptor including two N—H⋯Cl⋯H—N interactions as well as one C—H⋯Cl interaction , −175.0 (15), 179.7 (15), and −178.1 (9)°, respectively, while for C30–C34 they are C23—N3—C30—C31, N3—C30—C31—C32, C30—C31—C32—C33, and C31—C32—C33—C34 . Thus the first side chain is in an all-trans conformation while the second side chain has adopted a conformation where it curls up at the end.In the ligand, the dihedral angles between the benzimidazole moieties and central phenyl ring are 40.60 (9) and 38.08 (10)°, while the angle between them is 36.04 (6)°. One of the pentyl substituents was refined as disordered over two sets of sites, with occupancies of 0.733 (18)/0.267 (18). The two pentyl side chains have adopted different conformations  and this is illustrated by their torsion angles. For C8c-axis direction, as shown in Fig. 3x, −y, 2 − z) with centroid-to-centroid distances of 3.477 (2) Å.In addition to the inter-ionic hydrogen bonds mentioned above, there are several C—H⋯Cl interactions with C⋯Cl distances ranging from 3.492 (3) to 3.796 (3) Å (see Table1). These link the cations and anions into a zigzag chain in the n-hexyl rather than n-pentyl side chains  for salts containing both the benzimidazole moiety as well as the tetrachloridomercurate(II) anion gave eight hits, including a closely related ligand with 1  in dry 1,4-dioxane was added SbCl3  at room temperature. The reaction mixture was refluxed for 6 h under an inert atmosphere of N2 and filtered through Whatman filter paper. When the solvent was evaporated, a white-colored precipitate was obtained and purified by washing with hexane. The compound was dried under vacuum. Colourless block-shaped single crystals were obtained from MeOH at room temperature, yield 64% (0.120 g).The reaction scheme is shown in Fig. 11H NMR : δ 8.13 , 7.91 , 7.82 , 7.49–7.45 , 4.43 , 1.74 , 1.43 , 1.14 , 0.72 . 13C NMR : 153.1, 151.4, 137.9, 134.7, 129.4, 128.5, 128.2, 124.7, 124.5, 117.8, 112.6, 45.1, 35.5, 31.3, 29.1, 28.5, 21.9, 14.1.n-pentyl side chains was refined as disordered over two sets of sites, with occupancies of 0.733 (18) and 0.267 (18) and both conformers were constrained to have similar metrical parameters using the SAME command in SHELXL2016. H atoms were positioned geometrically and refined as riding: N—H = 0.88 Å with Uiso(H) = 1.2Ueq(N); C—H = 0.95–0.98 Å with 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989017004303/zl2697sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017004303/zl2697Isup2.hklStructure factors: contains datablock(s) I. DOI: 1538746CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


CD4+NKG2D+ T cells are associated with tumour, infection and autoimmune diseases. Some CD4+NKG2D+ T cells secrete IFN‐γ and TNF‐α to promote inflammation, but others produce TGF‐β and FasL to facilitate tumour evasion. Here, murine CD4+NKG2D+ T cells were further classified into NK1.1−CD4+NKG2D+ and NK1.1+CD4+NKG2D+ subpopulations. The frequency of NK1.1−CD4+NKG2D+ cells decreased in inflamed colons, whereas more NK1.1+CD4+NKG2D+ cells infiltrated into colons of mice with DSS‐induced colitis. NK1.1−CD4+NKG2D+ cells expressed TGF‐β and FasL without secreting IFN‐γ, IL‐21 and IL‐17 and displayed no cytotoxicity. The adoptive transfer of NK1.1−CD4+NKG2D+ cells suppressed DSS‐induced colitis largely dependent on TGF‐β. NK1.1−CD4+NKG2D+ cells did not expressed Foxp3, CD223 (LAG‐3) and GITR. The subpopulation was distinct from NK1.1+CD4+NKG2D+ cells in terms of surface markers and RNA transcription. NK1.1−CD4+NKG2D+ cells also differed from Th2 or Th17 cells because the former did not express GATA‐3 and ROR‐γt. Thus, NK1.1−CD4+NKG2D+ cells exhibited immune regulatory functions, and this T cell subset could be developed to suppress inflammation in clinics. Ligands of human NKG2D include MHC class I chain‐related protein A/B (MICA/MICB) and UL16‐binding proteins (ULBPs). Mouse NKG2D ligands include retinoic acid early induced transcript‐1 , H60 and murine ULBP‐like transcript 1 (MULT‐1) + T cells. NKG2D in association with its adaptor molecules, namely DAP10 or DAP12, transduces signalling by the activation of phosphatidylinositol 3‐kinase (PI3K), resulting in cell activation, survival, cytoskeletal rearrangement and release of cytokines and cytotoxic granules NKG2D is an activating receptor expressed on natural killer (NK) cells, CD8+ NKG2D+ T cells are associated with inflammatory diseases, such as rheumatoid arthritis (RA) + NKG2D+ T cells + NK2D+ T cells exhibit Th1‐like properties in tissues because of the produced IFN‐γ, TNF‐α and cytolytic granules. IL‐15 of the microenvironment either in cis or in trans form contributes to the induction of CD4+ NKG2D+ T cell subset CD4+ NKG2D+ T cell population, which is associated in regulatory activities, is normally found in healthy individuals; CD4+ NKG2D+ T cell population is inversely correlated with disease severity in patients with juvenile‐onset systemic lupus, suggesting that CD4+ NKG2D+ T cells acts in regulation rather than inflammation + NKG2D+ T cells with regulatory activity is largely dependent on FasL and TGF‐β; hence, this T cell subset features an immunosuppressive property CD4+ NKG2D+ T cell population significantly increased in RAE‐1ε transgenic mice, whose RAE‐1ε expression was controlled by the CD86 promoter. CD4+ NKG2D+ T cells produced TGF‐β to down‐regulate NKG2D expression on NK cells, whereas Foxp3 was not expressed in the cytoplasm + NKG2D+ T cells are associated with colitis induced by dextran sodium sulphate (DSS) in mice. Furthermore, whether the subsets of CD4+ NKG2D+ T cells with distinct function could be discriminated by additional cell markers remains unclear. Results show that the frequency of NK1.1− CD4+ NKG2D+ T cells in colon is negatively correlated with colitis induced by DSS, and NK1.1− CD4+ NKG2D+ T cell differs from NK1.1+ CD4+ NKG2D+ T cells in terms of cell membrane markers and transcriptional RNAs.The number of mouse CD4The following antibodies were obtained from Biolegend  or eBioscience : CD3 (17A2), γδ (GL3), CD8 (53.67), CD4 (GK1.5), NK1.1 (PK136), NKG2D (CX5), CD107a (1D4B), IFN‐γ (XMG1.2), NKp46 (29A1.4), NKG2A (16A11), Ly49D (4E5), Ly49H (3D10), TGF‐β (TW7‐16B4), FasL (MFL3), IL‐10 (JES5‐16E3), IL‐17 (eBio17B7), CD62L (MEL‐14), CD44 (IM7), granzyme B (NG2B), perforin (eBioOMAK‐D), CD25 (PC61.5), Foxp3 (FJK‐16S), GITR (YGITR 765), CTLA‐4 (UC10‐4B9), CD39 (24DMS1), CD69 (LG.3A10), CCR9 (CW‐1.2), CD28 (E18), T‐bet (4B10), GATA‐3 (16E10A23) and ROR‐γt (AFKJS‐9), neutralized TGF‐β antibody (1D11) and RAE‐1ε mAb (205001). C57BL/6 and pCD86‐RAE‐1 transgenic mice n = 5). All mice were weighed every day. To assess the extent of colitis, loss in bodyweight , stool consistency  and blood in the stool  were monitored daily by trained individuals blinded to the treatment groups. Disease activity scores are calculated using the total score, which ranged from 0 to 12. The mice were killed on day 8, and the spleens and intestinal tissues were removed for ex vivo analysis. All experimental protocols were approved by the Institutional Animal Care and Use Committee of Yangzhou University.Colitis was induced by administration of DSS  to drinking water for 7 days . The tissues were dissected longitudinally, washed completely and cut into smaller pieces. The tissues were then predigested by Hanks’ balanced salt solution (HBSS) with 5 mM EDTA and 1 mM DTT at 37°C for 20 min. Mixed cell solution was passed through a nylon filter (100 μm) and then digested in PBS containing collagenase D (0.5 g/L), DNase I (0.5 g/L) and dispase II (3 g/L) for another 20 min. The cell suspension was centrifuged, suspended and washed with RPMI 1640 three times. The mixed cells were supplemented with 35% Percoll and then centrifuged to isolate mononuclear cells. Finally, the mononuclear cells were washed with PBS for further study.Cytokine production was determined using an intracellular staining kit (eBioscience). Lymphocytes were cultured with PMA (200 ng/ml)/ionomycin (2 μg/ml) in the presence of brefeldin A (10 μg/ml) for 4 hrs at 37°C. At the end of the incubation period, the cells were pre‐stained with antibody against surface markers. The cells were fixed, permeabilized, stained with cytokine or isotype antibody and analysed by flow cytometry. Lymphocytes were also permeabilized in referenced buffer and incubated with antibodies against Foxp3, T‐bet, GATA‐3 or ROR‐γt.Mouse tissues were embedded in OCT and frozen instantly in liquid nitrogen for cryostat sections. After fixation, the sections were blocked with donkey serum and stained with goat antimouse RAE‐1ε antibody . The sections were washed and stained with Alexa‐546 labelled donkey anti‐goat as secondary antibody. The sections were covered with DAPI . Fluorescence was detected using Eclipse E600  microscope and analysed using NIS‐Elements software .− CD4+ cells from pCD86‐RAE‐1 transgenic mice were negatively isolated using a CD4+ T cell isolation kit. The cells were stained with PE‐antimouse NKG2D antibody and magnetic‐labelled anti‐PE antibody sequentially. The sorted CD4+ NKG2D+ T cells (5 × 105) were injected into the tail vein of DSS‐ or PBS‐treated mice (n = 5) on days 1, 3 and 5. On day 7, the mice were killed to obtain mononuclear colon cells and spleens. Frequencies of CD4+ NKG2D+ T cells were analysed using flow cytometry gated on 7‐AAD− CD45+ NK1.1− cells.Splenic NK1.1− CD4+ NKG2D+ and NK1.1+ CD4+ NKG2D+ cells of normal C57BL/6 mice were sorted using flow cytometry. The sorted cells were lysed in TRIzol reagent  and reverse‐transcribed into complementary DNAs. The DNA profiles were detected by GeneChip® Mouse Transcriptome Assay 1.0  in Shanghai GIMIX Information Technology Company. Data were analysed by GCBI online software.Splenic NK1.1− CD45+ CD4+ NKG2D+ cells were analysed. The frequency of CD4+ NKG2D+ cells was significantly down‐regulated in the local inflamed colons of DSS‐treated mice   and CTLA‐4, but expressed CD39 at low levels  profiles were analysed by gene chips. A total of 161 mRNA genes  + NKG2D+ cells was determined by costimulation of the MHC II molecule and NKG2D ligand − CD4+ NKG2D+ cell after coligation of TCR and NKG2D are still being studied.CD4+ NKG2D+ T cells was observed in patients with rheumatoid arthritis + NKG2D+ T cells were negative in grade 1 cervical intraepithelial neoplasia and melanoma patients treated with sorafenib + NKG2D+ T cells of patients with Crohn's disease. Th17 and Th1 represent 30% ± 17% and 12% ± 5%, respectively, of the lamina propria CD4+ NKG2D+ population + CD4+ NKG2D+ cells produced IFN‐γ, IL‐17 and IL‐21, indicating that the NK1.1+ CD4+ NKG2D+ subset may resemble human CD161+ CD4+ NKG2D+ cells involved with inflammation The pro‐inflammatory role of CD4− CD4+ NKG2D+ cells showed distinctive markers from NK1.1+ CD4+ NKG2D+ cells. NKp46 − CD4+ NKG2D+ cells. Given that IL‐15 stimulations can program T cells to express NK cell markers, such as NKp46 and NKG2A − CD4+ NKG2D+ cells may not depend on IL‐15 alone. Induction of the subset in vitro requires coligations of TCR and NKG2D. Naturally occurring regulatory CD4+ NKG2D+ cells were also found in humans − CD4+ NKG2D+ cells could be produced in thymus innately or induced outside.NK1.1− CD4+ NKG2D+ cells into the colon with colitis decreased, whereas the frequency of NK1.1− CD4+ NKG2D+ cells in the spleen of mice was enhanced. Under inflammatory conditions, NK1.1− CD4+ NKG2D+ cells would be redistributed because of the local environment. NK1.1− CD4+ NKG2D+ T cells expressed low levels of CD39 − CD4+ NKG2D+ T cells exhibit potential to migrate into colon tissues. The retention of NK1.1− CD4+ NKG2D+ T cells in spleens partly resulted from the enhanced expression level of NKG2D ligands of splenic macrophages or DCs under the DSS‐induced inflammatory situations. Macrophages or DCs would up‐regulate NKG2D ligand expression when they are stimulated by Toll‐like receptor ligand − CD4+ NKG2D+ T cells, because pCD86‐RAE‐1 transgenic mice showed higher expression levels of RAE‐1 in the colons after DSS treatment than those of the wild mice.The infiltration of NK1.1+ NKG2D+ T cells were further categorized into NK1.1− CD4+ NKG2D+ T and NK1.1+ CD4+ NKG2D+ T subsets. NK1.1− CD4+ NKG2D+ T cells suppressed colitis induced by DSS in mice via production of TGF‐β. Regulatory NK1.1− CD4+ NKG2D+ T cells differ from conventional CD4+ CD25+ Foxp3+ cells and do not have features of NK1.1+ CD4+ NKG2D+ T cells in both phenotype and RNA transcription. This article provides biological features of regulatory NK1.1− CD4+ NKG2D+ T cells of mice and indicated that NK1.1− CD4+ NKG2D+ T cells may be used for treatment of inflammation‐associated diseases.In conclusion, CD4All authors have declared there are no financial conflicts of interest with regard to this work.Figure S1 Detection of colonic T and NK cells of mice treated by DSS or PBS.Figure S2 Detection of splenic T and NK cells of mice treated by DSS or PBS.Figure S3 Detection of splenic CD3+ ɣδ− NK1.1+ CD4+ NKG2D+ T of mice treated by DSS or PBS.Figure S4 Expression of Foxp3 in splenic NK1.1−CD4+NKG2D+ Foxp3+ cells of CD86‐transgenic or wild type mice treated by DSS.Figure S5 Production of IFN‐ɣ, IL‐17, and IL‐21 by NK1.1+ CD4+NKG2D+ cells of mice treated by DSS or PBS.Figure S6 Membrane TGF‐β on NK1.1−CD4+NKG2D+ cells of spleens from mice treated by DSS or PBS.Click here for additional data file.


EXE) treats estrogen receptor positive (ER+) breast cancer in postmenopausal women by inhibiting the estrogen‐synthesizing cytochrome P450 CYP19A1. Variability in the severity and incidence of side effects as well as overall drug efficacy may be partially explained by genetic factors, including nonsynonymous variation in CYP19A1, also known as aromatase. The present study identified phase I EXE metabolites in human liver microsomes (HLM) and investigated mechanisms that may alter the extent of systemic estrogen deprivation in EXE‐treated women with breast cancer, including whether functional polymorphisms in aromatase cause differential inhibition by EXE and whether EXE metabolites possess anti‐aromatase activity. The potency of EXE and ten of its derivatives was measured with HEK293‐overexpressed wild type aromatase (CYP19A1*1) using a rapid novel UPLC tandem mass spectrometry method. Of the ten compounds assayed, five were poor inhibitors (IC50 ˃ 50 μmol/L) of wild type aromatase while five others, including the major metabolite, 17β‐dihydroexemestane (17β‐DHE), exhibited moderate potency, with IC50 values ranging between 1.2 and 7.1 μmol/L. The anti‐aromatase activity of EXE was also tested with two common allozymes, aromataseThr201Met (CYP19A1*3) and aromataseArg264Cys (CYP19A1*4). Differential inhibition of variant aromatase is unlikely to account for variable clinical outcomes as EXE‐mediated inhibition of aromataseThr201Met (IC50 = 0.86 ± 0.12 μmol/L) and aromataseArg264Cys (IC50 = 1.7 ± 0.65 μmol/L) did not significantly differ from wild type (IC50 = 0.92 ± 0.17 μmol/L). Although less potent than the parent drug, these results suggest that active metabolites may contribute to the therapeutic mechanism of EXE.Exemestane ( A key pβ‐DHE as a major metabolite in human plasma has been unequivocally confirmed in studies of postmenopausal women taking EXE   . Corning  and Integrated DNA Technologies  manufactured the NADPH regeneration system and oligonucleotide primers, respectively. A QuikChange II Site‐Directed Mutagenesis Kit was purchased from Agilent  to produce aromatase variant overexpression vectors. The HEK293 cell line was procured from ATCC . G418, penicillin/streptomycin, fetal bovine serum, Opti‐MEM, and DMEM supplemented with 4.5 g/L glucose, 110 mg/L sodium pyruvate, and L‐glutamine was purchased from Invitrogen  along with an XCell electrophoresis system. Lipofectamine 2000, PVDF membranes, Pierce BCA protein assay kit, SuperSignal West Femto Maximum Sensitivity Substrate, sodium dodecyl sulfate (SDS), glycine, tris base, ammonium persulfate (APS), goat anti‐rabbit HRP‐conjugated antibody (cat. No. 31466), and tetramethylethylenediamine (TEMED) were also purchased from Thermo Fisher Scientific. Nonfat dry milk was prepared by BioRad . Sigma‐Aldrich  supplied Ponceau staining solution, Tween 20, acrylamide/bis‐acrylamide solution, 2‐mercaptoethanol, estrone, androstenedione substrate, and estrone‐2,3,4‐13C3. Rabbit monoclonal anti‐aromatase antibody (cat. no. ab124776) was purchased from Abcam .Hangzhou DayangChem Co.  supplied the androgens boldenone, testosterone, and 4‐andostene‐3,17‐dione for the synthesis of EXE and its analogs. Tokyo Chemical Industry Co. , Thermo Fisher Scientific , and Sigma‐Aldrich  produced all other reagents (ACS grade or higher) needed for synthesis. Steroid purification required silica columns  and thin‐layer chromatography plates . LC/MS grade methanol, acetonitrile, and formic acid was purchased from Thermo Fisher Scientific. XenoTech  supplied pooled mixed gender human liver microsomes . Previous studies provide detailed descriptions of the synthesis, purification, and NMR‐based identity verification of each compound  in a chilled Beckman L7‐65 ultracentrifuge , resuspended in PBS, and stored at −80°C. The relative expression of aromatase was quantitated in triplicate by subjecting 20 μg of protein from each overexpressing cell line to SDS‐PAGE in a 10% tris‐glycine polyacrylamide gel. Following transfer to PVDF for 90 min at 30 V, the membrane was blocked overnight at 4°C in 5% nonfat dry milk, washed for 30 min in 0.1% Tween, and probed overnight with anti‐aromatase primary antibody (1:2500). The next day, the membrane was again washed for 30 min, and probed with HRP‐conjugated goat anti‐rabbit antibody (1:7500) for 1 h at ambient temperature. Following another 30 min wash, the blot was incubated with SuperSignal West Femto Maximum Sensitivity Substrate per the manufacturer instructions and imaged on a ChemiDoc Imager . Image J software  was used to measure band density while Ponceau staining was used to validate even loading between lanes.Stable overexpression of wild type aromatase in HEK293 was driven by a pcDNA3.1/V5‐His‐TOPO mammalian expression vector as previously described , 5 μmol/L androstenedione, a NADPH regeneration system , and 15 μg of microsomes from HEK293 overexpressing wild type or variant aromatase were individually incubated with varying concentrations of each steroid. The steroid concentrations used for anti‐aromatase activity assays are as follows: EXE (0.05‐15 μmol/L), 17β‐DHE (0.05–30 μmol/L), 17α‐DHE (100 μmol/L), 6α‐spirooxiranandrosta‐1,4‐diene‐3,17‐dione (0.05–30 μmol/L), 6β‐spirooxiranandrosta‐1,4‐diene‐3,17‐dione (0.05–40 μmol/L), 6α‐methylandrosta‐1,4,6‐triene‐3,17‐dione (0.5–30 μmol/L), 6α‐methylandrosta‐1,4‐diene‐3,17‐dione (0.2–30 μmol/L), 6‐hydroxymethylandrosta‐1,4,6‐triene‐3,17‐dione (2.5–300 μmol/L), 17β‐hydroxy‐6‐hydroxymethylandrosta‐1,4,6‐triene‐3‐one (100 μmol/L), 6α/β‐hydroxy‐6α/β‐hydroxymethylandrosta‐1,4‐diene‐3,17‐dione (100 μmol/L), and 6α/β,17β‐Dihydroxy‐6α/β‐hydroxymethylandrosta‐1,4‐diene‐3‐one (100 μmol/L). Organic solvent comprised <1% of the total volume of each enzymatic incubation, which proceeded at 37°C for 2 h. Reactions were terminated with 50 μl of ice cold acetonitrile and centrifuged at 4°C for 15 min at 13,200g. Supernatants were collected and spiked with 50 ng of estrone‐2,3,4‐13C3 as an internal standard. An incubation with microsomes derived from non‐transfected HEK293 was also performed to serve as a negative control. Aromatization catalyzed by wild‐type or variant aromatase was likewise monitored in the presence of vehicle rather than EXE or compounds from the reference library to reflect maximal uninhibited estrone formation. Estrone was measured using a novel 6‐min direct detection UPLC/MS/MS method on the Waters Acquity platform using m/z transitions 271.17→133.09 as a marker for estrone and 274.15→162 for estrone‐2,3,4‐13C3. Mobile phase (57% methanol in 0.1% formic acid) was infused isocratically from 0 to 4 min at a flow rate of 0.4 mL/min. The column was then washed with methanol for 1 min followed by 1 min of re‐equilibration with mobile phase. Cone and collision voltages were set at 35 V and 20 V respectively. Dwell time for both compounds was 0.1 sec. IC50 values from incubations with wild‐type aromatase were calculated for each compound in GraphPad Prism 6 . One‐way ANOVA was used to compare the IC50 value for EXE incubated with wild type aromatase with IC50 values for EXE incubated with overexpressed aromatase allozymes.Per 50‐μl incubation containing 50 μg of HLM in PBS (pH 7.4), 400 μmol/L EXE, and an NADPH regeneration system was placed in a 37°C water bath for 4 h before termination with 50 μL of cold acetonitrile. After a 15‐min refrigerated centrifugation at 13,200g, the supernatant was examined for phase I EXE metabolites. A 10‐min UPLC method was used to separate and detect EXE and the ten other reference compounds through multiple reaction monitoring with positive mode electrospray ionization on a Waters ACQUITY UPLC/MS/MS system . The 1.7 μm ACQUITY UPLC BEH C18 column  used for these analyses was protected by a 0.2 μm in‐line filter. The UPLC gradient conditions used have previously been described  and its major metabolite 17β‐DHE (IC50 = 4.3 ± 0.56 μmol/L) were potent and moderate inhibitors of aromatase respectively. These results agree with an earlier study which found that 17β‐DHE was approximately 2.6‐fold less potent than EXE , exhibiting nearly 5‐fold more potency than its 6β stereoisomer (IC50 = 5.7 ± 1.6 μmol/L). 17α‐DHE and three additional compounds exhibited negligible aromatase inhibition with IC50 values exceeding 100 μmol/L  than EXE in the present study, a large difference in potency also observed by Buzzetti et al. (50 = 3.3–7.1 μmol/L). In keeping with the observations of Buzzetti et al.  between wild type enzyme (0.92 ± 0.17 μmol/L), aromataseThr201Met (0.86 ± 0.12 μmol/L), and aromataseArg264Cys (0.97 ± 0.09 μmol/L) in AAA assays normalized for relative aromatase expression (Fig. ICion Fig. . The preion Fig. . One stuion Fig. .β‐DHE, 6‐HME, 6α/β‐hydroxy‐6α/β‐hydroxy‐methylandrosta‐1,4‐diene‐3,17‐dione, and 6α/β,17β‐dihydroxy‐6α/β‐hydroxymethyl‐androsta‐1,4‐diene‐3‐one were identified in incubations of EXE with pooled human liver microsomes through comparison to reference compounds (Fig. β‐DHE‐glucuronide produced by UGT2B17 (Sun et al. β‐DHE is not only the predominant EXE metabolite formed in human liver microsomes, but also capable of inhibiting aromatase with moderate potency suggesting that it may make clinically relevant contributions to the overall response to EXE in women with ER+ breast cancer (Platt et al. 17nds Fig.  detectedParticipated in research design: Peterson and Lazarus. Conducted experiments: Peterson. Contributed new reagents or analytic tools: Xia, Chen, and Peterson. Performed data analysis: Peterson. Wrote or contributed to the writing of the manuscript: Peterson, Chen, Xia, and Lazarus.None declared.


The structure of this complex was obtained by X-ray diffraction and supported by DFT calculations.The title compound, [Cu(dppaS 24H20NP2S2)(C18H15P)2]·CH2Cl2 or [Cu(dppaS2)(PPh3)2]·CH2Cl2, is a neutral mononuclear copper(I) complex bearing an N,N-bis(diphenylphosphorothioyl)amidate (dppaS2−) ligand and two triphenylphosphane ligands. The molecular structure shows that the two S atoms of the dppaS2− ligand [Cu—S = 2.3462 (9) and 2.3484 (9) Å] and the two P atoms of the two triphenylphosphane ligands [Cu—P = 2.3167 (9) and 2.2969 (9) Å] coordinate to the copper(I) atom, resulting in a tetrahedral coordination geometry. The crystallographically observed molecular structure is compared to the results of DFT calculations.The title compound, [Cu(C Several years ago, we reported some emissive copper(I) complexes bearing diphosphane disulfide (PPh3)2] bearing the anionic diphosphane disulfide ligand N,N-bis(diphenylphosphorothioyl)amidate (dppaS2−) and two triphenylphosphane ligands.Copper(I) complexes have been studied actively because of the abundance of the metal ore and their interesting luminescent properties (Costa 2)(PPh3)2] shows that the two sulfur atoms of the dppaS2− ligand and the two phosphorus atoms of the two triphenylphosphane ligands coordinate to the copper atom, resulting in a tetrahedral coordination geometry  and 2.3484 (9) Å, and those between the copper atom and the phosphorus atoms of the triphenylphosphane ligands are Cu—P = 2.3167 (9) and 2.2969 (9) Å. The diphosphine disulfide ligand forms a six-membered ring adopting a boat conformation. The bond order of the P6—S2 and P7—S3 bonds are considered to be slightly smaller than two because the lengths of the bonds are considerably longer than general P=S (= 1.91 Å) bond lengths amine (HdppaS2)  and potassium tert-butoxide . Triphenylphosphane  and [Cu(CH3CN)4]PF6  were then added to the reaction solution. After the solution had been stirred for one h at room temperature, a white powder (KPF6) precipitated. The mixture was then filtered. The solution was added to ethanol (20 ml) and the resulting colorless crystals were obtained by filtration. Yield 256 mg (82%). Analysis found: C, 69.43; H, 4.85; N, 1.36%. Calculated for [Cu(dppaS2)(PPh3)2], C60H50NS2P4Cu: C, 69.51; H, 4.86; N, 1.35%. 31P{1H} NMR  34.6 , −2.5 . Broadening of the 31P signals of the phosphorus atoms directly coordinating to the copper atom, which has a large quadrupole moment, has frequently been observed  = 1.2Ueq(C) for methylene groups, and 0.95 Å and Uiso(H) = 1.2Ueq(C) for aromatic groups.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989017009380/im2478sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989017009380/im2478Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017009380/im2478Isup3.molSupporting information file. DOI: 1557968CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The isomeric title compounds both display three-dimensional supramolecular architectures arising from N—H⋯O, C—H⋯O, C—H⋯π and π–π interactions. N-[(2-nitrophenyl)sulfonyl]benzamide, (I), and 4-bromo-N-[(4-nitrophenyl)sulfonyl]benzamide, (II), are described (molecular formula = C13H9BrN2O5S in each case). The asymmetric unit of (I) contains two independent molecules [(IA) and (IB)], while that of (II) contains one molecule. The benzoic acid aromatic ring of molecule (IA) is disordered due to rotation about the Car—C(=O) bond over two orientations in a 0.525 (9):0.475 (9) ratio. The dihedral angle between the benzene rings is 85.9 (3)° in (IA) and 65.22 (19)° in (IB), while in (II), the corresponding value is 56.7 (7)°. In the crystals of (I) and (II), N—H⋯O, C—H⋯O and C—H⋯π interactions generate three-dimensional networks.The syntheses and crystal structures of the isomeric 4-bromo- N-(arylsulfonyl)arylamides have received much attention as they constitute an important class of drugs for treating Alzheimer’s disease -arylamides are known to be potent anti-tumour agents against a broad spectrum of human tumour xenografts  in mice arylamides arylamides  and (IB), while that of (II)A) and (IB), the ortho-nitro substitution on the benzenesulfonyl ring is syn to the N—H bond in the central –C—SO2—N—C(O)– segment  is disordered due to rotation about the Car—C(=O) bond over two orientations in a 0.525 (9):0.475 (9) ratio, which are inclined to each other by 45.5 (4)°. The nitro groups in both the A and B molecules of (I)A) is 56.3 (4)°, while in (IB), the torsion angle C14—C15—N4—O9 is 35.6 (5)°, whereas in (II)A), 65.22 (19)° in (IB) and 56.7 (7)° in (II)S(7) motif.The asymmetric unit of (I)nt Fig. 1. The benN1⋯O6 and N3—HN3⋯O4  Å]. Further, C10—H10B⋯π1 [where π1 is the nitrobenzene ring of molecule (IB)] and C12—H12A⋯π2 [π2 is the bromobenzene ring of molecule (IA)] extend the zigzag sheets into a three-dimensional architecture, which is consolidated by several aromatic π–π stacking interactions .The crystal structure of (I)4 Table 1 between es Fig. 3. The A +s Table 1. A dimers Table 1 and the N1⋯O3 hydrogen bonds forming C(4) chains along [100] (Table 2C(5) chains. The molecules of neighbouring chains are interlinked via C3—H3⋯O4 and C12—H12⋯O4 interactions (i.e. O4 acts as a double acceptor) and thus, a zigzag sheet propagates in the ac plane (Table 2C(13) and C(5) chains, respectively, along [001]. Molecules in adjacent layers are linked via C9—H9⋯O2 and C10—H10⋯O1 interactions that form C(7) and C(8) chains propagating along the b-axis direction, and thus a three-dimensional network is obtained. A short O5⋯Br1 [3.173 (4) Å] contact is observed.The crystal structure of (II)] Table 2: these c] Table 2 forming e Table 2. The C12et al., 2016N-benzoylbenzenesulfonamide Uiso = 1.2Ueq(parent atom).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989017001578/hb7646sup1.cifCrystal structure: contains datablock(s) I, II, shelx. DOI: 10.1107/S2056989017001578/hb7646Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017001578/hb7646IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989017001578/hb7646Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989017001578/hb7646IIsup5.cmlSupporting information file. DOI: 1530208, 1530207CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The crystal structure of tetraisobutylthiuram disulfide reveals a −85.81 (1)° C—S—C—S torsion angle and multiple intra- and intermolecular S⋯C—H close contacts. 18H36N2S4, crystallizes in a general position in the triclinic space group P-1 but shows pseudo-C2 symmetry about the disulfide bond. The C—S—S—C torsion angle [−85.81 (2)°] and the dihedral angle between the two NCS2 mean planes [85.91 (5)°] are within the range observed for this compound type. Multiple intra- and intermolecular S⋯H—C close contacts appear to play a role in assisting the specific conformation of the pendant isobutyl groups and the packing arrangement of molecules within the cell. Tetraisobutylthiuram disulfide molecules of one optical configuration form sheets in the plane of the a and b axes. Inversion centers exist between adjoining sheets, which stack along the c axis and alternate in the handedness of their constituent molecules.Tetrakis(2-methylpropyl)thioperoxydicarbonic diamide, or tetraisobutylthiuram disulfide, C N,N,N′,N′-Tetraalkylthioperoxydicarbonic diamides, commonly called tetrathiuram disulfides, comprise a class of organosulfur compounds with applications that are both diverse and long-standing. Tetramethylthiuram disulfide, known by the commercial name thiram, is broadly useful both as a fungicide 2] that was more complex than anticipated, even considering the hindered rotation about the −S2–CNiBu2 bond thioperoxydicarbonic diamide (tetraisobutylthiuram disulfide) itself does not show evidence of such intramolecular interaction, several recent studies of tetrathiuram disulfides have suggested such interactions in the crystalline state . Despite the lack of strict C2 symmetry, tetraisobutylthiuram disulfide is nevertheless chiral. The image in Fig. 1a presents the molecule with a left-handed configuration to the core –H2CNC(S)S–SC(S)NCH2– portion. If Fig. 1a were to be viewed from above, along the pseudo C2 axis that bisects the S3—S4 bond, the C1—S1 and C2—S2 thione bonds would project forward and backward, respectively, from the plane of the paper and thereby define a left-handed propeller. The right-handed counterpart is necessarily the other occupant of the unit cell, as required by the racemic space group. Among the structurally characterized thiuram disulfides, crystallographically imposed C2 symmetry is also common  Å, while the thione C=S bonds are essentially identical at 1.642 (3) and 1.643 (3) Å. The C1—S3—S4—C2 torsion angle, τ, is −85.81 (2)° and, as is typical of tetrathiuram disulfides, very similar in magnitude to the angle of 85.91 (5)° between the mean planes defined by the Sb and shown in Table 1D—H⋯A angles are closer to 90° than to 180° , 3.810 (3) Å]. The geometric parameters for both these intramolecular and intermolecular S⋯C–H contacts fall within the range defined as consistent with a weak D—H⋯A interaction  and the dihedral angle (θ) between Set al., 20092Cl2 solution. 1H NMR : 3.83 , 2.39 , 0.98 , 0.87 .The synthesis procedure employed was that described by Kapanda 2) or 1.5 times (for –CH3) those of the carbon atoms to which they were attached. The C—H distances assumed were 1.00, 0.99, and 0.98 Å for the –CH–, –CH2, and –CH3 types of hydrogen atoms, respectively.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989017015158/lh5851sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017015158/lh5851Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017015158/lh5851Isup3.cmlSupporting information file. DOI: 1580550CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Solvents are the source of the protons at the ylidic C atom.Reaction of BI 3 with carbodiphosphorane, C(PPh3)2, gives a mixture of the dicationic compounds, methylenebis(triphenylphosphonium) diiodide dichloromethane disolvate, C37H32P22+·2I−·2CH2Cl2 or [Ph3PCH2PPh3]I2·2CH2Cl2 (I), methylenebis(triphenylphosphonium) bis(tetraiodoborate), C37H32P22+·2BI4− or [Ph3PCH2PPh3](BI4)2 (II). Solvents are the source of the protons at the ylidic C atom. The P—C—P angle is 124.1 (2)° for (I) and 121.7 (3)° for (II), while the two P—C bond lengths are 1.804 (4) and 1.807 (5) Å in (I), and 1.817 (5) and 1.829 (5) Å in (II). In the crystal of (I), the protons of the central P—CH2—P C atom exhibit weak C—H⋯I hydrogen bonds with the respective anions. The anions in turn are linked to the dichloromethane solvent molecules by C—H⋯I hydrogen bonds. In the crystal of (II), one of the BI4− anions is linked to a phenyl H atom via a weak C—H⋯I hydrogen bond.Reaction of BI The volume of the resulting solution was reduced to ca 3 ml and layered with ca 5 ml of hexane. A crop of crystals formed in a few days .(PhUiso(H) = 1.2Ueq(C). For both compounds, a small number of reflections were affected by the beam stop and were omitted from the final cycles of refinement.Crystal data, data collection and structure refinement details are summarized in Table 510.1107/S2056989017010295/su5375sup1.cifCrystal structure: contains datablock(s) Global, II, I. DOI: 10.1107/S2056989017010295/su5375Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017010295/su5375IIsup4.hklStructure factors: contains datablock(s) II. DOI: 1533031, 1552112CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The compound comprises an octahedral homoleptic Me2SO-solvated cobalt(II) cation and a tetrahedral cobaltate(II) anion attached to three chloro ligands and one quinoline moiety.Anhydrous cobalt(II) chloride reacts with quinoline (C 2SO) or quinoline (C9H7N). The title compound, [Co(C2H6OS)6][CoCl3(C9H7N)]2, is a cobalt salt in which the metal ion is complexed to both Me2SO and quinoline. In particular, we observed that anhydrous cobalt(II) chloride reacts with quinoline in Me2SO to form a salt that is to be formulated as [CoII(Me2SO)6]2+{[CoIICl3quinoline]2−}. The CoII atom in the cation portion of this molecule lies on a inversion center and is bound to the O atoms of six Me2SO moieties in an octahedral configuration, while the CoII atom in the anion is attached to three chloride ligands and one quinoline moiety in a tetrahedral arrangement.There are few reports that describe crystal structures of compounds containing cobalt complexed to either dimethyl sulfoxide (Me A closely related complex, [Co(Me2SO)6][CoCl4], contains a cobalt cation that is similarly surrounded by six oxygen atoms in a slightly distorted octahedral configuration with Co—O distances between 2.06 (1) and 2.10 (1) Å, with a mean Co—O distance of 2.08Å  bond angles in the title complex are close to 90°, ranging from 86.29 (7) to 93.71 (7)°, compared to 87.9 (5) to 90.8 (4)° in [Co(Me2SO)6][CoCl4] 6][CoCl4] also showed some distortion with Co—Cl distances ranging from 2.265 (6) to 2.305 (7) Å, giving an average Co—Cl distance of 2.284 (6) Å, and the Cl—Co—Cl angles ranging from 107.1 (2) to 112.4 (2)° 6][CoCl4] were ascribed to disorder, as indicated by the high anisotropic motion  to 2.2534 (10) Å, with an average Co—Cl distance of 2.252 Å, while the Co—N distance is 2.054 (3) Å. The Cl—Co—Cl angles range from 108.21 (5) to 114.26 (4)°, giving an average of 110.98°, and the average N—Co—Cl angle is 107.88° [range 107.09 (9) to 108.80 (8)°], indicating that while the anion is close to tetrahedral, there is some distortion. Interestingly, the [CoCl4 index that is reported and discussed elsewhere ]/141, where α and β represent the two largest angles; a τ4 value of 1.00 indicates an idealized tetrahedral geometry, whereas a value of 0.00 indicates an idealized square-planar geometry. In the title complex, α = 114.26 (4)° and β = 110.46 (4)°, such that τ4 is 0.96, which indicates very little deviation from a tetrahedral geometry. For comparison, τ4 for the [CoCl4]2− anion in [Co(Me2SO)6][CoCl4] is 0.98 6]2+ and [CoIICl3quinoline]− ions, with the exception of very weak C—H⋯Cl interactions. The distances between the Cl and the carbon atoms of the methyl groups of the Me2SO ligands are, for example, Cl1⋯C32—S3  [3.525 (3) Å], Cl1⋯C31—S3  [3.736 (4) Å], Cl2⋯C22—S2  [3.633 (4) Å], Cl2⋯C21—S2  [3.770 (4) Å], Cl3⋯C12—S1  [3.638 (4) Å] and Cl3⋯C32—S3  [3.819 (4) Å] and are comparable to the sum of the van der Waals radii of Cl and CH3 of 3.80 Å 6][CoCl4] complex as discussed above 6][CoCl4] 6][CoCl4], there are a few other examples of cobalt complexes solvated by Me2SO that are listed in the Cambridge Database 6][ClO4]2, one of which possesses Co—O distances in the range 2.0833 (17)–2.0934 (15) Å, giving a mean Co—O distance of 2.088 (5) Å, with O—Co—O (cis) angles between 90.11 (6) and 92.31 (6)°  angles between 85.26 (7) and 93.67 (8)° 6][SnCl6], both the cobalt and tin metal ions display an octahedral environments, with the Co—O bond lengths reported between 2.093 (4) and 2.113 (5) Å  angles vary between 89.0 (2) and 90.0 (2)° 6][NO3]3 is also known and possesses six equivalent Co—O bond lengths of 2.005 (2) Å, which are shorter than the values in the CoII complexes (Me2SO-S)(C2H5OH)]·C2H5OH (acv = acyclovir)  is rare, there are some notable examples. For example, the compound bis(dimethyl sulfoxide)hydridobis(triphenylphosphane)cobalt(I), [CoH(C18H15P)2(Me2SO)2], contains CoI coordinating a hydride anion, two phosphine ligands and two Me2SO moieties that are bound through the sulfur atom in a distorted trigonal–bipyramidal structure -porphyrinato)-cobalt(III) bis(dimethyl sulfoxide-κS)-porphyrinato)cobalt(III) bis(hexafluoroantimonate) dimethyl sulfoxide solvate 2]− of the title compound is 2.037 (5) Å while the Co–Cl bond lengths are 2.2517 (10)–2.2534 (10) Å, and the Cl—Co—Cl and Cl—Co—N angles range between 108.21 (5) and 114.26 (4)°, and 107.09 (9) and 108.80 (8)°, respectively. For comparison, the Co—N bond lengths in the CoIICl2(quinoline)2 complex are 2.061 (3) and 2.037 (5) Å and the Co—Cl bond lengths are 2.246 (2) and 2.241 (1) Å  in Me2SO (20 mL) and refluxed for one h. After cooling down, the mixture was transferred to a beaker and placed in a desiccator containing anhydrous calcium chloride pellets (4–20 mesh) to crystallize over a period of four months. Deep-blue crystals of [Co(Me2SO)6]2+{[CoCl3quinoline]2}− suitable for X-ray diffraction were obtained from this process of slow evaporation. Notably, when the reaction between anhydrous cobalt(II) chloride and quinoline is conducted in EtOH, rather than Me2SO, the previously reported [CoIICl2(quinoline)2] complex is obtained  chloride  was mixed with quinoline, CUiso(H) = 1.2Ueq(Csp2) or 1.5Ueq(Csp3).Crystal data, data collection and structure refinement details are summarized in Table 110.1107/S2056989018001652/lh5868sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018001652/lh5868Isup2.hklStructure factors: contains datablock(s) I. DOI: 1820336CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The synthesis and structural determination of bissulfone tetra(nitrate) monohydrate is reported. The crystal structure features N—H⋯O, O—H⋯O and C—H⋯O hydrogen-bonds and π–π interactions. 12H14N2O2S2+·4NO3−·H2O {alternative name: bis[bis sulfone] tetranitrate monohydrate}, the cations are conformationally similar, with comparable dihedral angles between the two benzene rings in each of 70.03 (18) and 69.69 (19)°. In the crystal, mixed cation–anion–water molecule layers lying parallel to the (001) plane are formed through N—H⋯O, O—H⋯O and C—H⋯O hydrogen-bonding interactions and these layers are further extended into an overall three-dimensional supramolecular network structure. Inter-ring π–π interactions are also present [minimum ring centroid separation = 3.693 (3) Å].In the title compound, the hydrated tetra(nitrate) salt of dapsone , 2C Ka ca 2), is a drug that has been used to treat a diversity of diseases including tuberculosis, leprosy, malaria and AIDS-related pneumonia , a very weak Lewis base anilinium 2-carboxy-4,6-dinitrophenolate monohydrate has been reported sulfone cations (A and B), four nitrate anions and one water molecule (O1W) in the asymmetric unit  (Aa) and (N1/C7–C12) (Ab)] and cation B [defined by (N3/C13–C18) (Ba) and (N4/ C19–C24) (Bb)] are 70.03 (18) and 69.69 (19)°, respectively. As expected the anilinium groups are planar with maximum r.m.s. deviations of 0.0044, 0.0120, 0.0114 and 0.0072 Å, respectively.The title compound crystallizes in the orthorhombic space group it Fig. 1. The divi and nitro O12vii acceptors. The two cations A and B are associated through π–π interactions [ring centroid separation CgAb⋯CgBai = 3.693 (3) Å [symmetry code: (i) −x + 1, y + z + a-axis direction  bond motif  motifs 3·9H2O  in EtOH (2 ml) was added dropwise to 4,4′-diaminodiphenyl sulfone  in EtOH (5 ml), with continuous stirring at room temperature for 72 h. Slow evaporation of this solution yielded yellow crystals suitable for X-ray analysis within 5 d.Fe(NOUiso(H) = 1.2Ueq(C). All N—H atoms were located by difference methods but were subsequently restrained in the refinement with N—H = 0.89 Å and Uiso = 1.2Ueq(N). The H atoms of the water molecule were also located in a Fourier map and were allowed to ride with a restrained O—H bond length = 0.85 (1) Å and H⋯H = 1.39 (2) Å and Uiso(H) = 1.5 Ueq(O). Although not of relevance in this achiral compound, the Flack absolute structure parameter  I. DOI: 10.1107/S2056989017014803/zs2390Isup2.hklStructure factors: contains datablock(s) I. DOI: 1579678CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Their structures and absolute configurations were unambiguously established by a combination of NMR and MS analysis and electronic circular dichroism (ECD) evidence. Callisalignenes H (2) and I (3) have a rare sec-butyl moiety at C-7. Meroterpenoids 1–3 exhibited cytotoxicity against HCT116 cells with IC50 values of 8.51 ± 1.8, 9.12 ± 0.3, and 16.33 ± 3.3 μM, respectively.Callisalignenes G–I  contains supplementary material, which is available to authorized users. Callistemon (Myrtaceae) are evergreen shrubs or small trees native to Australia and have been popularly cultivated in southern China as ornamental species with bottle brush inflorescence. Recently, acylphloroglucinols and their derivatives, including adducts of a phloroglucinol moiety coupled with its derivative or a terpenoid unit, have been extensively obtained from this genus . Further analysis of its experimental and calculated ECD spectra -4.Besides the three new meroterpenoids, two known compounds were identified as (–)-callistenone F (4)  and vimiS. aureus, E. coli, and P. aeruginosa) and three fungal strains . None of them showed antimicrobial effects (MIC >250 μg/mL). Additionally, cytotoxicities of 1–5 against six human cancer cells  were also conducted and the results were summarized in Table 1–3 exhibited cytotoxicity against HCT116 cells with IC50 values of 8.51 ± 1.8, 9.12 ± 0.3, and 16.33 ± 3.3 μM, respectively, compared to that of positive control . Moreover, 1 and 3 displayed cytotoxicity against A549 cells with IC50 values of 12.85 ± 8.2 and 10.03 ± 3.2 μM , respectively.All the isolates were evaluated for their antimicrobial effects toward three bacterial (cts MIC >50 μg/mL.δ) were expressed in ppm with reference to the solvent signals, and coupling constant (J) values were reported in Hz. HRESIMS data were measured using an Agilent 1290 UPLC/6540 Q-TOF mass spectrometer. Sephadex LH-20 , Si gel , and RP-18  were used for column chromatography (CC). Semi-preparative HPLC was performed on an Agilent 1260 instrument with a ZORBAX SB-C18 column . Fractions were monitored by Si gel GF254  or RP-18 F254  plates. Spots were visualized under UV light and by spraying with 10% H2SO4 in EtOH followed by heating.Optical rotations were measured on a Jasco P-1020 polarimeter. UV spectra were recorded on a Shimadzu UV2401 PC spectrophotometer. IR spectra were determined on Bruker FT-IR Tensor-27 infrared spectrophotometer with KBr discs. ECD spectra were recorded on an Applied Photophysics spectropolarimeter. 1D and 2D NMR spectra were recorded on Bruker AV 600 or 800 MHz spectrometers using TMS as an internal standard. Chemical shifts . A voucher specimen (HY0025) was deposited in the State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences.Twigs and leaves of C. salignus (10.0 kg) were percolated with petroleum ether (PE) at room temperature three times  and then filtered. After removal of solvent under reduced pressure, the crude extract (130 g) was subjected to silica gel CC, eluted with PE-EtOAc  to yield five fractions A–E. Fraction A (25 g) was applied to Sephadex LH-20 column  to give A3 (3 g), which was further separated on an RP-18 column and eluted with a gradient of MeCN–H2O  to obtain five subfractions (A3-1–A3-5). Subfraction A3-4 (225 mg) was subsequently purified by semi-preparative HPLC with MeCN–H2O  as mobile phase to afford 1 (5 mg), 2 (4 mg), 3 (8 mg), and 5 (35 mg). Similarly, fraction C (42 g) was separated by Sephadex LH-20 column  to give three subfraction (C1–C3). After repeated purification by RP-18 column with MeCN–H2O , 4 (18 mg) was obtained from C2 (0.5 g).Air-dried and powdered twigs and leaves of α] +188.3 ; UV (MeOH) λmax (log ε) 265 (4.18) nm; CD (MeOH) 265 (Δ ε + 36.23), 306 (Δε −7.57) nm; IR (KBr) vmax 3440, 2932, 1721, 1651, 1469, 1248 cm–1; 1H and 13C NMR data, see Table m/z 409.2714 [M + Na]+ .Colorless gum; [α] −221.4 ; UV (MeOH) λmax (log ε) 266 (4.20) nm; CD (MeOH) 267 (Δε −31.35), 309 (Δε + 4.11) nm; IR (KBr) vmax 3439, 2930, 1720, 1649, 1467, 1247 cm−1; 1H and 13C NMR data, see Table m/z 409.2708 [M + Na]+ .Colorless gum; [α] +164.7 ; UV (MeOH) λmax (log ε) 267 (4.24) nm; CD (MeOH) 267 (Δε +27.50), 306 (Δε −6.02) nm; IR (KBr) vmax 3428, 2962, 1718, 1651, 1467, 1384, 1174−1; 1H and 13C NMR data, see Table m/z 387.2899 [M + H]+ .Colorless gum; [α] −133.0 ; CD (MeOH) 235 (Δε +5.45), 248 (Δε +1.77), 286 (Δε +15.10), 317 (Δε −13.95) nm.Colorless gum; [The conformations generated by the MM2 force field in Chem-Bio3D software overlaid with key correlations observed in the ROESY spectrum were subjected to semi-empirical PM3 quantum mechanical geometry optimizations using the Gaussian 09 program . The cor1–5 were carried out against three bacterial strains  and three fungal strains  using the antimicrobial susceptibility assay [The antimicrobial activities compounds ty assay . The comAll the compounds were evaluated for their cytotoxicities against six tumor cell lines, including HCT116 , Huh7 (human hepatoma cell line), Hela , CCRF-CEM (human acute lymphocytic leukemia cell line), DU145 (human prostatic cancer cell line), and A549 (human lung cancer cell line), by MTT assay in 96-well plates [Supplementary material 1 (DOCX 12178 kb)Below is the link to the electronic supplementary material.


L3Phen (where L− is the sulfonylamidophosphate (SAPh)-type ligand N-{bis[methyl(phenyl)amino]phosphoryl}benzenesulfonamidate, C6H5SO2NHPO[N(CH3)C6H5]2 has been synthesized and its crystal structure determined.A lanthanum(III) complex with formula La 20H21N3O3PS)3(C12H8N2)] is created by one LaIII ion, three deprotonated N-{bis[methyl(phenyl)amino]phosphoryl}benzenesulfonamidate (L−) ligands and one 1,10-phenanthroline (Phen) molecule. Each LaIII ion is eight-coordinated (6O+2N) by three phosphoryl O atoms, three sulfonyl O atoms of three L− ligands and two N atoms of the chelating Phen ligand, leading to the formation of six- and five-membered metallacycles, respectively. The lanthanum coordination polyhedron has a bicapped trigonal–prismatic geometry. ‘Sandwich-like’ intramolecular π–π stacking interactions are observed between the 1,10-phenanthroline ligand and two benzene rings of two different L− ligands. The phenyl rings of L− that are not involved in the stacking interactions show minor positional disorder. Molecules form layers parallel to the (010) plane due to weak C—H⋯O intermolecular hydrogen bonds. Unidentified highly disordered solvate molecules that occupy ca 400 Å3 large voids have been omitted from the refinement model.The asymmetric unit of [La(C These types of compounds were first synthesized by Kirsanov , containing the functional fragment C(O)NHP(O), because of their properties as extractants (OMe)2] amidophosphate [(Me)PhSO2NHP(O)(OMe)2] and dimethyl 2-naphthylsulfonylamidophosphate [(C10H7)SO2NHP(O)(OMe)2] indicate that the ligand first excited singlet state plays a dominant role in intramolecular energy transfer processes in these Ln complexes amidophosphate [PhSON-(methyl(phenylamino)phosphoryl)benzenesulfonamide (HL) [PhSO2NHP(O)(N(Me)Ph)2] with the general formula 3PhenLa(L).Knowledge of the crystal structure is an essential part of understanding the luminescent properties of these types of lanthanide complexes. In this paper we would therefore like to report the molecular and crystal structure of a lanthanum coordination compound based on the amidic type SAPh ligand 3PhenLa(L) crystallizes with one molecule in the asymmetric unit  bond lengths [2.516 (2)–2.541 (2) Å] are all longer than those of their La—O(P) counterparts [2.424 (2)–2.463 (2) Å], with mean values of 2.435 and 2.456 Å, respectively. The mean average of all La—O bond lengths is 2.476 Å. The La—N distances are with 2.699 (3) and 2.700 (3) Å  shorter than those previously obtained for a 1,10-phenanthrolinate lanthanum (III) complex with hexafluoroacetylacetonate –1.474 (2) Å and 1.491 (2)–1.494 (2) Å in their expected ranges. The mean values are 1.468 and 1.492 Å, respectively. The corresponding bond lengths in the related neutral ligands are around 1.42 Å (Moroz A) and La1–O3–P3–N3–S3–O9 (B) rings both adopt twist-boat conformations  are 0.78 and 0.41 Å, respectively. The deviations of the La1 and O3 atoms from the mean plane through the remaining atoms of B (r.m.s.deviation = 0.06 Å) are 0.9 and 0.88 Å, respectively. The La1–O2–P2–N2–S2–O7 (C) ring adopts a flattened half-chair conformation . The deviation of the La1 atom from the mean plane carried through the remaining atoms of ring C (r.m.s.deviation 0.02 Å) is 0.36  Å.The six-membered metallocyclic rings with the chelate (O)PNS(O) fragments are all non-planar. The La1–O1–P1–N1–S1–O1  similar to that of the Tb(Pip)3(Phen) mixed-ligand complex with 2,2,2-trichloro-N-(dipiperidin-1-yl-phosphoryl)acetamide, HPip ⋯C69(π) of the 1,10-phenanthroline molecule interacts with the C41(π)⋯C46(π) phenyl ring at the sulfonyl group from another ligand , and with the C8(π)⋯C13(π) ring at the phosphoryl group from the other ligand . A similar intramolecular organization was described previously for related compounds (Beloso 3PhenLa(L) molecules are linked by weak C—H⋯O hydrogen bonds .In the crystal phase, the s Table 1, formings Table 1. There aet al., 2016N-(bis(diamino)phosphoryl)sulfonamide fragments yielded five hits, with only one metal complex structure with a neodymium metal atom among them --erbium(III) phosphoramidato-2O6 environment yielded 20 hits, with average La—O and La—N bond lengths of 2.476 and 2.693 Å, respectively. 11 complex structures with different lanthanoid metals (Ln) containing Ln–O–P–N–S–O metallocycles were found in the database, all with octacoordinated metal atoms. Most of those metallacyclic rings are non-planar with mean deviations of the O and N atoms of 0.329 and 0.434 Å, respectively.A search for octacoordinated La complexes with an LaN1H and 31P NMR spectra in DMSO-d6 solutions were recorded on a Varian 400 NMR spectrometer at room temperature. 1H chemical shifts were determined relative to the internal standard TMS whereas 31P chemical shifts were determined relative to 85% H3PO4 as an external standard. Infrared (FTIR) spectra were recorded on a Perkin–Elmer Spectrum BX spectrometer using KBr pellets. The resolution of the FTIR spectra is 1 cm−1.Sulfonylamidophosphate ligandN-(methyl(phenylamino)phosphoryl)benzenesulfonamide (HL) was synthesized via a three-step procedure based on the Kirsanov reaction  δ 2.95 , 7.05 , 7.14 , 7.21 , 7.56 , 7.65 , 7.91 .−1): 3062 , 2948 , 2780 , 2705 , 2655 , 1594 , 1495 (s), 1446 (m), 1400 (m), 1330 , 1279 (m), 1220 , 1168 , 1084 (m), 1069 (m), 1028 (m), 920 , 887 (ws), 765 (s), 758 (s), 723 (m), 696 (s), 685 (s), 602 (m), 573 (m), 558 (m), 551 (m), 542 (m), 508 (s), 490 (m), 442 (w).IR  was prepared by the reaction between equimolar amounts of sodium methanolate  and HL  in an methanol medium (20 ml). The mixture was heated with magnetic stirring at 337 K for 10 min. The resulting solution was evaporated and the fine crystalline powder was isolated (yield 83%) and washed with 2-propanol. Dry product NaL was used for the preparation of the complexes. 1H NMR  δ 3.46 , 3.48 , 7.26 , 7.53 , 7.6 , 7.77 . 31P NMR  δ 54.01.The sodium salt (−1): 3068 , 2944 , 2704 , 2660 , 1581 , 1490 (s), 1410 , 1263 , 1271 (m), 1173 , 1165 , 1080 (m), 1031 (m), 891 , 2943 , 2704 , 2660 , 1564 , 1490 (s), 1413 , 1252 , 1243  + ν(C—C)], 1270 (m), 1164 , 1165 , 1082 (m), 1030 (m), 990 , 892 [ws, ν, 763 (s), 747 (s), 720 (m), 678 (s), 682 (s), 564 (m), 547 (m), 534 (m), 502 (s), 485 (m), 427 (w).IR  = xUeq(C), where x = 1.5 for methyl H and 1.2 for all other H atoms. A rotating-group model was applied for the methyl groups.Crystal data, data collection and structure refinement details are summarized in Table 2A and B with refined occupancies of 0.50 (3) for both disorder components. The phenyl rings C15–C20, C21–C26 were refined as disordered over two positions with refined occupancies of 0.555 (17) and 0.445 (17), respectively. The bond lenghts C21A—C22A, C22A—C23A, C23A—C24A, C24A—C25A, C25A—C26A, C26A—C21A, C21—C22, C22—C23, C23—C24, C24—C25, C25—C26 and C26—C21 were restrained to have a value of 1.38 (1) Å (using a DFIX restraint). The ring carbon atoms C21A, C26A, C25A, C24A, C23A, C22A as well as C21, C22, C23, C24, C25, C26 were restrained to have planar geometries . Anisotropic parameters of all C atoms of disordered rings were restrained to have approximately similar values to within 0.01 Å2 (using a SIMU restraint).Phenyl ring C1–C6 was refined as disordered over two positions 3. Satisfactory results (R1 = 5.01%) were obtained modeling disordered C and O atoms, but very large displacement parameters for them were observed. The SQUEEZE procedure  per cell. However, the difference in R1 values for the structures with and without the SQUEEZE procedure implemented was rather small (0.5%). In the final refinement, the isolated peaks in the solvent-accessible voids were ignored.During the refinement, several small isolated electron-density peaks were located in solvent-accessible voids that were believed to be solvent molecules. The largest residual electron peak accounted to 0.66 e Å10.1107/S2056989017008970/zl2701sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: Click here for additional data file.10.1107/S2056989017008970/zl2701Isup4.cdxSupporting information file. DOI: 10.1107/S2056989017008970/zl2701Isup6.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017008970/zl2701sup5.txthkl-file. DOI: 1556367CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the title compound, the two indole ring systems are approximately perpendicular to one another, making a dihedral angle of 80.9 (5)°. In the crystal, pairs of N—H⋯O hydrogen bonds link the molecules into inversion dimers and these are further linked by N—H⋯O and hydrogen bonds and short Cl—Cl contacts into supramolecular chains. 29H24Cl2N2O4, the mean planes of the two indole ring systems (r.m.s. deviations = 0.1249 and 0.0075 Å) are approximately perpendicular to one another, with a dihedral angle of 80.9 (5)° between them. The benzene ring is inclined to the mean planes of the two indole ring systems by 76.1 (3) and 78.3 (4)°. Weak intramolecular C—H⋯π interactions affect the molecular conformation. In the crystal, pairs of N—H⋯O hydrogen bonds link the molecules into inversion dimers which are further linked into supramolecular chains by N—H⋯O hydrogen bonds and short Cl—Cl contacts.In the title compound, C C11—H11A⋯Cl1 and short Cl2⋯Cl2 contacts [Cl2⋯Cl2 = 3.467 (2) Å] bridge these chains and form sheets of molecules parallel to bis(1H-indole-2-carboxylate)     was dissolved in 20 ml ethanol; commercially available 2,4-dichlorobenzaldehyde  was added and the mixture was heated to reflux temperature. Concentrated HCl (0.5 ml) was added and the reaction was left for 1 h. After cooling, the white product was filtered off and washed thoroughly with ethanol. The reaction was monitored with TLC (AcOEt:hexane = 1:3). Colourless block-like crystals of the title compound suitable for X-ray analysis were obtained in 92% yield by slow evaporation of an ethanol solution.Uiso(H) = xUeq, where x = 1.5 for methyl H atoms and 1.2 for all others.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989017015730/sj5539sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017015730/sj5539Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017015730/sj5539Isup3.cmlSupporting information file. DOI: 1582719CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Crystal structures of hydrogen-bonded 1:2 compounds of chloranilic acid with 2-pyridone, 3-hydroxypyridine and 4-hyroxypyridine have been determined at 120 K. In each crystal structure, the acid and base molecules are linked by short O—H⋯O and N—H⋯O hydrogen bonds. 5H5NO·C6H2Cl2O4, (I), bis(3-hydroxypyridinium) chloranilate, 2C5H6NO+·C6Cl2O42−, (II), and bis(4-hydroxypyridinium) chloranilate, 2C5H6NO+·C6Cl2O42−, (III), have been determined at 120 K. In the crystal of (I), the base molecule is in the lactam form and no acid–base interaction involving H-atom transfer is observed. The acid molecule lies on an inversion centre and the asymmetric unit consists of one half-molecule of chloranilic acid and one 2-pyridone molecule, which are linked via a short O—H⋯O hydrogen bond. 2-Pyridone molecules form a head-to-head dimer via a pair of N—H⋯O hydrogen bonds, resulting in a tape structure along [201]. In the crystals of (II) and (III), acid–base interactions involving H-atom transfer are observed and the divalent cations lie on an inversion centre. The asymmetric unit of (II) consists of one half of a chloranilate anion and one 3-hydroxypyridinium cation, while that of (III) comprises two independent halves of anions and two 4-hydroxypyridinium cations. The primary intermolecular interaction in (II) is a bifurcated O—H⋯ hydrogen bond between the cation and the anion. The hydrogen-bonded units are further linked via N—H⋯O hydrogen bonds, forming a layer parallel to the bc plane. In (III), one anion is surrounded by four cations via O—H⋯O and C—H⋯O hydrogen bonds, while the other is surrounded by four cations via N—H⋯O and C—H⋯Cl hydrogen bonds. These interactions link the cations and the anions into a layer parallel to (301).The crystal structures of the 1:2 compounds of chloranilic acid  with 2-pyridone, 3-hydroxypyridine and 4-hyroxypyridine, namely, bis(2-pyridone) chloranilic acid, 2C A weak C—H⋯Cl interaction formed between the acid and base molecules ii; symmetry code as in Table 2bc plane  Å; symmetry code: (vi) −x + 1, y − z + In the crystal of (II)ne Fig. 7. Adjacenvia weak C—H⋯O and C—H⋯Cl interactions et al., 2016et al., 2010et al., 2016et al., 2009aet al., 2009bA search of the Cambridge Structural Database Uiso(H) = 1.5Ueq(O or N). C-bound H atoms were positioned geometrically (C—H = 0.95 Å) and were treated as riding with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S2056989017013536/lh5855sup1.cifCrystal structure: contains datablock(s) I, II, III, global. DOI: 10.1107/S2056989017013536/lh5855Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017013536/lh5855IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989017013536/lh5855IIIsup4.hklStructure factors: contains datablock(s) III. DOI: 1575722, 1575721, 1575720CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The synthesis, characterization and structural analysis of triphenylphosphoniummethylenetrifluoroborate are presented. 19H17BF3P {alternative name: triphenyl[(trifluoroboranyl)methyl]phosphanium}, was formed by the reaction of triphenylphosphine with potassium iodomethyltrifluoroborate. The molecule features a nearly staggered conformation along the P—C bond and a less than staggered conformation along the C—B bond. In the crystal, weak C—H⋯F hydrogen bonds between the meta-phenyl C—H groups and the trifluoroborate B—F groups form chains of R22(16) rings along [100]. These chains are are further stabilized by weak C—H⋯π interactions. A weak intramolecular C—H⋯F hydrogen bond is also observed.The title compound, C Additionally, they may be used to produce organodihaloboranes (RBX2)  with boron trifluoride diethyletherate (BF3-OEt2) yields triphenyl[(trifluoroboranyl)methyl]phosphonium (Ph3PCH2BF3). We have synthesized Ph3PCH2BF3via an alternate route, by reacting triphenylphosphine (PPh3) with potassium iodomethyltrifluoroborate (ICH2BF3K) in 45% yield.Alkyltriphenylphosphonium (PhDatabase survey). Phosphonium trifluoroborates have been shown to enhance the hydrolytic stability of the RBF3 moiety  ring °] and a less staggered conformation along the C1—B1 bond [F2—B1—C1—P1 torsion angle = 158.3 (2)°].The molecular structure of the title compound is shown in Fig. 1g Table 1. The molet al., 19873sp hybridized. The methylene carbon is predominantly 3sp hybridized, but has a distorted tetrahedral geometry with a P1—C1—B1 angle of 119.7 (2)°.The B-F bond lengths fall within normal ranges for organotrifluoroborate compounds. The methylene C—P bond length [1.787 (4) Å] and the C—B bond length [1.636 (4) Å] also fall within the normal range for similar compounds  and the resulting solid was dissolved in a minimal amount of acetone and the product was precipitated with water and collected by filtration, to afford a white solid  X-ray quality crystals were grown by slow diffusion of pentane into a solution of the title compound dissolved in dichloromethane.Potassium iodomethyltrifluoroborate  and triphenylphosphine  were combined in a pressure flask containing a stir bar under nitrogen, and anhydrous THF (25.0 mL) was added. The flask was sealed and heated to 343 K for 18 h. The reaction was cooled to room temperature and the solvent was removed 1H NMR  δ (ppm): 7.66 , 7.56 , 2.07 . 13C NMR  δ (ppm): 133.7 , 133.5 , 129.6  123.2  (C—B not observed). 11B NMR  δ (ppm): 2.49 . 19F NMR  δ (ppm): −138.9 . FTIR : 3070, 2960, 1587, 1484, 1438, 1146, 1104, 1025, 994, 969, 824, 754, 725, 691, 511, 497.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989017009884/lh5846sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017009884/lh5846Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017009884/lh5846Isup3.cmlSupporting information file. DOI: 1560028CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The molecular and crystal structure of the title imidazole derivative is reported. The structure is stabilized by an extensive O—H⋯N, C—H⋯O/Cl and C—H⋯π(ring) hydrogen-bonding network. 24H21ClN2O, crystallizes with two unique molecules in the asymmetric unit. In each molecule, the central imidazole ring is substituted at the 2-, 4- and 5-positions by benzene rings. The 2-substituted ring carries a Cl atom at the 4-position. One of the imidazole N atoms in each molecule has a propan-2-ol substituent. In the crystal, a series of O—H⋯N, C—H⋯O and C—H⋯Cl hydrogen bonds, augmented by several C—H⋯π(ring) interactions, generate a three-dimensional network of molecules stacked along the a-axis direction.The title compound, C Each moO⋯N23 hydrogen bonds supported by C242—H242⋯O112 contacts combine with O212—H22O⋯N13 hydrogen bonds to link alternate type 1 and 2 molecules in a head-to-tail fashion, forming C(7) chains along b, Fig. 4C(12) chains along the a-axis direction, Fig. 5Cg5 and C255—H255⋯Cg1 contacts combine with C113—H11D⋯Cg6, C213—H21D⋯Cg2 and two C—H⋯O hydrogen bonds, Table 1c axis, Fig. 63 across the unit cell. This large void is unexpected as no solvent appeared and the final difference map was reasonably flat . The molecules stack in an orderly fashion along each of the three principal crystallographic axes and the voids are clearly visible in views of the overall packing along these directions, see for example Fig. 7O112–H12et al., 2016H-imidazol-2-yl]benzoic acid . All other H atoms were refined using a riding model with d(C—H) = 0.95 Å, Uiso = 1.2Ueq(C) for aromatic, 1.00 Å for methine and 0.99 Å for CH2 H atoms, all with Uiso = 1.2Ueq(C) and 0.98 Å, Uiso = 1.5Ueq(C) for CH3 H atoms. Seven reflections with Fo >>> Fc, were omitted from the final refinement cycles.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016019332/hg5480sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989016019332/hg5480Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016019332/hg5480Isup3.cmlSupporting information file. DOI: 1520559CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In (I), the dithiocarbamate ligand coordinates the SnIV atom in an asymmetric manner, leading to a highly distorted trigonal–bipyramidal coordination geometry defined by a C3S2 donor set with the weakly bound S atom approximately trans to one of the ipso-C atoms. A similar structure is found in (II), but the dithiocarbamate ligand coordinates in an even more asymmetric fashion. The packing in (I) features supramolecular chains along the c axis sustained by C—H⋯π interactions; chains pack with no directional interactions between them. In (II), supramolecular layers are formed, similarly sustained by C—H⋯π interactions; these stack along the b axis. An analysis of the Hirshfeld surfaces for (I) and (II) confirms the presence of the C—H⋯π interactions but also reveals the overall dominance of H⋯H contacts in the respective crystals.The crystal and molecular structures of two triphenyltin dithiocarbamates, [Sn(C RSn(S2CNRR′)n4– where R, R′ = alkyl, aryl, most relate to their biological activities and their usefulness as molecular, single-source precursors for the formation of tin sulfide nanoparticles 3Sn[S2CN(Ben)CH2CH2Ph] (I)6H5)3Sn[S2CN(CH2CH2OMe)2] (II)Among the varied motivations for investigating organotin dithiocarbamate compounds, long and Sn—Sshort bond lengths, of 0.42 Å. This asymmetry is reflected in the relatively large disparity in the associated C—S bond lengths with the bond involving the tightly bound S1 atom being significantly longer than the bond involving the S2 atom, Table 1i.e. from a narrow 92.98 (4)° for S1—Sn—C17 to a wide 124.31 (4)° for S1—Sn—C29. The wide angle is due to the close approach to the tin atom of S2. Further, the Sn—C17 bond length is systematically longer than the other Sn—C bond lengths, an observation ascribed to the C17 atom being approximately trans to the incoming S2 atom, Table 13S2 donor set. The geometry is not ideal with the value of τ of 0.57, cf. τ values of 0.0 and 1.0 for ideal square–pyramidal and trigonal–bipyramidal geometries, respectively cf. 0.06 Å for (I)trans to the S2 atom, is the longest of all six Sn—C bonds in (I)i.e. 90.94 (4)° for S1—Sn—C14 to 119.54 (5)° for C8—Sn—C20, is slightly narrower at less than 30°. The value of τ computes to 0.58, i.e. virtually identical to that in (I)The molecular structure of (II)PLATON ac plane, Fig. 4a. The layers stack along the b axis without directional interactions between them, Fig. 4b.Even though there are oxygen atoms in the molecule of (II)Crystal Explorer di and de from the Hirshfeld surface to the nearest atom inside and outside, respectively, enable the analysis of the intermolecular interactions through the mapping of dnorm. The combination of de and di in the form of two-dimensional fingerprint plots dnorm (not shown). The curvature of the Hirshfeld surfaces around the phenyl rings participating as acceptors in the C—H⋯π contacts determine the strength of these interactions in the crystal packing. In the structure of (I)i.e. with the H13 and H23 hydrogen atoms. The other C—H⋯π contact involves methyl-H7C atom as the donor and phenyl (C8–C13) ring as the acceptor. The shape-indexed Hirshfeld surfaces highlighting the C—H⋯π contacts are shown in Fig. 7The different shapes of Hirshfeld surfaces for molecules (I)et al., 2007a–d, respectively; their relative contributions are summarized in Table 4de, di) ranges, i.e. between 1.2 and 2.6 Å, the densities and the areas of their distributions are different. It is evident from the data in Table 4b that these contacts make the most significant contribution to the Hirshfeld surfaces of both (I)b), all the points are situated at the  distances greater than or equal to their van der Waals separations i.e. 2 x 1.2 Å, hence there is no propensity to form such intermolecular contacts. The peak at  distances slightly less than van der Waals separations in the fingerprint plot for (II)A⋯H5Ai = 2.36 Å; symmetry code: (i) −x, 2 − y, 1 − z]. In the fingerprint plot delineated into C⋯H/H⋯C contacts for (I)c, the 32.9% contribution to the Hirshfeld surface and the symmetrical distribution of points showing bending of the pattern at (de + di)min ∼2.8 Å is the result of short interatomic C⋯H/H⋯C contacts . In the structure of (II)i.e. 24.4%, an observation ascribed to the presence of only C—H⋯π contacts in the molecular packing, with no other short inter-atomic contacts. The negligible contribution from C⋯C contacts to the Hirshfeld surfaces indicate that despite the presence of three Sn-bound phenyl rings in the structures of both (I)d, show that crowded geometries around the tin atoms prevent the sulfur atoms from forming such intermolecular contacts although these contacts have significant contributions to their respective Hirshfeld surfaces, Table 4et al., 2016The overall two-dimensional fingerprint plots for (I)et al., 2016R/R′ substituents. For example, the −S2CN(Ben)CH2CH2Ph anion in (I)2CN(Ben)CH2CH2Ph]2 2 anion, as in (II)et al., 2009et al., 2010According to a search of the Cambridge Structural Database  features the shortest Sn—S bond length of the series at 2.429 (3) Å  of 0.74 Å, is found in the structure of Ph3Sn(4-nitrophenylpiperazine-1-dithiocarbamate) , having Δ(Sn—S) of 0.42 Å Reflecting the interest in organotin dithiocarbamates, there are approximately 40 examples of triphenyltin dithiocarbamate structures in the CSD, all of which present the same basic structural motif as described herein for (I)N-Benzyl-2-phenylethylamine (2 mmol) dissolved in ethanol (10 ml) was stirred for 30 min in an ice-bath. 25% ammonia (1–2 ml) was added to generate a basic solution. After that, a cold ethanolic solution of carbon disulfide (2 mmol) was added to the solution followed by stirring for about 2 h. Then, triphenyltin(IV) chloride (2 mmol) dissolved in ethanol (30 ml) was added drop wise into the solution followed by further stirring for 2 h. The precipitate that formed was filtered off and washed with cold ethanol a few times to remove impurities. Finally, the precipitate was dried in a desiccator. Recrystallization was achieved by dissolving the compound in a chloroform and ethanol mixture (1:1 v/v): this solution was allowed to slowly evaporate at room temperature yielding colourless slabs of (I)34H31NS2Sn requires: C, 64.2; H, 4.9; N, 2.2; S, 10.1. IR (cm−1): 1476 ν(C—N), 1021 ν(C—S), 502 ν(Sn—C), 448 ν(Sn—S). 1H NMR (CDCl3): 7.44–7.86 , 7.16–7.39 , 5.03 , 3.96 , 3.04 . 13C{1H} NMR (CDCl3): δ 197.8 (S2C), 126.7–142.3 (Ar), 59.8 (CH2Ben), 56.4 (NCH2CH2), 32.8 (NCH2CH2). 119Sn{1H} NMR (CDCl3): −180.2.Synthesis of (I)N-benzyl-2-phenylethylamine. Recrystallization was from chloroform solution to yield colourless slabs. M.p.: 366–367 K. Yield: 89%. Analysis: found C, 54.4; H, 4.4; N, 2.9; S, 12.1. C25H29NO2S2 Sn requires: C, 53.8; H, 5.2; N, 2.5; S, 11.5. IR (cm−1): 1470 ν(C—N), 994 ν(C—S), 559 ν(Sn—C), 425 ν(Sn—S). 1H NMR (CDCl3): 7.40–7.74 , 4.13 , 3.72 , 3.35 . 13C{1H} NMR (CDCl3): δ 197.3 (S2C), 128.6–142.4 (Ar), 70.0 (OCH2), 59.0 (NCH2), 57.1 (CH3). 119Sn{1H} NMR (CDCl3): −185.0.Compound (II)Uiso(H) set to 1.2–1.5Ueq(C). In the refinement of (II)Crystal data, data collection and structure refinement details are summarized in Table 510.1107/S2056989016014985/hb7618sup1.cifCrystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989016014985/hb7618Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016014985/hb7618IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1505733, 1505732CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


E. The packing features amide-N—H⋯O(carbonyl) hydrogen bonds, leading to centrosymmetric aggregates, as well as C—H⋯O and C—H⋯π interactions, which significantly influence the packing.An intramolecular amine-N—H⋯N(imine) hydrogen bond is found in the disubstituted aminourea residue; the conformations about the imine and ethylene double bonds are  23H21N3O2, is constructed about an almost planar disubstituted aminourea residue (r.m.s. deviation = 0.0201 Å), which features an intramolecular amine-N—H⋯N(imine) hydrogen bond. In the ‘all-trans’ chain connecting this to the terminal methoxybenzene residue, the conformation about each of the imine and ethylene double bonds is E. In the crystal, amide-N—H⋯O(carbonyl) hydrogen bonds connect centrosymmetrically related molecules into dimeric aggregates, which also incorporate ethylene-C—H⋯O(amide) interactions. The dimers are linked by amine–phenyl-C—H⋯π(imine–phenyl) and methoxybenzene-C—H⋯π(amine–phenyl) interactions to generate a three-dimensional network. The importance of C—H⋯π interactions in the molecular packing is reflected in the relatively high contributions made by C⋯H/H⋯C contacts to the Hirshfeld surface, i.e. 31.6%.The title compound, C These compounds have attracted much attention due to their diverse pharmacological and biological activities 3O = 0.0201 Å), owing in part to an intramolecular amine-N—H⋯N(imine) hydrogen bond, Table 13O plane, forming a dihedral angle of 46.88 (4)°. The imine/ethylene sequence of bonds, i.e. N3=C8—C9=C10—C11, has an all-trans conformation but the N3—C8—C9—C10 and C8—C9—C10—C11 torsion angles of 154.62 (12) and −169.19 (11)°, respectively, indicate some twisting in this residue, especially about the C8—C9 bond; the conformation about each of the double bonds is E. The imine-bound phenyl ring forms a dihedral angle of 63.30 (7)° with the C4N atoms of the imine/ethylene sequence, and the corresponding angle for the terminal methoxybenzene ring is significantly less, at 8.29 (13)°. The methoxy group is twisted out of the plane of the ring to which it is connected as seen in the value of the C17—O18—C14—C15 torsion angle of 15.55 (17)°.The molecular structure of (I)2, Table 1a, as well as methoxy-C—H⋯π(amine-phenyl) contacts, Table 1via amine-phenyl-C—H⋯π(imine-phenyl) and methoxy-benzene-C—H⋯π(amine-phenyl) interactions, Fig. 2b.The most notable feature of the molecular packing of (I)et al., 2017N and carbonyl-O1 atoms on the Hirshfeld surface mapped over dnorm in Fig. 3a. The appearance of diminutive red spots near the N3 and C17 atoms, Fig. 3a, and the tiny faint-red spots near the C9 and H82 atoms in Fig. 3b, indicate the influence of short interatomic N3⋯C17 and C9⋯H82 contacts, Table 2a, the concave region around the imine-phenyl ring on one side and the biconcave region around the amine-phenyl ring indicate their involvement in one and two C—H⋯π contacts, respectively. The short interatomic O⋯H/H⋯O contacts s Table 3 as well a, and those delineated into H⋯H, C⋯H/H⋯C, O⋯H/H⋯O and N⋯H/H⋯N contacts c, which is due to the presence of a significant number of C—H⋯π interactions involving the imine- and amine-phenyl rings, as well as short interatomic C⋯H/H⋯C contacts, Table 3c. The pair of forceps-like long tips at de + di = 2.1 Å in the fingerprint plot delineated into O⋯H/H⋯O contacts, Fig. 6d, reflect the presence the N—H⋯O hydrogen bond; the pair of spikes corresponding to the C—H⋯O contacts and the points related to short interatomic O⋯H/H⋯O contacts, Table 2e, as their interatomic distances are greater than their van der Waals separations, they do not make a specific contribution to the molecular packing. The participation of the methyl-C17 atom in two close interatomic contacts, Table 2A and H17B atoms so are not surface contacts. Finally, the small contributions from other interatomic contacts summarized in Table 3The C⋯H/H⋯C contacts in the crystal make the second largest contribution, et al., 2016et al., 2005E-conformations about the two analogous double bonds in the molecule. However, there is considerable twisting about the equivalent bonds to C8—C9 in (I)i.e. the N—C—C—C torsion angles are 130.3 (6) and 136.0 (6)°, cf. 154.62 (12)° in (I)The title compound was prepared from the dehydrogenation reaction of 4-phenylsemicarbazide and 4-methoxychalcone. A search of the Cambridge Structural Database , m.p. 407 K. IR (cm−1): 3336 ν(N—H), 1679 ν(C=O), 1526 ν(C=N), 1242 ν(C—N), 1025 ν(C=S). MS (m/z): 371.25 [M+1]+.Analytical grade reagents were used as procured without further purification. 4-Phenylsemicarbazide  and 4-methoxychalcone  were dissolved separately in hot absolute ethanol (30 ml) and mixed with stirring. A few drops of concentrated hydrochloric acid were added as a catalyst. The reaction mixture was heated and stirred for about 20 min., then stirred for a further 30 min. at room temperature. The resulting yellow precipitate was filtered, washed with cold ethanol and dried Uiso(H) set to 1.2–1.5Ueq(C). The nitrogen-bound H atoms were located in a difference-Fourier map but were refined with a distance restraint of N—H = 0.88±0.01 Å, and with Uiso(H) set to 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S2056989017014128/hb7709sup1.cifCrystal structure: contains datablock(s) . DOI: 10.1107/S2056989017014128/hb7709Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017014128/hb7709Isup3.cmlSupporting information file. DOI: 1577439CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


IV atom in [Sn(C7H6F)2Cl2(C2H6OS)2] is located on a centre of inversion so the resulting donor C2Cl2O2 donor set is all-trans. The three-dimensional molecular packing is sustained by C—H⋯F, C—H⋯Cl and C—H⋯π interactions.The octahedrally coordinated Sn IV atom in the title diorganotin compound, [Sn(C7H6F)2Cl2(C2H6OS)2], is located on a centre of inversion, resulting in the C2Cl2O2 donor set having an all-trans disposition of like atoms. The coordination geometry approximates an octahedron. The crystal features C—H⋯F, C—H⋯Cl and C—H⋯π interactions, giving rise to a three-dimensional network. The respective influences of the Cl⋯H/H⋯Cl and F⋯H/H⋯F contacts to the molecular packing are clearly evident from the analysis of the Hirshfeld surface.The Sn The SnIV atom is coordinated by monodentate ligands, i.e. chloride, sulfoxide-O and methylene-C atoms. From symmetry, each donor is trans to a like atom resulting in an all-trans-C2Cl2O2 donor set about the SnIV atom. The donor set defines a distorted octahedral geometry owing, in part, to the disparate Sn—donor atom bond lengths, Table 1IV atom differ relatively little from the ideal octahedral angles with the maximum deviation of ca 6° noted for the C1—Sn—O1 angle, Table 1The molecular structure of (I)bc plane, Fig. 2a. Layers are connected along the a axis by phenyl-C3—H⋯F1 and methyl-C9—H⋯π(phenyl) interactions to consolidate the molecular packing, Fig. 2b.The molecular packing in (I)et al., 2016dnorm in Fig. 3B and a pair near Cl1 in Fig. 3dnorm- and shape-index-mapped Hirshfeld surfaces highlighting the various C—H⋯Cl, C—H⋯F and C—H⋯π interactions are illustrated in Fig. 5a–c, respectively.The Hirshfeld surface analysis on the structure of (I)et al., 2007a–f, respectively, and their relative contributions to the Hirshfeld surfaces are summarized in Table 4b, that although these contacts have the greatest contribution, i.e. 45.7%, to the Hirshfeld surface, the dispersion forces acting between them keep these atoms at the distances greater than the sum of their van der Waals radii, hence they do not contribute significantly to the molecular packing. The comparatively greater contribution of F⋯H/H⋯F contacts to the Hirshfeld surface cf. Cl⋯H/H⋯Cl contacts, Table 4c. The forceps-like distribution of points in the plot with tips at de + di ∼2.8 Å result from the bifurcated C—H⋯Cl interactions, and points at positions less than the sum of their van der Waals radii are ascribed to the short interatomic Cl⋯H/H⋯Cl contacts, the green appearance due to high density of interactions. Similarly, a pair of short spikes at de + di ∼2.5 Å in the fingerprint plot delineated into F⋯H/H⋯F contacts, Fig. 6d, are indicative of intermolecular C—H⋯F interactions with the short interatomic F⋯H/H⋯F contacts merged within the fingerprint plot. It is important to note from the fingerprint plot delineated into C⋯H/H⋯C contacts, Fig. 6e, that even though their interatomic distances are equal to or greater than the sum of their van der Waals radii, i.e. 2.9 Å, the 12.8% contribution from these to the Hirshfeld surfaces are indicative of the presence of C—H⋯π interactions in the structure. This is also justified from the presence of short interatomic C⋯C contacts, Fig. 5c and Table 3f, and the small contributions from the other contacts listed in Table 2The overall two-dimensional fingerprint plot and those delineated into H⋯H, Cl⋯H/H⋯Cl, F⋯H/H⋯F, C⋯H/H⋯C and O⋯H/H⋯O contacts (McKinnon R2SnX2(DMSO)2 in the crystallographic literature 2 compound tin dichloride was prepared in accordance with the literature method   and triethylamine  in ethyl acetate (25 ml) was added to di(p-fluorobenzyl)tin dichloride  in ethyl acetate (10 ml). The resulting mixture was stirred and refluxed for 4 h. The filtrate was evaporated until a dark-orange precipitate was obtained. The precipitate was dissolved in DMSO-d6 solution in a NMR tube for 1H NMR spectroscopic characterization. After the analysis, the tube was set aside for a month and colourless crystals of (I)−1): 1595(m) ν(C=C), 1504(s) ν(S=O), 1161(m), 578(w), 508(m) ν(Sn—O). 1H NMR (in CDCl3): 6.90–7.11, 7.35–7.40 , 3.11 , 2.17 .Uiso(H) set to 1.2–1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 610.1107/S2056989017005072/wm5381sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017005072/wm5381Isup2.hklStructure factors: contains datablock(s) I. DOI: 1541712CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The molecular and crystal structures of the centrosymmetric naphthoxazine derivative is reported. In the absence of hydrogen-bonding and π–π stacking interactions, the crystal structure is stabilized by short C—H⋯π contacts. 26H24N2O2, the oxazine moiety is fused to a naphthalene ring system. The asymmetric unit consists of one half of the molecule, which lies about an inversion centre. The C atoms of the ethylene spacer group adopt an antiperiplanar arrangement. The oxazine ring adopts a half-chair conformation. In the crystal, supramolecular chains running along the b axis are formed via short C—H⋯π contacts. The crystal studied was a non-merohedral twin with a fractional contribution of 0.168 (2) of the minor twin component.In the title compound, C Evaporation at room temperature afforded the title compound in 73% yield after recrystallization.The oxazine moiety is well known as a building block for high-performance phenolic resins, which are of great interest in industry due to their superior mechanical and physical properties together with unusually high thermal resistance  Å, θ = 51.5 (4)°, φ = 86.6 (4)°, and the ethylene spacer group adopts an antiperiplanar arrangement as observed in 3,3′-bis  1 − x, 1 − y, 1 − z]. However, unlike the related structures, which crystallized in monoclinic space groups with one molecule in the asymmetric unit .In general terms, the structure of the title compound Fig. 1 is similet al., 2007et al., 2015The aromatic C—C bonds of naphthalene ring system have a narrow range of distances [from 1.365 (5) to 1.431 (4) Å]. The central C5—C10 bond at 1.415 (4) Å is, however, shorter by 0.014 Å than those in related structures  set to 1.2Ueq of the parent atom. The crystal was a non-merohedral twin with a fractional contribution of 0.168 (2) of the minor twin component.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989017006673/sj5529sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017006673/sj5529Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017006673/sj5529Isup3.cmlSupporting information file. DOI: 1547729CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


II complex, the divalent Ni ion occupies a crystallographically imposed centre of symmetry and is coordinated by two O atoms from the carboxylate groups of two 2,4,6-trimethylbenzoate ligands, two N atoms from the pyridyl groups of two isonicotinamide ligands and two water molecules in a slightly distorted octahedral geometry. Hirshfeld surface analysis indicates that the most important contributions for the crystal packing are from H⋯H (59.8%), O⋯H/H⋯O (20.2%) and C⋯H/H⋯C (13.7%) interactions.In the title Ni II complex, [Ni(C10H11O2)2(C6H6N2O)2(H2O)2]·2H2O, the divalent Ni ion occupies a crystallographically imposed centre of symmetry and is coordinated by two O atoms from the carboxylate groups of two 2,4,6-trimethylbenzoate (TMB) ligands [Ni—O = 2.0438 (12) Å], two N atoms from the pyridyl groups of two isonicotinamide (INA) ligands [Ni—N = 2.1506 (15) Å] and two water molecules [Ni—O = 2.0438 (12) Å] in a slightly distorted octahedral geometry. The coordinating water molecules are hydrogen bonded to the non-coordinating carboxylate O atom of the TMB ligand [O⋯O = 2.593 (3) Å], enclosing an S(6) hydrogen-bonding motif. Two solvent water molecules are also present in the formula unit. In the crystal, a network of intermolecular N—H⋯O and O—H⋯O hydrogen bonds link the complexes into a three-dimensional array. Hirshfeld surface analysis indicates that the most important contributions for the crystal packing are from H⋯H (59.8%), O⋯H/H⋯O (20.2%) and C⋯H/H⋯C (13.7%) interactions.In the title Ni A deficiency in this vitamin leads to loss of copper from the body, giving rise to a condition known as pellagra disease. Victims of pellagra show unusually high serum and urinary copper levels  carboxylates are diverse and include one-dimensional (Guseinov 7H4ClO2)2(C6H6N2O)2(H2O)2]  ·2(H2O)    ·2H2O, and report its molecular and crystal structures, along with a Hirshfeld surface analysis.The structures of a number of mononuclear complexes of divalent transition-metal ions with both nicotinamide (NA) and benzoic acid derivatives as ligands have been previously reported and include   hydrogen bonds (Table 1The asymmetric unit of the mononuclear title compound (I)er Fig. 1. In the z] Fig. 1. The nons Table 1. Intrams Table 1 link H as Table 1.A (C2–C7), ring by 78.80 (14)°, while the benzene and pyridine, B (N1/C11–C15), rings are oriented at a dihedral angle of 24.33 (6)°.The near equalities of the C1—O1 [1.242 (2) Å] and C1—O2 [1.260 (2) Å] bonds in the carboxylate groups indicate delocalized bonding arrangements, rather than localized single and double bonds. The O2—C1—O1 bond angle [124.52 (17)°] is comparable the corresponding values of 124.4 (2)° in (II), 124.67 (14)° in (III), 124.22 (11)° in (IV), 125.71 (10)° in (V), 126.0 (3)° in (VI) and 120.47 (15) and 123.17 (15)° in (VII), where the benzoate ions also coordinate the metal atoms monodentately. The Ni1 atom lies 0.3523 (1) Å below the planar (O1/O2/C1) carboxylate group. In the TMB anion, the carboxylate group is twisted away from the attached benzene, coordW⋯OnoncoordW, O—HnoncoordW⋯Oc, N—HINA⋯OnoncoordW and N—HINA⋯OINA (INA = isonicotinamide and noncoordW = non-coordinating water) hydrogen bonds . The presence of these interactions may also be shown by the Hirshfeld surface mapped as a function of curvedness  in H2O (50 ml) and isonicotinamide  in H2O (25 ml) with sodium 2,4,6-trimethylbenzoate  in H2O (150 ml) at room temperature. The mixture was set aside to crystallize at ambient temperature for nine weeks and gave green single crystals . Combustion analysis: found; C, 54.70, H, 6.24; N, 8.13%. Calculated: C32H42N4NiO10 C, 54.80; H, 6.04; N, 7.99%. FT–IR: 3354, 3197, 2235, 1949, 1855, 1698, 1934, 1612, 1557, 1415, 1226, 1182, 1148, 1115, 1096, 1066, 1041, 1017, 985, 885, 855, 792, 772, 747, 682, 660, 638, 615, 520, 443 cm −1.The title compound was prepared by mixing solutions of NiSO2 groups and water molecules were located in difference Fourier maps and refined freely. The C-bound H atoms were positioned geometrically with C—H = 0.93 and 0.96 Å for aromatic and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = k × Ueq(C), where k = 1.5 for methyl H atoms and k = 1.2 for aromatic H atoms. The maximum and minimum residual density peaks were found at 0.83 and 0.78 Å from atoms O1 and O4, respectively.The experimental details including the crystal data, data collection and refinement are summarized in Table 210.1107/S205698901701060X/cq2020sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901701060X/cq2020Isup2.hklStructure factors: contains datablock(s) I. DOI: 1562879CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: