In the cation, the geometry around the Se atom is T-shaped, resulting from the coordination of Se by the C atom of the central aromatic ring and the N atoms of the benzimidazolyl moieties.In selenium} tetrakis(selenocyanato)mercury, (C34H41N4Se)2[Hg(SeCN)4], the arylselenenium cations, [C34H41N4Se]+, are linked through [Hg(SeCN)4]2− anions by C—H⋯N hydrogen bonds. In the cation, the geometry around the Se atom in the 5-tert-butyl-1,3-bis(1-pentyl-1H-benzimidazol-2-yl)benzene scaffold is T-shaped, resulting from the coordination of Se by the C atom of the central aromatic ring and the N atoms of both of the benzimidazole moieties. The trans Se—N bond lengths are almost equal [2.087 (3) and 2.099 (3) Å] and the Se—C bond length is 1.886 (3) Å. The N—Se—N angle is 159.29 (11)°. The geometry around the HgII atom in the [Hg(SeCN)4]2− anion is distorted tetrahedral, with Se—Hg—Se angles ranging from 88.78 (3) to 126.64 (2)°. In [Hg(SeCN)4]2−, the Hg—Se bonds are unsymmetrical [2.5972 (4) and 2.7242 (5) Å]. One of the pentyl substituents is disordered over two equivalent conformations, with occupancies of 0.852 (8) and 0.148 (8).In the title salt, bis{[5- Some of these were investigated for their photoluminescence properties (Wang tert-butyl)-2,6-bis(1-pentyl-1H-benzo[d]imidazol-2-yl)phenyl}(selenocyanato)mercury (3), mercury(II) chloride (1) was reacted with potassium selenocyanate in 1,4-dioxane under reflux conditions. It was observed that, instead of the formation of the desired compound, the reaction leads to the isolation of an arylselenenium(II) cation via auto-ionization 2 as by-products.In an attempt to synthesize {4-(2 reacts with an excess of KSeCN to form K2[Hg(SeCN)4] .HgCl2, crystallizes in the monoclinic space group C2/c. The asymmetric unit contains a selenenium cation along with half of a [Hg(SeCN)4]2− anion with the Hg atom located on a crystallographic twofold axis  Å, which is comparable with that found for a NCN pincer-based selenenium cation +[PF6]− C6H3Se]+[Br3]− (1.84 Å). The Se3—N1 and Se3—N2 bond lengths are almost equal [2.087 (3) and 2.099 (3) Å]. The Se—N distances are shorter than the sum of the van der Waals radii for Se and N [Σrvdw 3.45 Å] and longer than the covalent radii [Σrcov 1.91 Å]  form a plane (r.m.s deviation for fitted atoms of 0.0182 Å) with the Se in this plane [deviation from the plane of 0.011 (2) Å].The title compound, is Fig. 1. In the 4]2− acts as a bridging moiety between two selenenium cationic units. The Se3⋯Se2 distance is 4.189 (2) Å and the C1—Se3⋯Se2 angle is 163.40 (9)°, which indicates that there is a weak secondary interaction between the two different kinds of Se atoms in the cation and anion (Se3 and Se2). In the [Hg(SeCN)4]2− anion, two sets of Hg—Se bonds exist. One set is shorter [2.5972 (4) Å] and the other set is longer [2.7242 (5) Å]. The Hg–SeCN moieties are not linear, with Hg—Se—C angles of 101.31 (14) and 101.43 (11)°.In the anion, the mercury atom is coordinated by four selenocyanate anions  and the geometry around the mercury atom is distorted tetrahedral with Se—Hg—Se angles ranging from 88.78 (3) to 126.64 (2)°. The tetracyanoselenomercurate anion [Hg(SeCN)b-axis direction as shown in Fig. 2A⋯N1S and C18A—H18C⋯N2S interactions ]selenenium cation. However, there have been several reports of structures containing [Hg(SeCN)1  in 1,4-dioxane (30 ml) was added potassium selenocyanate  dissolved in MeOH. The reaction mixture was stirred for 6 h under a nitrogen atmosphere and refluxed. The reaction mixture was filtered and the precipitate was washed with dioxane. Colourless prism-shaped crystals of 2 were obtained by layering a MeOH solution with diethyl ether at room temperature.To a solution of −1): 3059 (w), 2957 (s), 2931 (s), 2869 (s), 2124 , 1614 (m), 1464 (s), 1458 (s), 1440 (s), 1330 (w), 1288 (w), 1273 (w), 1154 (w), 1137 (w), 1011 (w), 892 (w), 746 (s). ESI–MS: m/z calculated for C34H41N4Se: 585.2496. Found: 585.2552.Yield 11% ; m. p. turned blackish after 423 K was reached. FT–IR (KBr) (cmUiso(H) = xUeq(C), where x = 1.5 for methyl H atoms and 1.2 for all other C-bound H atoms. One of the pentyl substituents is disordered with an occupancy ratio of 0.852 (8):0.148 (8). It was refined as two equivalent conformations using SAME and SIMU instructions (SAME 0.01 and SIMU 0.01).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989018006394/zl2726sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018006394/zl2726Isup2.hklStructure factors: contains datablock(s) I. DOI: 1839609CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The copper(II) atom shows a typical Jahn–Teller distorted [4 + 2] octahedral coordination sphere. H-benzotriazol-1-yl)acetic acid  and monoethanolamine  with CuCl2·2H2O resulted in the formation of the title complex, [Cu(C8H6N3O2)2(C2H7NO)2] or [Cu(BTA)2(MEA)2]. Its asymmetric unit comprises one BTA anion coordinating to the Cu2+ cation (site symmetry R22(8) graph-set motif. The molecules are further linked by C—H⋯π interactions involving the triazole rings and methylene groups of MEA, thus generating an overall three-dimensional supramolecular framework.The reaction of 2-(1 The Cu2+ cation is located on a center of inversion. Its coordination polyhedron is a distorted N2O4 octahedron formed by two oxygen atoms (O2) of the carboxy groups of symmetry-related BTA anions, by two nitrogen atoms (N4) of two symmetry-related MEA ligands in the equatorial plane and by two O atoms (O3) of the same set of MEA ligands in the axial positions. The Cu—O2 and Cu—N4 bond lengths are 2.029 (1) and 1.980 (2) Å, respectively, whereas the length of the axial Cu—O3 bond is 2.492 (2) Å, typical for Jahn–Teller distortions. The MEA ligand is neutral and acts as a bidentate N- and O-donor ligand and forms CuNC2O five-membered chelate rings which have a twist conformation; the O3—C10—C9—N4 torsion angle is −60.3 (3)°. The planar benzotriazole ring system (N1–N3/C1–C6: r.m.s. deviation = 0.0064 Å) is co-planar with the methyl carbon atom C7 [deviation from the plane of 0.158 (2) Å], whereas the carboxylate group is nearly normal to this plane [88.0 (2)°]. The difference of the C8—O distances of the carboxylate group (Δ = 0.036 Å) is due to the monodentate coordination, with the longer C—O distance involving the coordinating O2 atom.The molecular structure of The molecular structure is stabilized by an intramolecular O3—H3⋯O1 hydrogen bond between the OH group of the MEA ligand and the non-coordinating carboxylate O atom Fig. 1.A⋯O1iii, N4—H4A⋯O2ii and N4—H4B⋯O3ii hydrogen bonds between the amino function and carboxylate/hydroxy O-atom acceptors  generate a three-dimensional supramolecular framework.In the crystal structure of (I)s Table 1, forming0) Fig. 3. AdditioH-benzotriazol-1-yl)acetic acid and different metal cations in the CSD  was slowly added an ethanol solution (5 ml) containing MEA  and HBTA  under constant stirring. Blue crystals of the product were obtained by solvent evaporation at room temperature after one week. Yield: 70%. Elemental analysis: Calc. for C20H26CuN8O6 (538.04): C, 44.65; H, 4.87 N, 20.83%. Found: C, 44.73; H, 4.93; N, 20.88%.To an aqueous solution (2.5 ml) of CuClUiso(H) = 1.2Ueq(C). The positions of the O- and N bound H atoms were located from a difference-Fourier map and were refined with soft distance restraints, 0.82 Å for the hydroxyl group and 0.95 Å for the primary amine group.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989019000744/wm5481sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019000744/wm5481Isup2.hklStructure factors: contains datablock(s) I. DOI: 1891272CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


II ion lies on a crystallographic twofold axis and has distorted tetrahedral coordination geometry. Two weak C—H⋯S intramolecular hydrogen bonds exist between the bipyridyl and thiol groups. In the crystal, molecules are linked by weak C—H⋯O and C—H⋯S hydrogen bonds, forming a three-dimensional supramolecular architecture.The Zn 2N,N′)bis(2-methoxyethyl xanthato-κS)zinc(II), [Zn(C4H7O2S2)2(C10H8N2)], the ZnII ion is coordinated to two N atoms of the 2,2′-bipyridine ligand and two S atoms from two 2-methoxyethyl xanthate ligands. The ZnII ion lies on a crystallographic twofold rotation axis and has distorted tetrahedral coordination geometry. In the crystal, molecules are linked by weak C—H⋯O hydrogen bonds, forming supramolecular chains propagating along the a-axis direction. Weak intramolecular C—H⋯S hydrogen bonds are also observed. The intermolecular contacts in the crystal were further analysed using Hirshfield surface analysis, which indicates that the most significant contacts are H⋯H (36.3%), followed by S⋯H/H⋯S (24.7%), C⋯H/H⋯C (15.1%), O⋯H/H⋯O (14.4%), N⋯H/H⋯N (4.1%) and C⋯C (2.9%).In the title compound, (2,2′-bipyridine-κ ROCS2−) have attracted the attention of scientific groups of researchers due to their diverse applications. Metal xanthates have been used as single-source precursors to metal sulfide materials  and 2.295 (2) Å, respectively, whereas the bond angles around the central ZnII ion are in the range 78.7 (3)–126.64 (10)° . The C—O bond lengths range from 1.346 (8) to 1.453 (8) Å although all of the C—O bonds show single-bond character. In the {S2C} part of the xanthate ligands, the C1—S1 distance is 1.727 (7) Å, which is typical of a single bond whereas the C1—S2 distance of 1.652 (7) Å is typical of a carbon-to-sulfur double bond. The C—N and C—C bond lengths in 2,2′-bipyridine are normal for 2-substituted pyridine derivatives (O-n-propyldithiocarbonato-S)zinc(II) zinc(II) and bis(O-isobutylxanthato)zinc(II) . 2H2O  in 2-methoxyethanol, was added a hot solution of 2,2′-bipy  in 2-methoxyethanol. A hot solution of potassium 2-methoxyethylxanthate  in 2-methoxyethanol was added under stirring. Colourless crystals were formed after 30 minutes. The crystals were washed with small amounts of 2-methoxyethanol and water and air-dried.To a hot solution of Zn(CHUiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) otherwise. The crystal was a weak diffractor (I/σ at 0.81 resolution was 5.1) and refinedas a two-component twin with HKLF 4 data (twin law −1 0 0 0 − 1 0 0 0 − 1) but this had little effect. The anisotropy of N1 was restrained with ISOR 0.01 0.02 in SHELXL  I. DOI: 10.1107/S2056989019014968/lh5934Isup2.hklStructure factors: contains datablock(s) I. DOI: 1424075, 1424075CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The asymmetric unit contains two independent molecules and two water molecules. The central parts of both the molecules are twisted as both molecules are bent at both the S and N atoms. The crystal structure features N—H⋯N, N—H⋯O, C—H⋯O and O—H⋯O intermolecular interactions. Two-dimensional fingerprint plots show that the largest contributions to the crystal stability come from O⋯H/H⋯O and H⋯H interactions. 9H8ClN3O3S2·H2O, consists of two independent molecules and two water molecules. The central parts of the molecules are twisted as both the molecules are bent at both the S and N atoms. In the crystal, N—H⋯N, N—H⋯O, C—H⋯O and O—H⋯O hydrogen-bonding interactions connect the molecules, forming layers parallel to the ab plane. Two-dimensional fingerprint plots associated with the Hirshfeld surface show that the largest contributions to the crystal packing come from O⋯H/H⋯O (32.9%) and H⋯H (22.6%) interactions.The asymmetric unit of the title thiazole derivative containing a sulfonylhydrazinic moiety, C The sulfonylhydrazide bond exists in the synclinal conformation preferred by aromatic sulfonamides benzenesulfonohydrazide -methyl 2-[(Z)-4-oxo-2-(2-tosylhydrazono)thiazolidin-5-ylidene]acetate and (Z)-methyl-2-[(Z)-2-(ethylimino)-4-oxo-3-(phenylamino)thiazolidin-5-ylidene]acetate phenyl]-1,3-thiazol-2(3H)-ylidene}benzenesulfonohydrazide  and related fingerprint plots were generated using CrystalExplorer17.5 /rivdw + (de − revdw)/revdw  with di + de ∼ 1.9 Å. The presence of water molecules in the unit cell provides the largest contribution to the stability of the crystal packing. The next largest contributor is from H⋯H interactions, which contribute 22.6%. A single sharp spike can be seen in the middle region of the plot, at di = de = 0.9 Å . The N⋯H contacts, which refer to N—H⋯N interactions, contribute 5.3% to the surface. Two sharp spikes having di + de = 1.8 Å  are observed. The C⋯H contacts contribute 5.9% to the Hirshfeld surface, featuring a wide region with di + de = 3.1 Å . The different interatomic contacts and percentage contributions to the Hirshfeld surface are Cl⋯H/H⋯Cl (8.3%), S⋯H/H⋯S (6.1%), Cl⋯O/O⋯Cl (3.0%), Cl⋯C/C⋯Cl (2.4%), S⋯O/O⋯S (1.7%), and C⋯O/O⋯C (1.6%) as depicted in the fingerprint plots .In order to explore the role of weak intermolecular interactions in the crystal packing, Hirshfeld surfaces benzene-1-sulfonohydrazide was prepared by adding 4-chloro benzenesulfonyl chloride (0.02 mol) under stirring to a solution of thiosemicarbazide (0.02 mol) in 5% aqueous NaOH solution (20 ml). The reaction mixture was stirred at room temperature for 1 h, then diluted twofold with water and neutralized with glacial acetic acid. The solid 2-(4-chlorobenzene-1-sulfonyl)hydrazine-1-carbothioamide (A) obtained was crystallized from acetic acid. Monochloroacetic acid (0.01 mol) and anhydrous sodium acetate (0.04 mol) were added to A (0.01 mol) in glacial acetic acid. The reaction mixture was refluxed for 8–10 h and the completion of the reaction was checked by TLC. The reaction mixture was then poured into cold water. The resulted precipitate of the title compound was separated by vacuum filtration. Prismatic colourless single crystals of the title compound were grown from a mixture of acetonitrile-DMF (5:1 v/v) by slow evaporation of the solvent. The purity of the compound was checked by TLC and characterized by IR spectroscopy. The characteristic IR absorptions observed at 3095.9, 1639.5, 1458.7, 1343.2, 1139.4, and 1215.7 cm−1 correspond to N—H, C=O, C=N, S=O asymmetric and symmetric, and C—S absorptions, respectively. The 1H and 13C spectra of the title compound are as follows: 1H ; δ 3.45 , 7.68–7.86 , 10.01 , 11.96 . 13C NMR ; δ 36.8, 128.4, 129.1, 131.1,132.5, 133.9, 137.2, 165.4, 185.5.4-Chloro-Ueq of the parent atom.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989018013658/rz5243sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018013658/rz5243Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018013658/rz5243Isup3.cmlSupporting information file. DOI: 1869597CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


N(4)-morpholinothiosemicarbazone forms sheets parallel to (002) and consisting of two parallel chains running in the a-axis direction and formed by N—H⋯O and C—H⋯O hydrogen bonds.In the crystalline state, salicylaldehyde  N-{[(2-hydroxyphenyl)methylidene]amino}morpholine-4-carbothioamide), C12H15N3O2S, was previously determined °. In the crystal, the molecules are connected into chains by N—H⋯O and C—H⋯O hydrogen bonds, which combine to generate sheets lying parallel to (002). The most prominent contribution to the surface contacts are H⋯H contacts (51.6%), as concluded from a Hirshfeld surface analysis.The structure of the title compound (systematic name:  Cisplatin is well known as an effective therapy to prohibit the proliferation of tumor cells -substituted thiosemicarbazide. Many reports have demonstrated that N(4)-aromatic or heterocyclic substituted thiosemicarbazides are biologically more active than thiosemicarbazones without substituted groups -morpholinothiosemicarbazone was published previously -morpholinothiosemicarbazone (3) together with its structural characteristics and crystal structure redetermination using present-day technology.The crystal and molecular structure of salicylaldehyde Pna21 with one molecule in the asymmetric unit °], which gives rise to an intramolecular O18—H18⋯N10 hydrogen bond with an ap conformation].The title compound crystallizes in the orthorhombic space group it Fig. 1. The N9—f Table 1. The plaQ = 0.554 (3) Å, θ = 173.2 (3)° and φ = 214 (3)°] with the thiosemicarbazone function in an equatorial position. The plane of the phenyl ring forms a dihedral angle of 43.44 (17)° with the best plane through the morpholino ring. A second intramolecular C6—H6A⋯S8 interaction is observed (Table 1The morpholino ring adopts a chair conformation .A search of the Cambridge Structural Database  and −175.97 (15)°] and τ2 [166.51 (16) and −174.99 (16)°] are similar to those observed for the title compound. An intramolecular hydrogen bond similar to O18—H18⋯N10 is also observed.The most similar compound present in the CSD is the 2-hydroxynaphthaldehyde-based thiosemicarbazone  is given in Fig. 7The reaction scheme for the synthesis of (Synthesis of 2-((morpholine-4-carbonothioyl)thio)acetic acid (1):A mixture consisting of carbon disulfide (0.2 mol) and concentrated ammonia (25 mL) was stirred to form a homogeneous solution at 278 K. Then, morpholine (0.2 mol) was added dropwise to this solution. The yellow solid that separated from the solution was filtered off and immediately dissolved in deionized water (300 mL) at room temperature to generate a yellow solution. Sodium chloroacetate (0.2 mol) was added to this solution and the reaction mixture maintained for 6 h at room temperature. The yellowish solution was acidified with concentrated hydrochloric acid and the resulting white precipitate was filtered off and recrystallized from ethanol.Synthesis of N(4)-morpholinothiosemicarbazide (2):1) (50 mmol), deionized water (10 mL) and hydrazine hydrate (25 mL) was refluxed for 30 minutes at 353 K. The white solid which precipitated from the transparent solution was filtered off and recrystallized from ethanol to give (2).A mixture composed of -morpholinothiosemicarbazone (3):2) in hot ethanol, the solution was added to an equivalent amount of salicylaldehyde. The final solution was refluxed at 353 K for 2 h in the presence of acetic acid as a catalyst. The resulting solution was gradually reduced in volume at room temperature overnight. The needle-shaped crystals that formed were filtered off and recrystallized from ethanol to give (3) in the form of transparent crystals (yield 60%), m.p. 461–463 K. FT–IR (cm−1): 3436 (O—H), 3279 (N—H), 1617 (CAr—H), 1540 (C=N), 1061 (N—N), 1348 and 959 (C=S). 1H NMR : 3.67 ; 3.92 ; 6.90 ; 7.28 ; 7.41 ; 8.47 ; 11.49 ; 11.55 . 13C NMR : 49.4 (C2 and C6), 66.2 (C3 and C5), 117.0 (C14), 118.9 (C12), 119.5 (C16), 130.4 (C17), 131.3 (C15), 146.9 (C13), 157.6 (C11), 180.1 (C7). UV–Vis : 200 (π→π*); 300 and 350 (n→π*).After dissolving (Uiso(H) values 1.2Ueq of the parent atoms, with C—H distances of 0.93  and 0.97 Å (CH2). In the final cycles of refinement, 4 outliers were omitted.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989019011812/mw2147sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019011812/mw2147Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019011812/mw2147Isup3.cmlSupporting information file. DOI: 1949697CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


EVs). Three mouse melanoma B16 variants with distinct metastatic potentials show similar gene expression levels and enzymatic activities of glycosyltransferases involved in N‐glycosylation. All melanoma variants and EVs have nearly identical profiles of de‐sialylated N‐glycans. The major de‐sialylated N‐glycan structures of cells and EVs are core‐fucosylated, tetra‐antennary N‐glycans with β1,6‐N‐acetylglucosamine branches. A few N‐glycans are extended by N‐acetyllactosamine repeats. Sialylation of these N‐glycans may generate cell‐type‐specific N‐glycomes on EVs. Taken together, melanoma‐derived EVs show high expression of tumor‐associated N‐glycans, and the core structure profile is inherited during multiple selection cycles of B16 melanomas and from tumor cells to EVs.We investigated the correlation between metastatic behaviors of tumor cells and asparagine‐linked glycosylation (N‐glycosylation) of tumor‐derived extracellular vesicles ( EVs, extracellular vesiclesPA, 2‐aminopyridineN‐acetylglucosamine (GlcNAc) may be fucosylated (core fucosylation) Most cell surface and secretory proteins are modified by asparagine‐linked glycans (N‐glycans) in vivo and in vitro selections have been performed to obtain mouse B16 malignant melanoma variants with distinct metastatic potentials. The B16‐F1 (poorly lung‐colonizing) and B16‐F10 (highly lung‐colonizing) variants are selected for their lung colonization abilities following intravenous injection of the parent B16 cells  in vitro, resulting in a highly spontaneous metastatic variant Blood‐borne tumor metastasis is a complex process involving tumor cell invasion into normal tissues, intravasation to the circulation, extravasation, and colonization at distant organs Tumor cells secrete small vesicles, termed extracellular vesicles (EVs), that contain various cargo molecules including nucleic acids, soluble proteins, and membrane proteins in vivo and in vitro selection cycles of B16 variants and is copied from tumor cells to their EVs. It was suggested that sialylation of these N‐glycans probably generates cell‐type‐specific N‐glycome on EVs. This study establishes the N‐glycosylation landscapes of B16 variants and their EVs, and indicates that the bulk N‐glycosylation of melanoma EVs does not reflect the metastatic potentials of their secreting tumor cells in the B16 model.In the present study, we investigated the correlation between metastatic potentials of three B16 variants  and N‐glycosylation of their EVs by characterizing N‐glycan structures and gene expression, as well as enzymatic activity, of glycosyltransferases involved in N‐glycosylation. The results demonstrate that the core structure profile of N‐glycans is inherited at the genetic level during multiple −1 penicillin, and 100 μg·mL−1 streptomycin at 37 °C in a 5% CO2 atmosphere.Mouse B16‐F1 and B16‐F10 melanoma cells were purchased from the American Type Culture Collection . B16‐BL6 cells were purchased from RIKEN Bioresource Center. All cell lines were maintained in complete Dulbecco's modified Eagle's medium containing 10% fetal bovine serum, 100 U·mL6 cells/10‐cm dish) were cultured for 24 h, washed twice with PBS, and incubated for 48 h in EV‐depleted medium. The conditioned medium was sequentially centrifuged at 130 g for 5 min, 20 000 g for 20 min, and 100 000 g for 70 min. The final pellet containing EVs was washed once with PBS and measured for its protein concentration with a BCA protein assay kit , using bovine serum albumin as an external standard.Extracellular vesicles were prepared as described m Tris‐HCl (pH 7.4), 150 mm NaCl, 1% Triton X‐100, 1 mm EDTA, and protease inhibitor cocktail . The homogenate was centrifuged at 20 000 g for 10 min and the supernatant was recovered as the whole cell lysate.Cells were lysed for 15 min at 0 °C in lysis buffer comprising 10 mN4‐(N‐acetyl‐β‐glucosaminyl)asparagine amidase F (PNGase F)  according to the manufacturer's instructions. The released N‐glycans were purified and fluorescently labeled with 2‐aminopyridine (PA) using a BlotGlyco Kit  according to the manufacturer's instructions.N‐glycans were released from EVs and whole cell lysates by treatment with peptide‐Arthrobacter ureafaciens in 10 mm sodium acetate buffer (pH 5.5) for 16 h at 37 °C. The sialidase‐digested samples and the neutral fraction were desalted on PD‐10 desalting columns  and subjected to reversed‐phase HPLC as described −1; Takara), as described PA‐labeled N‐glycans were initially separated into one neutral fraction and six sialidase‐sensitive fractions by anion‐exchange HPLC, as described PA‐labeled N‐glycans fractionated by reversed‐phase HPLC were subjected to matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometric analysis. PA‐glycans (1 μL) were mixed with 1 μL of 2,5‐dihydroxybenzoic acid (10 mg/mL in 50% acetonitrile/0.1% trifluoroacetic acid) on a target plate. After evaporation to dryness, spectra were obtained in the positive mode using an Autoflex mass spectrometer  operated in the reflector mode.http://www.glycoanalysis.info/galaxy2/ENG/index.jsp), using the masses and glucose units of individual glycans, the latter of which were calculated by the elution positions of PA‐glucose oligomers (degree of polymerization = 3–22) in the reversed‐phase and size‐fractionation chromatography The structures of PA‐labeled N‐glycans from melanoma EVs were determined by reference to a database, glycoanalysis by the three axes of MS and chromatography (GALAXY) Samples (10 μg protein) were denatured for 3 min at 100 °C, separated by SDS/PAGE, and analyzed by western blotting using an anti‐CD81 antibody .6 cells/10‐cm dish) that had been cultivated for 48 h using TRI Reagent  in accordance with the manufacturer's protocol, followed by treatment with DNase (Qiagen) and purification using RNeasy Mini kit . 1 μg total RNA was reverse‐transcribed using an R2 First Strand Kit (Qiagen) in a 40‐μL reaction mixture and then diluted with 182 μL RNase‐free water. The cDNA thus obtained was mixed with 2.7 mL RT2 SYBR Green qPCR Mastermix (Qiagen) and 2.496 mL water, and 25 μL of the mixture was applied to each well of a 96‐well plate that contained specific primers for glycotransferase mRNAs (Qiagen). Two types of 96‐well plates were used for quantification of 144 glycosyltransferase genes; a commercially available plate for Mouse Glycosylation (Cat. No. 330231 PAMM‐046ZA) covering 84 glyco‐related genes, and a 96‐Well Custom PCR Array in which we manually selected 86 glycosyltransferase genes, seven house keeping genes  and three primers for monitoring genomic contamination, cDNA synthesis and PCR reaction. cDNAs were amplified and analyzed using an ABI PRISM 7900HT thermocycler  according to the RT2 Profiler PCR Array Handbook (Qiagen). The abundance of glycotransferase mRNAs relative to that of housekeeping genes  was calculated using the ΔCt method. The values in Tables Real‐time PCR for glycosyltransferases was performed as described previously m MES pH 6.2, 10 mm MnCl2, 10 mm UDP‐Gal at 37 °C overnight. The enzymes were mixed with various concentrations of a fluorescence‐labeled acceptor substrate  equipped with an ODS column  Enzymatic activity of mannosyl ‐glycoprotein β1,4‐GlcNAc transferase (Mgat3), α‐1,3‐mannosyl‐glycoprotein 4‐β‐GlcNAc transferase (Mgat4), α‐1,6‐mannosylglycoprotein 6‐β‐GlcNAc transferase (Mgat5), fucosyltransferase 8 (Fut8), α2,3‐sialyltransferase and α2,6‐sialyltransferase were measured as described previously cDNAs encoding the catalytic regions of human MGAT3, mouse Magt4a, human MGAT5, human FUT8, human ST3GAL4 and human ST6GAL1 were amplified by PCR with primers: human MGAT3, 5′CGGAATTCGAGCCAGGAGGCCCTGACCT3′ and 5′CTAGACTTCCGCCTCGTCCA3′; mouse Mgat4a, 5′CGGAGCTAAACACCATTGTC3′ and 5′GTGCTCGAGTCTAAGCAGATCAACTGGTG3′; human MGAT5, 5′CTACAGCTGTTCCCAGCTTG3′ and 5′AGGCTCGAGCTATAGGCAGTCTTTGCAGA3′; human FUT8, 5′CGGAATTCCGGATACCAGAAGGCCCTAT3′ and 5′TTATTTCTCAGCCTCAGGAT3′; human ST3GAL4, 5′GAGGAATTCGAGCCGTGCCTCCAGGGTGA3′ and 5′TTGCTCGAGTCAGAAGGACGTGAGGTTCTTG3′; and human ST6GAL1, 5′GTGGAATTCAAGGACAGCTCTTCCAAAAA3′ and 5′AAACTCGAGTTAGCAGTGAATGGTCCGGAA3′.2+‐column and desalted with NAP‐5 gel filtration column .The PCR products were inserted into pcDNA‐IH as described previously Stt3a and Stt3b), protein quality control in the ER (Uggt1 and Uggt2), GlcNAc branch formation , lysosome targeting (Gnptab and Gnptg), galactosyltransferases , polylactosamine formation (B3gnt2 and B3gnt4), core fucosylation (Fut8), α2,3‐sialyltransferases  and α2,6‐sialyltransferase . The gene expression pattern of B16‐F1 and B16‐BL6 cells was similar to that of B16‐F10 cells, except that B4galt2 was undetectable in B16‐BL6 cells. We hardly detected expression of Mgat3 (bisecting GlcNAc formation), as well as Fut1‐7 and Fut9 , in all three variants. In comparison of cells with different lung colonization ability (B16‐F1 and B16‐F10), B16‐F1 cells showed higher expression of Mgat5 (1.5‐fold), B4galt2 (3‐fold), B3gnt2 (1.5‐fold), St3gal4 (2.0‐fold) and St6gal1 (1.4‐fold) than B16‐F10 cells. In contrast, B16‐F1 cells expressed lower levels of Stt3a (0.8‐fold), B3galt2 (0.7‐fold) and Fut8 (0.8‐fold) than B16‐F10 cells. In comparison of cells with different invasiveness (B16‐F10 and B16‐BL6), B16‐BL6 cells showed higher levels of Uggt2 (1.8‐fold), Mgat4b (1.4‐fold), B4galt1 (1.2‐fold), B3galt2 (1.2‐fold), St3gal4 (1.3‐fold) and St6gal1 (1.9‐fold) than B16‐F10 cells. In contrast, B16‐BL6 cells showed lower expression of Uggt1 (0.7‐fold), Mgat4a (0.7‐fold) and Mgat5 (0.8‐fold) than B16‐F10 cells, suggesting that low expression of Uggt1 and Mgat4a is compensated by high expression of Uggt2 and Mgat4b in B16‐BL6 cells. Together, these results indicate that B16 variants with distinct metastatic potential have unique glycosyltransferase gene expression patterns. However, overall N‐glycosylation‐related gene profiles are inherited during multiple selection cycles of B16 variants.The cellular N‐glycome is regulated by multiple factors including the expression profiles of glycosyltransferase genes Mgat3 gene was rarely expressed in all three B16 variants  Among the three B16 variants, the B16‐F10 variant is positioned in the middle of the selection cycles N‐acetyllactosamine repeats (polylactosamine), which can serve as ligands for galactose‐binding lectins  As the sialylation of N‐glycans generated considerable structural heterogeneity, de‐sialylated N‐glycans were subjected to further structural analyses. Neutral and de‐sialylated Sia 1‐6 fractions from anion‐exchange HPLC were further fractionated by reversed‐phase HPLC Fig. C and subTo investigate whether characteristic core N‐glycan structures were enriched in EVs, we compared reversed‐phase HPLC profiles of de‐sialylated complex‐type glycans between F10‐EVs and B16‐F10 cells. For the comparison, we chose eight major peaks that contained nine N‐glycans Fig. A and fouNext, we investigated whether the N‐glycosylation profiles of EVs differed among the B16 variants. Anion‐exchange HPLC analysis of sialylated glycans obtained from F1‐EVs, F10‐EVs, and BL6‐EVs revealed that although the number of sialic acids present on N‐glycans was similar among the three variants, the Sia 3 fraction showed distinct elution patterns , the Kodama Memorial Fund for Medical Research (YH), and MEXT/JSPS Grants‐in‐Aid for Scientific Research (JP17H06414 to HY and 17K07356 to YK).Fig. S1. Relative gene expression levels of 144 glycosyltransferases in B16 variants.Click here for additional data file.Fig. S2. Comparative analysis of sialylated N‐glycans from B16‐F10 cells and F10‐EVs.Click here for additional data file.Fig. S3. Relative amounts of sialylated N‐glycans in the Sia 1‐6 fractions of B16‐F10 cells and F10‐EVs.Click here for additional data file.Table S1. mRNA abundances of glycosyltransferases relative to the mean abundance of four housekeeping genes  in B16 variants.Table S2. Structural analysis of N‐glycans expressed on EVs from B16‐F10 cells.Click here for additional data file.


In the crystal structure, intermolecular N—H⋯N hydrogen bonds link the molecules into infinite ribbons extending along the [100] direction. 12H10N6, at 100 K has monoclinic (P21/n) symmetry. Crystals were obtained as a yellow solid by reduction of 3,6-bis(pyridin-2-yl)-1,2,4,5-tetrazine. The structure displays intermolecular hydrogen bonding of the N—H⋯N type, ordering molecules into infinite ribbons extending along the [100] direction.The structure of the title compound, C The substitution of four nitrogen atoms in a six-membered benzene-like ring results in strong π-electron deficiency and concentration of negative charge on the heteroatoms. As a result of these properties, s-tetrazines are used in organic synthesis  in ethanol solution -1,4-dihydro-1,2,4,5-tetrazine (I)on Fig. 1.P21/n. The atomic labelling scheme is shown in Fig. 2Compound (I)et al., 1987A) ring are of almost equal length, being 1.4285 (15) and 1.4306 (16) Å. The C6—N1 and C3—N4 [1.3953 (17) and 1.4051 (17) Å] bond lengths are longer than those for C6—N5 and C3—N2 , respectively. This is the result of the protonation of the N1 and N4 atoms. The C—N bond lengths in the B and C rings are comparable within 3σ, varying from 1.3384 (18) Å to 1.3416 (17) Å.The C—C bond lengths are within the expected values known for aromatic systems (Allen A) shows a boat conformation with pseudo-symmetry mirror planes passing through bonds N2—C3 and N5—C6 [ΔCs = 1.30 (16)°] and atoms N1, N4 [ΔCs = 2.00 (14)°]. In this conformation, hydrogen atoms are located in the equatorial positions of the ring and the N—H bonds are directed to the bottom of the boat (compare torsion angles in Table 1B and C) are not to parallel to each other. The dihedral angles between these rings and central tetrazine ring are 22.43 (7)° (A and B) and 25.71 (6)° (A and C). The dihedral angle between rings B and C is 27.13 (7)°. The overall molecular structure could be recognized as a butterfly-like conformation as shown in Fig. 3The central tetrazine ring (R22(6) ring motif  = 3.2418 (18) Å and C34⋯C61 = 3.3334 (19) Å], as shown in Fig. 5The crystal packing of (I)et al., 2016et al., 1998A search of the Cambridge Structure Database  were mixed in ethanol (4 ml). The resulting solution was warmed to 343 K and then kept at room temperature. Within two weeks, after slow evaporation of the solvent, two kinds of crystal were obtained in a crystallizer. X-ray studies confirmed that the pink crystals were of the known structure (II), while the yellow crystals were identified as being of a previously unreported structure, i.e. (I)Crystals suitable for X-ray measurements were obtained from a commercially available reagent  and used without further purification. 0.5 mmol of 3,6-bis(pyridin-2-yl)-1,2,4,5-tetrazine and 0.5 mmol of 2-mercaptopyridine Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S205698901801753X/ff2157sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901801753X/ff2157Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901801753X/ff2157Isup3.cmlSupporting information file. DOI: 1884403CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


One of these molecules exhibits excellent gelation behaviors in water, and the resultant hydrogels are found to display self-healing properties. Interestingly, the elasticity and strength of the resulting gel can be tuned by the addition of different kinds of Hofmeister salts. The gel formation mechanism was proposed based on the analysis of FT-IR,1HNMR, and XRD, indicating that the main driving force for the self-assembly was the π-π stacking of the benzene rings in the aqueous solution system. Overall, our research provides an efficient approach for facilely tuning the properties of the d-gluconic acetal-based hydrogel.Physical gelation behaviors of a series of The online version of this article (10.1186/s11671-018-2823-8) contains supplementary material, which is available to authorized users. Gels composed of low molecular mass gelators (LMMGs) can be obtained from the self-assembly of LMMGs via supramolecular interactions such as hydrogen bonding, van der Waals interactions, π-π stacking, and so on –13. Over4)2SO4 solutions at appropriate concentrations. However, it has only recently been appreciated in supramolecular chemistry and, more specifically, LWMGs-based hydrogels. For example, Mocerino et al. D2O, the signals of C–H protons on the benzene ring of the G1 mixed with kosmotropes anions  moved upfield, which indicated that the π-π stacking effects between benzene rings were enhanced. Correspondingly after the addition of I−, ClO42−, and SCN−, the peaks of C–H protons shifted to 7.993, 8.007, and 8.130 ppm, respectively. Compared with G1 in pure [d6]D2O, the signals of C–H protons on the benzene ring of the G1 mixed with chaotropes anions  moved downfield, which suggested that the π-π stacking effects between benzene rings were weakened. In Fig. −, Br−, and NO3−), the signals of C–H protons on the benzene ring shifted slightly, indicating that the π-π stacking effects between benzene rings were not influenced obviously.1H NMR spectra of the gelator G1 (2.5% . The result was consistent with the macro performance of the gelators (the changing trends of CGC and Tgel). It also reveals that the main driving force for the self-assembly is the π-π stacking force of the benzene rings in the aqueous solution system.From kosmotropes to chaotropes, H-shift on the benzene ring gradually moved toward the low field and the π-π stacking effect between benzene rings was gradually weakened42− , 2θ = 28.262 (d = 0.31551 nm), 2θ = 34.071 (d = 0.26292 nm), and 2θ = 38.843 (d = 0.23165), and the ratio of d-spacing values is about 1:1/√2:1:√3 indicating that the self-assembly of the G1 xerogel from water is composed of hexagonal closs packing possibly [d = 0.38002 nm), and d = 0.38 nm is the characteristic of π-π stacking force of the benzene rings. It reveals that the main driving force for the self-assembly is the π-π stacking force of the benzene rings in the aqueous solution system [2SO4 aqueous solution (concentration is 0.5 M) exhibited four diffraction peaks centered at 2θ = 19.084 (d = 0.46468 nm), 2θ = 28.075 (d = 0.31757 nm), 2θ = 33.901 (d = 0.26421 nm), and 2θ = 38.683 (d = 0.23257 nm), and it proved that the addition of SO42− did not affect packing modes of the gelator molecules.While patterns of the G1 xerogel from NaSCN aqueous solution (concentration is 0.5 M) exhibited diffraction peaks centered at 2θ = 26.184 (d = 0.34006 nm), 2θ = 30.263 (d = 0.29508 nm), 2θ = 38.904 (d = 0.23130 nm), and 2θ = 38.683 (d = 0.23257 nm), and patterns of the G1 xerogel from aqueous solution  exhibited four diffraction peaks centered 2θ = 23.076 (d = 0.38511 nm), 2θ = 29.563 (d = 0.30191 nm), 2θ = 32.101 (d = 0.27860 nm), and 2θ = 39.165 (d = 0.22982 nm). The ratio of d-spacing values were all 1:1/√2:1:√3 indicating that the self-assembly of the G1 xerogel from water is mainly composed of hexagonal closs packing [To explore the possible packing modes of the gelator molecules in water with the addition of Hofmeister salts in particular, wide-angle XRD (WXRD) of the G1 xerogels were examined. As shown in Fig. possibly . In addin system , 78. In Furthermore, the energy-minimized structure of G1  in in present of Hofmeister anions (concentration is 0.5 M): (a) Na2SO4, (b) Na2S2O3, (c) Na2HPO4, (d) NaF, (e) H2O, (f) NaCl, (g) NaBr, (h) NaNO3, (i) NaI, (j) NaClO4, (k) NaSCN at 25 °C, demonstrating high G’values , flowing point . The step-strain measurement shows the recovery ratios of G’ after the first cycle . Figure S2. (a) Frequency sweep of hydrogels from G1  with Hofmeister salts (concentration is 0.5 M) with a fixed strain (0.1%) at 25 °C; (b) Rheological data under oscillatory stress experiment on hydrogels from G1  with Hofmeister salts (concentration is 0.5 M) with a fixed frequency (1 Hz) at 25 °C; (c) Time scan tests under alternating strain of 0.1% and 100% of G1  with Hofmeister salts (concentration is 0.5 M) with a fixed frequency at 1 Hz at 25 °C. Figure S3. SEM images of G1 xerogel obtained from hydrogel (2.5% w/v) in present of Na2SO4 aqueous solution(concentration is 0.5 M); (b) SEM images of G1 xerogel obtained from hydrogel (2.5% w/v); (c) SEM images of G1 xerogel obtained from hydrogel (2.5% w/v) in present of NaCl aqueous solution(concentration is 0.5 M); (d) SEM images of G1 xerogel obtained from hydrogel (2.5% w/v) in presence of NaSCN aqueous solution (concentration is 0.5 M). Figure S4. The energy-minimized mode of G1. The length of molecular PG16 is 14.6 Å. (DOCX 3013 kb)


The title compound is built up from a planar quinoxalinone ring system linked through a methylene bridge to a 1,2,3-triazole ring, which is inclined by 67.09 (4)° to the quinoxalinone ring plane. 16H19N5O, is built up from a planar quinoxalinone ring system linked through a methylene bridge to a 1,2,3-triazole ring, which in turn carries an n-butyl substituent. The triazole ring is inclined by 67.09 (4)° to the quinoxalinone ring plane. In the crystal, the molecules form oblique stacks along the a-axis direction through intermolecular C—HTrz⋯NTrz (Trz = triazole) hydrogen bonds, and offset π-stacking interactions between quinoxalinone rings [centroid–centroid distance = 3.9107 (9) Å] and π–π interactions, which are associated pairwise by inversion-related C—HDhydqn⋯π(ring)  interactions. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (52.7%), H⋯N/N⋯H (18.9%) and H⋯C/C⋯H (17.0%) interactions.The title compound, C Diversely substituted quinoxalines and their derivatives embedded with variety of functional groups are important biological agents and a significant amount of research activity has been directed towards this class of compounds. These molecules exhibit a wide range of biological applications and are potentially useful in medicinal chemistry research and have therapeutic applications such as antimicrobial methyl substituent projecting well out of the mean plane of the dihydroquinxalone unit, as indicated by the C1—N2—C10—C11 torsion angle of 90.85 (16)°. The n-butyl group is oriented in the opposite direction as seen from the N4—N3—C13—C14 torsion angle of −95.26 (16)° N3 Fig. 1. The di)° Fig. 2.a-axis direction through intermolecular C—HTrz⋯NTrz (Trz = triazole) hydrogen bonds (Table 1A (C1–C6) and B (N1/N2/C1/C6–C8) rings  and π-interactions between the C8=O1 carbonyl group and the B rings . Pairs of stacks are associated through C—HDhydqn⋯π  interactions, generating small, diamond-shaped channels along the a-axis direction  generated 37 hits. Of these, the ones most comparable to the title molecule have R1 = CH3 and R = CH2C≡CH methyl methyl isomer shows that the latter has a U shape with the R group extending back over the bicyclic unit as the result of an intramolecular C—H⋯O hydrogen bond from the α hydrogen of the butyl group while in the former, the more remote position of the butyl group on the triazole ring disfavours such an interaction and the molecule adopts a Z shape. This conformation is favoured by the opportunity for π-stacking and C—H⋯π(ring) interactions in the crystal.A search of the CSD , and those delineated into H⋯H, H⋯N/N⋯H, H⋯C/C⋯H, H⋯O/O⋯H, C⋯C, O⋯C/C⋯O, N⋯C/C⋯N and N⋯N contacts –(i), respectively, together with their relative contributions to the Hirshfeld surface. The most important interaction is H⋯H contributing 52.7% to the overall crystal packing, which is reflected in Fig. 6b) as widely scattered points of high density due to the large hydrogen content of the molecule. The split spike with the tip at de = di = 1.13 Å in Fig. 6b) is due to the short interatomic H⋯H contacts (Table 2c), contribute 18.9% to the HS (Table 2de + di = 2.23 Å. In the presence of weak C—H⋯π interactions (Table 1d), with the tips at de + di = 2.65 Å (Table 2e)] contacts  analysis –(d), respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H⋯H, H⋯N/N⋯H, H⋯C/C⋯H and H⋯O/O⋯H interactions suggests that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing (Hathwar H)-one (0.68 mmol) in ethanol (15 mL) was added 1-azidobutane (1.03 mmol). The reaction mixture was stirred under reflux for 72 h. After completion of the reaction (monitored by TLC), the solution was concentrated and the residue was purified by column chromatography on silica gel by using as eluent the mixture (hexane/ethyl acetate 8:2). The solid product obtained was crystallized from ethanol to afford colourless crystals in 78% yield.To a solution of 3-methyl-1-(prop-2-ynyl)-3,4-dihydroquinoxalin-2 I, global. DOI: 10.1107/S205698901801589X/xu5949Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901801589X/xu5949Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S205698901801589X/xu5949Isup4.cmlSupporting information file. DOI: 1878133CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Parallel chains interact through N—H⋯O hydrogen bonds and π–π stacking of the trisubstituted phenyl rings.In the title pyrazoline derivative, the pyrazoline ring makes angles of 86.73 (12) and 13.44 (12)° with the trisubstituted and disubstituted benzene rings, respectively. In the crystal structure, the molecules are connected into chains running in the  16H16N2O3·H2O, the pyrazoline ring has an envelope conformation with the substituted sp2 C atom on the flap. The pyrazoline ring makes angles of 86.73 (12) and 13.44 (12)° with the trisubstituted and disubstituted benzene rings, respectively. In the crystal structure, the molecules are connected into chains running in the b-axis direction by O—H⋯N hydrogen bonding. Parallel chains interact through N—H⋯O hydrogen bonds and π–π stacking of the trisubstituted phenyl rings. The major contribution to the surface contacts are H⋯H contacts (44.3%) as concluded from a Hirshfeld surface analysis.In the title pyrazoline derivative, C There is a clear difference in both C—N bond distances in the pyrazoline ring: N1=C5 shows double-bond character [1.287 (3) Å] while N2—C3 [1.496 (3) Å] is a single bond. The dihedral angle between the two benzene rings is 80.66 (11)°. The planes of the C6–C11 benzene ring (r.m.s. deviation = 0.004 Å) and the pyrazoline ring make an angle of 86.73 (12)°. For the C15–C20 benzene ring (r.m.s. deviation = 0.006 Å), the dihedral angle with the pyrazoline ring is only 13.44 (12)°. Both the hydroxy and methoxy substituents of the C6–C11 phenyl group are within the phenyl plane with deviations of 0.011 (1) (O12), 0.166 (2) (C13) and −0.057 (2) Å (O14).The title compound crystallizes in the orthorhombic space group it Fig. 1. The pyr2, the O22 water molecule bridges three molecules by O—H⋯N and O—H⋯O hydrogen-bonding interactions with the N1 atom and the O21-hydroxy group  = 3.6627 (11) Å; slippage 1.442 Å; Cg1 is the centroid of the C6–C11 ring]. In addition, a C—H⋯O interaction is observed in the crystal packing . The associated two-dimensional fingerprint plots  followed by reciprocal C⋯H/H⋯C contacts . Significant contributions come from reciprocal O⋯H/H⋯O (20.7%) and N⋯H/H⋯N (7.0%) contacts, which appear as two symmetrical spikes at de + di = 1.65 and 1.80 Å, respectively . A further small contribution is from C⋯C contacts .The Hirshfeld surface -4,5-dihydro-1H-pyrazol-5-yl]phenol °, that between the pyrazoline ring and the nitrophenyl ring is 9.7 (1)° and that between the pyrazoline ring and the methoxyphenol ring is 56. 78 (9)°. The second structure, 3-(2′-hydroxy-5′-methoxy-phenyl)-5-(3-methoxy-4-hydroxyphenyl)-4,5-dihydro-1H-pyrazole °, while the dihedral angles between the pyrazoline ring and the phenyl rings at atom C3 and C5 are 12.1 (1) and 68.2 (1)°, respectively.A search of the Cambridge Structural Database -3-(4-Hydroxy-3-methoxyphenyl)-1-(4-hydroxyphenyl)prop-2-en-1-one, 1, was synthesized as described in a previous study -4,5-dihydro-1H-pyrazol-5-yl)-2-methoxyphenol (2):1 (0.01 mol), 2.5 mL of hydrazine hydrate and 25 mL of ethanol was refluxed at 353 K for 2 h. After pouring the reaction mixture into 200 mL of ice–water, the crude solid product was isolated by vacuum filtration, washed several times with cold water and recrystallized from ethanol:water (1:2) to give yellow crystals , m.p. 465 K. 1H NMR [Bruker XL-500, 500 MHz, d6-DMSO, δ (ppm), J (Hz), see Fig. 6d, 1H, J = 8.0, H2); 3.75 ; 6.74 ; 6.95 , 4.67 ; 3.30 ; 2.76 , 7.45 ; 6.76 .A mixture of chalcone A and H22B were found in difference electron density maps and refined freely. The other H atoms were placed in idealized positions and included as riding contributions with Uiso(H) values of 1.2Ueq or 1.5Ueq of the parent atoms, with C—H distances of 0.93 (aromatic), 0.98 (CH), 0.97 (CH2) and 0.96 Å (CH3). In the final cycles of refinement, eight outliers were omitted.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989019013379/sj5579sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019013379/sj5579Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019013379/sj5579Isup3.cmlSupporting information file. DOI: 1956698, 1956698CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


S(6) ring motif. In the crystal, molecules are linked by weak C—H⋯O and C—H⋯N hydrogen bonds, forming layers parallel to (011). π–π stacking interactions complete the three-dimensional network.The asymmetric unit contains two crystallographically independent molecules in which the dihedral angles between the benzene rings are 13.26 (5) and 7.87 (5)°. An intramolecular O—H⋯N hydrogen bonds results in the formation of an  15H12N2O2, contains two crystallographically independent molecules in which the dihedral angles between the benzene rings in each are 13.26 (5) and 7.87 (5)°. An intramolecular O—H⋯N hydrogen bonds results in the formation of an S(6) ring motif. In the crystal, molecules are linked by weak C—H⋯O and C—H⋯N hydrogen bonds, forming layers parallel to (011). In addition, π–π stacking interactions with centroid–centroid distances in the range 3.693 (2)–3.931 (2) Å complete the three-dimensional network.The asymmetric unit of the title compound, C The title compound displays a trans configuration with respect to the C8=N1 and C23=N3 double bonds. In each independent molecule, an intramolecular O—H⋯N hydrogen bond (Table 1G (N1/H2/O2/C2/C7/C8) and H (O4/H4/N3/C23/C22/C17)]; these are oriented at dihedral angles of A/G = 1.31 (5) and C/H = 0.42 (5)° with respect to the adjacent benzene rings.The asymmetric unit of the title compound contains two crystallographically independent molecules  = 3.860 (2) Å, Cg2⋯Cg2 = 3.693 (2) Å and Cg2⋯Cg4 = 3.931 (2) Å; where Cg1, Cg2, Cg3 and Cg4 are the centroids of the C2–C7, C9–C14, C17–C22 and C24–C29 rings, respectively  Fig. 2. In addily Fig. 3.π–π* type transition. The frontier orbital gap helps to characterize the chemical reactivity and the kinetic stability of the molecule. A molecule with a small frontier orbital gap is generally associated with a high chemical reactivity, low kinetic stability and is also termed a soft molecule. DFT quantum-chemical calculations for the title compound were performed at the B3LYP/6–311G level  and the lowest lying unoccupied molecular orbitals (LUMOs) are termed frontier molecular orbitals (FMOs), which play an important role in the optical and electric properties of compounds, as well as in their quantum chemistry and UV–vis spectra. According to molecular orbital theory, an interaction between HOMO and LUMO orbitals of a structure gives rise to a et al., 2002Molecular electrostatic potential (MEP) surface analysis is a technique of mapping electrostatic potential onto the iso-electron density surface, providing information about the reactive sites. The surface simultaneously displays molecular size and shape and the electrostatic potential value. In the colour scheme adopted, red indicates an electron-rich region with a partially negative charge and blue an electron-deficient region with partially positive charge, light blue indicates a slightly electron-deficient region, yellow a slightly electron-rich region and green a neutral region -2-[(2-hydroxy-5-methoxybenzylidene)amino]benzonitrile moiety: (Z)-2-[(2-hydroxy-1-naphthyl)methyleneamino]benzonitrile -2-[(5-bromo-2-hydroxybenzylidene)amino]benzonitrile benzonitrile-2-benzonitrile -2-(4-diethylamino-2-hydroxybenzylideneamino)benzonitrile -2-[amino]benzonitrile  ring motif, similar to title compound.A search of the Cambridge Structural Database  in ethanol (15 ml) and 2-aminobenzonitrile  in ethanol (15 ml). The reaction mixture was stirred for 5 h under reflux. Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution .Uiso(H) = 1.2Ueq(C) or 1.5Ueq.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989019008077/lh5907sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019008077/lh5907Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019008077/lh5907Isup3.cmlSupporting information file. DOI: 1912294CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The ribbons are connected into layers parallel to the bc plane by inversion-related C—HBnz⋯π(ring) interactions.The pyridazine ring deviates slightly from planarity. In the crystal, ribbons consisting of inversion-related chains of molecules extending along the  22H16N4O2, contains two pyridine rings and one methoxycarbonylphenyl group attached to a pyridazine ring which deviates very slightly from planarity. In the crystal, ribbons consisting of inversion-related chains of molecules extending along the a-axis direction are formed by C—HMthy⋯OCarbx (Mthy = methyl and Carbx = carboxylate) hydrogen bonds. The ribbons are connected into layers parallel to the bc plane by C—HBnz⋯π(ring) (Bnz = benzene) interactions. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (39.7%), H⋯C/C⋯H (27.5%), H⋯N/N⋯H (15.5%) and O⋯H/H⋯O (11.1%) interactions. Hydrogen-bonding and van der Waals interactions are the dominant interactions in the crystal packing. Computational chemistry indicates that in the crystal, C—HMthy⋯OCarbx hydrogen-bond energies are 62.0 and 34.3 kJ mol−1, respectively. Density functional theory (DFT) optimized structures at the B3LYP/6-311G level are compared with the experimentally determined molecular structure in the solid state. The HOMO–LUMO behaviour was elucidated to determine the energy gap.The title compound, C O-triphosphate can be used as a potential substrate for fluorescence detection and imaging of DNA pyridazine derivatives are a versatile class of nitrogen-containing heterocyclic compounds and they constitute useful intermediates in organic syntheses. Also, this nucleus is one of the important ligands in the field of coordination chemistry research. 5--2′-deoxyuridine-5′-B (atoms N2/N3/C6–C9), deviates slightly from planarity by ±0.021 (1) Å (r.m.s. deviation = 0.0134 Å)  and C (N4/C10–C14), are inclined to the mean plane of the pyridazine ring, B, by 18.68 (6) and 38.40 (6)°, respectively, while the benzene ring, D (C15–C20), is inclined to it by 62.59 (5)°. The pyridine and benzene rings are oriented at dihedral angles of A/C = 25.16 (4)°, A/D = 48.94 (4)° and C/D = 59.13 (4)°. The plane of the carboxyl group (defined by atoms C18/C21/O1/O2) is twisted out of the plane of the benzene ring, D, by 22.88 (5)°.The title compund contains two pyridine rings and one methoxycarbonylphenyl group attached to a pyridazine ring, where the central pyridazine ring, Å) Fig. 1. The plaa-axis direction are formed by C22—H22C⋯O1v hydrogen bonds  and those delineated into H⋯H, H⋯C/C⋯H, H⋯N/N⋯H, H⋯O/O⋯H, C⋯C and C⋯N/N⋯C contacts –(g), respectively, together with their relative contributions to the Hirshfeld surface. The most important interaction is H⋯H contributing 39.7% to the overall crystal packing, which is reflected in Fig. 6b) as widely scattered points of high density due to the large hydrogen content of the molecule with the tip at de = di = 1.10 Å, due to the short interatomic H⋯H contacts (Table 2c) with the tips at de + di = 2.75 Å. The pair of scattered points of wings resulting in the fingerprint plots delineated into H⋯N/N⋯H  contacts, with a 15.5% contribution to the HS, has a symmetrical distribution of points with the edges at de + di = 2.58 Å (Table 2e), with an 11.1% contribution to the HS, arises from the O⋯H/H⋯O contacts  have an arrow-shaped distribution of points with the tip at de = di = 13.50 Å. Finally, the tiny characteristic wings resulting in the fingerprint plots shown in Fig. 6g, a 2.4% contribution to the HS, arises from the C⋯N/N⋯C contacts  analysis –(d), respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H⋯H, H⋯C/C⋯H, H⋯N/N⋯H and H⋯O/O⋯H interactions suggest that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing   is the sum of the electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange–repulsion (Erep) energies  were calculated as −23.9 (Eele), −4.3 (Epol), −76.2 (Edis), 53.0 (Erep) and −62.0 (Etot) for the C22—H22C⋯O1 hydrogen-bonding interaction, and −22.0 (Eele), −8.5 (Epol), −28.5 (Edis), 32.3 (Erep) and −34.3 (Etot) for the C22—H22B⋯O1 hydrogen-bonding interaction.The intermolecular interaction energies were calculated using the CE–B3LYP/6-31G energy model available in via density functional theory (DFT) using the standard B3LYP functional and 6-311G basis-set calculations , hardness (η), potential (μ), electrophilicity (ω) and softness (σ) are all recorded in Table 4E = ELUMO − EHOMO] of the molecule is about 1.8908 eV, and the frontier molecular orbital (FMO) energies, i.e. EHOMO and ELUMO, are −4.3680 and −2.4772 eV, respectively.The optimized structure of the title compound, (I)et al., 2019a2N1,N6]copper(II) bis(trifluoromethanesulfonate) pyridazine]bis(μ-2-azido)dizaidodicopper monohydrate] methyl]phenyl analogue has been reported  to afford colourless crystals .3,6-Bis(pyridin-2-yl)-1,2,4,5-tetrazine (4 mmol) was dissolved in toluene (20 ml), and then 1 equiv. of methyl 4-ethynylbenzoate was added and the reaction mixture was stirred and refluxed at temperatures between 413 and 453 K. The solvent was then evaporated. The product obtained was separated by chromatography on a column of silica gel. The isolated solid was recrystallized from hexane–dichloromethane  I, global. DOI: 10.1107/S2056989019013732/lh5927Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019013732/lh5927Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989019013732/lh5927Isup4.cmlSupporting information file. DOI: 1958277, 1958277CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The pyrrolidine ring makes a dihedral angle of 14.83 (12)° with the 3,4-dimethoxyphenyl ring, which are attached to each other by an extended N—CH2—CH2—Car bridge. In the crystal, the structure features C—H⋯O intermolecular hydrogen bonds, an offset π–π interaction [intercentroid distance = 3.564 (1) Å] and a C—Cl⋯π interaction. The contribution of some disordered solvent to the scattering was removed using the SQUEEZE routine [Spek (2015PLATON. The solvent contribution was not included in the reported molecular weight and density.In the title compound, CSpek 2015. Acta Cr The two five-membered rings, A (C2/C3/C5–C7) and B (C5–C9), have envelope conformations with atom C6 as the flap: puckering parameters and the smallest displacement asymmetric parameters are Q2 = 0.619 (2) Å, φ2 = 108.6 (2)° and Δs = 1.09° for ring A, and Q2 = 0.582 (2) Å, φ2 = 215.5 (2)° and Δs = 0.74° for ring B. Atom C6 is displaced from the mean plane through the other four atoms by 0.908 (2) Å in ring A and 0.875 (2) Å in ring B. The dihedral angle between the pyrrolidine ring (N1/C1–C4) and the benzene ring (C12–C17) is 14.83 (12)°, with the torsion angle N1—C10—C11—C12 being 175.8 (3)°. The lengths of the C—Cl bonds involving the chlorine atoms attached to the C8=C9 double bond are 1.692 (2) Å for C8—Cl2 and 1.692 (2) Å for C9—Cl3. The lengths of the bonds to chlorine atoms attached to the single C—C bonds vary from 1.744 (2) to 1.768 (2) Å. These value are close to those found in similar compounds; see §4 Database survey.The molecular structure of the title compound is shown in Fig. 1A⋯O2i hydrogen bonds link the molecules to form a cyclic Cg1⋯Cg5iii of 3.564 (1) Å dec-8-ene-3,5-dione ° compared to 175.8 (3)° in the title compound.A search of the Cambridge Structural Database –1.692 (2) Å and 1.744 (2)–1.768 (2) Å, respectively.In all 17 structures, the five-membered ring has envelope conformations and the six-membered ring a boat conformation. The bond lengths and bond angles are very similar to those reported here for the title compound. For example, the C2CO3 and dried over anhydrous Na2SO4. It was then filtered and the filtrate was concentrated under reduced pressure followed by silica gel column purification to afford the title compound in 82% yield. Colourless block-shaped crystals were obtained by slow evaporation of a solution in ethanol.2- ethanamine (1 equiv.) and 1,4,5,6,7,7-hexachloro-5- norbornene −2,3-dicarboxylic anhydride (1 equiv.) were stirred at room temperature in dry ethyl acetate for 30 min. The ethyl acetate was removed under reduced pressure and the resulting residue was dissolved in toluene. To this reaction mixture was added acetyl chloride (5 equiv.) and refluxed for 1 h. The reaction mixture was brought to room temperature and washed with aqueous NaUiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms. The contribution of the disordered solvent to the scattering was removed using the SQUEEZE routine of PLATON  Global, I. DOI: 10.1107/S2056989019004109/su5485Isup3.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989019004109/su5485sup4.pdfCSD search S1. DOI: Click here for additional data file.10.1107/S2056989019004109/su5485Isup4.cmlSupporting information file. DOI: 1905872CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, C—HOxqn⋯OEthx and C—HPhyl⋯OCarbx  weak hydrogen bonds link the molecules into a three-dimensional network sturucture. A π–π interaction between the constituent rings of the oxoquinoline unit, with a centroid–centroid distance of 3.675 (1) Å may further stabilize the structure. Both terminal ethyl groups are disordered over two sets of sites. The ratios of the refined occupanies are 0.821 (8):0.179 (8) and 0.651 (18):0.349 (18). The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (53.9%), H⋯O/O⋯H (28.5%) and H⋯C/C⋯H (11.8%) interactions. Weak intermolecular hydrogen-bond interactions and van der Waals interactions are the dominant interactions in the crystal packing. Density functional theory (DFT) geometric optimized structures at the B3LYP/6-311G level are compared with the experimentally determined molecular structure in the solid state. The HOMO–LUMO molecular orbital behaviour was elucidated to determine the energy gap.The title compound, C Quinolone derivatives have constituted an important class of heterocyclic compounds which, even when part of a complex molecule, possesses a wide spectrum of biological activities, such as anticancer  and B (C4–C9), of the oxoquinoline unit are oriented at a dihedral angle of 1.04 (6)°. Thus, they are almost coplanar, with a maximum deviation of 0.017 (3) Å for atom C7. Atoms O1 and C10 deviate only by 0.007 (2) and 0.022 (2) Å from that plane and so are essential coplanar. The acetate substituent is nearly perpendicular to that plane, with a torsion angle of C1—N1—C10—C11 = −104.8 (2)°. The mean plane of the phenyl ring, C (C19–C24), is oriented with respect to the oxoquinoline unit at a dihedral angle of 68.17 (6)°. The carboxyl groups, O5/O6/C11 and O3/O4/C16, are twisted out of coplanarity with the best least-squares plane of the oxoquinoline unit and phenyl ring C by dihedral angles of 79.7 (2) and 62.9 (2)°, respectively.The title molecule is composed of ethyl 2-acetate and 4-[(2-ethoxy-2-oxoethyl)(phenyl)carbomoyl] units Fig. 1. The meaOxqn⋯OEthx and C—HPhyl⋯OCarbx  hydrogen bonds (Table 1i.e.A (N1/C1–C4/C9) and B (C4–C9), of the oxoquinoline unit, with Cg1⋯Cg2i = 3.675 (1) Å , may further stabilize the structure. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for crystal packing are from H⋯H (53.9%), H⋯O/O⋯H (28.5%) and H⋯C/C⋯H (11.8%) interactions. Weak intermolecular hydrogen-bond interactions and van der Waals interactions are the dominant interactions in the crystal packing.In the crystal, weak C—Hs Table 1 link thes Table 1. A π–π cCrystalExplorer17.5  and those delineated into H⋯H, H⋯O/O⋯H, H⋯C/C⋯H, C⋯C and O⋯C/C⋯O contacts –(f), respectively, together with their relative contributions to the Hirshfeld surface. The most important interaction is H⋯H, contributing 53.9% to the overall crystal packing, which is reflected in Fig. 6b) as widely scattered points of high density due to the large hydrogen content of the molecule, with the tip at de = di = 1.05 Å, due to the short interatomic H⋯H contacts. The pair of characteristic wings resulting in the fingerprint plot delineated into H⋯O/O⋯H contacts  has a 28.5% contribution to the HS and is viewed as a pair of spikes with the tips at de + di = 2.30 Å. In the absence of weak C—H⋯π interactions, the pair of characteristic wings resulting in the fingerprint plot delineated into H⋯C/C⋯H contacts , with a 11.8% contribution to the HS and are viewed as a pair of spikes with the tip at de + di = 2.83 Å. The C⋯C contacts  have an arrow-shaped distribution of points with the tip at de = di = 1.81 Å. Finally, the pair of the scattered points of wings from the fingerprint plot are delineated into O⋯C/C⋯O  contacts, with a 1.1% contribution to the HS, and has a nearly symmetrical distribution of points with the edges at de + di = 3.15 Å.In order to visualize the intermolecular interactions in the title compound, a Hirshfeld surface (HS) analysis –(d), respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of weak H-atom contacts in establishing the packing structure. The large number of H⋯H, H⋯O/O⋯H and H⋯C/C⋯H interactions suggest that van der Waals interactions and weak hydrogen-bond intermolecular interactions play major roles in the crystal packing  computational calculations using a standard B3LYP functional and a 6-311G basis set , hardness (η), potential (μ), electrophilicity (ω) and softness (σ), which are listed in Table 3E = ELUMO − EHOMO] of the molecule was about 4.2091 eV, and the frontier molecular orbital (FMO) energies, i.e. EHOMO and ELUMO, were −6.1141 and −1.9050 eV, respectively.The geometry optimized structure of the title compound in the gas phase was generated theoretically et al., 2016bet al., 2019aet al., 2014et al., 2012et al., 2018aet al., 2015A non-alkylated analogue, namely quinoline and its derivatives, has been reported  in dimethylformamide  were added ethyl bromoacetate (4.16 mmol), K2CO3 (5.67 mmol) and tetrabutylammonium bromide . The reaction mixture was stirred at room temperature for 6 h. After removal of the salts by filtration, the DMF was evaporated under reduced pressure and the resulting residue was dissolved in dichloromethane. The organic phase was dried with Na2SO4 and then concentrated under reduced pressure. The pure compound was obtained by column chromatography using as eluate hexane/ethyl acetate (3:1 v/v). The isolated solid was recrystallized from hexane–diethyl acetate (1:1 v/v) to afford colourless crystals .To a solution of 2-oxo-2 and CH3 H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = kUeq(C), where k = 1.5 for CH3 H atoms and k = 1.2 for other H atoms. The terminal ethyl groups are disordered with an occupancy ratio of 0.821 (8):0.179 (8) for C12 and C13, and 0.651 (18):0.349 (18) for C17 and C18.The experimental details, including the crystal data, data collection and refinement, are summarized in Table 410.1107/S2056989019014154/lh5924sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019014154/lh5924Isup2.hklStructure factors: contains datablock(s) I. DOI: 1959642, 1959642CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Glycyrrhiza on the Diuretic Function of Euphorbia kansui: An Ascites Mouse Model” [Y1 = 6.331∗X12∗X2 − 4.16∗X12 − 0.1637/X22 + 10.94 , displayed in Figure 3(a). Ascites volume/body weight of mice was defined as a dependent variable Y2 using the multivariate stepwise regression equation Y2 = 0.06416∗X1∗X22 − 0.006046/X22 + 0.3062  as shown in Figure 4(a).” should be corrected toIn the article titled “Effect ofe Model” , there wY1 = 6.331∗X12∗X2 − 4.16∗X12 − 0.1637/X22 + 11.62 , displayed in Figure 3(a). Ascites volume/body weight of mice was defined as a dependent variable Y2 using the multivariate stepwise regression equation Y2 = 0.06416∗X1∗X22 − 0.006046/X22 + 0.4288  as shown in Figure 4(a).”“Ascites volume was defined by the stepwise equation, In addition, the photograph of the renal pathological changes in the Furosemide group in Figure 7(b)-Furo was misplaced. The corrected version of the figure with its description is shown below:


II atom bridging two six-coordinate ZnII atoms in which the two terminal ZnII cations adopt distorted octahedral geometries and the central ZnII cation adopts a distorted tetrahedral geometry.The structure is reported of a complex containing a trinuclear Zn cation lying on a crystallographic twofold axis. It consists of a tetrahedral Zn 3(C14H11Br2N2O)4](ClO4)2·2CH3CN, crystallizes as a symmetrical trinuclear cation with all three metal atoms being located on a twofold rotation axis. It contains a tetrahedral ZnII atom that bridges two six-coordinate ZnII atoms. The complex contains N- and O-donor atoms of four tridentate 2,4-dibromo-6-{[2-(pyridin-2-yl)ethyl]iminomethyl}phenolate ligands. The ratio of ZnII atoms to ligands is 3:4. The two terminal ZnII cations adopt distorted octahedral geometries and the central ZnII cation adopts a distorted tetrahedral geometry. In the cation there are π–π interactions between the dibromophenyl rings, as well as halogen-bonding interactions between the dibromophenyl rings in the cation, which stabilize its conformation. In addition, there are C—H⋯O interactions between the anions and both the cations and solvent molecules as well as C—H⋯N interactions between the cation and solvent molecules. These interspecies interactions link the cations, anions and solvent molecules into a complex three-dimensional arrayThe title compound, [Zn Some enzymes containing zinc(II) include carbonic anhydrase, carboxypeptidase, and phosphatase 4](ClO4)2·2CH3CN, 1, contains a complex cation as well as perchlorate anions and acetonitrile solvent molecules and thus has an overall stoichiometry of [Zn3(L)4](ClO4)2.2CH3CN where L is 2,4-dibromo-6-{[(2-(pyridin-2-yl)ethyl]iminomethyl}phenolate. The compound crystallizes in the monoclinic space group C2/c and the cation consists of the four equivalent L ligands, uniformly coordinated to three ZnII cations.The crystal structure of the title compound, [Zn3(L)4]2+, lies on a crystallographic twofold axis  to 120.11 (8)° and Zn—O bond lengths of 1.9512 (19) and 1.9602 (19) Å. For the six-coordinate terminal zinc atoms, as is usual for complexes containing both Schiff base imine and pyridine N donors, the former form shorter bonds [Zn1—N1 = 2.122 (2) Å and Zn3—-N3 = 2.067 (2) Å] while the latter form longer bonds [Zn1—N2 = 2.148 (2) Å and Zn3—N4 = 2.177 (2) Å] to zinc. The metrical parameters involving the bridging phenolate O donors are significantly different. The bonds to the central Zn2 are considerably shorter than those to the terminal Zn1 and Zn3  and the bridging angles are Zn1—O1—Zn2 = 96.78 (8)° and Zn2—O2—Zn3 = 93.73 (8)°. The distortion from an octahedral geometry can be seen from the cis and trans angles which range from 77.49 (10) to 98.19 (9)° and 160.47 (13) to 173.41 (12)°, respectively. Since all three Zn atoms lie on the twofold axis, the Zn1—Zn2—Zn3 bond angle is exactly 180°. These metrical parameters are similar to those found in the most closely similar complex  to 2.117 (4) Å and 2.140 (4) to 2.176 (4) Å, respectively. In this complex there is no crystallographically imposed symmetry; however, the Zn—Zn—Zn bond angle is still close to 180 at 172.51 (3)°.The trinuclear complex cation,  as well as halogen-bonding interactions  between the dibromophenyl rings in the cation, which stabilize its conformation. In addition there C–H⋯O interactions between the anions and both the cations and solvent molecules as well as C—H⋯N interactions between the cation and solvent molecules (Table 1In the cation there are π–π interactions between the dibromophenyl rings imino}methyl)phenolato type ligands gave 26 hits of which only one was similar to the title compound in that it contained a trinuclear Zn complex where this ligand was acting as a bridging group to the central Zn atom 2·6H2O  with no added base. The mixture was stirred at room temperature overnight. The methanol was removed by rotary evaporation. The product was crystallized by slow evaporation of a solution in acetonitrile giving pale-yellow to colorless crystals.2-(2-Pyridyl)ethylamine  was dissolved in 50 mL of methanol. 3,5-Dibromosalicylaldehyde  was added to the solution and the mixture was refluxed for 5 h. The zinc(II) complex was prepared by reacting the ligand in 50 ml of methanol with Zn(ClOUiso(H) = 1.2Ueq(C) or 1.5Ueq(CH3).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989018012100/jj2202sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018012100/jj2202Isup2.hklStructure factors: contains datablock(s) I. DOI: 1863971CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Reaction of this complex with piperidine leads to partial decoordination of the 2-pyridylphosphine in the product, [P-{(C6H5)2(C5H5N)P}(C5H11N)Re(CO)3Br], which displays an intramolecular hydrogen bond between the piperidine aminic hydrogen atom and the uncoordinated pyridyl group, with D⋯A = 2.992 (9) Å.The reaction of the ligand dipyridylphosphine with (Re(CO) 2N,P]rhenium(I) chloroform disolvate, [ReBr(C17H14NP)(CO)3]·2CHCl3 or ·2CHCl3, (I·2CHCl3), is best described as a distorted octahedron with three carbonyls in a facial conformation, a bromide atom, and a biting P,N-diphenylpyridylphosphine ligand. Hirshfeld surface analysis shows that C—Cl⋯H interactions contribute 26%, the distance of these interactions are between 2.895 and 3.213 Å. The reaction between I and piperidine (C5H11N) at 313 K in dichloromethane leads to the partial decoordination of the pyridylphosphine ligand, whose pyridyl group is replaced by a piperidine molecule, and the complex bromidotricarbonyl[diphenyl(pyridin-2-yl)phosphane-κP](piperidine-κN)rhenium(I), [ReBr(C5H11N)(C17H14NP)(CO)3] or [P-{(C6H5)2(C5H5N)P}(C5H11N)Re(CO)3Br] (II). The molecule has an intramolecular N—H⋯N hydrogen bond between the non-coordinated pyridyl nitrogen atom and the amine hydrogen atom from piperidine with D⋯A = 2.992 (9) Å. Thermogravimetry shows that I·2CHCl3 losses 28% of its mass in a narrow range between 318 and 333 K, which is completely consistent with two solvating chloroform molecules very weakly bonded to I. The remaining I is stable at least to 573 K. In contrast, II seems to lose solvent and piperidine (12% of mass) between 427 and 463 K, while the additional 33% loss from this last temperature to 573 K corresponds to the release of 2-pyridylphosphine. The contribution to the scattering from highly disordered solvent molecules in II was removed with the SQUEEZE routine [Spek phosphane-κSpek 2015. Acta Cr The molecule is a rigid bidentate ligand Br)2 in chloroform as solvent leads to the complex P,N-{(C6H5)2(C5H5N)P}Re(CO)3Br]·2CHCl3 (I·2CHCl3). It presents a similar structure to the widely studied [Re(CO)3(L)] complexes, which have interesting photophysical and photochemical properties , leading to the complex [P-{(C6H5)2(C5H5N)P}(C5H11N)Re(CO)3Br] (II).The reaction of the diphenylpyridylphosphine ligand with the rhenium dimer (Re(CO)I complex I with a bidentate P,N (chelating) ligand crystallized from a chloroform solution in the monoclinic space P21/c. Selected geometrical data are summarized in Table 1I·2CHCl3 is given in Fig. 12Py, a bromide atom in an apical position and three carbonyl carbon atoms in a fac correlation, generating a distorted octahedral environment. Additionally, two chloroform molecules crystallize together with the complex molecule.The mononuclear ReI complex II, crystallized from a CH2Cl2/CH3CN (2:1) solution in the triclinic space group P2Py ligand, a piperidine C5H11N molecule and a bromide anion. The piperidine ring displays a chair-like conformation. An intramolecular hydrogen bond is defined between the non-coordinated pyridyl nitrogen atom and the amine hydrogen atom from piperidine, N2—H2N⋯N1, with D⋯A = 2.992 (9) Å (Table 4B) of the pypridine ring  vs 2119.2 (3) Å3 . In this dnorm view , blue represents the longest distances while the shortest distances are depicted as red spots .Compound II Br)2 and (C6H5)2(C5H5N)P were used as provided from supplier (Aldrich), with no purification before use. Seccosolv™ solvents were used without any further purification. Standard Schlenck techniques under argon atmosphere were used for all manipulations.The reagents, (Re(CO)Synthesis of I. 500 mg of (Re(CO)3(OC4H8)Br)2 (0.590 mmol) were dissolved in 5 ml of chloroform. 312 mg of diphenyl-2-pyridylphosphine (1.18 mmol) was dissolved in 10 ml of chloroform. The two solutions were mixed, changing from colourless to a translucent yellow after 10 minutes of reaction. The reaction was left to continue for a further 2 h. Addition of 2 ml of pentane to the mixture and standing by one day lead to yellow diffraction-quality crystals of I·2CHCl3 .Synthesis of II. The compound was prepared by direct reaction between I and an excess of piperidine (C5H11N) at 313 K in CH2Cl2. 50.0 mg of  (0.082 mmol) were dissolved in 10 ml of CH2Cl2 giving rise to a yellow solution. Then, 40 µL of piperidine (0.51 mmol) was slowly added. The reaction was allowed to continue for six days with constant agitation at 313 K. After cooling, the reaction mixture was layered with acetonitrile. Small orange–yellow diffraction-quality crystals were obtained after one week.Uiso(H) = 1.2Ueq(C). For II, the amine hydrogen atom of the piperidine ring was located in a Fourier-difference map and then subsequently refined with a distant constraint of 0.82 Å. During the last stages of the refinement of II, a region of highly disordered electron density was detected within the crystal structure. As no meaningful model could be achieved, SQUEEZE  I-2CHCl3, II, Global. DOI: 10.1107/S2056989019008089/nk2249I-2CHCl3sup2.hklStructure factors: contains datablock(s) I-2CHCl3. DOI: 10.1107/S2056989019008089/nk2249IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1921165, 1921164CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Each Cu2(CN)2 unit is connected to six FeII centres via two bridging 2-ethylpyrazine molecules and four cyanido groups, resulting in the formation of a polymeric three-dimensional bimetallic metal–organic framework, additionally stabilized by Cu⋯Cu contacts.In the title compound, {Fe(Etpz) 6H8N2)2{Cu(CN)2}2]n, the low-spin FeII ion lies at an inversion centre and displays an elongated octahedral [FeN6] coordination environment. The axial positions are occupied by two symmetry-related bridging 2-ethylpyrazine ligands, while the equatorial positions are occupied by four N atoms of two pairs of symmetry-related cyanide groups. The CuI centre is coordinated by three cyanide carbon atoms and one N atom of a bridging 2-ethylpyrazine molecule, which form a tetrahedral coordination environment. Two neighbouring Cu atoms have a short Cu⋯Cu contact [2.4662 (7) Å] and their coordination tetrahedra are connected through a common edge between two C atoms of cyanide groups. Each Cu2(CN)2 unit, formed by two neighbouring Cu atoms bridged by two carbons from a pair of μ-CN groups, is connected to six FeII centres via two bridging 2-ethylpyrazine molecules and four cyanide groups, resulting in the formation of a polymeric three-dimensional metal–organic coordination framework.In the title metal–organic framework, [Fe(C The axial positions are occupied by the N atoms of two symmetry-related 2-ethylpyrazine molecules [Fe1—N3 = 1.981 (2) Å]. The low-spin state of the FeII centre at the temperature of experiment (T = 173 K) is confirmed by the Fe—N bond lengths (i.e. < 2.0 Å). Each CuI ion (Cu1ii and Cu1iv) is coordinated by one bridging 2-ethylpyrazine molecule via the N atom and by the C atoms of three cyanido groups . The separation between two neighboring Cu atoms is 2.4662 (7) Å, which is significantly shorter than the sum of the corresponding van der Waals radii 2 pairs, in which two Cu atoms, centred about a twofold rotation axis, are interconnected by two μ-CN groups through C atoms. The resulting polymeric three-dimensional metal–organic coordination framework is additionally stabilized by supramolecular Cu⋯Cu contacts in each Cu2(CN)2 unit.Fig. 3et al., 20162(CN)2 unit, the majority of which are copper monometallic metal–organic frameworks (MOFs). Several bimetallic MOFs are slightly similar to the title compound, namely catena-[bis(μ3-chloro)bis(μ3-cyano)tetrakis(μ2-cyano)bisdicadmium(II)dicopper(I)copper(II)] tetrakis(μ2-cyano)tetrakis(dimethylformamidetetracopper(I)zinc(II)] tris(μ2-cyano)bis(μ2-2-ethylpyrazine)tetracopper(I)]  bridging 2-ethylpyrazine molecules and (ii) bridging cyano groups, thus forming one-dimensional {Cu(CN)}n chains and double-stranded {Cu(CN)}n ribbons, linked into a network by bridging ethylpyrazine ligands.A search through the CSD for 2-ethylpyrazine gave 20 hits, in most of which 2-ethylpyrazine molecule binds to Cu, Ag, Mn or Rh ions. In the majority of compounds containing copper, the 2-ethylpyrazine serves as a bridging ligand between two Cu atoms in MOFs. An example closely related to the title structure is 2]  in 1 ml of H2O; the second layer was an H2O/EtOH mixture ; the third layer was a solution of Fe(ClO4)2·6H2O  and 2-ethylpyrazine  in 0.5 ml of EtOH. After two weeks, brown crystals were formed in the middle layer. The crystals were kept under the mother solution prior to measurement.Crystals of the title compound were obtained by a slow diffusion within three layers in a 3 ml glass tube. The first layer was a solution of K[Cu(CN)Uiso(H) = 1.2Ueq(C) for aromatic hydrogens, C—H = 0.99 Å with Uiso(H) = 1.2Ueq(C) for CH2 groups and C—H = 0.98 Å with Uiso(H) = 1.5Ueq(C) for CH3 groups.Crystal data, data collection and structure refinement details are summarized in Table 110.1107/S2056989019009496/rz5262sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019009496/rz5262Isup2.hklStructure factors: contains datablock(s) I. DOI: 1937912CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The title compound is constructed by a 4-hydroxybenzyl ring, a 3,4-dihydroxybenzylidenyl ring and a hydrazide-connecting bridge. The overall conformation of the title compound are discussed and compared to the related structures. In the crystal, molecules are connected by N—H⋯O, O—H⋯O and π–π interactions. 14H12N2O4, the azomethine C=N double bond has an E configuration. The hydrazide connecting bridge, (C=O)—(NH)—N=(CH), is nearly planar with C—C—N—N and C—N—N=C torsion angles of −177.33 (10) and −174.98 (12)°, respectively. The 4-hydroxyphenyl and 3,4-dihydroxyphenyl rings are slightly twisted, making a dihedral angle of 9.18 (6)°. In the crystal, molecules are connected by N—H⋯O and O—H⋯O hydrogen bonds into a three-dimensional network, while further consolidated via π–π interactions [centroid–centroid distances = 3.6480 (8) and 3.7607 (8) Å]. The conformation is compared to those of related benzylidene-4-hydroxybenzohydrazide derivatives.In the title benzohydrazide derivative, C The bond lengths and angles of the central hydrazide connecting bridge are consistent with those in related structures °] and C7—N1—N2—C8 [−174.98 (12)°] are both in an anti-periplanar conformation, the overall conformation for the hydrazide connecting bridge is almost planar. Furthermore, the 4-hydroxyphenyl and 3,4-dihydroxyphenyl rings are also coplanar to the corresponding azomethine and carbonyl double bonds, with torsion angles N2—C8—C9—C10 [−0.76 (19)°] and C5—C6—C7—O2 [−1.18 (19)°] both in a syn-periplanar conformation. Those torsion angles result in an overall flat shape of the title compound with the dihedral angle between the terminal benzene rings being 9.18 (6)°.The title hydrazide derivative, (I), consists of a 4-hydroxyphenyl ring, a 3,4-dihydroxyphenyl ring and a hydrazide (C=O)—(NH)—N=(CH) connecting bridge Fig. 1. The C6—O4⋯O1iii hydrogen bond and those chains are further connected into two-dimensional plates parallel to the ac plane via N1—H1N1⋯O3i and O1—H1O1⋯O2i hydrogen bonds with an aavia an O3—H1O3⋯O2ii hydrogen bond with an bbCg1⋯Cg2iv = 3.6480 (8) Å and Cg1⋯Cg2v = 3.7607 (8) Å In the crystal, molecules are linked by N—H⋯O and O—H⋯O hydrogen bonds Table 1 into a tet al., 2016E)-N′-benzenylidene-4-hydroxybenzohydrazide as the reference moiety resulted in 31 structures with different substituents at the benzylidenyl ring. The different substituent (R) together with selected torsion angles, τ1 (C5—C6—C7—O2), τ2 (C6—C7—N1—N2), τ3 (C7—N1—N2—C8) and τ4 (N2—C8—C9—C10) as shown in Fig. 4τ2 and τ3 are anti-periplanar (151.7–179.8°), showing that the hydrazide connecting bridges are nearly planar. As for the torsion angle τ4, all structures adopt a syn-periplanar conformation (0.6–19.6°). Similar to the title compound, the τ1 torsion angles for most of the structures are syn-periplanar (2.0–29.1°). However, there are three outliers  whose τ1 torsion angles are syn-clinal (34.9–50.9°). By comparing the dihedral angles, the structures can be divided into planar compounds  and non-planar compounds . In general, as the hydrazide-connecting bridges are nearly planar, relatively flat τ1 and τ4 torsion angles are observed in the former compounds, while relatively twisted τ1 and τ4 torsion angles are observed in the latter.A search of the Cambridge Structural Database max 213, 327 nm; FT–IR (KBr) ν (cm−1): 3121 (O—H stretching), 2800 (C—H aromatic stretching), 1615 (amide C=O stretching), 1570 (C=N stretching), 1506 (C=C stretching of aromatic compound) cm−1; 1H NMR  δ 11.39 , 10.10 , 8.23 , 7.77 , 6.84 , 9.33 , 7.22 , 6.90 , 6.77 .M.p. 572–573 K. UV–Vis (MeOH) λ. C-bound H atoms were positioned geometrically (C—H = 0.93 Å) and refined using a riding model with Uiso(H) = 1.2Ueq(C). All O- and N-bound H atoms were located in a difference-Fourier map and refined freely [O—H = 0.80 (2)–0.88 (2) Å and N—H = 0.87 (2) Å].Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989019010442/is5518sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019010442/is5518Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019010442/is5518Isup3.cmlSupporting information file. DOI: 1942396CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: