Cations and anions are linked through C—H⋯O hydrogen bonds.The asymmetric unit of the title compound consists of one [Eu(C 3H7NO)8][PMo12O40], the asymmetric unit comprises one α-Keggin-type [PMo12O40]3− polyoxidometalate anion and one distorted dodecahedral [Eu(C3H7NO)8]3+ complex cation. In the crystal, the isolated polyoxidometalate anions are packed into hexagonally arranged rows extending parallel to [001]. The complex cations are situated between the rows and are linked to the neighbouring anions through weak C—H⋯O hydrogen-bonding interactions, leading to the formation of a three-dimensional network structure.In the title salt, [Eu(C The latter species are fused together by sharing corner atoms (Ob) and consist of three MoO6 octahedra condensed in a triangular arrangement by sharing edges (Oc). There is also a terminal oxygen atom (Od) in every MoO6 octahedron. The P—O bond lengths range from 1.521 (5) Å to 1.536 (4) Å and the Mo—O bond lengths from 1.690 (5) Å to 2.438 (4) Å. The O—P—O angles [109.1 (2)–109.8 (3)°] indicate only a slight distortion of the central PO4 tetrahedron. The EuIII cation is coordinated by eight dimethylformamide ligands through their oxygen atoms with Eu—O distances from 2.369 (5) to 2.416 (6) Å. These values are comparable to those of related oxido-europium(III) species, e.g for the [Eu(thd)3(DMF)2] complex  with Eu—O = 2.494 (5)–2.442 (5) Å 8]3+ cation is linked to four neighbouring α-Keggin-type [PMo12O40]3− anions through C—H⋯O hydrogen-bonding interactions between the methyl groups of the DMF ligands and the terminal-oxygen (Od) and the bridging-oxygen atoms  of the [PMo12O40]3− anions  distances are between 3.174 (10) and 3.541 (11) Å while the C⋯O distances are between 3.289 (11) and 3.473 (12) Å. In the crystal packing, the POM anions are packed into hexagonally arranged rows extending parallel to [001] with the [Eu(DMF)8]3+ cations located between the rows 4N)4H3][PMo11O39] was prepared using a literature method  and isonicotinic acid (C6H5NO2)  were dissolved in 10 ml of dimethylformamide. This solution was added dropwise to a yellow dimethylformamide solution of [(C4H9)4N)4H3][PMo11O39] (0.33 mmol in 10 ml). The mixture was heated under stirring for 1 h at 333 K. Single crystals of the title compounds were obtained by slow diffusion of 2-propanol through the dimethylformamide solution. UV–vis spectrum in dimethylformamide: λmax (nm) 315 and 205.The starting material [, νas(Mo=Od), νas(Mo—Ob—Mo) and νas(Mo—Oc—Mo) appear at 1065, 951, 885 and 974 cm−1, respectively  (rocking vibration), δa(CH3), δs(CH3) and ν(C-H) of the dimethylformamide ligand Uiso(H) = 1.2Ueq(C) for methine groups and C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for methyl groups. The refined Flack parameter  I. DOI: 10.1107/S2056989016003546/wm5274Isup2.hklStructure factors: contains datablock(s) I. DOI: 1456619CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Molecules in both polymorphs of the title compound display deviations from planarity owing to crystal packing effects. 12H11N3O2, is a second monoclinic polymorph  of the previously reported monoclinic  form [Akhmad Aznan et al.  to 26.24 (19)°. The geometry-optimized structure [B3LYP level of theory and 6–311 g+ basis set] has the same features except that the entire molecule is planar. In the crystal, the three-dimensional architecture is consolidated by a combination of C—H⋯O, C—H⋯π, nitro-N—O⋯π and π–π interactions [inter-centroid distances = 3.649 (2)–3.916 (2) Å].The title compound, C al. 2010. Acta Cr Similar conformations were observed for the two independent molecules in the previously reported P21/c polymorph  interaction to close the 10-membered {⋯HC2NO}2 synthon is a little longer that the standard distance criteria incorporated in PLATON  interactions ], and toluene C18–C23 and N8-pyridine rings . As summarized in Table 1via methyl–toluene C—H⋯π interactions, and layers are connected into a three-dimensional architecture ⋯(C18–C23) = 3.916 (2) Å, with an angle of inclination of 11.04 (19)°, and intercentroid distance for (C6–C11)⋯(N5/C13–C17) = 3.913 (2) Å, with an angle of inclination of 13.44 (19)° and symmetry operation .Globally, the crystal packing features alternating layers of molecules that stack along the s Table 1. Ten-memns Fig. 3. These cns Fig. 4. The π–πre Fig. 5 via weakN-(3-chlorophenyl)-3-nitropyridin-2-amine  hydrogen bond, the coplanarity of the nitro group and pyridine ring, and a conrotatory twist of the two rings, i.e. dihedral angles of 9.88 (5) and 84.77 (10)°, respectively. Finally, the structure of the all-phenyl analogue, 2-nitrodiphenylamine, has been reported -3-nitropyridin-2-amine , prepared according to the literature procedure of Akhmad Aznan et al.  set at 1.2Ueq(C). N-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 at 1.2Ueq(N). In the absence of significant anomalous scattering effects, 4208 Friedel pairs were averaged in the final refinement.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S1600536814012227/hb0011sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814012227/hb0011Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814012227/hb0011Isup3.cmlSupporting information file. DOI: 1004278CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The furan and one of the phenanthrene groups are fused in an almost coplanar arrangement [dihedral angle = 5.14 (8)°] and the furan unit makes dihedral angles of 70.27 (11) and 57.58 (8)° with the planes of the phenyl and the second phenanthrene group, respectively. In the crystal, neighbouring molecules are connected via two intermolecular hydrogen-bonding interactions (O—H⋯O and C—H⋯O) towards the carbonyl O atom with donor–acceptor distances of 2.824 (2) and 3.277 (3) Å, creating an inversion dimer. A non-classical C—H⋯Cl interaction [3.564 (2) Å] and three C—H⋯π interactions, with C⋯π distances of 3.709 (3), 3.745 (2) and 3.628 (3) Å, connect the molecules, forming a three-dimensional supramolecular architecture in the solid state.In the title compound, C The cenb-axis direction -furanone [2-(4-chlorophenyl)-2-hydroxy-1-oxacyclopenta[l]phenanthren-3-one] (4) (65%), which was purified by recrystallization from a mixture of methanol and dichloromethane (2:1 v/v). The title compound (3) was the minor product formed along with (4) during the reaction . Diffraction-quality single crystals were generated by slow evaporation from methanol. Yield 1.90 g (14%); m.p. 459 K; IR : 3374 (OH), 1591 (C=O) cm−1; 1H NMR (CDCl3): δ 8.79–7.26 , 8.69 ; MS: m/z 548 (M+). Analysis calculated for C37H21ClO3: C 80.94, H 3.86%; found: C 80.82, H 3.66%.A mixture of phenanthrenequinone (1) , 4-chloroacetophenone (2)  and powdered potassium hydroxide (1 g) in methanol (30 ml) was stirred at 333 K for 4 h and then kept in a refrigerator for 48 h. The main product obtained was a 3 = 1.2Ueq(C). The phenanthroline atom H3 was located from a difference Fourier map and refined with a distance restraint of O—H = 0.86 (1) Å. The reflection 101 was omitted owing to bad agreement. Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S1600536814022338/zl2597sup1.cifCrystal structure: contains datablock(s) 3. DOI: 10.1107/S1600536814022338/zl25973sup2.hklStructure factors: contains datablock(s) 3. DOI: 1024475CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Page 1: In the Acknowledgements: “project ID RFMEFI57614X0061” should read “project ID RFMEFI60414X0022.”Volume 2, no. 6,


The torsion angles indicate a non-helical conformation of the molecule.In a dehydroamino acid with a C=C bond between the α- and β-C atoms, the amino acid residues are linked  11H17BrN2O5, is a dehydroamino acid with a C=C bond between the α- and β-C atoms. The amino acid residues are linked trans to each other and there are no strong intramolecular hydrogen bonds. The torsion angles indicate a non-helical conformation of the molecule. The dipeptide folding is influenced by an intermolecular N—H⋯O hydrogen bond and also minimizes steric repulsion. In the crystal, molecules are linked by strong N—H⋯O hydrogen bonds, generating (001) sheets. The sheets are linked by weak C—H⋯O and C—H⋯Br bonds and short Br⋯Br [3.4149 (3) Å] interactions.The title compound, C This reaction proceeds in two steps, namely by halogenation of dehydroamino acids, which gives α-bromo-imines, followed by tautomerization to the desired products upon treatment with an amine  is 175.79 (16)°, while ω3 (O5—C6—N8—C9) is 176.12 (15)°. There are no strong intramolecular hydrogen bonds. The values of the ϕ2,3 and ψ2,3 angles corresponds to a non-helical conformation °], which may correspond to the presence of the bromine atom in the structure. The other angles are normal, as the backbone of the molecule is folded to minimize steric repulsion. The Boc group features two short intramolecular C—H⋯O contactsThe molecular structure of the title compound, (I)A⋯O17i and N12—H12A⋯O7ii) and one weak accompanying C9—H9A⋯O11i hydrogen bonds  −x + 3, −y, −z + 1]. The sheets are connected to each other by weak C14—H14A⋯O11iii and C19—H19B⋯Br15iii hydrogen bonds and one Br⋯Briv [3.4149 (3) Å] halogen bond  −x + 3, −y + 1, −z + 1].In the crystal, molecules form two strong twin N—H⋯O  of Boc–Gly–ΔAla–OMe was dissolved in 2.5 ml of dichloromethane and cooled to 193 K. Then, bromine 0.027 ml (0.5 mM) was added. The solution was stirred over 10 minutes followed by addition of triethylamine 0.210 ml (1.5 mM). After 15 minutes, the mixture was quenched with 20 ml of saturated aqueous NaHCO3 and warmed to room temperature. The product was extracted by dichloromethane (3 × 15 ml). The organic layer was washed with brine (3 × 10 ml) and dried over anhydrous Na2SO4. Evaporation of the solvent at reduced pressure gave 0.119 g (0.35 mM) of crude product (70% yield). Recrystallization was performed from mixtures of diethyl ether/ethyl acetate(2:1)/hexane solvents, yielding irregular colourless crystals. It is worth noting that in the case of our study, the formation of only the Z isomer was observed while in the preceding paper, the bromination of dehydroalanine-containing compound gave the E isomer. 1H NMR  δ 1.38 , 3.67 , 3.69 , 7.05 , 7.30 , 9.63 . 13C NMR  δ 28.21, 42.79, 52.54, 78.12, 113.26, 132.88, 155.80, 162.63, 168.80. Melting point = 386–388 K.Boc–Gly–ΔAla and its methyl ester were prepared according to the methodology described by Makowski  al. 1985 and Coss al. 2008. The β-bUiso (H) = 1.5Ueq(C); for N atoms, N—H = 0.86 Å and Uiso (H) = 1.2Ueq(C); for secondary C atoms, C—H = 0.97 Å and Uiso (H) = 1.2Ueq(C), with no refinement of their parameters.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S1600536814025677/hb7312sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814025677/hb7312Isup2.hklStructure factors: contains datablock(s) I. DOI: 1035539CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the complex cation, the SbV atom lies on an inversion center and is octahedrally coordinated by four N atoms from a macrocyclic tetraphenylporphyrinate ligand and two chloride ions. The complex cation has approximately a planar core with a maximum deviation of 0.018 (5) Å from the porphyrin mean plane. The average Sb—N distance is 2.062 (11) Å, while the Sb—Cl distance is 2.355 (1) Å. The SbV atom of the anion is also located on an inversion center. The [SbCl6]− octahedron exhibits rhombic distortion characterized by the Sb—Cl bond lengths . In the crystal, the cations and anions are linked C—H⋯ Cl hydrogen bonds, forming a layer parallel to (211).The asymmetric unit of the title compound, [Sb(C Cl2][SbCl6] = 0.065wR(F2) = 0.173S = 1.134749 reflections266 parametersH-atom parameters constrainedmax = 2.55 e Å−3Δρmin = −1.45 e Å−3ΔρCOLLECT  used to solve structure: SIR2004  I, New_Global_Publ_Block. DOI: 10.1107/S1600536814012653/is5356Isup2.hklStructure factors: contains datablock(s) I. DOI: 1006075CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


III ion in the title cationic complex is coordinated by four N atoms from the macrocyclic ligand, one water molecule and one chloride in a cis geometry, displaying a distorted octahedral environment. The crystal packing is stabilized by N—H⋯Cl, O—H⋯Cl and O—H⋯O hydrogen bonds.The Cr cis-[CrCl(cycb)(H2O)][ZnCl4]·3H2O , has been determined from synchrotron data. In the complex cation, the CrIII ion is bound by four N atoms from the tetradentate cycb ligand, a chloride ion and one water molecule in a cis arrangement, displaying a distorted octahedral coordination geometry. The distorted tetrahedral [ZnCl4]2− anion and three additional water molecules remain outside the coordination sphere. The Cr—N(cycb) bond lengths are in the range of 2.0837 (14) to 2.1399 (12) Å while the Cr—Cl and Cr—(OH2) bond lengths are 2.2940 (8) and 2.0082 (13) Å, respectively. The crystal packing is stabilized by hydrogen-bonding interactions between the N—H groups of the macrocyclic ligand, the O—H groups of the water molecules and the Cl atoms of the tetrachloridozincate anion, leading to the formation of a three-dimensional network.The structure of the title compound,  C-meso or racemic-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (cyca and cycb) ligands are known to exist in trans or cis octahedral coordination geometries when combined with two auxiliary ligands (OH2)]ZnCl4·3H2O, (I)Chromium(III) complexes containing III ion with an O1A—Cr1A—Cl1A bond angle of 85.74 (4)°. The rest of the coordination sites are occupied by four nitrogen atoms of the tetradentate macrocyclic cycb ligand, giving rise to a distorted octahedral coordination sphere.In the molecular structure of the complex cation, there is one chlorine atom and one water molecule coordinating the Crb ligand is folded about the N2A—Cr1A—N4A line and is in its most stable cis-V conformation  bond lengths are in the range 2.0837 (14) to 2.1399 (12) Å, in good agreement with those observed in cis-[Cr(OH)2(cycb)]ClO4·2H2O ClO4·H2O Br·H2O Cl ClO4·0.5H2O (NO3)2 Cl (NO3)2 (OH2)](ClO4)2·H2O  and 172.43 (5)°, respectively. The angles N1A—Cr1A—N2A and N3A—Cr1A—N4A are 87.01 (5) and 87.77 (5)°, reflecting the distorted octahedral coordination sphere. The tetrahedral [ZnCl4]2− anion and three additional water molecules remain outside the coordination sphere of CrIII. The complex anion is distorted due to its involvement in hydrogen-bonding interactions. Zn—Cl bonds in the anion span a range from 2.2569 (7) to 2.3131 (8) Å, and the Cl—Zn—Cl angles from 106.02 (4) to 111.49 (3)°.The cycon Fig. 1. The Cr—Extensive hydrogen-bonding interactions occur in the crystal structure Table 1. The supIII complexes involving the macrocyclic rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane ligand. The crystal structures of cis-[Cr(OH)2(cycb)]ClO4·2H2O 2(cycb)]ClO4·H2O (cycb)]Br·H2O 2(cycb)]Cl (cycb)]ClO4·0.5H2O (OH2)](NO3)2 (cyca)(OH2)](ClO4)2·H2O (OH2)]2+ cationic complex with any anion was found, although the preparation of cis-[CrCl(cycb)(OH2)](ClO4)2·0.4HClO4·3H2O has been reported ]Cl·H2O was prepared according to literature procedures ]Cl·H2O (0.07 g) was dissolved in 4 mL of 0.01 M HCl at 353 K and the 1 mL of 6 M HCl containing 0.15 g of solid ZnCl2 were added to this solution. The mixture was refluxed for 30 min and then cooled to room temperature. The resulting solution was filtered and the filtrate was allowed to stand at room temperature for one day to afford purple crystals of compound (I)All chemicals were reagent grade materials and used without further purification. The starting material, Uiso(H) values of 1.2 or 1.5 × Ueq of the parent atoms. The hydrogen atoms of water molecules were located in difference maps restrained with O—H = 0.84 Å using DFIX and DANG commands.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989015015212/wm5196sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015015212/wm5196Isup2.hklStructure factors: contains datablock(s) I. DOI: 1419197CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The structures of two isomeric compounds of isoquinoline with 3-chloro-2-nitrobenzoic acid and 4-chloro-2-nitrobenzoic acid have been determined at 190 K. In each compound, the acid and base molecules are held together by a short hydrogen bond between a carboxy O atom and a base N atom. In the hydrogen-bonded unit of the former, the H atom is disordered over two positions, while in the latter, an acid–base interaction involving H-atom transfer occurs and the H atom is located at the N site. 9H7.3N·C7H3.7ClNO4, (I), and C9H8N·C7H3ClNO4, (II), of isoquinoline with 3-chloro-2-nitrobenzoic acid and 4-chloro-2-nitrobenzoic acid, the two components are linked by a short hydrogen bond between a base N atom and a carboxy O atom. In the hydrogen-bonded unit of (I), the H atom is disordered over two positions with N and O site occupancies of 0.30 (3) and 0.70 (3), respectively, while in (II), an acid–base interaction involving H-atom transfer occurs and the H atom is located at the N site. In the crystal of (I), the acid–base units are connected through C—H⋯O hydrogen bonds into a tape structure along the b-axis direction. Inversion-related adjacent tapes are further linked through π–π interactions [centroid–centroid distances = 3.6389 (7)–3.7501 (7) Å], forming a layer parallel to (001). In the crystal of (II), the acid–base units are connected through C—H⋯O hydrogen bonds into a ladder structure along the a-axis direction. The ladders are further linked by another C—H⋯O hydrogen bond into a layer parallel to (001).In each of the title isomeric compounds, C In the hydrogen-bonded unit, the isoquinoline ring system make dihedral angles of 54.12 (15) and 71.89 (5)°, respectively, with the carboxy group and the benzene ring of the acid. In the acid molecule, the benzene ring makes dihedral angles of 26.59 (15) and 67.69 (15)°, respectively, with the carboxy and nitro groups.The molecular structure of (II)i; Table 1b-axis direction , Cg1⋯Cg2iv = 3.6674 (7), Cg1⋯Cg3iii = 3.6637 (7) and Cg1⋯Cg3iv = 3.6389 (7) Å, where Cg1, Cg2 and Cg3 are the centroids of the C1–C6 benzene ring of the acid, and the N2/C8–C10/C15/C16 rings of the base, respectively. Symmetry codes: (iii) −x, −y + 1, −z + 1; (iv) −x + 1, −y + 1, −z + 1.]In the crystal of (I)on Fig. 3. Adjacenon Fig. 3, formingi and C13—H13⋯O3ii; Table 2a-axis direction on Fig. 5. AdjacenA search of the Cambridge Structural Database Uiso(H) = 1.5Ueq(N or O). The positional parameters were refined with bond restraints of O—H = 0.84 (2) Å and N—H = 0.88 (2) Å. Atom H2 in (II)Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989014026152/lh5740sup1.cifCrystal structure: contains datablock(s) General, I, II. DOI: 10.1107/S2056989014026152/lh5740IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1036583, 1036582CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, the components are linked by N—H⋯Cl, N—H⋯O, O—H⋯Cl and O—H⋯O hydrogen bonds, generating double layers propagating in (100).In the cation of the title hydrated molecular salt, C As long ago as 1887, it was demonstrated -N--5-[amino]-2-hydroxy-4-oxocyclohexa-2,5-dien-1-iminium chloride, 4, which generates the zwitterion 5 when treated with base.In the course of our ongoing studies ] in the form of purple needles. This reaction must proceed via the elusive intermediate 6 which spontaneously hydrolyses. The first hydrolysis product should be intermediate 7. This contains a conjugated iminium salt and a vinylogous amide, which must hydrolyse rapidly, possibly because of the stability of the acidic enol formed. It appears to be a rapid hydrolysis for an amide under mild conditions and so stabilization of a tetrahedral intermediate by the positive iminium salt might occur.By careful oxidation of the tetrahydrochloride salt of amine 6H7N2O2+ cation (r.m.s. deviation for the non-hydrogen atoms = 0.028 Å), a chloride counter-ion and a water molecule of crystallization on Fig. 1. Despitevia the C—N and C—C bonds between them. In terms of the ‘oxygen side’ of the cation, the C6—O2 bond [1.320 (4) Å] is short for a C—O single bond whereas C2—O1 [1.227 (4) Å] is slightly lengthened for a nominal C=O double bond. This in combination with the C1—C2 and C1—C6 bond lengths again implies a degree of delocalization over these five atoms. However, the long C2—C3 and C5—C6 bonds imply little, if any, conjugation between the two delocalized components (O2/C6/C1/C2/O1 and N2/C5/C4/C3/N1) of the cation.The short C3—C4 and C4—C5 bonds correlate with the approximately equal C3—N1 [1.320 (4)] and C5—N2 [1.306 (4) Å] bond lengths, which imply equal delocalization of the positive charge of the cation over atoms N1 and N2, mediated viz. N1—H2n⋯O1 and N2—H4n⋯O2 (Table 1S(5) rings.The cation features two intramolecular N—H⋯O hydrogen bonds, 2 Table 1, which bc-glide symmetry. Each link in the chain comprises two cations and two anions and In the crystal, the components are linked by N—H⋯Cl, N—H⋯O, O—H⋯Cl and O—H⋯O hydrogen bonds Table 1. If the via the intramolecular N1—H2n⋯O1 hydrogen bond).When the cation and water molecule are considered together, an [001] chain also arises Fig. 3. The watw⋯Cl1 hydrogen bond providing the key link between the sheets. Overall, the chloride ion accepts four hydrogen bonds (three N—H⋯Cl and one O—H⋯Cl interactions) in an irregular geometry.When all components are considered together, (100) double sheets result Fig. 4, with thE)-N--5-[amino]-2-hydroxy-4-οxocyclohexa-2,5-dien-1-iminium chloride chloroform monosolvate  and stirred at room temperature for 24 h. The brown mixture was neutralized with NaHCO3 giving a brown or red precipitate, which was then extracted with CH2Cl2 (10 × 50 ml). The yellow extracts were combined, decanted, then stirred with methanol (50 ml) containing five drops of conc. HCl(aq). The yellow solution turned purple. This was evaporated to dryness, then the product was dissolved in methanol (50 ml) to yield a red solution and recrystallized by slow evaporation to leave the title compound  as purple needles: m.p. > 473 K; λmax (ethanol)/nm 503 (log ∊ 2.90) and 325(3.99); ν (diamond anvil)/cm−1 2953br, 1688s, 1547vs, 1401vs, 1310vs, 1251vs, 1141vs, 871vs, 853s, 711vs, 654vs, 579vs, 454s and 420s; m/z (orbitrap ASAP) 139.0498 , C6H7N2O2 requires 139.0502. The UV/visible spectrum of (I)1,2,4,5-Benzenetetraamine tetrahydrochloride  in distilled water (75 ml) was treated with an excess of KUiso(H) = 1.2Ueq(carrier) was applied in all cases. The crystal studied was found to be a twin with the components related by a 180° rotation about [001].Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016005107/sj5497sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016005107/sj5497Isup2.hklStructure factors: contains datablock(s) I. DOI: 1470620CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


A 1:1.4 molar equivalent of benzene-1,3,5-tricarboxylic acid cocrystallized with 4-hydroxypyridine yields the 4-hydroxypyridin-1-ium 3,5-dicarboxybenzoate salt. 5H6NO+·C9H5O6−, (I), shows that 4-hydroxypyridine has abstracted an H atom from benzene-1,3,5-tricarboxylic acid, yielding a pyridinium cation and carboxylate anion. The two ions form an extensive three-dimensional hydrogen-bonded network throughout the crystal. The hydrogen bonds that comprise the core of the network are considered strong, with O—H⋯O and N—H⋯O donor-to-acceptor distances ranging from 2.533 (2) to 2.700 (2) Å. Packing is further enhanced by π-stacking of the cations and anions with like species [centroid–centroid distance = 3.6206 (13) Å].The structure of the title salt, C This result allows for the hydroxy O and pyridine N atom to both act as hydrogen-bond donors, rather than the donor/acceptor situation of the 4-pyridone species. These two molecules have been incorporated as linker species in metal–organic frameworks  shows that the 4-hydroxypyridine has abstracted an H atom from the benzenetricarboxylic acid, yielding a pyridinium cation and a carboxylate anion  and 1.348 (3) Å, respectively]. The remaining bonds within the ring display typical aromatic distances [C2—C3 = 1.405 (3) Å and C3—C4 = 1.402 (3) Å]. The C3—O1 distance of 1.326 (2) Å is typical for a hydroxy O atom bound to an aromatic ring. Bond angles within the pyridine ring are unexceptional.The structure of  Å and C14—O7 = 1.332 (3) Å; C12—O2 = 1.224 (2) Å and C14—O6 = 1.204 (3) Å]. The remaining carboxylate group displays C—O bond distances that are similar to each other and indicate delocalization of the C—O bonds , supporting the proposed single negative charge on the benzenetricarboxylic acid molecule. This is further supported by the presence of H atoms, located in a difference Fourier map, on atoms O3 and O7. Bond distances and angles within the benzene ring are as expected.i [symmetry code: (i) −x + y + z − ii and O2iii, respectively [symmetry codes: (ii) −x, −y, z − x, −y + 1, z + The local intermolecular contacts consist of the pyridinium cation forming a hydrogen bond from the hydroxy group to the anionic carboxylate group  Å, i.e. the c-axis spacing. The centroid-to-perpendicular distances are 3.3629 (9) Å for the cation and 3.4372 (9) Å for the anion. Both measurements are within accepted π–π contact ranges -one  in MeOH (3 ml) in a 20 ml vial was added a solution of 4-hydroxypyridine  in MeOH (3 ml). The mixture was shaken vigorously, covered with perforated Parafilm and allowed to evaporate slowly over a period of 5 d, yielding colorless rod-like crystals.Uiso(H) = 1.2 Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 3x parameter refined to 0.20 (8), which suggests the possibility of a small amount of inversion twinnning  I, New_Global_Publ_Block. DOI: 10.1107/S2056989015011780/pk2555Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015011780/pk2555Isup3.cmlSupporting information file. DOI: 1407819CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Additional π–π interactions between pyridinium rings stabilize this arrangement.In the crystal structure of the title compound, the molecular components,  7H11N2)3[Cr(C2O4)3]·4H2O, the central CrIII ion of the complex anion (point group symmetry 2) is coordinated by six O atoms from three chelating oxalate(2−) ligands in a slightly distorted octahedral coordination sphere. The Cr—O bond lengths vary from 1.9577 (11) to 1.9804 (11) Å, while the chelate O—Cr—O angles range from 82.11 (6) to 93.41 (5)°. The 4-(dimethylamino)pyridinium cations  are protonated at the pyridine N atoms. In the crystal, N—H⋯O and O—H⋯O hydrogen bonds link the cations and anions into a three-dimensional network. π–π interactions between the pyridine rings of adjacent cations provide additional stabilization of the crystal packing, with the closest centroid-to-centroid distances being 3.541 (1) and 3.575 (1) Å.In the title hybrid salt, (C The chelate O—Cr—O angles range from 82.11 (6) to 93.41 (5)°. The Cr—O bond lengths vary from 1.9577 (11) to 1.9804 (11) Å and are similar to those found in the guanidinium trischromate(III) salt pyridinium cations and lattice water molecules Table 1. In addi6(H2O)17[Cr(C2O4)3]4}·7H2O , with an aqueous solution of 4-(dimethylamino)pyridine  and oxalic acid . The mixture was stirred at 333 K for about 30 minutes and then cooled to room temperature and filtered. The title compound crystallized by slow evaporation of the solvent at room temperature in form of light-violet crystals with dimensions up to 3 mm within a few weeks.The title compound was obtained by reaction of an aqueous solution of the freshly prepared barium-oxalatochromate(III) salt {BaUiso(H) = 1.2Ueq(C) for aromatic and 0.96 Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms. H atoms of water molecules as well as those bonded to N atoms were located from a difference Fourier map. Water H atoms were refined with soft restraints on O—H and H⋯H distances [O—H = 0.82 (1) Å and H⋯H = 1.30 (2) Å] and Uiso(H) = 1.5Ueq(O) whereas H atoms bonded to N atoms were refined freely.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989015020113/wm5230sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015020113/wm5230Isup2.hklStructure factors: contains datablock(s) I. DOI: 1400490CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Scientific Reports5: Article number: 17676; 10.1038/srep17676 Published online: 12032015; Updated: 04072016This Article contains an error in Supplementary Figure 1 where the value of the male chemotaxis index towards ascr#9 ‘0.26 ± 0.07’ was incorrectly depicted as ‘0.38 ± 0.07’. The correct Supplementary Figure 1 appears below as


N-[2-(trifluoromethyl)phenyl]benzamides are reported. The 3-fluorobenzamide crystallized with two independent molecules in the asymmetric unit; the dihedral angles between the two benzene rings are 43.94 (8) and 55.66 (7)°. In the 3-bromobenzamide and the 3-iodobenzamide, this dihedral angle is much smaller, viz. 10.40 (12) and 12.5 (2)°, respectively.The crystal structures of three  14H9F4NO, (I), C14H9BrF3NO, (II), and C14H9F3INO, (III), the two benzene rings are inclined to one another by 43.94 (8)° in molecule A and 55.66 (7)° in molecule B of compound (I), which crystallizes with two independent molecules in the asymmetric unit, but by only 10.40 (12)° in compound (II) and 12.5 (2)° in compound (III). In the crystals of all three compounds, N—H⋯O hydrogen bonds link the molecules to form chains propagating along the a-axis direction for (I), and along the b-axis direction for (II) and (III). In the crystal of (I), –A–B–A–B– chains are linked by C—H⋯O hydrogen bonds, forming layers parallel to (010). Within the layers there are weak offset π–π interactions present [intercentroid distances = 3.868 (1) and 3.855 (1) Å]. In the crystals of (II) and (III), the chains are linked via short halogen–halogen contacts [Br⋯Br = 3.6141 (4) Å in (II) and I⋯I = 3.7797 (5) Å in (III)], resulting in the formation of ribbons propagating along the b-axis direction.In the title compounds, C The dihedral angle between the two benzene rings is 43.94 (8)° in molecule A, while in molecule B it is larger, being 55.66 (7)°. The torsion angle of the central –Car—C(=O)—N—Car– segment is 176.74 (12)° in molecule A and −179.58 (12)° in molecule B.The molecular structure of compound (I)am Fig. 2. In both3 substitution on the aniline ring are anti to one another, and the 3-bromo and 3-iodo substituents are anti to the N—H bond in the central –Car—C(=O)—N—Car– segment of the molecules, similar to situation observed in (I)A and B of compound (I)ar—C(=O)—N—Car– segment is −175.5 (2)° in (II)A and B of compound (I)The molecular structures of compounds (II)A–B–A–B– C(4) chains running along the a-axis direction  Å and Cg2⋯Cg3i = 3.8553 (9) Å; Cg1 and Cg3 are the centroids of the aniline rings C1–C6 and C15–C20, respectively; Cg2 and Cg4 are the centroids of the benzoic acid rings C8–C13 and C22–C27, respectively; symmetry code (i) x − 1, y, z]. The crystal structure does not feature any C—H⋯F or F⋯F interactions n Table 1. Neighbos Table 1, formingne Fig. 6. Within ns Fig. 6.C(4) chains running parallel to the b axis  Å], forming ribbons along [010]; see Fig. 7The crystal structure of (II)is Fig. 7. AdjacenC(4) chains running parallel to the b axis (Table 3via short I⋯I contacts [3.7797 (5) Å], forming ribbons along [010]; see Fig. 8The crystal structure of (III)s Table 3. Adjacenmeta position of the benzoic acid ring have a similar effect on the molecular conformations and the supramolecular architectures exhibited by this class of compounds, whereas the fluoro substitution has a very different influence. For instance, there are two molecules in the asymmetric unit of (I)A and B) of (I)From the above observations, it can be concluded that the bromo and iodo substitutions on the et al., 2016viz. N-(2-(trifluoromethyl)phenyl)arylamides, gave four hits. They include N-(2-(trifluoromethyl)phenyl)benzamide, for which there are three reports: JOZFUB and JOZFUB01 in space group P43 phenyl)benzamide —Car– segment is 175.1 (5)°, which is very close to the values observed for the two independent molecules in compound (I)meta position of the benzoyl ring, as in compound (I)A search of the Cambridge Structural Database  were dissolved in phosphorous oxychloride taken in a 250 ml round-bottomed flask. The mixtures were refluxed for an hour and later cooled to 273 K. An equimolar amount of 2-(trifluoromethyl)aniline was added dropwise to these mixtures with continuous stirring. After completion of the addition, the reaction mixtures were brought to room temperature and stirring was continued for 1 h. The reaction mixtures were poured into ice-cold water. The solids that separated were washed thoroughly with water, followed by washing with dilute hydrochloric acid, water, aqueous sodium hydrogen carbonate solution and again with water. The compounds were filtered under suction, dried and recrystallized from aqueous ethanol to constant melting points. Prismatic colourless single crystals of all three compounds were obtained by slow evaporation of solutions in methanol, with a few drops of water.Uiso = 1.2Ueq(C). In the final cycles of refinement of compound (III)R1, wR2, and GOF.Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S2056989016007866/su5298sup1.cifCrystal structure: contains datablock(s) I, II, III, global. DOI: 10.1107/S2056989016007866/su5298Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016007866/su5298IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989016007866/su5298IIIsup4.hklStructure factors: contains datablock(s) III. DOI: Click here for additional data file.10.1107/S2056989016007866/su5298Isup5.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989016007866/su5298IIsup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989016007866/su5298IIIsup7.cmlSupporting information file. DOI: 1479657, 1479656, 1479655CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal of the title compound, a supramolecular sheet structure is formed through N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds. 19H19NO5, the amide carbonyl O atom is positioned anti to the other two carbonyl O atoms. The 4-hydroxyhydrocinnamate fragment is disordered over two positions with an occupancy ratio of 0.729 (12):0.271 (12). The N—(C=O)—C plane of the acetamide group and the acetate O—(C=O)—C plane are almost co-planar; the acetamide plane makes dihedral angles of 1.9 (6) and 16.0 (19)°, respectively, with the acetate planes of the major and minor occupancy components. In the crystal, N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds link the molecules into a supramolecular sheet structure parallel to (102).In the title compound, C The carbonyl O1 and O16 atoms are positioned anti with respect to the carbonyl O12 atom. These C=O bond lengths are in the range 1.176 (12)–1.226 (6) Å.The fragment O1/O12/N10/C2–C9/C11/C13 including the acetamide group is almost planar with an r.m.s. deviation of 0.034 (11) Å. The 4-hydroxyhydrocinnamate fragment is disordered over two positions with occupancy ratio of 0.729 (12):0.271 (12). The acetamide plane O12/N10/C11/C12 makes dihedral angles of 1.9 (6) and 16.0 (19)°, respectively, with the disordered acetate planes O14/O16/C15/C17 and O14via N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds -2-chloroacetamide in the presence of dimethyl formamide (DMF) solvent and triethylamine base  as eluent. The single crystals were obtained from a solvent mixture of ethyl acetate/n-hexane (3:1) upon slow evaporation at room temperature . FTIR νmax cm−1: 3428 (N—H), 3354 (O—H), 2971 (sp2 C—H), 2887 (sp3 C—H), 1735 (C=O ester), 1646 (C=O amide), 1601 (C=C aromatic), 1154 .The title compound was synthesized by direct condensation of 4-hydroxyphenyl propanoic acid with se Fig. 4. The reaA, O25A and C15A–C24A of the minor component were refined isotropically. Planarity restraints were applied for atoms C18–C24, O25, C18A–C24A and O25A. Bond-distance restraints were also applied for C20, C22, C23, O16A and C15A–C24A. H10 and H25 of the NH and OH groups, respectively, were located in a difference Fourier map and the coordinates were refined with Uiso(H) = 1.2Ueq(N) and 1.5Ueq(O) [N—H = 0.86 (5) Å and O—H = 0.95 (12) Å]. H25A of the minor occupancy OH group was refined with a restraint of O—H = 0.90 (2) Å, and with Uiso(H) = 1.5Ueq(O). All other H atoms were included as riding atoms, with C—H = 0.93–0.97 Å and with Uiso(H) = 1.5Ueq(C) for methyl H atoms or 1.2Ueq(C) otherwise.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S205698901600894X/is5453sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901600894X/is5453Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901600894X/is5453Isup3.cmlSupporting information file. DOI: 1483293CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


II cation is chelated by four pyrrole-N atoms of the porphyrinate anion and coordinated by a pyridyl-N atom of the 4-cyanopyridine axial ligand in a distorted square-pyramidal geometry. The non-coordinating 4-cyanopyridine molecule is disordered over two positions in the supramolecular channel formed by complex molecules.In the crystal, the Zn 72H44N4O8)(C6H4N2)]·C6H4N2 or [Zn(TPBP)(4-CNpy]·(4-CNpy) , the ZnII cation is chelated by four pyrrole-N atoms of the porphyrinate anion and coordinated by a pyridyl-N atom of the 4-CNpy axial ligand in a distorted square-pyramidal geometry. The average Zn—N(pyrrole) bond length is 2.060 (6) Å and the Zn—N(4-CNpy) bond length is 2.159 (2) Å. The zinc cation is displaced by 0.319 (1) Å from the N4C20 mean plane of the porphyrinate anion toward the 4-cyanopyridine axial ligand. This porphyrinate macrocycle exhibits major saddle and moderate ruffling and doming deformations. In the crystal, the [Zn(TPBP)(4-CNpy)] complex molecules are linked together via weak C—H⋯N, C—H⋯O and C—H⋯π interactions, forming supramolecular channels parallel to the c axis. The non-coordinating 4-cyanopyridine molecules are located in the channels and linked with the complex molecules, via weak C—H⋯N interactions and π-π stacking or via weak C—H⋯O and C—H⋯π interactions. The non-coordinating 4-cyanopyridine molecule is disordered over two positions with an occupancy ratio of 0.666 (4):0.334 (4).In the title compound, [Zn(C However, only three structures of zinc–4-NCpy non-porphyrinic species [CSD refcodes CYPYZN (4-CNpy)]·(4-CNpy) (I)During the last two decades, renewed attention to zinc metalloporphyrins has been noted for their applications in different fields II cation of the [Zn(TPBP)(4-CNpy)] complex has a distorted square-pyramidal coordination geometry  bond length [2.159 (2) Å] is in the range (2.055–2.248 Å) of those of the zinc–4-CNpy complexes reported in the literature [CSD refcodes LIMWUZ ]  [CSD refcodes ATUSOX . This value is close to those of the related five-coordinated zinc metalloporphyrins [Zn(TPP)(DMSO)]  nearly bisects the ‘cis’ Np—Fe—Np angle, which is also the case for the title zinc–4-CNpy derivative (I)The via weak non-classical C—H⋯N and C—H⋯O hydrogen bonds and by C—H⋯π interactions  Å and 3.457 (4) Å, respectively.Within the crystal structure of (I)s Table 1. The nitc axis  atom C82A of the free 4-NCpy molecule and atom O8 of a TPBP porphyrin [C82A—H82A⋯O8 distance = 3.226 (5) Å], (ii) the centroid (Cg18) of the C80A–C81A–C82A–N8A–C83A–C84A ring of the disordered free 4-CNpy molecule and the carbon atom C49 of an adjacent TPBR porphyrinato ligand with a C49—H49⋯Cg18 contact length of 3.448 (4) Å, (iii) by aromatic π–π interactions between the centroid (Cg19) of the C80A–C81B–C82B–N8B–C83B–C84B ring of a free disordered 4-CNpy molecule and the centroid (Cg11) of the phenyl porphyrin ring C28–C33  and the N8B nitrogen atom of this second 4-CNpy molecule is weakly bonded to the carbon atom C72 of a phenyl ring of a nearby TPBR porphyrinato ligand [C72__H72⋯N8B distance = 3.226 (15) Å] (4-CNpy)] complexes parallel to the is Fig. 4. Each frÅ] Fig. 5.2TPBP) and the starting [Zn(TPBP)] complex were synthesized using modified reported methods  dissolved in 33 mL of dichloromethane was added dropwise and stirred at 273 K and then at room temperature for 12 h. Upon completion, the reaction mixture was filtered and the solvent was evaporated to dryness, to afford 9.3 g of a pale-yellow solid (yield 86%), m.p. = 356–358 K, C14H10O3: C 74.33, H 4.46%; found: C 73.98, H 4.35%. Spectroscopic analysis: 1H NMR  δH (p.p.m.) 10.04 , 8.17 , 8.04 , 7.80 , 7.64 , 7.56 . 13C NMR  δC (p.p.m.) 192.09, 164.12, 155.21, 134.31, 134, 131.13, 129.91, 129.03, 128.47, 122.90.Benzoic acid , 4-hydroxybenzaldehyde  and dimethylaminopyridin DMAP  were dissolved at 273 K in 20 mL of dichloromethane. To this solution, 10.12 g of v/v as an eluent). A purple solid was obtained and dried under vacuum .4.5 mg of 4-formylphenylbenzoate (19.9 mmol) were dissolved in 50 mL of propionic acid. The solution was heated under reflex at 413 K. Freshly distilled pyrrole  was then added dropwise and the mixture was stirred for another 40 min. The mixture was cooled overnight at 277 K and filtered under vacuum. The crude product was purified using column chromatography  δ (p.p.m.) 8.94 , 8.39 , 8.29 , 7.71 , 7.62 , −2.80 . UV/Vis (CHCl3): λmax  420 (512.7), 516 (16.7), 552 (7.4), 591 (4.8), 646 (4.0).Spectroscopic analysis: 2TPBP porphyrin  and [Zn(OAc)2]·2H2O  in CHCl3 (30 mL) and CH3OH (5 mL) was stirred at room temperature overnight. The solvent was evaporated and a light-purple solid of the [Zn(TPBP)] complex was obtained .A mixture of the H1H NMR  δ(p.p.m. ) 9.04 , 8.40 , 8.30 , 7.85 , 7.64 , −2.80 . UV/Vis (CHCl3):λmax  (10−3 ∊) 425 (613.5), 554 (23.0), 596 (6.9).Spectroscopic analysis: To a solution of [Zn(TPBP)]  in dichloromethane (5 mL) was added an excess of 4-cyanopyridine . The reaction mixture was stirred at room temperature for 2 h. Single crystals of the title complex were obtained by diffusion of hexanes through the dichloromethane solution.1H NMR  δ(p.p.m. ) 9.04 , 8.40 , 8.30 , 7.67 , 7.53 . UV/Vis (CHCl3): λmax  425 (613.5), 554 (23.0), 596 (6.9).Spectroscopic analysis: −1 domain using a Perkin–Elmer Spectrum Two FTIR spectrometer. The spectrum presents characteristic IR bands of the TPBP porphyrinato moiety. The C—H stretching frequencies of the porphyrin are in the range 3060–2860 cm−1, the ester group of the meso-substituents of this porphyrin are identified by a strong band at 1736 cm−1, ν(C=O) stretch and by two strong bands at 1264 and 1061 corresponding to the ν(C—O) stretching vibration. The IR spectrum of (I)−1 attributed to the nitrile stretching frequency ν(C N). The value of this band is almost identical to the one of the free 4-cyanopyridine (2236 cm−1) which could be attributed both to the 4-CNpy ligand or the free 4-CNpy molecule in (I)et al., 2000−1 (vw: very weak), 1523 cm−1 (vw), 1505 cm−1(w: weak), 1406 cm−1 (m: medium), 996 cm−1 (s: strong), 707 cm−1 (m), 685 cm−1 (m) and 538 cm−1 (w) attributed to the pyridyl group of the coordinating and the free 4-cyanopyridine species (4-CNpy)]·(4-CNpy) (I)Uiso(H) = 1.2 Ueq(C). The non-coordinating 4-cyanopyridine molecule is disordered over two positions A and B with refined occupancies of 0.666 (4) and 0.334 (4), respectively. The bond lengths and angles of this molecule were restrained to ensure proper geometry using DFIX and DANG instructions of SHELXL2014  I, global. DOI: 10.1107/S2056989016000062/xu5882Isup2.hklStructure factors: contains datablock(s) I. DOI: 1445100CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The central C4N2O2 group of atoms in the dication are almost planar (r.m.s. deviation = 0.009 Å), and the carbonyl groups lie in an anti disposition to enable the formation of intramolecular amide-N—H⋯O(carbonyl) hydrogen bonds. To a first approximation, the pyridinium and amide N atoms lie to the same side of the molecule [Npy—C—C—Namide torsion angle = 34.8 (2)°], and the anti pyridinium rings are approximately perpendicular to the central part of the molecule [dihedral angle = 68.21 (8)°]. In the anion, one carboxylate group is almost coplanar with the ring to which it is connected [Cben—Cben—Cq—O torsion angle = 2.0 (3)°], whereas the other carboxylate and carboxylic acid groups are twisted out of the plane . In the crystal, anions assemble into layers parallel to (10-4) via hydroxy-O—H⋯O(carbonyl) and charge-assisted hydroxy-O—H⋯O(carboxylate) hydrogen bonds. The dications are linked into supramolecular tapes by amide-N—H⋯O(amide) hydrogen bonds, and thread through the voids in the anionic layers, being connected by charge-assisted pyridinium-N—O(carboxylate) hydrogen bonds, so that a three-dimensional architecture ensues. An analysis of the Hirshfeld surface points to the importance of O—H⋯O hydrogen bonding in the crystal structure.The asymmetric unit of the title salt, C N,N′-bis(pyridin-n-ylmethyl)ethanediamides, n = 2, 3 or 4, the molecule with n = 2 appears to have attracted the least attention in co-crystallization studies; for the chemical structure of the diprotonated form of the n = 2 isomer see Scheme 1. By contrast, the n = 3 and 4 molecules have attracted interest from the crystal engineering community in terms of their ability to form co-crystals with iodo-containing species leading to aggregates featuring N⋯I halogen bonding ethanediamide conducted in ethanol. The harvested crystals were shown by crystallography to comprise (2-pyridinium)CH2N(H)C(=O)C(=O)CH2N(H)(2–pyridinium) dications and 3,5-dicarboxybenzoate anions in the ratio 1:2; as the dication is located about a centre of inversion, one anion is found in the asymmetric unit. The confirmation for the transfer of protons during the co-crystallization experiment is found in (i) the pattern of hydrogen-bonding interactions as discussed in Supramolecular features, and (ii) the geometric characteristics of the ions. Thus, the C—N—C angle in the pyridyl ring has expanded by over 3° cf. that found in the only neutral form of N,N′-bis(pyridin-2-ylmethyl)ethanediamide characterized crystallographically in an all-organic molecule, i.e. in a 1:2 co-crystal with 2-aminobenzoic acid  and 1.250 (2) Å is consistent with deprotonation and the formation of a carboxylate group, and contrasts the great disparity in the C15—O4, O5 [1.206 (2) and 1.320 (2) Å] and C16—O6, O7 [1.229 (2) and 1.315 (2) Å] bond lengths.The title salt, Fig. 14N2O2 chromophore is almost planar, having an r.m.s. deviation of 0.009 Å and, from symmetry, the carbonyl groups are anti. An intramolecular amide-N—H⋯O(carbonyl) hydrogen bond is noted, Table 2syn as seen in the value of the N1—C1—C6—N2 torsion angle of 34.8 (2)°. This planarity does not extend to the terminal pyridinium rings which are approximately perpendicular to and lying to either side of the central chromophore, forming dihedral angles of 68.21 (8)°. The central C7—C7i bond length of 1.538 (4) Å is considered long for a C—C bond involving sp2-hybridized atoms  Å, and almost perpendicular in the salt, with N1—C1—C6—N2 being 73.84 (15)°. These differences are highlighted in the overlay diagram shown in Fig. 2In the dication, the central Cet al., 2009et al., 2015et al., 1998i.e. C_IV °, and for one of the carboxylic acid groups, i.e. 22.50 (10)°.In the anion, the C13—C8—C14—O2 and C9—C10—C15—O4 torsion angles of 15.3 (3) and 16.4 (3)°, respectively, indicate twisted conformations between these residues and the ring to which they are attached whereas the C11—C12—C16—O6 torsion angle of 2.0 (3)° shows this carboxylic acid group to be co-planar with the ring. The conformational flexibility in 3,5-dicarboxybenzoate anions is well illustrated in arguably the four most closely related structures in the crystallographic literature  hydrogen bonds to form a familiar eight-membered {⋯HOCO}2 synthon. These are connected by charge-assisted hydroxy-O—H⋯O(carboxylate) hydrogen bonds that form C(8) chains. The result is a network of anions lying parallel to  chains featuring pairs of amide-N—H⋯O(amide) hydrogen bonds and 10-membered {⋯HNC2O}2 synthons, Fig. 3b. The tapes are aligned along the a axis and, in essence, thread through the voids in the anionic layers to form a three-dimensional architecture, Fig. 3c. The links between the anionic layers and cationic tapes are hydrogen bonds of the type charge-assisted pyridinium-N—O(carboxylate). In this scheme, no apparent role for the carbonyl-O4 atom is evident. However, this atoms accepts two C—H⋯O interactions from pyridyl- and methylene-H to consolidate the molecular packing. Additional stabilization is afforded by pyridyl-C—H⋯O interactions, Table 2The molecular packing may be conveniently described in terms of O—H⋯O hydrogen bonding to define an anionic network which is connected into a three-dimensional architecture by N—H⋯O hydrogen bonds; Table 2Crystal Explorer 3.1  region between 1.7 and 2.7 Å. A small but significant contribution to the Hirshfeld surface of the dication due to N⋯O/O⋯N contacts is the result of intermolecular amide-N—H⋯O(amide) interactions.The overall two-dimensional fingerprint plot (FP) of the salt together with those of the dication and anion, and FP’s delineated into H⋯H, O⋯H/H⋯O, C⋯H/H⋯C and C⋯O/O⋯C contacts are illustrated in Fig. 7et al., 2014i.e. 0.8, due to a 23.7% contribution from the 54.5% available Hirshfeld surface and anticipated 29.7% random contacts. The ER value of 1.4 corresponding to O⋯H/H⋯O contacts results from a relatively high 43.2% contribution by O—H⋯O, N—H⋯O and C—H⋯O interactions. The carbon and oxygen atoms involved in the intermolecular C—H⋯O interactions and short inter C⋯O/O⋯C contacts are at distances shorter than the sum of their respective van der Waals radii, hence they also have a high formation propensity, so the ER value is > 1. The C⋯H/H⋯C contacts in the crystal are enriched due to the poor nitrogen content and the presence of short interatomic C⋯H/H⋯C contacts so the ratio is close to unity, i.e. 0.99. Finally, the ER value of 1.68 corresponding to N⋯O/O⋯N contacts for the surface of dication is the result of the charge-assisted N—H⋯O interactions consistent with their high propensity to form.The intermolecular interactions were further analysed using a recently reported descriptor, the enrichment ratio, ER ethanediamide (LH2), has not been as well studied as the n = 3 and 4 isomers. This notwithstanding, the coordination chemistry of LH2 is more advanced and diverse. Thus, co-crystals have been reported with a metal complex, i.e. [Mn3][ClO4]2·(LH2) 2 Pt}22+ ·H2O}n 2(LH2)3}n  chemistry, as in the aforementioned [CuL(LH2)(OH2)]2 , prepared in accord with the literature procedure (Schauer Uiso(H) set to 1.2Ueq(C). The oxygen- and nitrogen-bound H atoms were located in a difference Fourier map but were refined with distance restraints of O—H = 0.84±0.01 Å and N—H = 0.88±0.01 Å, and with Uiso(H) set to 1.5Ueq(O) and 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table 710.1107/S2056989016000980/hb7560sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016000980/hb7560Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016000980/hb7560Isup3.cmlSupporting information file. DOI: 1447965CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Refinement of the site-occupancy factors of the three disordered bromide ions converges with occupancies 0.701 (2), 0.831 (2) and 0.456 (2) summing to approximately two bromide ions per formula unit. The structure was refined as a two-component inversion twin with volume fractions 0.109 (8):0.891 (8) for the two domains. The central C3N unit of the bisamidinium ion is linked to the aliphatic propyl chain by a C—N single bond. The other two bonds in this unit have double-bond character as have the four C—N bonds to the outer NMe2 groups. In contrast, the three C—N bonds to the central N atom of the (dimethylazaniumyl)propyl group have single-bond character. Delocalization of the two positive charges occurs in the N/C/N and C/N/C planes, while the third positive charge is localized on the dimethylammonium group. The crystal structure is stabilized by O—H⋯O, N—H⋯Br, O—H⋯Br and C—H⋯Br hydrogen bonds, forming a three-dimensional network.The asymmetric unit of the title hydrated salt, C N,N,N′,N′-tetramethylchloroformamidinium chloride, see: Tiritiris & Kantlehner (2008N-[3-(dimethylamino)propyl]-N--N′,N′,N′′,N′′-tetramethylguanidinium bis(tetraphenylborate), see: Tiritiris & Kantlehner (2015N′′-[3-(dimethylamino)propyl]-N,N,N′,N′-tetramethylguanidine, see: Tiritiris & Kantlehner  Åb = 12.2932 (7) Åc = 10.6633 (6) Åβ = 97.454 (3)°V = 1190.39 (12) Å3Z = 2Kα radiationMo −1μ = 3.40 mmT = 100 K0.41 × 0.29 × 0.25 mmBruker Kappa APEXII DUO diffractometerTmin = 0.334, Tmax = 0.481Absorption correction: multi-scan 6391 reflections with Rint = 0.033R[F2 > 2σ(F2)] = 0.031wR(F2) = 0.069S = 0.997244 reflections265 parameters1 restraintH atoms treated by a mixture of independent and constrained refinementmax = 0.37 e Å−3Δρmin = −0.23 e Å−3ΔρAbsolute structure: refined as an inversion twinAbsolute structure parameter: 0.109 (8)APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S2056989015024305/sj5490Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015024305/sj5490fig1.tif. DOI: The structure of the title compound with displacement ellipsoids at the 50% probability level. All carbon-bonded hydrogen atoms are omitted for the sake of clarity.Click here for additional data file.10.1107/S2056989015024305/sj5490fig2.tifac . DOI: ac view).N—H⋯Br, O—H⋯Br and O—H⋯O hydrogen bonds (black dashed lines) in the crystal structure of the title compound . The N—H⋯Br, O—H⋯Br, O—H⋯O and C—H⋯Br hydrogen bonds are depicted by black dashed lines.Molecular packing of the title compound (1443022CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Vortioxetine, a new drug used to treat patients with major depressive disorder, has been crystallized as the free base and its methanol monosolvate. In both structures, the vortioxetine molecules have similar conformations. 18H22N2S, (1), systematic name 1-{2-[sulfanyl]phenyl}piperazine, a new drug used to treat patients with major depressive disorder, has been crystallized as the free base and its methanol monosolvate, C18H22N2S·CH3OH, (2). In both structures, the vortioxetine molecules have similar conformations: in (1), the dihedral angle between the aromatic rings is 80.04 (16)° and in (2) it is 84.94 (13)°. The C—S—C bond angle in (1) is 102.76 (14)° and the corresponding angle in (2) is 103.41 (11)°. The piperazine ring adopts a chair conformation with the exocyclic N—C bond in a pseudo-equatorial orientation in both structures. No directional interactions beyond normal van der Waals contacts could be identified in the crystal of (1), whereas in (2), the vortioxetine and methanol molecules are linked by N—H⋯O and O—H⋯N hydrogen bonds, generating [001] chains.Vortioxetine, C Views of the asymmetric units of (1) and (2), with atom labelling, are presented in Figs. 1A⋯O1i [symmetry code: (i) x, −y + z + c-axis direction (Table 1There are no hydrogen bonds or π–π stacking interactions linking the molecules in (1), while in (2) the presence of the additional methanol solvent molecule results in the formation of zigzag chains mediated by alternating O1—H1⋯N2 and N2—H2n Table 1. a packiVortioxetine was supplied by Zhejiang Jingxin Pharmaceutical Co., Ltd. Crystals of (1) and (2) suitable for X-ray diffraction were recrystallized by slow evaporation from acetonitrile and methanol–water solutions, respectively, at room temperature over a few days.Uiso(H) = 1.2Ueq or 1.5Ueq(carrier atom).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989015012256/hb7395sup1.cifCrystal structure: contains datablock(s) 1, 2, global. DOI: 10.1107/S2056989015012256/hb73951sup3.hklStructure factors: contains datablock(s) 1, 2. DOI: 10.1107/S2056989015012256/hb73952sup4.hklStructure factors: contains datablock(s) 2. DOI: Click here for additional data file.10.1107/S2056989015012256/hb73951sup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989015012256/hb73952sup5.cmlSupporting information file. DOI: 1408949, 1408948CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


A and B) in the asymmetric unit, the A and B molecules are linked via pairs of N—H⋯S hydrogen bonds, forming dimers with an via pairs of C—H⋯O hydrogen bonds and C—H⋯π interactions, forming ribbons propagating along [100].In the crystal of the title compound, which crystallized with two independent molecules  in the asymmetric unit. Both molecules have an L-shape but differ in the orientation of the benzyl ring with respect to the 3,4-dimethoxybenzylidine ring, this dihedral angle is 65.59 (8)° in molecule A and 73.10 (8)° in molecule B. In the crystal, the A and B molecules are linked via pairs of N—H⋯S hydrogen bonds, forming dimers with an R22(8) ring motif. The dimers are linked via pairs of C—H⋯O hydrogen bonds, giving inversion dimers of dimers. These units are linked by C—H⋯π interactions, forming ribbons propagating in the [100] direction.The title compound, C S-benzyldithiocarbazate (SBDTC) whose derivatives have shown promising biological activities  in the asymmetric unit. Both molecules have an l-shape but differ in the orientation of the benzyl ring with respect to the 3,4-dimethoxybenzylidine ring, this dihedral angle being 65.59 (8) ° in molecule A and 73.10 (8) ° in molecule B  are 1.331 (2) and 1.282 (2) Å, respectively, in molecule A, and 1.336 (2) and 1.280 (2) Å, respectively, in molecule B. The shorter length of the C—N bond suggests the existence of a double bond which belongs to the imine group. Similarly, the shorter C—S bond length  relative to that of  suggests that the former possesses double-bond character, indicating that the molecule exists in its thione form in the solid state. The functional group identities proposed from these bond lengths are further supported by data obtained from the IR analysis reported below. Furthermore, the bond distances in the title compound are similar to those found for other carbodithioate-derived Schiff bases —C bond lengths (C1—N1 and N2—C9 in A and B) crystallizes in the conformer in which the two aromatic rings of the compound are cis with respect to each other across the C=N bonds, while the thione sulfur atom is trans with respect to the same bond.Both molecules  ring motif -2-benzylidenehydrazine-1-carbodithioates gave 13 hits. One of these concerns a structure very similar to the title compound, namely benzyl (E)-2-(4-methoxybenzylidene)hydrazine-1-carbodithioate ° in molecule A and 73.10 (8)° in molecule B of the title compound.A search of the Cambridge Structural Database . IR : 3360, 3122, 1602, 1069, 1023, 950, 788, 695. LCMS (ESI+): 347.1 [M+H]+.1.98 g (0.01 mol) of Uiso(H) = 1.5Ueq(C) for methyl H atoms and = 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S205698901500095X/su5044sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901500095X/su5044Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901500095X/su5044Isup3.cmlSupporting information file. DOI: 1043887CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


II atom in this one-dimensional coordination polymer, with aqua, 4-formylbenzoate and bridging pyrazine ligands, is located on a twofold rotation axis and has a slightly distorted octahedral coordination sphere. Strong intramolecular O—H⋯O hydrogen bonds link the water molecules to the carboxylate O atoms.The Co 8H5O3)2(C4H4N2)(H2O)2]n, the CoII atom is located on a twofold rotation axis and has a slightly distorted octahedral coordination sphere. In the equatorial plane, it is coordinated by two carboxylate O atoms of two symmetry-related monodentate formylbenzoate anions and by two N atoms of two bridging pyrazine ligands. The latter are bisected by the twofold rotation axis. The axial positions are occupied by two O atoms of the coordinating water molecules. In the formylbenzoate anion, the carboxylate group is twisted away from the attached benzene ring by 7.50 (8)°, while the benzene and pyrazine rings are oriented at a dihedral angle of 64.90 (4)°. The pyrazine ligands bridge the CoII cations, forming linear chains running along the b-axis direction. Strong intramolecular O—H⋯O hydrogen bonds link the water molecules to the carboxylate O atoms. In the crystal, weak O—Hwater⋯Owater hydrogen bonds link adjacent chains into layers parallel to the bc plane. The layers are linked via C—Hpyrazine⋯Oformyl hydrogen bonds, forming a three-dimensional network. There are also weak C—H⋯π interactions present.In the title polymeric compound, [Co(C Atoms N1 and N2 of the pyrazine ligand and Co1 are located on a twofold rotation axis  x, y + 1, z] is 7.1193 (4) Å.The asymmetric unit of the title compound contains a Cois Fig. 1. The pyron Fig. 2. The disIIO4N2 coordination sphere is composed of two carboxylate O atoms  of two symmetry-related monodentate formylbenzoate anions and two N atoms  of two bridging pyrazine ligands, which are bisected by the twofold rotation axis. The axial positions are occupied by two O atoms (O4 and O4i) of the coordinating water molecules.The equatorial plane of the CoA (C2–C7) is 7.50 (8)°, while the benzene and pyrazine rings are oriented at a dihedral angle of 64.90 (4)°.The near equality of the C1—O1 [1.272 (2) Å] and C1—O2 [1.245 (2) Å] bonds in the carboxylate group indicates a delocalized bonding arrangement, rather than localized single and double bonds. The Co—N bond length is 2.165 (9) Å, while the Co—O bond lengths are 2.0551 (9) Å (for benzoate oxygen) and 2.1491 (11) Å (for water oxygen), close to standard values. The Co1 atom is displaced by 0.1034 (2) Å from the mean plane of the carboxylate group (O1/C1/O2). The dihedral angle between the carboxylate group and the adjacent benzene ring water⋯Owater hydrogen bonds  were located in a difference Fourier map and were refined freely. The methine H atom was also located in a difference Fourier map and the C—H distance restrained to 0.984 (13) Å. The aromatic C-bound H atoms were positioned geometrically with C—H = 0.93 Å, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).The experimental details including the crystal data, data collection and refinement are summarized in Table 24·7H2O  in H2O (25 ml) and pyrazine  in H2O (25 ml) with sodium 4-formylbenzoate  in H2O (70 ml) at room temperature. The mixture was filtered and set aside to crystallize at ambient temperature for one week, giving orange single crystals.The title compound was prepared by the reaction of CoSO10.1107/S205698901500403X/wm5129sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901500403X/wm5129Isup2.hklStructure factors: contains datablock(s) I. DOI: 1051344CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Compound (I) was the expected product and compound (II) was the oxidation product from air exposure.The title compounds C 17H14BrNO2, (I), and C17H15NO3, (II), were obtained from the reaction of 6-methoxy-3,4-dihydro-2H-naphthalen-1-one and 2-bromonicotinaldehyde in ethanol. Compound (I) was the expected product and compound (II) was the oxidation product from air exposure. In the crystal structure of compound (I), there are no short contacts or hydrogen bonds. The structure does display π–π interactions between adjacent benzene rings and adjacent pyridyl rings. Compound (II) contains two independent molecules, A and B, in the asymmetric unit; both are non-planar, the dihedral angles between the methoxybenzene and 1H-pyridin-2-one mean planes being 35.07 (9)° in A and 35.28 (9)°in B. In each molecule, the 1H-pyridin-2-one unit participates in intermolecular N—H⋯O hydrogen bonding to another molecule of the same type (A to A or B to B). The structure also displays π–π interactions between the pyridyl and the benzene rings of non-equivalent molecules .The title compounds C Our research strategy to synthesize novel compounds considered analogs of the natural product chalcone, which contains two aromatic rings and an α-β-unsaturated ketone. Chalcones, bioactive defense molecules found in plants and used in traditional Chinese medicine, have demonstrated anticancer, antibacterial, antifungal, and anti-inflammatory properties  and O1B—C1B = 1.257 (3) Å. The molecules are also non-planar, the benzene–pyridyl angle being 36.18 (10)° in A and 35.91 (10)° in B.Compound (I)Cg1i distance is 3.635 (3) Å  and has a ‘face-on’ geometry. There are two π–π interactions in the crystal between adjacent benzene rings, Cg1⋯Cg1ii = 3.944 (4) Å  and between adjacent pyridyl rings, Cg2⋯Cg2iii = 3.639 (4) Å . The π–π interactions form ribbons in the ne Fig. 3, which ane Fig. 3.H-pyridin-2-one unit participates in intermolecular N—H⋯O hydrogen bonding, with a classical A to A or B to B), see Fig. 5A–B or B–A interactions)  and Cg5⋯Cg6ii = 3.857 (4) Å .In each one of the independent molecules in (II)s) Fig. 6; Cg3⋯Cg4et al., 2016et al., 2002et al., 2005et al., 2002A search of the Cambridge Structural Database  and 2-bromonicotinaldehyde (1 mmol) were dissolved in ethanol (5 mL). An NaOH solution  was added and the reaction was stirred until a precipitate formed. The reaction mixture was cooled in an ice bath for 20 minutes. The solids were filtered off and recrystallized from MeOH/H2O. Slow evaporation of a methanolic solution gave dark purple/brown crystals, which proved to be 3-[(E)-methyl]pyridin-2(1H)-one, (II), and lighter purple crystals which proved to be (E)-2-[(2-bromopyridin-3-yl)methylidene]-6-methoxy-3,4-dihydronaphthalen-1(2H)-one, (I).6-Methoxy-3,4-dihydro-2Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016009300/bg2587sup1.cifCrystal structure: contains datablock(s) General, I, II. DOI: 10.1107/S2056989016009300/bg2587Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016009300/bg2587IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1484124, 1484123CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In this model CD8+ T cells mediate biliary ductular damage, whereas CD4+ T cells mediate induction of colon-specific autoimmunity. Importantly, IL-2Rα−/− mice have high levels of interferon γ (IFN-γ), and interleukin-17A (IL-17A). We produced unique double deletions of mice that were either IL-17A−/−IL-2Rα−/− or IFN-γ−/−IL-2Rα−/− to specifically address the precise role of these two cytokines in the natural history of autoimmune cholangitis and colitis. Of note, deletion of IL-17A in IL-2Rα−/− mice led to more severe liver inflammation, but ameliorated colitis. In contrast, there were no significant changes in the immunopathology of double knock-out IFN-γ−/− IL-2Rα−/− mice, compared to single knock-out IL-2Rα−/− mice with respect to cholangitis or colitis. Furthermore, there was a significant increase in pathogenetic CD8+ T cells in the liver of IL-17A−/−IL-2Rα−/− mice. Our data suggest that while IL-17A plays a protective role in autoimmune cholangitis, it has a pro-inflammatory role in inflammatory bowel disease. These data take on particular significance in the potential use of anti-IL-17A therapy in humans with primary biliary cirrhosis.IFN-γ is a signature Th1 cell associated cytokine critical for the inflammatory response in autoimmunity with both pro-inflammatory and potentially protective functions. IL-17A is the hallmark of T helper 17 (Th17) cell subsets, produced by γδT, CD8+ T, NK and NKT cells. We have taken advantage of our colony of IL-2Rα We report herein that deletion of IL-17A in IL-2Rα−/− mice aggravated cholangitis but ameliorated colitis. In contrast, there was no significant effect of the deletion of IFN-γ on the immunopathology of either autoimmune cholangitis or colitis. Importantly, T cells, particularly CD8+ T cells, were significantly increased in IL-17A−/−IL-2Rα−/− mice. Our data suggests that IL-17A plays a protective role in autoimmune cholangitis but a proinflammatory role in colitis in IL-2Rα−/− mice.To examine in specific detail the role of IFN-γ versus IL-17A in autoimmune cholangitis and colitis, we took advantage of IL-17A−/−  and IFN-γ−/− (B6.129S7-IFN-γtm1Ts) mice on a C57B/6J background were initially obtained from the Jackson Laboratory . IL-17A−/− mice were donated by Dr. Yoichiro Iwakura . All genetically modified mice studied herein have been backcrossed to C57BL/6 background for at least 10 generations. IL-2Rα−/− were bred to heterozygosity to these strains. To generate IL-17A−/−IL-2Rα−/− and IFN-γ−/−IL-2Rα−/− mice, IL-17A−/− or IFN-γ−/− mice were mated with IL-2Rα+/− mice to obtain IL-17A+/−IL-2Rα+/− or IFN-γ+/−IL-2Rα+/− mice, which were subsequently backcrossed with IL-17A−/− or IFN-γ−/− mice to obtain IL-17A−/−IL-2Rα+/− or IFN-γ−/−IL-2Rα+/− mice; IL-17A−/−IL-2Rα−/− or IFN-γ−/−IL-2Rα−/− mice were obtained by inter-breeding. The IL-2Rα gene was identified by flow cytometric analysis based on mean fluorescent intensity of CD25. All mice were studied between 12 and 16 weeks of age and animals were individually housed in ventilated cages under the specific pathogen-free conditions. All animal experimental protocols were approved by the Institutional Animal Care and Use Committee of the School of Life Sciences, University of Science and Technology of China, Hefei, China. Animals were anesthetized for blood collection with Xylazine (5 mg/kg)/Ketamine (25 mg/kg) administered subcutaneously. Euthanasia was performed by an overdose of CO2 by inhalation, consistent with the recommendations on the Panel on Euthanasia of the American Veterinary Medical Association. There was no surgery performed and any animals exhibiting discomfort or distress by the veterinary staff were euthanized.IL-2Rα2. Cells were then stained for surface markers using anti-CD4 PerCP/CY5.5, anti-NK1.1 PE/CY7, anti-CD3 Pacific Blue and anti-CD8β FITC (Biolegend), then intracellular stained with anti-IFN-γ PE and anti-IL-17A APC (Biolegend) after fixation and permeabilization with Fixation Buffer and Permeabilization Wash Buffer (Biolegend), Rat IgG1, κ PE and Rat IgG1, κ APC were used as isotype controls for anti-IFN-γ PE and anti-IL-17A APC respectively. Finally, samples were subjected to multiple-color analysis by BD FACSVerse flow cytometer (BD Biosciences). Acquired data were analyzed with FlowJo Software .Lymphocytes from spleen and liver were isolated using 40%/70% percoll  Liver and colon were fixed in 4% paraformaldehyde, embedded in paraffin and cut into 4 and 6 µm sections respectively, then deparaffinized, stained with hematoxylin and eosin (H&E), and evaluated using light microscopy. The quantitation of tissue damage was performed by a “blinded” pathologist. Firstly, the degree of portal inflammation was evaluated and scored according to the most severe lesions as follows: 0, no change; 1, minimal inflammation; 2, mild inflammation; 3, moderate inflammation; 4, severe inflammation. In addition, the degree of inflammatory frequency in a specimen was determined by the percentage of affected tissue within the total hepatic lobules per specimen and coded as follows: 0, none, 1, 1%–10%; 2, 11–20%; 3, 21–50%; 4, more than 50%. Finally, a summary score that includes severity and frequency analysis was generated as the sum of these scores. We note that lobular inflammation was scored in the same fashion as portal inflammation. Second, bile duct damage was evaluated firstly by the degree of severity in the most severe lesions as follows: 0, no change; 1, epithelial damage (only cytoplasmic change); 2, epithelial damage with cytoplasmic and nuclear change; 3, non-suppurative destructive cholangitis (CNSDC); 4, bile duct loss. The frequency of bile duct damage was then scored as follows: 0, none; 1, 1%–10%; 2, 11–20%; 3, 21–50%; 4, more than 50%. To evaluate bile duct loss, bile duct epithelium was highlighted by immunostaining using rabbit anti-keratin wide antibody . To obtain an integrative evaluation, the scores of severity and frequency were added together. Third, colon histopathology was scored as follows: 0, no significant changes; 1, minimal scattered mucosal inflammatory cell infiltrates, with or without minimal epithelial hyperplasia; 2, mild scattered to diffuse inflammatory cell infiltrates, sometimes extending into the submucosa and associated with erosions, with mild to moderate epithelial hyperplasia and mild to moderate mucin depletion from goblet cells; 3, moderate inflammatory cell infiltrates that were sometimes transmural, with moderate to severe epithelial hyperplasia and mucin depletion; and 4, marked inflammatory cell infiltrates that were often transmural and associated with crypt abscesses and occasional ulceration, with marked epithelial hyperplasia, mucin depletion, and loss of intestinal glands −ΔΔCt method Total RNA from liver and colon was extracted with RNeasy Mini Kit , and cDNA synthesized with the PrimeScript RT reagent Kit . Quantitative PCR was performed using a SYBR Premix Ex TaqTM II . Data were collected by an ABI StepOne real-time PCR system . The PCR primers used in this study are listed in The levels of IFN-γ, tumor necrosis factor α (TNF-α), IL-2, IL-4, IL-6 and IL-10 from serum were measured simultaneously with a cytometric bead array kit , using a FACSVerse flow cytometer with CBA software (BD Biosciences).Data are presented as the mean ± standard error. The histological scores of liver inflammation and colitis were compared using one-way analysis of variance (ANOVA) followed by Kruskal-Wallis multiple comparisons. The two-tailed unpaired Mann-Whitney test was used in other comparisons. A value of p<0.05 was considered statistically significant; a value of 0.05<p<0.1 was noted as only a trend.−/− mice. CD8+ T cells from IL-2Rα−/− mice produced a greater quantity of IFN-γ compared to IL-2Rα+/− in liver (P = 0.0159), but almost no IL-17A. In contrast, IL-2Rα−/− CD4+T cells produced more IL-17A than IL-2Rα+/− CD4+ T cells (P = 0.0159), while CD4+T cells also produced some IFN-γ but at levels lower than CD8+T cells (P = 0.0286) (P = 0.0190) and CD8+T cells expressing intracellular IFN-γ (P = 0.0095) comparing IL-2Rα−/− mice to IL-2Rα+/− mice (We determined the cellular source of IL-17A and IFN-γ in IL-2Rα 0.0286) . Similar+/− mice .−/− mice respectively to generate IFN-γ−/−IL-2Rα−/− mice and IL-17A−/−IL-2Rα−/− mice. Histological examination of the liver tissue sections from 12-16-week-old mice demonstrated that IL-17A−/−IL-2Rα−/− mice had more lymphocytes infiltrating around portal tracts compared to IL-2Rα−/− mice (P<0.05), and more severe lobular inflammation (P<0.05). IL-17A−/−IL-2Rα−/− mice also had more severe bile duct damage compared to IL-2Rα−/− mice (P<0.05). In contrast, there was no significant difference between IFN-γ−/−IL-2Rα−/− mice and IL-2Rα−/− mice (−/−IL-2Rα−/− mice compared to IL-2Rα−/− mice (P = 0.0058), but no significant difference between IFN-γ−/−IL-2Rα−/− mice and IL-2Rα−/− mice (P = 0.6720)  . All res−/− mice developed massive enlargement of lymph nodes and spleen −/−IL-2Rα−/− mice. There was also a greater frequency of splenomegaly in IL-17A−/−IL-2Rα−/− mice (8/22) compared to IL-2Rα−/− mice (0/17) and IFN-γ−/−IL-2Rα−/− mice (0/11) (−/−IL-2Rα−/− mice positively correlated with liver mononuclear cells (−/−IL-2Rα−/− compared to IL-2Rα−/− mice (P = 0.0005), due to the remarkable expansion of CD8+T cells (P = 0.0011). There were no differences between IFN-γ−/−IL-2Rα−/− and IL-2Rα−/− mice. The absolute number of total hepatic T cells (P = 0.0524) and CD8+T cells (P = 0.0630) trended toward an increase in total hepatic CD4+T cells (P = 0.0375) in IL-17A−/−IL-2Rα−/− mice compared to IL-2Rα−/− mice, but there were no differences noted in IFN-γ−/−IL-2Rα−/− or IL-2Rα−/− mice (−/−IL-2Rα−/− mice (P = 0.0355). The absolute number of splenic CD8+T cell was also increased in IL-17A−/−IL-2Rα−/− mice compared with IL-2Rα−/− mice (P = 0.0039) (It has been reported that IL-2Rae (0/11) . The splar cells . The per−/− mice . The fre 0.0039) .−/−IL-2Rα−/− and IL-2Rα−/−, but not IL-17A−/−IL-2Rα−/− mice frequently suffered from rectal prolapse and diarrhea. Therefore we examined these strains for colitis. There was no significant difference between IFN-γ−/−IL-2Rα−/− mice and IL-2Rα−/− mice. Colitis, however, was improved in IL-17A−/−IL-2Rα−/− mice compared to IL-2Rα−/− mice (P<0.05), although minimal colitis still occurred in IL-17A−/−IL-2Rα−/− mice (−/−IL-2Rα−/− mice compared to IL-2Rα−/− mice (P = 0.0034), but no significant difference was found in IFN-γ−/−IL-2Rα−/− mice (P = 0.2723) (IFN-γ−/− mice . Colon w 0.2723) .P = 0.0055) , CD4+T cells (P = 0.0185) and CD8+T cells (P = 0.0039) (P = 0.0463) (−/−IL-2Rα−/− mice compared to IL-2Rα−/− mice (P = 0.0050) (Mesenteric lymphocytes were significantly decreased ( 0.0055)  in IL-17 0.0039) . The fre 0.0463)  and the  0.0050) .−/−IL-2Rα−/− mice compared with IL-2Rα−/− mice contained significantly higher levels of IFN-γ (P = 0.0168) and IL-10 (P = 0.0444), but lower levels of IL-6 (P = 0.0221), and no changes in IL-2 (P = 0.3969) or TNF-α (P = 0.6019). Meanwhile serum from IFN-γ−/−IL-2Rα−/− mice compared with IL-2Rα−/− mice contained lower levels of IL-6 (P = 0.0111), and no changes in IL-2 (P = 0.5350), IL-10 (P = 0.4295) and TNF-α (P = 0.2769) , IL-27 (IL-27p28 and Ebi3), IL-6, TNFα and IFN-γ. As shown in P = 0.0012), TNF-α (P = 0.0023) and Ebi3 (P = 0.0012), but decreased the level of IL-6 (P = 0.0379) in the liver. There were no detectable changes of these cytokines in the colon. And after deletion of IFN-γ in IL-2Rα−/− mice there were lower levels of TNF-α (P = 0.0111) and IL-6 (P = 0.0006), but no change in Ebi3 (P = 0.8048) in the liver. In the colon tissue of IL-2Rα−/− mice, the mRNA levels of TNF-α (P = 0.0003) and Ebi3 (P = 0.0002) were decreased, whereas that of IL-6 (P = 0.2345) reflected no change. There was no change of mRNA levels of IL-17 expression in colon and liver after deletion of IFN-γ in IL-2Rα−/− mice (data not shown). We stimulated hepatic mononuclear cells and stained the cells for intracellular cytokines IFN-γ, IL-4 and IL-17F. The frequency of IFN-γ+ cells was significantly increased both in CD4+T (P = 0.0186) cells and CD8+T (P = 0.0759) cells from IL-17A−/−IL-2Rα−/− mice compared to IL-2Rα−/− mice, although there is only a trend toward significance in CD8+T cells (Serum from IL-17A 0.2769) . Further+T cells . Little −/− mice, IL-17A levels appear to peak at 8 weeks to 13 weeks of age and then steadily decline, indicating that IL-17 may be involved in earlier disease development −/− mice, autoimmune cholangitis is more severe. IL-2Rα−/− mice spontaneously develop clinically apparent autoimmune cholangitis at 8 weeks; the appearance of increased IL-17A, at that time, may serve an anti-inflammatory role.IL-17A is mainly produced by Th17 cells, also by γδT cells, CD8+T cells, natural killer (NK) cells and NKT cells. The functions of IL-17 are mediated via binding to IL-17RA and IL-17RC, two isoforms of the IL-17 receptor −/− hosts transferred with IL-17A−/− CD4+ CD45RBhigh T cells show more severe colitis compared to Rag1−/− mice received corresponding wild type CD4+ T cells, accompanying by increased IFN-γ level in colon reg cell–depleted CD4+ CD45RBlow cells into Rag−/− mice could also induce colitis, but with a slower onset than with CD4+ CD45RBhigh T cells. Colitis mediated by CD4+ CD45RBhigh T cells is characterized by increased Th1 cytokines and Treg cell–depleted CD4+ CD45RBlow cells are characterized by an increase in Th17 cytokines −/− mice, the ratio of effector/memory CD4+ T cells significantly increased. Hence, the colitis in IL-2Rα−/− mice may be mediated by CD4+ CD45RBlow T cells. The percentage of memory CD4+T cell in mesenteric lymph nodes decreased in IL-17A−/−IL-2Rα−/− mice compared to IL-2Rα−/− mice, while there was no change in IFN-γ−/−IL-2Rα−/− mice. Previous studies have identified that CD8+T cells mediate intrahepatic damage in IL-2Rα−/− mice. Herein we demonstrate that deletion of IL-17A in IL-2Rα−/− mice is associated with significantly increased intrahepatic CD8+T cells and increased intracellular expression of IFN-γ by CD8+T cells. We examined the IL-7 and IL-15 expression in liver (data not shown), which could promote CD8+T proliferation, but there were no significant differences in mRNA levels for these genes between IL-17A−/−IL-2Rα−/− and IL-2Rα−/− mice. These data take on particular significance in the possible use of cytokine blocking reagents to treat either autoimmune cholangitis or colitis. Our data suggest that IL-17A plays a different role in autoimmune cholangitis and colitis and raises concerns and caution regarding the therapeutic use of anti-IL-17A.The role of IL-17 in IBD is controversial. IL-17A plays a proinflammatory role in acute TNBS (Trinitro-Benzene-Sulfonic Acid)-induced colitis −/− mice develop simultaneous cholangitis and colitis. We also suggest that future work explore treatment of mice with established disease using antibodies against IL-17. Our data would further imply the potential of modulating IL-17A in patients with PBC, but also caution against such usage in inflammatory bowel disease. It is likely that the immunopathology in each of these human diseases will be different during different stages of immunopathology and it seems important that any clinical trials include a rigorous analysis of the patient's immune response, including monitoring cytokines. Finally, we should emphasize that this is the first report of the use of this combination of double knockouts as a model to explore autoimmune cholangitis and inflammatory bowel disease. The data, as with any animal model, should be interpreted with caution before any direct extrapolation to human therapy.IL-17 has pleiotropic effects and the data herein reflect the immunopathology in our unique model. Clearly, further work can potentially explore these relationships between IL-17A and IFN-γ. We emphasize that IL-2Rα


Scientific Reports6: Article number: 19829; 10.1038/srep19829 published online: 01292016; updated: 05202016.This Article contains typographical errors.In the Results section under subheading ‘Quantitative comparison of WNS on bats’,“The fungal load on qPCR-positive bats ranged from 0.21 pg to 3.41 μg across the surface of the left wing ”.should read:“The fungal load on qPCR-positive bats ranged from 0.21 fg to 3.41 ng across the surface of the left wing ”.−5 μg) overlapped that from UV-positive individuals ”.“The fungal load from UV-negative individuals (median = 3.78 × 10should read:−5 ng) overlapped that from UV-positive individuals ”.“The fungal load from UV-negative individuals (median = 3.78 × 102 (log10(ng))’ was incorrectly given as ‘Fungal load per cm2 (log10(μg))’In the upper panel of Figure 4, the y-axis ‘Fungal load per cmP. destructans load per cm2 (log10(ng))’ was incorrectly given as ‘P. destructans load per cm2 (log10(μg))’In the upper panel of Figure 5, the y-axis ‘P. destructans load per cm2 (log10(ng))’ was incorrectly given as ‘P. destructans load per cm2 (log10(μg))’In Figure 6, the x-axis ‘2 (log10(ng))’ was incorrectly given as ‘Fungal load per cm2 (log10(μg))’In Figure 8, the x-axis ‘Fungal load per cmIn the legend of Figure 8,n = 255) and negative  using UV trans-illumination”.“Bats were identified as positive  and negative  using UV trans-illumination”.“Bats were identified as positive (orange; The correct Figures 4, 5, 6 and 8 appear below as


The title molecular salt, obtained by the reaction of sulfamic acid with 2-amino-5-nitropyridine, is the result of a proton transfer from sulfamic acid to the N atom of the pyridine ring. In the crystal, the cations and anions are linked by a number of N—H⋯O and N—H⋯N hydrogen bonds, forming sheets lying parallel to (100). 5H6N3O2+ ·H2NO3S−, was obtained from the reaction of sulfamic acid with 2-amino-5-nitropyridine. A proton transfer from sulfamic acid to the pyridine N atom occurred, resulting in the formation of a salt. As expected, this protonation leads to the widening of the C—N—C angle of the pyridine ring, to 122.9 (3)°, with the pyridinium ring being essentially planar (r.m.s. deviation = 0.025 Å). In the crystal, the ion pairs are joined by three N—H⋯O and one N—H⋯N hydrogen bonds in which the pyridinium N atom and the amino N atom act as donors, and are hydrogen bonded to the carboxylate O atoms and the N atom of the sulfamate anion, thus generating an R33(22) ring motif. These motifs are linked by further N—H⋯O hydrogen bonds enclosing R33(8) loops, forming sheets parallel to (100). The sheets are linked via weak C—H⋯O hydrogen bonds, forming a three-dimensional structure. The O atoms of the nitro group are disordered over two sets of sites with a refined occupancy ratio of 0.737 (19):0.263 (19).The title molecular salt, C Some pyridine derivatives possess non-linear optical (NLO) properties  bond is clearly longer than that in the ring  Å] bond is shorter than the N3—C1 [1.357 (4) Å] and N3—C5 [1.340 (5) Å] bonds, and the C1—C2 [1.411 (5) Å] and C3—C4 [1.402 (6) Å] bonds lengths are significantly longer than bonds C2—C3 [1.348 (5) Å] and C4—C5 [1.338 (6) Å], similar to those observed previously for the aminopyridinium cation (Babu 2 [1.317 (5) Å] and C—NO2 [1.449 (6) Å] distances in the cations are, respectively, shortened and lengthened with respect to the same bond lengths [1.337 (4) and 1.429 (4) Å] observed for 2-amino-nitropyridine , which induces the aggregation of the independent organic cation 2-amino-5-nitropyridinium. This kind of arrangement is also observed in the related structure of 2-amino-5-nitropyridinium hydrogen selenate  hydrogen bonds  and C—N(O2) bond lengths are ca 1.32 and 1.45 Å, respectively. A search for the anion aminosulfamate gave 23 hits but only 17 contained atomic coordinates. Here the S—O bond lengths vary from ca 1.399 to 1.469 Å, while the N—S bond length varies from ca 1.63 to 1.80 Å. The bond lengths and angles in the title salt are very similar to those reported for the various structures in the CSD.A search of the Cambridge Structural Database  = 1.2Ueq(C). The O atoms of the nitro group are disordered over two sets of sites (O1/O1′ and O2/O2′) with a refined occupancy ratio of 0.737 (19):0.263 (19).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989015000365/su5048sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015000365/su5048Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015000365/su5048Isup3.cmlSupporting information file. DOI: 1042506CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Macrocycle A and molecule B both occupy special positions on a twofold rotation axis and the inversion centre, respectively. The supramolecular unit [A•B] is built by the simultaneous coordination of one of the nitrile N atoms of B to the three mercury atoms of the macrocycle A. The Hg⋯N distances range from 2.990 (4) to 3.030 (4) Å and are very close to those observed in the related adducts of the macrocycle A with other nitrile derivatives. The molecule of B is almost perpendicular to the mean plane of the macrocycle A at the dihedral angle of 88.20 (5)°. The donor–acceptor Hg⋯N interactions do not affect the C N bond lengths [1.136 (6) and 1.140 (6) Å]. The trans nitrile group of B coordinates to another macrocycle A, forming an infinite mixed-stack [A•B]∞ architecture toward [101]. The remaining N atoms of two nitrile groups of B are not engaged in any donor–acceptor interactions. In the crystal, the mixed stacks are held together by intermolecular C—F⋯C N secondary interactions [2.846 (5)–2.925 (5) Å].The title compound, [Hg Both macrocycle A and the molecule of B occupy special positions on a twofold rotation axis and inversion centre, respectively. The supramolecular unit of (I) is built by the simultaneous coordination of the nitrile N1 nitrogen atom of B to the three mercury atoms of the macrocycle A –2.99 (1) Å], acrylonitrile [2.87 (1)–2.96 (1) Å] and benzonitrile [2.97 (1)–3.13 (1) Å]  [3.102 (11)–3.134 (11) Å] °. It is very important to point out that the donor–acceptor Hg⋯N interactions do not affect the C N bond lengths [1.136 (6) and 1.140 (6) Å].Complex , F5⋯C12iv 2.846 (5) and F6⋯C11v 2.925 (5) Å; symmetry codes: (iii) −x, y, z; (iv) 1 − x, 1 − y, 1 − z; (v) −x, −y, z]  and (II) are very similar. In both complexes, the guest molecules of tetracyanoethylene B and tetracyanoquinodimethane C are arranged perpendicularly to macrocycle A, with the same coordination mode of the trans nitrile groups to the three mercury atoms  is A•B (a 1:1 ratio), whereas that in (II) is A•C•A (a 2:1 ratio)  includes the additional solvate CS2 (D) molecules. The molecules of D participate in the construction of the supramolecular architecture of (II), resulting in infinite mixed stacks [A•C•A•1.5D]∞  and (II) is equal .It is interesting to note that the crystal structures of  Fig. 4. Beside ∞ Fig. 4. RemarkaI) and (II) being structural analogs, they are substantially different in their chemical stability. The crystalline complex (II) decomposes over a few days, while complex (I) is stable in the solid state for several months under ambient conditions. As free B decomposes rapidly upon reaction with moisture to produce toxic hydrogen cyanide, the high chemical stability of complex (I) is surprising. Moreover, the thermal stability of complex (I) has been studied by thermogravimetric analysis (TGA) which revealed that, upon complexation, tetracyanoethylene is stable to higher temperatures , B is stable up to 393 K. Complex (I) decomposes in two different steps. The first step of a 18.3% weight loss is attributed to molecule B because the much lower decomposition temperature of this molecule compared to macrocycle A. Consequently, the second weight loss of 81.7% is attributed to decomposition of macrocycle A. The complete decomposition of the free B is complete at 445 K; however, its final decomposition temperature is equal to 467 K within the supramolecular complex (I). Final decomposition of complex (I) occurs at 573 K, and is likely due decomposition of macrocycle A.Despite complexes .Trimeric perfluoro-o-phenylene mercury  and tetracyanoethylene  were dissolved in dichloromethane in separate tubes using ultrasonication. The contents of the tubes were mixed carefully, and then left for slow evaporation of the solvents. Complex (I) was obtained as yellow prismatic crystals, m.p. = 499–500 K.Stoichiometric amounts of trimeric perfluoro-−3 near the Hg1 and Hg2 atoms due to considerable absorption effects which could not be completely corrected.Crystal data, data collection and structure refinement details are summarized in Table 110.1107/S2056989015019350/ru2064sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015019350/ru2064Isup2.hklStructure factors: contains datablock(s) I. DOI: 1430883CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


N-(quinolin-6-yl)-2H-chromene-3-carboxamide coumarin derivative displays intramolecular N—H⋯O and weak C—H⋯O hydrogen bonds, which probably contribute to the approximate planarity of the molecule [dihedral angle between the coumarin and quinoline ring systems = 6.08 (6)°]. The supramolecular structures feature C—H⋯O hydrogen bonds and π–π interactions, as confirmed by Hirshfeld surface analyses.The 6-methyl-2-oxo- 20H14N2O3, displays intramolecular N—H⋯O and weak C—H⋯O hydrogen bonds, which probably contribute to the approximate planarity of the molecule [dihedral angle between the coumarin and quinoline ring systems = 6.08 (6)°]. The supramolecular structures feature C—H⋯O hydrogen bonds and π–π interactions, as confirmed by Hirshfeld surface analyses.The title coumarin derivative, C In fact, the molecule is roughly planar, as may be evaluated by the set of values for the dihedral angles which are less than 7° (Table 2The C—N rotamer of the amide group governs the conformation of the molecule: the −p Table 1. Both th° Table 2.i hydrogen bond to form a C(8) chain, which runs parallel to the a axis , molecules are linked by a weak C314—H314⋯O31is Fig. 2. There aet al., 2008Crystal Explorer  plots  is built up by several π–π interactions Table 4. The redng Fig. 4. The molis Fig. 5. The molet al.  = 1.2Ueq(C), and methyl C—H = 0.98 Å, with Uiso(H) = 1.5Ueq(C). The amino H atoms were freely refined. Crystal data, data collection and structure refinement details are summarized in Table 5H atoms were treated as riding atoms, with aromatic C—H = 0.95 Å, with 10.1107/S2056989016011026/hb7596sup1.cifCrystal structure: contains datablock(s) 1, general. DOI: 10.1107/S2056989016011026/hb7596Isup2.hklStructure factors: contains datablock(s) I. DOI: 1491340CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the title compound, the silver atom is coordinated by two 1,3-bisimidazol-2-ylidene ligands, with the imidazole rings inclined to one another by 46.69 (13)°. In the crystal, molecules are linked by trifurcated C—H⋯ hydrogen bonds, forming two-dimensional networks parallel to (010). 27H36N2)2]Cl·C4H8O, the AgI atom is coordinated by two 1,3-bisimidazol-2-ylidene ligands. The imidazole rings are inclined to one another by 46.69 (13)° and the benzene rings in each ligand are almost normal to the imdazole ring to which they are attached, with dihedral angles varying from 82.39 (13) to 88.27 (12)°. There are C—H⋯π interactions present in the cation, involving the two ligands, and the solvent molecule is linked to the cation via a C—H⋯O hydrogen bond. In the crystal, molecules are linked by trifurcated C—H⋯ hydrogen bonds, forming slabs parallel to (101). One isopropyl group is disordered over two sets of sites with an occupancy ratio of 0.447 (17):0.553 (17) and the THF molecule is disordered over two positions with an occupancy ratio of 0.589 (6):0.411 (6).In the title salt, [Ag(C Herein, the crystal structure of one of the two products of this reaction, [Ag(NHC)2]Cl·THF, (I) Recently, we have shown that the pentaphosphenide NaH-imidazol-2-ylidene)silver(I) cations, chloride anions and a THF solvent molecule in a 1:1:1 ratio. The Ag atom is bonded to two C atoms with bond lengths Ag1—C4 = 2.103 (2) and Ag1—C1 = 2.1058 (19) Å. The C1—Ag1—C4 bond angle is almost perfectly linear at 179.36 (7)°. The dihedral angle between the two heterocycles is 46.70 (11)°. The two 2,6-di-isopropylphenyl rings (C11–C16 and C21–C26) are inclined to the imdazole ring (N1/N2/C1–C3) by 86.64 (12) and 88.27 (12)°, respectively. In the second ligand, the two 2,6-di-isopropylphenl rings (C31–C36 and C41–C46) are inclined to the imidazole ring (N3/N4/C4–C6) by 82.39 (13) and 83.41 (13)°, respectively. There are also C—H⋯π interactions present involving the two ligands ; Table 1viz. bissilver(I) tetrachloridogallate(III) (Ia)   and 2.128 and 2.129 Å in (Ib)]. However, while the dihedral angle between the two heterocycles is 46.70 (11)° in the title compound, it is significantly smaller in (Ia) (32.4°) and (Ib) (37.8°).The structures of the same cation but with different anions have been reported, viz. Ag1—C1 = 2.1058 (19) and Ag1—C4 = 2.103 (2) Å.A database search 3] (0.1 mmol) in 1 mL THF was treated with a solution of [Ag(NHC)Cl]  2 mL THF. The reaction mixture was stirred for 18 h at room temperature. After overlaying the THF solution with cyclohexane (6 mL), colourless block-like crystals of the title compound were obtained after 10 days at room temperature (yield: 41%).A solution of NaUiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms. One isopropyl group (atoms C481/C482 and C483/C484) is disordered over two sets of sites with an occupancy ratio of 0.447 (17):0.553 (17) while the THF molecule is disordered over two positions with an occupancy ratio of 0.589 (6):0.411 (6). Symmetry-equivalent bond lengths and angles in the two THF sites were restrained to be equal, distance C73′⋯C75′ was restrained to 2.30 (1) Å, and the displacement parameters of the C atoms were restrained to an isotropic behaviour.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989015007525/su5115sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989015007525/su5115Isup2.hklStructure factors: contains datablock(s) I. DOI: 1060013CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: