The asymmetric unit is composed of a copper(II) tetraacetate paddle-wheel complex, a Cl− anion situated on a twofold rotation axis, half a 1,3-bisimidazolium cation (the whole molecule being generated by twofold rotation symmetry) and one and a half of a dichloromethane solvent molecule (one being located about a twofold rotation axis). The central metal-organic framework comprises of a tetranuclear copper(II) acetate ‘paddle-wheel’ complex which arises from the dimerization of the copper(II) tetraacetate core comprising of three μ2-bidentate acetate and one μ3-tridentate acetate ligands per binuclear paddle-wheel complex. Both CuII atoms of the binuclear component adopt a distorted square-pyramidal coordination geometry (τ = 0.04), with a Cu⋯Cu separation of 2.6016 (2) Å. The apical coordination site of one CuII atom is occupied by an O atom of a neighbouring acetate bridge [Cu—O = 2.200 (2) Å], while that of the second CuII atom is occupied by a bridging chloride ligand [Cu⋯Cl = 2.4364 (4) Å]. The chloride bridge is slightly bent with respect to the Cu⋯Cu internuclear axis [Cu—Cl—Cu = 167.06 (6)°] and the tetranuclear units are located about a twofold rotation axis, forming the one-dimensional polymer that propagates along [101]. Charge neutrality is maintained by the inclusion of the 1,3-bisimidazolium cation within the crystal lattice. In the crystal, the cation and dichloromethane solvent molecules are linked to the coordination polymer by various C—H⋯O and C—H⋯Cl hydrogen bonds. There are no other significant intermolecular interactions present.The title copper(II) complex, {(C For the al. 2005; Bull et al. 2008. For det al. 1964; Zhang e al. 2005; Cotton  al. 2000, and for al. 2003. For exa al. 1973; Ackerma al. 2000. For chl al. 2015. For imi al. 2015. For the al. 1984.27H37N2)[Cu4(C2H3O2)8Cl]·3CH2Cl2 Åb = 13.146 (2) Åc = 23.607 (3) Åβ = 117.122 (4)°V = 6103.5 (13) Å3Z = 4Kα radiationMo −1μ = 1.74 mmT = 100 K0.22 × 0.13 × 0.05 mmBruker SMART CCD area-detector diffractometerSADABS; Bruker, 2001Tmin = 0.700, Tmax = 0.918Absorption correction: multi-scan (26111 measured reflections7274 independent reflectionsI > 2σ(I)5215 reflections with Rint = 0.079R[F2 > 2σ(F2)] = 0.054wR(F2) = 0.098S = 0.987274 reflections348 parametersH-atom parameters constrainedmax = 0.70 e Å−3Δρmin = −0.46 e Å−3ΔρSMART  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S2056989015013675/su5152Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015013675/su5152fig1.tif. DOI: A view of the molecular structure of the asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level.Click here for additional data file.10.1107/S2056989015013675/su5152fig2.tifx y z x y z x y z x y z x y z . DOI: x, y, −z + x + y + z + 1; (c) x + y + z + x, y, −z + x + 1, y, −z + A view of the tetranuclear paddle-wheel unit of the title polymeric compound [symmetry codes: (a) −Click here for additional data file.10.1107/S2056989015013675/su5152fig3.tifb 2 2 . DOI: b axis of the crystal packing of title compound. Colour code: coordination polymer black, organic cation red; CH2Cl2 solvent molecules green and blue.A view along the 999046CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: interactive version of Fig. 1dEnhanced figure:


The O—O bond length of the peroxide is 1.485 (6) Å and the mid-point of this bond is located at the inversion centre of the dimer. The U atom exhibits a distorted hexagonal–bipyramidal coordination geometry with two uranyl(VI) O atoms occupying the axial positions and one O atom of the monodentate nitrate ion, both O atoms of the peroxide ion and the three N atoms of the chelating tridentate 2,2′:6′,2′′-terpyridine (terpy) ligand in the equatorial positions. Two of the N atoms of the terpy ligand lie above and below the mean plane containing the equatorial ligand atoms and the U atom . The dihedral angle between the terpy ligand and the mean plane is 35.61 (7)°. The bond lengths around the U atom decrease in the order U—N > U—Onitrate > U—Operoxo > U=O. The dimeric complexes pack in a three-dimensional network held together by weak π–π interactions [centroid–centroid distance = 3.659 (3) Å] between pyridyl rings of the terpy ligands in neighbouring dimers, together with intermolecular C—H⋯O and C—H⋯π interactions. Weak intramolecular C—H⋯O interactions are also observed.In the title dimeric complex, [{UO For the al. 2001; Goff et al. 2008; John et al. 2004; Sigmon  al. 2009; Takao & al. 2009. For theuwer 2004.2(NO3)2(O2)O4(C15H11N3)2] = 0.030wR(F2) = 0.058S = 0.894695 reflections235 parametersH-atom parameters constrainedmax = 2.24 e Å−3Δρmin = −1.57 e Å−3ΔρAPEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S2056989015007987/cq2015Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015007987/cq2015fig1.tif2 3 15 11 3 2 2 x y z . DOI: 2(NO3)(C15H11N3)}2O2]. Displacement ellipsoids are drawn at the 50% probability level. H atoms are omitted for clarity. Structure of the dimer [{UOClick here for additional data file.10.1107/S2056989015007987/cq2015fig2.tif2 3 15 11 3 2 2 . DOI: 2(NO3)(C15H11N3)}2O2]. Dashed lines and dotted lines are π–π and C—H⋯π interactions, respectively.Packing diagram of [{UO1061056CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


These complexes are relevant to catalysis for CO2 reduction.The structures of two facially coordinated Group VII metal complexes,  fac-[ReCl(C10H8N2O2)(CO)3]·C4H8O (I·THF) and fac-[MnBr(C10H8N2O2)(CO)3]·C4H8O (II·THF), are reported. In both complexes, the metal ion is coordinated by three carbonyl ligands, a halide ligand, and a 6,6′-dihydroxy-2,2′-bipyridine ligand in a distorted octahedral geometry. Both complexes co-crystallize with a non-coordinating tetrahydrofuran (THF) solvent molecule and exhibit intermolecular but not intramolecular hydrogen bonding. In both crystal structures, chains of complexes are formed due to intermolecular hydrogen bonding between a hydroxy group from the 6,6′-dihydroxy-2,2′-bipyridine ligand and the halide ligand from a neighboring complex. The THF molecule is hydrogen bonded to the remaining hydroxy group.The structures of two facially coordinated Group VII metal complexes,  In this paper we report the synthesis and structural characterization of fac-[Re(CO)3Cl] as well as the synthesis and structural characterization of the related and previously unknown complex, fac-[Mn(CO)3Br]. Both complexes co-crystallize with a tetrahydrofuran (THF) solvent molecule.The fac-[Re(CO)3Cl]·THF (I·THF) and [Mn(CO)3Br]·THF (II·THF), respectively. Complexes I and II exhibit distorted octahedral geometries and contain primary coordination spheres similar to those of other fac-[Re(α-diimine)(CO)3Cl] and fac-[Mn(α-diimine)(CO)3Br] complexes, including [Re(bipyridine)(CO)3Cl] (III)    and 18.93 (3)° for the Re and Mn complexes, respectively. Neither I·THF nor II·THF exhibit intramolecular hydrogen bonding.In I, the bipyridine rings present a bite angle of 74.09 (8)° to Re, similar to that found in III [74.41 (9)°] and IV [74.9 (2)°]. The bipyridine–Mn bite angle in II, 78.35 (4)°, is similar to that in V [79.0 (5)°]. The bipyridine ligands are not strictly planar. The dihedral angles between the pyridine rings are 11.68 (9)° in I and 9.49 (5)° in II. Additionally, the bipyridine ligands are not oriented strictly perpendicularly to the coordination planes of the metal ions. The dihedral angles between the mean plane through the α-diimine ligands and the COa axis is formed by an O—H⋯Cl hydrogen bond between a hydroxy group (O16—H16) and the chloride ligand from the neighboring complex. The other hydroxy group (O26—H26) is hydrogen-bonded to the O atom of the THF molecule. The nearest pyridine rings between neighboring complexes have centroid–centroid distances of 3.9448 (16) Å, longer than the maximum distance typically given for π–π interactions  is hydrogen-bonded to O1S of the solvent THF molecule. There are weak π–π stacking interactions between pairs of complexes from neighboring chains. The centroid–centroid distance between pairs of pyridine rings is 3.7019 (9) Å and the angle between the ring normal and the vector between the ring centroids is 9.3°, within the parameters typically given for such π–π interactions 5 and ReCl(CO)5 were purchased commercially and used as received. The ligand 6,6′-dihydroxy-2,2′-bipyridine was synthesized according to the synthetic procedure of Umemoto et al.  were heated at 333 K in 50 mL methanol under nitrogen for five h. The flask was covered with aluminum foil to keep out light. The reaction was then allowed to cool to room temperature and the solvent was removed under vacuum to give a yellow precipitate. Slow cooling of a hot THF solution of the complex in a glove box under a nitrogen atmosphere gave yellow plate-shaped crystals suitable for single crystal X-ray diffraction. Due to limited solubility of the complex in THF, this method could not be used for a bulk recrystallization of the complex.I·THF: 6,6′-dihydroxy-2,2′-bipyridine  and ReCl(CO)5  were heated at 333 K in 24 mL methanol under nitrogen for five h. The flask was covered with aluminum foil to keep out light. The reaction was then allowed to cool to room temperature and the solvent was removed under vacuum to give an orange precipitate. The complex was recrystallized in bulk by layering pentane on a THF solution of the complex in a glove box under a nitrogen atmosphere at room temperature, giving the pure product in near quantitative yield. Slow diffusion of diethyl ether into a THF solution of the complex in a glove box under a nitrogen atmosphere gave yellow rod-shaped crystals suitable for single crystal X-ray diffraction.II·THF: 6,6′-dihydroxy-2,2′-bipyridine  and MnBr(CO)Uiso(H) = 1.5 Ueq(O). C-bound H atoms were placed in calculated positions and refined with riding coordinates, with Uiso(H) = 1.2 Ueq(C). In I·THF, disorder occurs for one carbon and six hydrogens of the THF solvent with occupancies of 0.748 (11) and 0.252 (11). Rigid bond (DELU) and similar ADP (SIMU) restraints were used for atoms O1S, C1S, C2S, C3T, C3S and C4S.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989016011841/is5457sup1.cifCrystal structure: contains datablock(s) Re_complex, Mn_complex, global. DOI: 10.1107/S2056989016011841/is5457Re_complexsup4.hklStructure factors: contains datablock(s) Re_complex. DOI: 10.1107/S2056989016011841/is5457Mn_complexsup5.hklStructure factors: contains datablock(s) Mn_complex. DOI: 1495018, 1495017CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The largest deviation from the ideal octahedral geometry is reflected by the small N—Fe—N bite angle of 76.0 (1)°. The Fe—N coordination bonds have markedly different lengths [2.1361 (17) and 2.243 (2) Å], with the shorter one to the pyrimidine N atom. The four Fe—O coordination bond lengths vary from 2.1191 (18) to 2.1340 (17) Å. In the crystal, the cations and anions are arranged by means of medium-strength O—H⋯O hydrogen bonds into layers parallel to the ab plane. Neighbouring layers further interconnect by N—H⋯O hydrogen bonds involving the imidazole fragment as donor group to one sulfate O atom as an acceptor. The resulting three-dimensional network is consolidated by C—H⋯O, C—H⋯π and π–π interactions.In the title compound, [Fe(C The distorted octahedral environment of the central FeII ion is defined by two N donor atoms of the pyim ligand and by the O atoms of two water molecules in the equatorial plane, while the two remaining water molecules coordinate at the axial sites. The bite angle N1—Fe—N2 of 76.04 (7)° shows the most significant deviation from the ideal octahedral geometry, with the other coordination angles deviating by 0.21 (7) to 11.91 (7)°.Fig. 12O)4]SO4 complex where dmbpy is 5,5′-dimethyl-2,2′-bipyridine °. The dihedral angle of 5.5 (1) ° between the aromatic rings of the pyim ligand is within the range of the values reported for the eight independent molecules in the crystal structure of the non-coordinating ligand SO4 complex, which range from 2.079 (2) to 2.110 (2) Å.The Fe—N coordination bonds with the chelate ligand have markedly different lengths, Fe—N1 = 2.243 (2) and Fe—N2 = 2.1361 (17) Å, which are also dissimilar to those in the previously reported [Fe(dmbpy)(H2O)4]2+ unit is surrounded by five [SO4]2− anions. Similarly to the crystal structure of [Fe(dmbpy)(H2O)4]SO4, pairs of axially and equatorially coordinating water molecules bind to pairs of O acceptor atoms from the same [SO4]2− group, forming eight medium-strength interactions  = −x + y + z; Cg1 is the centroid of the imidazole ring] and weak π–π interactions . C—H⋯O interactions are also observed s Table 1. These hne Fig. 2. Additione Fig. 2. The vicd Table 1.H-imidazole  and potassium tricyanomethanide KC(CN)3  in water-ethanol . The mixture was transferred to a Teflon-lined autoclave and heated at 423 K for 48 h. The autoclave was then allowed to cool to ambient temperature. Block-like yellow crystals of (I)The title compound was obtained under hydrothermal conditions from a mixture of iron(II) sulfate heptahydrate , 2-(pyridin-2-yl)-1Uiso(H) = 1.2Ueq(C). The H atoms attached to O and N atoms were located in a difference Fourier map and were refined isotropically.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989015004417/wm5132sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015004417/wm5132Isup2.hklStructure factors: contains datablock(s) I. DOI: 1051905CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the compound, a succession of MnII ions (situated on inversion centers) adopting a distorted octahedral coordination and bridged by oxalate ligands forms parallel zigzag chains running along the c axis. These chains are interconnected through O—H⋯O hydrogen-bonding interactions to form anionic layers parallel to (010). Individual layers are held together via strong hydrogen bonds involving the guanidinium cations (N—H⋯O and N—H⋯Cl) and the disordered non-coordinating water molecule (O—H⋯O and O—H⋯Cl), as well as by guanidinium π–π stacking. The structural data were confirmed by IR and UV–Visible spectroscopic analysis.As part of our studies on the synthesis and the characterization of oxalate-bridged compounds  A bond-valence-sum calculation, assuming Mn—O and Mn—Cl bonds, gives a BVS value  and IDa = 0.22 (4)%, respectively  Å] and one oxygen atom from the bridging oxalato group [Mn1—O4 = 2.248 (2) Å]. The two oxalato groups are almost perpendicular with a dihedral angle of 89.09 (6)°. The oxalate ion is located on an inversion center that also relates the two Mn atoms bonded to the oxalate ion with each other. The bridged metal ions are nearly coplanar with the oxalate plane with a mean deviation of 0.0147 (8) Å.The equatorial plane of the MnOII ion, as a d5 high-spin system with a spherical electron distribution, has a limited number of commonly observed coordination geometries that are based on minimization of ligand–ligand repulsion. Among the Mn—O distances, the shortest are those involving an oxygen atom from the oxalate ion trans to another oxygen atom from the second oxalate ion. The range of these distances is 2.180 (1) to 2.194 (1) Å, which is in accord with those observed in other oxalate-bridged compounds such as one of the polymorphs of catena-poly[[diaquamanganese(II)]-μ-oxalato-κ4O1,O2:O1′,O2′]  and 2.248 (2) Å.The MnII chains running along the c axis. The intra-chain Mn⋯Mn distances through bridging oxalate are 5.695 (2) and 5.778 (2) Å, somewhat longer than the value of 5.652 Å previously observed for {[Mn(C2O4)(C8H7N3)]·1.5H2O}n  −x + 2, −y + 1, −z], leading to the formation of anionic layers parallel to (010). A disordered non-coordinating water molecule acts as acceptor  x, y − 1, z]. Both disorder components of the non-coordinating water molecules act as hydrogen-bond donors towards oxygen atom O3  −x + 2, −y + 2, −z]. The combined water hydrogen bonds link the anionic layers into a 3D framework.Neighbouring oxalate-bridged zigzag chains are connected with each other s Table 1 towards s Table 1, OW1—HW2or Fig. 3 for the O3 Fig. 3 via the A⋯O2i, N1—H1B⋯O4, N2—H2A⋯Cl1ii, N2—H2B⋯Cl1iii, N2—H2A⋯O4, N3—H3A⋯O1iv and N3—H3B⋯Cl1iii , consolidating the anionic layers and giving additional stability to the three-dimensional structure as illustrated in Fig. 4via π–π stacking with an interplanar distance of 3.547 (3) Å between C3 and C3 −1 assigned to [ν(O—H) + νas(NH2)] and νs(NH2), respectively ], 1312 and 1409 cm−1 [νs(COO)] and 793 cm−1 [δ(COO)]  et al., 2009et al., 1996n→π* transition ·H2O dissolved in 10 cm3 of water in a 1:2:1 molar ratio. The resulting solution was left at room temperature and colourless crystals suitable for X-ray diffraction were obtained after two weeks of slow evaporation.Aqueous solutions of ammonium oxalate and guanidine hydrochloride were added to Mn using adequate HFIX instructions and refined with AFIX instructions. Hydrogen atoms of the coordinating water molecule were found in Fourier difference maps. O—H distances were restrained to a value of 0.85 (1) Å and H⋯H distances were restrained to a value of 1.387 (1) Å.Supramolecular features section and Fig. 3The oxygen atom of the non-coordinating water molecule had unusually high displacement parameters, and was refined as disordered over two alternative mutually exclusive positions. The solvent molecule may be considered as being located vertically between negative-charged anionic layers formed by hydrogen-bonded polymeric chains and located horizontally between positive-charged pairs of guanidinium cations. This pseudo-channel affects its hydrogen-bonding interactions, see the discussion in the first paragraph of the W2 and OW2B which were restrained to have similar geometries. Their hydrogen atoms were located from the Fourier difference maps. The O—H bond lengths were restrained to a value of 0.85 (1) Å and the H⋯H distances were restrained to a value of 1.387 (1) Å. The interatomic distances between the two pairs OW2 and HW5 and OW2B and HW3 were restrained to be equal using a SADI instruction with an effective standard deviation of 0.02. The hydrogen-bonding distance of hydrogen atom HW6 to chlorine atom Cl1 was restrained to 2.80 (1) Å. Subject to these and the above conditions, the occupancy ratio of the disordered non-coordinating water molecule refined to 0.816 (13):0.184 (13).The disordered oxygen atom was refined as disordered over two positions O10.1107/S2056989016006605/zl2659sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016006605/zl2659Isup2.hklStructure factors: contains datablock(s) I. DOI: 1474882CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


O—H⋯O interactions and π–π stacking interactions between the pyridine rings organize the crystal components into columns extending along the b axis while N—H⋯N hydrogen bonds link these columns into a two-dimensional framework parallel to (100).In C 6H6N2O2·H2O, consists of N-hydroxypicolinamide and water molecules connected through O—H⋯O and N—H⋯N hydrogen bonds. The O—H⋯O interactions and π–π stacking interactions between the pyridine rings [centroid–centroid distance = 3.427 (1) Å] organize the components into columns extending along the b axis and the N—H⋯N hydrogen bonds link these columns into a two-dimensional framework parallel to (100). The N-hydroxypicolinamide molecule adopts a strongly flattened conformation and only the O—H group H atom deviates significantly from the molecule best plane. The dihedral angle between the hydroxamic group and the pyridine ring is 5.6 (2)°. The conformation about the hydroxamic group C—N bond is Z and that about the C—C bond between the pyridine and hydroxamic groups is E.The crystal structure of the title compound, C R—C(=O)—NH—OH. HA can exist as keto and imino(enol) tautomers with two isomers, E and Z, for each form, and in the zwitterionic form (see Scheme below). They have found broad application in coordination chemistry due to their diversity and comparatively facile synthesis  are weak organic acids with the general formula N-Hydroxypicolinamide, known also as picoline-2-hydroxamic acid (o-PicHA), has been used extensively for the synthesis of polynuclear complexes, especially in the synthesis of diverse metallacrowns  and 1.325 (2) Å, respectively] and a water molecule. The N-hydroxypicolinamide molecule adopts a strongly flattened conformation and only the O—H group H atom deviates significantly from the molecular best plane. The maximum deviation from this plane for non-hydrogen atom is 0.083 (1) Å for O1 and the hydroxyl group H2 atom is displaced from the mean plane by 0.80 (1) Å in the direction of the water molecule. The dihedral angle between the hydroxamic group and the pyridine ring is 5.6 (2)°. The configuration about the hydroxamic group C—N bond is Z and that about the C—C bond between the pyridine and hydroxamic groups is E .The molecular structure of the title compound is presented in Fig. 1b axis while the N—H⋯N hydrogen bonds link these columns into a two-dimensional framework parallel to (100) .The molecular components of the title compound are connected by O—H⋯O and N—H⋯N hydrogen bonds Table 1 into a tet al., 2007et al., 2001et al., 2008A search of the Cambridge Structural Database  or Uiso = 1.5Ueq(O). The H atoms of the water molecule were located in the difference Fourier maps, the O—H distances standardized to 0.85 Å and refined in riding-model approximation with Uiso(H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989015024706/gk2650sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015024706/gk2650Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015024706/gk2650Isup3.cmlSupporting information file. DOI: 1444026CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the title compound, the carbazole ring system is essentially planar (maximum deviation = 0.025 Å). The crystal packing is stabilized by intermolecular C—H⋯π interactions, forming a three-dimensional supramolecular network. 29H24N2, the C=N bond of the central imine group adopts an E conformation. The dihedral angles between the mean plane of the essentially planar carbazole ring system [r.m.s. deviation = 0.039 (2) Å] and the two phenyl rings of the 3,3-diphenylallylidene unit are 75.9 (1) and 64.6 (1)°. In the crystal, molecules are linked by C—H⋯π interactions, forming a three-dimensional supramolecular network.In the title compound, C It has been reported that carbazole derivatives possess various biological activities, such as antitumor (Itoigawa E conformation. The carbazole ring system (N1/C1–C12) is essentially planar [maximum deviation = 0.039 (2) Å for atom C9]. The phenyl rings C18–C23 and C24–C29 of the  unit are oriented at dihedral angles of 75.9 (1) and 64.6 (1)°, respectively, to the mean plane of the carbazole ring system. The dihedral angle between the two phenyl rings is 76.1 (1)°. The sum of the bond angles around atom N1 (359.7°) of the pyrrole ring is in accordance with sp2 hybridization. The geometric parameters of the title molecule agree well with those reported for similar structures , and a methylene H atom of the ethyl group and a benzene ring of an adjacent molecule (C13—H13A⋯Cg1iii); see Table 1In the crystal, molecules are linked by six intermolecular C—H⋯π interactions, forming a three-dimensional supramolecular network Table 1. Four ofH-carbazol-3-amine (1 mmol), 3,3-diphenylacrylaldehyde (1 mmol) and sulfated SnO2-Bi2O3-fly ash catalyst (20 mg) in water (15 ml) and the mixture was refluxed at 363 K for 1h. On completion of the reaction (monitored by TLC with ethyl acetate and hexane as an eluent 20%) the mixture was cooled to ambient temperature. Dichloromethane (20 ml) was then added to separate the organic and aqueous layers. The organic layer was filtered, dried on anhydrous Na2SO4 and the solvent removed using a rotary evaporator. The crude product obtained was purified by column chromatography on silica gel (200 mesh) with hexane and ethyl acetate (4:1) as eluent, to afford the title compound in good yield (93%). Red crystals suitable for X-ray diffraction analysis were obtained after recrystallization in CH2Cl2.A 25 ml round-bottom flask was charged with 9-ethyl-9Uiso(H) = 1.5Ueq 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/S2056989015005770/su5095sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015005770/su5095Isup2.hklStructure factors: contains datablock(s) I. DOI: 967497CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The hydroxide ion is surrounded by five caesium cations, which form a distorted quadratic pyramidal polyhedron. A three-dimensional network is formed by Cs—Sn [3.8881 (7) Å to 4.5284 (7) Å] and Cs—NH3 [3.276 (7)–3.636 (7) Å] contacts.The title compound, pentacaesium nonastannide hydroxide tetraammonia, crystallized from a solution of CsSnBi in liquid ammonia. The Sn DOI: 10.1107/S1600536814011817/ru2058Isup2.hklStructure factors: contains datablock(s) I. DOI: 1004528CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The asymmetric unit of the title compound contains two crystallographically unique copper complexes. In each complex, the Cu atom is bound to two chloride ligands and to three N atoms of the 2-(4-trifluoromethylbenzylideneamino)ethylamine-bis(2–2aminoethyl)amine ligand to give a distorted square-based pyramidal geometry in which the axial Cu—Cl bond is elongated, indicative of Jahn–Teller distortion. A Cu atom from a symmetry-related molecule is in nearby proximity to the remaining axial Cu site, thus the overall geometry about each Cu atom could be described as being between distorted square-based pyramidal and very elongated Jahn–Teller-distorted octahedral. II atom in the title compound, [CuCl2(C14H21F3N4)], adopts a coordination geometry that is between distorted square-based pyramidal and very Jahn–Teller-elongated octahedral. It is coordinated by three N atoms from the bis(2-aminoethyl)(2-{[4-(trifluoromethyl)benzylidene]amino}ethyl)amine and two chloride ligands. The two crystallographically unique copper complexes present in the asymmetric unit exhibit noticeable differences in the coordination bond lengths. Considering the CuII atoms as having square-pyramidal geometry, the basal Cu—Cl bond lengths are typical [2.2701 (12) and 2.2777 (12) Å], while the apical distances are considerably elongated [2.8505 (12) and 2.9415 (12) Å]. For each molecule, a CuII atom from inversion-related molecules are in nearby proximity to the remaining axial CuII sites, but the Cu⋯Cl distances are very long [3.4056 (12) and 3.1645 (12) Å], attributable to van der Waals contacts. Nonetheless, these contacts appear to have some structure-directing properties, leading to association into dimers. These dimers associate via stacking of the aromatic rings to form extended zigzag chains.The Cu However, an elongated Cu1⋯Cl2i distance of 3.4056 (12) Å is also observed, which can be attributed to a van der Waals contact  direction  Å and a dihedral angle of 10.6 (3)° Fig. 3. Inspecton Fig. 3.i, N3⋯Cl2, N7⋯Cl4; symmetry code: (i) −x + 1, −y + 1, −z] have severely constrained N—H⋯Cl angles and are merely contacts to chlorine atoms bonded to the same CuII atom. The remaining hydrogen-bond contacts are intermolecular interactions, and while relatively long, they likely contribute to structure-directed organization.Inspection of intermolecular/intramolecular contacts reveals that amine nitrogen atoms N2, N3, N6 and N7 are involved in N—H⋯Cl hydrogen-bonds Table 2. HoweverN-2-bis(2-aminoethyl)aminoethyl ligand skeleton  and 2.609 (2) Å ethyl)amine ligand: In a drybox, tris(2-(amino)ethyl)amine  was dissolved in 100 mL methanol in a 250 mL round-bottom flask : δ 2.94 , 3.70 , 7.56 , 8.08 . 13C NMR : δ 55.62, 60.32, 122.85 (q), 125.73 (q), 128.35, 132.44 (q), 139.62, 160.42. FT–IR (solid) v (cm−1): 1321 (s), 1169 (s), 1118 (s), 1062 (s), 834 (s). Melting Point: 344 K. TOF–ESI–MS: (m/z) [M + (H)]+ calculated for C30H28N4F9 = 615.2165, found 615.2194 (4.8 p.p.m.).sk Fig. 4. Ligand Synthesis of 2-(4-trifluoromethylbenzylideneamino)ethyl)amine-bis(2-αminoethyl)amine copper(II) chloride complex:tris(2-(4-Trifluoromethylbenzylideneamino)ethyl)amine  was dissolved in 20 mL methanol in a 100 mL round-bottom flask. CuCl2  was added to the flask to give a teal-colored solution. The reaction was allowed to mix for six h then 20 mL of pentane was slowly added to the solution to generate a teal-colored precipitate. Solvent was removed from the round-bottom flask by connecting it to a rotary evaporator. The precipitate obtained was washed twice by transferring 15 mL of pentane into the flask and stirring vigorously for thirty minutes. Solvent was removed and precipitate dried under vacuum for one h to yield a teal-colored solid . FT–IR (solid): v (cm−1) = 1636 (m), 1506 (s), 1473 (s), 1317 (s), 1163 (s), 1109 (br), 830 (s). UV–Vis (MeOH) λmax = 668 nm. TOF–ESI–MS: (m/z) [M – 2(Cl)]2+ calculated for C30H27N4F9Cu = 677.1383, found 677.1381 (0.2 p.p.m.). Blue single crystal plates suitable for X-ray analysis were obtained by slow diffusion of diethyl ether into a complex solution made in acetonitrile at room temperature. The structure obtained is indicative of hydrolysis occuring on two amine positions of the intended copper(II) complex.Uiso(H) = 1.2Ueq for methylene, aromatic and amide groups with C—H distances set at 0.99 Å (methylene), 0.95 Å (aromatic) and N—H = 0.91 Å.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989015024147/pk2570sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015024147/pk2570Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989015024147/pk2570Isup3.pdfSupporting information file. DOI: 1442779CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


E conformation about the C=N bond and the molecules is planar . In the crystal, the lattice water molecule (Ow) links the molecules via Ow—H⋯O, Ow—H⋯N and N—H⋯Ow hydrogen bonds, forming sheets lying parallel to (100).The title compound, has an  13H10BrN3O2·H2O, the conformation about the azomethine double bond is E. The molecule exists in the amido form with a C=O bond length of 1.229 (2) Å. There is an intramolecular O—H⋯N hydrogen bond forming an S(6) ring motif. The whole molecule is almost planar, with an r.m.s. deviation of 0.021 Å for all non-H atoms, and the dihedral angle between the planes of the pyridine and benzene rings is 0.74 (12)°. In the crystal, the water molecule of crystallization links the organic molecules via Ow—H⋯O, Ow—H⋯N and N—H⋯Ow hydrogen bonds and short C—H⋯Ow contacts, forming sheets lying parallel to (100). Within the sheets there is a weak π–π interaction involving the pyridine and benzene rings [centroid-to-centroid distance = 3.8473 (15) Å]. The sheets are linked via C—H⋯Br interactions, forming a three-dimensional network.In the title compound, C The two aromatic rings (C1–C6 and N3/C9–C13), are inclined to the almost planar hydrazone moiety  by 2.12 (9) and 1.40 (8)°, respectively, and to each other by 0.74 (12)°. There is an intramolecular O—H⋯N hydrogen bond present in the molecule that involves the phenolic oxygen, O1 and the azomethine nitrogen atom, N1, forming an S(6) ring motif nicotinohydrazide. The crystal structure of N′-(2-hydroxybenzylidene)nicotinohydrazide itself is reported as a monohydrate °]. In the crystal structure of N′-(2-hydroxybenzylidene)nicotinohydrazide monohydrate (IDASUB), the water molecule forms three hydrogen bonds and is another example of a system where a single atom acts both as donor and acceptor.A search of the Cambridge Structural Database . Elemental analysis calculated for C13H10N3O2Br·H2O: C, 46.17, H, 3.58, N, 12.43%; found: C, 46.14, H, 3.57, N, 12.44%. IR FT–IR  3059 (NH), 3269(OH), 1680 (C=O), 1584 (C=N).The title compound was prepared by adapting a reported procedure  = 1.2Ueq(C). Three reflections were omitted owing to bad agreement, viz. 100, 110 and 200.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989015009627/su5132sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015009627/su5132Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015009627/su5132Isup3.cmlSupporting information file. DOI: 1401825CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The molecule is planar, with the hydroxy H atom forming an intramolecular O—H⋯N hydrogen bond. In the crystal, molecules form centrosymmetric dimers via two O—H⋯N hydrogen bonds. Thus, the hydroxy H atoms are involved in bifurcated O—H⋯N hydrogen bonds, leading to the formation of a central planar four-membered N2H2 ring. The dimers are bound by intermolecular π–π stacking [the shortest C⋯C distance is 3.2997 (17) Å] and C—H⋯π interactions into a three-dimensional framework. The crystal grown represents a new monoclinic polymorph in the space group P21/n. The molecular structure of the present monoclinic polymorph is very similar to that of the orthorhombic polymorph (space group Fdd2) studied previously . The structures of the two polymorphs are distinguished by the different geometries of the hydrogen-bonded dimers, which in the crystal of the orthorhombic polymorph possess twofold axis symmetry, with the central N2H2 ring adopting a butterfly conformation.In an attempt to grow 8-hydroxyquinoline–acetaminophen co-crystals from equimolar amounts of conformers in a chloroform–ethanol solvent mixture at room temperature, the title compound, C al. 1978. Acta CrSaha 1986. Acta Cr Åb = 9.243 (4) Åc = 11.070 (4) Åβ = 90.718 (6)°V = 677.3 (5) Å3Z = 4Kα radiationMo −1μ = 0.09 mmT = 100 K0.30 × 0.25 × 0.20 mmBruker APEXII CCD diffractometerSADABS; Bruker, 2003Tmin = 0.972, Tmax = 0.981Absorption correction: multi-scan (7049 measured reflections1795 independent reflectionsI > 2σ(I)1494 reflections with Rint = 0.023R[F2 > 2σ(F2)] = 0.039wR(F2) = 0.109S = 1.081795 reflections103 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.39 e Å−3Δρmin = −0.20 e Å−3ΔρAPEX2  used to solve structure: SHELXTL  global, I. DOI: 10.1107/S1600536814016110/rk2430Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814016110/rk2430Isup3.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S1600536814016110/rk2430fig1.tifI . DOI: I. Displacement ellipsoids are presented at the 50% probability level. H atoms are depicted as small spheres of arbitrary radius. The intramolecular O—H⋯N hydrogen bond is drawn by dashed line.Molecular structure of Click here for additional data file.10.1107/S1600536814016110/rk2430fig2.tifI . DOI: I. The hydrogen bonds are drawn by dashed lines.The centrosymmetric H–bonded dimers in the monoclinic polymorph of Click here for additional data file.10.1107/S1600536814016110/rk2430fig3.tifI . DOI: I, in which the molecules are related by the twofold axis. The hydrogen bonds are drawn by dashed lines.The H–bonded dimers in the orthorhombic polymorph of Click here for additional data file.10.1107/S1600536814016110/rk2430fig4.tifI . DOI: I. The hydrogen bonds are drawn by dashed lines.A portion of crystal packing of the H–bonded dimers in the monoclinic polymorph of 1013310CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Scientific Reports5: Article number: 1580110.1038/srep15801; published online: 10302015; updated: 02022016This Article contains errors in Figure 4 and Figure 5.B/f.u.)’ was incorrectly given as ‘M(·B/f.u.)’. In Figure 5, the y-axis ‘−ΔSM (10−3Jule/Kg.K)’ was incorrectly given as ‘−·SM (10−3Jule/Kg.K)’. The correct Figure 4 and Figure 5 appear below as In Figure 4, the y-axis ‘M (μ


The AgI atom adopts a slightly distorted linear coordination geometry. The symmetry-related right- and left-handed helical chains are arranged alternately via Ag⋯Ag and Ag⋯F interactions and π–π stacking interactions, resulting in the formation of a two-dimensional supramolecular network.The reaction of AgBF L]·BF4·0.5CH3OH}n, L = N-(pyridin-4-ylmethyl)pyridine-3-amine, C11H11N3, contains one AgI ion, one ligand L, one tetrafluoridoborate anion disordered over two orientations in a 0.669 (13):0.331 (13) ratio and one half of a methanol solvent molecule situated on an inversion center. Each AgI ion is coordinated by two N atoms from two L ligands in a distorted linear geometry [N—Ag—N = 174.70 (19)°]. Each L ligand bridges two AgI ions, thus forming polymeric helical chains propagating in [010]. In the crystal, Ag⋯Ag [3.3369 (10) Å] and π–π interactions between the aromatic rings [centroid-to-centroid distance = 3.676 (4) Å] link these chains into layers parallel to (10-1). Ag⋯F and weak N(C)—H⋯F interactions further consolidate the crystal packing.The asymmetric unit of the title compound, {[Ag The helical chain propagates along [010] ° with respect to each other. The two pyridine rings in the L ligand are almost perpendicular, the dihedral angle between their mean planes being 89.34 (15)°.The molecular components of the title structure are shown in Fig. 10] Fig. 2 with a p al. 2014. The twoA = 2.84 (2), Ag1⋯F1B = 2.815 (15) and Ag1⋯F4B  = 2.879 (10) Å] and π–π interactions between the pyridine rings of adjacent helical chains [centroid-to-centroid distance = 3.676 (4) Å], resulting in the formation of a two-dimensional supramolecular network parallel to the  Å] and Ag⋯F interactions [Ag1⋯F1ne Fig. 2. Furtherne Fig. 2 between et al.  nitrate and perchlorate complexes of the same ligand have been reported by Zhang  al. 2013. Our groN-(pyridin-4-ylmethyl)pyridine-3-amine ligand was synthesized according to a literature method  = 0.95 Å for Csp2—H, 0.88 Å for amine N—H, 0.84 Å for hydroxyl O—H, 0.98 Å for methyl C—H and 0.99 Å for methylene C—H. For all H atoms Uiso(H) = 1.2–1.5Ueq of the parent atom.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S205698901501837X/cv5498sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S205698901501837X/cv5498Isup2.hklStructure factors: contains datablock(s) I. DOI: 1428966CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The Co—O bond lengths in the [Co(H2O)6]2+ complex cation show very similar distances as in the related Tutton salt (NH4)2[Co(H2O)6)](SO4)2 [average 2.093 (17) Å], but are significantly longer than in the isotypic NiII compound (Δd ≃ 0.04 Å). The cobalt cation reaches an overall bond-valence sum of 1.97 valence units. The S—O distances are nearly equal, ranging from 1.454 (4) to 1.470 (3) Å [mean 1.465 (12) Å]; however, the O—S—O angles vary clearly from 108.1 (2) to 110.2 (2)° [average bond angle 109.5 (9)°]. The non-coordinating water molecules and dimethylammonium cations connect the sulfate tetrahedra and the [Co(H2O)6]2+ octahedron via O—H⋯O and N—H⋯O hydrogen bonds of weak up to medium strength into a three-dimensional framework whereby the complex metal cations and sulfate anions are arranged in sheets parallel to (001).The title salt, (C DOI: 10.1107/S2056989015003400/fk2085Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015003400/fk2085fig1.tifx y z . DOI: x, −y + 1, −z − 1.]The molecular entities in the structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) −Click here for additional data file.10.1107/S2056989015003400/fk2085fig2.tif. DOI: (100)-projection of the crystal structure of the title compound. Colour scheme: S (yellow), Co (red), O (blue), N (orange), C (grey), H (colourless), H⋯O bonds up to 1.8 Å are given as red dashed lines, and from 1.85 to 2.7 Å as light-blue dashed lines.1050102CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


N)bis[bis(pyridin-2-yl-κN)amine]cobalt(III)} sulfate dihydrate is comprised of discrete [Co(dpa)2(N3)2]+ cations, SO42− anions and solvent water molecules in a 2:1:2 ratio; extensive hydrogen-bonding interactions link the species into a three-dimensional supramolecular framework.The crystal structure of bis{bis(azido-κ 10H9N3) as a chelating ligand, led to the synthesis and structure determination of the title compound, [Co(N3)2(dpa)2]2SO4·2H2O. The crystal structure comprises discrete [Co(dpa)2(N3)2]+ cations, sulfate anions, as well as H2O solvent molecules. The CoIII cations display a slightly distorted octahedral coordination sphere defined by two N atoms from azide anions and four N atoms from the pyridyl rings of two dpa ligands. In the crystal, extensive C—H⋯O, N—H⋯O, and O—H⋯O interactions result in supramolecular sheets that lie parallel to the ab plane. The sheets are further linked through O—H⋯N interactions between the water molecules of one sheet and azide anions of another sheet, forming a supramolecular framework.The search for new molecular materials with interesting magnetic properties, using the pseudohalide azide ion and di-2-pyridylamine (dpa, C The sul° Table 1. While t0 Table 1, and the0 Table 1. The twoet al., 2004et al., 2004et al., 2001et al., 2005et al., 20052(N3)2]·2H2O, the two pyridyl rings of each chelating dpa ligand still coordinate to the metal in a cis-disposition, but the azide anions are coordinated trans to each other [CSD refcode: XUYWIX 2]ClO4 +, the Py1cent—N2—Py3cent and N1—Co1—N3 angles are 120.92 (7) and 86.48 (7)°, and the Py4cent—N5—Py5cent and N4—Co1—N6 angles are 125.49 (7) and 88.08 (7)°  (Table 1In [Co(dpa)) Table 1. The C—N) Table 1.III cation 2(N3)2]+ complex cation interacts with one water molecule through a C—H⋯O hydrogen bond (C10—H10⋯O3). The sulfate anions are sandwiched between two symmetry-related layers of complex cations and water molecules 2(N3)2]+ cations through twelve hydrogen bonds . The extensive C—H⋯O, N—H⋯O, and O—H⋯O interactions result in two-dimensional supramolecular sheets parallel to the ab plane , forming a supramolecular framework  are observed between neighboring dpa ligands and azide anions within the coordination sphere of the Con Table 2. The comes Fig. 4. Each suds Fig. 5. As the ne Fig. 5. Finallyrk Fig. 6.cis–trans conformation with an intramolecular C—H⋯N hydrogen bond between the two pyridyl rings ·H2O with M = Mn [CSD refcode: JANPOE 2(N3)2]·2H2O, the azide anions coordinate to the CuII ion weakly in a trans-fashion, resulting in a tetragonally elongated octahedral coordination sphere for the CuII ion, and hydrogen bonding and face-to-face π–π stacking interactions result in two-dimensional supramolecular sheets that lie parallel to the bc-plane [CSD refcode: XUYWIX 2]ClO4 is most closely related to the title complex in that the CoIII ions are coordinated by two chelating dpa ligands and two azide anions in a cis-fashion to form [Co(dpa)2(N3)2]+ complex cations [CSD refcode: HUFNUR  in water–methanol . The mixture was sealed in a Teflon-lined autoclave and heated at 423 K for two days and cooled to room temperature at 10 K h−1. The crystals were obtained in ca 20% yield based on cobalt.The title compound was synthesized hydrothermally under autogenous pressure from a mixture of cobalt(II) sulfate heptahydrate , di-2-pyridylamine  and sodium azide NaNCAUTION! Although not encountered in our experiments, azido compounds of metal ions are potentially explosive. Only a small amount of the materials should be prepared, and it should be handled with care.Uiso(H) = 1.2Ueq(C). The N—H and O—H-atoms were located in difference Fourier maps and then refined as riding on the carrying nitrogen or oxygen atom with Uiso(H) = 1.2Ueq(N) or Uiso(H) = 1.5Ueq(O). Two reflections considered to be affected by beam stop interference, 0 0 2 and 2 0 0, were omitted from the refinement.Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S2056989016003662/zl2656sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016003662/zl2656Isup2.hklStructure factors: contains datablock(s) I. DOI: 1457112CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The amide group of the ACP–AZT anion is disordered (occupancy ratio 0.5:0.5), with one part forming an N—H⋯O (involving C=O⋯H4N+) hydrogen bond and the other an O—H⋯N (involving C—NH2⋯OH2) hydrogen bond with the components of the split NH4+/H2O position. The pseudorotation parameters of ACP–AZT set it apart from previously studied AZT and thymidine. In the crystal, the various components are linked by N—H⋯O, O—H⋯O, N—H⋯N, C—H⋯O and C—H⋯N hydrogen bonds, forming a three-dimensional framework.The asymmetric unit of the title compound, NH Atoms C3′ and C4′ deviate from the plane of atoms C1′/O4′/C2′ by 0.458 and −0.101 Å, respectively. Unlike the AZT molecules and the molecule of thymidine, which exhibit a C3′-exo- class of pucker, the ACP–AZT molecule exhibits a C3′-endo pucker. The orientation of the thymine base relative to the deoxyribose ring in the ACP–AZT molecule is anti, similar to that in natural thymidine and AZT, the glycosyl torsion angle χACP–AZT(O4′—C1′—N1—C2) = −147.75 (16)°. The geometric parameters of the azido residue and the orientation relative to the deoxyribose ring in ACP–AZT and AZT coincide within experimental error.The molecular structure of the title compound, ACP–AZT, is illustrated in Fig. 12 group of ACP–AZT is disordered, one part forming a C=O⋯H4N+ hydrogen bond and the other a C—NH2⋯OH2 hydrogen bond with the components of the NH4+/H2O position NHn Table 1. In the n Table 1, formingon Fig. 2; howeveret al., 1986et al., 1987et al., 1987et al., 1988et al., 1988Earlier, in 1986, we studied the crystal and molecular structures of AZT and then some other HIV replication inhibitors by X-ray analysis  = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms. The other distance restraints and SIMU parameters are given below: DFIX 1.234 0.005 O7A C6′ O7 C6′; DFIX 0.9 N7 H7a N7 H7b; DFIX 0.95 N2S H2Sc N2S H2Sd N2S H2Sa N2S H2Sb O2S H2Sb O2S H2Sa; DFIX 1.325 0.005 N7 C6′ N7A C6′; DFIX 0.9 N7A H7Aa N7A H7Ab; SIMU 0.01 0.005 1.7 N2S O2S; SIMU 0.01 0.005 1.7 N7A O7 O7A N7. The split NH4+/H2O position was refined with an occupancy of 0.5 for each atom.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S1600536814022405/su2792sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814022405/su2792Isup2.hklStructure factors: contains datablock(s) I. DOI: 1028847CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


This induces a geometry quite different than that predicted by theory.In the crystal, molecules pack in a centrosymmetric fashion and interact  14H10Br2O4, the dihedral angle between the aromatic rings is 67.29 (19)°. Both methoxy-group C atoms lie close to the plane of their attached ring [deviations = −0.130 (4) and 0.005 (5) Å]. In the crystal, molecules pack in a centrosymmetric fashion and interact via a mixture of weak π–π stacking interactions [centroid–centoid separations = 4.044 (2) and 4.063 (3) Å], weak C—H⋯O hydrogen bonding, and Br⋯Br halogen bonding. This induces a geometry quite different than that predicted by theory.In the title compound, C This effect is rationalized as a loss of overlap between two π systems. Interrupting conjugation is a prerequisite for the design of unimolecular rectifiers ° in the crystal structure. DFT (B3LYP-DGDZVP) calculations performed on the target molecule in the gas phase predict an angle of −38.54°. This significant discrepancy is probably due to packing interactions in the solid phase.ortho to these positions. Finally, the quinone ring is slightly buckled (r.m.s. deviation = 0.064 Å), probably due to supramolecular packing effects.Substituents on the HBQ system behave as expected. The C—Br bond distances reflect the natures of the electron-deficient quinone and electron-rich dimethoxybenzene rings: the C1—Br1 bond distance is 1.872 (5) Å, while the C10—Br2 bond is 1.897 (4) Å. Thus Br1 has a slightly stronger π-donating character into the quinone moiety, strengthening the bond relative to the C10—Br2 bond of the dimethoxybenzene ring. The methoxy substituents are nearly coplanar to the benzene ring, with a C12—C11—O4—C14 torsion angle of 1.5 (6)° and a C9—C8—O3—C13 torsion angle of −4.4 (5)°. The methyl portions of each of these groups point away from the sterically restricting groups c axis show some face-to-face π-stacking.Each molecule is surrounded by eight neighboring molecules, which interact through hydrogen bonding, halogen bonding, and π–π interactions Figs. 2 and 3 ▸.a axis, the benzene rings ‘nestle’ closely to one another in an antiparallel geometry, where one quinone points up and the layer behind it points down. Within the cb plane, the benzene rings are coplanar; hydrogen atoms from C14 on one molecule project closely to O3 on the adjacent molecule and vice versa for a hydrogen atom attached to C13 to the adjacent O4 . The Br1⋯Br2 separation is 3.4204 (8) Å, with almost linear C1—Br1⋯Br2 and C10—Br2⋯Br1 angles of 178.2 (4) and 170.9 (4)°, respectively. Equivalent rings from molecules packed along this axis are parallel to one another; the quinone and benzene rings aligned coplanar to the corresponding ring in the next molecule.Molecules are aligned linearly in a head-to-tail manner where the bromine atoms participate in Br⋯Br halogen bonding Fig. 3. As disc2O. A solution of 2-bromo-1,4-dimethoxybenzene  in 25 ml of acetonitrile was quickly added with vigorous stirring. After three hours, the product had precipitated as a grey–green powder. The precipitate was filtered, washed with water, and dried. The crude product was purified using flash chromatography , yielding 0.0959 g of the desired product (20.3%). Crystals were obtained by slow evaporation of a solution in chloroform.Cerium(IV) ammonium nitrate  was dissolved in 30 ml of HUiso(H) = 1.5Ueq(C) for methyl H atoms, C—H = 0.95 Å and Uiso(H) = 1.5Ueq(C) for other H atoms]. Hydrogen atoms on methyl groups were refined with a riding rotating model. Crystal data, data collection and structure refinement details are summarized in Table 2Hydrogen atoms were placed in calculated positions, and their coordinates and displacement parameters were constrained to ride on the carrier atom [C—H = 0.98 Å and 10.1107/S2056989015020472/hb7514sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015020472/hb7514Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015020472/hb7514Isup3.cmlSupporting information file. DOI: 1433845CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


A receptors are the main inhibitory neurotransmitter receptors in the brain and are targets for numerous clinically important drugs such as benzodiazepines, anxiolytics and anesthetics. We previously identified novel ligands of the classical benzodiazepine binding pocket in α1β2γ2 GABAA receptors using an experiment-guided virtual screening (EGVS) method. This screen also identified novel ligands for intramembrane low affinity diazepam site(s). In the current study we have further characterized compounds 31 and 132 identified with EGVS as well as 4-O-methylhonokiol. We investigated the site of action of these compounds in α1β2γ2 GABAA receptors expressed in Xenopus laevis oocytes using voltage-clamp electrophysiology combined with a benzodiazepine site antagonist and transmembrane domain mutations. All three compounds act mainly through the two β+/α− subunit transmembrane interfaces of the GABAA receptors. We then used concatenated receptors to dissect the involvement of individual β+/α− interfaces. We further demonstrated that these compounds have anesthetic activity in a small aquatic animal model, Xenopus laevis tadpoles. The newly identified compounds may serve as scaffolds for the development of novel anesthetics.GABA A) receptor. These receptors are composed of five homologous subunits organized around a central Cl− selective channelA receptor have been cloned , integrating experimental data with homology modeling of the GABAin vivo, revealing potencies similar to propofol.Here we describe the actions of two compouds identified by EGVS, 31 and 132A receptors we screened 198 compounds for displacement of the high affinity benzodiazepine site  antagonist [3H]-Ro 15-1788 at receptors expressed in HEK-cells. Many high affinity ligands were identified3H]-Ro 15-1788 from site 1 but potently enhanced GABAA receptor activation. 4-O-methylhonokiol shares these characteristics, potentiating α1β2γ2 receptors with an EC50 of 5.4 ± 1.8 μM, independent of the high affinity site for benzodiazepinesIn an attempt to find novel ligands for the high affinity site for benzodiazepines on GABA1β2γ2 GABAA receptors expressed in Xenopus oocytes. These compounds elicited at the concentration of 3 μM and 30 μM currents amounting to 0.1 ± 0.06%  and 0.3 ± 0.13% , respectively of the maximal current amplitude elicited by GABA in the same oocytes. Thus neither of the compounds tested acts as an appreciable agonist on α1β2γ2 receptors.First, we investigated if compounds 31 and 132 were able to act as agonists. 1β2γ2 receptors. For compound 31, at high concentrations apparent desensitization was observed, that could be partly due to open channel blocker effect. For both compounds no saturation at the highest concentration was obtained, because of poor solubility we could not test higher concentrations.Both compounds strongly enhanced currents elicited by GABA. We established the concentration response curves of this positive allosteric modulation. After two applications of GABA at a concentration eliciting 0.5–1.5% of the maximal current amplitude, the same concentration of GABA was co-applied with increasing concentrations of the tested compounds. 1β2γ2 receptors. Nevertheless, we tested whether 1 μM of the site 1 antagonist Ro 15-1788 inhibits potentiation of GABA currents by compounds 31 or 132. Either compound (3 μM) strongly potentiated currents elicited by GABA. Potentiation by either drug was not inhibited by 1 μM Ro 15-1788 (t test) for compound 31, and 115 ± 14%  for compound 132. This confirms that potentiation by compounds 31 and 132 does not result from action at the benzodiazepine site 1.From the binding data we did not expect that the two compounds are acting through the high affinity benzodiazepine binding site 1 in α 15-1788 . Relativ1β2γ2 receptors, α1S269I, β2N265I and γ2S280I, eliminated the potentiation by high concentrations of diazepam1M, β2M and γ2M. Recently, we described the potency of GABA to activate all of these receptor subtypes expressed in Xenopus oocytes3 receptor3 subunits were renamed α1, β2 and γ2 , and by compound 132 to 118 ± 44% . Modulation in α1β2γ2M receptors by compound 31 was 87 ± 52% , and by compound 132 was 91 ± 21% . In contrast, modulation by both compounds was strongly impaired in α1β2Mγ2 and triply mutated α1Mβ2Mγ2M receptors. Potentiation by 3 μM compound 31 in α1β2Mγ2 was 10.4 ± 8.5% , and in α1Mβ2Mγ2M receptors was 2.3 ± 0.8% . Potentiation by compound 132 relative to that in α1β2γ2 was also dramatically reduced in α1β2Mγ2 7.3 ± 6.8%  and α1Mβ2Mγ2M −0.4 ± 5.1% , respectively.1β2Mγ2 and α1Mβ2Mγ2M receptors, similar to compounds 31 and 132. Relative to wild-type α1β2γ2 receptors, modulation in α1Mβ2γ2 mutated amounted to 63 ± 6% , and in α1β2γ2M receptors to 79 ± 16% . Relative to α1β2γ2, residual potentiation in α1β2Mγ2 receptors amounted to 15.6 ± 1.5% , and to 2.2 ± 0.2%  in α1Mβ2Mγ2M.Potentiation by 1 μM 4-O-methylhonokiol was also significantly reduced only in α1β2γ2 GABAA receptors.The above data suggests that the modulatory site(s) for the three compounds we studied is located in one or both of the β+/α− TMD subunit interfaces on αA receptor contains two β+/α− subunit interfaces. Combined mutation at these interfaces greatly reduces the modulatory effects of compounds 31, 132 and 4-O-methylhonokiol. Using α1-β2-α1 and γ2-β2 subunit concatemers, we studied the effects of individual mutated interfaces. We designated receptors containing the mutant in the γ2-β2 construct interface 1 M, and the mutation in the α1-β2-α1 construct interface 2 M  potentiation for all three compounds was abolished. Relative to α1-β2-α1/γ2-β2 concatenated receptors, in the double mutant α1-β2M-α1/γ2-β2M receptor modulation by compound 31 was reduced to 1 ± 5% , by compound 132 to −2 ± 0.4% , and by 4-O-methylhonokilol to 1 ± 0.6% . In receptors containing only one mutation, either interface 1 or interface 2, modulation by compound 31 was reduced significantly compared to concatenated wild type receptors α1-β2-α1/γ2-β2. With interface 1 M, residual relative potentiation was 28 ± 6%  and with interface 2 M it was 51 ± 3%  of wild-type. Potentiation of interface 1 M and interface 2 M receptors differed significantly . Therefore, both TMD β+/α− sites seem to contribute differently to modulation by compound 31, interface 1 being more efficacious.Wild type concatenated receptors αTukey posthoc test), and in interface 2 M receptors to 39 ± 19% . Again, interface 1 M produced a larger impact than 2 M, although the difference was at the statistical limit . Modulation by 4-O-methylhonokiol in interface 1 M and 2 M receptors was reduced to 11 ± 6%  and 28 ± 8% , respectively. The two mutations produced significantly different effects , with the interface 1 M effect again larger.Likewise, modulation by compound 132 was sensitive to the mutations at both sites. In interface 1 M receptors relative potentiation was reduced to 8 ± 4% , to 125 ± 25% in the mutated receptor . In contrast, this mutation did not significantly reduce potentiation by 3 μM compound 132: 415 ± 126% in wild-type receptors (mean ± SD n = 6) versus 280 ± 36% in the mutated receptor . We have shown earlier that potentiation by 4-O-methylhonokiol in receptors carrying the β2N265S mutation was greatly reduced to about 40%The β1 subunit by different α subunit isoforms: α1β2γ2, α2β2γ2, α3β2γ2, α4β2γ2, α5β2γ2 and α6β2γ2 , α2β2γ2 receptors, 407 ± 172% , α3β2γ2 receptors, 735 ± 234%, , and α4β2γ2 receptors, 412 ± 175% . The α5β2γ2 receptor showed a significant decrease in potentiation compared to α1β2γ2 receptors to 253 ± 92% , and the α6β2γ2 receptor an increase in potentiation, amounting to 780 ± 236% . This discrepancy in modulation of α5β2γ2 and α6β2γ2 receptors maybe explained by the fact that 3 of the first 7 residues of M1 located at the minus side of the α subunit are different  in α2β2γ2 receptors, 652 ± 215%  in α3β2γ2 receptors, 476 ± 152%  in α4β2γ2 receptors, 399 ± 147%  in α5β2γ2 receptors, and 542 ± 175%  in α2β2γ2 receptor type. These results indicate that although the type of α subunit has differential effects on potentiation between compounds 31 and 132, these compounds modulate all receptor subtypes studied.From the above experiments we inferred that the β+/α− TMD subunit interfaces mediate potentiation of compounds 31 and 132. We also wanted to know if potentiation by these compounds depends on subunit isoforms. First we replaced the αd α6β2γ2 . Compounifferent . Compoun2 by β1 or β3. For compounds 31 and 132, α1β3γ2 receptors showed a similar potentiation as α1β2γ2 receptors. Amounting to 381 ± 115% for compound 31 and 555 ± 169% for compound 132 . In the case of α1β1γ2 receptors, potentiation by both compounds was significantly reduced compared to that in α1β2γ2, 41 ± 13% for compound 31 and 37 ± 7% for compound 132 . These results indicate that the type of β subunit is important for the potentiation by both compounds. It is interesting to note in this context that β1 and β2/β3 differ not only in the residue 265, but also in the fourth residue of M3 predicted to be close to the latter residue . Compound 132 also showed a similar potentiation between both receptors, potentiation in α1β2 receptors amounting to 625 ± 219% . When the γ2 subunit was replaced by a δ subunit, in the case of α1β2δ receptors, potentiation was affected only in the case of compound 31, where a significant reduction was observed relative to α1β2γ2 receptors. Where potentiation amounted to 168 ± 48%  for compound 31, and 640 ± 275%  for compound 132. In α4β3δ receptors, potentiation by both compounds was statistically reduced relative to α4β3γ2 receptors. For compound 31 potentiation amounted to 345 ± 77%  in α4β3γ2 receptors, and was reduced to 125 ± 22%  in α4β3δ receptors. Potentiation of compound 132 in α4β3γ2 receptors was 728 ± 203% , and was reduced to 214 ± 71%  in α4β3δ receptors.When the γ5 and α6 subunits. The type of β subunit was also important, as the presence of the β1 subunit strongly reduced potentiation by this compound. On the contrary, the presence of a γ or a δ subunit did not affect potentiation.Previous workXenopus tadpoles, 50 of 2.7 μM , while the EC50 compound 132 was 1.2 μM , and 4-O-methylhonokiol EC50 = 1.0 μM . For comparison, the EC50 for propofol-induced LoRR in tadpoles is 1.3 μMThe anesthetic activity for compounds 31, 132 and 4-O-methylhonokiol was determined as loss of righting reflex (LoRR) in 1β2γ2 GABAA receptors that do not act at site 1. We suspected that they instead act through the low affinity TMD site(s) for benzodiazepines (site 3). Indeed, potentiation by compounds 31, 132 and 4-O-methylhonokiol was abolished in the triple mutant receptor α1S269Iβ2N265Iγ2S280I as well as by the single mutation β2N265I, but unaffected by the homologous mutations α1S269I and γ2S280I. Assuming that these TM2 mutations alter drug actions through local steric effects in adjacent TMD interfacial sites, our results indicate that of the five such sites, only the two β+/α− interfaces 1 and 2 mediate the potentiating effects of these three compounds.Here we functionally characterized compounds 31, 132 and further investigated the properties of 4-O-methylhonokiol. All three compounds are potent allosteric potentiators of αWe further dissected the contribution of the individual β+/α- subunit interfaces using concatenated subunit assemblies. The γβ+/α−β interface (interface 1) and αβ+/α−γ interface (2) participated differently in modulation by the three compounds studied. For all compounds the contribution of the interface 1 to drug modulation is apparently greater than that of the interface 2.1β2γ2 receptors, β2N265I reduced potentiation by all compounds, α1S269I reduced potentiation exclusively by pentobarbital, and the γ2S280I mutation increased potentiation by etomidate, while reducing potentiation by propofol and pentobarbital23243342We and others have shown that the intravenous anesthetics etomidate, propofol and pentobarbital also act via TMD interfacial sites262728292M286W) and different concatenated subunit assemblies suggest that etomidate interactions are equivalent in the two β+/α− sites of α1β2γ2 receptorsWork by our group using receptor concatenation determined that both β+/α− subunit interfaces participated equally in modulation by propofol. In contrast, modulation by etomidate was found to be more affected by the γβ+/α−β interface site (interface 1) than the αβ+/α−γ site (interface 2)2N265 in β1 and β3 are serine and asparagine, respectively, and this single residue dramatically influences sensitivity to loreclezole262829391β1γ2 receptors, compared to α1β2γ2 receptors. Potentiation by 4-O-methylhonokiol is also reduced by the β2N265S mutation or substitution of β1 for β2The homologs of β4 and α6 subunits, contrasting with benzodiazepine site 1 agonists. Both compounds also potentiated receptors carrying the δ subunit, although to different degrees. Thus, these compounds not only acted at receptors shown to be located synaptically as α1β2–3γ2, α2β2γ2 and α3β2γ25β2γ2 receptors and receptors containing the δ subunit, which are all located extra-synaptically546In subunit specificity studies, compounds 31 and 132 potentiated receptors containing the αXenopus laevis tadpoles with EC50s comparable to the anesthetics propofolThe similarities between the three compounds we studied and the clinical anesthetics propofol, etomidate and pentobarbital suggested their possible use as sedative-hypnotics in animals. Indeed, all three compounds induced reversible loss of righting reflexes (LoRR) in A receptors at molecular sites different from the classical benzodiazepine pocket. These compounds, together with 4-O-methylhonokiol, act through β+/α− TMD interfaces, with strongest effects through the interface 1. These compounds potently produced LoRR in aquatic animals and thus may be useful lead compounds in the search for novel anesthetic, sedative-hypnotic or anxiolytic drugs.In summary, the newly identified compounds 31 and 132 modulate both synaptic and extrasynaptic GABA1S269I, β2N265I, β2N265S and γ2S280I were prepared using the QuikChangeTM mutagenesis kit .The point mutations α2-β2, and triple construct α1-β2-α1 has been described previously2N265 to I was done in the tandem construct and the triple construct using the QuikChangeTM mutagenesis kit .Construction of tandem and triple subunit cDNAs. The tandem construct γCapped cRNAs were synthesized  from the linearized plasmids with a cytomegalovirus promotor (pCMV vectors) containing the different subunits, respectively. A poly-A tail of about 400 residues was added to each transcript using yeast poly-A polymerase . The concentration of the cRNA was quantified on a formaldehyde gel using Radiant Red stain (Bio-Rad) for visualization of the RNA. Known concentrations of RNA ladder (Invitrogen) were loaded as standard on the same gel. cRNAs were precipitated in ethanol/isoamylalcohol 19:1, the dried pellet dissolved in water and stored at −80 °C. cRNA mixtures were prepared from these stock solutions and stored at −80 °C.1, β2 and γ2 subunits of the GABAA receptors at a concentration of 10 nM:10 nM:50 nMAnimal experiments were carried out in strict accordance to the Swiss ethical guidelines, and have been approved by the local committee of the Canton Bern Kantonstierarzt, Kantonaler Veterinärdienst Bern (BE85/15). Surgery was done under anesthesia, and all efforts were made to diminish animal suffering. Xenopus laevis oocytes were prepared, injected and defolliculated as described previously492, 1 mM CaCl2, and 5 mM Na-HEPES (pH 7.4). Concentration response curves for the compounds were fitted with the equation I(c) = Imax/[1 + (EC50/c)n], where c is the concentration of the compound, EC50 the concentration eliciting half-maximal current amplitude, Imax is the maximal current amplitude, I the current amplitude, and n is the Hill coefficient. Maximal current amplitudes (Imax) were obtained from the fits of the concentration-response curves. For all receptors studied, modulation was measured at a GABA concentration eliciting 0.5–1.5% of the maximal GABA current amplitude. GABA was applied twice alone for 20–60 s, and then in combination with the different compounds for 45 s or 1 min. The duration of washout periods was 4 min in between agonist or agonist/drug aplications to prevent receptor desentization. At the beginning of the experiments, GABA applications were repeated when the elicited current amplitude altered by >5%. Potentiation was calculated by the following equation: (IModulator + GABA/IGABA − 1) * 100%. The perfusion solution was applied through a glass capillary with an inner diameter of 1.35 mm, the mouth of which was placed about 0.4 mm from the surface of the oocyte. This allowed fast changes in agonist concentration around the oocyte. The rate of change was estimated 70% in less than 0.5 sCurrents were measured using a modified two-electrode voltage clamp amplifier Oocyte clamp OC-725 (Warner Instruments) in combination with a XY-recorder (90% response time 0.1 s) or digitized at 100 Hz using a PowerLab 2/20 (AD Instruments) using the computer programs Chart . Tests with a model oocyte were performed to ensure linearity in the larger current range. The response was linear up to 15 μA. The holding potential was −80 mV. The perfusion medium contained 90 mM NaCl, 1 mM KCl, 1 mM MgClt test was used to compare two means. One-way analysis of variance (ANOVA) was used for multiple comparisons followed by a Tukey post hoc test. *p < 0.05; **p < 0.01; ***p < 0.001.All data are from at least two different batches of oocytes. Data represent mean ± SD. An unpaired Xenopus laevis tadpoles as previously described415250 − Log[Drug])*HillSlope)) using Graphpad Prism 6. Results are reported as EC50s and 95% confidence intervals.Animals were used and experiments were carried out with approval and according to the guidelines of the MGH Institutional Animal Care and Use Committee. General anesthetic potency was assessed in How to cite this article: Maldifassi, M. C. et al. Novel positive allosteric modulators of GABAA receptors with anesthetic activity. Sci. Rep.6, 25943; doi: 10.1038/srep25943 (2016).


The molecule is arranged around a center of symmetry with half the crown ether molecule and one molecule of acetonitrile symmetry independent. All O—C—C—O torsion angles are gauche while all C—O—C—C angles are trans. The sequence of torsion angles is [(+ttg)(−ttg)]3; the geometry of oxygen atoms is close to pseudo-Dd3 with three atoms below and three atoms above the mean plane, with an average deviation of ±0.16 (1) Å from the mean plane. This geometry is identical to that observed in metal ion complexes of dicyclohexane-18-crown-6 but differs significantly from the conformation of a free unsolvated molecule. Each acetonitrile molecule connects to a crown ether molecule via two of its methyl group H atoms (C—H⋯O). Weaker interactions exist between the third H atom of the acetonitrile methyl group and an O atom of a neighbouring crown ether molecule (C—H⋯O); and between the N atom of the acetonitrile molecule and a H atom of another neighbouring crown ether molecule. All these intermolecular interactions create a three-dimensional network stabilizing the disolvate.The title compound (systematic name:  Åb = 9.5286 (5) Åc = 9.8927 (6) Åα = 80.415 (2)°β = 81.697 (2)°γ = 80.927 (2)°V = 632.53 (6) Å3Z = 1Kα radiationMo −1μ = 0.09 mmT = 173 K0.49 × 0.34 × 0.28 mmBruker PHOTON-100 CMOS diffractometerSADABS; Bruker, 2014Tmin = 0.956, Tmax = 1.000Absorption correction: multi-scan (20203 measured reflections3045 independent reflectionsI > 2σ(I)2476 reflections with Rint = 0.031R[F2 > 2σ(F2)] = 0.041wR(F2) = 0.104S = 1.073045 reflections229 parametersAll H-atom parameters refinedmax = 0.29 e Å−3Δρmin = −0.19 e Å−3ΔρAPEX2  used to solve structure: SHELXT  I. DOI: 10.1107/S2056989015011056/zl2627Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015011056/zl2627Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989015011056/zl2627Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989015011056/zl2627fig1.tifx z . DOI: x, 1 − y, 1 − z).Structure of the title compound with atom labeling. The second half of the crown ether molecule and the second acetonitrile molecule molecule are created by an inversion center located at the center of the crown ether molecule (symmetry operator: 1 − Click here for additional data file.10.1107/S2056989015011056/zl2627fig2.tif. DOI: Intermolecular short contacts of acetonitrile molecules with neighboring crown ether molecules.1405283CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The coordinating water molecule is located on a twofold rotation axis while the L2− anion sits about an inversion center. The L2− anions bridge the CuII cations, forming polymeric chains propagating along the [101] direction. In the crystal, O—H⋯O, N—H⋯O hydrogen bonds and weak C—H⋯π interaction link the polymeric chains and the solvent water molecules into a three-dimensional supramolecular architecture.In the title polymeric complex, {[Cu(C DOI: 10.1107/S205698901500626X/xu5844Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901500626X/xu5844fig1.tifx y z x y z . DOI: x, y, −z + x + y + z + 1]The molecular structure of (I), a drawing of the asymmetric unit (multi-colored portion) with displacement ellipsoids at the 30% probability level. [symmetry code: (i) 1 − Click here for additional data file.10.1107/S205698901500626X/xu5844fig2.tif. DOI: The polymeric chain of (I).1056415CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The geometry around the cationic PdII centre is distorted square planar, chelated by the imine N- and phenolate O-donor atoms of the two Schiff base ligands. The N- and O-donor atoms of the two ligands are mutually trans, with Pd—N and Pd—O bond lengths of 2.028 (2) and 1.9770 (18) Å, respectively. The fluorophenyl ring is tilted away from the coordination plane and makes a dihedral angle of 66.2 (2)° with the phenolate ring. In the crystal, molecules are linked into chains along the [101] direction by weak C—H⋯O hydrogen bonds. Weak π–π interactions with centroid–centroid distances of 4.079 (2) Å stack the molecules along c.The asymmetric unit of the title complex, [Pd(C II and NiII complexes of Schiff bases have attracted much attention as they play important roles in bioinorganic chemistry and may provide the basis for models of active sites of biological systems 2], is related to the previously reported compound bis{2-[(E)-(4-fluorobenzyl)iminomethyl]phenolato-κ2N,O1}nickel(II)  was screened for catalytic activity in the Suzuki cross-coupling reaction between phenylboronic acid and iodobenzene with a catalyst loading of 1 mmol%. The conversion of iodobenzene was found to occur with a yield of 52%.II cation lying on an inversion centre and the Schiff base anion acting as an N,O bidentate chelate ligand  Å, θ = 112.8 (3) and ϕ = 206.9 (3)°. Other bond lengths and angles observed in the structure are also normal. The fluorophenyl ring (C1–C6) makes a dihedral angle of 66.2 (2)° with the phenolate ring (C9–C14).The asymmetric unit of (1) contains one-half of the molecule with the Pdnd Fig. 1. The PdIs Table 1 are typiA⋯O1 interactions  Å . These combine with the C—H⋯O contacts to generate sheets in the ac plane , the molecules are linked into chains along the [101] direction by weak C4—H4ns Fig. 2. A weak ns Fig. 2, with a ne Fig. 4. These sII complexes with related Schiff base N2O2 donor sets have been reported -2-(1-(4-fluorobenzylimino)ethyl)phenol  in a round-bottomed flask. Palladium(II) acetate  was dissolved separately in CH3CN (20 mL) and was then added into the flask containing the ligand solution. The mixture was stirred and refluxed for 5 h upon which a turmeric yellow solid was formed. The solid was filtered off, washed with ice-cold CH3CN and air dried at room temperature. The solid product was recrystallized from chloroform, yielding yellow crystals (yield 48.5%). 1H NMR, 13C NMR and IR spectral bands have been studied and agree well with the structure obtained from the values of the CHN analyses and X-ray structure determination.The ligand, : 1598 ν(C=N), 1319 ν(C—N), 1216 ν(C—O), 1321 ν(CH3), 556 ν(Pd—N), 450 ν(Pd—O). 1H NMR : δ (p.p.m.) 2.32 , 5.11 , 6.53–7.46 (ArC). 13C NMR : δ (p.p.m.) 19.5 (C—CH3), 54.2 (CH2), 115.3, 115.6, 121.3, 128.6, 130.2 (ArC), 169.8 (C=N).Melting point 508–510 K. Analytical data for C−1 assignable to the C=N stretching frequency of the azomethine moiety. Weak bands at 556 and 450 cm−1 attributable to Pd—N and Pd—O vibrations, respectively  as that observed by Gupta et al. (20132) and methyl (–CH3) protons appear at 5.11 and 2.32 p.p.m., respectively. The 13C chemical shift for the imine carbon (C=N) is found at 169.8 p.p.m., agreeing with data reported by Şenol et al. (2011The infrared spectrum of (1) exhibits a strong band at 1598 cm al. 2013. Singlet al. 2011.The title compound was screened for catalytic activity in the Suzuki cross-coupling reaction between phenylboronic acid with iodobenzene. The reaction was carried out under nitrogen at 373 K in dimethylacetamide with a catalyst loading of 1 mmol%. The conversion of iodobenzene was monitored using GC–FID after 24 hours of reaction time. This resulted in a 52% conversion of iodobenzene in the reaction.d(C—H) = 0.93 Å for aromatic, 0.97 Å for CH2 and 0.96 Å for CH3 hydrogen atoms. The Uiso values were constrained to be 1.5Ueq of the carrier atom for methyl H atoms and 1.2Ueq for the remaining H atoms. A rotating group model was used for the methyl groups.Crystal data, data collection and crystal structure refinement details are summarized in Table 310.1107/S2056989015004405/sj5444sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015004405/sj5444Isup2.hklStructure factors: contains datablock(s) I. DOI: 1045879CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The molecular conformation and crystal packing are governed by a network of hydrogen bonds and by π–π stacking.The crystal structure of the title compound allowed the  14H15ClN2O4, prepared by reaction of a methacryloyl dimer with nitroaniline, was determined to establish the relative substituent orientation on the cyclopentanone ring. In agreement with an earlier proposed reaction mechanism, the amide group and the methyl group adjacent to the chloro substituent adopt equatorial positions and relative cis orientation, whereas the Cl substituent itself and the methyl group adjacent to the amide have axial orientations relative to the mean plane of the five-membered ring. The conformation of the molecule is stabilized by one classical N—H⋯O (2.18 Å) and one non-classical C—H⋯O (2.23 Å) hydrogen bond, each possessing an S(6) graph-set motif. The crystal packing is defined by several non-classical intramolecular hydrogen bonds, as well as by partial stacking of the aromatic rings.The structure of the title compound, C Compounds (3) and (4) show similar 1H and 13C NMR spectra, making the direct assignment of the relative orientation of the cyclopentanone substituents almost impossible. The crystal structure of (1), as well as the crystal structure of another aromatic amide, cis-3-chloro-N--1,3-dimethyl-2-oxocyclopentanecarboxamide, solved and reported earlier -1,3-dimethyl-2-oxocyclopentanecarboxamide with cis orientation of two methyl groups, see Fischer et al. (1985Dimer (2) forms in the oxa-Diels–Alder reaction of two methacryloyl chloride molecules and, in the presence of a Lewis acid  Å for N1. The conformation of the amide is stabilized by one classical N1—H1⋯O1 (2.18 Å) and one non-classical C10—H10⋯O2 (2.23 Å) hydrogen bonds  graph-set motif  Å], the aromatic rings of neighboring molecules show partial stacking with several short contacts centered near their nitro-substituent: C14⋯C13i , and C13⋯N2i [3.1860 (14) Å]. The C7—H7A⋯O1i hydrogen bond (2.53 Å) provides additional cohesion between neighboring enantiomeric molecules in the columns  −x + 1, −y + 1, −z + 1], and along the a axis by C7—H7C⋯O4ii  non-classical hydrogen bonds  −x + 1, y + z + The crystal packing is governed by several short contacts, which may be classified as non-classical hydrogen bonds  and readily afforded large transparent X-ray quality crystals upon slow evaporation of CHCl3/heptane solution (m.p. 402–403 K). 1H NMR : δ 8.89 , 8.26–8.16 , 7.78–7.70 , 2.91–2.78 , 2.49–2.40 , 2.12–2.05 , 2.05–1.98 , 1.75 , 1.51 . 13C NMR : δ 212.4, 168.9, 143.7, 143.3, 125.0, 119.3, 69.7, 55.0, 35.6, 29.4, 25.0, 24.1. MS (EI): m/z (%) 310 (85) [M]+., 173 (85) [M–NHAr]+. HRMS (EI): m/z [M]+ calculated for C14H15ClN2O4 310.07203, found 310.07170.The title compound was prepared as described by Warneke  al. 2014 by reactUiso(H) values were fixed at 1.5Ueq(C) for methyl H atoms, and 1.2Ueq for all other carrier atoms.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S1600536814017711/hg5403sup1.cifCrystal structure: contains datablock(s) 1. DOI: 10.1107/S1600536814017711/hg54031sup2.hklStructure factors: contains datablock(s) 1. DOI: 1017486CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The three molecular components are held together through hydrogen bonds.The crystal structure of the title salt hydrate contains discrete DABCOH 6H13N2+·S2O32−·2H2O, contains a centrosymmetric cyclic motif of eight hydrogen-bonded molecular subunits. Two DABCOH+ cations  are linked to two water molecules and two thiosulfate anions via O—H⋯N and O—H⋯O hydrogen bonds, respectively. Two other water molecules close the cyclic motif through O—H⋯O contacts to the first two water molecules and to the two thiosulfate anions. A second pair of DABCOH+ cations is N—H⋯O hydrogen bonded to the two anions and is pendant to the ring. Adjacent cyclic motifs are bridged into a block-like arrangement extending along [100] through O—H⋯O interactions involving the second pair of water molecules and neighbouring thiosulfate anions.The crystal structure of the hydrated title salt, 2C The thiosulfate anion exhibits approximate Cv3 symmetry. However, in the crystal it has C1 symmetry with S—O distances in the range 1.4688 (8) to 1.4898 (8) Å and an S—S bond length of 2.0047 (4) Å, and O—S—O and S—S—O angles ranging from 107.47 (4) to 110.48 (5)°. In both DABCOH+ cations, the three N—C bonds involving the protonated N atom are elongated [mean value 1.499 (2) Å] compared to the three N—C bonds involving the non-protonated N atoms [mean value 1.472 (4) Å].The asymmetric unit Fig. 1 consistsvia charge-assisted N—H⋯O hydrogen bonds to two DABCOH+ cations. The third oxygen atom (O2) of the anion acts as a hydrogen-bond acceptor for one of the water molecules (O4). The second hydrogen bond involving this water molecule is directed towards a symmetry-related thiosulfate anion. The second water molecule (O5) is the donor of one O—H⋯O hydrogen bond to the other water molecule and of one N—H⋯O hydrogen bond to one of the DABCOH+ cations. Numerical details of the hydrogen-bonding interactions are given in Table 1+ cations  global, I. DOI: 10.1107/S2056989016001535/wm5264Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016001535/wm5264Isup3.cmlSupporting information file. DOI: 1449673CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Weak ‘secondary’ Te bonds and O—H⋯O hydrogen-bonding interactions, involving water molecules and layer O atoms, link the layers and interlayer species. IR spectroscopic data are also presented.A new hydrated yttrium copper tellurite nitrate, yttrium(III) copper(II) bis[trioxidotellurate(IV)] nitrate trihydrate, has been synthesized hydrothermally in a Teflon-lined autoclave and structurally determined using synchrotron radiation. The new phase is the first example containing yttrium, copper and tellurium in one structure. Its crystal structure is unique, with relatively strongly bound layers extending parallel to (020), defined by YO Tellurite and nitrate anions (involving atoms O1–O9) are clearly distinguished from water molecules OW1–OW3 by their bond-valence sums (Table 12− and 2 × H2O at 2.290 (3)–2.497 (3) Å. Cu is in square-planar coordination, with four close oxygen neighbours at 1.904 (3)–1.999 (3) Å. Two more oxygen ligands at 2.811 (4) and 2.817 (4) Å complete an octahedron that is very elongated due to the Jahn-Teller distortion. Te1 is trigonal–pyramidally coordinated by three oxygen atoms at 1.883 (3)–1.911 (3) Å. Three ‘secondary bonds’ to O atoms at 2.657 (3)–2.837 (3) Å complete a polyhedron that can be described as an octahedron that is very distorted due to the lone-pair stereoactivity. Te2 has very similar coordination, with three primary Te—O bonds of 1.893 (3)–1.905 (3) Å and three secondary bonds of 2.681 (4)–2.798 (3) Å. In each case, two of the secondary bonds provide additional bracing within the {Y⋯Cu⋯Te} layer, while the third is to a nitrate oxygen , and thus provides weak bridging between the layers and interlayer species. The nitrate oxygen atom O9 makes a seventh very distant ligand for both Te1 [3.231 (4) Å] and Te2 [3.350 (4) Å], further than the shortest Te⋯Cu distances and with bond valences < 0.05 valence units, using the parameters of Mills & Christy  are defined by YOs Table 1. Within isty 2013.et al. 4]4− of {Cu⋯Te⋯Cu⋯Te} squares running parallel to [001] 8 polyhedra 2] and its Er—Cl and Er—Br analogues , DTGS (Deuterated Triglycine Sulfate) detector, 4 cm al. 2013. Numeric3)2(NO3)(H2O)3 were synthesized hydrothermally. For the synthesis, Y(NO3)3·6H2O , Cu(NO3)2·3H2O (Sigma–Aldrich ≥99%) and Te 200 mm mesh  were used as starting materials. A 1:1:1 molar ratio of the reagents in 20 ml water was reacted in a Teflon autoclave bomb at 473 K for 3 days. Crystals of YCu(TeO3)2(NO3)(H2O)3 were separated manually from a blue powder of undetermined composition in a few percent yield. Several unsuccessful attempts were made to synthesize YCu(TeO3)2(NO3)(H2O)3 from a stoichiometric mixture of the reagents, using the molar ratio 1:1:2. We also were unsuccessful in producing new compounds, with the same structure type or not, using La, Ce, Nd or Gd in place of Y.Dark blue prisms of YCu Å.Single crystal X-ray diffraction experiments were carried out on the micro-focus macromolecular beam line MX2 of the Australian Synchrotron. Details of data collection and structure refinement are provided in Table 410.1107/S2056989016011464/wm5307sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016011464/wm5307Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016011464/wm5307sup3.pdfSupporting information file. DOI: 1493330CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The molecules form a closely spaced lattice structure in which neighbouring porphyrins are oriented in inversion-related dimers.The title compound contains one independent molecule which exhibits an overall  48H60N4O2)], contains one independent molecule. The average Ni—N bond length is 1.917 (13) Å. The molecules are arranged in a closely spaced lattice structure in which neighbouring porphyrins are oriented in inversion-related dimers. The nickel(II) porphyrin is characterized by a significant degree of a ruffled (Bu1) conformation with small contributions from saddle (Bu2) and wave (y) [gE(y)], as determined using normal structural decomposition. Disorder in the 2,5-dimethoxyphenyl substituent was modelled over two positions with a 60% occupancy for the major moiety. One of the ethyl groups is also disordered over two positions and was modelled with the major moiety being present in 51.3% occupancy.The asymmetric unit of the title nickel(II) porphyrin, [Ni(C There are many studies available on metal coordination porphyrinato]nickel(II), which has an average Ni—N bond length of 1.925 Å  and the meso carbon (Cm) can be used to determine structural differences between similar porphyrins and differences within the individual porphyin structure. The Cα—Cm(butyl)—Cα angle of 119.12 (2)° is smaller than the Cα—Cm(H)—Cα angle, and the Cα—Cm—Cα angle at 123.2 (2)° is similar to both Cα—Cm(H)—Cα angles, 122.1 (3)° (C20) and 124.8 (3)° (C15). The 2,5-dimethoxyphenyl group is tilted at an angle of 75.80 (7)° from the 24-atom least-squares plane of the porphyrin ring.The average Ni—N distance is 1.917 (13) Å. The largest deviation occurs at the Ni—N2 bond [1.906 (2) Å], which lies between both substituted et al., 1998ruffled (Bu1) with small contributions from saddle (Bu2) and wave (y) [gE(y)] , [gE(x)] and domed (Au2), which is similar to both highly substituted and other Ni(II) porphyrins . The tilt of the pyrrole rings against the 24-atom plane are N1 [24.85 (8)°], N2 [25.22 (8)°], N3 [15.79 (10)°] and N4 [17.58 (8)°], with the highest deviation from the mean plane associated with the pyrrole rings closest to the butyl group at C5. The maximum deviations from the least-squares plane are associated with the meso C atoms. C5 deviates from the least-squares plane by 0.880 (2) Å, whereas C10, C15 and C20 deviate from the plane at 0.551 (2), 0.512 (3) and 0.667 (2) Å, respectively. Table 1A conformational analysis was performed using the NSD  method developed by Shelnutt and co-workers (Shelnutt )] Fig. 2. There an-butyl group (C51 > C54) with the phenyl methoxy unit, specifically between H54A⋯C104, at 2.851 (4) Å, the methoxy group (O1 > C111) with the ethyl group (C181 > C182) between O1⋯H18C at 2.552 (4) Å, the methoxy group (O2B > C108) with the ethyl group (C21 > C22) between O2B⋯H22A at 2.486 (3) Å and the ethyl group (C121 > C122) with the C15 atom, between C15⋯H12E at 2.833 (3) Å. However, there are no π–π interactions or hydrogen bonds evident in the crystal structure.The unit cell of the title compound consists of two molecules, each at a distance of 4.949 Å from the 24-atom mean plane of the other. The molecules are arranged in a closely spaced lattice structure in which ethyl groups and butyl groups point towards each other to form a cage-like inversion-related dimer Fig. 3. Molecuet al. (1992a—Cm(H)—Ca angles (122.85–123.58°) compared to the title compound. We also determined the structure of nickel(II) with and without deuterated chloroform nickel(II) and zinc(II)  derivative exhibits angles that are similar to the title compound, 122.12–122.35° for the substituted meso-positions and 123.42–123.78° for the unsubstituted meso-positions. The average Ni—N bond length of 1.923 Å is comparable to that of the title compound. The zinc derivative of this compound exhibits a larger average metal–nitrogen bond length of 2.054 Å and wider Cα—Cm—Cα angles, 124.85–125.95° for the substituted meso-positions and 126.81–127.78° for unsubstituted meso-positions, as to be expected for zinc porphyrins.A search of the Cambridge Structural Database . The solution was heated to room temperature and over the course of 1 h added to a solution of nickel(II)  yielding purple crystals of the title compound . The compound was recrystallized from a solution of 1%vol MeOH in CH2Cl2 layered with hexane to yield single crystals suitable for X-ray diffraction.The title compound was prepared as reported previously (Senge Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms. Disorder in the 2,5-dimethoxyphenyl substituent was modelled over two positions with a 60% occupancy for the major moiety. The ethyl group at C12 was modelled over two positions with the major moiety being present in 51.3% occupancy. Restraints and constraints were used to model the disorder with SHELXL2014  I, publication_text. DOI: 10.1107/S2056989015020058/wm5222Isup2.hklStructure factors: contains datablock(s) I. DOI: 1427139CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Each Cd2+ cation is coordinated by two N atoms and one O atom of the tridentate ligand and three chloride anions, forming a distorted CdNOCl3 octahedron. Each pair of adjacent metal cations is linked by two bridging chloride ligands, resulting in a dinuclear complex unit. The molecular conformation is stabilized by intramolecular N—H⋯N and C—H⋯O hydrogen bonds. In the crystal, molecules are linked by nonclassical C—H⋯O and C—H⋯Cl hydrogen bonds into a three-dimensional network. In addition, π–π stacking interactions [centroid–centroid distances = 3.777 (2) and 3.631 (2) Å] contribute to the stabilization of the crystal packing.The title compound, [Cd DOI: 10.1107/S1600536814010630/rz5124Isup2.hklStructure factors: contains datablock(s) I. DOI: 1001915CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


S)-ABOC], two amino acid residues [(S)-Ala and (S)-Phe], and protecting groups of Boc and OBn. The tetramer folds into a right-handed mixed 11/9 helix stabilized by intramolecular i,i + 3 and i,i-1 C=O⋯H—N hydrogen bonds. The oligomers are linked into chains by N—H⋯O=C hydrogen bonds with the chloroform solvent molecules intercalated between the folded chains via C—H⋯O=C interactions.In the title compound, the α,β-hybrid peptide contains two non-proteinogenic amino acid residues [( S)-2-[(S)-(1-{2-[(S)-(1-{[(tert-butoxy)carbonyl]amino}bicyclo[2.2.2]octan-2-yl)formamido]propanamido}bicyclo[2.2.2]octan-2-yl)formamido]-3-phenylpropanoate chloroform monosolvate, C42H56N4O7·CHCl3, the α,β-hybrid peptide contains two non-proteinogenic amino acid residues of (S)-1-aminobicyclo[2.2.2]octane-2-carboxylic acid [(S)-ABOC], two amino acid residues of (S)-2-aminopropanoic acid [(S)-Ala] and (S)-2-amino-3-phenylpropanoic acid [(S)-Phe], and protecting groups of tert-butoxycarbonyl (Boc) and benzyl ester (OBn). The tetramer folds into a right-handed mixed 11/9 helix stabilized by intramolecular i,i + 3 and i,i − 1 C=O⋯H—N hydrogen bonds. In the crystal, the oligomers are linked by N—H⋯O=C hydrogen bonds into chains along the a-axis direction. The chloroform solvent molecules are intercalated between the folded chains via C—H⋯O=C interactions.In the title compound, phenyl ( S)-1-aminobicyclo[2.2.2]octane-2-carboxylic acid [(S)-ABOC] is a β2,3,3-trisubstituted bicyclic amino acid which exhibits a high propensity to induce both a reverse turn into short peptides and helices in oligoureas and in α,β-hybrid peptides  and the NH of the α-residue (i + 3) and two C9 pseudocycles between the CO of the α-residue (i) and the NH of the β-residue (i − 1). The backbone torsion angles are quite similar to those of the characteristic 11/9 helix reported in the same α,β-hybrid oligomers  Å] and a C—H⋯O hydrogen bond [C⋯O = 3.071 (4) Å].The intermolecular interaction N2—H2⋯O5i Table 1 connectson Fig. 2. In the iPrCO instead of Boc are not isomorphous. This latter crystallized in the space group P21 with two independent molecules in the asymmetric unit. One independent molecule shows a single fully folded 11/9 helix as the title compound while the hydrogen-bond network is incomplete in the other molecule. The last C9 hydrogen bond between the carbonyl of the Phe residue and the β-residue amide proton was disrupted by the incorporation of a water molecule  parameters were fixed at 1.2Ueq for methine, methylene, aromatic groups and NH groups, and at 1.5Ueq(C) for methyl groups.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989015016941/is5415sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015016941/is5415Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015016941/is5415Isup3.cmlSupporting information file. DOI: 1423394CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The crystal packing features C—H⋯π and π—π interactions, which generate a three-dimensional network.In the title compound, C 25H20ClN3O, the C=N bond of the central imine group adopts an E conformation. The mean planes through the essentially planar carbazole [maximum deviation = 0.052 (2)Å] and quinoline [maximum deviation = 0.050 (2) Å] ring systems form a dihedral angle of 50.2 (1)°. In the crystal, molecules are linked by C—H⋯π and π—π interactions [centroid–centroid distances ranging from 3.635 (2) to 3.739 (2) Å], forming a three-dimensional supramolecular network.In the title compound, C The sum of the bond angles around N1 (360.05°) of the pyrrole ring is in accordance with sp2 hybridization. Atom Cl1 deviates from the plane of the attached quinoline ring system by 0.100 (1) Å. The geometric parameters of the title molecule agree well with those reported for similar structures , 3.739 (2), 3.739 (2), 3.635 (2) and 3.635 (2) Å, respectively, forming a three-dimensional supramolecular network  −x, −y, 1 − z; (ii) 1 − x, y, z; (iii) 1 − x, −y, 1 − z and (iv) −x, 1 − y, 1 − z).In the crystal, molecules are linked by two C—H⋯π interactions; the first one between the benzene H atom of the carbazole ring system and the benzene ring of an adjacent molecule, with a C1—H1⋯H-carbazol-3-amine (1 mmol) and sulfated SnO2-fly ash catalyst (50 mg) in water (15 ml) and was refluxed at 353 K for 5–10 minutes. The completion of the reaction was monitored by TLC (ethyl acetate and hexane as an eluent 20%). After completion, the reaction mixture was cooled to ambient temperature. Then dichloromethane (20 ml) was added and the organic layer filtered, dried on anhydrous Na2SO4 and the solvent removed using a rotary evaporator. The crude product was purified by column chromatography on silica gel (200 mesh) with hexane and ethyl acetate (4:1) as eluent to afford the title compound in good yield (10%). Red blocks suitable for X-ray diffraction analysis were obtained by recrystallization from dichloromethane solution at room temperature.A 25 ml round-bottom flask was charged with dimedone (1 mmol), 2-chloro-6-methoxyquinoline-3-carbaldehyde (1 mmol) 9-ethyl-9Uiso(H)=1.5Ueq 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/S2056989015005794/hb7384sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015005794/hb7384Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015005794/hb7384Isup3.cmlSupporting information file. DOI: 1027676CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: