III(N**)3] . Surprisingly, complex 1 exhibits a trigonal planar geometry in the solid state, which is unprecedented for three-coordinate actinide complexes that have exclusively adopted trigonal pyramidal geometries to date. The characterization data for [UIII(N**)3] were compared with the prototypical trigonal pyramidal uranium(III) triamide complex [UIII(N“)3] (N”=N(SiMe3)2−), and taken together with theoretical calculations it was concluded that pyramidalization results in net stabilization for [UIII(N“)3], but this can be overcome with very sterically demanding ligands, such as N**. The planarity of 1 leads to favorable magnetic dynamics, which may be considered in the future design of UIII single-molecule magnets.We report the synthesis and characterization of the uranium(III) triamide complex [U Both covalent[19] and electrostaticIII(N“)3],III(N**)3] 2−), which adopts an unprecedented trigonal planar geometry for an actinide triamide complex. Complex 1 is closely related to [UIII(N”)3], allowing the contributions to pyramidalization to be assessed, together with the impact of geometry on magnetic (including dynamic) and electronic properties of UIII complexes, for the future rational design of useful An materials.f-Block metal centers favor high CNs, because Ln and An cations have relatively large ionic radii and bonding regimes that are dominated by electrostatic contributions.1 was prepared by a modification of the revised synthesis of [UIII(N“)3].III(I)3(THF)4]2tBu)2}]2 in THF, followed by work-up and recrystallization from hexane to give 1 as dark purple needles in 62 % yield (1 at −1 are attributed to the UNSi2 stretching modes of the silylamide ligand. The asymmetric stretch (950 cm−1) is 40 cm−1 lower than that observed for [UIII(N”)3] (990 cm−1),3] MNSi2 asymmetric stretches (ca. 50 cm−1).6aComplex  % yield .21 Absor1H NMR spectrum of 1 exhibits two resonances at δ=3.8 (ν½=206 Hz) and −47.0 ppm (ν½=4597 Hz) in a 54:36 ratio that are assigned to the tBuSi and Me2Si protons, respectively. The Me2Si resonance of 1 is much broader than the analogous resonance for [UIII(N“)3] ,δ=−32.9 ppm, ν½=266 Hz).13C NMR spectrum of 1 exhibited two resonances for the Me2Si (δ=−2.1 and 1.5 ppm) and tBuSi quaternary carbons (δ=18.2 and 32.0 ppm), but only one for the tBuSi primary carbons (δ=26.4 ppm). In contrast, in the 13C NMR spectrum of [UIII{N(SiPhMe2)2}3], the Me2Si group resonates at δ=−57.1 ppm.29Si NMR spectrum of 1 at δ −296.0 ppm (ν½=73 Hz), which has not been reported for similar systems,III complex.23The 13→5f26d1 transitions at 20 000 (ε=776 m−1 cm−1) and 22 500 cm−1 (ε=770 m−1 cm−1) that are typical of UIII[24] and comparable to a broad absorption observed for [UIII{N(SiPhMe2)2}3] at 21 500 cm−1 (ε=430 m−1 cm−1).−1 region, weak Laporte forbidden 5f→5f transitions were observed (ε=15–64 m−1 cm−1).III complexes, such as [U(I)3(THF)4]III{N(SiPhMe2)2}3],[27]The electronic absorption spectrum of 1 was determined and is depicted in Figure 1 crystallizes in the C2/c space group, with a twofold axis bisecting the U(1)–N(1) bond. This contrasts to [Fe(N“)3],III(N”)3],III(N“)3],III(N”)3],P31c space group, and [UIII{N(SiPhMe2)2}3], which crystallizes in R3.1 is almost ideally trigonal planar, with U–N bonds that are statistically identical within experimental uncertainty [U-N range 2.403(3)–2.415(6) Å]. These distances are longer than those observed in [UIII(N“)3] [2.320(4) Å]III{N(SiPhMe2)2}3] [2.34(2) Å],1 arising from the sterically demanding tBu groups. The U centroid/N(1)-N(2)-N(2A) mean plane distance in 1 is 0.008(2) Å, and the N-U-N bond angles (range 119.1(2)–120.47(9)°) sum to 360°; in contrast, [UIII(N”)3] and [UIII{N(SiPhMe2)2}3] exhibit U centroids 0.456(1) and 0.874 Å from the N3 planes, and the N-U-N angles average 116.24(7) (Σ angles 348.72(7)°) and 106.88° (Σ angles 320.64°), respectively.2 fragments of 1 are essentially planar and all bisect the UN3 plane (range 53.23–61.35°) to form a molecular propeller.The crystal structure of III(N“)3] and [UIII{N(SiPhMe2)2}3] are predicted by the polarized-ion model, whereby net stabilization was achieved by dipole formation.III(N”)3] exhibits unequal U-N-Si angles (108.50(7) and 125.25(7)°), because one Si–C bond for each N“ ligand is relatively close to the U center .⋅⋅⋅Si–Cγ interactions, as have been discussed for [UIII{CH(SiMe3)2}3]III(N”)3].[31] The shortest U⋅⋅⋅Cγ and U⋅⋅⋅Si distances in 1 are 3.119–3.301 Å and 3.433–3.510 Å, respectively, and they are not correctly orientated to interact with the U center. Although there is no evidence for agostic U⋅⋅⋅Si–Cγ interactions in 1, stabilizing U⋅⋅⋅C–H contacts cannot be discounted.The pyramidal geometries of [U1 and [UIII(N“)3].1 , providing qualitative models 3] 0.393 Å). In both models, the HOMO, HOMO−1 and HOMO−2 represent the three unpaired UIII 5f electrons 3] 86.81, 86.32, 84.17 % U 5f, respectively). Both models exhibit essentially insignificant degrees of U 6d/5f orbital contributions to the U–N bonds, with the HOMO−3, HOMO−4. and HOMO−5, representing the π components 3] 4.29/0, 0/2.06, 1.63/1.39 % U 5f/6d, respectively) and the HOMO−6, HOMO−7, and HOMO−8 the σ components 3] 0/5.04, 0/5.26, 2.14/0 % U 5f/6d, respectively). This concurs with gas-phase photoelectron spectroscopy (PES) studies of [U(N”)3], which have shown that π bonding between the ligand and U center is insignificant in this complex.1=−3.26; [UIII(N′′)3]=−3.26) are identical, which also supports similar bonding patterns for 1 and [UIII(N“)3].Unrestricted DFT calculations were carried out on full models of III(CH3)3] III(NH2)3] 1 and [UIII(N“)3] together with the small U 6d/5f contributions to the U–N σ and π components, we suggest that the experimentally determined trigonal planar geometry of 1 results from steric interactions involving the large N** ligands. These interactions could predominate over crystal packing forces, which are often only approximately 10 kJ mol−1.1 and [UIII(N”)3], therefore, the planar geometry of 1 derives principally from steric effects involving the ligands.Ab initio calculations on [An1 was calculated to be 2.59 μB in [D6]benzene at 298 K by using the Evans method.[36] Magnetometry measurements on a powdered sample of 1 suspended in eicosane gave a magnetic susceptibility temperature product, χT, of 1.07 cm3 Kmol−1 (2.92 μB) at 298 K,3 4I9/2 ground state (3.69 μB), because not all crystal field levels are thermally occupied,III complexes described in the literature (range 2.13–4.63 μB).[38] The χT value of 1 decreases to 0.41 cm3 Kmol−1 at 2 K; ac measurements give a low-temperature plateau in the in-phase χ′T at 0.48 cm3 Kmol−1[21] consistent with thermal depopulation into a Kramers doublet ground state.1 are consistent with UIII,[27] and simulation gives geff=3.55, 2.97, and 0.553 for the ground Kramers doublet 3] is an SMM,1 to probe differences in the dynamic magnetic behavior as a result of the higher symmetry. Compound 1 is also an SMM, with clear frequency-dependent behavior 3], and maxima in the out-of-phase susceptibility χ′′(T) are seen to significantly higher temperatures for 1 than for [UIII(N“)3] at equivalent frequencies . An Arrhenius treatmentUeff=21.4±0.2 K for 1. Although this is lower than that reported for [UIII(N”)3] (31 K), the latter value was derived from an extremely limited temperature rangeτ) at 2 K is 2.6 ms for 1; from the previously reported dataIII(N“)3] at 2 K, an order of magnitude quicker. The pre-factor τ0 for 1 is greater by four orders of magnitude (3.1×10−7 cf. 10−11 s for [UIII(N”)3]).χ′ and χ“ at 1.8 K for 1α=0.001–0.03 from Cole–Cole analysis), an order of magnitude lower than in [UIII(N”)3] (α=0.09–0.34).1 at 1.8 K on a conventional superconducting quantum interference device (SQUID) magnetometer 3].Compound  from optical studies.1 and [UIII(N”)3] are SMMs despite their easy-plane anisotropy: this highlights the complexity of interpreting f-block relaxation data,1 compared with [UIII(N“)3] on flattening the geometry is because of quenched mixing. In Dh3 |zJ|=1/2 cannot mix with any other doublet within the 4I9/2 term, whereas in Cv3, it can mix with both |zJ|=5/2 and 7/2.In the trigonal planar geometry of 1 and [UIII(N“)3] can be attributed to differences in symmetry that may be useful to consider in the future design of UIII SMMs with greater relaxation times. Computational analyses of 1 and [UIII(N”)3] have shown only minor differences in their calculated bonding schemes, therefore, the energy gained by pyramidalization, which leads to favorable agostic M⋅⋅⋅Si–Cγ interactions in [UIII(N“)3],To conclude, we have prepared and fully characterized an unprecedented trigonal planar actinide triamide complex. Differences in the spectroscopic and magnetic data between Synthesis of 1: THF (20 mL) was added to a precooled (−78 °C) mixture of [K{N(SiMe2tBu)2}]2  and [U(I)3(THF)4] . The reaction mixture was allowed to warm to RT slowly with stirring over 48 h, with precipitation of a pale solid. Volatiles were removed in vacuo, and the dark purple solid was extracted with hexanes (3×10 mL). Recrystallization from hexanes (5 mL) at −30 °C gave 1 as dark purple needles .1H NMR : δ=−47.04 2), 3.79 ppm 3); 13C{1H} NMR : δ=−2.13 (Si(CH3)2), 1.45 (Si(CH3)2), 18.22 (SiC(CH3)3), 26.40 (SiC(CH3)3), 31.98 ppm (SiC(CH3)3); 29Si{1H} NMR : δ=−296.04 ppm ; FTIR (Nujol); 2), 825 , 761 , 655 (m), 604 (s) cm−1; μeff=2.59 μB (Evans method); elemental analysis calcd for C36H90Si6N3U (971.67 g mol−1): C 44.5, H 9.34, N 4.33; found: C 38.29, H 9.10, N 4.22. Low carbon values were obtained upon repeating the analysis multiple times on different batches and is ascribed to 1 being a silicon-rich molecule, as was observed previously.42


H-1,2,4-triazol-3-yl-κN4)acetato-κO]diaqua)nickel(II) dihydrate, is the first transition metal complex of 2-acetic acid (ATAA).The title compound, bis[(5-amino-1 4H5N4O2)2(H2O)2]·2H2O, represents the first transition metal complex of the novel chelating triazole ligand, 2-acetic acid (ATAA), to be structurally characterized. In the molecule of the title complex, the nickel(II) cation is located on an inversion centre and is coordinated by two water molecules in axial positions and two O and two N atoms from two trans-oriented chelating anions of the deprotonated ATAA ligand, forming a slightly distorted octahedron. The trans angles of the octahedron are all 180° due to the inversion symmetry of the molecule. The cis-angles are in the range 87.25 (8)–92.75 (8)°. The six-membered chelate ring adopts a slightly twisted boat conformation with puckering parameters Q = 0.542 (2) Å, Θ = 88.5 (2) and ϕ = 15.4 (3)°. The molecular conformation is stabilized by intramolecular N—H⋯O hydrogen bonds between the amino group and the chelating carboxylate O atom of two trans-oriented ligands. In the crystal, the complex molecules and lattice water molecules are linked into a three-dimensional framework by an extensive network of N—H⋯O, O—H⋯O and O—H⋯N hydrogen bonds.The title compound, [Ni(C C-amino-1,2,4-triazoles are employed as polydentate ligands for the synthesis of coordination compounds with various metals that demonstrate useful spectroscopic, magnetic, biological and catalytic properties  can act as chelating polydentate ligands acetic acid 2(H2O)2]·2H2O (1).In a continuation of our work on the synthesis and reactivity of aminotriazole carboxylic acids –92.75 (8)°. The third water molecule is not involved in coordination. The anions of ATAA coordinate the NiII cation through the nitrogen atom N1 of the triazole ring and the oxygen atom O53 of the carboxylate group  Å, Θ = 88.5 (2), ϕ = 15.4 (3)°. The Ni—N1 bond length is 2.051 (2) Å, and the Ni—O1 and Ni—O53 bond lengths are 2.083 (2) and 2.059 (2) Å, respectively, within the normal ranges for other reported NiII complexes , the Nion Fig. 2. The traup Fig. 2, similards Fig. 2.In the crystal, molecules of the complex and lattice water molecules are linked into a three–dimensional framework by extensive N—H⋯O, O—H⋯O and O—H⋯N hydrogen bonds Table 1.et al., 2010H-1,2,4-triazole-3-carboxylic acid (ATCA) with various metals acetate (2) in an aqueous solution of nickel nitrate 2·6H2O in water (5 ml). After standing at room temperature for two weeks, the formed crystals were collected by filtration yielding the target compound (1).All attempts to prepare crystals of complex (1) suitable for X-ray investigation by mixing solutions of te Fig. 4. A solut2 group and refined as riding, with Uiso(H) = 1.2Ueq(C). The N,O-bound H atoms that are involved in hydrogen bonds were found from difference Fourier maps. Their distances to the parent atoms were refined to be equal, with a common Uiso(H) value for pairs of related H atoms.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S1600536814021436/wm5066sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814021436/wm5066Isup2.hklStructure factors: contains datablock(s) I. DOI: 1026535CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Each AgI ion is bridged by the ligands, forming a helical chain propagating along the b-axis direction. The right- and left-handed helical chains are alternately arranged via Ag⋯Ag [3.2639 (5) Å] and π–π stacking interactions [centroid–centroid distance = 3.523 (1) Å], resulting in the formation of a two-dimensional supramolecular network extending parallel to (101). Weak Ag⋯F interactions [longest Ag⋯F interaction = 3.153 (2) Å], as well as N—H⋯F and C—H⋯F hydrogen-bonding interactions, occur between the helical chains and the anions.In the title polymeric complex, {[Ag(C I coordination polymers with symmetrical dipyridyl ligands, see: Lee et al. ]PF6 = 0.027wR(F2) = 0.071S = 1.052740 reflections199 parametersH-atom parameters constrainedmax = 0.86 e Å−3Δρmin = −0.44 e Å−3ΔρSMART  used to solve structure: SHELXS97  I, New_Global_Publ_Block. DOI: 10.1107/S1600536814011465/sj5402Isup2.hklStructure factors: contains datablock(s) I. DOI: 1003661CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The coordinating water molecules are hydrogen bonded to the carboxyl O atoms [O ⋯ O = 2.6230 (17) Å], enclosing an S(6) hydrogen-bonding motif, while intermolecular O—H⋯O hydrogen bonds link two of the non-coordinating water molecules to the coordinating water molecules and NA anions. In the crystal, O—H⋯O and N—H⋯O hydrogen bonds link the molecules, enclosing The asymmetric unit of the monomeric cobalt complex, [Co(C 11H13O2)2(C6H6N2O)2(H2O)2]·2H2O, contains one half of the complex molecule, one coordinating and one non-coordinating water molecule, one 4-tert-butylbenzoate (TBB) ligand and one nicotinamide (NA) ligand; the Co atom lies on an inversion centre. All ligands coordinating to the Co atom are monodentate. The four nearest O atoms around the Co atom form a slightly distorted square-planar arrangement, with the distorted octahedral coordination completed by the two pyridine N atoms of the NA ligands at distances of 2.1638 (11) Å. The coordinating water molecules are hydrogen bonded to the carboxyl O atoms [O ⋯ O = 2.6230 (17) Å], enclosing an S(6) hydrogen-bonding motif, while intermolecular O—H⋯O hydrogen bonds link two of the non-coordinating water molecules to the coordinating water molecules and NA anions. The dihedral angle between the planar carboxylate group and the adjacent benzene ring is 29.09 (10)°, while the benzene and pyridine rings are oriented at a dihedral angle of 88.53 (4)°. In the crystal, O—H⋯O and N—H⋯O hydrogen bonds link the molecules, enclosing R22(8), R22(10) and R44(12) ring motifs, forming layers parallel to (001). The C and H atoms of the tert-butyl group of the TBB ligand are disordered over two sets of sites with an occupancy ratio of 0.631 (5):0.369 (5). The asymmetric unit of the mononuclear cobalt complex, [Co(C The Co—O bond lengths are 2.1104 (11) Å (for water oxygens) and 2.1252 (9) Å (for benzoate oxygens) and the Co—N bond length is 2.1638 (11) Å, close to standard values. The Co1—O2—C1—C2 torsion angle [−163.00 (9)°] causes a slight downward tilt of the ligand.The dihedral angle between the planar carboxylate group (O1/O2/C1) and the adjacent benzene (C2–C7) ring is 29.09 (10)°, while the benzene and pyridine (N1/C9–C13) rings are oriented at a dihedral angle of 88.53 (4)°.w⋯Oc  hydrogen bonds (Table 1S(6) hydrogen-bonding motifs, while intermolecular O—Hw⋯Ow and O—Hw⋯Ona (na = nicotinamide) hydrogen bonds link two of the non-coordinating water molecules to the coordinating water molecules and NA anions  in water (75 ml) and nicotinamide  in water (25 ml) with sodium 4-tert-butylbenzoate  in water (250 ml). The mixture was filtered and set aside to crystallize at ambient temperature for five days, giving pink single crystals.The title compound was prepared by the reaction of CoSO2), H41, H42, H51 and H52 (for H2O) were located in a difference Fourier map and were refined freely. The C-bound H atoms were positioned geometrically, with C—H = 0.93 and 0.96 Å for aromatic and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = k × Ueq(C), where k = 1.5 for methyl H atoms and k = 1.2 for aromatic H atoms. During the refinement process the disordered t-butyl group atoms were refined with major:minor occupancy ratios of 0.631 (5):0.369 (5).Experimental details including the crystal data, data collection and refinement are summarized in Table 210.1107/S2056989016008689/pk2579sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016008689/pk2579Isup2.hklStructure factors: contains datablock(s) I. DOI: 1482507CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


One of these P atoms belongs to a bridging dppb ligand [Cu—P = 2.2381 (5) Å] and two belong to a chelating dppb ligand [Cu—P = 2.2450 (6) and 2.2628 (5) Å]. The bridging dppb ligand lies on an inversion centre. In the crystal, the cation and the PF6− anion are linked by C—H⋯F interactions, forming a tape along [110]. The cation and the diethyl ether solvent molecule are also linked by a C—H⋯O interaction.In the centrosymmetric dinuclear copper(I) complex cation of the title compound, [Cu For cop al. 1999; Kitagaw al. 1995. For our al. 2006.2(C28H28P2)3](PF6)2·2C4H10O = 0.036wR(F2) = 0.090S = 1.069436 reflections523 parametersH-atom parameters constrainedmax = 0.41 e Å−3Δρmin = −0.35 e Å−3ΔρCrystalClear  used to solve structure: SIR92  global, I. DOI: 10.1107/S1600536814009763/is5355Isup2.hklStructure factors: contains datablock(s) I. DOI: 1000315CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Two copper(II) complexes, a dinuclear and a hexanuclear complex with bridging hydroxyl and nitrate ligands, were obtained from reaction of copper nitrate with dihydroxybipyridine at neutral and slightly acidic pH. Formation of multi-nuclear complexes contrasts with the equivalent sulfate compounds which formed discrete mononuclear complexes. The complexes feature intramolecular and intermolecular hydrogen bonding. 3)2 and 6,6′-dihydroxybipyridine (dhbp) exhibit bridging nitrate and hydroxide ligands. The dinuclear complex (μ-hydroxido-1:2κ2O:O′)(μ-nitrato-1:2κ2O:O′)(nitrato-1κO)dicopper(II), [Cu2(C10H7N2O2)(OH)(NO3)2(C10H8N2O2)] or [Cu(6-OH-6′-O-bpy)(NO3)(μ-OH)(μ-NO3)Cu], (I), with a 2:1 ratio of nitrate to hydroxide anions and one partially deprotonated dhbp ligand, forms from a water–ethanol mixture at neutral pH. The hexanuclear complex bistetrakistetrakis(μ-hydroxido-κ2O:O′)bis(methanol-κO)tetrakis(μ-nitrato-κ2O:O′)hexacopper(II), [Cu6(C10H6N2O2)2(CH4O)2(OH)4(NO3)4(C10H8N2O2)4] or [Cu(μ-NO3)2(μ-OH)Cu(μ-OH)Cu(CH3OH)]2, (II), with a 1:1 NO3–OH ratio and two fully protonated and fully deprotonated dhbp ligands, was obtained by methanol recrystallization of material obtained at pH 3. Complex (II) lies across an inversion center. Complexes (I) and (II) both display intramolecular O—H⋯O hydrogen bonding. Intermolecular O—H⋯O hydrogen bonding links symmetry-related molecules forming chains along [100] for complex (I) with π-stacking along [010] and [001]. Complex (II) forms intermolecular O—H⋯O hydrogen-bonded chains along [010] with π-stacking along [100] and [001].Two multinuclear complexes synthesized from Cu(NO A new coordination mode is observed for the mono-deprotonated (6-O-6′-OH-bpy) ligand in which it bridges two metals, through  coordination of N1,N2 to Cu1 and through bridging to Cu2 via the pyridinolate oxygen O2 [1.946 (3) Å]. The C—O bond lengths (Å) for the dhbp ligands are 1.335 (5) (C1—O1), 1.322 (5) (C11—O3), and 1.316 (4) (C20—O4) for the protonated hydroxyl groups and slightly shorter at 1.310 (4) (C10—O2) for the pyridinolate, reflecting double-bond character. Both copper atoms have a distorted square-pyramidal geometry with τ = 0.394 at Cu1 and τ = 0.119 at Cu2  Å hydrogen bond from O5 to O11 (hydroxyl to nitrate) with a bond angle of 164 (4)°. Numerical details of the hydrogen bonds are given in Table 1The dinuclear copper(II) dhbp complex (I)et al., 1984N,N bound), one bridging hydroxide to Cu2 (O14), one bridging nitrate to Cu2 (O11), and one bridging nitrate (O7) which tethers the two asymmetric units. The coordination of Cu2 entails one deprotonated dhbp , one bridging nitrate to Cu1 (O12), and two bridging hydroxides to Cu1 and Cu3 . The remaining coordination sphere of Cu3 entails one dhbp , one methanol (O15), one bridging hydroxide (O13), and one bridging nitrate (O8) which tethers the two asymmetric units. Each deprotonated oxygen of dhbp acts as an acceptor for intramolecular hydrogen bonds from the two protonated dhbp ligands, O2 to O3 at 2.499 (3) Å (O—H⋯O bond angle of 172°), and O6 to O4 at 2.495 (3) Å (O—H⋯O bond angle of 168°) shown in Fig. 4The hexanuclear copper(II)Comparison of complex (I)II ions is charge balanced with one terminal and one bridging nitrate each with a single negative charge, one deprotonated hydroxyl group of dhbp, and one bridging hydroxide. The bond lengths to the bridging hydroxide from Cu1 to O5 is 1.964 (3) Å and Cu2 to O5 is 1.939 (3) Å where the proton of O5 hydrogen bonds to one acceptor. A comparable bond length is 1.946 (3) Å from Cu2 to O2 of the deprotonated dhbp ligand. The remaining oxygen atoms of the dhbp ligands are each protonated and engaged in hydrogen bonding as described above. The asymmetric unit of complex (II)The bridging oxygen species for both complexes (I)vide supra. The dinuclear complex (I)x, −y, −z at a distance of 3.894 (3) Å between the centroids of the rings. The pyridine ring containing N1 interacts with its symmetry-equivalent ring across the symmetry operation 1 − x, 1 − y, −z with a centroid-to-centroid distance of 3.969 (3) Å. The dhbp ligand coordinating to Cu2 also shows π-stacking via two alternating inversion-symmetry operations, forming chains along [100]. The pyridine rings containing N3 and N4 intercross by the symmetry operation 1 − x, −y, 1 − z where the centroid of the ring defined by N3 is at a distance of 3.604 (2) Å from the centroid of the ring defined as N4 on side of the dhbp plane with the bridging hydroxide. These rings also π-stack on the opposite face of the plane at a distance of 3.768 (2) Å from the centroid of the ring defined by N3 to N4 through the symmetry operation −x, −y, 1 − z. Intermolecular hydrogen bonding from the bridging hydroxide ligand to the terminal oxygen of the bridging nitrate ligand interlinks neighboring molecules primarily along [100]. See Fig. 6Some intermolecular hydrogen-bonding interactions in both complexes have already been discussed, ac plane and exhibit π-stacking but in a less regular fashion than for complex (I)x, −y, −z with a centroid-to-centroid distance of 3.784 (2) Å of the pyridine rings containing N1 to the ring containing N2 and vice versa. A single ring of each dhbp ligand bound to Cu2 and Cu3 π-stack via translation at a distance of 3.551 (2) Å between the centroids of the pyridine rings defined by N3 and N5, respectively. Additionally, the Cu3 dhbp ligand π-stacks via the symmetry-equivalent ring defined by N5 of a neighboring molecule across the symmetry operation −x, −y, 1 − z at a centroid-to-centroid distance of 3.887 (2) Å. Close proximity occurs in plane between the pyridine ring containing N4 of the dhbp ligand bound to Cu2 at a distance of 3.818 (2) Å between C18 to C19 and vice versa across the symmetry operation 1 − x, 1 − y, −z.The hexanuclear complex (II)et al., 2007et al., 2013et al., 2009et al., 2013et al., 2006et al., 2006et al., 2002Although many structures have been reported featuring a hydroxide anion bridging two copper(II) ions each bound by 2,2′-bipyridine, no analogous structure has been reported with a 6,6′-dihydroxy-2,2′-bipyridine ligand. A search of the Cambridge Structural Database  Copper(II)The neutral copper hexanuclear complex (II) Copper(II)Crystal data, data collection, and structure refinement details are summarized in Table 3Cell Now  involve domain 2 only, mean I/σ 8.2, 34813 data (9811 unique) involve 2 domains, mean I/sigma 9.5, 11 data (11 unique) involve 3 domains, mean I/σ 8.7 and 4 data (2 unique) involve 4 domains, mean I/σ 57.6 The exact correlation matrix as identified by the integration program was found to be 1.00336 0.02923 −0.02720, −0.01894 1.02272 −0.04903, 0.02520 0.05747 0.97055. The data were corrected for absorption using TWINABS arom = 0.95 Å with Uiso(H) = 1.2Ueq(C), C—Hmethyl = 0.98 Å with Uiso(H) = 1.5Ueq(C). O—H were refined for complex (I)Uiso(HOH) were set to 1.5Ueq(O).C- and O-bound H atoms were placed in calculated positions and allowed to ride on their carrier atoms: aromatic C—H10.1107/S205698901502037X/lh5780sup1.cifCrystal structure: contains datablock(s) I, II. DOI: 10.1107/S205698901502037X/lh5780Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S205698901502037X/lh5780IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1433678, 1000450CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The coordination geometry of the metal ion is distorted trigonal bipyramidal, with the ligand O atoms in the axial sites. Two of the carboxylate groups of the ligand remain protonated and form short symmetric O—H⋯O hydrogen bonds. In the crystal, the ribbons interact via a network of O—H⋯O hydrogen bonds in which coordinating water molecules act as donors and carboxylate O atoms within adjacent ribbons act as acceptors, giving rise to a three-dimensional framework. O—H⋯N interactions are also observed. The asymmetric unit contains quarter of the ligand and the complete ligand has 2/m symmetry; the Li+ ion lies on a special position with m.. site symmetry. Both bridging water molecules have m2m site symmetry and both lattice water molecules have m.. site symmetry; one of the latter was modelled with a site occupancy of 0.25.The title coordination polymer, {[Li For the structures of related lithium complexes with pyrazine-2,3,5,6-tetracarboxylate and water ligands, see: Starosta & Leciejewicz 2010, 2014 ▶.2(C8H2N2O8)(H2O)2]·2.5H2O = 0.042wR(F2) = 0.122S = 1.071151 reflections85 parameters3 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.25 e Å−3Δρmin = −0.29 e Å−3ΔρCrysAlis PRO  used to solve structure: SHELXS97  I, New_Global_Publ_Block. DOI: 10.1107/S160053681401174X/hb7224Isup2.hklStructure factors: contains datablock(s) I. DOI: 1004410CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


N-(arylsulfonyl)-4-fluorobenzamides, namely 4-fluoro-N-(2-methylphenylsulfonyl)benzamide, (I), N-(2-chlorophenylsulfonyl)-4-fluorobenzamide, (II), and N-(4-chlorophenylsulfonyl)-4-fluorobenzamide monohydrate, (III), are described and compared with related structures. The conformation of the three molecules is very similar with the aromatic rings being inclined to one another by 82.83 (11) and 85.01 (10)° in the two independent molecules of (I), 89.91 (10)° in (II) and 81.82 (11)° in (III).The crystal structures of three  N-arylsulfonyl-4-fluorobenzamides, namely 4-fluoro-N-(2-methylphenylsulfonyl)benzamide, C14H12FNO3S, (I), N-(2-chlorophenylsulfonyl)-4-fluorobenzamide, C13H9ClFNO3S, (II), and N-(4-chlorophenylsulfonyl)-4-fluorobenzamide monohydrate, C13H9ClFNO3S·H2O, (III), are described and compared with related structures. The asymmetric unit of (I) contains two independent molecules (A and B), while that of (II) contains just one molecule, and that of (III) contains a molecule of water in addition to one main molecule. The dihedral angle between the benzene rings is 82.83 (11)° in molecule A and 85.01 (10)° in molecule B of (I), compared to 89.91 (10)° in (II) and 81.82 (11)° in (III). The crystal structure of (I) features strong N—H⋯O hydrogen bonds between the A and B molecules, resulting in an R44(16) tetrameric unit. These tetrameric units are connected into sheets in the bc plane by various C—H⋯O interactions, and adjacent sheets are further interlinked via C—H⋯πaryl interactions, forming a three-dimensional architecture. The crystal structure is further stabilized by πaryl–πaryl and S=O⋯πaryl interactions. In the crystal of (II), molecules are connected into R22(8) and R22(14) dimers via N—H⋯O hydrogen bonds and C—H⋯O interactions, respectively; the dimers are further interconnected via a weak C=O⋯πaryl interaction, leading to the formation of chains along [1-10]. In the crystal of (III), N—H⋯O and O—H⋯O hydrogen bonds involving both the main molecule and the solvent water molecule results in the formation of sheets parallel to the bc plane. The sheets are further connected by C—H⋯O interactions and weak C—Cl⋯πaryl, C—F⋯πaryl and S=O⋯πaryl interactions, forming a three-dimensional architecture.The crystal structures of three  An intramolecular C14B–-H14B⋯O2B hydrogen bond S(6) ring motif.The asymmetric unit of compound (I)B) Fig. 1, that diB) Fig. 1 containsB) Fig. 1 crystallnt Fig. 1. This isA—H1A⋯O1B and N1B—H1B⋯O1A hydrogen bonds , while in the second level the tetrameric unit has a graph-set motif of R44(16). Adjacent tetramers are connected into sheets in the bc plane  aryl–πaryl interactions  Å; Cg1 and Cg2 are the centroids of the fluorobenzoyl rings of molecules A and B, respectively] and also by weak S1A=O2A⋯πaryl interactions .The crystal structure of (I)s Table 1 between it Fig. 4. The unine Fig. 4 via C6A—s Table 1. AdjacenB) Fig. 5 to form ns Fig. 6  connect these dimers, thus forming a one-dimensional architecture .In the crystal of (II)re Fig. 7b.via bridging water molecules, through strong N1—H1⋯O4, O4—H1O4⋯O1, O4—H2O4⋯O2 and O4—H2O4⋯O3 hydrogen bonds  Å], C11—F1⋯Cg2 [F1⋯Cg2 = 3.8674 (17) Å] and S1=O2⋯Cg1 interactions [O2⋯Cg1 = 3.2039 (17) Å] , forming a complex three-dimensional architecture s Table 3, resultie Figs. 8 and 9 ▸.viz N-(arylsulfonyl)-4-(substituted)benzamides, gave 14 hits. These fourteen compounds along with the three title compounds, (I)–(III), are grouped into three series; series 1: N-(2-methylphenylsulfonyl)benzamide, N-(2-methylphenylsulfonyl)-4-(chloro/methyl/nitro/methoxy)benzamides and (I)series 2: N-(2-chlorophenylsulfonyl)benzamide, N-(2-chlorophenylsulfonyl)-4-(chloro/methyl/nitro/methoxy)benzamides and (II)series 3: N-(4-chlorophenylsulfonyl)benzamide, N-(4-chlorophenylsulfonyl)-4-(chloro/methyl/nitro)benzamides and (III)A search of the Cambridge Structural Database benzamide -4-nitrobenzamide -4-methoxybenzamide -4-chlorobenzamide -4-methylbenzamide -4-fluorobenzamide (I)ortho-methyl group on the benzenesulfonyl ring is syn to the N—H bond in the central –C–SO2--N–C(O)– segment. The values of the dihedral angle between the two aromatic rings in the molecules of series 1 fall in the range 73.9 (1)– 89.4 (1)°, the smallest dihedral angle being in N-(2-methylphenylsulfonyl)benzamide and the largest in N-(2-methylphenylsulfonyl)-4-chlorobenzamide  hydrogen bonds. However, except for compound (I)1 Table 4, the asye Table 4. CompariSeries 2: The asymmetric units of all of the compounds in series 2 – segment. The values of the dihedral angle between the two aromatic rings in the molecules fall in the range 73.3 (1)–89.91 (10)°, which is almost the same as in series 1, the smallest being in N-(2-chlorophenylsulfonyl)benzamide -4-fluorobenzamide (II)N-(2-chlorophenylsulfonyl)-benzamide, N-(2-chlorophenylsulfonyl)-4-chlorobenzamide -4-methylbenzamide  hydrogen bonds, while strong N—H⋯O(S) hydrogen bonds in N-(2-chlorophenylsulfonyl)-4-nitrobenzamide -4-methoxybenzamide -4-fluorobenzamide (II)via C=O⋯πaryl interactions, forming a one-dimensional architecture.2 Table 5 contain Series 3: In series 3, the parent compound N-(4-chlorophenylsulfonyl)benzamide -4-chlorobenzamide -4-methylbenzamide -4-nitrobenzamide -4-fluorobenzamide (III)N-(4-chlorophenylsulfonyl)benzamide and the largest for N-(4-chlorophenylsulfonyl)-4-methylbenzamide (Table 6e Table 6. Except Compounds (I)–(III) were prepared by refluxing a mixture of 4-fluorobenzoic acid, the corresponding substituted benzenesulfonamides and phosphorousoxychloride for 3 h on a water bath. The resultant mixtures were cooled and poured into ice-cold water. The solids obtained were filtered, washed thoroughly with water and then dissolved in sodium bicarbonate solutions. The compounds were later re-precipitated by acidifying the filtered solutions with dilute HCl. They were filtered, dried and recrystallized. [Melting point (m.p.) of (I)Uiso = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms. In the final cycles of refinement, reflections (0 1 1), (0 0 2) and  I, II, III, global. DOI: 1470505, 1470504, 1470503CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The title compounds, (I), (II) and (III), are indole derivatives. Compounds (I) and (II) present two independent moieties in the asymmetric unit, and their packing is led by C—H⋯O hydrogen bonds and C—H⋯π interactions. In compound (III), the C—H⋯O hydrogen bonds form  17H13NO2S, (I), C17H13NO3S, (II), and C24H17ClN2O5S·CHCl3, (III), are indole derivatives. Compounds (I) and (II) crystalize with two independent molecules in the asymmetric unit. The indole ring systems in all three structures deviate only slightly from planarity, with dihedral angles between the planes of the pyrrole and benzene rings spanning the tight range 0.20 (9)–1.65 (9)°. These indole ring systems, in turn, are almost orthogonal to the phenylsulfonyl rings [range of dihedral angles between mean planes = 77.21 (8)–89.26 (8)°]. In the three compounds, the molecular structure is stabilized by intramolecular C—H⋯O hydrogen bonds, generating S(6) ring motifs with the sulfone O atom. In compounds (I) and (II), the two independent molecules are linked by C—H⋯O hydrogen bonds and C—H⋯π interactions, while in compound (III), the molecules are linked by C—H⋯O hydrogen bonds, generating R22(22) inversion dimers.The title compounds, C The corresponding bond lengths and bond angles of molecules A and B [in compounds (I)A and B of compound (I)], 0.20 (9) and 0.86 (9) [molecules A and B of compound (II)], and 1.34 (14)° [compound (III)].The molecular structures of title compounds (I)The indole ring systems are almost orthogonal to the phenylsulfonyl rings [dihedral angles = 77.21 (8) and 89.26 (8)° in (I)sp2 bond lengths are longer than the mean value of 1.355 (14)Å for the N—C bond length  ring motifs with the sulfone O atom (Tables 1The sums of the bond angles around atoms N1 are 351.55 and 356.16° in (I) Tables 1 and 3 ▸.via intermolecular C16B—H16B⋯O2A hydrogen bonds running parallel to the [101] direction. The crystal packing is further stabilized by intermolecular C10A—H10A⋯Cg1, C11A—H11A⋯Cg2 and C16A—H16A⋯Cg3 interactions, with separations of 3.727 (2), 3.546 (2) and 3.699 (3) Å at  and , respectively. Cg2 is the centre of gravity of pyrrole ring N1B/C1B/C6B/C7B/C8B, and Cg1 and Cg3 are the centres of gravity of benzene rings C1B–C6B and C1A–C6A, respectively. C—H⋯π interactions run parallel to the [210] direction n Table 1.A and B) are linked by intermolecular C12B—H12B⋯O2A hydrogen bonds and are further connected by C5A—H5A⋯Cg1 and C17B—H17C⋯Cg2 interactions, with separations of 3.550 (2) and 3.729 (2) Å at  (1 and Cg2 are the centres of gravity of benzene rings C9A–C14A and C1A–C6A), respectively). The C12B—H12B⋯O2A and C17B—H17C⋯Cg2 interactions run parallel to the [101] direction and C5A—H5A⋯Cg1 interactions run along the triphenylphosphonium ylide  in dry toluene (20 ml) was refluxed for 12 h under an N2 atmosphere. After consumption of the starting material [monitered by thin-layer chromatography (TLC)], removal of the solvent in vacuo followed by column chromatographic purification  gave (I)A solution of triphenylphosphonium ylide  and 5-chloronitrobenzaldehyde  in dry chloroform (50 ml) was refluxed for 10 h under an N2 atmosphere. Removal of the solvent in vacuo followed by titration of the crude product with methonal (10 ml), gave (III)A solution of [(3-acetyl-1-phenylsufanyl-1Uiso(H) = 1.5Ueq(methyl C) and 1.2Ueq(nonmethyl C). The rotation angles for methyl groups were optimized by least squares.Crystal data, data collection and structure refinement details for compounds (I)10.1107/S2056989015014917/bg2558sup1.cifCrystal structure: contains datablock(s) I, II, III, global. DOI: 10.1107/S2056989015014917/bg2558Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989015014917/bg2558IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989015014917/bg2558IIIsup4.hklStructure factors: contains datablock(s) III. DOI: Click here for additional data file.10.1107/S2056989015014917/bg2558IIsup5.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989015014917/bg2558IIIsup6.cmlSupporting information file. DOI: 1417660, 1417659, 1417658CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the title compound, the hydrogen phosphate anions are linked by O—H⋯O hydrogen bonds into chains parallel to [100]. The inorganic anionic chains and the organic cations are linked by N—H⋯O and N—H⋯N hydrogen bonds, forming a two-dimensional supramolecular network extending parallel to (001). 6H9N2+·HPO42−, comprises two 2-aminoanilinium cations and one hydrogen phosphate dianion. In the crystal, the HPO42− dianions are linked by O—H⋯O hydrogen bonds into chains along [100]. The inorganic anionic chains and organic cations are linked by N—H⋯O and N—H⋯N hydrogen bonds, forming a two-dimensional supramolecular network extending parallel to (001).The asymmetric unit of the title compound, 2C Organic monohydrogen (HPO42−) and dihydrogen phosphate (H2PO4−) compounds provide a class of materials with numerous practical and potential uses in various fields such as biomolecular sciences, catalysis, liquid-crystal-material development, ferroelectrics, non-linear optical and supramolecular studies °].The asymmetric unit of the title compound comprises two 2-aminoanilinium cations and one hydrogen phosphate dianion Fig. 1. The exiviz. O—H⋯O, N—H⋯O and N—H⋯N (Table 1D⋯O2i hydrogen bond  connects adjacent hydrogen phosphate anions, forming anionic chains extending along [100]. The oxygen atom O3 acts as a trifurcated hydrogen-bond acceptor for the donor nitrogen atom N1 at ,  and , forming a one-dimensional supramolecular ladder extending along [100] as shown in Fig. 2C⋯O3, N3—H3A⋯O3i and N3—H3B⋯O3iv  hydrogen bonds, forming two types of fused rings of B⋯O2, N1—H1A⋯O4ii and N1—H1C⋯O4iii  hydrogen bonds, resulting in the formation of a two-dimensional organic–inorganic supramolecular layered network parallel to (001)  −x, −y + 2, −z + 2; (v) x, −1 + y, z] hydrogen bonds stabilize the (001) network. In the crystal structure  Fig. 3. In the re Fig. 4, adjacenConQuest 1.17; Groom & Allen, 2014et al., 2002et al., 2012et al., 2010et al., 1998et al., 2005A CSD database search  = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016004709/rz5186sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016004709/rz5186Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016004709/rz5186Isup3.cmlSupporting information file. DOI: 1469440CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The two symmetry-related tetrabromophthalate anions bridge the two CuII cations, forming a centrosymmetric dinuclear complex in which the Cu⋯Cu separation is 5.054 (2) Å. Intramolecular classic O—H⋯O hydrogen bonds and weak C—H⋯O hydrogen bonds occur in the dinuclear molecule. In the crystal, the molecules are linked by weak C—H⋯Br and C—H⋯O interactions into supramolecular chains propagating along the b-axis direction.In the title complex, [Cu For the al. 2004; Colacio al. 2009; Rodpun  al. 2015; Yang et al. 2002. For the al. 2009; Kozlevč al. 2004. For sup al. 2013; Stibran al. 2009; Aakeröy al. 2003; Valdés- al. 1993; Julve e al. 1984. For mol al. 1984; Mendy e al. 2010.2(C8Br4O4)2(C6H16N2)2(H2O)2] = 0.016wR(F2) = 0.039S = 1.073739 reflections245 parameters2 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.80 e Å−3Δρmin = −0.41 e Å−3ΔρAPEX2  used to solve structure: SHELXS97  I, New_Global_Publ_Block. DOI: 10.1107/S2056989015015194/xu5866Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015015194/xu5866fig1.tif. DOI: The structure with displacement ellipsoids drawn at the 30% probability level and H atoms shown as small spheres of arbitrary radii.Click here for additional data file.10.1107/S2056989015015194/xu5866fig2.tif. DOI: View of interactions in the crystal.1418832CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


I atoms in the dication of the title structure, [(C6H5)2PCH2P(C6H5)2Au2]Cl2·(CH3)2C=O·H2O, show an aurophilic interaction of 2.9743 (2) Å.The Au 2{(C6H5)2PCH2P(C6H5)2}]Cl2·(CH3)2C=O·H2O, the dication forms an eight-membered {—PCPAu}2 ring with a transannular aurophilic interaction [Au⋯Au = 2.9743 (2) Å]. The ring approximates a flattened boat conformation, with the two methylene C atoms lying ca 0.58–0.59 Å above the least-squares plane defined by the Au2P4 atoms (r.m.s. deviation = 0.0849 Å). One Cl− anion functions as a weak bridge between the AuI atoms [Au⋯Cl = 2.9492 (13) and 2.9776 (12) Å]. The second Cl− anion forms two (water)O—H⋯Cl hydrogen bonds about a centre of inversion, forming a centrosymmetric eight-membered {⋯HOH⋯Cl}2 supramolecular square. Globally, the dications and loosely associated Cl− anions assemble into layers lying parallel to the ac plane, being connected by C—H⋯Cl,π(phenyl) interactions. The supramolecular squares and solvent acetone molecules are sandwiched in the inter-layer region, being connected to the layers on either side by C—H⋯Cl,O(acetone) interactions.In the title complex salt, [Au These compounds are cytotoxic and kill cancer cells by initiating apoptotic pathways  carbonimidothioates, 2C6H4} ]Cl2, was isolated as an acetone monosolvate monohydrate, (I)2(Ph2PCH2PPh2)]Cl2 salts characterized as an acetone solvate  thiolates, reactions with the bipodal molecule, {1,4-[MeOC(=S)N(H)]2(Ph2PCH2PPh2)]2+ dication, two Cl− anions, and a solvent molecule each of acetone and water; all species are in general positions. The molecular structure of the dication is shown in Fig. 1I atoms are bridged by two Ph2PCH2PPh2 ligands, forming an eight-membered {—PCPAu}2 ring. The ring has the form of a boat with the methylene-C1 and C2 atoms lying to one side of the ring and 0.589 (5) and 0.581 (5) Å, respectively, above the least-squares plane through the Au2P4 atoms which have a r.m.s. deviation of 0.0849 Å. There is a transannular Au1⋯Au2 (aurophilic) interaction of 2.9743 (2) Å. This interaction is partly responsible for the deviations of the P1—Au1—P3 and P2—Au2—P4 angles from the ideal 180°, i.e. 173.24 (4) and 170.04 (4)°, respectively. The Au—P bond lengths are almost equivalent, ranging from a short Au1—P1 2.3061 (12) to a long Au2—P4 2.3130 (12) Å. The Cl1− anion forms a weak bridge between the two AuI atoms with Au1⋯Cl1 and Au2⋯Cl2 separations of 2.9492 (13) and 2.9776 (12) Å, respectively. The second Cl− anion participates in hydrogen bonding as described below in Supramolecular features.The asymmetric unit of (I)2 supramolecular squares with edge lengths of 3.217 (5) and 3.200 (5) Å, Table 1ac plane, corresponding to the inter-layer region between layers of dications and Cl1− anions, Fig. 2− anion forms a single (phenyl)C—H⋯Cl contact, a reduced propensity reflecting its close association with the AuI atoms (see above). By contrast, the Cl2− anion forms four independent C—H⋯Cl2 interactions, i.e. a (methylene)C—H⋯Cl2 and three (phenyl)C—H⋯Cl2 interactions, providing links between the {⋯HOH⋯Cl}2 rings and the cations. The acetone solvent molecule accepts a (methylene)- and a (phenyl)C—H⋯O contact.The most notable feature of the crystal packing of (I)2(Ph2PCH2PPh2)]Cl2 salt has been characterized twice previously, originally as an acetone solvate 2(Ph2PCH2PPh2)]Cl2 salts relates to the mode of association between the complex Au cations and Cl− anions. As noted above and shown in Fig. 4a, the Cl1− anion in (I)I atoms. In the acetone solvate  Å. A similar pattern is noted in the acetonitrile solvate ]Cl2 salts with loosely associated Cl− anions having greater distortions from linearity, in particular for the acetone solvate (AuCl)2  in acetonitrile (50 ml) was added NaOH  and {1,4-[MeOC(=S)N(H)]2C6H4}  in acetonitrile (50 ml). The resulting mixture was stirred at 323 K for 2 h. The final product was extracted with dichloromethane (100 ml) and the solution was left for evaporation at room temperature. After 3 weeks a slurry formed. This was redissolved in a solvent mixture of acetone/acetonitrile  and left for slow evaporation. Colourless crystals were obtained after 10 days. Yield: 0.213 g (43%). M.p. 477–479 K. 1H NMR : δ 7.96 , 7.49 , 7.41 , 4.84 , 2.82 . Analysis calculated for C53H52Au2Cl2O2P4: C, 48.61; H, 4.00. Found: C, 48.64; H, 3.99. IR (cm−1): 3044 (m) ν(C—H), 1484 (s) ν(C—C).The title compound is an unexpected product from the reaction of bis[chloridogold(I)] bis(diphenylphosphane)methane with an equimolar amount of {1,4-[MeOC(=S)N(H)]Uiso(H) set to 1.2–1.5Uequiv(C). The water-bound H atoms were refined with O—H = 0.84±0.01 Å, and with Uiso(H) = 1.5Uequiv(O). The U33 parameter was elongated for the C93 atom. In the final refinement this was restrained to be nearly isotropic using the ISOR command in SHELXL  I, global. DOI: 10.1107/S2056989015013341/wm5185Isup2.hklStructure factors: contains datablock(s) I. DOI: 1412185CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The title platinum(II) complex shows a trigonal–bipyramidal coordination and intermolecular C—H⋯Cl, C—H⋯π and (C/O)—H⋯O hydrogen bonds. 11H13O2)Cl(C5H11N)]·C2H5OH, the PtII cation is pentacoordinated in a distorted square-planar geometry. In the crystal, inversion dimers showing C—H⋯Cl and C—H⋯π interactions are further stacked in columns along the a axis via C—H⋯π interactions. The ethanol solvate molecule interacts with neighbouring methoxy groups of methyleugenol through O—H⋯O hydrogen bonds.In the title compound, [Pt(C In order to avoid steric hindrance between Cl1 and the two ring systems, especially atoms C2 and C12, both rings rotate along their bond with Pt1. This is easier for the piperidine ring [resulting in a C12—N1—Pt1—Cl1 torsion angle of 70.7 (2)°] than for the phenyl ring [C2—C1—Pt1—Cl1 torsion angle of only −25.0 (4)°]. As a consequence the H12B⋯Cl1 distance (2.831 Å) is larger than the H2⋯Cl1 distance (2.789 Å).In [PtCl(Meug-1H)(piperidine)], the Ptom Fig. 1. The twoA⋯Cg1 interactions, Cg1 is the centroid of the C1–C6 aromatic ring, see Table 1A⋯Cg1 interactions. The ethanol molecule interacts by bifurcated O—H⋯O hydrogen bonds with both methoxy groups of methyleugenol and further on by C—H⋯O interactions to a neighboring methoxy group. No voids are present in the crystal packing.In the crystal packing Fig. 2, the com3 torsion angles vary between −28 and +32° (only 11 torsion angles are outside this region).The Cambridge Structural Database 2] was prepared from K[PtCl3(Meug)] in high yield (85%) according to Da et al. 2] and 6ml of acetone. The reaction mixture was stirred at room temperature for 30 min. The obtained solution was cooled to 255 K after which the precipitate was collected and washed with Et2O. The yield was 320 mg (65%). The powder was dissolved in an acetone–ethanol mixture. Colourless plate-like crystals were harvested after slow evaporation of acetone at room temperature.The title compound was synthesized by adding a solution of 1 mmol of piperidine in 3 ml of acetone to a mixture of 408 mg (0.5 mmol) of : C16H24ClNO2Pt, M = 491–495 au; found : 490–494 ([M−H]+).IR  with C—H distances of 0.95 (aromatic), 0.98 (methyl) and 0.99 Å (methylene), N—H distance of 0.93 (NH) and O—H distance of 0.84 Å.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S1600536814023575/rz5134sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814023575/rz5134Isup2.hklStructure factors: contains datablock(s) I. DOI: 1031185CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the brightly green fluorescent Zn-complex of the hardly luminescent dipyrrin, the metal ion is bound by two dipyrrin ligands, as revealed first by its mass spectra. The crystal structure of this Zn-complex of the dipyrrin confirmed a regular 2:1 composition of the bidentate dipyrrin ligand and the metal ion. The latter was coordinated in a distorted tetrahedral fashion, as found in other dipyrrin Zn-complexes. The here studied Zn-complex of a designed dipyrrin ligand provides insights into the coordination properties of the proposed (2:1)- and (2:2)-complexes of phylloxanthobilin and bilirubin, respectively, which are two abundant natural bilin-type tetrapyrroles.A high yield preparation, spectroscopic and crystallographic investigation of the crystalline Zn-complex of a di( Dipyrrins (or dipyrromethenes) feature two conjugated pyrrole rings and represent  dipyrrolic building blocks for the construction of porphyrins and related tetrapyrrolic macrocycles . The comβ,β′-sulfoleno)pyrrin 2.In the context of our recent interest in the metal coordination properties of yellow chlorophyll catabolites (phylloxanthobilins) , and of β,β′-sulfoleno)pyrrin 2 relied on the earlier made corresponding dipyrromethane (1), available, in turn, from condensation of 3,5-di-tert-butylbenzaldehyde and β,β′-sulfolenopyrrole + at m/z = 1087.2. Corresponding significant fragments occurred at m/z = 1023.3, 894.4, and 830.4, due to consecutive loss of the one, three, and four SO2-groups, respectively. The derived molecular formula of the Zn-complex 3 suggested the presence of two dipyrrin ligands 2 and one Zn(II)-ion, i.e. to represent Zn-(2)2 (see Scheme The molecular formula of the dipyrrin Zn-complex 3 displayed a UV/Vis-spectrum in CH2Cl2 that featured a maximum at 487 nm (and a shoulder at 463 nm), corresponding to a 51 nm bathochromic shift, when compared with the spectrum of the dipyrrin 2 (see above). Similar bathochromic shifts of the absorption spectrum upon coordination of a Zn(II) ion were observed in Zn-complexes of bilirubin , a signal of an HN was lacking (which was found at 12.76 ppm in the spectrum of the dipyrrin 2), consistent with bidentate binding of the dipyrrin ligand 2 to the coordinated Zn(II) ion. Signals of aryl-o hydrogens and aryl-p hydrogen are slightly shifted to lower field while signals of β-methylene groups and pyrrole-α hydrogens are slightly moved to higher field.In the 3 grew from a solution of 3 in CH2Cl2 when n-C6H14 was mixed in slowly at 4 °C. The Zn-complex 3 crystalized in the triclinic system with space group P-1 (no. 2). A unit-cell contained four molecules of 3. The crystal structure of 3 showed two bidentate dipyrrin moieties wrapped around one Zn(II) center leading to coordination in a distorted tetrahedral fashion with N–Zn–N angles of about 94, 113, and 121°  Zn-complexes -cycloaddition reactions. As was recently developed with porphyrinoids, such as tetra-sulfolenoporphyrins  were reagent grade commercial chemicals from Fluka and were used as received; EtOAc, dichloromethane, methanol (MeOH), and n-C6H14 were from Acros and were distilled before use. Column chromatography (CC): Fluka silica gel 60 (230–400 mesh). Thin layer chromatography (TLC): Merck 0.25 mm silica gel 60 plates. Equipment: UV/Vis: Agilent Cary 60 UV–Visible, λmax in nm (log ε). Fluorescence (FL): Varian Cary Eclipse, λ in nm (rel. intensity); Nuclear magnetic resonance (1H) spectra: Bruker 300 at 298K, chemical shifts (δ) in ppm, with δ (CHCl3) = 7.26 ppm, signal assignment follows the X-ray numbering scheme. FAB-MS: Finnigan MAT-95, positive ion mode, NOBA matrix; X-ray analyses: data collection on a Nonius Kappa CCD, equipped with graphite mono-chromatized Mo-Kα-radiation (λ = 0.71073 Å) at 233K. Melting point: Büchi 535.Dichlorodicyano-1 (3.8 μmol) +), 894.4 ([M–3SO2]+), 830.4 ([M–4SO2]+).Dipyrrin 54H62N4O8S4Zn × CH2Cl2 × 0.75 C6H14, formula weight: 1238.24; temperature 233(2) K; radiation wavelength 0.71073 Å; crystal system triclinic; space group P-1 (no. 2); unit cell dimensions a = 18.5998(4) Å, b = 18.9173(3) Å, c = 21.6741(5) Å, α = 98.771(1)°, β = 104.394(1)°, γ = 109.204(1)°; volume 6743.1(2) Å3; Z = 4; density  1.220 g/cm3; absorption coefficient 0.618 mm−1; crystal size 0.45 × 0.25 × 0.03 mm3; F(000) 2606; theta range for data collection 1.335°–24.145°; index ranges −21 ≤ h ≤ 21, −21 ≤ k ≤ 21, −24 ≤ l ≤ 24; reflections collected 36397; independent reflections 21231 [R(int) = 0.0379]; completeness to theta (24.145°) 98.5 %; absorption correction none; refinement method Full-matrix least-squares on F2; data/restraints/parameters 21231/29/1489; goodness-of-fit on F2 1.032; final R indices [I >2σ(I)] R1 = 0.0769, wR2 = 0.1998; R indices  R1 = 0.1148, wR2 = 0.2209. Crystallographic data of 3 (Zn-(2)2) (excluding structure factors) have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication number CCDC no. 1453954. Copies of the data can be obtained free of charge from the Cambridge Crystallographic Data Centre via http://summary.ccdc.cam.ac.uk/structure-summary-form.Crystallographic data: C


S(6) ring and therefore establishes a syn relationship for the N atoms. In the crystal, molecules are linked by N—H⋯N hydrogen bonds, generating [100] chains containing alternating A and B molecules.The two molecules of 2-(2-aminophenyl)-1,3-benzoxazole in the asymmetric unit feature an intramolecular N—H⋯N hydrogen bond, which closes an  13H10N2O, were grown from a dichloromethane/ketone/methanol solvent mixture. It crystallizes with two molecules, A and B, in the asymmetric unit with very similar almost planar conformations . Each molecule features an intramolecular N—H⋯N hydrogen bond, which closes an S(6) ring and therefore establishes a syn relationship for the N atoms. In the crystal, molecules are linked by N—H⋯N hydrogen bonds, generating [100] chains containing alternating A and B molecules. Weak aromatic π–π stacking [minimum centroid–centroid separation = 3.6212 (9) Å] links the chains into a three-dimensional network.Crystals of the title compound, C The oriA and B, respectively. The dihedral angles between the benzene ring and the fused ring system are 0.74 (8) and 0.67 (6)° for molecules A and B, respectively. The two independent molecules are very similar, with an r.m.s. overlay fit of 0.019 Å.The skeleton of each molecule is practically planar: to analyse the planarity of the molecule we use the torsion angle N3—C2—C8—C9, indicating the rotation of the aromatic ring C8—C13: these angles are −1.2 (2) and 0.9 (2)° for molecules 2 group forms an intramolecular hydrogen bond of the type N2—H2B⋯N3 (Table 1A and 2.146 (18) Å in molecule B, and an intermolecular N2—H2A⋯N2 hydrogen bond with a distance of 2.289 (15) Å for N2—H2A⋯N2′ and 2.522 (16) Å for N2′—H2A′⋯N2, forming zigzag chains propagating in the [100] direction and containing alternating A and B molecules  of o-aminophenol were added followed by the addition of 0.30 ml (10% mol) of a solution of ZnCl2 (1 M). The mixture was then stirred and heated slowly to reflux temperature during 18 h. The crude reaction product was concentrated on a rotary evaporator with an azeotropic mixture of AcOEt/xylene to obtain a reddish brown solid which was dissolved in EtOAc and washed with 10% aq. NaCl solution. The crude reaction product was purified by column chromatography to give 356 mg (55%) of the amine (I)γmax cm−1: 3408 NH2, 3051 C—H(arom), 1624 C=N; : δ = 6.20 , 6.79 , 7.29 , 7.33 , 757 , 7.72 , 8.09 ; 13C NMR  δ = 108.7, 110.4, 116.3, 116.8, 119.4, 124.3, 124.8, 128.8, 132.5, 141.9, 147.9, 149.3, 163.2 . Analysis calculated for C13H10N2O: C, 74.27; H, 4.79%; Found: C, 74.43; H, 5.05%.500 mg (3.00 mmol) of isatoic anhydride were dissolved in 50 mL of sage 2003; 1H NMR The single crystal used in the experiment was obtained by the method of liquid–liquid diffusion by slow evaporation. The pure compound was dissolved in the minimum amount of dichloromethane to be added by the walls of the tube the same amount of acetone followed by methanol. The tube was sealed to leave the solution in a vibration-free environment at room temperature. After a few days, the solution had evaporated, leaving colourless blocks of the title compound.isoU(H) = 1.2eqU(C). Hydrogen atoms of the amine group were found in a difference map and refined freely.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989015000481/hb7320sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015000481/hb7320Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015000481/hb7320Isup3.cmlSupporting information file. DOI: 1042858CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal structure of the title compound, the sulfonamide N—H group forms an intermolecular hydrogen bond to the amine N atom. 15H24N2O2S, was synthesized via a substitution reaction between the enantiopure -(+)-1,2-diaminocyclohexane and 2,4,6-trimethylbenzene-1-sulfonyl chloride. The cyclohexyl and phenyl substituents are oriented gauche around the sulfonamide S—N bond. In the crystal, molecules are linked via N—H⋯N hydrogen bonds, forming chains propagating along [100].The title compound, C A weak intramolecular interaction is present between the amine H2A atom and the sp2-hybridized sulfonamide N1 atom  interactions with an H2B⋯O1 distance of 2.72 Å between the donor amine N2—H2B and the acceptor sulfonamide O1 atoms can also be noticed within this chain.Molecules of the title compound are held together in the solid state by intermolecular hydrogen-bonding interactions between the donor sulfonamide N1—H1 and the acceptor amine N2 atoms Table 1. These hD⋯H = 0.860 (7) Å; H⋯A = 2.160 (8) Å; D⋯A = 3.011 (8) Å; D—H⋯A = 169.9 (5)°].As for the racemic crystal FAVHEP, in the model deposited in the CSD there is one intermolecular hydrogen bond present between a donor sulfonamide N1—H1 and a nearby amine acceptor N atom [et al., 2012et al., 2014et al., 2010trans-1,2-diaminocyclohexane ring are bonded to a mesitylsulfonamide group. Structure FAVHEP -(+)-1,2-diaminocyclohexane  in 5 ml of CH2Cl2 at 273 K was added a solution of 2,4,6-trimethylbenzene-1-sulfonyl chloride  in 5 ml CH2Cl2. After the addition was complete (20 min), the mixture was allowed to warm to room temperature and stirred overnight. The reaction mixture was washed with H2O (3 × 25 ml) and the aqueous layer was back-extracted with CH2Cl2 (20 ml). The combined organic extracts were dried over Na2SO4 and the solvent was removed under reduced pressure. The residue was purified by column chromatography over silica gel (CH2Cl2/EtOAc 1:1 v/v) to afford a pale-yellow–white solid . Part of the purified product was redissolved in CH2Cl2 and after slow evaporation for several days, white large chunky crystals (stained yellow) were formed that were suitable for analysis by X-ray diffraction (m.p. 406–407 K).To a stirred solution of (1Uiso(H) = 1.2Ueq(C) for methine, methylene and aryl groups, and Uiso(H) = 1.5Ueq(C) for methyl groups. H atoms bonded directly to N atoms  were located in difference-Fourier maps and refined isotropically.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S205698901502191X/gk2646sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901502191X/gk2646Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901502191X/gk2646Isup3.cmlSupporting information file. DOI: 1437453CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


L2(H2O)4]·2H2O , the CdII ion is situated on an inversion centre being coordinated by four aqua molecules in the equatorial plane and two deprotonated phosphonate O atoms from two L ligands in the axial positions in a distorted octahedral geometry. Each ligand L exists in a zwitterionic form, and with an intramolecular O—H⋯O interaction forming an S(6) ring motif and two intramolecular N—H⋯O interactions each generating an S(5) ring motif. In the crystal, N—H⋯O and O—H⋯O hydrogen bonds link complex molecules into a three-dimensional network with voids of 38 Å3 filled with ordered lattice water molecules, which are also involved in O—H⋯O hydrogen bonding.In the compound [Cd L2(H2O)4]·2H2O , the CdII ion is situated on an inversion centre being coordinated by four aqua molecules in the equatorial plane and two phosphonate O atoms from two deprotonated L ligands in the axial positions in a distorted octahedral geometry. The asymmetric unit contains one-half of the complex molecule and one lattice water molecule. The ligand L exists in a zwitterionic form, with a positive charge on the NH3 group and a negative charge on the O atom of the non-coordinating phosphonate group, and with an intramolecular O—H⋯O interaction forming an S(6) ring motif and two intramolecular N—H⋯O interactions each generating an S(5) ring motif. In the crystal, N—H⋯O and O—H⋯O hydrogen bonds link the complex molecules into a three-dimensional network in which the voids of 38 Å3 are filled with ordered lattice water molecules, which are also involved in O—H⋯O hydrogen bonding.In the title compound, [Cd All bond lengths and angles in (I)et al., 1991et al., 1997et al., 2005et al., 2006et al., 2007et al., 2007et al., 2009et al., 2010et al., 2010II atom occupies a special position on an inversion centre and shows a slightly distorted octahedral coordination environment formed by two phosphonic O atoms in trans positions and four aqua O atoms in the equatorial plane. The distorted octahedral coordination polyhedron is slightly compressed in the axial direction; the Cd1—O2 bond length is 0.1 Å shorter than the Cd1—O1W and Cd1—O2W bonds. The values of the axial O—Cd—O angles are in the range 80.1 (4)–99.9 (4)°, indicating a significant deviation from ideal values. The ligand L exists in a zwitterionic form, with a positive charge on the NH3 group and a negative charge on the O atom of the non-coordinating phosphonate group, and with an intramolecular O—H⋯O interaction forming an S(6) ring motif and two intramolecular N—H⋯O interactions each generating an S(5) ring motif f Table 1.b axis. Intermolecular N—H⋯O and O—H⋯O hydrogen bonds  at 273 K to produce the title compound (I)1H and 13C{1H} NMR spectra were recorded on a Bruker Bio spin 400 spectrometer.All reactions and manipulations were carried out in air with reagent grade solvents. 1-Aminoethane-1,1-diyldiphosphonic acid was prepared according to the literature method of Rukiah & Assaad 2013. The titSpectroscopic data for (I)1H NMR : δ 1.67 . 13C{1H} NMR : δ 20.5 , 54.7 . 31P{1H} NMR : δ 13.61. IR : 3446.2 (NH3), 2351.5 (POH), 1605.0 (O=P—O—H).α1 radiation (λ= 1.54060 Å) selected with an incident-beam curved-crystal Ge(111) monochromator with a linear position-sensitive detector (PSD). The pattern was scanned over the angular range 6.0–90.0° (2θ). For pattern indexing, extraction of the peak positions was carried out with the program WinPLOTR  = 37.1, F(20) = 78.5]. The best estimated monoclinic space group was P21/c.Crystal data, data collection and structure refinement details are summarized in Table 2et al., 1988FULLPROF . These μ·d values were determined experimentally. The preferred orientation was modelled with 12 coefficients using a spherical harmonics correction  = 0.011009 and χ2 = 8.940) indicate that the preferred orientation improvement of the refinement is considerable.The powder pattern was subsequently refined with cell and resolution constraints  on bond lengths were applied to normal values for these bonds. The final refinement cycles were performed varying isotropic displacement parameters for Cd and water O atoms, and fixed isotropic displacement parameters for P, C, N,O and H atoms. The final Rietveld plot is shown in Fig. 3Before the final refinement, the H atoms of the CH10.1107/S2056989015004028/cv5484sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015004028/cv5484Isup2.rtvRietveld powder data: contains datablock(s) I. DOI: 1051338CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Nature Communications7: Article number: 10269 10.1038/ncomms10269 (2016); Published: 01052015; Updated: 05112016x axis in Supplementary Figure 3 (lower panel). The x axis in this panel should have been labelled ‘22 °C Mock; 22 °C GDA; 29 °C Mock; 29 °C GDA'. The correct version of this figure appears below.This Article contains errors in the labelling of the Supplementary Figure 3


The cyclohexene ring adopts an envelope conformation in both molecules, with the C atom to which is attached the central benzene ring as the flap. The crystal packing, is stabilized by C—H⋯π interactions. 27H26O3, crystallized with two independent molecules (A and B) in the asymmetric unit. In molecule A, the plane of the central benzene ring forms dihedral angles of 75.78 (14) and 52.75 (16)° with that of the terminal benzene rings, and the dihedral angle between the planes of the terminal benzene rings is 51.49 (17)°. The corresponding values for molecule B are 75.18 (14), 58.11 (16) and 47.91 (16)°, respectively. The cyclohexene ring adopts an envelope conformation in both molecules, with the C atom to which is attached the central benzene ring as the flap. The crystal packing, is stabilized by C—H⋯π interactions.The title compound, C Cyclohexenone and cyclohexenone derivatives are known for anti-inflammatory and analgesic activities  in the asymmetric unit  and 1.224 (3) Å, respectively, indicate double-bond character. In both molecules, the C—O bond lengths are in the range 1.362 (3)–1.414 (4) Å and represent single-bond character. In molecule A, the torsion angles C5—C4—C7—C8 = 69.2 (4)° and C24—C9—C10—C11 = −16.0 (4)° show that the benzyloxyphenyl and methoxyphenyl groups have a +sc and -sp orientation with respect to the cyclohexene moiety. The arrangement in molecule B is slightly different, with torsion angles C5A—C4A—C7A—C8A = 111.5 (3)° and C24A—C9A—C10A—C11A = 20.8 (4)°. The cyclohexene ring in both molecules adopts an envelope conformation with atoms C7 and C7A as the flaps in molecules A and B, respectively.The title compound crystallized with two molecules -3-(4-Benzyloxyphenyl)-1-(4-methoxyphenyl)prop-2-en-1-one was synthesized following the literature procedure of Ezhilarasi et al. -3-(4-benzyloxyphenyl)-1-(4-methoxyphenyl)prop-2-en-1-one (0.01 mol) and ethyl methyl ketone (0.01 mol) were refluxed in absolute alcohol (50 ml) in the presence of 10% sodium hydroxide solution (10 ml) for 1 h in an oil bath. The reaction mixture was then cooled and the precipitate obtained filtered, washed with distilled water and dried. The crude product was recrystallized twice from absolute alcohol (yield 80%), giving yellow block-like crystals. = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989014025390/su5016sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989014025390/su5016Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989014025390/su5016Isup3.cmlSupporting information file. DOI: 1035112CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The sulfonate group is disordered over two positions with occupancy factors of 0.655 (5) and 0.345 (5). The hexaaquanickel(II) cation interacts through hydrogen bonding with eight QOH molecules and two water molecules. The six-membered rings of quinoline show π–π stacking [centroid-to-centroid distances of 3.679 (2) Å and 3.714 (2) Å].The asymmetric unit of the title compound, [Ni(H Quinine, cinchonine, chloroquine, plasmoquine and acriquine, for instance, are known to be able to cure malaria  has been synthesized from eugenol and its antibacterial activities have been reported . As quinoline rings are known to complex with metal ions, the formation of a complex between QOH and NiII was studied. The reaction product, however, could not be characterized unambiguously by IR or 1H NMR spectroscopic methods. The spectroscopic data are different from those obtained for free QOH and in favour of a deprotonated carboxylic acid group, but give no indication about a possible complex formation. X-ray diffraction now shows that QOH is not complexing directly with NiII.Recently, the new quinoline derivative 6-hydroxy-3-sulfoquinolin-7-yloxyacetic 6]2+ is located about an inversion center and has an octahedral volume of 11.629 Å3 with Ni—O bond lengths between 2.034 (3) and 2.106 (2) Å.The structure determination shows that the carboxyl group of rm Fig. 1, which wQOH moieties and two water molecules through O—H⋯O and N—H⋯O hydrogen bonding (Table 1The hexaaquanickel(II) cation plays the role of glue in the crystal packing. In total, it interacts with eight g Table 1.Cg1⋯Cg1ix = 3.679 (2) Å, Cg1⋯Cg2ix = 3.714 (2) Å; Cg1 and Cg2 are the centroids of the rings C12/C13/N14/C15–C17 and C15/C16/C18–C21, respectively; symmetry code: (ix) −x + 1, −y + 2, −z + 1; Fig. 3Furthermore, π–π stacking between the quinoline rings results in the formation of inversion dimers [QOH molecule and furthermore with the sulfonate group (O7) of a second QOH molecule and the hexaaqua complex (O2). Whereas hydroxyl group O23—H23 only interacts with water molecule O29, the second hydroxyl group O22—H22 is involved in the formation of another type of inversion dimers through C—H⋯O hydrogen bonding and interacts with a sulfonate group (O8) (Table 1Lattice water molecule O29 interacts with the carboxylate (O27) and hydroxyl (O23) groups of a neighboring ) Table 1.A search of the Cambridge Structural Database  was synthesized and further transformed to 5,6-dihydroxy-3-sulfoquinolin-7-yloxyacetic acid (QOH) according to a procedure described by Dinh et al.  in ethanol–water  was added dropwise to a solution of QOH  in ethanol–water . The obtained solution was stirred for three hours, at 313–323 K, during reflux. A few days later, the green–yellow precipitate was collected by filtration, washed consecutively with ethanol and diethyl ether and dried in vacuo. The obtained crystals are soluble in water and DMSO, but only slightly soluble in ethanol, acetone and chloroform. The yield was 65%. Single crystals suitable for X-ray investigation were obtained by slow evaporation from a ethanol–water (1:1 v/v) solution at room temperature. IR : 3420 (νOH); 3080, 2918 (νC-H); 1620 (νCOOas); 1426(νCOOs); 1528 (νC=Cring or νC=N); 466 (νNi-O). 1H NMR : δ 8.74 , 8.17 , 7.2 , 4.64 ; : δ 9.26 , 9.01 , 7.01 , 4.80 .A solution containing NiClB, H3B, H4B, H14, H29A and H29B were located in difference Fourier maps. All other H atoms were placed at idealized positions and refined in riding mode, with C—H distances of 0.95 (aromatic) and 0.99 Å (methylene), and O—H distances of 0.84 Å. The H atoms of water molecule O29 were refined with an O—H distance restraint of 0.85 Å and H⋯H distance restraint of 1.39 Å. For all H atoms, Uiso(H) values were assigned as 1.2Ueq of the parent atoms (1.5Ueq for H22 and H23). The SO3 group is disordered over two positions, the occupancy ratio refines to 0.655 (5):0.345 (5) for part 1  and part 2 , respectively.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989015015662/vn2096sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015015662/vn2096Isup2.hklStructure factors: contains datablock(s) I. DOI: 1419884CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Scientific Reports5 Article number: 14289; 10.1038/srep14289 published online: 09232015; updated: 12182015.In Supplementary Figure 1a, the Linzizong volcanic rock samples ‘12LZ14-1’ and ‘12LZ13-1’ should read ‘13LZ14-1’ and ‘13LZ13-1’ respectively. The correct Supplementary Figure 1a appears below as In Table S1, samples ‘12LZ13-1@02’ and ‘12LZ14-1@02’ should read ‘13LZ13-1@02’ and ‘13LZ14-1@02’ respectively.


The angles at the NiII cation, which lies on a twofold rotation axis, are Cl—Ni—Cl = 115.58 (3)° and S—Ni—S = 94.55 (3)°. All other angles at the central NiII atom range from 109.46 (2) to 112.96 (2)°. The C—S—Ni angle is 99.91 (6)°. The planes of two imidazolium rings make a dihedral angle of 70.56 (6)°.In the molecular structure of the title compound, [NiCl DOI: 10.1107/S2056989015012281/hp2071Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015012281/hp2071fig1.tif. DOI: Molecular structure of the title compound with anisotropic displacement parameters drawn at the 50% probability level.1408996CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The asymmetric unit consists of one Cd2+ cation, two thiocyanate anions and two 4-(hydroxymethyl)pyridine ligands in general positions. Two Cd2+ cations are linked by two μ-1,3 N- and S-bonding thioycanate anions into dimers which are further linked into branched chains along [100] by two μ-1,6 N- and O-bonding 4-(hydroxymethyl)pyridine ligands. One additional N-bonded 4-(hydroxymethyl)pyridine ligand and one additional N-bonded thiocyanate anion are only terminally bonded to the metal cation. Interchain O—H⋯S hydrogen bonds between the hydroxy H atoms and one of the thiocyanate S atoms connect the chains into a three-dimensional network.The crystal structure of the title compound, [Cd(NCS) DOI: 10.1107/S2056989015008890/wm5156Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015008890/wm5156fig1.tifx y z x y z . DOI: x + 1, −y + 1, −z + 1; (ii) −x + 2, −y + 1, −z + 1.]Part of the crystal structure of the title compound with labelling and displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (i) −Click here for additional data file.10.1107/S2056989015008890/wm5156fig2.tif. DOI: Crystal structure of the title compound in a view approximately along [001]. Intermolecular O—H⋯S hydrogen bonding is shown as dashed lines; the disordered pyridine rings are omitted for clarity.1063786CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Solvent-dependent outcomes are noted in co-crystallization experiments between DABCO and 4-nitrobenzoic acid with mono- and diprotonated forms of DABCO are isolated. 6H13N2+·C7H4NO4−·2H2O, (1), whereas from methanol, the salt C6H14N22+·2C7H4NO4−, (2), was isolated. In (1), the cation and anion are linked by a strong N—H⋯O hydrogen bond, and the carboxylate anion is close to planar [dihedral angle between terminal residues = 6.83 (9)°]. In (2), a three-ion aggregate is assembled by two N—H⋯O hydrogen bonds, and the carboxylate anions are again close to planar [dihedral angles between terminal residues = 1.7 (3) and 5.9 (3)°]. Through the intervention of solvent water molecules, which self-assemble into helical supramolecular chains along the b axis, the three-dimensional architecture in (1) is stabilized by water–DABCO O—H⋯N and water–carboxylate O—H⋯O hydrogen bonds, with additional stability afforded by C—H⋯O interactions. The global crystal structure comprises alternating layers of water molecules and ion pairs stacked along the c axis. In the crystal of (2), the three-ion aggregates are assembled into a three-dimensional architecture by a large number of methylene–carboxylate/nitro C—H⋯O interactions as well as π–π contacts between inversion-related benzene rings [inter-centroid distances = 3.5644 (16) and 3.6527 (16) Å]. The cations and anions assemble into alternating layers along the c axis.The 1:1 co-crystallization of 1,4-diazabicyclo[2.2.2]octane (DABCO) with 4-nitrobenzoic acid in ethanol–water (3/1) gave the salt dihydrate C In this context, it is not surprising that a search of the Cambridge Structural Database  comprises a 1,4-diazabicyclo[2.2.2]octan-1-ium mono-cation, a 4-nitrobenzoate anion and two water molecules of hydration Fig. 1. The mosi.e. 1.281 (3) and 1.228 (3) Å, is slightly greater than that in C8—O5, O6 of 1.273 (3) and 1.231 (3) Å, respectively. In each case the longer bond forms a strong N—H⋯O hydrogen bond  and 8.7 (2)°, respectively, and the dihedral angle between the terminal groups is 1.7 (3)°. The comparable angles for the O5-containing anion are 2.2 (3), 7.4 (2) and 5.9 (3)°, respectively. As discussed below in Supramolecular features, the ions participate in strong N—H⋯O hydrogen bonds, forming a three-ion aggregate  comprises a 1,4-diazabicyclo[2.2.2]octane-1,4-diium di-cation and two 4-nitrobenzoate anions Fig. 2. In the d Table 2. In ordete Fig. 2 in whichb axis. Adjacent columns stack along the a axis to form layers in the ab plane. The layers are interspersed by layers of water molecules which self-assemble into helical chains along the b axis, where each independent water molecule donates and accepts a water-O—H⋯O(water) hydrogen bond (Table 1In (1), the cation and anion are linked by a strong N2—H⋯O1 hydrogen bond Fig. 1. The twod Table 1. This led Table 1.W—H⋯N3 and water-OW2—H⋯O2(carboxylate). Additional stability to the supramolecular assembly is afforded by methylene-C—H⋯O2(carboxylate) and O2W(water) interactions; it is noteworthy that both of the former interactions involve hydrogen atoms derived from the same methylene-C12 atom  Å for interactions between the C2–C8 rings  and 3.6527 (16) Å between C9–C14 rings . An alternate description of the global crystal packing is based on alternating of layers of cations and layers of anions along the c axis , the di-cation is linked to two anions ds Fig. 4. GloballÅ Table 2. All intÅ Table 2. Additiois Fig. 5.Chemical context, there are 57 species in the crystallographic literature containing DABCO or its mono- or diprotonated forms and a carboxylic acid or carboxylate anion. In fact, co-crystals are rare, being around 10% of all structures. Co-crystals are formed with several dicarboxylic acids where the functional groups are separated by long chains of over four carbon atoms , was mixed with 4-nitrobenzoic acid  in a solution containing ethanol (30 ml) and water (10 ml). The solution was heated for 2 h at 350 K. The mixture was then left for slow evaporation and colourless crystals of (1) formed after 4 days. In a similar experiment, 1,4-diazabicyclo[2.2.2]octane  was mixed with 4-nitrobenzoic acid  in a solution of methanol (50 ml). The solution was heated for 2 h at 345 K. The mixture was then left for slow evaporation and colourless crystals of (2) formed after 4 days.Uiso(H) = 1.2Ueq(C). The N-bound H-atoms were located in a difference Fourier map but were refined with a distance restraint: N—H = 0.88 (1) Å with Uiso(H) = 1.2Ueq(N). For (1), the water-bound H atoms were refined with distance restraints: O—H = 0.84 (1) and H⋯H = 1.39 (2) Å with Uiso(H) =1.5Ueq(O). For (2), the maximum and minimum residual electron density peaks of 0.60 and 0.58 e Å−3, respectively, were located 0.81 and 0.10 Å from atoms O5 and H4N, respectively. In order to confirm the location of the N-bound H atoms, in a separate refinement these were refined without distance restraints. For (1), the N2—H2N bond length was 0.948 (17) Å. For (2), the N3—H3N and N4—H4N bond lengths were 0.93 (4) and 1.08 (3) Å, respectively. In the refinement of (1), one reflection, i.e. (180), was omitted from the refinement owing to poor agreement. For the same reasons, the following reflections were omitted from the final refinement of (2): (550),  1, 2, global. DOI: 10.1107/S1600536814011532/su00051sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S1600536814011532/su00052sup3.hklStructure factors: contains datablock(s) 2. DOI: Click here for additional data file.10.1107/S1600536814011532/su00051sup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S1600536814011532/su00052sup5.cmlSupporting information file. DOI: 1004283, 1004284CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


III ion has a distorted O5Cl octahedral coordination environment defined by two bidentate 2-ethoxy-6-formylphenolato ligands, one Cl atom and one water molecule. In the crystal, O—H⋯O hydrogen bonds link the two independent molecules to form a dimer while the solvent molecule is linked to the complex molecule by a weak C—H⋯O hydrogen bond. Further weak C—H⋯O interactions along with weak C—H⋯Cl hydrogen bonds link the components into chains parallel to [001].In both complex molecules in the asymmetric unit, the Fe L)2Cl(H2O)]·0.5CH3CN, , there are two independent complex molecules and one acetonitrile solvent molecule in the asymmetric unit. In each complex molecule, the FeIII ion has a distorted O5Cl octahedral coordination environment defined by two bidentate 2-ethoxy-6-formylphenolato ligands, one Cl atom and one water molecule. In the crystal, O—H⋯O hydrogen bonds link the two independent molecules to form a dimer. The solvent molecule is linked to the complex molecule by a weak C—H⋯O hydrogen bond. Further weak C—H⋯O interactions along with weak C—H⋯Cl hydrogen bonds link the components into chains parallel to [001].In the title compound, [Fe( Those complexes display dominant ferromagnetic interactions between metal ions.Recently, we have investigated the coordination behavior of the tridentate 2-hydroxy-benzaldehyde ramification ligand 3-ethoxy-2-hydroxy-benzaldehyde and reported two heterometallic polymers [ZnNa(ehbd)L)2Cl(H2O)]·0.5CH3CN (HL = C9H10O3), was prepared similarly to the cubane cluster [Ni4(μ3-OMe)4(heb)4(MeOH)1.05(H2O)2.95] ·6H2O was replaced by FeCl3·6H2O in an attempt to prepare a cubane-type iron cluster. The crystals obtained, however, were those of the title mononuclear FeIII complex.The title compound, [Fe(L)2Cl(H2O)] molecules and a acetonitrile solvent molecule. One of the independent molecules is shown in Fig. 1III ion is coordinated by four O atoms from two different −L ligands, one Cl− ion and one terminal water molecule, forming a distorted octahedral geometry. The Fe—O bond lengths are in the range 1.909 (2)–2.157 (2) Å (Table 1trans-angles at the FeIII atom lie in the range 169.4 (1)–171.4 (1)°, the cis-angles vary from 81.6 (1) to 99.9 (1)°. The −L ligand displays a μ1:κ1:κ1 coordination mode, which is the same as that of [Ni4(μ3-OMe)4(heb)4(MeOH)1.05(H2O)2.95] 2(N3)6]n Å is observed, where Cg1 and Cg2 are the centroids defined by ring atoms C1–C6 and C19–C24, respectively. The solvent molecule is linked to the complex molecule by a weak C—H⋯O hydrogen bond. Further weak C—H⋯O interaction along with weak C—H⋯Cl hydrogen bonds link the components into chains parallel to [001] , 3-ethoxy-2-hydroxy-benzaldehyde , methanol (5 mL) and acetonitrile (5 mL), with a pH adjusted to 7.5 by addition of triethylamine, was poured into a Teflon-lined autoclave (15 mL) and then heated at 413K for 3 days. Black crystals of the title compound were collected by filtration, washed with methanol and dried in air. Phase pure crystals were obtained by manual separation .A mixture of FeCl2) or 0.97 Å (CH3) with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl). H atoms bonded to O atoms were included with O—H = 0.84–0.85 Å and with Uiso(H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S1600536814021205/lh5728sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814021205/lh5728Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814021205/lh5728Isup3.cdxSupporting information file. DOI: 1025672CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Hypoxia inducible factor 1α (HIF-1α) is a stress-responsive transcription factor to hypoxia and its expression is correlated to tumor progression and angiogenesis. Several single nucleotide polymorphisms (SNPs) of HIF-1α gene in the oxygen-dependent degradation (ODD) domain was reportedly associated with increased HIF-1α activity.In this study, we focused on the relationship between SNP 1772 C > T (rs11549465) of HIF-1α gene and its breast cancer risk, as well as its correlation with HIF-1α expression and tumor angiogenesis. Ninety six breast cancer patients and 120 age-matched controls were enrolled. We found that 1772 T allele of HIF-1α gene was associated with increased breast cancer risk . This SNP was not associated with clinicopathologic features of angiogenesis such as VEGF activity and the micro-vessel density and survival of breast cancer patients.Taken together, the 1772 C > T of HIF-1α gene is a potential biomarker for breast cancer susceptibility. Single nucleotide polymorphisms (SNPs), the most common variants in human genome , are popTumor hypoxia is common in tumorigenesis. Hypoxia inducible factor-1 (HIF-1) is a crucial transcription factor in cellular response to tumor hypoxia and is considered as an adverse prognostic factor in breast cancers -14. AddiRecent studies demonstrated that another SNP located in ODD of HIF-1α, 1772 C > T (rs11549465), may lead to an amino acid change from proline 582 to serine (P582S) and are reportedly associated with renal ,19, headThe purpose of this study is to investigate the association between SNP 1772 C > T of the HIF-1α gene in breast cancer patients and healthy control subjects. Furthermore, HIF-1 has been reported to transactivate many oxygen responsive genes such as vascular endothelial growth factor (VEGF) . TherefoBetween 1991 and 2001, a total of 96 randomly-selected female patients with breast cancer at Kaohsiung Medical University Hospital, Kaohsiung, Taiwan, were enrolled in this study. All patients underwent a standard modified radical mastectomy. Ninety-four patients  received adjuvant systemic chemotherapy with 6 cycles of 5-fluorourcil, doxorubicin and cyclophosphamide. After completion of chemotherapy, all patients received hormone therapy with tamoxifen and 92 patients  received radiation therapy. The principle of treatment was followed as described previously . We coll2, 0.2 μl of 10 mM dNTP each, 0.6 μl DMSO, 0.14 μl of Taq enzyme, 0.12 μl of 350 μg/ml primers mix (1:1), 2 μl DNA extracts and 5.64 μl distilled water. PCR was performed with the following protocol: 94°C (1 min); 4 cycles of 94°C (15 s), 64°C (15 s), 70°C (8 s); 4 cycles of 94°C (15 s), 61°C (15 s), 70°C (8 s); 4 cycles of 94°C (15 s), 58°C (15 s), 70°C (8 s); 60 cycles of 94°C for (15 s), 55°C (15 s), 70°C (8 s); 94°C (1 min) and 60°C (5 min). The available restriction enzyme for HIF-1α 1772 C > T (rs11549465) was retrieved from the SNP-RFLP freeware [Hph I restriction enzyme (NEB) at 37°C for overnight and then they were subjected to 3% agarose electrophoresis and stained with SYBR Safe™ DNA gel stain (Invitrogen) for visualization of the PCR-restriction fragment length polymorphism (PCR-RFLP) patterns.Genomic DNA was isolated from paraffin-embedded tumor tissues of surgical specimens and peripheral blood of 120 normal controls as described ,28. The freeware -31. PCR Typical patterns of genotyping by PCR-RFLP have confirmed by sequencing. DNA amplicon from PCR reaction was purified using a MiniElute PCR purification kit (Qiagen)  for commStreptoavidin-biotin based immunohistochemical staining (IHC) was performed to detect HIF-1α and VEGF protein levels as previously described . ImmunorMicrovessel density (MVD) represents tumor angiogenesis by using immunostaining of endothelial cells with monocloncal antibody, recognizing the CD31 endothelial glycoprotein. Each slide was scanned at low magnification (× 100) to identify the four areas of high density of microvessels (hotspots). The number of stained vessels per in each hotspot was counted at high power fields (× 400). Any stained endothelia cell was considered as a countable single microvessel. Large vessels with thick muscular walls were excluded. MVD was classified as either low (≦35.0) or high (>35.0/high power field (HPF)); 35.0 was the median value.p values smaller than 0.05 are regarded as significance.Statistical significance was evaluated by the chi-square test and Fisher exact test. Overall survival curves were analyzed by the Kaplan-Meier method, and differences between the curves were analyzed by log-rank test. The p = 0. 22).In Table In Figure p < 0.001). The allele frequencies in controls and cancer patients were 232 C (97%)/8 T (3%) and 127 C (66%)/65 T (34%), respectively. The T-allele distribution in breast cancer patients differed significantly from that of controls .Based on PCR-RFLP analysis, the genotype distribution of control group was 116 CC (97%), 0 CT (0%) and 4 TT (3%). In contrast, the genotype distributions of breast cancer patients were 53 CC (55%), 21 CT (22%), and 22 TT (23%). The genotype distribution in breast cancer patients differed significantly from that of controls , T-stage (p = 0.303), N-stage (p = 0.936), local recurrence (p = 0.817), distant metastasis (p = 0.572), HIF-1α expression (p = 0.311), VEGF expression (p = 0.375) and microvessel density (p = 0.211).When connecting the results of these stainings with HIF-1α genotypes with clinicopathological analysis Table , there wp < 0.001) and microvessel density (Exp. (B) = 2.6082, p < 0.05) were the most influential factors  and overall survival  by multi-variable analyses. Similarly, Kaplan-Meier analysis  and overall survival curves , respectively.In Table rs Table . HoweverThe SNP 1772 C > T of HIF-1α gene chosen in current study are located within ODD of the HIF-1α. We found that T allele of the SNP 1772 C > T (P582S) of HIF-1α gene was significantly higher in 96 breast cancer patients than in 120 controls. In contrast, the association results of SNP 1772 C > T of HIF-1α gene with different kinds of cancers were not consistent in literature review. For example, the SNP 1772 C > T of HIF-1α gene was detected in several cancers -21,23 buWithin ODD of the HIF-1α, proline residues 402 and 564 were reported to independently determine tightly binding to the von Hippel-Lindau (VHL) protein for HIF-1α ubiquitination and degradation under nonhypoxia condition ,36-39. IFurthermore, the genotypes of SNP 1772 C > T of HIF-1α gene are not significantly associated with clinicopathologic characteristics and clinical outcome of breast cancer (Table p = 0.059) and disease-free survival (p = 0.110) [p = 0.0732) but weak association with overall survival (p = 0.3225)  . SimilarThe phenomena mentioned above may be partly explained by the multigene theory for carcinogenesis . FurtherTaken together, SNP 1772 C > T (P582S) of HIF-1α gene confers significant association with breast cancer risk but it show no association with the clinicopathologic features and survival of breast cancer patients.


In the title salt, the cations and anions are linked through O—H⋯O,N—H⋯O, N—H⋯N and π–π stacking interactions, forming double layers parallel to (101). Weak C—H⋯O and C—H⋯S hydrogen bonds connect the double layers into a three-dimensional network. 6H9ClN3+·C6H3O4S−, the cations and anions are linked via O—H⋯O and N—H⋯O hydrogen bonds, forming R66(37) ring motifs that are interconnected with each other, producing sheets. Separate parallel inversion-related sheets are linked through N—H⋯N and π–π stacking interactions [centroid–centroid distance = 3.5414 (13) Å], forming double layers parallel to (101). Weak C—H⋯O and C—H⋯S hydrogen bonds, as well as C—H⋯π interactions, connect the double layers into a three-dimensional network.In the title salt, C The mixture was cooled slowly and kept at room temperature. After a few days colourless plate-like crystals were obtained.3). Isotropic displacement parameters for these atoms were set to 1.2 (CH) or 1.5 (CH3) times Ueq of the parent atom. Idealized Me H atoms were refined as rotating groups. There are larger than expected residual density peaks close to the Cl and S atoms but these are not chemically sensible and are assumed to be related to the quality of the crystal.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016010148/lh5814sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016010148/lh5814Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016010148/lh5814Isup3.cmlSupporting information file. DOI: 1486940CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information: