Acridine–acridine stacking, thiophene–thiophene stacking and acridine–thiophene C—H⋯π interactions also occur in the crystal.In the title co-crystal, C The internal angle at N1 [C6—N1—C18 = 119.30 (15)°] and bond lengths [C18—N1 = 1.346 (2) and C6—N1 = 1.354 (2) Å] agree with those reported for neutral acridine structures , Cg1⋯Cg1ii = 3.7526 (9), Cg1⋯Cg2ii = 3.7293 (12), Cg2⋯Cg3i = 3.6748 (12) and Cg2⋯Cg3ii = 3.7298 (12) Å where Cg1 is the centroid of the N1/C6/C11/C12/C13/C18 ring, Cg2 is the centroid of the C6–C11 ring and Cg3 is the centroid of the C13–C18 ring; symmetry codes: (i) −x, 2 − y,1 − z; (ii) 1 − x, 2 − y,1 − z] and between the thiophene rings . The crystal structure also features C—H⋯π interactions, forming a three-dimensional supramolecular architecture (Table 1The 3TPC and acridine moieties are linked by an O—H⋯N hydrogen-bonding interaction between (O1—H1) of the carboxyl group and the acridine nitrogen atom (N1) Table 1. This O—e Table 1.et al., 2001aet al., 2014et al., 2011et al., 2001bet al., 2011The crystal structures of a number of acridine co-crystals, acridinium salts and their metal complexes have been investigated in a variety of crystalline environments such as diphenic acid–acridine (1:1) (Shaameri 1) were obtained.To 10 ml of a hot methanol solution of 3TPC  were added 10 ml of a hot methanolic solution of acridine . The resulting solution was warmed over a water bath for half an hour and then kept at room temperature for crystallization. After a week yellow plate-like crystals of (Uiso(H) = kUeq, where k = 1.5 for hydroxy and 1.2 for all other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016005685/hg5473sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016005685/hg5473Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016005685/hg5473Isup3.cmlSupporting information file. DOI: 1472507CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The crystal structure is formed by an alternating packing of organic and inorganic layers along [001] and contains isolated (Bi2Cl10)4− bioctahedra.The title salt, (C 6H14N2)2[Bi2Cl10]·2H2O, was obtained by slow evaporation at room temperature of a hydrochloric aqueous solution (pH = 1) containing bismuth(III) nitrate and 1,4-diazabicyclo[2.2.2]octane (DABCO) in a 1:2 molar ratio. The structure displays a two-dimensional arrangement parallel to (100) of isolated [Bi2Cl10]4− bioctahedra (site symmetry -1) separated by layers of organic 1,4-diazoniabicyclo[2.2.2]octane dications [(DABCOH2)2+] and water molecules. O—H⋯Cl, N—H⋯O and N—H⋯Cl hydrogen bonds lead to additional cohesion of the structure.The title compound bis di-μ-chlorido-bis[tetrachloridobismuthate(III)] dihydrate, (C These components are linked by strong hydrogen bonds. The inorganic moiety is an edge-sharing dioctahedron located site with symmetry 2)2+ dications  to 176.64 (15)° for the trans arrangement. Using Shannon’s method 2[Bi2Cl10]·2H2O structure is very close to that of (C6H14N2)2[Sb2Cl10]·2H2O  in the Pnnm antimony unit cell to be comparable to the bismuth one  × 10−3] . It is worth noting that the water molecule plays a more efficient role in the bismuth based compound. In (C6H14N2)2[Sb2Cl10]·2H2O, the H2O molecules are only linked to (DABCOH2)2+ and in the (C6H14N2)2[Bi2Cl10]·2H2O structure they are directly hydrogen bonded to both the organic and inorganic parts  Å] because the metallic coordination polyhedra are aligned along this axis. On the other hand, a roughly equivalent decrease of the b parameter is observed causing the unit-cell volume of the two compounds approximately to be the same. A general comparison of the two structures reveals that they have a similar 3D pattern, built up by isolated bioctahedra, (DABCOH2)2+ cations and water molecules leaving empty the same voids. On the other hand, the water molecule immediate environment is more regular in the Sb structure  and the (DABCOH2)2+ cation is more distorted in the Bi structure  explaining the lowering of the symmetry in the title compound.The  x, −y + 0.5, z + 0.5] and O—HW2⋯Cl5 interactions. The DABCO cations are hydrogen bonded to water molecules, leading to chains composed of organic moieties, inorganic clusters and H2O molecules running along the b direction 2[Bi2Cl10]·2H2O crystals were obtained at ambient conditions by dissolving Bi(NO3)3·5H2O and DABCO (C6H12N2) in water in a 1:2 molar ratio. The pH of the solution was adjusted to 1 with HCl. The mixture was stirred and kept for several days. Colourless crystals were obtained after a few weeks. I. DOI: 10.1107/S2056989015019933/vn2102Isup2.hklStructure factors: contains datablock(s) I. DOI: 971956CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


B-Spline curves. Since modal intervals are used in many fields, we introduce a new sequence space h(gI) called the Hahn sequence space of modal intervals. We have given some new definitions and theorems. Some inclusion relation and some topological properties of this space are investigated. Also dual spaces of this space are computed.The history of modal intervals goes back to the very first publications on the topic of interval calculus. The modal interval analysis is used in Computer graphics and Computer Aided Design (CAD), namely, the computation of narrow bounds on Bezier and  Goes and S. Goes ββ.(ii)E(gI)]βββ = [E(gI)]β.[(iii)E1(gI)⊃E(gI) then [E1(gI)]β ⊂ [E(gI)]β.If Let The same results hold for dual also.Let (i) Suppose E(gI). Hence E(gI)⊂[E(gI)]ββ. The proof for (ii) follows similarly.This means that E1(gI)⊃E(gI), E1(gI)]β ⊂ [E(gI)]β.(iii) Suppose B-transform of a sequence Define the sequence l∞(gI) is the set of all sequences such that the B-transforms of them are in l∞(gI). That is, That is, σ(l∞(gI)) is a complete metric space with the metric σ(l∞(gI)).σ(l∞(gI)) where ε > 0, there exists a positive integer n0(ε) such that k ∈ N from  that i ≥ n0(ε), taking limit j → ∞ first and letting m → ∞ in (σ(l∞(gI)), we have Consider the sequence ave from  for eachm → ∞ in , we obtaNow, σ(l∞(gI)) is complete.Since β-dual and γ-dual of h(gI) are σ(l∞(gI)).The ε > 0, there exists n0 such that Let k and n.Since M > 0 such that k and n.Hence there exists an M-test.Now, k ∈ N.Thus h(gI)]β = σ(l∞(gI)). This completes the proof.Hence gI. From  and 31)(31)v~k∈σConsiderh(gI) ⊂ l1(gI)∩∫c0(gI).(i) h(gI) = l1(gI)∩∫bv(gI) = l1(gI)∩∫bv0(gI).(ii) (i) Let Consider And also since h(gI) ⊂ l1(gI)∩∫c0(gI).Therefore, k = 1,2,…, (ii) For h(gI) ⊂ l1(gI). Hence also h(gI) ⊂ ∫bv(gI).The last series is convergent since Hence versely,  implies h(gI) = l1(gI)∩∫bv(gI).Therefore, nce from  and 36)(36)l1gI∩Similarly, we can prove other equalities.


II atom coordinated by two Cl atoms and two dimethyl N-cyanodithioiminocarbonate ligands bonded through the terminal N atom in a distorted tetrahedral manner. The complex molecules interact through C—H⋯Cl and Cl⋯S interactions to give a layered structure in the crystal.The title complex consists of a Zn II atom in the title complex, [ZnCl2(C4H6N2S2)2], is coordinated in a distorted tetrahedral manner by two Cl atoms and two terminal N atoms of two dimethyl N-cyanodithioiminocarbonate ligands. In the crystal, the complex molecules are connected through C—H⋯Cl hydrogen bonds and Cl⋯S contacts, leading to a two-dimensional structure extending parallel to the ab plane.The Zn N-cyanodithioiminocarbonate (DMCDIC), which are expected to act as hard and soft donors, respectively, according to Pearson’s concept, give an interesting coordination potential to this molecule. However, only one structure of a metal complex with DMCDIC acting as a ligand has been reported 2] ; τ4 = [360 - (α + β)]/141, where α and β are the two largest tetrahedral angles.The structure of the title compound Fig. 1 is isotyB⋯Cl1ii and C7—H7B⋯Cl1ii; Table 1B⋯Cl2i hydrogen bond (Table 1i short contact [3.3812 (7) Å], giving infinite chains along , leading to a layer parallel to the ab plane .All chemicals are purchased from Aldrich Company, Germany and used as received. Dimethyl cyanocarbonimidodithioate was mixed in acetonitrile with ZnCl2CNCN)2Cl2]  = 1.5Ueq(C), and were allowed to rotate to minimize their contribution to the electron density.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016002607/is5443sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016002607/is5443Isup2.hklStructure factors: contains datablock(s) I. DOI: 1453191CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The title compound, an arylsulfonyl glycinyl aryl hydrazone Schiff base, crystallizes with two independent molecules in the asymmetric unit. In the crystal, a series of N—H⋯O and C—H⋯O hydrogen bonds and C—H⋯π and slipped parallel π–π interactions link the molecules, forming a three-dimensional structure. 17H19N3O3S, containing an amino acid moiety and electron-donating substituents attached to both the phenyl rings, crystallized with two independent molecules (A and B) in the asymmetric unit. The molecules are bent at the S atom, with C—SO2—NH—CH2 torsion angles of −67.3 (2) and 67.7 (3)° in molecules A and B, respectively. Further, the dihedral angles between the sulfonylglycine segments and the p-toluenesulfonyl rings are 76.1 (1) and 85.8 (1)° in molecules A and B, respectively. The central hydrazone segments and the toluene rings attached to them are almost co-planar with their mean planes being inclined to one another by 5.2 (2) (molecule A) and 2.9 (2)° (molecule B). The dihedral angles between the benzene rings are 86.83 (12) (molecule A) and 74.00 (14)° (molecule B). In the crystal, the A molecules are linked by a pair of N—H⋯O hydrogen bonds, forming inversion dimers with an R22(8) ring motif. The dimers are linked via three N—H⋯O hydrogen bonds involving the B molecules, forming chains along [100] and enclosing R22(12) and R44(16) ring motifs. The chains are linked via C—H⋯O hydrogen bonds and a C—H⋯π interaction, forming sheets parallel to (010). There is a further C—H⋯π interaction and a slipped parallel π–π interaction [inter-centroid distance = 3.8773 (16) Å] between the sheets, leading to the formation of a three-dimensional framework.The title acylhydrazone derivative, C N-acylhydrazones containing a glycine residue have been investigated extensively for their biological and medical activities  due to the presence of the C=O group, an additional donor site. N-(aryl)-amides  of the title compound are shown in Fig. 1A has an extended conformation while molecule B is U-shaped. In molecule A, the conformations of the hydrazide N—H and C—H bonds are syn to each other, while the N—H and C=O bonds are anti to each other. On the sulfonamide side, the conformations of the sulfonamide N—H and C=O bonds are syn to each other. In molecule B, the conformations of the hydrazide N—H and C—H bonds, the hydrazide N—H and C=O, and the C=O and sulfonamide N—H bonds are all syn to each other.The molecular structures of the two independent molecules °. The mean plane through atoms C9/N3/N2/C8/O3/C7 [maximum deviation of 0.043 (2) Å for N2], the central section of the molecule, is inclined to the two benzene rings, C1–C6 and C10–C15, by 86.38 (12) and 7.22 (12)°, respectively. In molecule B, the benzene rings (C18–C23 and C27–C32) are inclined to one another by 74.00 (14)°, and by 76.85 (13) and 2.91 (12)°, respectively, to the mean plane through atoms C26/N6/N5/C25/O6/C24 [maximum deviation of 0.061 (2) Å for C26]. The different conformations of molecules A and B are further demonstrated by the differences in the equivalent torsion angles; N1—C7—C8—N2 = 29.3 (3) ° in A, compared to N4—C24—C25—N5 = 177.2 (2)° in B, and C1—S1—N1—C7 = −67.3 (2)° in A, compared to C18—S2—N4—C24 = 67.7 (3)° in B.In molecule A and C25—O6 in B, are 1.214 (3) and 1.229 (3) Å, respectively, indicating that the molecules exist in the keto form in the solid state. The C9=N3 and C26=N6 bond lengths, both 1.272 (3) Å in molecules A and B, respectively, confirm their significant double-bond character. The N2—N3 and N5—N6 bond distances are 1.383 (3) and 1.379 (3) Å, respectively, and the C8—N2 and C25—N5 bond distances are 1.339 (3) and 1.334 (3) Å, respectively, which indicates significant delocalization of π-electron density over the hydrazone portions of the molecules.The carbonyl bonds lengths, C8—O3 in A molecules are linked by a pair of N—H⋯O hydrogen bonds, forming inversion dimers with an via three N—H⋯O hydrogen bonds involving the B molecules, forming chains along [100] that enclose via C—H⋯O hydrogen bonds and a C—H⋯π interaction, forming sheets parallel to (010). The is a C—H⋯π interaction and a slipped parallel π–π interaction , between the sheets, leading to the formation of a three-dimensional framework –NH–N=CH– yielded only one hit, namely N-(2-hydroxy-1-naphthylmethylene)-N′-(N-phenylglycyl)hydrazine -N-{2-[2-(3-chlorobenzylidene) hydrazinyl]-2-oxoethyl}-4-methylbenzenesulfonamide monohydrate  was added to glycine (0.02 mol) dissolved in an aqueous solution of potassium carbonate . The reaction mixture was stirred at 373 K for 6 h, left overnight at room temperature, then filtered and treated with dilute hydrochloric acid. The solid N-(p-toluenesulfonyl)glycine (L1) obtained was crystallized from aqueous ethanol.L1 (0.02 mol) dissolved in ethanol (30 ml) and the mixture was refluxed. The reaction was monitored by TLC at regular intervals. After completion of the reaction, the reaction mixture was concentrated to remove the excess ethanol. The product, N-(p-toluenesulfonyl)glycine ethyl ester (L2) was poured into water, neutralized with sodium bicarbonate and recrystallized from acetone.Sulfuric acid (0.5 ml) was added to L2 (0.01 mol) was then added in small portions to a stirred solution of 99% hydrazine hydrate (10 ml) in 30 ml ethanol and the mixture was refluxed for 6 h. After cooling to room temperature, the resulting precipitate was filtered, washed with cold water and dried to give N-(p-toluenesulfonyl)glycinyl hydrazide (L3).The pure L3 (0.01 mol) and p-methylbenzaldehyde (0.01 mol) in anhydrous methanol (30 ml) and two drops of glacial acetic acid was refluxed for 8 h. After cooling, the precipitate was collected by vacuum filtration, washed with cold methanol and dried. It was recrystallized to constant melting point from methanol (455–457 K). Prism-like colourless single crystals were grown from a DMF solution by slow evaporation of the solvent. The purity of the compound was checked by TLC and characterized by its IR spectrum. The characteristic absorptions observed are 3286.7, 1678.1, 1606.7, 1323.2 and 1157.3 cm−1 for the stretching bands of N—H, C—O, C—N, S—O asymmetric and S—O symmetric, respectively.A mixture of Uiso(H) = 1.2Ueq(N). The C-bound H atoms were positioned with idealized geometry and refined using a riding model: C—H = 0.93–0.97 Å with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989015009330/su5131sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015009330/su5131Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015009330/su5131Isup3.cmlSupporting information file. DOI: 1401257CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Deionised water (negative) and Solcoseryl (positive) were applied on the control groups. Histochemical and biochemical assays were used to evaluate cellular and bio-molecular changes in the wound.Excision wounds were created on the dorsum of Sprague Dawley rats and treated topically twice/day with 20 μL of PE and WE (5 mg extract/mL), 0.5 μgSe2+) only increased significantly (p < 0.05) wound total protein content  on day 10 post wounding. PES increased significantly (p < 0.05) the number of fibroblasts/high power field (HPF) (75.60 ± 9.66) but decreased significantly (p < 0.05) the number of polymorphonuclear leukocytes/HPF (59.20 ± 12.64) in the wound compared to positive control  on day 4. Similar results were recorded for WES. PES demonstrated increased neovascularization, TGF-β1 and VEGFA expressions at day 4 and increased collagen at day 10.PES (PE + 0.5 μg Se2+ addition.Papaya extract improved wound repair by increasing fibroblasts recruitment and reducing polymorphonuclear leukocytes infiltration through early transient expressions of TGF-β1 and VEGFA at the wound area. The processes were amplified with SeThe online version of this article (doi:10.1186/s12906-015-0900-4) contains supplementary material, which is available to authorized users. Carica papaya L (papaya) has been attributed to its high content of cystein endopeptidase, mineral nutrients and vitamins .2O); gently shaken at 37 °C for 8 h, centrifuged at 200 × g for 30 min at 4 °C and finally freeze-dried . Glucosamine hydrochloride (0.05 mg) was used as a standard. Values were corrected to the initial wound tissue dry weight.Wound tissue samples were completely dried in oven at 60 °C and ground to powder. The HAM content was determined at 530 nm following the established protocol . A correp < 0.05.Data were analyzed using the statistical software SPSS . Data were expressed as mean ± standard error of mean (SEM). One way-Anova was used to analyse all data and Tukey’s post-hoc test was used to find the mean differences within the groups at different time interval. Data were considered statistically significant at p < 0.05) increase in the total protein content of the wound tissue (95.14 ± 1.15 mg/g tissue) as compared to the treatment with PC (80.42 ± 0.86 mg/g tissue). In contrast, Zn added extracts did not show any significant changes in the wound total protein content on day 4 and day 10 post wounding as compared to NC   increase in HOP content (20.07 ± 3.19 μg/mg tissue and 19.80 ± 2.51 μg/mg tissue respectively) on day 4 compared to NC (8.47 ± 1.50 μg/mg tissue) and significantly (p < 0.05) increase HOP content (55.15 ± 1.06 μg/mg tissue and 52.61 ± 1.02 μg/mg tissue respectively) on day 10 compared to NC (25.35 ± 1.04 μg/mg tissue), PC (40.62 ± 0.60 μg/mg tissue), PE (37.74 ± 1.24 μg/mg tissue) and WE (27.25 ± 1.03 μg/mg tissue). Treatment with PEZ and WEZ also resulted in significant (p < 0.05) increase in HOP content (30.52 ± 1.23 μg/mg tissue and 31.32 ± 1.34 μg/mg tissue respectively) on day 10 compared to NC (25.35 ± 1.04 μg/mg tissue) (Table p < 0.05) after treatment with PE (53.41 ± 6.21 mg/g tissue), PES (60.84 ± 6.08 mg/g tissue) and WES (53.81 ± 7.36 mg/g tissue) compared to NC (20.71 ± 4.36 mg/g tissue) and WE (25.45 ± 5.32 mg/g tissue) on day 4 and only after treatment with PES (18.12 ± 3.32 mg/g tissue) compared to NC (5.82 ± 1.28 mg/g tissue) on day 10. Treatment with only PES resulted in significantly increased (p < 0.05) HAM content (35.23 ± 4.95 mg/g tissue and 18.21 ± 3.03 mg/g tissue) both on day 4 and day 10 respectively compared to NC (12.54 ± 4.53 mg/g tissue day 4 and 4.59 ± 1.57 mg/g tissue day 10) (Table Treatment with PES and WES resulted in significant (p < 0.05) lower both on day 4  of the mean number of PMNL/HPF compared to NC (164.40 ± 25.93), PC (101.00 ± 27.99) and WE (126.00 ± 23.53) on day 4  higher on day 4 in all treatment groups compared to NC (5.60 ± 3.21). However, significantly increased (p < 0.05) number of fibroblasts/HPF was observed on day 4 in PES (75.60 ± 9.66) treated only group compared to that of PC, PE and WE groups   when treated with PES (69.60 ± 13.07) as compared to NC (40.80 ± 9.09)  Fig. . On day 09) Fig. .On day 4, wound tissue sections from all groups exhibited disrupted wound-dermis interface, with the absence of overlying epithelia  which are affected due to injury [2+ supplementation was shown to improve healing of the wound caused by surgical incision, trauma, and burns [2+ added unripe C. papaya improves healing of excision wound through enhanced anti-inflammatory and antioxidant effect [Sentiation , 21. Whiferation . Both Seo injury . In reland burns . Earliert effect .The present study used female rats for the experimentation. Female rats are known to exhibit shorter period for complete wound healing and this has been linked to the circulating oestrogen level –26. Thou2+ added papaya mediates improved wound healing by reducing inflammation associated oxidative damage apparently via cyclooxygenase specific inhibition, arginine metabolism and up-regulation of antioxidant enzymes. These could be linked to the added Se2+ [Depending on the type and aetiology of wound, wound healing involves inflammation (day 1–4 or more), proliferative/repair day 5–10 or 11), and remodelling phases (day 11–21 or more) , 10. Pro or 11, aded Se2+ .2+ added PE/WE treated groups albeit the reduction was not as significant as Se2+ added PE/WE treated groups  and biochemical events , a model is proposed Fig.  to descrPE through mechanisms associated with cyclooxygenase and prostaglanding E2 inhibition  reduced Consistently, PE induced a transient up-regulation of TGF-β1 and VEGFA on day 4 which in turn enhanced cellular activity  as evidenced in the increased fibroblasts recruitment and early appearance of new blood vessels  in PE treatment. These effect was more pronounced in Se added PE.In addition, the establishment of new blood vessels enhanced nutrient delivery to the fibroblasts and enhanced fibroblastic synthesis of provisional matrix, primary molecules in the extracellular matrix and collagen. In line with this, Se added PE exclusively enhanced the synthesis of primary molecules of ground substances i.e. HUA and HAM. PE alone showed little effect in these regard. However, hydroxyproline an index for collagen turnover was found to be markedly increased, later on day 10, with PE treatment. Concurrently, well aligned collagen fibres and reconstructed dermis and epidermis were observed later on day 10 after treatment with PE and PES especially. Collectively, the increased recruitment of fibroblasts and their bio-molcular products resulted in the significant increase in wound total protein content later on day 10 in PE treated group.2+ added papaya extracts might (i) reduce PMNL infiltration to speed up the inflammatory phase as well as (ii) induced transient up-regulation of TGF-β1 and VEGFA expression to enhance angiogenesis and fibroblast recruitment thereby enhanced cutaneous wound repair.Se


III ion in the title complex is coordinated by two 1,10-phenanthroline (phen) ligands, one water molecule and a chloride in a cis geometry, displaying a distorted octahedral environment. The [ZnCl4]2− anion has a slightly distorted tetrahedral coordination geometry.The Cr 12H8N2)2(H2O)][ZnCl4]·H2O, has been determined from synchrotron data. The CrIII ion is bonded to four N atoms from two 1,10-phenanthroline (phen) ligands, one water molecule and a Cl atom in a cis arrangement, displaying an overall distorted octahedral coordination environment. The Cr—N(phen) bond lengths are in the range of 2.0495 (18) to 2.0831 (18) Å, while the Cr—Cl and Cr—(OH2) bond lengths are 2.2734 (7) and 1.9986 (17) Å, respectively. The tetrahedral [ZnCl4]2− anion is slightly distorted owing to its involvement in O—H⋯Cl hydrogen bonding with coordinating and non-coordinating water molecules. The two types of water molecules also interact through O—H⋯O hydrogen bonds. The observed hydrogen-bonding pattern leads to the formation of a three-dimensional network structure.The structure of the title compound, [CrCl(C These complexes are promising materials for the development of new molecule-based magnets, solar energy storage media or tunable solid state lasers ][ZnCl4]·H2O , (I)We report here on the synthesis and crystal structure of the title compound, (ClO4)3·H2O 2]ClO4·H2O 2]Cl  bond lengths in (I)2) bond length is comparable to those of 1.947 (4), 1.9579 (10) and 1.996 (4) Å found in cis-[Cr(dpp)(phen)2(H2O)](NO3)2·H2O·CH3CN [Hdpp = (C6H5O)2·PO2H] 2(H2O)](ClO4)2·2H2O (H2O)](ClO4)2·H2O  2]Cl 2Cl2]Cl  A—Cr1A—N2A and N3A—Cr1A—N4A are 79.76 (5) and 80.23 (7)°.The Cr—N(phen) bond lengths are in the range of 2.0495 (18) to 2.0831 (18) Å and are in good agreement with those observed in 2− anion and the second water molecule remain outside the coordination sphere. The ZnII atom in the complex anion exhibits a slightly distorted tetrahedral coordination sphere caused by the influence of hydrogen bonding on the Zn—Cl bond lengths and the Cl—Zn—Cl angles. The Zn—Cl bond lengths range from 2.2443 (7) to 2.2854 (7) Å and the Cl—Zn—Cl angles from 107.54 (4) to 111.57 (3)°.The [ZnClB of the [ZnCl4]2− anion and the Cl1A ligand atom are not involved in hydrogen bonding. An extensive array of O—H—O and O—H⋯Cl contacts (phen)2(H2O)](NO3)2·H2O·CH3CN 3·H2O 2]ClO4 2]Cl ]2+ with any anions have been deposited.A search of the Cambridge Structural Database 2]ClO4·H2O was prepared according to a literature procedure 2]ClO4·H2O (0.2 g) was dissolved in 10 mL of 0.01 M HCl at 313 K, and 5 mL of 1 M HCl containing 1.2 g of solid ZnCl2 were added to this solution. The mixture was refluxed at 328 K for 30 min and then cooled to room temperature. The resulting solution was filtered and allowed to stand at room temperature for 3–5 days, giving purple crystals of (I)All chemicals were reagent-grade materials and used without further purification. The starting material, Uiso(H) set to 1.2Ueq(C). The H atoms of water molecules  were located from difference Fourier maps and refined with restraints and an O—H distance of 0.84 (1) Å, with Uiso(H) values of 1.2 Ueq.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989015003266/wm5123sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015003266/wm5123Isup2.hklStructure factors: contains datablock(s) I. DOI: 1049598CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The crystal structure of the title compound consists of discrete octahedral cobalt(II) complexes that are linked by a variety of hydrogen-bonding interactions into a three-dimensional network. 2(C6H6N2O)4]·2C6H6N2O·C2H5OH, comprises one CoII cation, two thiocyanate anions, four coordinating and two solvent isonicotinamide molecules and one ethanol solvent molecule. The CoII cations are octahedrally coordinated by four N-coordinating isonicotinamide ligands and two terminally N-bonded thiocyanate anions. These discrete complexes are linked by intermolecular N—H⋯O and N—H⋯S hydrogen-bonding interactions into a three-dimensional network. The two isonicotinamide and the ethanol solvent molecules are embedded in channels of this network and are linked through further N—H⋯O and N—H⋯N hydrogen bonds to the network. The ethanol solvent molecule is disordered over two sets of sites (occupancy ratio 0.6:0.4).The asymmetric unit of the title compound, [Co(NCS) However, instead of the expected chain compound, a discrete complex with additional solvate molecules of composition [Co(NCS)2(C6H6N2O)4]·2C6H6N2O·C2H5OH was obtained in the current study and characterized by single-crystal X-ray diffraction.There is an increasing interest in compounds showing cooperative magnetic properties, such as ferromagnetism, antiferromagnetism and metamagnetism or a slow relaxation of the magnetization, indicative of single-molecule or single-chain magnetism  and one positionally disordered ethanol solvent molecule. The CoII cation is coordinated by two terminal N-bonded thiocyanate anions and four N-coordinating isonicotinamide ligands, forming a slightly distorted octahedron –178.32 (11)° for trans angles] are indicative for a slight distortion and are comparable with those in similar coordination compounds with CoII, thiocyanate anions and N-bound co-ligands.The asymmetric unit of the title compound consists of one Coon Fig. 1. Bond lea axis by intermolecular N—H⋯O hydrogen-bonding interactions  with 73.3 mg isonicotinamide (0.6 mmol) in ethanol (1.5 ml) after being allowed to stand for a few days at room temperature.Cobalt(II) thiocyanate and isonicotinamide were obtained from Alfa Aesar and were used without further purification. Single crystals suitable for structure analysis were obtained by the reaction of 26.3 mg Co(NCS)Uiso(H) = 1.2Ueq (1.5 for methyl and O—H hydrogen atoms) using a riding model with C—H = 0.95 Å for aromatic, C—H = 0.98 Å for methyl, N—H = 0.88 Å and O— H = 0.84 Å, respectively. The ethanol molecule was found to be disordered over two sets of sites and was refined with fixed occupation factors of 0.6 and 0.4, respectively.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016010951/wm5305sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016010951/wm5305Isup2.hklStructure factors: contains datablock(s) I. DOI: 1491089CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Within the complex, intramolecular C—H⋯S, C—H⋯π, N—H⋯Br and π–π stacking interactions are observed. In the crystal, the components are linked by N—H⋯Br and C—H⋯N hydrogen bonds and weak π–π stacking interactions, generating chains propagating in the [100] direction.In the solvated dinuclear complex ·2C2H3N or [Cu2Br2(ATU)(dppm)2]·2CH3CN. Both Cu+ ions adopt distorted tetrahedral geometries, being coordinated by one terminal Br atom, one μ2-S atom of the bridging ATU ligand and two P atoms of the bridging dppm ligands. Within the complex, intramolecular C—H⋯S, C—H⋯π, N—H⋯Br and π–π stacking interactions are observed. In the crystal, the components are linked by N—H⋯Br and C—H⋯N hydrogen bonds and weak π–π stacking interactions, generating chains propagating in the [100] direction.The reaction of cuprous bromide with a mixture of 1,1-bis(diphenylphosphanyl)methane (dppm: C Both CuI atoms share a tetrahedral corner via an S-atom bridge.The title complex [Cu2I2(C3H8N2S)(C25H22P2)2]·1.5CH3CN 3]·CH3CN 2P2 plane of the Cu1–S1–Cu2–P3–C38–P4 chair conformation by an angle [72.59 (3)°] that is significantly larger than that for the Cu1–S1–Cu2–P1–C13–P2 plane [45.68 (2)°]. Thus, the C—H⋯S effect might be the influence that leads to the longer distance between the centroids  of the phenyl rings, Cg8⋯Cg9 [4.0356 (17) Å] compared with the Cg4⋯Cg5 distance [3.6097 (19) Å]. The intramolecular C—H⋯π interaction (C31—H31⋯Cg6) also imposes a contact, of 3.476 (3) Å, between the Csp2 atom of the phenyl ring and another phenyl ring centroid (C20–C25) of the other dppm ligand. An interaction (C12—H12⋯N2) between Cg5 and the NH2 group is also observed. In addition, two intramolecular N—H⋯Br interactions are found between the NH2 group of ATU and Br atoms. A perspective view of all the intramolecular interactions in (I)The intramolecular interaction C44—H44⋯S1 Table 2 has an ex, 2 − y, −z), which generates Cg8⋯Cg8iii rings  generating a chain of alternating N—H⋯Br links and π–π stacking running along [100], as shown in Fig. 3ii and C50—H50⋯N3i; symmetry codes: (i) −x + 1, y + z + x, y − z + In the crystal, neighbouring dinuclear molecules form a hydrogen-bonded dimer held together by two N—H⋯Br bonds as a cyclic pattern with its symmetry–equivalent partner, generated by a crystallographic inversion center (symmetry code: −2I2(C3H8N2S)(dppm)2]·1.5CH3CN, studied by Nimthong et al.  was added and further refluxed for four h and the precipitate slowly disappeared. Colorless crystals were obtained after the clear solution was left to evaporate at room temperature for a few days. The yield was 33% based on CuBr. Calculated for C58H58Br2Cu2N4P4S: C 55.55, H 4.66, N 4.47 and S 2.56%. Found: C 55.28, H 4.28, N 3.68 and S 2.54%. The main IR bands : 3282 [ν(NH2)], 3168 [ν(NH2)], 3058 [ν(=C—H)ph], 1580 [ν(C=S)] and 1110 [ν(P—Cph)].Copper(I) bromide  was added to a solution of 1,1-bis(diphenylphosphino)methane  in 30 ml acetonitrile at 338 K. The mixture was refluxed for two h and a white precipitate was formed. After that, Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl). The N—H atoms were located in a difference map and the coordinates were refined with an N—H distance restraint of 0.86 Å and with Uiso(H) = 1.2eqU(N). Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989015015637/hb7479sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015015637/hb7479Isup2.hklStructure factors: contains datablock(s) I. DOI: 1419827CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Scientific Reports6: Article number: 2482310.1038/srep24823; published online: 04212016; updated: 05312016This Article contains a typographical error in the Results section under subheading ‘5G2 mAb recognized sugar chain epitopes’,a GlcNAc), Lec , core1 , core2 GalNAc), and Siaα2-6core1 GalNAc) structures .”“The 5G2 mAb recognized the Leshould read:a GlcNAc), Lec , core1 , core2 GalNAc), and Siaα2-6core1 GalNAc) structures .”“The 5G2 mAb recognized the Le


H)-one compound that has been designed and synthesized to explore a new electron-donor (D) and -acceptor (A) conjugated complex, the two cyclopentadienyl rings adopt an eclipsed conformation. The anthracene tricycle is distorted towards a butterfly conformation.In a ferrocenyl–anthracen-9(10 5H5)(C27H16NO)], designed and synthesized to explore a new electron-donor (D) and -acceptor (A) conjugated complex, the two cyclopentadienyl rings adopt an eclipsed conformation. The anthracene tricycle is distorted towards a butterfly conformation and the mean planes of the outer benzene rings are inclined each to other at 22.7 (3)°. In the crystal, molecules are paired into inversion dimers via π–π interactions. Weak intermolecular C—H⋯π interactions link further these dimers into one-dimensional columns along the b axis, with the ferrocenylethynyl arms arranged between the stacks to fill the voids.In the title compound, [Fe(C D) and -acceptor (A) molecules have attracted much attention owing to their unique structures and various characteristic properties  demonstrate guest-molecule absorption and valence tautomerization etc. We have synthesized the title compound 1-(ferrocenylethynyl)-10-(phenylimino)anthracen-9(10H)-one [1-(Fc)AqPHI] and herein we report its crystal structure, determined by synchrotron radiation (SR) X-ray powder diffraction.Compounds containing a mixture of electron-donor 2Aq. Distances between the ring centroids cover the range from 4.09 Å in 1,4 Fc2Aq down to 3.68 Å in 1,2-(FcPh)2Aq. The smallest perpendicular distance for all the materials was close to 3.45 Å . C—H⋯π interactions are also found in 1,4-Fc2Aq, 1,5-Fc2Aq and 1,2-(FcPh)2Aq. Two kinds of C—H⋯π interactions in 1,4-Fc2Aq connect the CP rings and the rings of the Aq groups of neighbouring molecules. A C—H⋯π interaction in 1,5-Fc2Aq links a CH– group from the Aq unit and a CP ring of Fc fragment. There are three C—H⋯π interactions in 1,2-(FcPh)2Aq.In the reported examples compiled in the Cambridge Structural Database -one , ethynylferrocene , Pd(PPh3)2Cl2 (3.1 mg), and CuI (5 mg) were suspended in Et3N (15 ml). After refluxing for 5 h, Et3N was removed in vacuo, and the resultant residue was dissolved in CH2Cl2. The solution was washed with water (150 ml), and dried over Na2SO4. After evaporation of the solvent, the crude product was purified with alumina column chromatography (activity II–III) with a mixture of dichloromethane and hexane (1:2 v/v) as eluent. The third fraction was collected, and produced a red–brown solid of the title compound . Very small single crystals unsuitable for conventional X-ray structure analysis were obtained by recrystallization from dichloromethane–hexane. 1H NMR : δ 8.1–8.5 , 7.0–7.9 , 6.80 , 4.1–4.8 . IR (KBr pellet): 2208 (ν C=C/ cm−1), 1668 (ν C=O/ cm−1), 1483 (ν C=N/ cm−1). MALDI–TOF–MS: m/z = 490.1.Under a nitrogen atmosphere, 1-bromo-10-(phenylimino)anthracen-9 standard powder sample was used for wavelength calibration. The calibrated wavelength was 0.80200 (1) Å. The powder profile was measured at 100 K with 120 min X-ray exposure time.The size of 1-(Fc)AqPHI crystals was small, less than 1 µm. SR powder-diffraction techniques were employed for the structure determination. The powder crystallites were installed in a 0.4 mm glass capillary. The X-ray powder diffraction data were measured using a large Debye–Scherrer camera with an imaging-plate (IP) as a detector installed at SPring-8 BL02B2  was 63.2. The space group P21/n was assigned on the basis of systematic extinctions.Indexing was carried out using the program SP . Uiso for H atoms connected to the Aq and Ph parts were fixed at 0.05 Å2. isoU for H atoms connected to the C25–C29 and C30–C34 CP rings were fixed at 0.09 Å2 and 0.04 Å2, respectively. A split-type pseudo-Voigt profile function  global, I, 1FcAqPHI-100K_powder_data. DOI: 10.1107/S1600536814025252/cv5475Isup2.rtvRietveld powder data: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814025252/cv5475Isup3.molSupporting information file. DOI: 1034683CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The two compounds are isotypic and the two-dimensional polymeric structure is based on centrosymmetric dinuclear bridged complex units. Within the layers, which lie parallel to (100), the coordinating water molecule forms an O—H⋯O hydrogen bond to the single bridging carboxylate O atom. 3-2-acetato]dipotassium], [K2(C8H5Cl2O3)2(H2O)]n, and poly[μ-aqua-bis[μ3-2-acetato]dirubidium], [Rb2(C8H5Cl2O3)2(H2O)]n, respectively, have been determined and are described. The two compounds are isotypic and the polymeric structure is based on centrosymmetric dinuclear bridged complex units. The irregular six-coordination about the alkali cations comprises a bridging water molecule lying on a twofold rotation axis, the phenoxy O-atom donor and a triple bridging carboxylate O atom of the oxoacetate side chain of the 3,5-D ligand, and the second carboxyate O-atom donor also bridging. The K—O and Rb—O bond-length ranges are 2.7238 (15)–2.9459 (14) and 2.832 (2)–3.050 (2) Å, respectively, and the K⋯K and Rb⋯Rb separations in the dinuclear units are 4.0214 (7) and 4.1289 (6) Å, respectively. Within the layers which lie parallel to (100), the coordinating water molecule forms an O—H⋯O hydrogen bond to the single bridging carboxylate O atom.The two-dimensional coordination polymeric structures of the hydrated potassium and rubidium salts of acetic acid , namely, poly[μ-aqua-bis[μ The comparative M—O bond length range for the two metals (Tables 1O:O1)-chelate interaction .The hydrated complexes (I)on Fig. 2, three b Tables 1 and 2 ▸ M—O complex network with the aromatic rings of the ligands peripherally located between the layers. Within the layers there are a number of short metal⋯metal contacts, the shortest being across an inversion centre [K⋯Kii = 4.0214 (7) Å and Rb⋯Rbii = 4.1289 (6) Å], the longest being K⋯Kvi = 4.3327 (5) Å and Rb⋯Rbvi = 4.5483 (5) Å  or Rb2CO3 (115 mg) (for (II)] to a hot solution of acetic acid  (220 mg) in 10 ml of 50% (v/v) ethanol/water. After heating for 5 min, partial room temperature evaporation of the solutions gave in all two cases, colourless needles from which specimens were cleaved for the X-ray analyses.Compounds (I)aromatic = 0.95 Å or C—Hmethylene = 0.99 Å] and were allowed to ride in the refinements, with Uiso(H) = 1.2Ueq(C). The water H-atom in both structures was located in a difference Fourier map and was allowed to ride in the refinements with an O—H distance restraint of 0.90±0.02 Å and with Uiso(H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details for (I)10.1107/S2056989015016722/wm5206sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S2056989015016722/wm5206Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989015016722/wm5206IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989015016722/wm5206Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989015016722/wm5206IIsup5.cmlSupporting information file. DOI: 1422835, 1422834CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


O—H⋯O hydrogen bonds between water molecules and ClO4 units lead to the formation of a three-dimensional network in the structures.The crystal structures of the tetra- and hexahydrate phases of Ca6(ClO4)]2 dimers by sharing two ClO4 tetrahedra. The dimers are arranged in sheets parallel (001) and alternate with layers of non-coordinating ClO4 tetrahedra. O—H⋯O hydrogen bonds between the water molecules as donor and ClO4 tetrahedra and water molecules as acceptor groups lead to the formation of a three-dimensional network in the two structures. Ca(ClO4)2·6H2O was refined as a two-component inversion twin, with an approximate twin component ratio of 1:1 in each of the two structures.The title compounds, calcium perchlorate tetrahydrate and calcium perchlorate hexahydrate, were crystallized at low temperatures according to the solid–liquid phase diagram. The structure of the tetrahydrate consists of one Ca The resulting coordination polyhedron is a distorted square anti-prism . The Ca—O bond lengths involving the water molecules range from 2.3284 (17) to 2.4153 (16) Å and are considerably shorter than the Ca—O bond lengths involving the perchlorate O atoms [2.5417 (16) to 2.5695 (17) Å].The Casm Fig. 1b. The C2+ cations in Ca(ClO4)·6H2O are each coordinated by six water molecules and two perchlorate tetrahedra . Nevertheless, according to the bond-valence model 6(ClO4)]2 dimers oriented in layers parallel to (001).The two different Cara Fig. 2. Again, 4)·4H2O are shared between two adjacent Ca2+ ions, forming chains extending parallel to 2 sheets along [001] 2·4H2O phases, see: Robertson & Bish (2010M = Mg); Hennings et al. (2014M(ClO4)2·6H2O phases, see: Ghosh et al. ; Ghosh & Ray 2·4H2O was crystallized from an aqueous solution of 62.96 wt% Ca(ClO4)2 at 273 K after one day and Ca(ClO4)2·6H2O from an aqueous solution of 57.55 wt% Ca(ClO4)2 at 238 K after one week. For the preparation of these aqueous solutions, Ca(ClO4)2·4H2O  was used. The Ca2+ content was analysed via complexometric titration with EDTA. The crystals remain stable in the saturated aqueous solution over at least four weeks.Ca2·4H2O, distance restraints were applied for all water molecules, with O—H and H—H distance restraints of 0.82 (1) and 1.32 (1) Å, respectively. For Ca(ClO4)2·6H2O, Uiso values were set at 1.2Ueq(O) using a riding-model approximation. Distance restraints were applied for that structure for all water molecules, with O—H and H—H distance restraints of 0.84 (2) and 1.4 (2) Å, respectively. Ca(ClO4)2·6H2O was refined as a two-component inversion twin, with an approximate twin component ratio of 1:1.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S1600536814024532/wm5079sup1.cifCrystal structure: contains datablock(s) CaClO4_4H2O_200K, CaClO4_6H2O_180K. DOI: 10.1107/S1600536814024532/wm5079CaClO4_4H2O_200Ksup2.hklStructure factors: contains datablock(s) CaClO4_4H2O_200K. DOI: 10.1107/S1600536814024532/wm5079CaClO4_6H2O_180Ksup3.hklStructure factors: contains datablock(s) CaClO4_6H2O_180K. DOI: Click here for additional data file.10.1107/S1600536814024532/wm5079CaClO4_4H2O_200Ksup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S1600536814024532/wm5079CaClO4_6H2O_180Ksup5.cmlSupporting information file. DOI: 1033323, 1033324CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Crystal structures of morpholinium hydrogen bromanilate have been determined at 130, 145 and 180 K. The asymmetric unit comprises one morpholinium cation and two halves of crystallographically independent bromanilate monoanions. The conformations of the two independent bromanilate anions are different from each other with respect to the O—H orientation. The two different anions are linked alternately into a chain though a short O—H⋯O hydrogen bond, in which the H atom is disordered over two positions. 4H10NO+·C6HBr2O4−, were determined at three temperatures, viz. 130, 145 and 180 K. The asymmetric unit comprises one morpholinium cation and two halves of crystallographically independent bromanilate monoanions, which are located on inversion centres. The conformations of the two independent bromanilate anions are different from each other with respect to the O—H orientation. In the crystal, the two different anions are linked alternately into a chain along [211] through a short O—H⋯O hydrogen bond, in which the H atom is disordered over two positions. The refined site-occupancy ratios, which are almost constant in the temperature range studied, are 0.49 (3):0.51 (3), 0.52 (3):0.48 (3) and 0.50 (3):0.50 (3), respectively, at 130, 145 and 180 K, and no significant difference in the molecular geometry and the molecular packing is observed at the three temperatures. The morpholinium cation links adjacent chains of anions via N—H⋯O hydrogen bonds, forming a sheet structure parallel to (-111).Crystal structures of the title compound , C The anomalous behavior was ascribed to a drastic temperature variation of the disordered O—H⋯O hydrogen bond, as revealed by multi-temperature X-ray diffraction  Å at 114 K to 1.2951 (10) Å at 180 K; C6—O4: from 1.290 (10) Å at 114 K to 1.2946 (10) at 180 K], which corresponds to population changes of the two disordered proton sites in the hydrogen bond (Tobu i: 3.1698 (13) Å (130 K), 3.1725 (13) Å (145 K) and 3.1763 (13) Å (180 K); Br2⋯C1i: 3.2673 (15) Å (130 K), 3.2716 (15) Å (145 K) and 3.2808 (15) Å (180 K); symmetry code: (i) x- 1, y − 1, z] are observed. A weak C—H⋯Br interaction is also observed between the sheets.In the crystal, the two independent bromanilate anions with different conformations are linked alternately by short O—H⋯O hydrogen bonds Tables 1 and 3 ▸,A form  of bromanilic acid (200 mg) with morpholine (60 mg) at room temperature.Uiso(H) = 1.2Ueq(C). The N-bound H atom was located in a difference Fourier map and refined freely [refined N—H = 0.85 (3)–0.89 (3) Å]. Two disordered positions of the H atom in the O—H⋯O hydrogen bond were located in a difference Fourier map. Since site occupancy factors and isotropic displacement parameters are correlated and bonding effects also make the site-occupancy factors less reliable, the positional parameters and the occupancies of the H atom were refined, with Uiso(H) = 1.5Ueq(O), and with distance restraints of O—H = 0.84 (2) Å.Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S2056989015017272/lh5788sup1.cifCrystal structure: contains datablock(s) General, 1, 2, 3. DOI: 10.1107/S2056989015017272/lh57881sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989015017272/lh57882sup3.hklStructure factors: contains datablock(s) 2. DOI: 10.1107/S2056989015017272/lh57883sup4.hklStructure factors: contains datablock(s) 3. DOI: Click here for additional data file.10.1107/S2056989015017272/lh57881sup5.cmlSupporting information file. DOI: 1424714, 1424713, 1424712CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The crystal packing features π–π stacking interactions between tpy–tpy ligands.In this first crystal structure of an Ru complex with 6′,6"-bis(pyridin-2-yl)-2,2′:4′,4":2",2"’-quaterpyridine, a ‘half’ of the ligand (one of the two terpyridyl units) is N^N^N  10H8N2)(C30H20N6)]PF6, which contains the bidentate ligand 2,2′-bipyridine (bpy) and the tridendate ligand 6′,6′′-bis(pyridin-2-yl)-2,2′:4′,4′′:2′′,2′′′-quaterpyridine (tpy–tpy). The [RuCl(bpy)(tpy–tpy)]+ monocation has a distorted octahedral geometry at the central RuII ion due to the restricted bite angle [159.32 (16)°] of the tridendate ligand. The Ru-bound tpy and bpy moieties are nearly planar and essentially perpendicular to each other with a dihedral angle of 89.78 (11)° between the least-squares planes. The lengths of the two Ru—N bonds for bpy are 2.028 (4) and 2.075 (4) Å, with the shorter bond being opposite to Ru—Cl. For tpy–tpy, the mean Ru—N distance involving the outer N atoms trans to each other is 2.053 (8) Å, whereas the length of the much shorter bond involving the central N atom is 1.936 (4) Å. The Ru—Cl distance is 2.3982 (16) Å. The free uncoordinated moiety of tpy–tpy adopts a trans,trans conformation about the interannular C—C bonds, with adjacent pyridyl rings being only approximately coplanar. The crystal packing shows significant π–π stacking interactions based on tpy–tpy. The crystal structure reported here is the first for a tpy–tpy complex of ruthenium. We report the structural characterization of chloridoruthenium(II) hexafluoridophosphate, [RuCl(C In this and other related photocatalysts containing the {(tpy)Ru(bpy)(L)} moiety (L = H2O or Cl−), the aqua species is typically formed by easy ligand substitution from its chlorido precursor in water Ru(tpy–tpy)Ru(bpy)(Cl)]3+  crystallizes in the triclinic ° in agreement with those found in similar chlorido RuII-bpy complexes °]. The RuII atom and atoms N2, N4, N5, and Cl1 form an equatorial plane with a maximum deviation of 0.032 (4) Å. The Ru-bound tpy moiety and bpy are approximately planar  and their mean planes are essentially perpendicular to each other with a dihedral angle of 89.78 (11)° between planes. For the tridentate ligand, the mean Ru—N distance involving the outer N1 and N3 atoms trans to each other is 2.053 (8) Å, whereas the bond distance involving the central N2 is much shorter [1.936 (4) Å] as a result of the structural constraint imposed by these mer-arranged ligands  and plane–plane dihedral angles (α) are respectively: 3.723 (3) Å and 2.8 (2)° for ⋯ ; 3.812 (4) Å and 3.2 (2)° for ⋯ ; 3.826 (4) Å and 5.6 (3)° for ⋯ ; and 3.630 (4) Å and 15.5 (3)° for ⋯ . In all these π–π stacking interactions, the slip angles from the parallel displacement  are smaller than 30°.The intramolecular Cl⋯H contact of 2.70 Å involving the hydrogen of the nearest C atom at bpy (H25) is similar to that observed earlier for complexes containing the {RuCl(bpy)} moiety -2,2′:4′,4′′:2′′,2′′′-quaterpyridine. Other than one structure for the metal-free ligand itself (DMSO)2Cl2 into a solution of the tpy–tpy ligand  at reflux. The reaction solution was refluxed for another 2.5 h and then cooled down to room temperature. After evaporation of the solvent on a rotavap, water was added to dissolve the solid and excess NH4PF6 was added to form the precipitate, which was filtered off and dried under vacuum. Further purification was performed by column chromatography using alumina and a mixture of acetonitrile/toluene (1:2) as the eluant. The product was collected from the first band. The solvent was evaporated and the dark-red solid was collected and dried under vacuum (yield: 30%). Analysis calculated for C40H28N8F6PClRu: C, 53.25; H, 3.13; N, 12.42. Found: C, 52.71; H, 3.12; N, 11.86. Single crystals for X-ray structural analysis were grown by slow diffusion of diethyl ether into acetonitrile solutions of the complexes in long thin tubes.Compound + was also characterized in MeCN solutions by other techniques. Mass spectra (ESI–MS: m/z 757) are in agreement with the formulation for the cation, i.e. [1(-PF6)]+ . 1H-NMR : δ 10.27–10.26 , 9.07 , 8.89 , 8.73–6.95 . Electrochemical measurements by cyclic voltammetry gave a redox potential of 0.83 V vs SCE for the reversible RuII/RuIII couple. This potential is anodically shifted by only 20 mV relative to the [Ru(Cl)(bpy)(tpy)]+ complex (bpy)(tpy–tpy)]Uiso(H) = 1.2Ueq(C). Each atom in the anion was modeled in two positions, with site occupancies tied to 1.0. A total of 48 temperature-factor restraints were used to force convergence. The SQUEEZE routine in PLATON  I. DOI: 10.1107/S2056989015014632/pk2553Isup2.hklStructure factors: contains datablock(s) I. DOI: 1416756CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, molecules are linked by N–H⋯N 11H9N5OS2, a 1-thiophen-2-ylmethyleneaminopyrimidine derivative, displays an essentially planar C—NH2 group. The conformation across the N=C bond linking the pyrimidine and thienyl groups is E. The pyrimidine and thienyl ring systems subtend an inter-planar angle of 42.72 (5)°. In the crystal, molecules are linked by N–H⋯Nnitrile and N–H⋯O=C hydrogen bonds, forming chains parallel to the b axis.The title compound, C Many drugs, such as 5-fluorouracil, containing a pyrimidine moiety have been developed and used as anticancer agents. It is difficult to find a general method for the introduction of specific substituents into the pyrimidine nucleus directly, and thus many synthetic methods have been developed for the construction of pyrimidine rings bearing potential functional groups  Å. Both ring systems are, as expected, planar (r.m.s. deviations are 0.017 Å for the pyrimidine and 0.001 Å for the thienyl ring). Atom N2 lies 0.189 (2) Å out of the pyrimidine plane; all other immediate substituent atoms lie effectively in the ring plane. Carbon atom C7 of the thiomethyl group is rotated slightly out of the ring plane, with torsion angle N3—C4—S1—C7 being −6.30 (10)°. The inter-planar angle between the rings is 42.72 (5)°; the relative orientation is influenced by the torsion angles C6—N1—N2—C10 = −51.78 (13), N1—N2—C10—C11 = 174.68 (9) and N2—C10—C11—S12 = 5.22 (15)°. The NH2 group is planar; the nitrogen atom lies only 0.048 (9) Å out of the plane of its substituents. The intramolecular contact H041⋯N2 = 2.22 (2) Å may be construed as a hydrogen bond, although the angle at the H atom is necessarily narrow at 108.4 (14) °  Å and H042⋯O1 2.14 (2) Å  Table 1.A search of the Cambridge Structural Database  was added to a stirred solution of 1-cyanoacetyl-4-thiophenemethylidenesemicarbazide (0.01 mol) in dry dioxane (50 ml), containing potassium hydroxide (0.01 mol), at room temperature. The solution was stirred overnight at room temperature, after which a colourless solid product was collected by filtration and crystallized from ethanol (m.p. 541–542 K), giving colourless block-like crystals.Dimethyl Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms. The methyl group was refined as an idealized rigid group, allowed to rotate but not to tip.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S205698901501885X/su5217sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901501885X/su5217Isup2.hklStructure factors: contains datablock(s) I. DOI: 1430030CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The dihedral angle between the mean plane of the benzene and piperidine rings is 89.03 (3)°. In the crystal structure, inversion dimers are formed via N—H⋯Cl hydrogen-bond interactions, resulting in chains parallel to the [001] direction. The benzene rings within the chains show π–π stacking interactions [centroid-to-centroid distances of 3.801 (3) Å] and neighbouring chains interact via N—H⋯O hydrogen bonds.In the title complex, [PtCl Then, in the reaction solution, the cis complex converts into the trans complex and the thermodynamics of this conversion are currently under investigation by us.To explain this we suppose that et al. °]. The piperidine ring adopts the usual chair conformation, with the N2—Pt1 bond in the equatorial position. The piperidine ring is oriented nearly perpendicular to the coordination plane of the PtII atom, thereby reducing the van der Waals repulsion; the dihedral angle between the least-squares mean planes through the piperdine ring and the four atoms coordinated to the Pt atom is 89.6 (2)°. One short intramolecular contact is observed, i.e. H7B⋯Cl8 = 2.83 Å. The mean planes through the piperidine ring and the benzene ring make a dihedral angle of 89.0 (3)°. The dihedral angle between the mean planes of the nitro substituent and the benzene ring is 16.6 (3)°.The molecular structure of the title compound is illustrated in Fig. 1via N—H⋯Cl interactions between the aniline N atom and both Cl atoms, resulting in chains of molecules along the [001] direction  Å; Cg is the centroid of the C11–C16 ring; symmetry code: (iv) −x, y, −z + via N—H⋯O hydrogen bonds between the piperidine N atom and a nitro O atom , with the remaining 239 structures showing a trans coordination. There is no difference in the Pt—Cl distances between both configurations. The average Pt—Cl distances are 2.300 (15) and 2.299 (12) Å for the cis and trans arrangements, respectively, and correspond to the observed distances of 2.3039 (11) and 2.2917 (12) Å for Pt1—Cl8 and Pt1—Cl9, respectively.A search of the Cambridge Structural Database ] , prepared according to the synthetic procedure of Da et al. (2001p-nitroaniline (1 mmol) in ethanol (10 ml) was added gradually while stirring at 413–318 K. After 1 h, a brown powder appeared and the reaction mixture was then stirred further for 24 h until all the precipitate was completely dissolved. The solvent was removed in vacuo to give a brown–yellow product. The product was washed consecutively with a 0.1 M HCl solution (2 × 2 ml), warm water (2 × 2 ml) and diethyl ether (2 × 2 ml). The yield was 80%. Single crystals suitable for X-ray determination were obtained by slow evaporation within 12 h from an acetone solution at room temperature. IR : 3199, 3113 (νNH); 3070, 2927, 2862 (νCH); 1596, 1525, 1479 (νC=C arom); 1342, 1325 (νNO); 1H NMR : δ 8.21 , 7.47 , 5.49 , 3.66 , 3.26 , 2.99  = 13.0 Hz, C510HNH), 1.69–1.43 . 13C{1H} NMR : δ 149.6, 125.1, 124.2 (O2N6CH4NH2), 54.0, 27.2, 24.3 (5CH10NH).The starting complex K[PtCl al. 2001 with sliUiso(H) values assigned as 1.2Ueq of the parent atoms, with C—H distances of 0.95 (aromatic) and 0.99 Å (methylene), and N—H distances of 0.93 (NH) and 0.92 Å (NH2).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989015009196/rz5159sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015009196/rz5159Isup2.hklStructure factors: contains datablock(s) I. DOI: 1400786CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


N-(aryl)-2,2,2-tribromoacetamides show different weak interactions in their crystal structures.Three  N-aryl-2,2,2-tribromoacetamides, namely, 2,2,2-tribromo-N-(2-fluorophenyl)acetamide, C8H5Br3FNO, (I), 2,2,2-tribromo-N-[3-(trifluoromethyl)phenyl]acetamide, C9H5Br3F3NO, (II) and 2,2,2-tribromo-N-(4-fluorophenyl)acetamide, C8H5Br3FNO, (III) were synthesized and their crystal structures were analysed. In the crystal structure of (I), C—Br⋯πaryl interactions connect the molecules into dimers, which in turn are connected via Br⋯Br contacts [3.6519 (12) Å], leading to the formation of a one-dimensional ladder-type architecture. The crystal structure of (II) features chains linked by N—H⋯O and C—H⋯O hydrogen bonds. Two such chains are interlinked to form ribbons through Br⋯Br [3.6589 (1) Å] and Br⋯F [3.0290 (1) Å] interactions. C—Br⋯πaryl and C—F⋯πaryl interactions between the ribbons extend the supramolecular architecture of (II) from one dimension to two. In (III), the molecules are connected into R22(8) dimers via pairs of C—H⋯F interactions and these dimers form ribbons through Br⋯Br [3.5253 (1) Å] contacts. The ribbons are further interlinked into columns via C—Br⋯O=C contacts, forming a two-dimensional architecture.Three  N-Aryl-haloamides show a broad spectrum of pharmacological properties, including antibacterial acetamide, (I)N-[3-(trifluoromethyl)phenyl]acetamide, (II)N-(4-fluorophenyl)acetamide, (III)The molecular structures of (I)syn to the 2-fluoro substituent in the benzene ring, similar to that observed in the crystal structures of other ortho substituted compounds (see database survey). Contrast to the above, in (II)anti to the 3-CF3 substituent.In (I)In (I)The dihedral angle between the benzene ring and the C1–N1–C7(O)–C8 segment in (II)The dihedral angle between the benzene ring and the C1–N1–C7(O)–C8 segment in (III)aryl interactions °. The crystal structure of (I)In the crystal structure of (I)s Table 4 connect re Fig. 4. The Br1aryl and C9—F2⋯πaryl interactions between the ribbons extend the supramolecular architecture of (II)et al., 2012cis contact.The crystal structure of (II)via pairs of C3—H3⋯F1 interactions ns Fig. 7, formings Table 6, formings Table 6. The pacN-aryl-2,2,2-tribromoacetamides, namely, 2,2,2-tribromo-N-phenylacetamide, 2,2,2-tribromo-N-(2/3/4-chlorophenyl)acetamides and 2,2,2-tribromo-N-(2/3/4-methylphenyl)acetamides have been previously reported. Comparison of the crystal systems of these series of compounds show that all the chloro-substituted compounds crystallize in the orthorhombic crystal system, while the methyl-substituted compounds crystallize in the monoclinic system (Table 7i.e. (I)Seven m Table 7. Howeversyn to the 2-fluoro substituent in the benzene ring, similar to that observed in the crystal structures of 2,2,2-tribromo-N-(2-chlorophenyl)acetamide (Ia) acetamide (Ib) acetamide (Ia) acetamide (Ib)  intramolecular hydrogen bonds. Further, compounds (I)In (I)i.e. unsubstituted) compound is closer to those of chloro-substituted ones, thus the order is F < Cl(=H) < CH3.A comparison of the dihedral angle between the benzene ring and the C1–N1–C7(O)–C8 segment in all of the compounds shows that the dihedral angles in the fluoro-substituted compounds are smaller than those observed in chloro-substituted ones, which in turn have smaller values than the methyl-substituted tribromoacetamides Table 7. The diha)] reported in the literature feature strong N—H⋯O hydrogen bonds leading into C(4) chains forming a one-dimensional architecture. Compound (Ia) (2-chloro derivative) does not exhibit any conventional intermolecular interactions and therefore exhibits a zero-dimensional supramolecular architecture. However, the packing of molecules in the three structures reported here are very different and are controlled by interactions mainly involving the halogen atoms.The crystal structures of all of the seven compounds [except  = 1.2Ueq.Crystal data, data collection and structure refinement details are summarized in Table 810.1107/S2056989015015248/hb7472sup1.cifCrystal structure: contains datablock(s) I, II, III, global. DOI: 10.1107/S2056989015015248/hb7472Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989015015248/hb7472IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989015015248/hb7472IIIsup4.hklStructure factors: contains datablock(s) III. DOI: 1064065, 1419188, 1419189CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In membrane proteins, proline-mediated helix kinks are indispensable for the tight packing of transmembrane (TM) helices. However, kinks invariably affect numerous interhelical interactions, questioning the acceptance of proline substitutions and evolutionary origin of kinks. Here, we present the structural and thermodynamic basis of proline-induced integrin αIIbβ3 TM complex stabilization to understand the introduction of proline kinks in membrane proteins. In phospholipid bicelles, the A711P substitution in the center of the β3 TM helix changes the direction of adjacent helix segments to form a 35 ± 2° angle and predominantly repacks the segment in the inner membrane leaflet due to a swivel movement. This swivel repacks hydrophobic and electrostatic interhelical contacts within intracellular lipids, resulting in an overall TM complex stabilization of −0.82 ± 0.01 kcal/mol. Thus, proline substitutions can directly stabilize membrane proteins and such substitutions are proposed to follow the structural template of integrin αIIbβ3(A711P). In the evolution of globular proteins, structural complexity and functionality can be increased by combining independently folding protein domains13456Indirect support for this hypothesis is abundant. Inspection of membrane protein structures reveals that helix kinks are frequently centered around proline residues 4689. Eve468TM, of −4.84 ± 0.01 kcal/mol  and β3(W715), which are located at the N- and C-helix termini, and by detecting NOEs to the aromatic ring of αIIb(F993) in fractionally deuterated samples (21To understand the basis of β3(A711P), we determined the structure of the αIIbβ3(A711P) TM complex in isotropic phospholipid bicelles by multidimensional heteronuclear NMR spectroscopy. In the structure determination of the wild-type αIIbβ3 TM complex, we had used selectively methyl-labeled protein and deuterated lipids to obtain interhelical NOE distance restraintsHα pairs , albeit  samples . Membranamples 21.15N chemical shift differences between αIIb when complexed with either β3 or β3(A711P) illustrated that structural changes predominantly took place for IMC residues and residues that pack near the mutation site  − (ΔG°αIIbβ3(A711P),mutant −ΔG°αIIbβ3(A711P)) was quantified to compare the disturbance created by a mutation relative to its respective αIIbβ3 and αIIbβ3(A711P) reference structure. In accordance with largely invariant OMC interactions, ΔΔG°,′ was small for αIIb(G972A) with 0.16 ± 0.03 kcal/mol  and αIIbβ3 TM complexes. Specifically, ΔΔG°,′ = , prolines in membrane protein structures are frequently encountered near the center of TM helices422TM must be balanced with the affinity of intra- and extracellular receptor agonists and with the stability of the inactive versus the active ectodomains15ΤΜ came at the expense of αIIb(R995)-β3(D723) destabilization. This interaction is disrupted during talin-mediated integrin activationThe alternative to maintaining interhelical contacts near the proline kink would be to preserve interactions at the TM helix termini. When inspecting this possibility for αIIbβ3(A711P), it is apparent that mostly αIIb(R995)-β3(D723) benefits whereas packing on β3(G708) and αIIb(G976) would be less intimate . This mo7-glucose, 99% 15ND4Cl and 99% D2O. A fractionally deuterated 2H/13C/15N-αIIb(A963C)–β3(G690C/A711P) sample was prepared by growing E. coli cells in 60% D2O using protonated precursors. Freeze-dried peptide was reconstituted in 320 μL of 350 mM 1,2-dihexanoyl-sn-glycero-3-phosphocholine (DHPC), 105 mM 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC), 6% D2O, 0.02% w/v NaN3 buffered by either 25 mM NaH2PO4/Na2HPO4, pH 7.4 or 25 mM HEPES·NaOH, pH 7.4 for a final concentration of 0.8 mM and bicelle q-factor of 0.3.The disulfide-linked αIIb(A963C)–β3(G690C/A711P) dimer was prepared applying published protocols1HN, 15N, 13Cα, 13Cβ, and 13C′ assignment of the αIIbβ3 TM complex and the β3(A711P/K716A) TM segment152H/13C/15N-αIIb(A963C)–2H/13C/15N-β3(G690C/A711P) were achieved employing HNCA, HNCO, HNCACB and NOESY-TROSY experiments. 15N-edited NOESY-TROSY experiments using 2H/15N-αIIb(A963C)–β3(G690C/A711P) or αIIb(A963C)–2H/15N-β3(G690C/A711P) dimers were acquired with mixing times of 120, 150 and 175 ms. Using [60% 2H]/13C/15N-αIIb(A963C)–β3(G690C/A711P), an aromatic 13C-edited NOESY-HSQC experiment (mixing time 150 ms) was recorded. Sidechain assignments started again from the αIIbβ3 TM complex and were similar to the aforementioned NOESY spectra. In a general case, NOESY experiments for 2H/14N-α–1H/15-β and 1H/15N-α–2H/14-β can establish sidechain assignments in combination with standard experiments. Sidechain and NOE assignments were carried out manually using the program CARA. H-N residual dipolar couplings (RDC) were measured twice in compressed polyacrylamide gels  using 2H/15N-αIIb(A963C)–2H/15N-β3(G690C/A711P) dimerStarting from the 15N, 13Cα, 13Cβ, and 13C′ chemical shift patternsα-C′, N-C′ RDCs measured for these monomers to further restrict the individual αIIb and β3(A711P) backbone conformations. An employed torsion angle potential of mean force1 angles detected in the monomeric αIIb and β3(A711P/K716A) TM segments, which mostly corresponded to their default values. Moreover, the sidechains of αIIb(Phe992) and β3(Lys716) were adjusted to snorkel. Aside from standard force field terms for covalent geometry  and nonbonded contacts , dihedral angle restraints were implemented using quadratic square-well potentials. In addition, a backbone-backbone hydrogen-bonding potential was employed1D). The final values for the force constants of the different terms in the simulated annealing target function were as previously describedStructure calculations were carried out by simulated annealing, starting at 3000 K using the program XPLOR-NIHsn-glycero-3-phosphocholine (DHPC), 17 mM 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), 25 mM NaH2PO4/Na2HPO4 pH 7.4 at 28 °C. Prior to data analysis, the measurements were corrected for the heat of dilutions of the αIIb and β3 peptides. The αIIbβ3 complex stoichiometry was fixed at 1:1XY were calculated from the measured heat changes, δHi, as described previouslyITC measurements of the peptides listed in How to cite this article: Schmidt, T. et al. Structural and thermodynamic basis of proline-induced transmembrane complex stabilization. Sci. Rep.6, 29809; doi: 10.1038/srep29809 (2016).


E conformation about the azobenzene linkage and the benzene rings are almost coplanar to one another [dihedral angle = 1.36 (7)°]. In the crystal, a combination of O—H⋯O and C—H⋯O hydrogen bonds and C—H⋯π interactions leads to the formation of slabs parallel to (001).The title compound has an  16H14N2O3, has an E conformation about the azobenzene [—N=N– = 1.2481 (16) Å] linkage. The benzene rings are almost coplanar [dihedral angle = 1.36 (7)°]. The O atoms of the carboxylic acid group are disordered over two sets of sites and were refined with an occupancy ratio of 0.5:0.5. The two disordered components of the carboxylic acid group make dihedral angles of 1.5 (14) and 3.8 (12)° with the benzene ring to which they are attached. In the crystal, molecules are linked via pairs of O—H⋯O hydrogen bonds, forming inversion dimers. The dimers are connected via C—H⋯O hydrogen bonds, forming ribbons lying parallel to [120]. These ribbons are linked via C—H⋯π interactions, forming slabs parallel to (001).The title compound, C Hence, liquid crystallinity may be induced by the formation of hydrogen-bonded dimers. A number of liquid crystal (LC) systems containing hydrogen bonds that function between identical molecules have been reported  linkage, the length of the N1—N2 bond is 1.2481 (16) Å and the torsion angle for the azo unit (C7—N1=N2—C10) is 179.99 (10)°, which is comparable with the values of ca ±180° observed in 4,4-azinodibenzoic acid -ethyl-4-{[4-(decanoxloxy)phenyl]diazenly} benzoate -2-[4-(but-3-en-1-yloxy)phenyl]-diazen-1-yl}benzoic acid, , as shown in Fig. 3In the crystal, molecules are linked s Table 1. The dimet al., 2012. The terminal double bonds-containing azobenzene compound was hydrolysed under basic conditions to yield the title compound. Red plate-like crystals were obtained by crystallization from an ethanol–ethyl acetate mixture (1:1); m.p. 494 K. 1H NMR (CDCl3): δ 8.18 , 7.94 , 7.93 , 7.05 , 6.04 , 5.45 , 5.31 , 4.60 .The title compound was synthesized by a literature procedure (Rahman Uiso(H) = 1.5 Ueq(O). The C-bound H atoms were positioned geometrically and refined using a riding model: C—H = 0.93–0.97 Å with Uiso(H) = 1.2Ueq(C). Two outlier reflections, 341 and 309, were omitted from the refinement.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S1600536814023745/su2790sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814023745/su2790Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814023745/su2790Isup3.cmlSupporting information file. DOI: 1031374CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, molecules are linked by weak C—H⋯O and C—H⋯π contacts, resulting in a three-dimensional supramolecular structure.The title spiro-compound bears  17H18O3, the two non-spiro C atoms of the cyclopropane ring bear a formyl and a phenyl substituent which are trans-oriented. In the crystal, molecules are linked by weak C—H⋯O and C—H⋯π contacts resulting in a three-dimensional supramolecular structure.In the title compound, C The angles in the three-membered ring range from 58.80 (13)° (C2—C4—C3) to 61.67 (13)° (C3—C2—C4) being close to the ideal value of 60° for such a ring. The six-membered ring containing the spiro atom C4 and ring atoms C5–C9 adopts a chair conformation with a puckering amplitude Q of 0.491 (2) Å and θ = 16.8 (2)°, which indicates a slight deviation from an ideal chair conformation with θ = 0°. The plane of the central cyclopropane ring forms dihedral angles of 66.89 (16) and 89.33 (16)°, respectively, with the plane of the phenyl ring and the mean plane of the cyclohexane ring [maximum deviation from this plane is 0.272 (2) Å for atom C7]. The latter two planes form a dihedral angle of 64.15 (10)°. The plane of the formyl group, consisting of atoms C1, H1 and O1, is almost normal to the cyclopropane ring with a dihedral angle of 81.3 (3)°.The molecular structure of the title compound is depicted in Fig. 1B⋯O2 contacts (red dotted lines) which are further linked to double strands along the 21-screw axes along [100] by C3—H3⋯O1 contacts (blue dotted lines). The remaining C—H⋯O as well as the C—H⋯π interactions are displayed in Fig. 3B⋯O3 contacts (green dotted lines). These strands are linked by two different C—H⋯π contacts (Table 1Cg is the centroid of this ring). Along [100] the strands are linked by C12—H12⋯iCgv contacts (orange dotted lines) while along [001] the links are established by C17—H17B⋯Cgv interactions (violet dotted lines) enclosing angles between the C—H bond and the plane of the π-system of ca 39° and 75° respectively. As a result of these interactions, a three-dimensional supramolecular structure is formed.The crystal packing of the title compound shows weak C—H⋯O and C—H⋯π interactions Table 1 and 3 ▸.et al., 1998trans-1,2-bis(methoxycarbonyl)-6,6-dimethylspiro(2.5)octane-4,8-dione -1,1-dichloro-6,6-dimethyl-2-[(1′S*)-1′-nitroethyl]spiro[2.5]octane-4,8-dione octane 1,4-dioxane solvate -5-benzyl-2,2,3-trimethyl-4-oxo-1-[(E)-3-phenylallylidene]-imidazolidin-1-ium hexafluorophosphate  and phenyliodonium-4,4-dimethylcyclohexane-2,6-dione  in acetonitrile (5 ml). After 24 h stirring at ambient temperature, water (10 ml) was added. The aqueous phase was extracted with CH2Cl2 (15 ml). The organic layers were combined, washed with brine, and dried over MgSO4. After evaporation of the solvent under vacuum, the crude product was purified by column chromatography (n-pentane/Et2O: 7/3 and 6/4) to give the title compound  as colourless crystals (m.p. 397–399 K).A 10 ml round-bottomed flask equipped with a magnetic stirring bar was charged with a solution of the (Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms. The methyl groups were allowed to rotate along the C—C bonds to best fit the experimental electron density. As a result of the absence of anomalous scatterers and high angle data, the Flack test results can be considered meaningless. The synthesis resulted in a racemic mixture, hence the structure was refined as an inversion twin.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S205698901600164X/su5275sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901600164X/su5275Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901600164X/su5275Isup3.cmlSupporting information file. DOI: 1450224CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


If Mo—Mo bonds are ignored, each Mo atom can be considered as six-coordinated in a distorted octahedral geometry. The Mo—Mo distance of 2.6880 (5) Å for two the Mo atoms bridged by the acetate ligand is shorter than the other two Mo—Mo distances [2.7490 (5) and 2.7566 (5) Å]. One ethyl group is disordered between two conformations in a 0.65 (3):0.35 (3) ratio. In the crystal, weak C—H⋯O interactions link the trinuclear molecules related by translation in [100] into chains. The crystal packing exhibits short intermolecular S⋯S contacts of 3.1886 (13) Å. In other words, in this crystal packing, a supramolecular structure is constructed by the C—H⋯O and S⋯S interactions.In the title compound, [Mo DOI: 10.1107/S1600536814012501/cv5459Isup2.hklStructure factors: contains datablock(s) I. DOI: 1005735CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The least-squares planes through the two aromatic ring systems make an angle of 47.3 (3)° for (I) and 38.6 (2)° for (II). Both structures show disorder for the PtCl2 fragment, in the case of (I) even further extended towards the CH2—CH=CH2 ligand. An intramolecular C—H⋯Cl hydrogen bond occurs in (I). In the crystal packing of (I), which is dominated by N—H⋯O and C—H⋯Cl interactions, a partially occupied water molecule is observed on a twofold rotation axis with a refined site occupancy of 0.10 (1). A C—H⋯π interaction is also present. In (II), inversion dimers form chains along the b-axis direction by N—H⋯O hydrogen bonds.In the title complexes,  In both complexes, the Cl atoms are trans with respect to each other 2CH2=CH—CH2 fragment is disordered over two positions [population parameters 0.679 (8) and 0.321 (8)], while in (II)2 fragment is disordered over two positions [population parameters 0.872 (6) and 0.128 (6)]. The angles between the best planes through the two aromatic rings are 47.3 (3) and 38.6 (2)° for (I)A⋯Cl9 distance of 2.73 Å. In (I)A⋯Cl9.The complexes crystallize in different space groups, er Fig. 1. The eugThe crystal packing of (I)AB⋯O28i hydrogen bonds are further linked into chains in the b-axis direction by N2—H2AA⋯ hydrogen bonds .The crystal packing of (II)B⋯Cg1iii, H27B⋯Cg1iii = 2.72 Å; Cg1 is the centroid of the C20-C25 ring; symmetry code: (iii) −x + 1, y, −z + No π–π interactions are observed in the packing of either structure. For (I)B) due to the disorder from the average Pt—N distance of 2.09 (5) Å for Pt—NH2—phenyl fragments present in the Cambridge Structural Database  and 2.305 (2) Å and agree well with the average Pt—Cl distance of 2.32 (3) Å for trans complexes present in the CSD. One Pt1B—Cl distance [2.151 (2) Å] deviates significantly from this average.The Pt—N distances in (I)2 and C=C shows 11 hits. As fourth ligand we notice an additional Cl atom  or C atom (two hits) or O atom (one hit). In the complex [PtCl(methyleugenol)(o-toluidine)] A search in the CSD for Pt complexes with Pt coordinated by Cl, NH3]:Synthesis of K[Pt(Alkeug)Cl3]  were synthesized following the protocol of Da and coworkers Cl2(Alkeug)(C6H6NCl)]:Synthesis of trans-[PtClv/v) was added to a mixture of 1.0 mmol [K[Pt(Alkeug)Cl3] and 10 mL acetone/ethanol (1:1 v/v). After two h stirring, a white precipitate of KCl was separated out. The remaining solution was stirred for two h at room temperature to obtain a yellow precipitate, which was collected by filtration, washed with ethanol and diethyl ether and dried in vacuum. The obtained crystals are soluble in chloroform and acetone, slightly soluble in ethanol and insoluble in water. The yield was 70–80%. Single crystals suitable for X-ray investigation were obtained by slow evaporation from a chloroform/ethanol (1:2 v/v) solution at room temperature.A solution of 127.0 mg (1.0 mmol) p-chloroaniline in 10 mL acetone/ethanol (1:1 2(Meteug)(C6H6NCl)] (I)Data for  (II)Data for  and refined with constraints for the bond lengths present in this fragment. Refinement of the population parameter of oxygen atom O34  converged to 0.10 (1). Water H atoms were not located.In (I)2 fragment is disordered over two positions [population parameters 0.872 (6) and 0.128 (6)].In (II)Uiso(H) values assigned as 1.2Ueq of the parent atoms (1.5 times for methyl groups), with C—H distances of 0.95 (aromatic and =CH2), 0.98 (CH3), 0.99 (CH2) and 1.00 Å (CH), and N—H distances of 0.91 Å (NH2). Enhanced rigid bond restraints were used for the anisotropic temperature factors of the non-H atoms. In the final cycles of refinement, 7 and 15 outliers were omitted for (I)All H atoms were placed in idealized positions and refined in riding mode, with 10.1107/S2056989016008872/rz5189sup1.cifCrystal structure: contains datablock(s) I, II. DOI: 10.1107/S2056989016008872/rz5189Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016008872/rz5189IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1483067, 1483066CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The complexes each form tetrahedral C 2(C8H11BrO3)(CO)6], (1), and [Co2(C12H16Br2O4)(CO)6], (2), result from the replacement of two carbonyl ligands from dicobalt octacarbonyl by the alkynes 4-hydroxybut-2-ynyl 2-bromo-2-methylpropanoate and but-2-yne-1,4-diyl bis(2-bromo-2-methylpropanoate), respectively. Both molecules have classic tetrahedral C2Co2 cluster cores with the CoII atoms in a highly distorted octahedral coordination geometry. The alkyne ligands both adopt a cis-bent conformation on coordination. In the crystal structure of (1), classical O—H⋯O and non-classical C—H⋯O contacts form inversion dimers. These combine with weak O⋯O and Br⋯O contacts to stack the molecules into interconnected columns along the b-axis direction. C—H⋯O and C—H⋯Br contacts stabilize the packing for (2), and a weak Br⋯O contact is also observed. Interconnected columns of molecules again form along the b-axis direction.The title compounds, [Co The two carbonyl groups in (2) each lie on the same side of the molecule, with the 2-bromo-2-methylpropanoate units arranged symmetrically with respect to the central Cet al., 1995A⋯O1 and C8—H8A⋯O12 hydrogen bonds  and Br1⋯O1  contacts stack the molecules into interconnected columns along the b-axis direction , classical O1—H1⋯O3 hydrogen bonds Table 3 are augmds Fig. 3. These con Fig. 4.B⋯O2 and C8–H8A⋯O2 contacts  Å, symmetry operation x, −1 + y, z], form b-axis direction , although in this molecule no classical hydrogen bonds are possible. Bifurcated C3—H3s Table 4 produce gs Fig. 5. The oth0] Fig. 6. The neton Fig. 7.et al., 2002The first structure, of dicobalt hexacarbonyl diphenylacetylene, was reported using film data Sly, 1959. The cur2(CO)8 were allowed to react at room temperature for 1 h in CH2Cl2 under nitrogen. The reaction mixtures were filtered through silica gel to remove any insoluble impurities and the filtrates taken to dryness in vacuo. The complexes were then purified by recrystallization from hexane at 273 K. Yields were in the range 70–80%. Complexation was confirmed by the absence of a band at 1860 cm−1 in the infrared spectrum, attributable to the μ2 (bridging) carbonyl groups of the dicobalt octacarbonyl starting material. In addition, a hypsochromic shift of approximately 30 cm−1 of the remaining carbonyl stretching frequencies is seen, due to the decrease in electron density at the metal atoms upon coordination of these alkynes. Characteristic IR spectra were recorded for both products as follows: IR : (1): 3300 , ν(C≡O) 2099, 2062, 2032, ν(C=O) 1735; (2): ν(C≡O) 2096, 2058, 2031, ν(C=O) 1734.In typical preparations, 1:1 molar quantities of 4-hydroxybut-2-ynyl 2-bromo-2-methylpropanoate for (1) or a 2:1 molar ratio of but-2-yne-1,4-diyl bis(2-bromo-2-methylpropanoate) for (2) with Cod(C—H) = 0.99 Å, Uiso = 1.2Ueq (C) for CH2, 0.98 Å, Uiso = 1.5Ueq (C) for CH3 atoms. In the final refinement, two reflections from the data for (2) with Fo << Fc were omitted from the refinement.All H atoms bound to carbon were refined using a riding model with 10.1107/S1600536814009659/hb0001sup1.cifCrystal structure: contains datablock(s) global, 1, 2. DOI: 10.1107/S1600536814009659/hb00011sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S1600536814009659/hb00012sup3.hklStructure factors: contains datablock(s) 2. DOI: 1004257, 1004258CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The benzylidine and benzoate rings are inclined to one another by 24.58 (8)°, and the conformation about the C=N bond is E.The title  p-hydroxy Schiff base, C17H17NO4, was synthesized via the condensation reaction of benzocaine with vanillin. The benzylidine and benzoate rings are inclined to one another by 24.58 (8)°, and the conformation about the C=N bond is E. In the crystal, molecules are linked by O—H⋯N hydrogen bonds, forming zigzag chains propagating along [010]. Adjacent chains are linked by C—H⋯π and weak offset π–π interactions [intercentroid distance = 3.819 (1) Å], forming sheets parallel to (10-2).The title  The m-methoxy group (O1/C13/C16) is slightly out of the plane of the benzene ring (C11–C14/C20/C21) to which it is attached by 5.37 (18)°, while the mean plane of the ethylacetate group (O3/O17/C1/C2/C4) is inclined to the benzene ring (C5–C8/C18/C19) to which it is attached by 10.23 (11)°. This non-linearity is consistent for Schiff bases.The title Schiff base, (I)Cg1⋯Cg1i = 3.819 (1) Å, interplanar distance = 3.672 (2) Å, slippage = 1.05 Å, Cg1 is the centroid of ring C5–C8/C18/C19; symmetry code: (i) −x + 2, −y + 1, −z + 1],In the crystal, molecules are linked by O—H⋯N hydrogen bonds, forming zigzag chains propagating along [010]; see Table 1para rather than the ortho position, this Schiff base cannot form the intramolecular C=N⋯O—H hydrogen bond responsible for keto–enol tautomerism. However, the close proximity of the C=N and O—H groups gives rise to the possibility that external stimulation of the material by heat or light may lead to the zwitterionic form. The potential for compound (I)The crystal structure analysis of compound (I)et al., 2016et al., 2010et al., 2012In the Cambridge Structural Database Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016008999/su5304sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989016008999/su5304Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016008999/su5304sup3.pdfSupporting information file. DOI: Click here for additional data file.10.1107/S2056989016008999/su5304Isup4.cmlSupporting information file. DOI: 1483394CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The dihedral angles between the benzothiazole ring systems and the phenol rings are 4.1 (4) and 5.8 (4)°, indicating an almost planar geometry. Weak intra- and intermolecular C—H⋯O hydrogen bonds are observed. In the crystal, weak π–π interactions between aromatic and thiazole rings [centroid–centroid distances = 3.626 (3) and 3.873 (3) Å] link the molecules into a two-dimensional supramolecular network along the bc plane.In the title complex, [Cu(C DOI: 10.1107/S2056989015015303/bq2400Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015015303/bq2400fig1.tif. DOI: Molecular structure of the title complex, showing the atom-numbering scheme and 30% probability ellipsoids.Click here for additional data file.10.1107/S2056989015015303/bq2400fig2.tifvia . DOI: via C—H⋯O (black dashed lines) and π-π (red) interactions.Dimeric formation Click here for additional data file.10.1107/S2056989015015303/bq2400fig3.tif. DOI: Part of the crystal structure of the title complex, showing the 2-D network of molecules linked by intermolecular C—H⋯O hydrogen bonds (black dashed lines) and π-π interactions (red).1419096CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The packing is stabilized  42H42N2P22+·2Br−·2CH2Cl2, lies on a crystallographic twofold rotation axis. The 1,2-diaminocyclohexane fragment has a chair conformation with two N atoms in a transoid conformation [N—C—C—N = 163.4 (2)°]. In the crystal, the cations are linked to the anions by N—H⋯Br and C—H⋯Br hydrogen bonds, forming a chain structure along the c axis. The dichloromethane molecule takes part in the hydrogen-bond network through C—H⋯π and C—H⋯Br interactions.The cation of the title solvated salt, C P,P,P-triaryl-P-aminophosphonium salts bearing a primary amino group are isolable intermediates in the Horner & Oediger °; symmetry code: (i) −x + 1, y, −z + The cation is situated on a crystallographic twofold rotation axis Fig. 1. The 1,2trans-1,2-diaminocyclohexane molecule and the last is donated by the solvent dichloromethane molecule  in 100 ml of the same solvent. After four h of stirring at room temperature and the formation of white precipitate, a mixture of half an equivalent of (±)-trans-1,2-diaminocyclohexane  and one equivalent of triethylamine  in 10 ml of CH2Cl2 was added dropwise under stirring at 273 K. The suspension was left under continuous stirring for 12 h at room temperature. Then the reactant was extracted twice with 25 ml of distilled water, and the organic phase was dried over MgSO4. All volatiles were eliminated under vacuum, and the resulting light-yellow solid was stirred with Et2O overnight. After filtration, 6.0 g of the title compound was obtained as a white powder . Single crystals suitable for X-ray diffraction were grown by slow evaporation of a dichloromethane solution at room temperature.Under an NUiso(H) = 1.2Ueq(N). Other H atoms were positioned geometrically (C—H = 0.93 or 0.97 Å) and constrained using the riding-model approximation with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016004576/is5441sup1.cifCrystal structure: contains datablock(s) Global, I. DOI: 10.1107/S2056989016004576/is5441Isup2.hklStructure factors: contains datablock(s) I. DOI: 1469040CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The ruthenocenecarbonitrile molecule exhibits mirror symmetry in the solid state. 5-C5H4C N)(η5-C5H5)], exhibits point group symmetry m, with the mirror plane bisecting the molecule through the C N substituent. The RuII atom is slightly shifted from the η5-C5H4 centroid towards the C N substituent. In the crystal, molecules are arranged in columns parallel to [100]. One-dimensional intermolecular π–π interactions [3.363 (3) Å] between the C N carbon atom and one carbon of the cyclopentadienyl ring of the overlaying molecule are present.The molecular structure of ruthenocenecarbonitrile, [Ru(η A synthesis for ferrocenecarbonitrile has already been described in 1957  Å]. Both cyclopentadienyl rings adopt an ideally eclipsed conformation and are virtually oriented parallel towards each other, which is expressed by the bond angle at the RuII between the two centroids (= D), with D(C5H4)—Ru1—D(C5H5) = 178.87 (1)°. However, the RuII atom is slightly shifted from the centre of the C5 ring to the nitrile-bonded C2 atom, which can be explained best by the significantly different Ru—C bond lengths sp (ethynyl)  as compared to (I)et al., 2008The ruthenocene backbone is hardly described in the literature. Reported derivatives contain et al., 2008et al., 2010et al., 1996et al., 2007et al., 2007Comparison of the C—C [1.431 (3) Å] and the C N distances [1.148 (3) Å] with the respective ferrocene carbonitrile derivatives  solution were added in a single portion, and stirring was continued for additional 20 min. Solid particles were removed by filtration and the filtrate was extracted with ethyl acetate (3 × 50 ml). The combined organic layers were dried over MgSO4. All volatiles were removed under reduced pressure and the crude product was purified by flash chromatography on aluminum oxide using dichloromethane as eluent. Greenish crystals of (I)−1): ν = 2226 , 2854 (s), 2925 (s), 3082 . 1H NMR : δ 4.69 , 4.70 , 4.70 . 13C{1H} NMR : δ = 55.3 (Ci-C5H4), 72.4 (C5H4), 72.9 (C5H5), 73.5 (C5H4), 119.4 (CN). HRMS : C11H9NRu: m/z = 256.9792 .Formylruthenocene was prepared according to a published procedure (Mueller-Westerhoff isoU(H) = 1.2Ueq(C) and a C—H distance of 0.93 Å. Crystal data, data collection and structure refinement details are summarized in Table 2C-bonded H atoms were placed in calculated positions and constrained to ride on their parent atoms, with 10.1107/S205698901500540X/wm5119sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901500540X/wm5119Isup2.hklStructure factors: contains datablock(s) I. DOI: 1054219CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The Zn⋯Zn separation is 11.3893 (14) Å and the ligands wrap around the two ZnII atoms, forming a triple helix as defined by the Zn—N—N—Zn torsion angles of 104.05 (18), 99.06 (19) and 101.40 (19)°. The Zn—N(pyridyl) distances in the octahedral ZnN6 coordination sphere are in the range 2.128 (5)–2.190 (5) Å and the Zn—N(imine) distances are in the range 2.157 (5)–2.277 (5) Å.The asymmetric unit of the title compound, [Zn DOI: 10.1107/S205698901502455X/fk2093Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901502455X/fk2093fig1.tif. DOI: Molecular structure of the title compound. Anisotropic displacement ellipsoids are drawn at the 50% probability level and H atoms are represented by circles of arbitrary size.1443648CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The [Re6Se8]2+ cluster core displays a non-crystallographic center of symmetry and is bonded through the ReIII atoms to five triethylphosphane ligands and one p-toluenesulfonate ligand. One p-toluenesulfonate counter-ion and two dichloromethane solvent molecules are also present in the asymmetric unit. One of the ethyl chains of one triethylphosphane ligand and one of the CH2Cl2 solvent molecules are disordered over two sets of sites . The Re—O(sulfonate) bond length of 2.123 (5) Å is similar to other Re—O bond lengths of hexanuclear rhenium chalcogenide clusters containing other O-donor ligands such as dimethyl sulfoxide (DMSO), dimethylformamide (DMF) and hydroxide.The title compound, [Re Later, Eremenko et al. (1993iPr)3)2(CO)(NO)(OTs)2] (OTs− = p-toluenesulfonate anion) which represented the first structural report of a rhenium complex containing tosylate ligands. In the synthesis of octahedral rhenium chalcogenide cluster complexes, the substitution of either halide or nitrile ligands has proven an effective means for generating a variety of new cluster complexes  cluster complexes (C6H15P)5](C7H7O3S)·2CH2Cl2 = 0.036wR(F2) = 0.097S = 1.0216405 reflections693 parametersH-atom parameters constrainedmax = 2.67 e Å−3Δρmin = −1.26 e Å−3ΔρSMART  used to solve structure: DIRDIF99  I, isu0804. DOI: 10.1107/S2056989015014334/pj2021Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015014334/pj2021fig1.tif6 8 3 5 3 6 4 + . DOI: 6Se8(PEt3)5(O3SC6H4Me)]+ ion showing the atom labelling scheme. Non-hydrogen atoms are represented by Gaussian ellipsoids at the 30% probability level. Hydrogen atoms omitted for clarity.Perspective view of the [Re1010097CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Each water molecule is disordered over three sets of sites, with a refined occupancy ratio of 0.310 (9):0.275 (9):0.415 (9) for one molecule and 0.335 (9):0.288 (9):0.377 (9) for the other molecule. The MnII atoms exhibit a distorted octahedral geometry, while the WV atoms adopt a distorted square-antiprismatic geometry. The MnII and WV atoms are linked alternatively through cyanide groups, forming a tetranuclear 12-atom rhombic metallacycle. Adjacent metallacycles are further connected by μ2-bridging cyanide anions, generating a 3,2-chain structure running parallel to [101]. Interchain π–π interactions are observed [centroid–centroid distances = 3.763 (3) and 3.620 (2) Å].The asymmetric unit of the title compound, {[Mn DOI: 10.1107/S1600536814007235/rz5113Isup2.hklStructure factors: contains datablock(s) I. DOI: 994877CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


N2-amino group of the guanine residue exists in the cyclic aminoglycoside form.Crystallographic analysis of a nucleoside analog of the 2′-deoxyguanosine/abasic site cross-link is presented. This structure corroborates an earlier two-dimensional NMR analysis, concluding that the 2-deoxyribose unit attached at the exocyclic  R,4S,5R)-4-hydroxy-5-(hydroxymethyl)tetrahydrofuran-2-yl]-2-{[-4-methoxy-5-(methoxymethyl)tetrahydrofuran-2-yl]amino}-1H-purin-6(9H)-one, C17H25N5O7, crystallizes with two independent molecules (A and B) in the asymmetric unit. In the crystal, the guanosine moieties of molecules A and B are linked by N—H⋯N and O—H⋯N hydrogen-bonding interactions, forming ribbons which are stacked to form columns along [100]. These columns are then linked by O—H⋯O hydrogen bonds between the ribose moieties and numerous C—H⋯O interactions to complete the three-dimensional structure.The title compound, 9-[(2 The disposition of these furanose rings relative to the purine rings can be described by the torsion angle C2—N4—C6—O2, which is 70.9 (3)° in molecule A and 61.7 (3)° in molecule B. The furanose ring attached to the N5 position in molecule A is again a half-chair, with the maximum deviation from planarity between C11A and C12A , while this furanose ring in molecule B is an envelope with C11B at the flap . The disposition of these furanose rings relative to the purine rings can be described by the angle C1—N5—C11—O5, which is −87.4 (2)° in molecule A and −93.7 (2)° in molecule B.The two independent molecules  were dissolved in 0.8 ml of a 3:1 mixture of DMSO and 25 mM sodium phosphate buffer (pH 7.0) in a round-bottom flask. The flask was heated to 333 K and the mixture stirred for 22 h. The solvent removed in vacuo and the product purified by column chromatography on silica gel eluted with 0–15% methanol in dichloromethane  to yield 36 mg (12% yield) of the title compound as a colorless oil. The precursor 3,5-bis-O-methyl-2-deoxy-d-ribofuranose was synthesized according to previously reported procedures  and 3,5-bis-Uiso(H) = 1.2Ueq(C). Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S205698901600517X/hb7568sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901600517X/hb7568Isup2.hklStructure factors: contains datablock(s) I. DOI: 1448235CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: