Single-crystal X-ray Diffraction Research Articles

Garciyunnanones A–R: Caged polycyclic polyprenylated acylphloroglucinols decorated with a lavandulyl substituent from Garcinia yunnanensis

Garciyunnanones A–R (1–18), eighteen undescribed caged polycyclic polyprenylated acylphloroglucinols, two undescribed biogenetic congeners (19–20), and nineteen known analogues (21–39), were isolated from the stem barks of Garcinia yunnanensis Hu. All of these isolates are decorated with a C-5 lavandulyl substituent. Their structures and absolute configurations were confirmed by HRESIMS, 1D & 2D NMR spectroscopic analysis, quantum chemical calculations of electronic circular dichroism data, and single-crystal X-ray diffraction analysis. The X-ray crystallographic data of ten isolated caged compounds ascertained the absolute configuration of C-23 in the lavandulyl as S. The cytotoxicity on three cancer cell lines and the anti-nonalcoholic steatohepatitis activity of the isolates were tested. In a free fatty acid-induced L02 cell model, compounds 33 and 39 decreased intracellular lipid accumulation significantly.

Solvent-controlled structural variation of two Cd(II) compounds derived from thiophene dicarboxylate and 4-imidazol-1-yl-pyridine mixed ligands

Two solvent-controlled Cd(II) compounds, formulated as {[Cd2(Htdc)4(µ-imyp)(H2O)4]} (1), [Cd2(µ 2-tdc)2(µ-imyp)(DMF)2(H2O)2]n (2) (H2tdc= 2,5-thiophenedicarboxylic acid, imyp = 4-imidazol-1-yl-pyridine and DMF = N,N-dimethylformamide) have been synthesized by reactions of Cd(NO3)2·4H2O and H2tdc with imyp in different solvents, respectively. Both compounds were then characterized by single-crystal X-ray diffraction and other physicochemical methods. In 1, partially deprotonated Htdc− anion as terminal ligand and µ-imyp ligand connect Cd2+ ions to generate a discrete structure. In 2, completely deprotonated µ 2 – tdc2− anions and µ-imyp ligand link Cd2+ ions into a 1D double chain structure. Both compounds display 3D supramolecular structures through hydrogen bonding interactions. The results provided interesting insights into solvent effects on the structural formation of compounds 1 and 2. In addition, the solid-state photoluminescent properties of compounds 1 and 2 were also investigated. Two solvent-controlled Cd(II) compounds have been synthesized by reactions of Cd(NO3)2·4H2O and 2,5-thiophenedicarboxylic acid with 4-imidazol-1-yl-pyridine in the different solvents. One compound is a discrete structure, while the other compound has a 1D double chain structure. The results provided interesting insights into solvent effects on the structural formation of compounds.

Thermolysis of Ru3(CO)10(µ-dppp): A new Ru4- cluster derived from 1,3-bis(diphenylphosphino)propane

The reaction of Ru3(CO)12 and dppp [dppp = 1,3-bis(diphenylphosphino)propane/Ph2P(CH2)3PPh2] in the presence of benzophenone ketyl radical anion afforded [Ru3(CO)11]2(µ-dppp) (1) Ru3(CO)10(µ-dppp) (2), Ru3(CO)9(µ-dppp)(ƞ1-dppp) (3) and Ru3(CO)8(µ-dppp)2 (4). Refluxing 2 in octane yields new triruthenium clusters Ru3(CO)9(μ3-PPh(CH2)3PPh(C6H4)) (5) and Ru4(CO)9(µ-CO){µ4-η2-P(CH2)3PPh2}(µ4-η4-C6H4) (6), as a result of CH and CP bond activation involving the Ph2P(CH2)3PPh2 ligand. Compounds 2 and 6 have been structurally determined by the single crystal X-ray diffraction. As expected, the Ph2PCH2CH2CH2PPh2 ligand in 2 is equatorially bonded to Ru–Ru bond in µ2-η2 mode. In contrast, the X-ray structure of 6 shows an µ4-η2-PCH2CH2CH2PPh2 and a benzyne group coordinated to a square of Ru atoms. A rotation of benzyne group on a square of Ru atoms was supported by variable temperature NMR studies. The topological analysis was performed on 6 to further elucidate their chemical bond properties.

A novel Fe(III) and 2-amino-perimidinium based hybrid material catalyzed friedel–Crafts type hydroarylation of alkynes: Scope and mechanism

A new inorganic-organic hybrid material with the structural formula (C51H66N9)3[FeCl4]·2Cl consisting of iron(III) center, 2-amino-perimidinium ligand and free chloride ions was synthesized. In addition, the compound was characterized by single-crystal X-ray diffraction and Fourier-transform infrared spectroscopy techniques. The structural arrangements and hydrogen bonding interactions in the compound were studied and successfully employed in the catalytic hydroarylation of alkynes and arenes to produce the corresponding 1,1-diaryl alkene derivatives. Gratifyingly, when nitromethane was employed as a solvent, the title compound displayed excellent catalytic activity with moderate to high conversions. Stoichiometric reactions and experimental data both provided key evidence in support of the reaction mechanism.

Structural and electrochemical properties of a Cu(I) Schiff-base complex: Catalytic application to the synthesis of tetrahydropyrimidine derivatives

Herein, we report the synthesis and spectroanalytical characterization of one-dimensional polymeric Cu(I) complex [Cu(L2Br)I]n, incorporating N,N′-bis(2-bromobenzylidene)ethane-1,2-diamine Schiff base ligand, L2Br. Single crystal X-ray diffraction (SC-XRD) was used to examine the specific organization of atoms in thecomplex. The results showed that the Cu ion was coordinated only throughthe N donor sitesof the Schiff base. The complex’s tetrahedral shape was distorted, as demonstrated by the bond angles around the metal atom. The natural bond orbital and atoms in molecules investigations were also carried out in order to gain greater knowledge of the Cu(I) complex’s intermolecular charge transfer characteristics. The redox nature of the the complex was assessed by the cyclic voltammetry (CV) technique. The Cu(I)/Cu(II) redox arrangement has been observed to exhibit characteristics consistent with a quasi-reversible method. Furthermore, the catalytic activity of the Cu(I) complex was executed in the first-time synthesis of new tetrahydropyrimidine derivatives by treating various aryl nitriles with 2,2-dimethyl-1,3-propanediamine under conventional thermal conditions. A mechanism for the catalytic reaction was suggested and investigated by density functional theory (DFT).

Optical Upconversion in Mononuclear Lanthanide Co-Crystal Assemblies.

In this work, we developed two kinds of co-crystal assemblies systems, consisting of discrete mononuclear Yb3+ and Er3+ and mononuclear Yb3+ and Pr3+, which can achieve Er3+ and Pr3+ upconversion luminescence, respectively, by Yb3+ sensitization under 980 nm excitation. The structure and composition of two co-crystal assemblies were determined by single crystal X-ray diffraction. By investigation of the series of two assemblies, respectively, it is found that the strongest upconversion luminescence is both obtained when the molar ratio of Yb3+ and Ln3+ (Ln=Er or Pr) is 1 : 1. The energy transfer mechanism of Er3+ assemblies is determined as energy transfer upconversion, while that of Pr3+ assemblies is determined as energy transfer upconversion and cooperative sensitization upconversion. This is the first example of Pr3+ upconversion luminescence at the molecular dimension at room temperature, which enriches the research in the field of upconversion luminescence with lanthanide complexes.

Crystal Structures, Molecular Docking and In Vitro Investigations of Two 4-Substituted 2-(5,5-dimethyl-3-styrylcyclohex-2-enylidene)malononitrile Derivatives as Potential Topoisomerase II Inhibitors

Type II topoisomerases (TOP2s) play a key role in altering the DNA topology by transiently cleaving both strands of a DNA duplex. Therefore, increased TOP2 activity is associated with many cancers. Herein, we present the synthesis, structural characterization, virtual screening, and structural exploration, as well as evaluation of the antiproliferative effects of two new 4-substituted 2-(5,5-dimethyl-3-styrylcyclohex-2-enylidene)malononitrile derivatives with potential application in the drug design of isoform-specific TOP2 inhibitors. Both compounds 1 and 2 were verified by ESI-TOF-MS, NMR, and single-crystal X-ray diffraction (SCXRD) analysis. Furthermore, we applied our recently proposed SCXRD/HYdrogen DEsolvation (HYDE) technology platform in order to perform molecular modeling, virtual screening, and structural exploration with 1 and 2. For this purpose, we used the crystal structure of human TOP2β complexed to DNA and the anticancer drug etoposide. Moreover, we further evaluated the antiproliferative activity of 1 and 2 on human hepatocarcinoma HepG2 cells and compared the observed effects with those of the reference hTOP2β inhibitor etoposide. Based on the obtained results, compounds 1 and 2 showed a virtually higher binding affinity (Ki HYDE values) over etoposide towards hTOP2β but lower antiproliferative activity compared to those of etoposide.

Novel Salts of Heterocyclic Polyamines and 5-Sulfosalicylic Acid: Synthesis, Crystal Structure, and Hierarchical Supramolecular Interactions

A series of novel salts of heterocyclic polyamines with 5-sulfosalicylic acid (C4H7N4+)(C7H5O6S−)∙2(H2O) (1), (C4H6ClN4+)(C7H5O6S−)∙H2O (2), (C5H8N3+)(C7H5O6S−)∙H2O (3), (C5H7N6+)(C7H5O6S−)∙H2O (4), (C6H14N22+)(C7H4O6S2−)∙H2O (5), and (C14H19N2+)(C7H5O6S−) (6) have been successfully synthesized. Their crystal structures have been determined by single-crystal X-ray diffraction. Overall, compounds adopt a layered structure with aminium cations and 5-sulfosalicylic anions linked via water molecules. The solid-state architectures of these compounds are dominated by O(N,H)-H⋯O and N-H⋯N hydrogen bonds and stabilized by weak interconnects. C-Cl⋯π and S-O⋯π interactions, apart from π⋯π and C-H(O)⋯π, were reported. Diverse approaches were used to study the effect of substituents in the polyamines in solid-state arrangement. A Hirshfeld surface analysis, with associated 3D Hirshfeld surface maps and 2D fingerprint plots, molecular electrostatic potential, and energy frameworks were used to comprehensively investigate the nature and hierarchy of non-covalent interactions and inspect supramolecular differences. The contact enrichment ratio calculations provided deeper insight into the propensity of interconnects to influence crystal packing. The evaluation of the effects of H-bonding synthons resulting from different substituents in the polyamines on self-assemblies is also presented. In the context of crystal engineering, a specific intramolecular synthon via O-H⋯O observed in nearly all crystals can be employed in the pseudo-cyclic replacement strategy in the design of new molecules.

A Green one-pot three component synthesis of thiazolidine-2,4-dione based bisspirooxindolo-pyrrolidines with [Bmim]BF4: their in vitro and in silico anti-TB studies.

A simple and effective three-component one-pot green methodology was employed for the synthesis of a new thiazolidine-2,4-dione based bisspirooxindolo-pyrrolidine derivatives using [Bmim]BF4 ionic liquid via [3 + 2] cycloaddition reaction. It is an environmentally benign, column chromatography-free, shorter reaction time, good yield and easy product isolation method. The synthesized compounds 10a-x, were thoroughly characterized by using various spectroscopic methods like FT-IR, 1H NMR, 13C NMR, Mass spectrometry and finally by single crystal X-ray diffraction method. In vitro anti-tubercular (anti-TB) activity studies were carried out on these synthesized compounds, and they showed good to moderate anti-TB activity against Mycobacterium tuberculosis H37Rv strain. The compound 10a exhibited good anti-TB activity, with an MIC (Minimum Inhibitory Concentration) value of 12.5µg/mL, and the compounds 10m, 10o and 10r showed moderate activity with an MIC value of 25.0µg/mL. Remaining compounds exhibited poor activity against Mycobacterium tuberculosis. Ethambutol, rifampicin and isoniazid were used as standard drugs. Furthermore, in silico molecular docking experiments on the TB protein (PDB ID: 1DF7) were carried out to understand the binding interactions, and they showed least binding energy values ranging from -8.9 to -7.2kcal/mol.

Dual Antimicrobial-Anticancer Potential, Hydrolysis, and DNA/BSA Binding Affinity of a Novel Water-Soluble Ruthenium-Arene Ethylenediamine Schiff base (RAES) Organometallic

The need for a systematic approach in developing new metal-based drugs with dual anticancer-antimicrobial properties is emphasized by the vulnerability of cancer patients to bacterial infections. In this context, a novel organometallic assembly was designed, featuring ruthenium(II) coordination with p-cymene, one chlorido ligand, and a bidentate neutral Schiff base derived from 4-methoxybenzaldehyde and N,N-dimethylethylenediamine. The compound was extensively characterized in both solid-state and solution, employing single crystal X-ray diffraction, nuclear magnetic resonance, infrared, ultraviolet–visible spectroscopy, and density functional theory, alongside Hirshfeld surface analysis. The hydrolysis kinetic was thoroughly investigated, revealing the important role of the chloro-aqua equilibrium in the dynamics of binding with deoxyribonucleic acid and bovine serum albumin. Notably, the aqua species exhibited a pronounced affinity for deoxyribonucleic acid, engaging through electrostatic and hydrogen bonding interactions, while the chloro species demonstrated groove-binding properties. Interaction with albumin revealed distinct binding mechanisms. The aqua species displayed covalent binding, contrasting with the ligand-like van der Waals interactions and hydrogen bonding observed with the chloro specie. Molecular docking studies highlighted site-specific interactions with biomolecular targets. Remarkably, the compound exhibited wide spectrum moderate antimicrobial activity against Staphylococcus aureus, Pseudomonas aeruginosa, and Candida albicans, coupled with low micromolar cytotoxic activity against human colorectal adenocarcinoma cells and significant activity against human leukemic monocyte lymphoma cells. The presented findings encourage further development of this compound, promising avenues for its evolution into a versatile therapeutic agent targeting both infectious diseases and cancer.

Are Selenides the Same as Sulfides? Structure, Spectroscopy, and Properties of Narrow-Gap Rare-Earth Semiconductors RE2Sn(S1-xSex)5 (RE = La, Ce; x = 0-0.8).

The ternary rare-earth sulfides RE2SnS5 (RE = La-Nd) and the partial solid solutions RE2Sn(S1-xSex)5 (RE = La, Ce; x = 0-0.8) were prepared in the form of polycrystalline samples by reaction of the elements at 900 °C and as single crystals in the presence of KBr flux. They adopt the La2SnS5-type structure (orthorhombic, space group Pbam, Z = 2) consisting of chains of edge-sharing SnCh6 octahedra separated by RE atoms. Although the cell parameters evolve smoothly in RE2Sn(S1-xSex)5, detailed structural analysis by single-crystal X-ray diffraction revealed a pronounced preference for the Se atoms to occupy two out of the three chalcogen sites, which offers a rationalization for why the all-selenide end-members RE2SnSe5 do not form. Solid-state 119Sn NMR spectra confirmed the nonrandom distribution of SnS6-nSen local environments, which could be resolved into individual resonances. The Raman spectra of RE2SnS5 compounds show an intense peak at 307-320 cm-1 assigned to a symmetric A1g mode, which is dominated by Sn-S bonds; the Raman peak intensities varied with Se substitution in La2Sn(S1-xSex)5. Optical diffuse reflectance spectra, band structure calculations, and electrochemical impedance spectra indicated that these compounds are narrow band gap semiconductors; the optical band gaps are insensitive to RE substitution in RE2SnS5 (0.7 eV) but they gradually decrease with greater Se substitution in RE2Sn(S1-xSex)5 (0.7-0.4 eV).

Catalytic activity of TiO2 nanoparticles in cyclization reactions for pyrazolone formation: DNA binding analysis via spectroscopy, X-ray crystallography, and molecular docking

This method of sustainable synthesis utilizes a range of aromatic/heterocyclic aldehydes, phenylhydrazine, and ethyl acetoacetates. The TiO2 nanoparticle catalyst facilitates cyclization reactions, yielding pyrazolone derivatives with exceptional efficiency (95–97 %) under reflux conditions at 80 °C. The current method achieves high yields of the corresponding cyclo-products in a short reaction time. A variety of physicochemical methods were employed to ascertain the chemical characteristics and structure of the synthesized heterocycles, and the geometrical structure of the well-crystallized compound (Z)-4-((5-bromofuran-2-yl)methylene)-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one was characterized by the use of single-crystal X-ray diffraction measurement. The morphology and elemental composition of TiO2 nanoparticles were examined using SEM/EDX before and after the model reaction. A drop in the Ti (titanium) signal following the reaction indicates surface alterations. The present process provides a new and improved synthesis process for the formation of pyrazolones that is more convenient, well organized in terms of good yields, a simple handling procedure, a short reaction time, and user-friendliness compared to other surviving procedures. One of the synthesized compounds, (Z)-4-((5-bromofuran-2-yl)methylene)-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one (2), exhibited significant DNA binding activity. This was further confirmed by a molecular docking study, which revealed a binding energy of −7.2 kcal/mol, and by analyzing the mode of interaction.

On-Purpose Oligomerization by 2-t-Butyl-4-arylimino-2,3-dihydroacridylnickel(II) Bromides

In this study, 2-t-butyl-4-arylimino-2,3-dihydroacridylnickel dibromides were synthesized by nickel-template one-pot condensation, and well characterized along with the single-crystal X-ray diffraction to one representative complex, revealing a distorted tetrahedral geometry around nickel. When activated with modified methylaluminoxane (MMAO), all nickel complexes exhibited high activities (up to 1.91 × 106 g mol−1 (Ni) h−1) toward major trimerization of ethylene. When activated with ethylaluminum dichloride (EtAlCl2), however, the title complexes performed good activities (up to 1.05 × 106 g mol−1 (Ni) h−1) for selective dimerization of ethylene. In comparison to analogous nickel complexes, higher activities were achieved with the substituent of t-butyl group, especially in the rare case of nickel complexes performing trimerization of ethylene.

Self-Assembly of a Water-Soluble Pd16 Square Bicupola Architecture and Its Use in Aerobic Oxidation in Aqueous Medium.

Designing supramolecular architectures with uncommon geometries has always been a key goal in the field of metal-ligand coordination-driven self-assembly. It acquires added significance if functional building units are employed in constructing such architectures for fruitful applications. In this report, we address both these aspects by developing a water-soluble Pd16L8 coordination cage 1 with an unusual square orthobicupola geometry, which was used for selective aerobic oxidation of aryl sulfides. Self-assembly of a benzothiadiazole-based tetra-pyridyl donor L with a ditopic cis-[(tmeda)Pd(NO3)2] acceptor [tmeda = N,N,N',N'-tetramethylethane-1,2-diamine] produced 1, and the geometry was determined by single-crystal X-ray diffraction study. Unlike the typically observed tri- or tetrafacial barrel, the present Pd16L8 coordination assembly features a distinctive structural topology and is a unique example of a water-soluble molecular architecture with a square orthobicupola geometry. Efficient and selective aerobic oxidation of sulfides to sulfoxides is an important challenge as conventional oxidation generally leads to the formation of sulfoxide along with toxic sulfone. Cage 1, designed with a ligand containing a benzothiadiazole moiety, demonstrates an ability to photogenerate reactive oxygen species (ROS) in water, thus enabling it to serve as a potential photocatalyst. The cage showed excellent catalytic efficiency for highly selective conversion of alkyl and aryl sulfides to their corresponding sulfoxides, therefore without the formation of toxic sulfones and other byproducts, under visible light in aqueous medium.

Zhonghongite, Cu29 (As, Sb)12S33, a new mineral from the high-sulfidation vein of Jiama porphyry system, Tibet, China

Abstract Zhonghongite (IMA2023-046), ideally Cu29(As, Sb)12S33, is a new mineral discovered in the high-sulfidation vein of the Jiama deposit (E 91°45′, N 29°42′), southern Tibet, China. It forms complex intergrowths with watanabeite and tennantite-tetrahedrite, creating veined or massive aggregates ranging from millimeters to centimeters in size. The single crystals of zhonghongite are anhedral grains, with sizes ranging from several micrometers to approximately 100 micrometers. The mineral is gray in color with a black streak and metallic luster. It is brittle, with uneven fractures, and has a calculated density of 4.925g/cm3. The average values of electron microprobe analyses (wt.%) are as follow: Cu 42.19, As 11.11, Sb 16.09, S 25.45, Hg 3.73, Mn 0.67, and Te 0.28. The empirical formula, based on 33 sulfur apfu, is (Cu27.60Hg0.77Mn0.51Fe0.07Ag0.02)Σ28.97(As6.16Sb5.49Te0.09)Σ11.74S33. In zhonghongite, the substitution of Sb for As is limited, with the atomic ratio of As/(As+Sb) ranging from 0.457 to 0.629. Hg, Mn, and Fe, together with minor Cu, are divalent and serve for charge balance. Zhonghongite is orthorhombic, space group F2mm (42), a = 10.37741(5) Å, b = 14.69821(9) Å, c = 36.7645(2) Å and V = 5607.66(5) Å3. The crystal structure has been solved and refined by single-crystal X-ray diffraction with a final R1 = 0.0235 for 27028 (2467 unique) reflections. It is composed of individual AsS3 tripyramids and clustered tripyramids As4S7, CuS4 tetrahedra and CuS3 planar triangles, connected through corner S atoms in tetrahedral coordination and octahedral coordination with Cu and/or As. The structure is a derivative of tetrahedrite-type structure. Zhonghongite was formed under high-temperature conditions and is classified as an intermediate-sulfidation state mineral.

Discovery of a Biocontrol Strain Trichaptum laricinum: Its Metabolites and Antifungal Activity against Pathogenic Fungus Colletotrichum anthrisci.

Finding safe and environmentally friendly fungicides is one of the important strategies in modern pesticide research and development. In this work, the antipathogenic effects of the fungus Trichaptum laricinum against the anthracnose pathogen Colletotrichum anthrisci were studied. The EtOAc extract of T. laricinum showed remarkable antifungal activity against C. anthrisci with an inhibition rate of 50% at 256 μg/mL. Bioguided isolation of the cultural broth of T. laricinum produced four new drimane sesquiterpenes, trichalarins A-D (1-4), and six other metabolites (5-10). Their structures were established by extensive spectroscopic methods, quantum chemical calculations, and single-crystal X-ray diffraction. All compounds exhibited antifungal activity against C. anthrisci with minimum inhibitory concentrations (MICs) of 8-64 μg/mL in vitro. Further in vivo assay suggested that compounds 2, 6, and 9 could significantly inhibit C. anthrisci growth in avocado fruit with inhibition rates close to 80% at the concentration of 256 μg/mL, while compounds 2 and 6 had an inhibition rate over 90% at the concentration of 512 μg/mL. The EtOAc extract of T. laricinum had no inhibitory effect on Pinus massoniana seed germination and growth at the concentration of 2 mg/mL, showing good environmental friendliness. Thus, the fungus T. laricinum could be considered as an ideal biocontrol strain, and its metabolites provided a diverse material basis for the antibiotic agents.

Development of mixed-ligand ruthenium complexes bearing phosphine and imine ligands for utilisation as catalysts in Suzuki-type C–C cross-coupling reactions

ABSTRACT Herein we report the development of two mixed-ligand ruthenium (II) complexes bearing phosphine and imine ligands, their thorough characterisation and their utilisation as homogeneous catalysts in Suzuki-type C–C cross-coupling reactions. Reactions of two tetradentate Schiff base ligands, derived from imidazole-2-carboxaldehyde and ethylenediamine (H2L1 ) or propylenediamine (H2L2 ), with [Ru(PPh3)3Cl2] in refluxing ethanol in the presence of NEt3 afforded two complexes of type [Ru(L1)(PPh3)2] and [Ru(L2)(PPh3)2], respectively. The solid-state structure of [Ru(L2)(PPh3)2] was determined by single crystal X-ray diffraction analysis. The molecular structure of [Ru(L1)(PPh3)2] was optimised by the DFT method. Electronic spectra of the complexes showed intense absorptions spanning over the visible and ultra-violet regions, the origin of which was probed with TDDFT calculations. Redox properties of the complexes were studied by cyclic voltammetry. These mixed-ligand ruthenium(II) complexes serve as efficient catalyst-precursors for Suzuki-type C–C cross-coupling reactions.

A New Rare Halogenated Depside from Lichen and Study of its Anti-Proliferative Activity.

Lichens are a symbiotic association of algae and fungus, belonging to the family Parmeliaceae. Some lichen species are edible and used as an active ingredient for preparation of exotic spices as well as folklore medicine to cure different kinds of ailments. A specimen of lichen was collected from Munner in the Kerala State of South India for chemical profiling. Chemical analyses of the diethyl ether extract of the defatted lichen led to the isolation of six phenols 1-6 with variation of relative abundance. Amongst them, the relative abundance of compound 3 was the greatest (1 % of crude extract) and it was identified as atranorin. The structures of known compounds were confirmed by comparison of their 1H-NMR, 13C NMR, and mass data with published values available in the literature. In vitro bioassay for anti-proliferative activity of these compounds has been conducted against various human cancer cell lines in comparison with paclitaxel as control using SRB assay. Interestingly, a new compound 5 was found along with previously reported compounds from this lichen. This new compound was designated as fluoroatranorin 5 which was reported for the first time herein. The structural characterization of a new depside was determined by spectral methods such as 1H-NMR, 13C NMR, 19F NMR, IR, LC-HRESI-MS, and LC-MS/MS study. Its structure was confirmed by single crystal X-ray diffraction study. This new compound was designated as fluoroatranorin 5 which was reported first time herein. Anti-proliferative activity of all these compounds was evaluated against six different cancer cell lines. The inhibitory activity, IC50 value of compounds 1-3 and 5 exhibited at 99.64, 102.04, 109.20, 53.0 and 2.4 μM on cancer cell lines HT-29 (colon), Hela (cervical), HT-29, HPAC (pancreas) and A2780 (ovarian cancer cell line) respectively in comparison with paclitaxel as control. The new compound 5 exhibited significant activity with IC50 value 2.4 μM on A2780 ovarian cancer cell line.

Flexible rhenium metallocages: Self-assembly, solid-state structures, and solution dynamics

Neutral heteroleptic tetranuclear rhenium coordination cages fac-[{Re(CO)3(im)}4(L)2] (1) and fac-[{Re(CO)3(tz)}4(L)2] (2) were self-assembled using Re2(CO)10, from carbonyldiimidazole (CO-im2)/ 1,2,4-triazole (H-tz), and bis(benzimidazol-1-yl)methane (L) via a one-pot solvothermal approach. The cages were characterized using AT-IR, NMR spectroscopy, mass spectrometry and single crystal X-ray diffraction analysis. The molecular structures of the cages indicate that the cage is composed of a tetranuclear cyclic core [(Re-im)]4 or [(Re-tz)]4 which resembles a butterfly, along with two dbim (L) ligand motifs positioned both above and below the tetranuclear motif. The cage 1 in DMSO exhibits flexibility, and its dynamic behavior was investigated through variable temperature 1H NMR studies.

Trigonal Planar [PN3]4- Anion in the Nitridophosphate Oxide Ba3[PN3]O.

Nitridophosphates, with their primary structural motif of isolated or condensed PN4 tetrahedra, meet many requirements for high performance materials. Their properties are associated with their structural diversity, which is mainly limited by this specific building block. Herein, we present the alkaline earth metal nitridophosphate oxide Ba3[PN3]O featuring a trigonal planar [PN3]4- anion. Ba3[PN3]O was obtained using a hot isostatic press by medium-pressure high-temperature synthesis (MP/HT) at 200MPa and 880°C. The crystal structure was solved and refined from single-crystal X-ray diffraction data in space group R-3c (no.167) and confirmed by SEM-EDX, magic angle spinning (MAS) NMR, vibrational spectroscopy (Raman, IR) and low-cost crystallographic calculations (LCC). MP/HT synthesis reveals great potential by extending the structural chemistry of P to include trigonal planar [PN3]4- motifs.