Single-crystal X-ray Diffraction Analysis Research Articles

Sesquiterpene coumarins with anti-vitiligo and cytotoxic activities from Ferula samarkandica

Two undescribed sesquiterpene coumarins (1–2) and eight known analogues (3–10) were isolated from the roots of Ferula samarkandica Korovin, growing in Uzbekistan. Their structures were established by comprehensive spectroscopic analysis including NMR, HRESIMS, UV and IR data. The absolute configurations were determined based on ECD calculations and confirmed by single-crystal X-ray diffraction analysis. Six compounds carrying 7′-carbonyl, 3′-carbonyl and 3′-acetoxy (4, 5, 6, 7, 9, 10) demonstrated anti-vitiligo potentials, in addition to five (4, 7, 8, 9, 10) with cytotoxic effects. Evaluation of anti-vitiligo activity in B16 cells revealed that compounds 4–7 and 9 exhibited promotion effects on melanin synthesis in B16 cells more potent than the positive control 8-methoxypsoralen (8-MOP), while 5, 7, 9 and 10 could also stimulate the tyrosinase activity superior to 8-MOP. Besides, compounds 4 and 7–10 also presented certain cytotoxic activities against HeLa, HT-29 and A549 cell lines, wherein 8 displayed a significant cytotoxicity against HT-29 cells with an IC50 value of 8.33 ± 0.34 μM.

Toward New Horizons in Verdazyl-Nitroxide High-Spin Systems: Thermally Robust Tetraradical with Quintet Ground State.

High-spin organic tetraradicals with significant intramolecular exchange interactions have high potential for advanced technological applications and fundamental research, but examples reported to date exhibit limited stability and processability. In this work, we designed the first tetraradical based on an oxoverdazyl core and nitronyl nitroxide radicals and successfully synthesized it using a palladium-catalyzed cross-coupling reaction of an oxoverdazyl radical bearing three iodo-phenylene moieties with a gold(I) nitronyl nitroxide-2-ide complex in the presence of a recently developed efficient catalytic system. The molecular and crystal structures of the tetraradical were confirmed by single crystal X-ray diffraction analysis. The tetraradical possesses good thermal stability with decomposition onset at ∼125 °C in an inert atmosphere; in a toluene solution upon prolonged heating at 90 °C in air, no decomposition was observed. The resulting unique verdazyl-nitroxide conjugate was thoroughly studied using a range of experimental and theoretical techniques, such as SQUID magnetometry of polycrystalline powders, EPR spectroscopy in various matrices, cyclic voltammetry, and high-level quantum chemical calculations. All collected data confirm the high thermal stability of the resulting tetraradical and quintet multiplicity of its ground state, which makes the synthesis of this important paramagnet a new milestone in the field of creating high-spin systems.

Gas adsorption and fluorescence studies of Cd2+ and Zn2+ metal organic frameworks based on the same fluorinated ligand

Two new metal organic frameworks (MOFs) were synthesized by solvent-thermal synthesis with fluorinated 4,4′-(pyridine-3, 5-diyl) bis (3-fluorobenzoic acid) ligands (L1), namely {[Cd(L1)H2O]·DMF}n (MOF 1) and {[Zn(L1)]·3H2O}n (MOF 2). Single crystal X-ray diffraction analysis shows that MOF 1 is a two-dimensional structure with binuclear unit of [Cd2(COO)4N2O2]. MOF 2 displays a three-dimensional structure based on binuclear unit of Zn2(COO)2. The PXRD determination demonstrates the purity of the synthesized MOF 1 and MOF 2 samples, while the TGA shows the thermal stability of the structures. The gas adsorption studies show that MOF 1 and MOF 2 exhibit good gas adsorption characteristics, and MOF 2 has high selectivity for C2H2/CH4. Moreover, both MOF 1 and MOF 2 can selectively and sensitively detect Fe3+ in water.

Hydrothermal preparation, crystal structure, Hirshfeld surface analysis, photophysical properties and antifungal activity of a series of complexes assembled by 5-bromo-2-(carboxymethoxy)benzoic acid ligands

Five complexes [Co(BCBA)(H2O)3]n (1), [Co(BCBA)(4,4′-Bipy)2·(H2O)]n (2), [Cu(BCBA)(H2O)]n (3), [Zn(BCBA)(H2O)]n (4) and [Cd(BCBA)(2,2′-Bipy)(H2O)·(H2O)]n (5) (H2BCBA= 5‑bromo-2-(carboxymethoxy)benzoic acid, 4,4′-Bipy = 4,4′-bipyridine and 2,2′-Bipy = 2,2′-bipyridine) have been synthesized with H2BCBA ligand by solvothermal condition. All the complexes have been structurally characterized by infrared spectra (IR), elemental analyses and single-crystal X-ray diffraction analyses. Complex 1 is a zero-dimensional structure, and complexes 2–5 are one-dimensional chain structure. Furthermore, thermogravimetric analyses (TGA), Hirshfeld surface analysis, photo-luminescence properties, Solid-state UV–Vis diffuse reflectance spectroscopy and antifungal activity for complexes 1–5 were investigated. The reciprocal H···O/H/Br/C contacts dominate over 86 % of total Hirshfeld surface. Complexes 1–5 have certain inhibitory effects on 8 pathogenic fungi. Among them, complex 5 has the strongest antibacterial activity against Rhizoctonia solani AG1, Sphaeropsis sapinea and Colletotrichum fructicola, and the inhibitory rate reached 100 %.

A lithium-aluminium heterobimetallic dimetallocene.

Homobimetallic dimetallocenes exhibiting two identical metal atoms sandwiched between two η5 bonded cyclopentadienyl rings is a narrow class of compounds, with representative examples being dizincocene and diberyllocene. Here we report the synthesis and structural characterization of a heterobimetallic dimetallocene, accessible through heterocoupling of lithium and aluminylene fragments with pentaisopropylcyclopentadienyl ligands. The Al-Li bond features a high ionic character and profits from attractive dispersion interactions between the isopropyl groups of the cyclopentadienyl ligands. A key synthetic step is the isolation of a cyclopentadienylaluminylene monomer, which also enables the structural characterization of this species. In addition to their structural authentication by single-crystal X-ray diffraction analysis, both compounds were characterized by multinuclear NMR spectroscopy in solution and in the solid state. Furthermore, reactivity studies of the lithium-aluminium heterobimetallic dimetallocene with an N-heterocyclic carbene and different heteroallenes were performed and show that the Al-Li bond is easily cleaved.

Crotonoids A-H, Labdane-Type Diterpenoids with Anti-Inflammatory Activity from Croton sublyratus.

Croton sublyratus (Euphorbiaceae) is a traditional medicinal plant used by the Thai populace to treat helminthic infections and dermatologic conditions. In present study, eight new labdane-type diterpenoids, crotonoids A-H (1-8) and one known analogue (9) were isolated from the aerial parts of C. sublyratus. Compounds 6 and 7 belong to the rare class of 14,15-dinor-labdane diterpenoids. Compound 8 exhibited a rare 14,15,17-trinor-labdane skeleton. The structures of all these diterpenoids were elucidated by spectroscopic data analysis, electronic circular dichroism calculations, and single-crystal X-ray diffraction analysis. Compound 9 exhibited moderate anti-inflammatory activity via the inhibition of NO production in lipopolysaccharide-induced RAW 264.7 cells.

Highly scalable and robust ribbon-like coordination polymer as green catalyst for Hantzsch condensation in synthesis of DHPs and bioactive drug molecule

Ribbon-like coordination polymers (CP) represents a highly unexplored innovative class of metal-coordination network. Herein, we have developed a highly scalable and chemically robust (pH = 3–10 stable) ribbon-like CP [{Cu(Pim)(L)(H2O)·H2O}]n(1) following a complete environment-friendly green synthesis route. Considering the presence of surface flanked labile coordinated water molecules and their appealing correlation with one-dimensional structural characteristics, such sort of ribbon-like CP was explored for the first time as excellent heterogeneous surface catalyst for largely unexplored three-component Hantzsch condensation for synthesis of different classes of dihydropyridine (DHP). Moreover, 1 is employed to synthesize bio-responsive drug ‘Ethidine’ (possessing high anti-oxidant and anticarcinogenic properties) characterized with Single Crystal X-ray Diffraction (SCXRD) analysis. Several DHP-based products are also analysed through in-depth SCXRD analysis. This report inaugurates the usage of a Cu(II) based ribbon-like CPs as heterogeneous surface catalyst following environmentally benign manner for synthesis of bioactive DHPs and Drugs.

Synthesis, Characterization, and Properties of a Titanium(IV)-Tetrathiafulvalene-Based Complex.

To deeply investigate the interaction between a tetrathiafulvalene (TTF) unit and a Ti(IV) center, a monomeric heteroleptic octahedral Ti(IV) complex containing a diimine ligand composed of a 1,10-phenanthroline core fused with a TTF fragment (ligand 2a) was prepared. The stable complex formulated as Ti(1)2(2a), where 1 is a 2,2'-biphenolato derivative, was efficiently synthesized by following a one-step approach. This complex and its model species [Ti(1)2(2b)] were fully characterized in solution, and their solid-state structures were established by single-crystal X-ray diffraction analysis. Density functional theory calculations allowed the assignment of the frontier orbitals involved in the electronic transitions characterized by ultraviolet-visible absorption spectroscopy. Electrochemical and spectroelectrochemical studies revealed that the TTF unit within Ti(1)2(2a) can undergo two reversible one-electron oxidation processes; a reversible one-electron reduction of the Ti(IV) atom was highlighted. The photophysical measurements performed for this donor-acceptor molecular system indicated that an electron transfer process upon light excitation occurred within Ti(1)2(2a).

Experimental and theoretical investigation on the SR method grown semi-organic Piperazinium Tetrachlorozincate Monohydrate (PTZM) single crystal for optoelectronic applications

Efficient semi organic nonlinear optical (NLO) Piperazinium Tetrachlorozincate monohydrate (PTZM) [C4H12N2][ZnCL4]·H2O single crystals have been grown by slow evaporation solution technique (SEST) and Sankaranarayanan-Ramasamy (SR) method using water as solvent. Single crystal X-ray diffraction (SXRD) analysis reveals the unit cell parameters of the grown crystal. The morphology of the grown crystal was identified by the single crystal XRD analysis. The electrical properties, dielectric constant, dielectric loss and piezoelectric (d33) coefficient were determined. The etch pit density of PTZM crystal has been calculated by using the chemical etching analysis. The laser damage threshold (LDT) analysis was investigated by Nd: YAG laser and the wavelength of laser is 1064 nm. The mechanical stability of the grown PTZM crystal was studied using Vickers microhardness measurement. Utilizing quantum chemical calculations, the PTZM compound is analyzed for vibrational properties, HOMO and LUMO characteristics, NBO interactions, and the determination of first-order hyperpolarizability. The nonlinear susceptibility and first-order hyperpolarizability results provide compelling evidence and affirm the PTZM molecule’s potential as a strong candidate for nonlinear optical (NLO) applications.

Synthesis and Structure of a Coordination Polymer of Ni(II) with 2-(4-Bromophenoxy)acetohydrazide

The coordination compound [NiCl2L(2-PrOH)]n (where L is 2-(4-bromophenoxy)acetohydrazide; 2-PrOH is isopropanol) was obtained for the first time. The complex was characterized by means of elemental analyses, molar conductance, thermogravimetric analysis, IR spectroscopy, and single crystal X-ray diffraction analysis. It was determined that the coordination compound exhibits a polymeric structure. The complexing agent is six-coordinated, and its distorted octahedron forms due to the bidentate coordination of 2-(4-bromophenoxy)acetohydrazide through the carbonyl oxygen atom and the amine nitrogen. The oxygen of the molecule of isopropanol, the chlorine atom, and two chlorine atoms serve as bridges between two metal atoms.

New 19(10 → 9)abeo-euphane-type triterpenoids from Trichilia dregeana leaves and NO production inhibitory activities

Phytochemical investigation of the EtOAc soluble fraction from leaves of Trichilia dregeana Sond. (Meliaceae) afforded naturally rare four new pentacyclic triterpenoids (1–4), together with five known pentacyclic analogs (5–8, and 11) and two steroids (9 and 10). Their structures were elucidated by extensive spectroscopic techniques such as 1D and 2D NMR and HRESIMS data analyses. The absolute configuration of 1 was determined by using the single-crystal X-ray diffraction analysis. The nitric oxide (NO) production inhibitory assay indicated that the EtOAc fraction as well as 4 and 7 inhibited the NO production in lipopolysaccharide (LPS)-stimulated RAW264.7 macrophage cells with the IC50 values of 83.53 μg/mL and 81.31 and 85.71 μM, respectively. Compounds 1–4 are rare 19(10 → 9)abeo-euphane-type triterpenoids bearing a 3,10-ether bridge. To the best of our knowledge, this study is the first isolation of triterpenoids with the 3,10-ether bridge in their skeleton from the genus Trichilia, providing new insights into the chemodiversity of the terpenoids in T. dregeana.

Dauresorcinols A and B, two pairs of merosesquiterpenoid enantiomers with new carbon skeletons from Rhododendron dauricum

Five pairs of new merosesquiterpenoid enantiomers, named dauresorcinols A−E (1−5), were isolated from the leaves of Rhododendron dauricum. Their structures were elucidated by comprehensive spectroscopic data analysis, quantum chemical calculations, Rh2(OCOCF3)4-induced ECD, and single-crystal X-ray diffraction analysis. Dauresorcinols A (1) and B (2) possess two new merosesquiterpene skeletons bearing an unprecedented 2,6,7,10,14-pentamethyl-11-oxatetracyclo[8.8.0.02,7.012,17]octadecane and a caged 15-isohexyl-1,5,15-trimethyl-2,10-dioxatetracyclo[7.4.1.111,14.03,8]pentadecane motif, respectively. Plausible biosynthetic pathways of 1−5 are proposed involving key oxa-electrocyclization and Wagner−Meerwein rearrangement reactions. (+)/(−)-1 and 3−5 showed potent α-glucosidase inhibitory activity, 3 to 22 times stronger than acarbose, an antidiabetic drug targeting α-glucosidase. Docking results provide a basis to design and develop merosesquiterpenoids as potent α-glycosidase inhibitors.

Atomically Precise Nanometer-Sized Pt Catalysts with an Additional Photothermy Functionality.

Atomically precise ~1-nm Pt nanoparticles (nanoclusters, NCs) with ambient stability are important in fundamental research and exhibit diverse practical applications (catalysis, biomedicine, etc.). However, synthesizing such materials is challenging. Herein, by employing the mixture ligand protecting strategy, we successfully synthesized the largest organic-ligand-protected (~1-nm) Pt23 NCs precisely characterized with mass spectrometry and single-crystal X-ray diffraction analyses. Interestingly, natural population analysis and Bader charge calculation indicate an alternate, varying charge -layer distribution in the sandwich-like Pt23 NC kernel. Pt23 NCs can catalyze the oxygen reduction reaction under acidic conditions without requiring calcination and other treatments, and the resulting specific and mass activities without further treatment are sevenfold and eightfold higher than those observed for commercial Pt/C catalysts, respectively. Density functional theory and d-band center calculations interpret the high activity. Furthermore, Pt23 NCs exhibit a photothermal conversion efficiency of 68.4 % under 532-nm laser irradiation and can be used at least for six cycles, thus demonstrating great potential for practical applications.

Penifuranone A: A Novel Alkaloid from the Mangrove Endophytic Fungus Penicillium crustosum SCNU-F0006.

One previously undescribed alkaloid, named penifuranone A (1), and three known compounds (2-4) were isolated from the mangrove endophytic fungus Penicillium crustosum SCNU-F0006. The structure of the new alkaloid (1) was elucidated based on extensive spectroscopic data analysis and single-crystal X-ray diffraction analysis. Four natural isolates and one new synthetic derivative of penifuranone A, compound 1a, were screened for their antimicrobial, antioxidant, and anti-inflammatory activities. Bioassays revealed that penifuranone A (1) exhibited strong anti-inflammatory activity in vitro by inhibiting nitric oxide (NO) production in lipopolysaccharide-activated RAW264.7 cells with an IC50 value of 42.2 μM. The docking study revealed that compound 1 exhibited an ideal fit within the active site of the murine inducible nitric oxide synthase (iNOS), establishing characteristic hydrogen bonds.

Toward an understanding of the role of structural organization and point defects in the formation of functional pure and Tm3+-doped (Ca3-xSrx)(VO4)2 for diode-pumped and SRS lasers

Whitlockite-type polycrystalline and single-crystal (Ca3−xSrx)(VO4)2 solid solutions were successfully obtained by solid-state synthesis and Czochralski method, respectively. Synchrotron powder X-ray diffraction allowed to reveal actual compositions of polycrystalline (Ca3−xSrx)(VO4)2 solid solutions with х = 0.3, 0.54, 0.9, 1.2, 1.35 refined by Rietveld method, which are slightly different from the initial ones. Synchrotron X-ray single-crystal diffraction analysis of Czochralski-grown undoped (Ca1.8Sr1.2)(VO4)2 (CSVO) revealed its actual composition (Ca2.982(11)Sr0.031)(VО4)2. Difference between initial and refined compositions is analyzed and discussed. In the CSVO structure, Sr2+ ions partially occupy monocapped Ca2 and two-capped Ca3 trigonal prismatic sites and Ca2+ ions are in the Ca5 and Ca5A sites, forming two independent strongly distorted tetrahedral Ca5O4 and octahedral Ca5AO6 oxygen environments. Synchrotron X-ray single-crystal diffraction analysis together with X-ray absorption spectroscopic study of (Сa2.4Sr0.6)(VO4)2 doped with 0.5 and 1.0 wt% Tm2O3 (СSVO:0.5Tm and CSVO:1.0Tm) allowed to establish the absence of cations in the Ca5A site, the localization of Sr2+ ions in the Ca2 and Ca3 sites and additionally in octahedral Ca4 site together with Tm3+ ions, forming an individual eight-coordinated environment, in the refined compositions (Ca2.776(7)Sr0.210(4)Tm3+0.008(1))(VO4)2 and (Ca2.855(7)Sr0.140(7)Tm3+0.009(1)□0.022(7))(VO4)2, respectively, with vacancies (marked by a square,□) in the two-capped Ca1 trigonal prismatic site in the CSVO:1.0Tm structure. Additional interstitial oxygen, participating in the formation of the Tm3+ environment, found in the residual electron density, together with vacancies in the Ca1 site provides electroneutrality to CSVO:0.5Tm and CSVO:1.0Tm crystals. Several structural models of the coordination environment of Tm3+ ions were analyzed and the most correct one was proposed.

Chiral Induction in a Self-Assembled Pd4 Coordination Cage with Chiral Guests.

The dynamic interplay of coordination bonds within metal-organic cages offers a unique avenue for structural evolution in response to external stimuli, presenting a promising strategy for the construction of chiral assemblies. This adaptability is crucial for the selective synthesis of homochiral assemblies and advancement of asymmetric catalysis. In this study, we report the self-assembly of an achiral square-planar Pd(II) acceptor with a C2-symmetric tetrapyridyl donor resulted in the formation of a racemic mixture of the chiral octahedral cage Pd4L2. The existence of this racemic mixture was confirmed using circular dichroism spectroscopy as well as single crystal X-ray diffraction analysis. We encoded chiral information into the asymmetric cavity of the cage by encapsulating chiral aromatic guests through efficient π-π stacking and hydrophobic interactions in aqueous media. The inclusion of a chiral guest induces a preference for one enantiomeric conformation of the cage over the other, effectively shifting the equilibrium towards a single, enantiopure host-guest complex. While the concept of chiral guest recognition by a chiral host is well-established, this work constitutes a remarkable example of guest-mediated chirality transfer leading to the formation of a single enantiopure coordination complex from achiral building blocks.

[Ti{η5-1-(SiMe3)-3-(R)-C9H5}Cl2(OEt)] half-sandwich complexes: Synthesis, solid-state structure, hirshfeld surface analysis and theoretical studies

Indenyl-titanium trichloride complexes of type [Ti{η5-1-(SiMe3)-3-(R)-C9H5}Cl3] (R = SiMe3 (3a); R = tBu (3b)) were obtained by treatment of Li[1-(SiMe3)-3-(R)-C9H5] (R = SiMe3 (1a); R = tBu (1b)) with titanium tetrachloride (2) in a 1:1 molar ratio in the presence of isopropanol and SOCl2. Compounds [Ti{η5-1-(SiMe3)-3-(R)-C9H5}Cl2(OEt)] (R = SiMe3 (4a); R = tBu (4b)) are accessible by reacting 1a,b (R = SiMe3 (1a); R = tBu (1b)) with TiCl4 (2) in the presence of ethanol and SOCl2, or when 3a,b were treated with equimolar amounts of EtOH in refluxing benzene. Spectroscopic methods and single crystal X-ray diffraction analysis confirmed the piano-stool geometry of 3a and 4b in the solid state. Hirshfeld surface analysis using 2D fingerprint plots of 3a and 4b were conducted to elaborate non-covalent, intermolecular interactions existing in the solid state, which accounted for the strengthening of the crystal lattice. The molecular structures of the 3 and 4 were further investigated by quantum-chemical calculations. The geometries of the compounds were optimized at the B3LYP/6-31G(d)+LANL2DZ level of theory, and their related molecular parameters including frontier orbital energy gap and molecular electrostatic surface potential have also been calculated to better understand their properties.

Coordination Polymer Based on a Triangular Carboxylate Core {Fe(μ3-O)(μ-O2CR)6} and an Aliphatic Diamine.

Interaction of the pre-organized complex of iron(II) trimethylacetate and 1,10-phenanthroline (phen) [Fe2(piv)4(phen)2] (1) (piv = (Me)3CCO2-)) with 1,6-diaminohexane (dahx) in anhydrous acetonitrile yielded a 1D coordination polymer [Fe3O(piv)6(dahx)1.5]n (2) and an organic salt of pivalic acid (H2dahx)(piv)2 (3). The structure of the obtained compounds was determined by single-crystal X-ray diffraction analysis. The phase purity of the complexes was determined by powder X-ray diffraction analysis. According to the single-crystal X-ray analysis, coordination polymer 2 is formed due to the binding of a triangular carboxylate core {Fe3(μ3-O)(μ-piv)6} with an aliphatic diamine ligand. Thermal behavior was investigated for compounds 1 and 2 in an argon atmosphere.

Experimental study, theoretical calculations, investigation on the molecular docking, spectroscopic insights and antimicrobial appraisal of a new Co(II) complex

The new bis(1–4(chlorophenyl)piperazinium) tetraisothiocyanatecobaltate(II) crystal was prepared by slow evaporation method, and structurally characterized by single crystal X-ray diffraction analysis. The anhydrous compound (C10H14N2Cl)2 [Co(NCS)4] crystallized in the space group (P1¯, Z = 2), its structure consisted of NH2+ groups and inorganic anions, which are linked via NH…S hydrogen bonds to form anionic layer’s parallel to (a,b) plane. The organic cations are trapped between anionic layers to form a three-dimensional network structure. The inter-contacts in the crystal packing were envisioned quantitatively using Hirshfeld surface method by 2D fingerprint plots. The vibrational properties were discussed experimentally by means of IR spectroscopy. Electronic and computational features are examined by quantum chemical studies. The antimicrobial effects were surveyed in vitro against clinical bacterial strains. Molecular docking investigation divulged significant interactions and binding affinities into active sites. From these results, the Co(II) complex displayed considerable biological activity against Human Immunodeficiency Virus (HIV) II Protease.

Palladium-Catalyzed Arylation of C(sp2)-H Bonds and C(sp3)-H Bonds with 4-Amino-benzotriazole as the Bidentate Directing Group.

The arylation of C(sp2)-H and C(sp3)-H bonds in carboxylic acids catalyzed by Pd(II) with 4-aminobentriazole as the directing group was investigated. In addition to activation of the C(sp2)-H bond, selective arylation of alkyl carboxylic acids and amino acids in the β position can also be achieved. This strategy involved a 5,5-bicyclic Pd intermediate complex whose structure was determined by X-ray single crystal diffraction analysis. Importantly, the DG (directing group) can be easily removed under mild conditions.