Metal-Organic Framework Based on Isonicotinate N-Oxide for Fast and Highly Efficient Aqueous Phase Cr(VI) Adsorption.

Synthesis of new porous materials has been developed for efficient capture of pollutants in environmental sciences. Here, the application of a new metal-organic framework (TMU-30) has been reported based on isonicotinate N-oxide as an adsorptive site for fast and highly efficient aqueous phase adsorption of Cr(VI). The adsorption process showed no remarkable effect over a pH range of 2-9. The maximum capacity of the adsorption was reached in just less than 10 min and followed the pseudo-second-order kinetics. The maximum capacity of 2.86 mol mol(-1) (145 mg/g) was obtained according to Langmuir model at 298 K. The spontaneous adsorption and an endothermic process were controlled by positive entropy changes. XPS analysis revealed electrostatic interactions between N-oxide groups of TMU-30 and Cr(VI) species, which were responsible for the adsorption process.

Synthesis, Spectroscopic, Structural and Quantum Chemical Studies of a New Imine Oxime and Its Palladium(II) Complex: Hydrolysis Mechanism.

In this work, we report synthesis, crystallographic, spectroscopic and quantum chemical studies of a new imine oxime, namely (4-nitro-phenyl)-(1-phenyl-ethylimino)-acetaldehyde oxime (nppeieoH). Spectroscopic and X-ray diffraction studies showed that nppeieoH is hydrolyzed in aqueous solution, forming nitroisonitrosoacetophenone (ninap) and the hydrolysis product binds to Pd(II) to yield [Pd(nppeieo)(ninap)]. The mechanism of the hydrolysis reaction has been theoretically investigated in detail, using density functional theory (DFT) with the B3LYP method. The vibrational and the electronic spectra of nppeieoH and its Pd(II) complex, the HOMO and LUMO analysis, Mulliken atomic charges and molecular electrostatic potential were also performed. The predicted nonlinear optical properties of both compounds are higher than those of urea.

Synthesis, Characterization and DFT-Based Investigation of a Novel Trinuclear Singly-Chloro-Bridged Copper(II)-1-Vinylimidazole Complex.

A novel trinuclear copper(II) complex [Cu3(µ-Cl)2Cl4(1-Vim)6] with monodentate 1-vinylimidazole (1-Vim) and chloro ligands has been prepared and experimentally characterized by elemental analysis, thermogravimetry (TGA, DTG, DTA), X-ray single crystal diffractometry, TOF-MS and FT-IR spectroscopies. The electronic and structural properties of the complex were further investigated by DFT/TD-DFT methods. Density functional hybrid method (B3LYP) was applied throughout the calculations. The calculated UV-Vis results based on TD-DFT approach were simulated and compared with experimental spectrum. Based on the data obtained, DFT calculations have been found in reasonable accordance with experimental data.

Di- and polynuclear silver(I) saccharinate complexes of tertiary diphosphane ligands: synthesis, structures, in vitro DNA binding, and antibacterial and anticancer properties.

A series of new silver(I) saccharinate (sac) complexes, [Ag2(sac)2(µ-dppm)H2O]·H2O (1), {[Ag2(µ-sac)2(µ-dppe)]·3H2O·CH2Cl2} n (2), [Ag2(µ-sac)2(µ-dppp)] n (3), and [Ag(sac)(µ-dppb)] n (4) [dppm is 1,1-bis(diphenylphosphino)methane, dppe is 1,2-bis(diphenylphosphino)ethane, dppp is 1,3-bis(diphenylphosphino)propane, and dppb is 1,4-bis(diphenylphosphino)butane], have been synthesized and characterized by C, H, N elemental analysis, IR spectroscopy, (1)H NMR, (13)C NMR, and (31)P NMR spectroscopy, electrospray ionization mass spectrometry, and thermogravimetry-differential thermal analysis. Single-crystal X-ray studies show that the diphosphanes act as bridging ligands to yield a dinuclear complex (1) and one-dimensional coordination polymers (2 and 4), whereas the sac ligand adopts a µ2-N/O bridging mode in 2, and is N-coordinated in 1 and 4. The interaction of the silver(I) complexes with fish sperm DNA was investigated using UV-vis spectroscopy, fluorescence spectroscopy, and agarose gel electrophoresis. The binding studies indicate that the silver(I) complexes can interact with fish sperm DNA through intercalation, and complexes 1 and 3 have the highest binding affinity. The gel electrophoresis assay further confirms the binding of the complexes with the pBR322 plasmid DNA. The minimum inhibitory concentrations of the complexes indicate that complex 1 exhibits very high antibacterial activity against standard bacterial strains of Escherichia coli, Salmonella typhimurium, and Staphylococcus aureus, being much higher than those of AgNO3, silver sulfadiazine, ciprofloxacin, and gentamicin. Moreover, complexes 1-3 exhibit very high cytotoxic activity against A549 and MCF-7 cancer cell lines, compared with AgNO3 and cisplatin. The bacterial and cell growth inhibitions of the silver(I) complexes are closely related to their DNA binding affinities.

Crystal structure of (E)-N-(3,4-di-meth-oxy-benzyl-idene)morpholin-4-amine.

In the title compound, C13H18N2O3, the benzene ring makes a dihedral angle of 17.19 (11)° with the least-squares plane formed by the four C atoms of the morpholine ring, which adopts a chair conformation. In the crystal, C-H⋯N hydrogen bonds link the mol-ecules into supramolecular chains running along a 21 screw axis parallel to the b-axis direction. Weak C-H⋯π inter-actions are also observed.

Crystal structure of (E)-1(anthracen-9-ylmethylidene)[2-(morpholin-4-yl)eth-yl]amine.

The title compound, C21H22N2O, crystallizes with two independent mol-ecules in the asymmetric unit. In both mol-ecules, the anthracene ring systems are almost planar, with maximum deviations of 0.071 (8) and 0.028 (7) Å, and make dihedral angles of 73.4 (2) and 73.3 (2)° with the least-squares planes formed by the four C atoms of the morpholine rings, which adopt a chair conformation. An intra-molecular C-H⋯π inter-action occurs. In the crystal, the packing is stabilized by weak C-H⋯O hydrogen bonds, which connect pairs of molecules into parallel to the c axis, and C-H⋯π inter-actions.

Crystal structure of {(E)-4-[(1-allyl-1H-1,2,3-triazol-4-yl)meth-oxy]benzyl-idene}[2-(morpholin-4-yl)eth-yl]amine.

In the title compound, C19H25N5O2, the morpholine ring has a chair conformation. The plane of the central benzene ring makes dihedral angles of 88.75 (12) and 60.02 (7)°, respectively, with the mean plane formed by the four planar C atoms of the morpholine ring and with the plane of the triazole ring. In the crystal, mol-ecules are linked via C-H⋯π inter-actions, forming slabs lying parallel to (10-1). The C atoms of the bridging ethyl-ene group, between the morpholine and benzene rings, and the terminal ethene group of the prop-1-ene substituent attached to the triazole ring, are disordered over two sets of sites, with an occupancy ratio of 0.634 (13):0.366 (13).

Synthesis, crystal structures, DNA binding and cytotoxicity of two novel platinum(II) complexes containing 2-(hydroxymethyl)pyridine and pyridine-2-carboxylate ligands.

Two new platinum(II) complexes, trans-[Pt(2-mpy)(2)]·4H(2)O (1) and [PtCl(2-pyc)(2-hmpy)]·H(2)O (2), where 2-hmpy=2-(hydroxymethyl)pyridine, 2-mpy=deprotonated 2-hmpy and 2-pyc=pyridine-2-carboxylate, have been synthesized and characterized by elemental analysis, IR, NMR, and X-ray crystallography. The DNA binding affinities of these complexes for Fish Sperm DNA (FS-DNA) were investigated using fluorescence, viscosity, thermal denaturation and gel electrophoresis measurements. Fluorescence analysis indicates that complex 1 binds to DNA by a single intercalative mechanism, while complex 2 exhibits two types of interactions such as intercalation and covalent binding. Gel electrophoresis assay demonstrates ability of the complexes to cleavage the supercoiled pBR322 plasmid DNA. The in vitro cytotoxicities of both complexes were preliminarily evaluated and the cytotoxicity of complex 1 against the human lung cancer cells (H1299) is similar to oxaliplatin, but higher than transplatin and carboplatin.

Synthesis, structural characterization and cell death-inducing effect of novel palladium(II) and platinum(II) saccharinate complexes with 2-(hydroxymethyl)pyridine and 2-(2-hydroxyethyl)pyridine on cancer cells in vitro.

Four palladium(II) and platinum(II) saccharinate (sac) complexes with 2-(hydroxymethyl)pyridine (2-hmpy) and 2-(2-hydroxyethyl)pyridine (2-hepy), namely trans-[Pd(2-hmpy)2(sac)2]·H2O (1), trans-[Pt(2-hmpy)2(sac)2]·3H2O (2), trans-[Pd(2-hepy)2(sac)2] (3) and trans-[Pt(2-hepy)2(sac)2] (4), have been synthesized and characterized by elemental analysis, UV-vis, IR and NMR. Single crystal X-ray analysis reveals that the metal(II) ions in each complex are coordinated by two sac and two 2-hmpy or 2-hepy ligands with a trans arrangement. Anticancer effects of 1-4 were tested against four different cancer cell lines (A549 and PC3 for lung cancer, C6 for glioblastoma, and Hep3B for liver cancer). Cytotoxicity was first screened by the MTT assay and the results were further confirmed by the ATP assay. The mode of cell death was determined by both histological and biochemical methods. Among the metal complexes, complex 2 resulted in relatively stronger anti-growth effect in a dose-dependent manner (3.13-200µM), compared to the others, by inducing apoptosis.

5-Chloro-N'-cyclo-hexyl-idene-3-methyl-1H-indole-2-carbohydrazide.

In the title compound, C16H18ClN3O, the cyclo-hexane ring adopts a distorted chair conformation. In the crystal, pairs of mol-ecules are linked by N-H⋯O hydrogen bonds into inversion dimers, forming R 2 (2)(10) ring motifs. These dimers are connected through C-H⋯N hydrogen bonds into chains along the a axis, forming layers parallel to (101).

1-{(Z)-[2-Meth-oxy-5-(trifluoro-meth-yl)anilino]methyl-idene}naphthalen-2(1H)-one.

The title compound, C(19)H(14)F(3)NO(2), crystallizes in the keto-amine tautomeric form, with a strong intra-molecular N-H⋯O hydrogen bond. The mol-ecule is almost planar; the dihedral angle between the naphthalene ring system and the benzene ring is 4.60 (7)°. In the crystal, mol-ecules are linked into chains along the c axis by C-H⋯O hydrogen bonds. The F atoms of the trifluoro-methyl group are disordered over two positions with refined site occupancies of 0.668 (9) and 0.332 (9).

2-[Anilino(phen-yl)meth-yl]cyclo-heptan-one.

In the title compound, C20H23NO, the cyclo-hepta-none ring adopts a twist-chair conformation, with the amino-methyl substituent in an equatorial position. The relative configuration of the two stereocenters is R,R. In the crystal, mol-ecules are linked by N-H⋯O hydrogen bonds into chains along [100].

1-{(E)-[4-Bromo-2-(trifluoro-meth-oxy)phen-yl]imino-meth-yl}naphthalen-2-ol.

The title compound, C18H11BrF3NO2, crystallizes in the phenol-imine tautomeric form, with a strong intra-molecular O-H⋯N hydrogen bond. The dihedral angle between the naphthalene ring system and the benzene ring is 28.54 (10)°.

5-Fluoro-3-phenyl-N'-(4-propyl-cyclo-hexyl-idene)-1H-indole-2-carbohydrazide.

In the title compound, C24H26FN3O, the cyclo-hexane ring adopts a chair conformation; the propyl substituent is in an equatorial orientation and the bond-angle sum at the C atom bonded to the carbohydrazide N atom is 360.0°. The dihedral angle between the 1H-indole ring system and the phenyl ring is 82.77 (13)°. A weak intra-molecular C-H⋯π contact occurs. In the crystal, pairs of mol-ecules related by a crystallographic twofold axis are linked by bifurcated N-H⋯(O,N) hydrogen bonds; a C-H⋯O inter-action occurs between the same pair. The dimers are linked by C-H⋯F and C-H⋯π inter-actions, generating a three-dimensional network.

5-Fluoro-N'-(4-methyl-cyclo-hexyl-idene)-3-phenyl-1H-indole-2-carbohydrazide.

The title compound, C22H22FN3O, crystallized with two independent mol-ecules (A and B) in the asymmetric unit; these are linked by a pair of N-H⋯O hydrogen bonds, forming a pseudo-centrosymmetric dimer with an R (2) 2(10) motif. In addition, a number of C-H⋯π inter-actions are also observed. The 1H-indole ring systems in mol-ecules A and B are essentially planar [maximum deviations of 0.019 (2) and 0.014 (2) Å, respectively] and make dihedral angles of 77.64 (10) and 69.50 (9)°, respectively, with thephenyl rings.

5-Fluoro-N-(2-methyl-3-oxo-1-thia-4-aza-spiro-[4.5]dec-4-yl)-3-phenyl-1H-indole-2-carboxamide.

In the title compound, C24H24FN3O2S, the 1,3-thia-zolidine ring adopts an envelope conformation with the S atom as the flap, while the cyclo-hexane ring is in a chair conformation. In the crystal, mol-ecules are linked by N-H⋯O and C-H⋯F hydrogen bonds, forming a three-dimensional network. The unit cell contains six voids of 57 Å(3), but the residual electron density (highest peak = 0.23 e Å(-3) and deepest hole = -0.19 e Å(-3)) in the difference Fourier map suggests no solvent mol-ecule occupies this void.

N'-(4-Ethyl-cyclo-hexyl-idene)-5-fluoro-3-phenyl-1H-indole-2-carbohydrazide.

The title compound, C23H24FN3O, crystallizes with two independent mol-ecules (I and II) in the asymmetric unit. These pairs of mol-ecules are linked to each other as N-H⋯O dimers with an R 2 (2)(10) motif. Furthermore, the crystal structure also exhibits C-H⋯π inter-actions. The atoms of the ethyl group in mol-ecule I are disordered over two sites with an occupancy ratio of 0.817 (6):0.183 (6).

(3aR,6S,7aR)-7a-Chloro-2-[(4-nitro-phen-yl)sulfon-yl]-1,2,3,6,7,7a-hexa-hydro-3a,6-ep-oxy-iso-indole.

In the title compound, C14H13ClN2O5S, the chlorine-substituted tetrahydrofuran ring adopts a twist conformation and the other tetra-hydro-furan ring an envelope conformation with the O atom as the flap. The pyrrolidine ring adopts a twist conformation. In the crystal, C-H⋯O hydrogen bonds link the mol-ecules into zigzag chains running along the b-axis direction.

2-[(E)-(Morpholin-4-yl-imino)-meth-yl]-6-(morpholin-4-ylmeth-yl)phenol.

The title compound, C16H23N3O3, contains two morpholine rings, each of which adopts a chair conformation. The mol-ecular conformation is stabilized by an intra-molecular O-H⋯N hydrogen bond, leading to a S(6) ring. In the crystal, mol-ecules are linked into zigzag chains along the c-axis direction by C-H⋯O and C-H⋯π inter-actions.

(E)-N-(1,3-Benzodioxol-5-yl)-1-(4-{[1-(prop-2-en-1-yl)-1H-1,2,3-triazol-4-yl]meth-oxy}phen-yl)methanimine.

In the title compound, C20H18N4O3, the dihedral angles between the central benzene ring and the 1H-1,2,3-triazole ring and the fused benzene ring are 65.34 (19) and 3.64 (18)°, respectively. The dioxole ring adopts a shallow envelope conformation, with the methyl-ene C atom displaced by 0.156 (5) Šfrom the other four atoms (r.m.s. deviation = 0.007Å). In the crystal, the mol-ecules are linked by C-H⋯O and C-H⋯N hydrogen bonds, generating a three-dimensional network.