Identification of a 3-(5-methyl-2-thiazolylamino)phthalide as a new minor groove agent.

A new 3-(5-methyl-2-thiazolylamino)phthalide molecule, 3-((5-methylthiazol-2-yl)amino)isobenzofuran-1(3H)-one, was synthesized and characterized experimentally by FT-IR, NMR, UV-Vis, and single-crystal X-ray analysis and theoretically by quantum chemical calculations. The single-crystal X-ray studies revealed that the compound crystallizes in the monoclinic space group P-21/c with unit-cell parameters a = 8.0550(6) Å, b = 6.1386(3) Å, c = 23.3228(18) Å, ß = 97.724(6)° and Z = 4. Optimized geometries and the vibrational frequencies were studied at the density functional theory (DFT) level by using the hybrid functional B3LYP with a 6-311 G (d,p) basis set. The title compound was evaluated for its anti-quorum sensing (anti-QS) activity on Chromobacterium violaceum 12472 and additionally for its antibacterial activity against Staphylococcus aureus 29213, Staphylococcus epidermidis 12228, Pseudomonas aeruginosa 27853, Escherichia coli 25922, and Proteus mirabilis 14153. The lowest MIC value was 0.24 µg/mL for S. aureus 29213 and the highest MIC value was 30.75 µg/mL for E. coli 25922. While anti-bacterial activity was observed in those other than the S. epidermidis and P. Mirabilis, anti-QS activity wasn't detected. Investigations on dsDNA binding affinity indicate that the title compound binds to dsDNA via the groove binding mode. Molecular docking calculations and molecular dynamics simulations results showed also that the title compound prefers binding to the minor groove of dsDNA and remains stable in the minor groove throughout the molecular dynamics simulation.Communicated by Ramaswamy H. Sarma.

Crystal structure and theoretical study of N,N-bis-[(5-chloro-2-oxo-2,3-di-hydro-benzo[d]oxazol-3-yl)meth-yl]-2-phenyl-ethanamine.

In the mol-ecular structure of the title compound, C24H19Cl2N3O4, the three C atoms of the central N,N-di-methyl-methanamine moiety are bonded to the N atoms of the two 5-chloro-1,3-benzoxazol-2(3H)-one groups and to the methyl C atom of the methyl-benzene group. One of the nine-membered 2,3-di-hydro-1,3-benzoxazole rings and the phenyl ring are almost parallel to each other, making a dihedral angle of 5.30 (18)°, but they are almost normal to the mean plane of the other nine-membered 2,3-di-hydro-1,3-benzoxazole ring, subtending dihedral angles of 89.29 (16) and 85.41 (18)°, respectively. The crystal structure features C-H⋯O hydrogen bonds and π-π stacking inter-actions [centroid-to-centroid distances = 3.5788 (19) Å, slippage = 0.438 and 3.7773 (16) Å, and slippage = 0.716 Å].

Synthesis, structures and biomolecular interactions of new silver(i) 5,5-diethylbarbiturate complexes of monophosphines targeting Gram-positive bacteria and breast cancer cells.

A series of new silver(i) 5,5-diethylbarbiturate (barb) complexes with the formulas [Ag2(µ-barb)2(PPh3)2] (1), [Ag(barb)(PPh2Cy)] (2), [Ag(barb)(PPhCy2)] (3) and [Ag(barb)(PCy3)] (4) (PPh3 = triphenylphosphine, PPh2Cy = diphenylcyclohexylphosphine, PPhCy2 = dicyclohexylphenylphosphine and PCy3 = tricyclohexylphosphine) were synthesized and fully characterized by elemental analysis, IR, NMR, ESI-MS and X-ray crystallography. All the complexes display a significant affinity towards DNA with a groove binding mode and also strongly bind to BSA via hydrophobic interactions. Lipophilicity increases from 1 to 4 with an increasing number of Cy groups in the phosphine ligands. Screening of the in vitro antimicrobial activity of 1-4 against the strains of Gram-negative (S. typhimurium ATCC 14028, E. coli ATCC 25922 and O157:H7) and Gram-positive (L. garvieae 40456, S. aureus ATCC 25923, and ATCC 33591) bacteria demonstrated that all the complexes exhibit very high activity and specific selectivity against the Gram-positive bacteria, compared to AgNO3 and silver sulfadiazine. Furthermore, the growth inhibitory effects of 1-4 on four human cancer cell lines (MCF-7, PC-3, A549 and HT-29) showed that 4 has a potent cytotoxic activity against MCF-7 cells, significantly higher than cisplatin and carboplatin. The effects of the complexes on the inhibition of the cells are closely related to their lipophilicity as well as DNA/protein binding. The induction of apoptosis of MCF-7 cells treated with 4 was probed through Hoechst 33342 staining, Annexin V positivity and caspase 3/7 activity. In addition, increased ROS levels in the presence of 4 are most likely responsible for damage to both mitochondria and genomic DNA.

Crystal structure of 2-(aza-niumylmeth-yl)pyridinium bis(hydrogen squarate).

The asymmetric unit of the title compound, C6H10N22+·2C4HO4-, comprises two hydrogen squarate (Hsq-; systematic name: 2-hy-droxy-3,4-dioxo-cyclo-butano-late) anions and a 2-(aza-niumylmeth-yl)pyridinium dication. The squaric acid mol-ecules each donate an H atom to the N atoms of the pyridine ring and the amino-methyl units of a 2-(amino-meth-yl)pyridine mol-ecule, forming the 1:2 salt. The Hsq- anions are linked by strong O-H⋯O hydrogen bonds and an N-H⋯O hydrogen bond links the 2-(aza-niumylmeth-yl)pyridinium cation to one of the squaric acid anions. The crystal structure features additional N-H⋯O and O-H⋯O hydrogen bonds, π-π stacking and unusual weak C-O⋯π(ring) inter-actions.

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.

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.

Antimony(III) complexes with 2-amino-4,6-dimethoxypyrimidines: Synthesis, characterization and biological evaluation.

Novel pyrimidine compound bearing disulfide bridge, 5,5'-disulfanediylbis(2-amino-4,6-dimetoxypyrimidine) (3) was synthesized by reduction of 2-amino-4,6-dimethoxy-5-thiocyanatopyrimidine for the first time, and its structure was confirmed by X-ray crystallographic analysis. Novel binuclear antimony(III) compound of (3), {Sb[5,5'-disulfanediylbis(2-amino-4,6-dimetoxypyrimidine)]Cl3}2 (4) and mononuclear antimony(III) compounds, SbL2Cl3, [L: 2-amino-5-thiol-4,6-dimethoxy pyrimidine (2) and 2-amino-5-(1H-tetrazol-5-ylthio)-4,6-dimethoxypyrimidine (6)] were synthesized and characterized with the help of elemental analysis, molecular conductivity, FT-IR, (1)H-NMR and LC-MS techniques. The geometrical structures optimized by a DFT/B3LYP/LANL2DZ method of the compounds, indicated that monomeric compounds have square pyramidal shape. Both antileishmanial activity against Leishmania tropica promastigote and glutathione reductase inhibitory activity were determined in vitro. The results showed that (3) has the best biological activity.

Crystal structure of 4-(4-chloro-phen-yl)-6-(morpholin-4-yl)pyridazin-3(2H)-one.

In the title compound, C14H14ClN3O2, the morpholine ring adopts a chair conformation, with the exocyclic N-C bond in an equatorial orientation. The 1,6-di-hydro-pyridazine ring is essentially planar, with a maximum deviation of 0.014 (1) Å, and forms a dihedral angle of 40.16 (7)° with the plane of the benzene ring. In the crystal, pairs of centrosymmetrically related mol-ecules are linked into dimers via N-H⋯O hydrogen bonds, forming R 2 (2)(8) ring motifs. The dimers are connected via C-H⋯O and C-H⋯Cl hydrogen bonds, forming a three-dimensional network. Aromatic π-π stacking inter-actions [centroid-centroid distance = 3.6665 (9) Å] are also observed. Semi-empirical mol-ecular orbital calculations were carried out using the AM1 method. The calculated dihedral angles between the pyridizine and benzene rings and between the pyridizine and morpholine (all atoms) rings are 34.49 and 76.96°, respectively·The corresponding values obtained from the X-ray structure determination are 40.16 (7) and 12.97 (9)°, respectively. The morpholine ring of the title compound in the calculated gas-phase seems to have a quite different orientation compared to that indicated by the X-ray structure determination.

Cationic Pd(II)/Pt(II) 5,5-diethylbarbiturate complexes with bis(2-pyridylmethyl)amine and terpyridine: Synthesis, structures,DNA/BSA interactions, intracellular distribution, cytotoxic activity and induction of apoptosis.

Four new cationic Pd(II) and Pt(II) 5,5-diethylbarbiturate (barb) complexes, [M(barb)(bpma)]X·H2O [M = Pd(II), X = Cl (1); M = Pt(II), X = NO3(-) (2)] and [M(barb)(terpy)]NO3·0.5H2O [M = Pd(II) (3); M = Pt(II) (4)], where bpma = bis(2-pyridylmethyl)amine and terpy = terpyridine, were synthesized and characterized by elemental analysis, IR, UV­vis, NMR, ESI-MS and X-ray crystallography. The DNA binding properties of the cationic complexes were investigated by spectroscopic titrations, displacement experiments, viscosity, DNA melting and electrophoresis measurements. The results revealed that the complexes effectively bind to FS-DNA (fish sperm DNA) via intercalative/minor groove binding modes with intrinsic binding constants (Kb) in the range of 0.50 × 10(4)­1.67 × 10(5) M(-1). Absorption, emission and synchronous fluorescence measurements showed strong association of the complexes with protein (BSA) through a static mechanism. The mode of interaction of complexes towards DNA and protein was also supported by molecular docking. Complexes 1 and 3 showed significant nuclear uptake in HT-29 cells. In addition, 1 and 3 showed higher inhibition than cisplatin on the growth of MCF-7 and HT-29 cells and induced apoptosis on these cells much more effectively than the rest of the complexes as evidenced by pyknotic nuclear morphology. The levels of caspase-cleaved cytokeratin 18 (M30 antigen) in HT-29 cells treated with 1 and 3 increased in a dose-dependent manner, suggesting apoptosis. Moreover, qRT-PCR experiments showed that 1 and 3 caused significant increases in the expression of TNFRSF10B in HT-29 cells, indicating the initiation of apoptosis via cell surface death receptors.

Crystal structure of 2-{[2-meth-oxy-5-(tri-fluoro-meth-yl)phen-yl]iminomethyl}-4-nitro-phenol.

In the title compound, C15H11F3N2O4, the N=C bond of the central imine group adopts an E conformation. The dihedral angle between two benzene rings is 6.2 (2)°. There is an intra-molecular bifurcated O-H⋯(N,O) hydrogen bond with S(6) and S(9) ring motifs. In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds into a helical chain along the 31 screw axis parallel to c. The -CF3 group shows rotational disorder over two sites, with occupancies of 0.39 (2) and 0.61 (2).

Analysis of tautomeric equilibrium in (E)-4,6-dibromo-2-[(4-fluorophenylimino)methyl]-3-methoxyphenol compound.

In this study, the tautomeric equilibrium between the phenol-imine and keto-amine structural forms of (E)-4,6-dibromo-2-[(4-fluorophenylimino)methyl]-3-methoxyphenol compound has been investigated with experimental (XRD, UV-vis and NMR) and theoretical (DFT and TD-DFT) methods. The results clearly show that structural preference of the compound is definitely depended on its state. Namely, the compound exists in phenol-imine form in the solid state while one or both of these forms can be seen in solvent media. For example, the compound prefers phenol-imine form in benzene while both forms exist in EtOH and DMSO solvents. Coexistence of two forms has been quantified with NMR studies, giving a ratio of 11:9 for phenol and keto structures of the compound in acetone-d6 solvent.

Syntheses, crystallographic, mass-spectroscopic determination and antioxidant studies of Co(II), Ni(II) and Cu(II) complexes of a new imidazol based Schiff base.

A new imidazole-based Schiff base, 2-((1H-imidazol-4-yl)methyleneamino)benzylalcohol (HL) and corresponding analogous bis(2-((1H-imidazol-4-yl)methyleneimino)benzylalcohol)metal(II) perchlorates (M: Co(1), Ni(2), Cu(3)) have prepared and characterized by elemental analyses, ESI-MS, IR, UV-Vis spectroscopies and conductivity measurements. X-ray single crystal structures of 1 and 2 have been also determined. Elemental analyses, spectroscopic and conductance data of 3 demonstrated similar structural features with these of crystallographically characterized complexes and based upon this relevances, HL ligands are neutrally coordinated to metal(II) ions in tridentate mode and all complexes are isostructural, dicathionic, contain perchlorate anions as complementary ions and, are in octahedral geometry with the formulae of [M(HL)2](ClO4)2 (for 3) and [M(HL)2](ClO4)2·H2O (for 1 and 2). Radical scavenging activities of the complexes have been evaluated by using DPPH, DMPD(+), and ABTS(+) assays. SC50 values (µg/mL) of the complexes and standards on DPPH, DMPD(+), ABTS(+) follow the sequences, BHA (9.06±0.33)>CMPD3 (15.62±0.52)>CMPD2 (17.43±0.29)>Rutin (21.65±0.60)>CMPD1 (25.67±0.51)>Trolox (28.57±0.37), Rutin>BHA>CMPD3>CMPD2>Trolox>CMPD1, and Trolox>BHA>CMPD3>CMPD2>Rutin>CMPD1 respectively.

Crystal structure of 4-[(E)-(4-nitro-benzyl-idene)amino]-phenol.

The asymmetric unit of the title compound, C13H10N2O3, contains four independent mol-ecules (I, II, III and IV). Mol-ecule IV shows whole-mol-ecule disorder over two sets of adjacent sites in a 0.669 (10):0.331 (10) ratio. The dihedral angles between the aromatic rings are 32.30 (13)° in mol-ecule I, 2.24 (14)° in II, 41.61 (13)° in III, 5.0 (5)° in IV (major component) and 10.2 (3)° in IV (minor component). In the crystal, mol-ecules are linked into layers lying parallel to (024) by C-H⋯O and O-H⋯O inter-actions. The layers inter-act by C-H⋯π and weak aromatic π-π stacking inter-actions [centroid-centroid distances = 3.8476 (16), 3.725 (3) and 3.733 (5) Å].

New palladium(II) and platinum(II) 5,5-diethylbarbiturate complexes with 2-phenylpyridine, 2,2'-bipyridine and 2,2'-dipyridylamine: synthesis, structures, DNA binding, molecular docking, cellular uptake, antioxidant activity and cytotoxicity.

Novel palladium(ii) and platinum(ii) complexes of 5,5-diethylbarbiturate (barb) with 2-phenylpyridine (Hppy), 2,2'-bipyridine (bpy) and 2,2'-dipyridylamine (dpya) have been prepared and characterized by elemental analysis, IR, UV-Vis, NMR and ESI-MS. Single-crystal diffraction measurements show that complex consists of binuclear [Pd2(µ-barb-κN,O)2(ppy-κN,C)2] moieties, while complexes are mononuclear, [M(barb-κN)2(L-κN,N')] (L = bpy or dpya). has a composition of [Pt(dpya-κN,N')2][Ag(barb-κN)2]2·4H2O and was assumed to have a structure of [Pt(barb-κN)(Hppy-κN)(ppy-κN,C)]·3H2O. The complexes were found to exhibit significant DNA binding affinity by a non-covalent binding mode, in accordance with molecular docking studies. In addition, complexes and displayed strong binding with supercoiled pUC19 plasmid DNA. Cellular uptake studies were performed to assess the subcellular localization of the selected complexes. A moderate radical scavenging activity of and was confirmed by DPPH and ABTS tests. Complexes , , and showed selectivity against HT-29 (colon) cell line.

Synthesis, spectral analysis, structural elucidation and quantum chemical studies of (E)-methyl-4-[(2-phenylhydrazono)methyl]benzoate.

The title compound, (E)-methyl-4-[(2-phenylhydrazono)methyl]benzoate, (I), (C15H14N2O2), has been synthesized by condensation reaction of methyl-4-formylbenzoate and phenylhydrazine. The compound has been characterized by elemental analysis, IR, (1)H NMR, (13)C NMR, UV-Vis spectroscopies and single crystal X-ray diffraction techniques. Optimized molecular structure, harmonic vibrational frequencies, (1)H and (13)C NMR chemical shifts have been investigated by B3LYP/6-31G(d,p) method using density functional theory (DFT). Global chemical reactivity descriptors, natural population analysis (NPA), thermodynamic and non-linear optical (NLO) properties have also been studied. The energetic behavior of the compound has been examined in solvent media using the integral equation formalism polarizable continuum model (IEF-PCM).

Crystal structure of (Z)-4-[1-(4-acetyl-anilino)ethyl-idene]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one.

In the solid state, the title compound, C20H19N3O2, adopts the keto-amine tautomeric form, with the H atom attached to the N atom, which participates in an intra-molecular N-H⋯O hydrogen bond with an S(6) ring motif. The dihedral angles between the pyrazole ring and the phenyl and benzene rings are 3.69 (10) and 46.47 (9)°, respectively. In the crystal, mol-ecules are linked by weak C-H⋯O hydrogen bonds, generating C(16) chains propagating in [301]. Weak aromatic π-π stacking inter-actions [centroid-centroid distances = 3.6123 (10) and 3.6665 (10) Å] link the chains into a three-dimensional network.

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

The list of authors in the paper by Çelikesir et al. [Acta Cryst. (2014), E70, o935] is corrected.[This corrects the article DOI: 10.1107/S160053681401678X.].

The spectroscopic (FT-IR, UV-vis), Fukui function, NLO, NBO, NPA and tautomerism effect analysis of (E)-2-[(2-hydroxy-6-methoxybenzylidene)amino]benzonitrile.

A new o-hydroxy Schiff base, (E)-2-[(2-hydroxy-6-methoxybenzylidene)amino]benzonitrile was isolated and investigated by experimental and theoretical methodologies. The solid state molecular structure was determined by X-ray diffraction method. The vibrational spectral analysis was carried out by using FT-IR spectroscopy in the range of 4000-400cm(-)(1). Theoretical calculations were performed by density functional theory (DFT) method using 6-31G(d,p) basis set. The results of the calculations were applied to simulated spectra of the title compound, which show excellent agreement with observed spectra. The UV-vis spectrum of the compound was recorded in the region 200-800 nm in several solvents and electronic properties such as excitation energies, and wavelengths were calculated by TD-DFT/B3LYP method. The most prominent transitions were corresponds to π→π∗. Hybrid density functional theory (DFT) was used to investigate the enol-imine and keto-amine tautomers of titled compound. The titled compound showed the preference of enol form, as supported by X-ray and spectroscopic analysis results. The geometric and molecular properties were compaired for both enol-imine and keto-amine forms. Additionally, geometry optimizations in solvent media were performed with the same level of theory by the integral equation formalism polarizable continuum (IEF-PCM). Stability of the molecule arises from hyperconjugative interactions, charge delocalization and intramolecular hydrogen bond has been analyzed using natural bond orbital (NBO) analysis. Mulliken population method and natural population analysis (NPA) have been studied. Also, condensed Fukui function and relative nucleophilicity indices calculated from charges obtained with orbital charge calculation methods (NPA). Molecular electrostatic potential (MEP) and non linear optical (NLO) properties are also examined.

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.