Triclinic Space Group Research Articles

Synthesis, Crystal Structure, Hirshfeld Surface Analysis and Docking Studies of a Novel Flavone–Chalcone Hybrid Compound Demonstrating Anticancer Effects by Generating ROS through Glutathione Depletion

The flavone–chalcone hybrid compound, (E)-6-bromo-3-(3-(2-methoxyphenyl)-3-oxoprop-1-enyl)-4H-chromen-4-one (3), was synthesized and its three dimensional structure was identified by X-ray crystallography. The compound 3, C19H13BrO4, was crystallized in the triclinic space group P-1 with the following cell parameters: a = 8.2447(6) Å; b = 8.6032(6) Å; c = 11.7826(7) Å; α = 92.456(2)°; β = 91.541(2)°; γ = 106.138(2)°; V = 801.42(9) Å3 and Z = 2. In an asymmetric unit, two molecules are packed by a pi–pi stacking interaction between two flavone rings that are 3.790 Å apart from each other. In the crystal, two hydrogen bonds form inversion dimers and these dimers are extended along the a axis by another hydrogen bond. Hirshfeld analysis revealed that the H–H (34.3%), O–H (19.2%) and C–H (16.7%) intermolecular contacts are the major dominants, while the C–O (6.7%) and C–C (6.5%) are minor dominants. When HCT116 cells were treated with various concentrations of hybrid compound 3, reduced cell viability and induced apoptosis in HCT116 cells were observed in a dose-dependent manner. The treatment of HCT116 colon cancer cells with compound 3, decreased the intracellular glutathione (GSH) levels and generated a reactive oxygen species (ROS). In silico docking experiments between the compound 3 and glutathione S-transferase (GST) containing glutathione were performed to confirm whether the compound 3 binds to glutathione. Their binding energy ranged from −6.6 kcal/mol to −5.0 kcal/mol, and the sulfur of glutathione is very close to the Michael acceptor regions of the compound 3, so it is expected that they would easily react with each other. Compound 3 may be a promising novel anticancer agent by ROS generation through glutathione depletion.

Single oxygen vacancy in BaCoO3: Hybrid DFT calculations and local site symmetry approach

We use the hybrid B1WC density functional calculations and the supercell model to analyze properties of BaCoO3 (BCO) in the corner-sharing CoO6 octahedra geometry. We compare the atomic and electronic structures for ideal and defective BCO containing a single oxygen vacancy (Vo). We find that the ideal BCO is better described by the triclinic space group (SG) P1 supercell than the cubic SG Pm3¯m model. The site symmetry approach allows us to derive several Vo supercell models on the basis of SGs P4mm, Pmm2 or Amm2 from the aristotype cubic SG Pm3¯m. The low symmetry Pmm2 model suggests the 0.4 eV formation energy of Vo in BCO. Furthermore, stability of this result is confirmed by the calculation of Vo in the supercell without symmetry (SG P1). The ideal and defective BCO are characterized by the intermediate spin (IS) states of Co4+ and Co4+&Co3+ ions, respectively. Additional complexity is introduced by the smooth Co magnetic moment dependence on the Co–Vo distance.

Synthesis and Structural Characterization of New Ladder Organostannoxanes Derived from Sulfonic Acid Derivatives

Two new ladder n-dibutyltin(IV) compounds with general formulae [n-Bu₂Sn]₄(<i>μ₃</i>-O)₂(<i>μ₂</i>-OH)₂(OSO₂R)₂ with R=4-HO-C₆H₄-(1) and CH₃-(2) have been synthetized and characterized by elemental analysis, FT-IR, ¹H NMR and Mass spectroscopies techniques as well as single crystal X-ray diffraction study. The complex 1 crystallizes in the triclinic space group <i>P</i>1 with <i>a=</i>12.808 (8), <i>b</i>=15.391 (9), <i>c</i>=15.803 (10) Å, <i>α=</i>87.910 (5), <i>β=</i>66.650 (6), <i>γ=</i>80.283 (5)°, <i>V=</i>2817.6 (3) ų and <i>Z</i>=1. The crystal structure reveal them to be tetranuclear tin (IV) ladder-like structure containing two deprotonated ligands an three-rung-staircase Sn₄O₄ core. The structure is a centro-symmetric dimer of an oxoditin (IV) unit having a central four-member ring. In this complex, the central tin (IV) atoms are pentacoordinated, where the sulfonate base acts as monodentate ligands. Supramolecular architecture is formed by extensive hydrogen-bonding interactions, O-H…O.

Synthesis, Spectroscopic, Characterization and X-ray Structures of Lanthanide(III) Complexes Derived from 1,5-bis(phenyl(pyridin-2-yl)methylene)carbonohydrazide

The use of 1,5-bis (phenyl (pyridin-2-yl) methylene) carbonohydrazide (H₂L) in the coordination chemistry of lanthanides (III) yielded complexes in which two ligand molecules are present. The synthesis was carried out using a Ln/H₂L ratio of 1/2 to lead mononuclear complexes of [Ln(H₂L)₂(<i>η</i>²-NO₃)_3-x](NO₃)_x (Ln=La (1), Sm (4), Gd (6) and Yb (7)), [Ln(H₂L)₂(NO₃)₃] (Ln=Pr(2), Eu(5) and a co-crystal {[Nd(H₂L)₂(<i>η</i>²-NO₃)₂(<i>η¹</i>-NO₃)], [Nd(H₂L)₂(<i>η²-</i>NO₃)(<i>h¹-</i>NO₃)(H₂O)]}.(NO₃).2CH₃OH} (3). The structures of the complexes (2) and (3)were solved by X-ray crystallography on a single crystal. In the mononuclear complex of Pr<SUP>III</SUP>, two neutral ligand molecules act in tridentate fashion. In the co-crystal complex, one of the Nd<SUP>III</SUP> atom is coordinated by two ligand molecules acting tridentately in neutral form and three nitrate anions acting in bidentate fashion while the second Nd<SUP>III</SUP> atom is coordinated by two ligand molecules acting tridentately in neutral form, one monodentate nitrate anion, one bidentate nitrate anion and one water molecule. The neutrality of the complex is ensured by one free nitrate anion. Two free methanol molecules are present. Complex (2) crystallizes in the triclinic space group P-1 with the following parameters: a=10.128 (2) Å, b=12.2285 (19) Å, c=20.816 (5) Å, α=85.634 (4), β=81.870 (4)°, γ=87.210 (5)°, V=2542.9 (9) ų, Z=2, R₁=0.0640, wR₂=0.1377. Complex (3) crystallizes in the monoclinic space group P2₁/c with the following parameters: a=10.4554 (12) Å, b=44.089 (6) Å, c=23.212 (3) Å, β=90.851 (2)°, V=10699 (2) ų, Z=4, R₁=0.0630, wR₂=0.1690. The coordination sphere of the twelve-coordinated Pr<SUP>III</SUP> atom is best described as distorted icosahedron. In the co-crystal one of the Nd<SUP>III</SUP> atom is eleven-coordinated while the second Nd<SUP>III</SUP> atom is ten-coordinated. The environments around the Nd<SUP>III</SUP> atoms are respectively best described as distorted pentacapped trigonal prism and a distorted bicapped square antiprism, respectively. Supramolecular structures are consolidated by numerous hydrogen bonds.

Cadmium(II) and copper(II) complexes containing benzoate derivatives and 2-aminopyrimidine ligands: Synthesis, crystal structures and antibacterial activity

The new Cd(II) and Cu(II) complexes namely [Cd2(2-OHbza)4(apm)4] (1), [Cu2(2-OHbza)4(apm)]n•2(2-OHbza) (2) and [Cu2(2-CH3bza)4(apm)]n (3) (2-OHbza = 2-hydroxybenzoate, 2-CH3bza = 2-methylbenzoate and apm = 2-aminopyrimidine) were successfully prepared by using direct one pot synthesis method. All complexes were characterized by using CHN elemental analysis, FT-IR spectroscopy, powder X-ray diffraction and single crystal X-ray diffraction techniques. Compound 1 crystallized in monoclinic space group P21/c, while compound 2 and 3 crystallized in triclinic space group P-1. The dinuclear compound 1 consists of two seven-coordinated Cd(II) centers which are doubly bridged by 2-OHbza bridging ligands, while the rest two 2-OHbza and two apm are terminal ligand. The crystal structure of compound 1 is stabilized by the intermolecular hydrogen bonding and C-H•••π interaction and π•••π interactions. Compounds 2 and 3 present zigzag one-dimensional chainlike-structure which dimer Cu(II) units are linked by apm ligand. The crystal structure of these compounds is stabilized by π•••π and C-H•••π interactions. The photoluminescence properties of compound 1 has been studied comparing to those of 2-OHbza and apm ligands. The solid state PL emission spectrum of compound 1 shows similar intensity of free apm ligand and shape to free 2-OHbza ligand which present a single broad band centered at λem 525 nm (λex = 325 nm), but blue-shift. For solution PL experiment of compound 1 in various solvents, the results showed that compound 1 is selective PL quenching acetone. Electronic spectra for solid state and solution in different solvents of compounds 2 and 3 present the d-d absorption bands centered in the range of 701 – 794 nm. The highest red shifts of λmax are found for compounds 2 and 3 in DMSO. In addition, the antibacterial activity of all compounds are investigated for S.aureus and E.coil by agar diffusion method. The results show that compound 1 exhibits the activity against S.aureus better than E.coil.

Investigation of ab-inito, Photoluminescence and electrical studies of Li2Co(WO4)2

The optical properties of the material is depends on the site occupancy of the doping in the host lattice. In the present study, wereport the synthesis, characterisation, optical properties and ab-initio studies of Li2Co(WO4)2microcrystals synthesized by traditional and easy solid state method. The x-ray diffraction study shows the compound which arecrystallized in the triclinic crystal system space group PÏ.The average crystallite size was estimated from diffraction study found to be 109 nm. From UV-Visible spectroscopic study the calculated band gap is 2.69 eV for the phosphor. The Li2Co(WO4)2 phosphors shows the Photoluminescence under an excitation wavelength of 331 nm. A strong blue green peak emission at 447 nm was observed due to the transition from 3T1u levels to the 1A1g level. The electrical impedance studies were carried out to enunciate the impedance behaviour of Li2Co(WO4)2and to depict different conduction and relaxation processes.Further, theab-initiostudies were carried out in detail to understand electronic properties of the phosphor.

Crystal structure, charge-distribution and bond-valence-sum investigations of a new layered phosphate SrFe(HPO4)(PO4)

The new compound SrFe(HPO4)(PO4), has been prepared using mild hydrothermal conditions under autogenous pressure and characterized by single-crystal X-ray diffraction. The crystal structure of this compound crystallizes in the triclinic system space group P-1 with Z = 2 and the cell parameters a = 5.1766 (2) Å, b = 7.1346 (2) Å, c = 8.5695 (3) Å, α = 91.093 (2)°, β = 91.029 (2)°, γ = 90.313 (2)°, V = 316.36 (2) Å3. The structure exhibits a layered framework which could be described as a stacking [Fe(HPO4)(PO4)]∞2− layers of corner sharing FeO6 octahedra and the bridging PO4/PO3(OH) tetrahedra along the [010] direction. Such hetero-polyhedral arrangement gives a rise to a strong O—H···O hydrogen bonds into the intra-layers region. Adjacent layers are held to each other through the Sr2+ cations located in the resulting corrugated interstitial space. The validation of the proposed structural model is supported by means bond-valence-sum (BVS) and charge-distribution (CHARDI) methods.

Transition metal precursor impact on thiocyanate complexes crystallization: Isomorphous cobalt and nickel properties

A novel hybrid organic-inorganic isomorphs, 2-Amino Piridinium di(isothiocyanate) cobalt (1) and 2-Amino Piridinium tetra(isothiocyanate)Nickel (2), were prepared by evaporation crystal growth method at room temperature and characterized by X-ray crystal structure, spectroscopic, electric and optical studies. The crystal structural analysis reveals that the solid (1) crystallizes in the monoclinic space group P 21/c and the solid (2) crystallizes in the triclinic space group P1-.In (1) the metal cations are linked by pairs of μ-1,3-bridging thiocyanate anions into corrugated chains parallel to the b direction, whereas in (2) the [Ni(NCS)4]2− anions are arranged in pairs along the c-axis direction to form anionic layers parallel to the (a, c) plane. The crystal structure of (1) and (2) was determined from XRPD data, which shows that it is strongly related to the DRX mono-crystal obtained results. Intermolecular interactions were investigated by Hirshfeld surfaces and contact enrichment tools. Different interactions packed the system through NH…N, and NH…S hydrogen bonds forming a ring. The organic entities are grouped into dimers for (2) through weak interactions NH…N and NH…S. The robustness of the crystals is also enhanced by CH…π of the piridinium ring and NH…S intermolecular interactions. HOMO and LUMO energy gaps have been computed, where Gap energies revealed a semiconductor behavior. The vibrational absorption bands were identified by infrared spectroscopy. The solid-state UV–Visible absorption spectrum and the photoluminescence spectrum of the title compounds were obtained at room temperature in order to spotlight the optical properties. The di-electrical investigations on (1) and (2) shows an interesting electrical behavior. In the [20–400 °C] range, the thermal behaviors were investigated and showed the decomposition of the two complexes with metal complexes residues.

Synthesis, characterization and crystal structure of a glycylglycinate chelate of zinc(II)

The reaction of glycylglycine (H2GG) with zinc oxide in a 2:1 ratio in water produced [Zn2(HGG1-)4(H2O)2] in high yield. The compound was characterized by elemental analysis, thermogravimetric analysis/differential scanning calorimetry, and FTIR spectroscopy. In addition, a single crystal structure revealed a binuclear complex with the H2GG ligand in two distinct coordination modes. The first coordination mode exhibits each Zn(II) site coordinated to a terminal, bidentate HGG1- via amine nitrogen atoms and the carbonyl amide oxygen atom. The second coordination mode shows a bridging tridentate HGG1- linked to one Zn site through the amine nitrogen and the carbonyl amide oxygen, and to the neighbouring Zn site through a carboxylate oxygen donor. In addition, each Zn site bonds to an aqua ligand to complete the six-coordinate coordination sphere. Crystal data: triclinic space group P-1, a = 7.374 Å, α = 105.57°, b = 10.054 Å, β = 91.084°, c = 10.756 Å, γ = 102.676°, V = 746.88 Å3.

Synthesis and Characterization of Novel Copper(II)-Sunitinib Complex: Molecular Docking, DFT Studies, Hirshfeld Analysis and Cytotoxicity Studies

The main goal of this work was to report the synthesis, characterization, and cytotoxicity study of a novel copper(II)-sunitinib complex, CuSun. It has been synthesized and characterized in solid state and in solution by different methods (such as DFT, FTIR, Raman, UV-vis, EPR, NMR, etc.). The solid-state molecular structure of trichlorosunitinibcopper(II), where sunitinib: N-[2-(diethylamino)ethyl]-5-[(Z)-(5-fluoro-2-oxo-1H-indol-3-ylidene)methyl]-2,4-dimethyl-1H-pyrrole-3-carboxamide, for short Cu(Sun)Cl3, was determined by X-ray diffraction. It crystallizes in the triclinic space group P-1 with a = 7.9061(5) Å, b = 12.412(1) Å, c = 13.7005(8) Å, α = 105.021(6)°, β = 106.744(5)°, γ = 91.749(5)°, and Z = 2 molecules per unit cell. Also, we have found π-π interactions and classic and non-classic H-bonds in the crystal structure by using Hirshfeld surface analysis. In the speciation studies, the complex has dissociated in protonated sunitinib and chlorocomplex of copper(II), according to 1HNMR, EPR, UV-vis and conductimetric analysis. Molecular docking of the complex in both, ATP binding site and allosteric site of VEGFR2 have shown no improvement in comparison to the free ligand. Besides, cytotoxicity assay on HepG2 cell line shows similar activity for complex and ligand in the range between 1–25 μM supporting the data obtained from studies in solution.

Synthesis, Crystal Structures, and Molecular Properties of Three Nitro-Substituted Chalcones

Three functionalized chalcones containing combinations of nitro functional groups have been synthesized via Claisen-Schmidt condensation between 2-nitroacetophenone and nitrobenzaldehyde, and the crystal structures obtained ((E)-1,3-bis(2-nitrophenyl)prop-2-en-1-one, 1a, (E)-1-(2-nitrophenyl)-3-(3-nitrophenyl)prop-2-en-1-one, 1b and (E)-1-(2-nitrophenyl)-3-(4-nitrophenyl)prop-2-en-1-one, 1c), C15H10N2O5, are reported. Compounds 1a and 1c crystallized in the triclinic centrosymmetric space group P1¯, whereas compound 1b crystallized in the orthorhombic space group Pbca. The X-ray analysis reveals that structures 1a and 1b exhibits s-trans conformation, whereas structure 1c exists in s-cis conformation, concerning the olefinic double bonds. In addition, the results show that the position of the nitro substituent attached to the aromatic B-ring has a direct effect on the molecular coplanarity of these compounds. The Hirshfeld surface analysis suggests that the non-covalent π-π stacking interactions are the most important contributors for the crystal packing of 1a and 1b. In 1c, the crystal packing is mainly stabilized by weak intermolecular C―H···O interactions due to the planar nature of the molecule.

Copper(II) complexes of 1,3-dimethyl-5-(4′/3′-pyridylazo)-6-aminouracil: Structures, redox, magnetic and protein binding properties

Two new monomeric copper(II) complexes based on 1,3-dimethyl-5-(4′/3′-pyridylazo)-6-aminouracil (HL1: 4′-pyridylazo, complex 1: cis-CuIIL12.MeOH; HL2: 3′-pyridylazo, complex 2: cis-CuIIL12.H2O) were synthesized, characterized and investigated for redox, magnetic and protein-binding properties. The complex 1 is in monoclinic space group C2/c, Z = 4 whereas the complex 2 is in triclinic space group P-1, Z = 2. The complexes hold similar structure in solid and solution state as could be infered from the EPR spectra of 1 having well-resolved hyperfine features, g|| > g┴ > ge (g|| =2.20 and g┴ =2.05). The E½ values for oxidative response of Cu(III)/Cu(II) couple are 1.030 V (ΔE = 133 mV) for 1 and 0.982 V (ΔE = 128 mV) for 2, indicating high redox stability of Cu(II) ions in the complex environment. Direct current (DC) variable-temperature magnetic susceptibility measurements on polycrystalline sample of 1 were carried out in the temperature range 1.8-300 K. The magnetic behavior indicates a weak antiferromagnetic interaction between Cu(II) ions in the crystal lattice below 25 K. The study of Bovin Serum Albumin (BSA)-complex interactions reveals that the BSA binds the complexes through the sites of tryptophan residues in 1:1 manner (n = 0.9007 & KA = 1.482 × 104M−1 for 1 and 0.7433 & KA =2.394×103M−1 for 2). Thus, the developed complexes could be treated as muti-functional materials.

Treatment and Nursing Activities of Cu(II)-Based Coordination Polymers on Obstructive Jaundice in Liver Cancer by Regulating Farnesoid X Receptor and Wingless Int1–Catenin Activity

Two novel coordination polymers, namely, [Cu3(qptc)2(H2O)3]·3.5H2O·3Me2NH (1) together with [Cu3(qptc)2(H2O)4]·5H2O (2) (H4qptc is 1,1′:4′,1″:4″,1‴-quaterphenyl-2,4,2″,4″-tetracarboxylic acid), were produced under a hydrothermally condition using the rigid aromatic multicarboxylic acid ligand. Structural analysis results indicated that compound 1 exists in a triclinic space group of P-1 and displays a 4,8-linked 3-D open structure containing the trinuclear nickel Cu3 secondary building units (SBUs), which exists in scu topology with (44 · 62) and (416 · 612) point symbols. And the complex 2 exists in a monoclinic space group of C2/c and displays a 3-D structure involving Cu3 SBUs, which exists in flu topology with (46) and (412 · 612 · 84) point symbols. Moreover, the novel complexes’ bio-activities against obstructive jaundice in liver cancer was investigated, and the specific mechanism was discussed. The expression of the bile acid receptor, farnesoid X receptor, on liver cancer cells was tested by Western blot analysis. Wnt–catenin activity activation in liver cancer cells was tested through exploiting RT-PCR.

Synthesis, X-ray crystal structure, Hirshfeld surface analysis, DFT, AIM, ELF, RDG and molecular docking studies of bis[4-(dimethylamino)pyridinium]di-µ-chlorido-bis[dichloridomercurate(II)

Bis[4-(dimethylamino)pyridinium]di-µ-chlorido-bis[dichloridomercurate(II)] has been achieved from a mixture of mercury(II) chloride in water with an aqueous HCl solution containing 4-dimethylaminopyridine by the slow evaporation technique. The structure of this compound has been determined by single-crystal X-ray diffraction. This compound crystallizes in the triclinic space group P with the following lattice parameters: a = 7.5505(7) Å, b = 11.8684(12), c = 13.4777(12) Å, α = 82.836(3), β = 76.516(3), γ = 76.355(3) Å, Z = 2 and V = 1138.22(19) Å3. The structure of the compound can be described as organic-inorganic layers stacked along the b and c-axes which are connected by weak N-H···Cl and C-H···Cl hydrogen bonds forming a three-dimensional network. The IR spectra confirmed the presence of organic cations and the thermal stability of the compound was measured by thermal analysis DSC/TG. Hirshfeld surface analysis and the associated two-dimensional fingerprint plots were used to explore and quantify the intermolecular interactions in the crystal. The geometrical optimization, electronic, topological and biological properties of the compound were theoretically studied using DFT. The HOMO/LUMO analysis was used to determine the charge transfer within the structure. Good consistency was found between the calculated results and the experimental structure and IR spectra. Furthermore, thermodynamic functions for the compound revealed significant evolution with temperature and the potential biological activities were investigated by using molecular docking analysis.

A novel rare-earth luminescent coordination polymer showing potential semiconductor characteristic constructed by anthracene-based dicarboxylic acid ligand (H2L)

• A new member of rare-earth coordination polymer based on H 2 L was successfully synthesized using a solvothermal method. • The crystal structure, morphology feature and thermostability of the obtained La-CP were systematically characterized and analyzed by a series of measurement techniques. • La-CP exhibited a yellow fluorescence emission band with a QY of 1.81%. • Its semiconductor characteristic was confirmed by the optical band gaps from DRS data as well as the electronic structure calculation. In this study, one new rare-earth lanthanum(Ⅲ) metal-organic coordination polymer {[La(L) 1.5 (H 2 O)(DMF)]∙DMF} n (H 2 L = 4,4’-(diethynylanthracene-9,10-diyl) dibenzoic acid) labeled as La-CP was successfully constructed via a solvothermal process. Structure analysis of the obtained La-CP revealed that it crystallized in the triclinic space group P -1, in which each La 3+ ion was coordinated to eight oxygen atoms to form a distorted square antiprism geometry. It was important to observe π-π stacking between adjacent ligand moieties of La-CP with face-to-face distances of 3.385 and 3.447 Å, endowing charge carriers with the possibility of through-space transport. The optical band gap of 2.23 eV evaluated from the UV-vis diffuse reflectance spectrum, coupled with electronic band structure calculation, provided reliable evidence of its potential semiconductor characteristic. In addition, La-CP exhibited a yellow fluorescence emission and a comparable quantum yield of 1.81% to that of free ligand H 2 L in terms of its optical properties. This work not only expands the list of rare-earth lanthanide coordination polymers but also offers useful guidance for materials design and related properties modulation of coordination polymers to some extent.

Tin(II) Ureide Complexes: Synthesis, Structural Chemistry, and Evaluation as SnO Precursors

In an attempt to tailor precursors for application in the deposition of phase pure SnO, we have evaluated a series of tin (1-6) ureide complexes. The complexes were successfully synthesized by employing N,N'-trialkyl-functionalized ureide ligands, in which features such as stability, volatility, and decomposition could be modified with variation of the substituents on the ureide ligand in an attempt to find the complex with the ideal electronic, steric, or coordinative properties, which determine the fate of the final products. The tin(II) ureide complexes 1-6 were synthesized by direct reaction [Sn{NMe2}2] with aryl and alkyl isocyanates in a 1:2 molar ratio. All the complexes were characterized by NMR spectroscopy as well as elemental analysis and, where applicable, thermogravimetric (TG) analysis. The single-crystal X-ray diffraction studies of 2, 3, 4, and 6 revealed that the complexes crystallize in the monoclinic space group P2(1)/n (2 and 4) or in the triclinic space group P-1 (3 and 6) as monomers. Reaction with phenyl isocyanate results in the formation of the bimetallic species 5, which crystallizes in the triclinic space group P-1, a consequence of incomplete insertion into the Sn-NMe2 bonds, versus mesityl isocyanate, which produces a monomeric double insertion product, 6, under the same conditions, indicating a difference in reactivity between phenyl isocyanate and mesityl isocyanate with respect to insertion into Sn-NMe2 bonds. The metal centers in these complexes are all four-coordinate, displaying either distorted trigonal bipyramidal or trigonal bipyramidal geometries. The steric influence of the imido-ligand substituent has a clear effect on the coordination mode of the ureide ligands, with complexes 2 and 6, which contain the cyclohexyl and mesityl ligands, displaying κ2-O,N coordination modes, whereas κ2-N,N' coordination modes are observed for the sterically bulkier tert-butyl and adamantyl derivatives, 3 and 4. The thermogravimetric analysis of the complexes 3 and 4 exhibited excellent physicochemical properties with clean single-step curves and low residual masses in their TG analyses suggesting their potential utility of these systems as MOCVD and ALD precursors.

Synthesis and crystal structure of the lanthanum cyanurate complex La[H2N3C3O3]3 · 8.5 H2O

Abstract Single crystals of La[H2N3C3O3]3 · 8.5 H2O were obtained from stoichiometric amounts of as-precipitated La(OH)3 with cyanuric acid (CYA) [H3N3C3O3]3 in a boiling aqueous solution, followed by slow cooling and evaporation of water under ambient conditions. According to the X-ray structure analysis of the colorless and transparent crystals, La[H2N3C3O3]3 · 8.5 H2O adopts the triclinic space group P1 (no. 1) and exhibits the unit-cell parameters a = 987.24(7), b = 1110.97(8), c = 1179.81(9) pm, α = 113.716(2), β = 97.053(2), γ = 101.502(2)° for Z = 2. The CYA is singly deprotonated to give monoanions [H2N3C3O3]– which are O,N-coordinated to the La3+ cations. These dihdrogencyanurate anions are assembled in ribbons with two crystallographically different La3+ cations coordinating to either one or two different ligands, respectively. The coordination sphere of the La3+ cations is comprised of water molecules, and interstitial water molecules fill the dead volume of the crystals. The anionic ribbons are stacked to maximize the contact between the six-membered rings, showing distances of about 330 pm.

Molecular structural, vibrational assignments, electronic structure and DFT calculations, and molecular docking of N-benzylideneaniline and N-salicylidene-o-aminoaphenol Schiff bases

Two Schiff bases N-benzylidenaniline (BZA) and N-salicylidene-o-aminoaphenol (SAP) were synthesized. Structure of SAP was determined by Xrd analysis. It was found that SAP crystallized with two molecules perpendicular to each other and connected by inter- and intramolecular hydrogen bonding. The compound crystallized in the triclinic space group P-1 with a Z value of 2. Geometry optimization of BZA and SAP were investigated by DFT (Gaussian 09W) and REDF2 (Spartan 14). The optimized structure of SAP is consistent with that obtained from the Xrd analysis. Quantum global reactivity descriptors of the two compounds were calculated using the HOMO and LUMO energy values. IR, Raman and theoretical calculations (DFT method) of the vibrational modes of the two derivatives in the wavenumber range 1700–200 cm−1 using Gaussian 09W and Spartan 14 software were carried out. Molecular docking of the two reported compounds with either B-DNA (1ZEW) or protein (4MZI) were studied.

Nitroisatin dithiocarbazate: Synthesis, structural characterization, DFT, and docking studies

The reaction between 5-nitroisatin with S-benzyl dithiocarbazate affords a new isatindithio carbazate so-called NO2Isadtc (Benzyl 2-(5-nitro-2-oxoindolin-3-ylidene)hydrazinecarbodi thioate) which was characterized by means of 1H NMR, FT-IR, UV-visible and single crystal X-ray diffraction - Crystal data for C16H12N4O3S2 (M =372.42 g/mol): triclinic space group P-1, (n°. 02), a = 6.640 Å, b = 8.256 Å, c = 15.908 Å, V = 849.6 Å3, Z = 2, T = 293 K, μ(MoKα) = 0.337 mm-1, Dcalc = 1.456 g/cm3, 27515 reflections measured (2.499° ≤ 2Θ ≤ 26.524°), 3518 unique (Rint = 0.0533, Rsigma =0.0222) which were used in all calculations. The final R1 was 0.0367 (I &gt; 2σ(I)) and wR2 was 0.1045 (all data). Computational methods were applied to NO2Isadtc and its nonsubstituted parent compound Isadtc for structure optimization, electronic distribution, and infrared calculations using B3LYP functional with 6-31G(d,p) basis set in ethanol as a polarizable continuum model. Furthermore, docking studies using human thioredoxin reductase 1 (TrxR) as enzyme target also were performed using NO2Isadtc and the optimized structure of Isadtc. The results demonstrated that both NO2Isadtc and Isadtc may act as inhibitors of TrxR, having different interactions detected, highlighting the contact between the NO2 group and the S111 at the helix which is found for NO2Isadtc.

Investigation of stable solid diazonium salt by molecular structure, Hirshfeld surface analysis, optical and electrochemical studies, and applications.

The title compound is a new pyrazolone derivative which was synthesized starting from p-sulphophenyl-3-methyl-5-pyrazolone (1) by nitrosation at low temperature to afford the corresponding p-sulphophenyl-3-methyl-4-nitroso-5-pyrazolone which can exist both in nitroso (2a) and oxime tautomeric forms (2b). Reduction of the latter using zinc with hydrochloric acid furnished the 4-amino-p-sulphophenyl-3-methyl-5-pyrazolone (3). The diazotization of (3) under careful control of temperature and pH afforded the p-sulphophenyl-3-methyl-5-pyrazolone diazonium salt (4) which was re-crystallized from acidified ethanol to afford crystal suitable for X-ray studies. UV-visible spectrum and cyclic voltammetric studies were also carried out indicating λmax at 420nm and HOMO-LUMMO energy gap was also calculated (Eg) of 2.95eV. The molecular and crystal structures of the compound were clarified by single crystal X-ray diffraction indicated that it crystallizes as the sodium salt in the triclinic space group P -1, with the 4-azo-pyrazolone and the sulphophenyl groups being nearly coplanar. To get an insight to the intermolecular interactions in the crystal, a Hirshfeld surface analysis was also carried out.