Crystal Structure Of Compound Research Articles

Crystal structures, Hirshfeld surface analysis, thermogravimetric, and spectroscopic properties of three Zn(Ⅱ) complexes bridged by 4,4′-bipy with organic sulfonate anions as counterions

Three Zn(Ⅱ) sulfonate compounds: {[Zn3(Ac)4(4,4′-bipy)4]·2(3-pySO3)·H2O}n (1), {[Zn(4,4′-bipy)(H2O)4]·2(Me-phSO3)}n (2), and {[Zn(4,4′-bipy)(H2O)4]·2(NH2-phSO3)}n (3), were synthesized through solvent diffusion method at room temperature (3-pySO3H = Pyridine-3-Sulfonic acid; Me-phSO3H = P-Toluene Sulfonic acid; NH2-phSO3H = Sulfanilic acid). Single-crystal X-ray diffractions reveal that the crystal structure of compound 1 contains a 2D cationic layer with pseudo-square grid motifs formed by trinuclear Zn(II) units which connected by 4,4′-bipy ligands. Water molecule forms hydrogen bonds with free 3-PySO3− anions which are located in the voids of the cationic grids. Compounds 2 and 3 show isostructural 1D [Zn(4,4′-bipy)(H2O)4]2+ chains with sulfonate anions connected to the chain via hydrogen bonding. The weak interactions in the structures of the three compounds have been assessed using Hirshfeld surface analyses and 2D fingerprint plots. The Hirshfeld surface shows that the most important contributions for the crystal packing are from H···H and H··O/O··H interactions, which indicate dominant van der Waals interactions. In addition, the compounds were investigated by powder X-ray diffraction (PXRD), elemental analyses, UV–vis, FT-IR, solid-state fluorescence spectroscopy, and thermal analyses (TG-DSC).

Complexity of the KNa2ZrF7, KNa2HfF7, and KNa2(Hf,Zr)F7 compounds

New mixed-cation fluorides KNa2HfF7 (Pmn21, a = 8.213(2) Å, b = 6.126(2) Å, c = 5.979(2) Å, Z = 2) and KNa2(Hf,Zr)F7 (refined composition KNa2Hf0.44(1)Zr0.56(1)F7; Pmn21, a = 8.2210(8) Å, b = 6.1288(6) Å, c = 5.979(1) Å, Z = 2) together with isostructural KNa2ZrF7 (Pmn21, a = 8.221(2) Å, b = 6.118(2) Å, c = 5.994(2) Å, Z = 2) have been synthesised in aqueous solutions and structurally characterised at room temperature by powder and single-crystal X-ray diffraction. The solid-solid phase transformations have been revealed during the differential scanning calorimetry experiments and further confirmed by temperature-dependent X-ray powder diffraction. It has been found that mixed-cation phases KNa2ZrF7, KNa2HfF7 and KNa2(Hf,Zr)F7 undergo irreversible phase transformations, which can be explained by their decomposition over 673 K. XPS analysis confirmed the presence of exclusively terminated fluorines around the transition metals and the absence of oxygen impurities in the crystal structures of compounds.

Study on the anti-cancer activity of α-phenethylamine ferrocenecarboxylic acid co-crystals.

Ferrocene derivatives show a wide range of pharmacological activities in the medical field, especially in the anti-tumor field, and can be used as candidate drugs or lead compounds for the treatment of tumors and other diseases. And α-phenethylamine is an important intermediate for the preparation of fine chemical products. (R)-(+)-1-Phenethylamine ferrocenecarboxylic acid/(S)-(-)-1-phenethylamine ferrocenecarboxylic acid were prepared, named compounds 1 and 2, respectively. Single crystal X-ray diffraction showed that compounds 1 and 2 crystallized in the orthorhombic system space group P21 21 21 , and the crystal structures of compounds 1 and 2 exhibited mirror symmetry. The inhibitory effect of two compounds on SW480, MDA-MB-231, and H1299 cells was tested by MTT colorimetry. The IC50 values of the compounds against cancer cells were also calculated. The anti-cancer effect was more pronounced for compounds in the S-configuration. Compound 2 made the wild-type cancer cells undergo apoptosis, thus preventing cancer; it also had the function of helping the cell gene repair defects.

5‐Aryl Substituted 2‐(2‐Methoxyphenyl)benzoxazoles with Large Stokes Shifts: Synthesis, Crystal Structures and Optical Properties

Abstract2‐(2‐methoxyphenyl)benzoxazole (MBO) displays similar photophysical properties to 2‐(2‐hydroxyphenyl)benzoxazole (HBO), but it lacks the large Stokes shifts necessary for fluorescence microscopy applications. In this paper, we report the 5‐substitution of MBO with aryl groups to produce 2‐(4‐methoxy‐[1,1’‐biphenyl]‐3‐yl)benzoxazoles (MBBOs) with large Stokes shifts. The synthesis of MBBOs 6–15 was accomplished in moderate to good yields by microwave‐assisted Sonogashira cross couplings. Crystal structures for compounds 6–9 and 15 are provided. MBBOs 6–10, 12, and 14 displayed considerably blue‐shifted absorption maxima and slight bathochromic shifts of their fluorescence maxima relative to the unsubstituted MBO.

New cyclotriphosphazenes with butylated oxyanisole motif; synthesis, characterization and biological properties

In the present work, new cyclotriphosphazene derivatives containing butylated oxyanisole (BA) group (3, 4a/b, 6a/b, 7, 11a/b and 12) were synthesized and characterized with using elemental analysis, mass, and NMR (1H and 31P) spectroscopic techniques in detailed. The molecular and crystal structure of compound 3 was also determined by single-crystal X-ray crystallography. The antimicrobial activities of the compounds (3, 7 and 12) were evaluated against strains of Staphylococcus aureus ATCC 29213 as Gram positive cocci, Bacillus cereus DSMZ 4312 as Gram positive bacilli, Escherichia coli ATCC 8739 as Gram negative bacilli, and Candida albicans ATCC 10231, a dimorphic yeast species representing fungi as well as antioxidant activities of these compounds. In the biological and antioxidant activity tests carried out, compound 3 stood out with both antibacterial and antioxidant activity compared to other compounds.

Synthesis of a novel triptycene-derived protected dithiolene ligand precursor for tri-nuclear mixed ligand metal dithiolene complexes

Abstract We synthesized a novel triptycene analogue, 3,3′,3″,3″′,3″″,3″″′-((triptycene-2,3,6,7,14,15-hexayl)hexakis(sulfanediyl))hexapropanenitrile (3), which served as a valuable precursor for the triptycene-derived tris-bidentate bridging dithiolene ligand, triptycene-2,3,6,7,14,15-hexakis(thiolate) (4), following the removal of the cyanoethyl moiety protection group. We determined the molecular and crystal structures of compound 3 and confirmed its capacity to yield compound 4. By reacting 3 with [NiCl2(BPY)] and [PtCl2(BPY)] (BPY: 2,2′-bipyridine) in methanol, we obtained crude samples of [Ni3(4)(BPY)3] and [Pt3(4)(BPY)3], respectively.

STRUCTURAL INVESTIGATION AND HIRSHFELD SURFACE ANALYSIS OF TWO [ONO]-TYPE SCHIFF BASES

Two novel [ONO]-type tridentate Schiff base compounds namely (E)-2-(((2-hydroxyphenyl)imino)methyl)-4,5-dimethoxyphenol, C15H15NO4 (1), and (E)-2-(((5-chloro-2-hydroxyphenyl)imino)methyl)-4,5-dimethoxyphenol, C15H14ClNO4 (2) were synthesized. These compounds were characterized using various spectroscopic techniques, including single crystal X-ray diffraction (XRD), infrared (IR), proton nuclear magnetic resonance (1H NMR), carbon-13 nuclear magnetic resonance (13C NMR), and UV-Vis spectroscopy. The X-ray crystallographic analysis revealed that both compounds 1 and 2 contain two independent molecules within the asymmetric unit. Compound 1 crystallizes in the orthorhombic system with the Pna21 space group, while compound 2 crystallizes in the monoclinic system with the P21/c space group. An important feature observed in the crystal structure of compound 1 is the presence of O–H···N and O–H···O hydrogen bonds. In compound 2, the hydrogen bonding interactions involve C–H···O, O–H···O and O–H···N. Additionally, both compounds exhibit C–H···π interactions. To further understand the bonding interactions in compounds 1 and 2, Hirshfeld surface analyses and 2D fingerprint graphs were performed. The results indicate that the Hirshfeld surfaces are predominantly influenced by H⋯H, O⋯H, and C⋯H contacts.

Two bimetallic compounds with attractive structures and properties

Two new bimetallic lanthanide-mercury isonicotinic acid compounds were successfully synthesized through classical hydrothermal reactions using DyCl3·6H2O or LuCl3·6H2O, HgCl2, isonicotinic acid, and distilled water. The resulting compounds, [Dy2(IA)6(H2O)2(H3O)2(Hg2Cl5)2]n(3nHgCl2) (1; IA refers to isonicotinic acid anions) and [Lu(HIA)(IA)2(H2O)2Hg2Cl5]2n[3n(HgCl2)]·6nH2O (2; HIA refers to isonicotinic acid), exhibit intriguing crystal structures and photophysical properties. The crystal structures of compounds 1 and 2 were determined through single crystal X-ray diffraction, revealing their two-dimensional (2D) nature. Compound 1 displays upconversion yellow photoluminescence, attributed to the 4F9/2 → 6H13/2 electronic transition of the trivalent dysprosium ion. In contrast, compound 2 exhibits blue photoluminescent emission. The Commission Internationale de I'Éclairage (CIE) chromaticity coordinates of (0.4874, 0.5115) for 1 and (0.1225, 0.0678) for 2. The correlated color temperatures (CCT) are 2960 K and 5503 K for compounds 1 and 2, respectively. Furthermore, the semiconductor band gaps for compounds 1 and 2, determined by solid-state diffuse reflectance experiments, are 2.92 eV and 4.75 eV, respectively. Additional insights into their thermal stability are provided via thermogravimetric analysis (TG) results.

Enhanced Method for the Synthesis and Comprehensive Characterization of 1-(4-Phenylquinolin-2-yl)propan-1-one.

We present an enhanced method for synthesizing a novel compound, 1-(4-phenylquinolin-2-yl)propan-1-one (3), through the solvent-free Friedländer quinoline synthesis using poly(phosphoric acid) as an assisting agent. The crystal structure of compound 3 is analyzed using FT-IR, and the chemical shifts of its 1H- and 13C NMR spectra are measured and calculated using B3LYP/6-311G(d,p), CAM-B3LYP/6-311G(d,p), and M06-2X/6-311G(d,p) basis sets in the gas phase. Additionally, the optimized geometry of quinoline 3 is compared with experimental X-ray diffraction values. Through density functional theory calculations, we explore various aspects of the compound's properties, including noncovalent interactions, Hirshfeld surface analysis, nonlinear optical properties, thermodynamic properties, molecular electrostatic potential, and frontier molecular orbitals. These investigations reveal chemically active sites within this quinoline derivative that contribute to its chemical reactivity.

Supramolecular assembly involving weak hydrogen bonds, anti-parallel π···π stacking and O···C tetrel bonding interactions and LOX studies in a 1H-pyrazol-1-yl)thiazole-4-carboxylate derivative: An experimental and theoretical study

In this manuscript, we synthesized a novel ethyl 2-(5-(4-methoxyphenyl)-3-phenyl-4,5-dihydro-1H-pyrazol-1-yl)thiazole-4-carboxylate (5) from the reaction acetophenone with 3-methoxybenzaldehyde in basic condition to afford the chalcone derivative (3) which has ability to cyclized with thiosemicarbazide to afford the corresponding dihydro-1H-pyrazole-1-carbothioamide (4). Compound 4 easily reacts with ethyl-3‑bromo-2-oxopropanoate to give the ethyl-2-(5-(3-methoxyphenyl)-3-phenyl-4,5-dihydro-1H-pyrazol-1-yl)thiazole-4-carboxylate (5). The structure of the synthesized compound was confirmed through spectral analysis (FT-IR, 1HNMR, 13CNMR). Moreover, the crystal structure of compound (5) has been solved using single-crystal X-ray diffraction measurements. These results indicate that 5 crystallizes in the monoclinic crystal system in the P21/n space group. The solid-state structure is mainly stabilized by a combination of intermolecular interactions such as weak hydrogen bonds, CH···π, π···π stacking and O···C tetrel bonding interactions involving the O-atom of the ester group and the C-atom of the methoxy moiety. In order to confirm the presence of the mentioned intermolecular contacts, we have performed Hirshfeld surface analysis and their associated two-dimensional fingerprint plots. In addition, the strength and nature of the intermolecular interactions have been evaluated by using different computational tools including QTAIM and NCIplot index analysis. Molecular docking analysis was performed with both the enantiomers of pyrazolyl thiazole carboxylate and it was found that 1R bounds deeply into the pocket than 1S, furthermore 1R and indomethacin forms hydrogen bonds while 1S do not. The Molecular results are in good agreement with the experimental data

Determination of bond length and some crystal structures of compounds containing the dioxygenyl cation [O2]+

Determination of bond length and some crystal structures of compounds containing the dioxygenyl cation [O₂]⁺

Design, Synthesis and Biological Evaluation of Novel Pyrazolotriazolopyrimidine Derivatives as Potential Anticancer Agents

Three novel pyrazolo-[4,3-e][1,2,4]triazolopyrimidine derivatives (1, 2, and 3) were designed, synthesized, and evaluated for their in vitro biological activity. All three compounds exhibited different levels of cytotoxicity against cervical and breast cancer cell lines. However, compound 1 showed the best antiproliferative activity against all tested tumor cell lines, including HCC1937 and HeLa cells, which express high levels of wild-type epidermal growth factor receptor (EGFR). Western blot analyses demonstrated that compound 1 inhibited the activation of EGFR, protein kinase B (Akt), and extracellular signal-regulated kinase (Erk)1/2 in breast and cervical cancer cells at concentrations of 7 and 11 µM, respectively. The results from docking experiments with EGFR suggested the binding of compound 1 at the ATP binding site of EGFR. Furthermore, the crystal structure of compound 3 (7-(4-bromophenyl)-9-(pyridin-4-yl)-7H-pyrazolo[4,3-e][1,2,4]triazolo[1,5-c]pyrimidine) was determined by single crystal X-ray analysis. Our work represents a promising starting point for the development of a new series of compounds targeting EGFR.

Structure Guiding Supramolecular Assemblies in Metal-Organic Multi-Component Compounds of Mn(II): Experimental and Theoretical Studies

Two multi-component coordination compounds of Mn(II), viz. [Mn(H2O)6](2-Mepy)2(4-NO2bz)2·2H2O (1) and [Mn(H2O)6][Mn(2,3-PDCH)3]2 (2) (where, 2-Mepy = 2-methylpyridine, 4-NO2bz = 4-nitrobenzoate, 2,3-PDC = 2,3-pyridinedicarboxylate), have been synthesized and characterized using elemental, spectroscopic (FT-IR and electronic), TGA and single-crystal X-ray diffraction analyses. Complex 1 is a co-crystal hydrate of Mn(II) involving uncoordinated 2-Mepy, 4-NO2bz and water molecules; while compound 2 is a multi-component molecular complex salt of Mn(II) comprising cationic [Mn(H2O)6]2+ and anionic [Mn(2,3-PDCH)3]−complex moieties. The uncoordinated 2-Mepy and 4-NO2bz moieties of 1 are involved in lone-pair (l.p)-π and C–H⋯π interactions which stabilize the layered assembly of the compound. The crystal structure of compound 2 has been previously reported. However, we have explored the unusual enclathration of complex cationic moieties within the supramolecular host cavities formed by the molecular assembly of complex anionic moieties. The supramolecular assemblies obtained in the crystal structure have been further studied theoretically using DFT calculations, quantum theory of atoms-in-molecules (QTAIM) and non-covalent interaction plot (NCI plot) computational tools. Theoretical studies reveal that the combination of π-staking interactions (l.p-π, π-π and C–H···π) have more structure-guiding roles compared to the H-bonds. The large binding energy of π-stacking interactions in 2 is due to the antiparallel orientation of aromatic rings and their coordination to the metal centers, thereby increasing the contribution of the dipole–dipole interactions.

Relativistic two-component time dependent density functional studies and Hirshfeld surface analysis of halogenated arylidenehydrazinylthiazole derivatives

Crystal structures of compounds 2-(2-chlorobenzylidene)hydrazinylthiazole (2a) 2-(2-bromobenzylidene)hydrazineylthiazole (2b) were analyzed with single crystal XRD. Both compounds possess Monoclinic crystal system and P21/n space group. Intermolecular interactions in single crystals were studied with Hirshfeld surface analysis (HSA). Electronic spectrum of 2a and 2b has been studied with two-component relativistic sf-X2C-S-TD-DFT approach and induction of spin–orbit couplings in organic skeleton by bromine and chlorine atoms has been explored. Magnitude of spin–orbit couplings in 2b at B3LYP-D3/x2c-TZVPPall level of theory promises its use as triplet sensitizer in photodynamic therapy and solar light-based fuel cells.

Proton-transfer salts of diphenylphosphinic acid with substituted 2-aminopyridine: crystal structure, spectroscopic and DFT studies.

Three proton-transfer salts of diphenylphosphinic acid (DPPA) with 2-amino-5-(X)-pyridine (AMPY, X= Cl, CN or CH3), namely, 2-amino-5-chloropyridinium diphenylphosphinate, C5H6ClN2+·C12H10O2P- (1, X= Cl), 2-amino-5-cyanopyridinium diphenylphosphinate, C6H6N3+·C12H10O2P- (2, X= CN), and 2-amino-5-methylpyridinium diphenylphosphinate, C6H9N2+·C12H10O2P- (3, X= CH3), have been synthesized and characterized by FT-IR and 1H NMR spectroscopy, and X-ray crystallography. The crystal structures of compounds 1-3 were determined in the space group P\overline{1} for 1 and 2, and C2/c for 3. All three compounds contain N-H...O hydrogen-bonding interactions due to proton transfer from the O=P-OH group of DPPA as donor to the pyridine N atom of AMPY as acceptor. The proton transfer of compounds 1-3 was also verified by 1H NMR and FT-IR spectroscopy. The stoichiometry of all three proton-transfer salts was determined to be 1:1 and the Benesi-Hildebrand equation was applied to determine the formation constant (KCT) and the molar extinction coefficient (ϵCT) in each case. Theoretical density functional theory (DFT) calculations were performed to investigate the optimized geometries, the molecular electrostatic potentials (MEP) and the highest occupied molecular orbitals (HOMO) and lowest unoccupied molecular orbitals (LUMO) of all three proton-transfer salts. The results showed good agreement between the experimental data and the DFT computational analysis.

Molecular modeling of 3‑chloro-3-phenylquinoline-2,4‑dione, crystal structure and cytotoxic activity for developments in a potential new drug

3-Chloro-3-phenylquinoline-2,4‑dione (2) is an intermediate product in the synthesis of 1-phenyl-2H,6H-imidazo[1,5-c]quinazoline-3,5‑dione (PhIC). PhIC, its intermediates, and derivatives belong to quinolines or quinazolines - heterocyclic compounds with biological activity. However, only compound 2 contains nitrogen and chlorine atoms in the structure and has the most probability of having anticancer properties. In this work, the crystal structure of compound 2 was investigated by X-Ray crystallography and the molecular modeling was made by DFT methods. The cytotoxic activities of 3‑hydroxy-3-phenylquinoline-2,4‑dione, 3‑chloro-3-phenylquinoline-2,4‑dione and 3-amino-3-phenylquinoline-2,4‑dione, respectively compounds 1, 2, and 3 (with quinoline ring), and 2-(2-hydroxypropyl)-6-H-imidazo[1,5-c]quinazoline-3,5‑dione – compound 4 (with imidazoquinoline ring) against the cell lines: mouse fibroblast L929 and human gastric adenocarcinoma cells (AGS) were tested. The crystal structure of compound 2 was established and the intermolecular interactions were described. Only one pair of enantiomers was found in the unit cell, whereas molecular modeling showed two pairs of enantiomers AA’ and BB’ are stable. The enantiomer pairs can transform into each other to better spatial packing in the crystal. Compounds 2 and 4 show high cytotoxic activity against the L929 line at the concentration range 0.05– 50 µg/ml, and AGS cells (0.1– 50 µg/ml). When bound to an appropriate carrier to deliver the compound directly to neoplastic cells, their use as anti-neoplastic substances cannot be excluded.

Features of the magnetization in ceramics Bi0.86Sm0.14Fe1-xMnxO3 in the rhombohedral - orthorhombic morphotropic phase boundary

Crystal structure of the ceramic compounds Bi0.86Sm0.14Fe1-xMnxO3 prepared by solid state reaction method was studied using X-ray diffraction, scanning electron microscopy and Raman spectroscopy; magnetometry measurements were performed to study magnetic properties and to investigate a correlation between the magnetic and crystal structures of the compounds. The compounds with 0 = x ≤ 0.1 are characterized by the coexistence of the polar rhombohedral and the antipolar orthorhombic phases, an increase of Mn doping causes a stabilization of the orthorhombic phase. Room temperature magnetization data show a gradual reduction of the remanent magnetization with an increase of Mn concentration, while a decrease of temperature causes a nontrivial reduction of remanent magnetization which is determined by a transformation of the non-collinear antiferromagnetic structure towards the collinear antiferromagnetic structure. The magnetic state of the compounds notably depends on the phase ratio of the coexisting structural phases and consists of the antiferromagnetic phases associated with the respective rhombohedral and the orthorhombic phases as well as the ferromagnetic component associated with the phase boundary spins. An evolution of the mentioned magnetic subsystems is discussed as a function of the chemical composition and temperature.

Interaction of Components and Crystal Structure of Compounds in the Pr–Cu–Ge System

Interaction of Components and Crystal Structure of Compounds in the Pr–Cu–Ge System

Facile synthesis of three low-sensitivity energetic materials based on pyrimidine backbones

Using commercially available raw materials, novel pyrimidine-based energetic compounds were synthesized, namely N-(7-oxo-6,7-dihydro-[1,2,5]oxadiazolo[3,4-d]pyrimidin-5-yl)nitramide (1), 2,4,6-triamino-5-nitropyrimidin-1-ium nitrate (2), and 4,6-diamino-5-nitro-2-oxo-2,3-dihydropyrimidin-1-ium nitrate (3). They were fully characterized using NMR (1H and 13C), IR spectroscopy, and elemental analysis. The crystal structures of compounds 1 and 3 were determined using single-crystal X-ray diffraction. The decomposition temperatures of compounds 1–3 were measured to be 190.2 ​°C, 156.8 ​°C, and 234.6 ​°C, respectively. Their densities were tested to be 1.84, 1.85 ​g ​cm−3, and 1.81 ​g ​cm−3, respectively. They exhibited desirable insensitive properties, with impact sensitivity ≥15 ​J and friction sensitivity >360 ​N. In addition, the detonation performances of compounds 1–3 were calculated with detonation pressure of 26.9, 29.6 ​GPa, and 26.0 ​GPa, respectively; detonation velocity of 8089, 8644 ​m ​s−1, and 7996 ​m ​s−1, respectively). Simple synthetic processes and high performance make them potential candidates for low-sensitivity energetic materials.

A structural phase transition in La2Ti2O7 at high pressure

High-pressure effects on the crystal structure and vibration spectra of the perovskite-like layered La2Ti2O7 compound were studied using X-ray diffraction and Raman spectroscopy at pressures up to 30 GPa. The crystal structure of the compound was measured by means of a neutron diffraction at room temperature and ambient pressure. At P = 17.3 GPa, phase transition from the initial monoclinic phase of P21 symmetry to the monoclinic phase of P2 symmetry has been observed. The pressure-induced phase transitions in La2Ti2O7 are accompanied by anomalies in the pressure dependences of the unit cell parameters, as well as the vibrational modes. The baric dependences of lattice parameters, unit cell volume and vibration frequencies were obtained; the bulk modules for initial and pressure-induced phases of La2Ti2O7 were calculated.