Crystal Structure Of Compound Research Articles

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

Isomeric Molecular Forms of Pseudo-Binuclear Bismuth(III) Dithiocarbamate [Bi2{S2CN(CH2)6}6]: Preparation, Thermal Behavior, and Structural Effect of Its Solvation with DMSO, [Bi2{S2CN(CH2)6}6]⋅2(CH3)2SO

Bismuth(III) hexamethylenedithiocarbamate (HmDtc) [Bi2{S2CN(CH2)6}6] (I) and its solvated with dimethyl sulfoxide form [Bi2(S2CNHm)6]⋅2(CH3)2SO (II) have been obtained. The crystal structure of compound I shows an unusual alternation of two unsymmetrical isomeric pseudo-binuclear [Bi1/1B(HmDtc)3···Bi1A/1C(HmDtc)3] molecules, each of which involves two non-equivalent mononuclear moieties combined by secondary Bi···S bonds. The solvation of complex I leads to the structural unification of isomeric [Bi(HmDtc)3] molecules followed by their self-organization into centrosymmetric pseudo-dimers in the structure of compound II. All HmDtc ligands coordinate in S,S'-anisobidentate mode to form four isomeric (in I) or structurally unique [Bi(HmDtc)3] molecules (in II), whose distorted polyhedra can be approximated by pentagonal pyramid or octahedron. Solvating DMSO molecules are retained in the structure II by C–H···O hydrogen bonds. The analysis of energy dispersive X-ray spectra allowed one to identify the residual matter obtained by thermolysis of the complexes as Bi2S3 with admixture of Bi0.

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.

Synthesis and structural elucidation of cage-shaped phosphonium trisphenolato gallium compounds

The reaction of GaX3 with the phosphorus-centered trisphenol (2-HO-3,5-tBu2-C6H2)3P, 1, affords the cage shaped phosphonium trisphenolates XGa{(2-O-3,5-tBu2-C6H2)3PH} (X = Et, 2; Cl, 3). The new compounds are C3 symmetric and isostructural with the previously reported aluminum analogs EtAl{(2-O-3,5-tBu2-C6H2)3PH}, 5, and ClAl{(2-O-3,5-tBu2-C6H2)3PH}, 6, but display longer M–O bonds due to the lower polarity of the Ga-O bonds. Compounds 2 and 3 were characterized by IR and multinuclear NMR spectrometry and mass spectrometry, and the crystal structure of compound 2 was also determined. No single products were observed in reactions aimed at the alcoholysis of the Ga-Et group in 2 as well as in attempts to abstract the ethide group with the trityl salt [Ph3C][B(C6F5)4] or Me3SiOTf (OTf = OSO2CF3), possibly a result of the lower polarity of Ga-C bonds.

Synthesis, Characterization and Cytotoxic Activity of Organotin(IV) Diisopropyldithiocarbamate Compounds Towards K562 Myeloid Leukaemia Cell Lines

In this work, two organotin(IV) compounds viz. triphenyltin(IV) diisopropyldithiocarbamate (1) and dimethyltin(IV) diisopropyldithio-carbamate (2) were synthesized via in situ method. Both synthesized organotin(IV) complexes were characterized by elemental, FT-IR and 1H, 12C and 119Sn NMR spectroscopies. The single-crystal structure of compound 1 was determined by X-ray single-crystal analysis. The elemental analysis data showed agreement with the suggested formulas of (C6H5)3Sn[S2CN(C3H7)2] (1) and (CH3)2Sn[S2CN(C3H7)2]2 (2). The important infrared absorbance peaks, ν(C=N) and ν(C=S), were detected in the ranges 1477-1474 cm-1 and 1038-997 cm-1 respectively. The chemical shift of carbon in the NCS2 group for compounds 1 and 2 was observed at 196.97 ppm and 198.11 ppm, respectively. The crystal structure of compound 1 showed that it is 5-coordinated and crystallized in a triclinic, P1 space group with the crystal cell parameter: a = 9.7572(1) Å, b = 11.7030(2) Å, c = 11.7602(2)Å, α = 74.419(1)°, β = 80.114(1)°, γ = 67.285(2)° and R = 0.002. The cytotoxicity (IC50) of these two compounds against K562 leukaemia cells was 0.25 μM and 4.3 μM, respectively, as assessed using MTT assay. In conclusion, the study demonstrates that both compounds showed potent cytotoxicity towards the K562 cell line tested, with compound 1 displaying a greater effect.

Cupric coordination compounds with multiple anions: a promising strategy for the regulation of energetic materials.

To seek new high energetic materials, N-methylene-C-bridged nitrogen-rich heterocycle 1-((4,5-diamino-4H-1,2,4-triazol-3-yl)methyl)-1H-1,2,4-triazol-3,5-diamine (DATMTDA) (2) was first synthesized, and two copper coordination compounds ([Cu12(OH)4(ClO4)4(H2O)4(DATMTDA)12](ClO4)16·12H2O (3) and [Cu3(OH)(ClO4)(DATMTDA)3](ClO4)3(NO3) (4)) based on 2 were formed by introducing different anions. These compounds were characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction analysis. The crystal structures of compounds 3 and 4 are similar and crystallize in monoclinic systems with the P21/c space group, while the central copper atoms show different coordination behaviors. However, the structure of compounds 3 and 4 is analogous to a three dimensional structure owing to the O atom of OH-, forming coordinate bonds with three copper cations. The NBO charge of 2 was calculated using density functional theory to understand its coordination modes. The Hirshfeld surface calculation reveals that 3 and 4 have strong intermolecular interactions. The thermal decomposition processes, non-isothermal kinetics, and enthalpies of formation and sensitivities of these compounds were investigated. By introducing one NO3- of compound 4 to replace one ClO4- in compound 3, compound 4 shows lower density and lower decomposition peak temperature but lower sensitivity and a higher formation enthalpy than compound 3. The complex 4 possesses an outstanding catalytic effect for the decomposition of AP than that of complex 3. The results illustrate the possibility of introducing various anions into energetic coordination compounds for the regulation of energetic materials.

Giant low-field magnetocaloric effect in hexagonal Eu3B2O6 compound

A modified solid-phase reaction method was used to synthesize the polycrystalline Eu3B2O6-as a novel cryogenic magnetocaloric material. In addition, investigations into the magnetocaloric effect (MCE), magnetic properties and crystal structure of compound have been precisely completed. The results indicate that the compound undergoes a second-order magnetic-phase transition from ferromagnetic to paramagnetic at 8 K and has a hexagonal structure that belongs to the R-3c space group. Meanwhile, the MCE was evaluated by using magnetic entropy change (-ΔSM), temperature averaged entropy change (TEC) as well as the refrigeration capacity (RC) for Eu3B2O6. Under the field change from 0 to 5 T, the maximal values of -ΔSM and TEC (5) are 38.6 and 35.7 J kg−1 K−1, respectively, while the corresponding RC reaches 435.9 J kg−1. The giant low-field MCE facilitates device miniaturization and cost reduction, making Eu3B2O6 compound a promising candidate for cryogenic magnetic refrigeration.

Diverse coordination architectures based on a flexible multidentate carboxylate ligand and N-donor linkers: Synthesis, structure, supramolecular chemistry and related properties

Three new metal–organic framework (MOF) containing compounds, namely {Cu2(tci)(btx)0.5(µ3-OH)(H2O)}n (1), {Cu1.5(tci)(biip)}n (2), {Co1.5(tci)(biip)}n (3) [H3tci = tris(2-carboxyethyl)isocyanurate, btx = 1,4-bis(triazol-1-yl-methyl)benzene, biip = 3,5-bis(imidazole-1-yl)pyridine] have been successfully synthesized through the assembly of metal ions [Cu(II) ion for compounds 1 and 2, Co(II) for compound 3] with H3tci and two different N-donor ligands (btx and biip) under solvothermal conditions. All compounds were characterized by IR spectroscopy, elemental and thermogravimetric (TG) analyses, powder X-ray diffraction (PXRD) studies and finally, the structures of all compounds were unambiguously determined by single-crystal X-ray diffraction (SCXRD) technique. Compound 1 is a 1D coordination polymer, constructed by the connectivity of copper tetramer as a secondary building unit (SBU) with the H3tci and btx ligands. Whereas the crystal structure of compound 2 possesses two different SBUs i.e., paddlewheel and square planar involving Cu(II). The connectivity of these two SBUs results in the formation of 2D layers which are further pillared by biip ligand to result in a 3D structure. In the case of compound 3, both Co1 and Co2 exhibit distorted octahedral geometry in their SBUs. Further, the connectivity of these SBUs with tci3- and biip ligands results in the formation of a 3D framework.

Exploration of Molecular Structure, DFT Calculations, and Antioxidant Activity of a Hydrazone Derivative.

The hydrazine derivatives are known to possess several biological activities including anticancer, antibacterial and anti-fungal, anticonvulsant, and antioxidant. This communication presents the synthesis, X-ray crystal structure analysis, DFT calculations, cell cytotoxicity, and antioxidant activity of the Schiff base 4,4'-((1E,1'E)-hydrazine-1,2-diylidenebis(ethan-1-yl-1-ylidene))bis(benzene-1,3-diol) (compound 2). We have also isolated the side product compound 1 and characterized it using single X-ray crystallography. The crystal structure of compound 1 depicts that the ensuing C-H···N hydrogen bonding interaction is presented and discussed herein. In addition, the calculations using density functional theory (DFT) approximation supported by experimental 1H and 13C NMR studies on the key compound 2 are reported. The results of theoretical and experimental 1H and 13C NMR were concordant. The antioxidant activity of compound 2 was determined by using 2,2'-azinobis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS•+) radical cation assays and 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical assay. Compound 2 demonstrated excellent antioxidant activity in ABTS assay (IC50 = 4.30 ± 0.21 µM) and DPPH assay (IC50 = 81.06 ± 0.72 µM) with almost no cytotoxicity below 25 µM.

Recent Advances in Organic Room-Temperature Phosphorescence of Heteroatom (B/S/P)-Containing Chromophores

Recent Advances in Organic Room-Temperature Phosphorescence of Heteroatom (B/S/P)-Containing Chromophores