The Development of Organotin(IV) N-Ethyl-N-Benzyldithiocarbamate Complexes: A Study on Their Synthesis, Characterization, and Cytocidal Effects on A549 Cell Line.

BACKGROUND: Organotin(IV) complexes of dithiocarbamate are vital in medicinal chemistry, exhibiting potential in targeting cancer cells due to their unique properties that enhance targeted delivery. This study aimed to synthesize and characterize organotin(IV) N-ethyl-N-benzyldithiocarbamate complexes (ONBDCs) and evaluate their cytotoxicity against A549 cells, which are commonly used as a model for human lung cancer research. METHOD: The two ONBDC derivatives - ONBDC 1 (dimethyltin(IV) N-ethyl-N-benzyldithiocarbamate) and ONBDC 2 (triphenyltin(IV) N-ethyl-N-benzyldithiocarbamate) - were synthesized via the reaction of tin(IV) chloride with N-ethylbenzylamine in the presence of carbon disulfide. A range of analytical techniques, including elemental analysis, IR spectroscopy, NMR spectroscopy, UV-Vis spectrometry, TGA/DTA analysis, and X-ray crystallography, was conducted to characterize these compounds comprehensively. The cytotoxic effects of ONBDCs against A549 cells were evaluated using MTT assay. RESULTS: Both compounds were synthesized and characterized successfully via elemental and spectroscopies analysis. MTT assay revealed that ONBDC 2 demonstrated remarkable cytotoxicity towards A549 cells, with an IC50 value of 0.52 µM. Additionally, ONBDC 2 displayed significantly higher cytotoxic activity against the A549 cell line when compared to the commercially available chemotherapeutic agent cisplatin (IC50: 32 µM). CONCLUSION: Thus, it was shown that ONBDC 2 could have important anticancer properties and should be further explored as a top contender for creating improved and specialized cancer treatments.

Green synthesis, characterization, and biochemical impacts of new bioactive isoxazoline-sulfonamides as potential insecticidal agents against the Sphodroxia maroccana Ley.

BACKGROUND: Sphodroxia maroccana Ley is a pest of cork oak crops that damages the roots of seedlings and can severely impair cork oak regeneration. Since the banning of carbosulfan and chlorpyriphos, which were widely used against the larvae of Sphodroxia maroccana because of their harmful impact on the environment, until now there has been no pesticide against these pests. Therefore, it is particularly urgent to develop highly effective insecticidal molecules with novel scaffolds. Isoxazolines are a class of insecticides that act on γ-aminobutyric acid (GABA)-gated chloride channel allosteric modulators. In this work, a green synthesis of novel 3,5-disubstituted isoxazoline-sulfonamide derivatives was achieved in water via ultrasound-assisted four-component reactions, and their insecticidal activities against fourth-instar larvae of S. maroccana were evaluated. RESULTS: Most of the tested compounds showed insecticidal activity compared to fluralaner as positive control and commercially available insecticide. Especially, the isoxazoline-secondary sulfonamides containing halogens (Br and Cl) on the phenyl group attached to the isoxazoline, 6g (LC50 = 0.31 mg/mL), 6j (LC50 = 0.38 mg/mL), 6k (LC50 = 0.18 mg/mL), 6L (LC50 = 0.49 mg/mL), 6m (LC50 = 0.24 mg/mL), 6q (LC50 = 0.46 mg/mL), exhibited much higher larvicidal activity than fluralaner (LC50 = 0.99 mg/mL). CONCLUSION: Novel isoxazolines containing sulfonamide moieties were designed, synthesized and confirmed by two single-crystal structures of 4e and 6q. Their bioassay results showed significant larvicidal activity with significant morphological changes in vivo. These results will lay the foundation for the further discovery and development of isoxazoline-sulfonamide derivatives as novel crop protection larvicides of cork oak. © 2023 Society of Chemical Industry.

A Dual Approach on Experimental, Theoretical Insight of Structural Elucidation, Hirshfeld Surface Analysis, Optical and Electrochemical Properties of Acyl Thiourea-Ethynyl Hybrid Derivatives.

Hybrid moieties of ethynylated-thiourea, Th1 and Th2 have been synthesised via the addition reaction between ethynyl derivatives and 4-tert-butylbenzoyl isothiocyanate in acetone, and were characterised by selected spectroscopic methods (i.e., 1H and 13C NMR, UV-visible, FT-IR) and elemental analysis. Thermogravimetric analysis indicated that Th1 and Th2 were relatively stable up to ca. 210 °C. Single-crystal X-ray diffraction was used to identify the crystal structure of Th2 in which the centre of 1-acyl thiourea moiety (-C(O)NHC(S)NH) exhibits S conformation. The Hirshfeld surface analysis has allowed visualizing the crystal packing, which is characterised by the prolonged intermolecular N-H⋯O = C and N-H⋯S = C hydrogen-bonding interactions within Th2 molecule. Electrochemical data of both compounds correspondingly exhibit irreversible redox potential processes. Besides, frontier molecular orbitals and Natural Bond Orbital population analysis were computed at the B3LYP/6-31G (d, p) level of approximation, suggesting strong delocalization of the electronic density through a conjugated π-system involving the ethynyl-phenyl and thiourea groups. Graphical Abstract: Figure of molecular structure for acyl thiourea-ethynyl derivative. Two derivatives of acyl thiourea-ethynyl were synthesised and characterised by selected spectroscopic methods such as 1H and 13C NMR, UV-visible, FT-IR, elemental, thermal, electrochemical, X-ray diffraction, and density functional theory (DFT) calculation for molecular orbitals and natural bond orbital population analysis.

Fused ring effect on optical nonlinearity and structure property relationship of anthracenyl chalcone based push-pull chromophores.

The Ultraviolet-visible (UV-Vis) spectra indicate that anthracenyl chalcones (ACs) have high maximum wavelengths and good transparency windows for optical applications and are suitable for optoelectronic applications owing to their HOMO-LUMO energy gaps (2.93 and 2.76 eV). Different donor substituents on the AC affect their dipole moments and nonlinear optical (NLO) responses. The positive, negative, and neutral electrostatic potential regions of the molecules were identified using molecular electrostatic potential (MEP). The stability of the molecule on account of hyperconjugative interactions and accompanying charge delocalization was analyzed using natural bond orbital (NBO) analysis. Open and closed aperture Z-scans were performed using a continuous-wave frequency-doubled diode-pumped solid-state (DPSS) laser to measure the nonlinear absorption and nonlinear refractive index coefficients, respectively. The valley-to-peak profile of AC indicated a negative nonlinear refractive index coefficient. The obtained single crystals possess reverse saturation absorption due to excited-state absorption. The structural and nonlinear optical properties of the molecules have been discussed, along with the role of anthracene substitution for enhancing the nonlinear optical properties. The calculated third-order susceptibility value was 1.10 x10-4 esu at an intensity of 4.1 kW/cm2, higher than the reported values for related chalcone derivatives. The NLO response for both ACs offers excellent potential in optical switching and limiting applications.

Synthesis, X-Ray Structure, Hirshfeld Surface Analysis, DFT Calculations, and Molecular Docking Studies of Nickel(II) Complex with Thiosemicarbazone Derivative.

This article presents both experimental and computational study of a new Ni(II) complex, namely, bis{2-(2-trifluoromethylbenzylidene)hydrazine-1-carbothioamido-κ 2N2, S}nickel(II) (abbreviate as NiL2). The complex was synthesized and well characterized using various spectroscopic methods. The single X-ray crystallographic study revealed a distorted square planar geometry around Ni(II) metal ion centre in which the angles deviated from ideal 90° with a maximum value of 6.57° occupied by nitrogen and sulphur donor atoms. The theoretical bond lengths and angles for the NiL2 complex were obtained by using the B3LYP level of density function theory (DFT) with LANL2DZ/6-311G (d, p) basis sets. These results showed very good agreement with the experimental X-ray values. The electrophilicity index (ω = 50.233 eV) shows that the NiL2 complex is a very strong electrophile. In addition, strong F⋯H/H⋯F interactions with 28.5% of the total Hirshfeld surface analyses in NiL2 were obtained indicating that the complex could bind with protein effectively. Furthermore, the new NiL2 complex was docked with plasma retinol-binding protein 4 (RBP4) (PDB id: 5NU7), which implied that the NiL2 complex bound to Tyrosine 133 and Aspartate 102 amino acids via N-H intermolecular hydrogen bonds.

Comparative analyses of new donor-π-acceptor ferrocenyl-chalcones containing fluoro and methoxy-fluoro acceptor units as synthesized dyes for organic solar cell material.

Two organometallic compounds known as (E)-1-ferrocenyl-(3-fluorophenyl)prop-2-en-1-one (Fc1) and (E)-1-ferrocenyl-(3-fluoro-4-methoxyphenyl)prop-2-en-1-one (Fc2) are designed and synthesized for application in dye-sensitized solar cell (DSSC) based on a donor-π-acceptor (D-π-A) architecture. By strategically introducing a methoxy group into the acceptor side of the compound, Fc2 which has adopted a D-π-A-AD structure are compared with the basic D-π-A structure of Fc1. Both compounds were characterized by utilizing the IR, NMR and UV-Vis methods. Target compounds were further investigated by X-ray analysis and studied computationally using Density Functional Theory (DFT) and Time-Dependent DFT (TD-DFT) approaches to explore their potential performances in DSSCs. An additional methoxy group has been proven in enhancing intramolecular charge transfer (ICT) by improving the planarity of Fc2 backbone. This good electronic communication leads to higher HOMO energy level, larger dipole moment and better short-circuit current density (Jsc) values. Eventually, the presence of methoxy group in Fc2 has improved the conversion efficiency as in comparison to Fc1 under the same conditions.

Ultrasound-assisted one-pot green synthesis of new N- substituted-5-arylidene-thiazolidine-2,4-dione-isoxazoline derivatives using NaCl/Oxone/Na3PO4 in aqueous media.

A rapid and green method for the synthesis of novel N-thiazolidine-2,4-dione isoxazoline derivatives 5 from N-allyl-5-arylidenethiazolidine-2,4-diones 3 as dipolarophiles with arylnitrile oxides via 1,3-dipolar cycloaddition reaction. The corresponding N-allyl substituted dipolarophiles were prepared by one-pot method from thiazolidine-2,4-dione with aldehydes using Knoevenagel condensation followed by N-allylation of thiazolidine-2,4-dione in NaOH aqueous solution under sonication. In addition, the isoxazoline derivatives 5 were synthesized by regioselective and chemoselective 1,3-dipolar cycloaddition using inexpensive and mild NaCl/Oxone/Na3PO4 as a Cl source, oxidant and/or catalyst under ultrasonic irradiation in EtOH/H2O (v/v, 2:1) as green solvent. All synthesized products are furnished in good yields in the short reaction time, and then their structures were confirmed by NMR, mass spectrometry and X-ray crystallography analysis.

Structural, Hirshfeld and DFT studies of conjugated D-π-A carbazole chalcone crystal.

A new conjugated carbazole chalcone compound, (E)-3-[4-(9,9a-di-hydro-8aH-carbazol-9-yl)phen-yl]-1-(4-nitro-phen-yl)prop-2-en-1-one (CPNC), C27H18N2O3, was synthesized using a Claisen-Schmidt condensation reaction. CPNC crystallizes in the monoclinic non-centrosymmetric space group Cc and adopts an s-cis conformation with respect to the ethyl-enic double bonds (C=O and C=C). The crystal packing features C-H⋯O and C-H⋯π inter-actions whose percentage contribution was qu-anti-fied by Hirshfeld surface analysis. Quantum chemistry calculations including geometrical optimization and mol-ecular electrostatic potential (MEP) were analysed by density functional theory (DFT) with a B3LYP/6-311 G++(d,p) basis set.

Correlation data of (Z)-1-[4-(trifluoromethyl)benzylidene]thiosemicarbazide via spectroscopic methods and Density Functional Theory studies.

New compound, namely (Z)-1-[4-(trifluoromethyl)benzylidene]thiosemicarbazide was successfully synthesized using thiosemicarbazide with 4-(trifluoromethyl)-benzaldehyde in ethanol solution. The data presented in this articles is related to our research articles entitled "Crystal Structure of (Z)-1-[4-(Trifluoromethyl)benzylidene]thiosemicarbazide" (Osman et al., 2017) [1]. This work shows the continue data from experimental spectroscopic measurement which are Fourier Transform Infrared (FTIR) and 13C Nuclear Magnetic Resonance (13C NMR). Assessment on the correlation with theoretical computational data was also carried out through GaussView 5.0.9 and Gaussian09 software. Molecular Electrostatic Potential (MEP) and Highest Occupied Molecular Orbital-Lowest Unoccupied Molecular Orbital (HOMO-LUMO) were also illustrated.

Crystal structure, DFT study and Hirshfeld surface analysis of ethyl 6-chloro-2-eth-oxy-quinoline-4-carboxyl-ate.

In the title quinoline derivative, C14H14ClNO3, there is an intra-molecular C-H⋯O hydrogen bond forming an S(6) graph-set motif. The mol-ecule is essentially planar with the mean plane of the ethyl acetate group making a dihedral angle of 5.02 (3)° with the ethyl 6-chloro-2-eth-oxy-quinoline mean plane. In the crystal, offset π-π inter-actions with a centroid-to-centroid distance of 3.4731 (14) Šlink inversion-related mol-ecules into columns along the c-axis direction. Hirshfeld surface analysis indicates that H⋯H contacts make the largest contribution (50.8%) to the Hirshfeld surface.

(E)-1-(Benzo[d][1,3]dioxol-5-yl)-3-([2,2'-bi-thio-phen]-5-yl)prop-2-en-1-one: crystal structure, UV-Vis analysis and theoretical studies of a new π-conjugated chalcone.

In the title compound, C18H12O3S2, synthesized by the Claisen-Schmidt condensation method, the essentially planar chalcone unit adopts an s-cis configuration with respect to the carbonyl group within the ethyl-enic bridge. In the crystal, weak C-H⋯π inter-actions connect the mol-ecules into zigzag chains along the b-axis direction. The mol-ecular structure was optimized geometrically using Density Functional Theory (DFT) calculations at the B3LYP/6-311 G++(d,p) basis set level and compared with the experimental values. Mol-ecular orbital calculations providing electron-density plots of HOMO and LUMO mol-ecular orbitals and mol-ecular electrostatic potentials (MEP) were also computed both with the DFT/B3LYP/6-311 G++(d,p) basis set. The experimental energy gap is 3.18 eV, whereas the theoretical HOMO-LUMO energy gap value is 2.73 eV. Hirshfeld surface analysis was used to further investigate the weak inter-actions present.

Crystal structure and optical properties of fused-ring chalcone (E)-3-(anthracen-9-yl)-1-(4-nitro-phen-yl)prop-2-en-1-one.

The title compound, C23H15NO3, adopts an s-cis conformation with respect to the ethyl-ene C=C and carbonyl C=O double bonds in the enone unit. The mol-ecule is significantly twisted with a dihedral angle of 48.63 (14)° between the anthracene ring system and the benzene ring. In the crystal, mol-ecules are linked into inversion dimers with an R 2 2(10) graph-set motif via pairs of C-H⋯O hydrogen bonds. The inter-molecular inter-actions were analysed and qu-anti-fied by Hirshfeld surface analysis. The mol-ecular structure was optimized and a small HOMO-LUMO energy gap of 2.55 eV was obtained using the DFT method at the B3LYP/6-311 G++(d,p) level of theory. This value is in close agreement with the experimental value of 2.52 eV obtained from the UV-vis analysis. The crystal used was a two-component merohedral twin with a refined ratio of 0.1996 (16):0.8004 (16).

Crystal structure, Hirshfeld surface analysis and DFT studies of (E)-1-(4-bromo-phen-yl)-3-(3-fluoro-phen-yl)prop-2-en-1-one.

The asymmetric unit of the title halogenated chalcone derivative, C15H10BrFO, contains two independent mol-ecules, both adopting an s-cis configuration with respect to the C=O and C=C bonds. In the crystal, centrosymmetrically related mol-ecules are linked into dimers via inter-molecular hydrogen bonds, forming rings with R 1 2(6), R 2 2(10) and R 2 2(14) graph-set motifs. The dimers are further connected by C-H⋯O inter-actions into chains parallel to [001]. A Hirshfeld surface analysis suggests that the most significant contribution to the crystal packing is by H⋯H contacts (26.3%). Calculations performed on the optimized structure obtained using density functional theory (DFT) at B3LYP with the 6-311 G++(d,p) basis set reveal that the HOMO-LUMO energy gap is 4.12 eV, indicating the suitability of this crystal for optoelectronic and biological applications. The nucleophilic and electrophilic binding site regions are elucidated using the mol-ecular electrostatic potential (MEP).

Crystal structure and optical spectroscopic analyses of (E)-3-(1H-indol-2-yl)-1-(4-nitro-phen-yl)prop-2-en-1-one hemihydrate.

The asymmetric unit of the title compound, 2C17H12N2O3·H2O comprises two mol-ecules of (E)-3-(1H-indol-2-yl)-1-(4-nitro-phen-yl)prop-2-en-1-one and a water mol-ecule. The main mol-ecule adopts an s-cis configuration with respect to the C=O and C=C bonds. The dihedral angle between the indole ring system and the nitro-substituted benzene ring is 37.64 (16)°. In the crystal, mol-ecules are linked by O--H⋯O and N-H⋯O hydrogen bonds, forming chains along [010]. In addition, weak C-H⋯O, C-H⋯π and π-π inter-actions further link the structure into a three-dimensional network. The optimized structure was generated theoretically via a density functional theory (DFT) approach at the B3LYP/6-311 G++(d,p) basis level and the HOMO-LUMO behaviour was elucidated to determine the energy gap. The obtained values of 2.70 eV (experimental) and 2.80 eV (DFT) are desirable for optoelectronic applications. The inter-molecular inter-actions were qu-anti-fied and analysed using Hirshfeld surface analysis.

Crystal structure, spectroscopic characterization and DFT study of two new linear fused-ring chalcones.

The structures of two new anthracenyl chalcones, namely (E)-1-(anthracen-9-yl)-3-(4-nitro-phen-yl)prop-2-en-1-one, C23H15NO3, and (E)-1-(anthracen-9-yl)-3-(4-iodo-phen-yl)prop-2-en-1-one, C23H15IO are reported. A structural comparative study between the two chalcones was performed and some effects on the geometrical parameters, such as planarity and dihedral angles, are described. The mol-ecular geometry was determined by single-crystal X-ray diffraction, and density functional theory (DFT) at B3LYP with the 6-311++G(d,p) basis set was applied to optimize the ground-state geometry. In addition, inter-molecular inter-actions responsible for the crystal packing were analysed. The electronic properties, such as excitation energies and HOMO-LUMO energies were calculated by time-dependent density functional theory (TD-DFT) and the results complement the experimental findings. The mol-ecular electrostatic potential (MEP) was also investigated at the same level of theory in order to identify and qu-antify the possible reactive sites.

Crystal structures, DFT studies and UV-visible absorption spectra of two anthracenyl chalcone derivatives.

The crystal structures of (E)-1-(anthracen-9-yl)-3-(3H-indol-2-yl)prop-2-en-1-one, C25H17NO, and (E)-1-(anthracen-9-yl)-3-[4-(di-methyl-amino)-naphthalen-1-yl]prop-2-en-1-one, C29H23NO, are reported. In each case the anthracene ring system and pendant ring system are almost perpendicular to each other [dihedral angles = 75.57 (7)° and 70.26 (10)°, respectively]. In the extended structures, weak N-H⋯O, C-H⋯O and C-H⋯π inter-actions influence the centrosymmetric crystal packing. Density functional theory calculations were carried out using a 6-311 G++(d,p) basis set and the calculated structures are in good agreement with the crystal structures. The compounds were also characterized by UV-Vis absorption spectroscopy and the smallest (HOMO-LUMO) energy gaps of 2.89 and 2.54 eV indicate the enhanced non-linear responses (inter-molecular charge transfers) of these systems.

Crystal structure and theoretical studies of two π-conjugated fused-ring chalcones: (E)-1-(anthra-cen-9-yl)-3-(9-ethyl-9H-carbazol-3-yl)prop-2-en-1-one and (E)-1-(anthracen-9-yl)-3-[4-(9H-carbazol-9-yl)phen-yl]prop-2-en-1-one.

The title chalcones, C31H23NO and C35H23NO, were synthesized via Claisen-Schmidt condensation reactions. Both structures were solved and refined using single-crystal X-ray diffraction data and optimized at the ground state using the density functional theory (DFT) method with the B3LYP/6-311++G(d,p) level. In the crystals, π-π inter-ations and weak C-H⋯O and C-H⋯π inter-actions are observed. The effect of these inter-molecular inter-actions in the solid state can be seen by the difference between the experimental and theoretical optimized geometrical parameters. The structures have also been characterized by UV-Vis spectroscopy. The smallest energy gaps of 2.86 and 2.96 eV enhance the nonlinear responses of such mol-ecular systems. Hirshfeld surface analyses and 2D (two-dimensional) fingerprint plots were used to qu-antify the inter-molecular inter-actions present in the crystal, indicating that these are the most important contribution to the crystal packing.

Mol-ecular structure, DFT studies and UV-Vis absorption of two new linear fused ring chalcones: (E)-1-(anthracen-9-yl)-3-(2-meth-oxy-phen-yl)prop-2-en-1-one and (E)-1-(anthracen-9-yl)-3-(3-fluoro-4-meth-oxy-phen-yl)prop-2-en-1-one.

The title compounds, C24H18O2 and C24H17FO2, were synthesized using the Claisen-Schmidt condensation method and characterized by UV-Vis spectroscopy. Weak inter-molecular C-H⋯O, C-H⋯π and π-π hydrogen-bonding inter-actions help to stabilize the crystal structures of both compounds. The geometrical parameters obtained from the mol-ecular structure were optimized using density functional theory (DFT) calculations at the B3LYP/6-311++G(d,p) level, showing a good correlation with the experimental results. The small HOMO-LUMO energy gaps of 3.11 and 3.07 eV enhances the non-linear responses of these mol-ecular systems.

Mol-ecular structure, DFT studies and Hirshfeld analysis of anthracenyl chalcone derivatives.

The mol-ecular and crystal structure of two new chalcone derivatives, (E)-1-(anthracen-9-yl)-3-[4-(piperidin-1-yl)phen-yl]prop-2-en-1-one, C28H25NO, (I), and (E)-1-(anthracen-9-yl)-3-[4-(di-phenyl-amino)-phen-yl]prop-2-en-1-one, C35H25NO, (II), with the fused-ring system at the same position are described. In the crystals of (I) and (II), the mol-ecules are linked via C-H⋯O hydrogen bonds into inversion dimers, forming R22(22) and R22(14) ring motifs, respectively. Weak inter-molecular C-H⋯π inter-actions further help to stabilize the crystal structure, forming a two-dimensional architecture. The mol-ecular structures are optimized using density functional theory (DFT) at B3LYP/6-311 G++(d,p) level and compared with the experimental results. The smallest HOMO-LUMO energy gaps of (I) (exp . 2.76 eV and DFT 3.40 eV) and (II) (exp . 2.70 eV and DFT 3.28 eV) indicates the suitability of these crystals in optoelectronic applications. All inter-molecular contacts and weaker contributions involved in the supra-molecular stabilization are investigated using Hirshfeld surface analysis. The mol-ecular electrostatic potential (MEP) further identifies the positive, negative and neutral electrostatic potential regions of the mol-ecules.

The effect of the fused-ring substituent on anthracene chalcones: crystal structural and DFT studies of 1-(anthracen-9-yl)-3-(naphthalen-2-yl)prop-2-en-1-one and 1-(anthracen-9-yl)-3-(pyren-1-yl)prop-2-en-1-one.

The title chalcone compounds, C27H18O (I) and C33H20O (II), were synthesized using a Claisen-Schmidt condensation. Both compounds display an s-trans configuration of the enone moiety. The crystal structures feature inter-molecular C-H⋯O and C-H⋯π inter-actions. Quantum chemical analysis of density functional theory (DFT) with a B3LYP/6-311++G(d,p) basis set has been employed to study the structural properties of the compound. The effect of the inter-molecular inter-actions in the solid state are responsible for the differences between the experimental and theoretical optimized geometrical parameters. The small HOMO-LUMO energy gap in (I) (exp : 3.18 eV and DFT: 3.15 eV) and (II) (exp : 2.76 eV and DFT: 2.95 eV) indicates the suitability of these compounds for optoelectronic applications. The inter-molecular contacts and weak contributions to the supra-molecular stabilization are analysed using Hirshfeld surface analysis.