Single Crystal Studies Research Articles

Structural, mechanical and antimicrobial studies of GZnA single crystal via slow solvent evaporation process

Structural, mechanical and antimicrobial studies of GZnA single crystal via slow solvent evaporation process

Investigation on growth, structural, spectral, optical, thermal, third order nonlinear optical and DFT studies of dibenzoylmethane single crystal for photonic and optoelectronic applications

Investigation on growth, structural, spectral, optical, thermal, third order nonlinear optical and DFT studies of dibenzoylmethane single crystal for photonic and optoelectronic applications

Novel Benzohydrazide Derivative as a Potential Anticarcinogenic Agent for Breast Cancer: Synthesis, Crystal Structure, In Vitro and In Silico Assessments

Polycyclic aromatic compounds (PACs) are a class of organic molecules known for their significant biological activity, including anticancer properties. These compounds often interact with biological macromolecules, making them crucial in the development of new therapeutic agents. In this study, we report a new benzohydrazide derivative, (E)-4-(hexyloxy)-N'-(1-(naphthalen-2-yl)ethylidene)benzohydrazide (2), which incorporates a naphthalene ring, a typical PAC, as a core structural element. The structure of the compound was analyzed using FTIR, 1H NMR, 13C NMR and elemental analysis. Moreover, single crystal X-ray crystallography studies demonstrated that the compound adapted monoclinic crystal system with C 2/c space group. In the crystal structure, the intermolecular N–H···O hydrogen bonds link the molecules into infinite chains along the b-axis direction. The dominant interactions formed in the crystal packing were found to be hydrogen bonding and van der Waals interactions according to the Hirshfeld surface (HS) analysis. The evaluation of energy frameworks showed that stabilization of the compound was dominated by dispersion energy contribution. The anticancer activity of the compound was tested by employing several cellular assays. The compound showed strong anticancer effects, with IC50 values of 85 µM for MCF7 cells and 115 µM for MDA-MB-231 cells, indicating dose-dependent suppression of cell viability, migration, and colony formation. Computational analyses indicated favorable binding of compound 2 to ERRγ and predicted good oral availability of the generated compound. Pathway analysis using KEGG pathways identified significant enrichment in pathways related to cancer. These results highlight the compound's promise as a potential treatment option for breast cancer, prompting further exploration in future studies.

Multi-Stage Optimization of Pore Size and Shape in Pore-Space-Partitioned Metal-Organic Frameworks for Highly Selective and Sensitive Benzene Capture.

Compared to exploratory development of new structure types, pushing the limits of isoreticular synthesis on a high-performance MOF platform may have higher probability of achieving targeted properties. Multi-modular MOF platforms could offer even more opportunities by expanding the scope of isoreticular chemistry. However, navigating isoreticular chemistry towards best properties on a multi-modular platform is challenging due to multiple interconnected pathways. Here on the multi-modular pacs (partitioned acs) platform, we demonstrate accessibility to a new regime of pore geometry using two independently adjustable modules (framework-forming module 1 and pore-partitioning module 2). A series of new pacs materials have been made. Benzene/cyclohexane selectivity is tuned, progressively, from 4.5 to 15.6 to 195.4 and to 482.5 by pushing the boundary of the pacs platform towards the smallest modules known so far. The exceptional stability of these materials in retaining both porosity and single crystallinity enables single-crystal diffraction studies of different crystal forms (as-synthesized, activated, guest-loaded) that help reveal the mechanistic aspects of adsorption in pacs materials.

The Gauche‐Effect in 1,2‐Bis(arylsulfonate)ethanes

AbstractWith an aim of obtaining a fundamental understanding of C−C bond conformation theory, the molecular structure of an ethane with electron‐withdrawing groups, 1,2‐bis(4‐methoxybenzene‐sulfonate)ethane, was elucidated. According to the general conformation rule for alkanes, which states that molecules adopt a stabilized structure to avoid steric repulsion, ethanes typically adopt anti‐conformation. However, the title compound exhibited gauche‐conformation, as revealed by a single crystal diffraction study. Theoretical studies also support this behavior. Natural Bond Orbital (NBO) analysis suggests that the orbital interaction between the σ*CO orbital, attributable to the sulfonate groups, and the adjacent σCH orbital stabilizes the gauche‐conformation. The authors conclude that the sulfonate group acts as a gauche‐effect synthon, which is widely applicable in organic chemistry.

Application of enaminone ruthenium(II) complexes as catalysts in the transfer hydrogenation of ketones

This study reported the synthesis of two new ligands (1,2) and their Ru(II)-enaminone complexes (3,4). The Ru(II) complexes were obtained from the reaction of the [RuCl2(p-cymene)]2 dimers with the new enaminone derivative ligands (1,2). The use of standard spectroscopy techniques entirely characterized the compounds. Single crystal studies investigated the crystal structure of ligand (1) and complexes (3,4). X-ray diffraction data analysis was used to confirm the enaminone form of 1. Also, 3 and 4 exhibited the classical three-legged piano stool structure with Ru(II) coordinated by the nitrogen and oxygen atoms of 1 and a chloride ligand as the legs and the η6-π-bound p-cymene ligand occupies the seat of the piano stool. The Ru(II) complexes have been studied as catalysts in the transfer hydrogenation of acetophenone and other various ketones in the presence of KOtBu. The catalytic conditions were optimized using different substrate/catalyst and base/catalyst ratios. We found that the complexes show good activities and up to 100 % selectivity. The best turnover frequency (1667 h−1) was found for 3 when using acetophenone as the substrate.

Synthesis, single crystal study, molecular docking, and in vitro anticancer screening of a series of isoxazolone derivatives of chlorovinyl benzalaldehydes

A series of isoxazole derivatives (2a-i) were synthesized by conventional method using various substituted chlorovinyl benzaldehydes as precursors. Structures of all the synthesized compounds were confirmed by spectroscopic data (1H NMR, FTIR, HRMS). Single crystal X-ray study of four compounds was carried out. Molecular docking study was performed and the compounds were screened for in vitro anticancer activity. The results show that compounds with no substituent or smaller substituents on benzene ring have significant antiproliferative activity against tested cell line i.e. MCF7.

Synthesis and Performance Evaluation of Zwitterionic C-N Bonded Triazole-Tetrazole-Based Primary Explosives.

Developing advanced metal-free nitrogen-enriched primary explosives is challenging due to the inherent risks associated with their synthesis and handling. However, there is an urgent need to develop novel lead-free, nitrogen-rich primary explosives that offer balanced energetic properties. C-N bonded bicyclic compound 3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine (4), its salts, and 3,5-diazido-1H-1,2,4-triazole (8) were synthesized from inexpensive starting materials resulting in a fine blend of sensitivity and stability. These compounds exhibit high nitrogen content (79.78 to 83.43%), good thermal stability (129-210 °C), excellent detonation performance (VOD: 8592-9361 ms-1, DP: 27.1-33.8 GPa), and acceptable sensitivity (IS: 2.5-30 J, FS: 72-288 N). The hot needle tests of compounds 4 and 8 exhibit excellent ignition performance. All of the newly synthesized compounds were fully characterized using infrared spectroscopy (IR), high-resolution mass spectroscopy (HRMS), multinuclear magnetic spectroscopy (NMR), elemental analysis (EA), thermogravimetric analysis-differential scanning calorimetry (TGA-DSC), and 2, 4, and 8 were confirmed by single-crystal X-ray crystallographic studies. The molecular electrostatic potential (ESP), noncovalent interactions reduced density gradient (NCI-RDG) method, and QTAIM analysis were performed to investigate the intermolecular interactions. Together with promising performance properties, ease of synthesis, and ignitability, they are highly suitable candidates to pave new avenues for future applications.

Comment on the paper “synthesis, nucleation kinetics, spectral, structural, mechanical, and thermal studies of semi-organic barium-doped γ-glycine single crystal” by K. Premlatha et al. [J. Mater. Sci.: Mater. Electron. 32 (2021) 28494]

Comment on the paper “synthesis, nucleation kinetics, spectral, structural, mechanical, and thermal studies of semi-organic barium-doped γ-glycine single crystal” by K. Premlatha et al. [J. Mater. Sci.: Mater. Electron. 32 (2021) 28494]

Novel schiff base as potent antimalarial: Synthesis, single crystal x-ray structure, spectroscopic analysis, theoretical investigation and molecular docking studies

The title compound N’-[(E)-(2-Hydroxy-1-naphthyl)methylene]benzohydrazide was compounded completely by the condensation reaction between 2-hydroxynaphthaldehyde and benzhydrazide. The Schiff base obtained was attributed by single-crystal X-ray diffraction (SCXRD), FT-IR, UV–Visible spectroscopy, and mass spectrometry. Computational validation was performed using DFT- B3LYP/6–311 + G(d,p) theory to ascertain the optimal geometry of the compound. Thermodynamic parameters and nonlinear optical (NLO) plots were also investigated. The HOMO-LUMO energy gap was found to be 3.6380 eV. Mulliken charges were found and electrostatic field surface mapping conducted to explore various properties. Theoretical findings were consistent with experimental results. Molecular docking studies revealed that the Schiff base exhibits antimalarial activity against Plasmodium falciparum, with the LibDock score and binding energy assessed for the malaria-causing protein 4WZ3. ADMET analysis indicated favorable pharmacokinetic properties of the synthesized ligand compared to current antimalarial drugs, highlighting its potential for malaria treatment.

Synthesis, Characterization, Crystal structure determination and DFT study of a six coordinated Cu (II) complex of a phosphorous based tris-(2-pyridinylamino) phosphene sulphide ligand and its acid catalysed hydrolysis

One mono nuclear copper(II) complex (Cu-TPPS-OOCCH3 with structural formula C17H19CuN6O3PS) is synthesized using a novel tripodal tetradentate ligand, tris-(2-pyridinylamino)phosphene sulphide (TPPS), which has three pyridinylamino groups attached to a phosphorus atom connected to a sulphur atom (PS). The equatorial positions of the complex are occupied by three amino N-atoms of three aminopyridyl groups and one O-atom of the acetate group. The apical position is occupied by other O-atom of acetate group and one secondary N-atom of the tripodal ligand. The complex has been synthesized and purified as green solid and characterized by various spectroscopic techniques and the structure has been determined by X-ray single crystal diffraction study. The geometry optimizations and calculations of energies of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the compounds are performed by using the hybrid B3LYP density functional theory (DFT) along with the def2TZVP basis set.

Unique magnetic structure of the vdW antiferromagnet VBr3

VBr3 is a van der Waals antiferromagnet below the Néel temperature of 26.5 K with a saturation moment of 1.2 µB/f.u. above the metamagnetic transitions detected in the in-plane and out-of-plane directions. To reveal the AFM structure of VBr3 experimentally, we performed a single-crystal neutron diffraction study on a large high-quality crystal. The collected data confirmed a slight monoclinic distortion of the high-temperature rhombohedral structure below 90 K. The magnetic structure was, nevertheless, investigated within the R-3 model. The antiferromagnetic structure propagation vector k = (1, 0, ½) was revealed. In an attempt to determine the magnetic structure, 72 non-equivalent magnetic reflections were recorded. The experimental data were confronted with the magnetic space groups dictated by the R-3 lattice symmetry and propagation vector. The best agreement between the experimental data and the magnetic structure model was obtained for the space group P-1.1′_c. The magnetic unit cell of the proposed unique antiferromagnetic structure with periodicity 6c is built from two identical triple layers antiferromagnetically coupled along the c axis. Each triple layer comprises a Néel antiferromagnetic monolayer sandwiched between two antiferromagnetically coupled ferromagnetic monolayers.

An Insight Into Experimental and Theoretical Investigation of Structure, Photophysical Property by ESIPT Processes and Biological Activities of Schiff Base Copper Complex

ABSTRACTA novel Schiff base (BSSMO) and its copper complex have been synthesized, and their structure was delineated using single crystal XRD studies. Computational techniques were used to design and evaluate BSSMO‐based luminophores, revealing a significant intramolecular hydrogen bond within the molecule. Understanding ESIPT is crucial for optimizing photophysical and luminophore properties of organic molecules, especially for advancing optoelectronic devices. The study also explored the mechanisms of GSIPT and ESIPT for these BSSMO‐based luminophores using transition state theory, charge distribution, molecular orbital analysis, and quantum theory of atoms in molecules. Results advocated that BSSMO‐L2 exhibits higher absorption compared with BSSMO‐L1 and the same trend is observed in emission spectral studies. However, the intensity of enol emissions in BSSMO‐L2 is lower than that of keto (BSSMO‐L3) emissions and the S1 (Keto form) emission of BSSMO‐L3 shows significantly larger values, making it attractive for optoelectronic devices. The findings offer valuable insights for the development of ESIPT emitters with distinct photophysical properties. The in silico antidiabetic study of BSSMO‐L2 explores the interaction with PPAR‐γ protein, revealing a moderate affinity and stable complex, enhancing its bio‐potential for future applications. The in vitro anticancer study of Cu‐BSSMO‐L2 complex shows a potential anticancer effect through mitochondrial and extrinsic death receptor mediated pathways. These insights contribute to the design of novel benzenesulfonamide‐based bioactive molecules.

Photoluminescence and scintillation properties of rare earth doped Lu2O3 single crystal grown by floating zone method

A series of Lu2O3 single crystals doped with rare earth (RE) ions (RE = Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb, dopant concentrations are 1 %) was synthesized by the floating zone method. Their photoluminescence (PL) and scintillation properties were evaluated. In PL, emissions due to 4f-4f transitions of trivalent rare earth ions were observed, and those doped with Nd3+, Eu3+, Tb3+ and Er3+ showed the highest emission intensities among the samples. As a scintillation property, those doped with Eu, Gd, and Dy showed a clear photoabsorption peak under 137Cs 662 keV γ-ray irradiation. Among them, the Eu3+-doped Lu2O3 showed the highest scintillation light yield of 67000 photons/MeV. The current work conducted the first systematic study of rare earth doped Lu2O3 single crystals grown by the floating zone method.

Gold(III) complexes with chloride and cyanopyridines: Facilitated hydrolysis of nitrile ligand to amide and antibacterial activity

A range of novel simple gold(III) compounds has been synthesized in their monocrystalline form, including two previously unknown chloro-complexes of Au3+ with 2-cyanopyridine or 3-cyanopyridine, respectively. Our investigations have revealed the intricate nature of the reaction between 2-cyanopyridine and tetrachloroauric acid, yielding at least three distinct products. The main product, obtained in high yield, is a salt featuring a tetrachloroauric anion and a pyridinium cation stabilized by a hydrogen bond to a further 2-cyanopyridine molecule. Moreover, we observed the in-situ formation of a 2-cyanopyridine-AuCl3 complex, which undergoes hydrolysis of the nitrile bond to yield a picolinamide-Au(III) complex. The complexes were characterized by IR and Raman spectroscopies, NMR spectroscopy, and single-crystal XRD studies. Additional computational studies were conducted to explain unusual spectral features, the observed disparities in the complexation reactions of the three isomeric cyanopyridine ligands and the distinct reactivity of the complex with 2-cyanopyridine. Based on these studies, we propose a mechanism for the catalyzed hydrolysis of the nitrile bond within the Au(III) complex. Finally, we assessed the antimicrobial efficacy of the synthesized gold(III) complexes against a spectrum of bacteria and fungi.

One dimensional water chain as a zipper in a new polymorph of trans [Cu(vanilin)2(H2O)2].2(H2O) crystal–A case of water induced polymorphism

A new polymorph [Cu(II)(vanillin)2(H2O)2].2(H2O) has been synthesized and characterized by single crystal X-ray structural studies. Two other crystals having same formula and coordination unit but differing supramolecular arrangement due to slightly different role played by water molecules have already been reported in the literature [B. Kozlevˇcar et al. Z. Naturforsch., B: Chem. Sci. 2005, 60, 1273][Kozlevčar et al. Acta Chim. Slov. 2005, 52, 40–43]. The current compound is another polymorph in this system which has arisen again due to a different supramolecular arrangement which is water induced. Hirshfeld surface and energy framework analysis have been employed to compare these three polymorphs by assessing the nature of intermolecular interactions. In the current compound strong OH···O hydrogen bonding interactions between coordinated water molecules and –OH group attached to vanillin ligand leads to parallel alignment of successive coordination units leading to a supramolecular ribbon topology that runs along the crystallographic a-axis. A zigzag chain of single file water chain is positioned in between successive ribbons which acts as a zipper giving rise to a 2D supramolecular arrangement of the molecular complexes. In two other reported polymorphs instead of a single file water chain a cyclic water motif has been observed. The electronic structure of the complex explored using DFT methodology. This set of three polymorphs is an interesting example of water induced polymorphism.

Inclusion complexes of α-cyclodextrin with p-aminobenzoic acid and nicotinic acid: Crystal structure, DSC and IR spectroscopy analysis in solid state and 1H NMR and ITC calorimetric studies of complexation in solutions

In this work, inclusion complexes of α-cyclodextrin with p-aminobenzoic acid (PABA) and nicotinic acid (NIK) were studied. Solid-state complexes were obtained and studied with single-crystal X-ray diffraction, powder X-ray diffraction, differential scanning calorimetry, and FT-IR spectroscopy. Additionally, the formation of complexes was studied in aqueous solutions with isothermal titration calorimetry and 1H NMR spectroscopy in DMSO‑d6 solutions. Single crystal studies, FT-IR spectroscopy and powder diffraction confirmed the inclusion of PABA and NIK inside the cyclodextrin cavity. From the results of the isothermal titration calorimetry, the stoichiometry (n) and standard thermodynamic functions (ΔH, ΔG, ΔS) of complexation, as well as binding constants (K) for the formed complexes were calculated. The obtained results confirmed the thermodynamically spontaneous formation of complexes in exothermic reactions. Furthermore, the results obtained were compared for complexes of PABA/NIK acids with β-cyclodextrin. A database survey of α-cyclodextrin complexes with different benzoic acids available in the CSD database was performed.

Mixed ligand complexes of Pt(II) Tertiary phosphines and 1-(benzo[d]thiazol-2-yl)-3-phenylthiourea; Crystal structure and DFT of [Pt(C14H9N3S2)(dppe)].CH2Cl2

This paper describes a series of Pt(II) thiourea complexes (1–4). The complexes were synthesized by a reaction between [PtCl2(diphos)] and the ligand 1-(benzo[d]thiazol-2-yl)-3-phenylthioure in the presence of triethylamine, with all reactants present in equimolar amounts. The produced complexes exhibited square planar geometry, which was validated by FT-IR and 1HNMR . Single crystal XRD study revealed that the coordination geometry was distorted square planar in [Pt(Btzt)(dpppe)]. Hirshfeld surface analysis was used to delve deeper into the intermolecular interactions which showed that the combined contribution of H⋯H and H⋯C contacts in the stabilization of the supramolecular assembly was 81.3%. A void analysis was carried out which showed that there was no large cavity in the supramolecular assembly. Theoretical studies were also conducted on [Pt(Btzt)(dpppe)]. The DFT analysis was carried out using the B3LYP Hybrid method in combination with Def2-SVP. The theoretical findings indicated just 3% differences between the theoretical and experimental Figures. Furthermore, the computed HOMO-LUMO gap was 3.4 eV, which was close to the anatase photocatalyst's band gap. DFT predicted that all complexes are non-magnetic with μB=0. There are high electron donation and back-donation between heteroatoms and transition metals in the complexes.

(C3H7NH3)4Bi1-xSbxI9: 0D hybrid halide perovskite-like compounds with isolated triiodide units.

Antimony/bismuth-based organic-inorganic hybrid halide perovskite-like compounds have generated enormous research interest due to their excellent optical properties. Exploration of new compounds and understanding of their structural stability and optoelectronic properties is of utmost importance for practical applications of these materials. We report two new 0D perovskite-like compounds and their solid solution, (C3H7NH3)4Bi1-xSbxI9, having propyl amine as the spacer cation and iodine as the halide ion. All compounds crystallized in the space group C2/m at room temperature and undergo a phase transition from C2/m to P21/c at low temperature (90 K) as observed from the single-crystal study. A low-temperature (250 K, 180 K, 150 K and 90 K) single-crystal study shows that the (PA)4BiI9 compound retains the monoclinic space group C2/m until 150 K and undergoes a phase transition to the P21/c space group at 90 K. Further, it is observed that ordering, rearrangement and relaxation of the long-chain propyl amine group are primarily responsible for the structural transition. The structure contains [(Bi/Sb)I6]3- polyhedra along with linear I3- units, giving rise to the formula of (PA)3(Bi/Sb)I6·(PA)I3. The I3- units interact poorly while the [MI6]3- (M = Bi, Sb) octahedral units interact significantly with spacer cations via the H-bond, resulting in more distortion in these octahedral units. Theoretical calculations revealed that iodide ions have dual roles and contribute largely to both the valence band maxima and conduction band minima in these compounds. From both experimental and theoretical calculations, it is observed that the pristine compounds are of the indirect band gap-type and Sb substitution in (PA)4Bi1-xSbxI9 led to a gradual decrease in the band gap.

Lanthanide-based F-MOFs: Structure, hydrolytic stability, spectral and magnetic properties

A series of five novel lanthanide-based fluorinated metal-organic frameworks (Ln-F-MOFs) have been synthesized under solvothermal conditions by the reaction of 3,3′-bis(trifluoromethyl)-[1,1′-biphenyl]-4,4′-dicarboxylic acid (H2L) and lanthanide Ln(III) ions (Ln(III)La, Ce, Pr, Nd and Eu). Powder X-ray diffraction (PXRD) analysis revealed that all prepared complexes are isostructural. A single-crystal X-ray crystallographic study of one representative of the isostructural group, namely {[La2(L)3(DMF)2(H2O)2]}n showed, that compound crystallizes in a triclinic system with space group P-1. The lattice parameter values are a = 8.563(2) Å, b = 13.199(3) Å, c = 16.008(4) Å, α = 104.588(7) °, β = 92.904(7) ° and γ = 92.717(7) °, with two formula units in the unit cell. The overall structure is formed by 2D polymeric layers, which are arranged into a semi-3D supramolecular structure through hydrogen bonds and other intramolecular interactions. The study of the hydrophobic properties of the complexes showed that the complexes exhibit surface hydrophobicity with a “rose petal effect” and a contact angle of approximately 107°. However, the structures are not hydrolytically stable in the long term and the structure starts to delaminate after two days in water. This is a manifestation of the fact that the complexes do not form a 3D polymer network, it is made up of 2D layers connected only by weak non-bonding interactions. The photoluminescence properties of the Ln(III) complexes are determined by the characteristic 5d-4f or 4f-4f electron transitions for the individual lanthanide ions. The magnetic properties of Nd(III), Pr(III) and Eu(III) variants were studied. The magnetic properties of {[Pr2(L)3(DMF)2(H2O)2]}n are characterized by the presence of a low-lying quasi-doublet with 15.6 cm−1 energy splitting, whereas Eu(III) variant is nonmagnetic at low temperatures, but the magnetic 7F1 state is accessible by thermal excitation. For Nd(III) complex, the X-band EPR measurements were performed. Since 1D channels with dimensions of 4.90 × 7.23 Å2 are present within the structure, the adsorption of N2, CO2 and H2 gases was also studied.