Molecular Hirshfeld Surface Research Articles

A new one-pot microwave-assisted synthesis and structural analysis of 6,N2,N4-trisubstituted 1,3,5-triazine-2,4-diamines

The substituted 1,3,5-triazine-2,4-diamine motif is a well-recognised scaffold for the construction of bioactive compounds. To improve the synthetic accessibility of these compounds and expand their molecular diversity, a convenient one-pot, two-step method for the synthesis of 6,N2,N4-trisubstituted 1,3,5-triazine-2,4-diamines was developed. The three-component acid-catalysed reaction of arylaldehydes, amines, and N-arylcyanoguanidines under microwave irradiation resulted in the dihydrotriazine ring closure. The subsequent microwave irradiation of the reaction mixture after treatment with a base afforded fully aromatic 6,N2,N4-trisubstituted 1,3,5-triazine-2,4-diamines as products of dehydrogenative aromatisation. The method was rather general, tolerated structural variations of all reactants and afforded a high chemical diversity of products. The molecular structure and intermolecular interactions in the crystal of N2-phenyl-4-morpholino-6-(4-methylphenyl)-1,3,5-triazine-2-amine as a representative example were studied using X-ray crystallography and molecular Hirshfeld surface analysis. The crystal packing was stabilised by two one-dimensional motifs: hydrogen bonding between the secondary amino group and morpholine moiety oxygen and π-π stacking interactions, common for the electron-deficient 1,3,5-triazine ring.

Silver Complexes of Miconazole and Metronidazole: Potential Candidates for Melanoma Treatment.

Melanoma, arguably the deadliest form of skin cancer, is responsible for the majority of skin-cancer-related fatalities. Innovative strategies concentrate on new therapies that avoid the undesirable effects of pharmacological or medical treatment. This article discusses the chemical structures of [(MTZ)2AgNO3], [(MTZ)2Ag]2SO4, [Ag(MCZ)2NO3], [Ag(MCZ)2BF4], [Ag(MCZ)2SbF6] and [Ag(MCZ)2ClO4] (MTZ-metronidazole; MCZ-miconazole) silver(I) compounds and the possible relationship between the molecules and their cytostatic activity against melanoma cells. Molecular Hirshfeld surface analysis and computational methods were used to examine the possible association between the structure and anticancer activity of the silver(I) complexes and compare the cytotoxicity of the silver(I) complexes of metronidazole and miconazole with that of silver(I) nitrate, cisplatin, metronidazole and miconazole complexes against A375 and BJ cells. Additionally, these preliminary biological studies found the greatest IC50 values against the A375 line were demonstrated by [Ag(MCZ)2NO3] and [(MTZ)2AgNO3]. The compound [(MTZ)2AgNO3] was three-fold more toxic to the A375 cells than the reference (cisplatin) and 15 times more cytotoxic against the A375 cells than the normal BJ cells. Complexes of metronidazole with Ag(I) are considered biocompatible at a concentration below 50 µmol/L.

Theoretical Investigation Non-covalent Interactions of N-(diphenylphosphinothioyl)-2-pyrazinecarboxamide

Abstract. Phosphine chalcogenides can form reliable and reproducible supramolecular synthons through noncovalent interactions that can be employed for designing high dimensional supramolecular architectures. Here, we systematically study the influence of non-covalent interactions in the fabrication of these synthons and the stability of the crystalline structure of (N2C4H3)C(O)NHP(S)(C6H5)2 (1) through non-covalent interactions (NCI) analysis, molecular Hirshfeld surfaces and the corresponding two-dimensional (2D) fingerprint plots. The theoretical studies were employed to further confirm the presence of these synthons by comparing the stabilization energies of the dimers and monomers. The nature and electronic structure of the phosphor-chalcogenid bond in (N2C4H3)C(O)NHP(E)(OC6H5)2(E = S(1), O(2), and Se (3)) have also been evaluated by QTAIM, NBO, MEP, and HOMO-LUMO energy gaps.

Synthesis, characterization and catalytic activities of palladium(II)-imidazopyridine

The ligand 2-phenylimidazo(1,2-α)pyridine (1) was synthesized by neat reaction 2-aminopyridine and 1-bromo-acetophenone; reaction of 1 with acetonitrile solution of PdCl2 leads to [Pd(1)Cl2(CH3CN)] (2). Refluxing [Pd(1)Cl2(CH3CN)] (2) in pyridine leads to [Pd(1)Cl2(py)] (3).The complexes were characterized by various spectroscopic techniques and the solid state structure of 2 was elucidated by single crystal X-ray diffraction (SCXRD) analyses. SCXRD analyses support the square planar geometry of 2. A series of DFT calculations were also performed to gain further insight into the respective structures of the complexes. From molecular hardness calculation it is observed slightly better reactivity of 2 compared to 3. Molecular Hirshfeld surface analyses support various non-covalent secondary interactions that observed in packing of solid state structure of 2. Complexes 2 and 3 were found to facilitate Suzuki coupling reactions under relatively mild conditions and slightly better yields were obtained in case of 2.

Synthesis, structure, growth, characterization and quantum chemical studies on 2-amino-5-bromopyridinium trichloroacetate: A novel phasematchable organic NLO single crystal

Organic crystals have become excellent candidates towards nonlinear optical (NLO) applications as they possess superior second and third order optical nonlinearities and high electro-optic coefficients when compared with their inorganic counterparts. In this direction, 2-Amino-5-bromopyridinium trichloroacetate (2A5BPT), a new organic second-order nonlinear optical compound is synthesized and optical grade single crystals are formed utilizing a slow evaporation solution growth approach at room temperature while using methanol as the solvent. Single crystal X-ray diffraction study shows that the title compound is assigned to monoclinic crystal system having non-centrosymmetric space group Cc. The crystal is transparent ( ̴ 85%) throughout the whole visible spectrum, according to the Ultraviolet-Visble (UV–Vis) spectra, with a cutoff wavelength of 367 nm and an optical energy band gap Eg of 3.32 eV. The crystal possesses good thermal stability. The compound has a 1.6 times greater powder second harmonic generation (SHG) efficiency than potassium dihydrogen phosphate (KDP). The phase matchability of the 2A5BPT is studied through particle size dependence of SHG. The intermolecular connection demonstrated by numerous inter contacts has been shown by a molecular Hirshfeld surface analysis of the crystal structure, and the related 2-dimensional finger print analysis further evaluates the individual contribution from each atom. In order to examine the first order hyperpolarizability, molecular electrostatic potential, and Highest occupied molecular orbital-Lowest unoccupied molecular orbital (HOMO-LUMO) energies, the quantum chemical calculations for the title molecule (2A5BPT) were carried out by density functional theory (DFT) utilizing the B3LYP/6–311++G(d,p) basis set. According to these results, the 2A5BPT crystal could be suitable for optoelectronic applications.

Structure Elucidation, Hirshfeld Surface Analysis, Molecular Docking and Computational Studies of a Jahn-Teller Distorted Octahedral Cobalt (II) Complex with Saccharin Ligand

A Jahn-Teller distorted octahedral cobalt(II) complex with saccharin and water ligands was synthesized and characterized using single-crystal X-ray diffraction, density functional theory calculation, surface analysis (MEP and Hirshfeld) and molecular docking studies. Co(II) center is six-coordinated in a distorted octahedral arrangement, with the two water O atoms located in the axial positions, and the two water O atoms and the saccharin N atoms located in the equatorial plane. Theoretical molecular modeling was carried out with Density Functional Theory (DFT) using UB3LYP with hybrid function LANL2DZ. To support intra-molecular and inter-molecular bondings in crystal structure, molecular electrostatic potential (MEP) and Hirshfeld surfaces are generated and visualized. The molecular docking analysis was investigated between cobalt complex ligand and the receptor of breast cancer mutant PDB: 3HB5-oxidoreductase.

Experimental Spectroscopic, Structural (Monomer and Dimer), Molecular Docking, Molecular Dynamics Simulation and Hirshfeld Surface Analysis of 2-Amino-6-Methylpyridine

2-Amino-6-methylpyridine (2-AMP) was investigated experimentally using FT-IR, 1H, NMR, and UV-Vis spectra, as well as theoretically using DFT calculations. The quantum computational calculations (the optimized structure, FT-IR, NMR and UV-Vis.) to support experimental data were performed by DFT approach at B3LYP functional and 6–311 + +G(d,p) basis set. The optimized molecular geometry and wavenumber calculations were done in the gas phase, while theoretical NMR was performed in Chloroform (CHCL3) solvation. The “Potential Energy Distribution analysis” (PED) of the title compound was performed with VEDA analysis and these assignments were compared with the experimental FT-IR spectrum. Hirshfeld analysis was also performed and analyzed intermolecular interactions on the surface of crystal, However, the most significant contributions to the Hirshfeld surface come from N···H (17.3%), C···H/H···C (23%) and H···H (68.8%). Chemical reactivity studies, Molecular Electrostatic Potential (MEP) maps, and surface area maps were also conducted. To show electron delocalization in the molecule, researchers used the electron localization function (ELF). Other topics included topological and mulliken charge distribution studies. Natural Bond Order Analysis (NBO) was performed to interpret intermolecular charge transfer.The effect of temperature on thermodynamical parameters such as Gibbs free energy, enthalpy, and entropy was examined. TD-DFT analysis was also used to shed more light on how the electronic transitions in the UV–Vis spectra were estimated. For different solvents, the estimated maximum wavelength (λ) absorbance and the band-gap energy of 2-AMP were calculated and compared to experimental results. The molecule's bioactivity is described theoretically using the Electrophilicity index and the interaction between the ligand-protein is depicted using Molecular docking. The proteins 3DQS, 4UX6, 5ADF, 5TUD, and 6E9L were studied via molecular docking. The nature of the molecule was determined by its drug-likeness. A molecular dynamics simulation was used to explore biomolecular stability.

Structural investigations and catalytic performances of a new oxovanadium complex derived from 1,2-bis((E)-5-bromo-2-hydroxybenzylideneamino)-4-methylbenzene

A new unsymmetrical oxovanadium Schiff-base complex VOL was prepared by using stoichiometric amounts of Schiff-base ligand 1,2-bis((E)-5-bromo-2-hydroxybenzyl-ideneamino)-4-methylbenzene and VO(acac)2. Characterization of the ligand H2L and the corresponding VOL complex were performed using elemental analysis, spectroscopic methods as FT-IR, UV-Vis, 1H and 13C NMR. The VOL complex crystallizes, in the monoclinic crystal system, with P21/c space group. All experimental results were proved and explained theoretically exploiting Density Functional Theory calculations, DFT. Molar conductance measures confirmed the non-electrolytic nature of the metal complex. Similarly, the electrochemical behavior for both the ligand and the VOL complex have been investigated by cyclic voltammetry, CV. The complex gave a one-electron quasi-reversible redox couple at +568 mV/SCE corresponding to the VOIV/VOV redox process. The various inter contacts present within the crystal were visualized through 3D molecular hirshfeld surface analysis and their percentage contribution towards the total hirshfeld surface area has been quantized using 2D finger print plot method.The catalytic performances of the VOL complex in the epoxidation of cyclohexene were explored by various reaction parameters including temperature and solvent effects, oxidant, cyclohexene/oxidant ratio and the catalyst amount. The results show that the system corresponds to an active and a selective catalyst in the oxidation of cyclohexene. Superb catalytic activity of 98% cyclohexene conversion with 86% cyclohexene oxide selectivity were obtained over 5h.

Hirshfeld surface analysis and quantum chemical study of molecular structure of phosphate

ABSTRACT. In this present study, Density fuctional theoretical computations are performed at (B3LYP, PBEPBE), HF and MP2 level with 3-21G basis sets to derive optimized geometry and bonding features. The calculated geometrical parameters have been compared with experimental data. The intermolecular O–H…O and N–H…O hydrogen bonds are involved in crystal structure stabilization. An intramolecular O–H…N hydrogen bond is observed between the phosphate OH group and the N atom. Further, the molecular Hirshfeld surface analysis was carried out to reveal the nature of intermolecular contacts and the fingerprint plot provides the information about the percentage contribution and reveals that the O…H (44.1%) interactions have the major contribution to form the crystal. The Mulliken population analysis and the HOMO-LUMO energy gaps show that the molecule has a good stability and from the calculation, we conclude that the molecule is really hard materials.
 
 KEY WORDS: Energy gaps, Hydrogen bonds, Hirshfeld surface, Mulliken population, Phosphate
 
 Bull. Chem. Soc. Ethiop. 2021, 35(3), 625-638.
 DOI: https://dx.doi.org/10.4314/bcse.v35i3.13

Electron density of a benzoylated tetrafructopyranose

Abstract The electron density distribution (EDD) of a tetrasaccharide composed of four benzoylated fructopyranosyl units was obtained by refinement with scattering factors from the invariom library. X-ray diffraction data was downloaded from the Cambridge Structural Database (CSD). Bond topological and atomic properties were obtained by application of Bader’s QTAIM formalism. From a large number of 105 C–C bonds in the molecule average bond orders for 33 single and 72 aromatic bonds were calculated yielding values of 1.33 and 1.61. Molecular Hirshfeld and electrostatic potential (ESP) surfaces show that only weak non-covalent interactions exist. The phenyl rings of the benzoyl fragments in the outer regions of the molecule generate a positive ESP shell with repulsive properties between adjacent molecules. Weak surface interactions result in a rather unusual low density around 1.3 g cm−3, which is understandable when compared to other carbohydrates where strong O–H⋯O hydrogen bonds allow a 20% more dense packing with densities >1.5 g cm−3 as determined by single crystal X-ray diffraction.

Theoretical studies on structure-directing interactions of diphenyl N-(2-pyrazinyl carbonyl) phosphoramidate

Herein, we report the strength of structure-directing interactions in the crystal packing of diphenyl N-(2-pyrazinyl carbonyl) phosphoramidate (1) through computing their binding energies by DFT. Further, the non-covalent interaction (NCI) analysis, molecular Hirshfeld surfaces, and the corresponding two-dimensional fingerprint plots are obtained to gain a deep understanding of the importance of these interactions in the stability of a crystal structure. Despite the important role of the phosphorus—chalcogenid bond in optimizing tertiary phosphine chalcogenides, their computational studies have been lagging far behind. The nature and electronic structure of this bond in (N2C4H3)C(O)NHP(E)(OC6H5)2 (E = O (1), S (2), and Se (3)) are evaluated by QTAIM, MEP, and HOMO—LUMO energy gaps.

Experimental, computational analysis of new organic NLO crystal: Piperazinium nicotinic acid and its efficiency in optoelectronic applications

Abstract Slow evaporation solution growth method was adapted for the effective growth of single crystals of piperazinium nicotinic acid (PNA) in distilled water. Single crystal X-ray diffraction analysis was used to investigate the cell parameters of crystalline PNA and the grown crystal belongs to triclinic crystal family with the space group Pī. 3-D molecular hirshfeld surface analysis was supported to visualize the various inter contacts present within the crystal and their percentage contribution to the total hirshfeld surface area was quantified using the 2D finger print plot process. DFT approach was carried out to conduct the theoretical investigation and HOMO-LUMO energy band difference was calculated. B3LYP level of theory with 6-31++G (d,p) basis set was employed to compute the Molecular optimized geometry, FT-IR, FT-Raman and HOMO-LUMO energy distance. FT-IR and FT-Raman spectral studies have accompanied for looking into the modes of vibration of various functional groups in the PNA crystal. UV–visible NIR transmittance studies have revealed that the grown crystal has high transmittance in the entire visible region. Single beam Z-scan technique was explored to determine the third-order nonlinear optical nature and susceptibility of the grown PNA crystal. The results of computational and experimental values suggest suitability and potentiality of PNA crystal for NLO and optical limiting applications.

Growth, computational studies, and docking analysis on α-pyrrolidinopentiophenone hydrochloride monohydrate single crystal

The title compound, α -pyrrolidinopentiophenone hydrochloride monohydrate (α-PVP) was grown using the solvent methanol through solution growth technique at room temperature. The crystalline nature and its parameters were confirmed by single and powder X-ray diffraction (XRD) studies. The Fourier Transform Infrared Spectroscopy was used to identify the presence of vibrational frequencies for the title compound. UV–vis-NIR spectral and fluorescence analyses were carried out in order to ascertain its optical properties. Through 3D molecular Hirshfeld surface analysis, the crystal with multi inter contacts was pictured while its total surface area was quantified using a 2D fingerprint generated by DFT/B3LYP/6–311++G (d,p) in the standard basis set method, and the bandgap energy was measured. The MEP map was examined, for analyzing electrophilic and nucleophilic attack sites. The molecular NLO properties such as static dipole moment, mean polarizability, anisotropy of polarizability, and first-order hyperpolarizability were calculated. To investigate the biological activity of the α-PVP molecule, molecular docking was used to determine the lengths of hydrogen bonds and binding energy with various antifungal proteins.

Guest-Mediated Hierarchical Self-Assembly of Dissymmetric Organic Cages to Form Supramolecular Ferroelectrics

Guest-Mediated Hierarchical Self-Assembly of Dissymmetric Organic Cages to Form Supramolecular Ferroelectrics

Synthesis, structure and molecular Hirshfeld surface analysis of polymeric cadmium(II) complex involving tetradentate N3S-donor ligand and dicyanamide as bridging ligand

One new polymeric cadmium(II) complex {[Cd(bdmpe)(µ 1,5 -dca)]ClO 4 .CH 3 OH} n has been synthesized by the reaction of cadmium perchlorate with ligand N,N -bis((3,5-dimethyl- 1H -pyrazol-1-yl)methyl)-2- phenylthio)ethan-1-amine (bdmpe) in presence of dca (dicyanamide, N(CN) 2 - ) as bridging ligand in methanol and characterized by spectroscopic techniques. Single crystal X-ray diffraction study of the complex confirmed that it has polymeric 1D chain and each cadmium centre has distorted octahedral geometry with N 5 S coordination and is bonded through two terminal nitrile group of the dca ligand using m 1,5 coordination modes. Intermolecular interactions and packing modes of the compound are described by Hirshfeld surface analysis and two dimensional finger print plots.

Synthesis, crystal and structural characterization, Hirshfeld surface analysis and DFT calculations of three symmetrical and asymmetrical phosphonium salts

Three stable phosphonium salts of 1,4-butanediylebis(triphenylphosphonium) dibromide I, butane-4‑bromo-1-(triphenylphosphonium) bromide II and 1,3-propanediylbis(triphenylphosphonium) tetrahydroborate III were synthesized and structurally characterized. Single crystal X-ray diffraction analysis, spectroscopic methods and thermal analysis methods were used for the characterization of titled compounds. Crystallographic data showed that compound I crystallized in the triclinic crystal system with Pī space group and compound II crystallized in the monoclinic crystal system with P21/c space group. The crystal packing structures of I and II were stabilized by various intermolecular interactions, especially of CH···π contacts. The molecular Hirshfeld surface analysis and 2D fingerprint revealed that the C···H contacts have 24.3% and 18.4% contributions in the crystal packings of compounds I and II, respectively. In addition, the H···Br (28.5%) contact has a considerable contribution to the crystal architecture of compound II. Theoretical studies were performed by DFT method to investigate the structural properties of the titled compounds. The isotopic ratio of boron in tetrahydroborate anion of compound III calculated by 1H NMR spectroscopy. The isotopic ratio for 10B/11B was 19.099 / 80.900%. Reduction of some carbonyl compounds to corresponding alcohols was performed by compound III and the optimum conditions were determined.

Study of dielectric relaxation and polaron conductivity mechanism in sodium nitroprusside (SNP): Na2[Fe(CN)5(NO)]·2H2O

In this study, the crystal structure of sodium nitroprusside, Na 2 [Fe(CN) 5 (NO)]·2H20, has been determined by an analysis by X-ray diffraction (XRD). The crystal is orthorhombic, space group Pnnm. This compound is characterized by different techniques: X-ray diffraction (XRD), differential scanning calorimetry (DSC) and impedance spectroscopy. For electrical properties, impedance spectroscopy was performed at a frequency range of 20 Hz–2 MHz. The dependence of AC conductivity on frequency was found to satisfy Jonscher's universal power law at different temperatures σ ( ω ) = σ D C ( ω , T ) + A ω S ( T , ω ) . This suggested hoping conduction due to three theoretical models. The latter can be attributed to the correlated barrier hopping (CBH) model in region I, overlapping large polaron tunneling (OLPT) in region II and non-overlapping small polaron tunneling (NSPT) mechanism in region III. The temperature dependence and dielectric relaxation of the DC conductivity satisfied the Arrhenius law. The activation energy ranged from 0.033 to 0.164 eV and was similar in the conduction and relaxation mechanisms, indicating that the transport mechanisms were based on hopping phenomena. Moreover, the modulus plots has been characterized by full width at half height or in terms of a non-experiential decay function ϕ(t) = exp(−t/τ)β. The values of the activation energies obtained from the electrical conductivity and electric modulus are near; which suggests that the transport is probably due to the ion hopping mechanisms. Furthermore, this behavior was confirmed by both Nyquist and Argand's plots of dielectric impedance at different measuring temperatures. Crystal structure, Molecular Hirshfeld surfaces, hydrogen bonding, UV absorption and phase transition of the β-NH 3 (CH 2 ) 2 NH 3 SnCl 6 compound. • This compound is crystallized in the orthorhombic system (Pnnm space group). • Differential scanning calorimetric (DSC) experiments show a phase transition at 130 K and 155 K. • The conduction mechanism is attributed to the (CBH) model, (OLPT) and (NSPT) mechanism. • The activation energies suggest that the transport is probably due to the ion hopping mechanisms. • The near value of activation energies obtained from the analysis of M.

Towards the Synthesis of Imidazopyridine Derivatives: Characterization, Single Crystal XRD, Hirshfeld Analysis, and Biological Evaluation

AbstractThis study explores the synthesis of different imidazopyridine derivatives, their characterization, single crystal x‐ray diffraction, molecular Hirshfeld surface analysis along with their anticancer and other supportive biological evaluations. X‐ray crystallography study resolved the crystal structure of 2,7‐dimethyl‐N‐(1,3‐dioxoisoindolin‐2‐yl)H‐imidazo[1,2‐a]pyridine‐3‐carboxamide (2 a) as monoclinic crystal system (space group P21/n). Graphical tool, Hirshfeld surface analysis quantified the major contribution of H⋅⋅⋅H, O⋅⋅⋅H, and C⋅⋅⋅H interactions towards the HS. Among the synthesized compounds, 2‐(4‐(4‐fluorophenyl)‐5‐(2,8‐dimethylH‐imidazo[1,2‐a]pyridin‐3‐yl)‐4H‐1,2,4‐triazol‐3‐ylthio)‐N‐(4‐fluorophenyl)acetamide (5 a) exhibited the highest cytotoxicity against lung adenocarcinoma with IC50 value of 43.04 μM. Selective action of 5 a was assured by cell death analysis using AO‐EB assay. In addition, the study was also supported by molecular docking studies. Together the study revealed, the compound 5 a, to be a likely candidate for further exploratory study in cancer treatment.

Synthesis, Characterization, Crystal Structure and Quantum Chemical Calculations of 2-oxo-2H-chromen-3-yl Acetate

This paper is focused on a combined experimental and theoretical study of 3-substituted coumarin derivative, the 2-oxo-2H-chromen-3-yl acetate (I). The compound was synthesized by reacting chroman-2,3-dione and acetic anhydride in dried diethyl ether in the presence of dried pyridine and crystallized in the orthorhombic crystal system with Pbca space group. The lattice parameters of the structure are a=14.6770 (1), b=7.1079 (1), c=17.6767 (2) Å, α=β=γ=90° with 8 molecules per unit cell (Z=8). The compound has been characterized structurally by Spectroscopy utilizing ¹H NMR, ¹³C NMR and IR techniques and by crystallography using the X-Ray diffraction (XRD) analysis. In the crystallographic study, the positions of the atoms were determined by direct methods and refined to a final R value of 0.038 for 1768 independent reflections. The stabilization of the structure is provided by intermolecular C-H•••O hydrogen bonds extending along [010] direction. Likewise, the presence and nature of intermolecular contacts are determined by the 3-D molecular Hirshfeld surface and 2-D fingerprint plot analysis which indicate the main contributions to the Hirshfeld surface, 38.7% for O ••• H and 28.7% for H •• H. Moreover, the molecular geometry of (I) was as well minimized utilizing density functional theory (DFT/RB3LYP), the frequency calculations with RB3LYP method, the basic <i>ab initio</i> model i.e the restricted Hartree-Fock (RHF) and the exchange component of Perdew and Wang’s 1991 functional B3PW91 methods with the 6-311⁺⁺G(d, p) basis set in ground state. The derived structural parameters highlight very good correlation with the crystallographic results. Frontier molecular orbitals (HOMO-LUMO), their energy gap, the non-linear optical effects (NLO) and related reactive parameters were also computed to better apprehend the properties of the molecule.

Molecular structure, Hirshfeld surface and density functional theoretical analysis of a NLO active chalcone derivative single crystal—A quantum chemical approach

Nonlinear optically active thienyl chalcone, with molecular formula C16H15ClO4S has been synthesized by adopting claisen-schimdt condensation reaction method. FT-IR and NMR spectral study was used to identify the functional groups present in the newly synthesized compound and confirm the molecular structure. Based on the solubility study DMF is chosen as solvent to grow single crystals of the compound using slow evaporation (solution growth) technique. The single crystal XRD study reveals that the grown crystal belongs to the orthorhombic crystal system with Pbca space group and the associated cell parameters are, a = 16.6575 (6) Å, b = 8.1147 (3) Å, c = 23.6618 (9) Å, α = β = γ = 90°. The linear optical properties were studied using UV-–visible, Photoluminescence method. The energy band gap of the material was calculated using tauc's plots. The refractive index (1.47) of the crystal was determined using Brewster's angle method. Second harmonic generation (SHG) test was carried out using Kurtz and Perry powder technique and SHG efficiency of 1.82 times that of urea was estimated. The thermal stability of the compound was tested by thermo gravimetric and differential thermal analysis. Various inter contacts present within the crystal were visualized through 3-D molecular hirshfeld surface analysis and their percentage contribution towards the total hirshfeld surface area has been quantized using 2D finger print plot method. The theoretical investigation was carried out using DFT method and HOMO-LUMO energy band gap was determined. The different global chemical reactivity descriptors (GCRDs) parameters were calculated. The molecular electrostatic potential map of the molecule was analyzed and the sites of electrophilic and nucleophilic attacks were predicted. The molecular NLO properties such as static dipole moment, mean polarizability, anisotropy of polarizability and first order hyper polarizability values were theoretically determined.