Hirshfeld Analysis Research Articles

Crystal structures and Hirshfeld analysis of 4,6-di-bromo-indole-nine and its quaternized salt.

4,6-Di-bromo-2,3,3-trimethyl-3H-indole, C11H11Br2N, exists as a neutral mol-ecule in the asymmetric unit. The asymmetric unit of 4,6-di-bromo-2,3,3-trimethyl-3H-indol-1-ium iodide, C12H14Br2N+·I-, contains one organic cation and one iodine anion. The positive charge is localized on the quaternized nitro-gen atom. In the crystal, mol-ecules of 4,6-di-bromo-indole-nine are linked by C-Br⋯π halogen bonds, forming zigzag chains propagating in the [001] direction. The mol-ecules of the salt form layers parallel to the (010) plane where they are linked by C-H⋯Br hydrogen bonds, C-Br⋯Br and C-Br⋯I halogen bonds. The Hirshfeld surface analysis and two dimensional fingerprint plots were used to analyse the inter-molecular contacts present in both crystals.

Structure-property correlation of halogen substituted benzothiazole crystals

• Three halogen substituted benzothiazole crystals were grown by slow evaporation technique. • One crystal is found to be elastically bendable and the other two were found to be brittle. The crystals were fluorescent as well. • Crystal packing analysis, Hirshfeld analysis etc. were done to get insights of structure-property correlation. We have synthesized 3 benzothiazole crystals ( 1–3 ) based on existing knowledge of combining flexibility and optical properties towards achieving applications for flexible optoelectronics. However, one crystal was found to be elastically bendable and was found to comply necessary packing features for elasticity. Other two crystals do not obey packing features for elasticity hence they are brittle in nature. Further, Hirshfeld analysis illustrates that elastic crystal 1 possess more number of weak and dispersive interactions compared to other crystals. These interactions were instrumental in invoking elasticity. Moreover, crystals 1–3 were found to be fluorescent as well at specific excitation wavelengths. Therefore, among these crystals, particularly crystal 1 is considered as more promising candidate for flexible optoelectronics.

Design, spectroscopy, quantum chemical study and Hirshfeld analysis of single crystal ferrocene-based boronate ester

• Theoretical results obtained by density functional theory (DFT/LanL2DZ) were compared with the experimental results. • FT-IR and 1 H– 13 C- 11 B NMR spectra were recorded and compared with the theoretical results. • NLO, NBO and Hirshfeld surface analysis of the molecule were studied. • HOMO and LUMO energies, MEP distribution of the molecule were calculated. Ferrocene-based boronate ester (FeBE) , given by the C 18 H 21 BFeO 2 formula, has been prepared by the reactions of 4,4-Bis(hydroxymethyl)-1-cyclohexene and ferrocene boronic acid and the Dean-Stark system have been used for the remove the water formed during the reaction. The structure of this boronate ester has been characterized using 1 H, 13 C, and 11 B NMR (Nuclear magnetic resonance), FT/IR (Fourier Transform Infrared) spectroscopy, UV/Vis absorption spectroscopy (Ultraviolet Visible spectroscopy), LC-MS/MS spectrometer (Liquid Chromatography with tandem mass spectrometry), elemental analyses, and Single Crystal XRD. Further, the intermolecular H-bonds and π-ring interactions have been demonstrated through 3D-Hirshfeld surface (HS) analysis. The compound has crystallization in the monoclinic space group I2/a, a = 20.74(9), b = 6.05(3), c = 25.12(10) Å, β = 90.06(4)°, and V = 3155.0(2)Å 3 in the unit cell. Further, the molecular geometry, FT/IR frequencies, UV/Vis wavelengths were obtained by using the DFT (Density Functional Theory) with LanL2DZ.

Molecular, Supramolecular Structures Combined with Hirshfeld and DFT Studies of Centrosymmetric M(II)-azido {M=Ni(II), Fe(II) or Zn(II)} Complexes of 4-Benzoylpyridine

The supramolecular structures of the three metal (II) azido complexes [Fe(4bzpy)4(N3)2]; 1, [Ni(4bzpy)4(N3)2]; 2 and [Zn(4bzpy)2(N3)2]n; 3 with 4-benzoylpyridine (4bzpy) were presented. All complexes contain hexa-coordinated divalent metal ions with a slightly distorted octahedral MN6 coordination sphere. Complexes 1 and 2 are monomeric with terminal azido groups while 3 is one-dimensional coordination polymer containing azido groups with μ(1,1) and μ(1,3) bridging modes of bonding. Hirshfeld analysis was used to quantitatively determine the different contacts affecting the molecular packing in the studied complexes. The most common interactions are the polar O…H and N…H interactions and the hydrophobic C…H contacts. The charges at the M(II) sites are calculated to be 1.004, 0.847, and 1.147 e for complexes 1–3, respectively. The degree of asymmetry is the highest in the case of the terminal azide in complexes 1 and 2 while was found the lowest in the μ(1,1) and μ(1,3) azide bonding modes in the Zn(II) complex 3. These facts were further explained in terms of atoms in molecules (AIM) topological parameters.

Supramolecular Assembly of Morpholin-4-ium hydroxy(diphenyl)acetate—Structural, Spectral and Nonlinear Optical Analyses

A supramolecular assembly of Morpholin-4-ium hydroxy(diphenyl)acetate (MHA) was synthesized by acquiring morpholine and benzilic acid in equimolar ratio via solvent vaporization technique using methanol as a solvent. The structure of MHA was analyzed by single-crystal X-ray diffraction analysis, which confirms that the crystal is crystallized in a monoclinic crystal system with C2/c centrosymmetric space group. The molecule was stabilized via NH….O and OH..O supramolecular assembly networks. Close contacts are observed over dnorm surface with red spots, from Hirshfeld analysis which are owing to OH…O and NH…O intermolecular interactions. 1H NMR analysis confirmed the migration of proton from benzilic acid to morpholine and in 13C NMR analysis, the signal at δ 176.36 ppm confirmed the presence of highly deshielded carboxylate carbon in the molecule. The vibrational frequencies associated with the functional groups in the MHA crystal are estimated using Fourier transform infrared spectroscopy. Refractive index (n) and extinction coefficient (K), bandgap, optical conductivity (σop), electrical conductivity (σel), optical susceptibility (χop) and polarization (P) were estimated using UV–vis spectroscopy. Fluorescence peaks were observed at 334 and 380 nm via photoluminescence spectroscopy. The third order nonlinear optical properties were obtained using Z-scan studies. The Z-scan curve in the closed aperture configuration indicates the change in refractive index of the MHA crystal with a strong self-defocusing effect.

The position of NH2-subsituted group controlled the luminescent properties based on 4-amino-4H-1,2,4-triazole: Syntheses, crystal structures and Hirshfeld analyses

The tunable photoluminescent materials has drawn extensive attention in recent years. The position of the substituents tuned the luminescent materials are one of attractive methods. Herein, we present a feasible and facile strategy to achieve a 4-amino-1,2,4-1H-triazole-based organic materials. A set of compounds based on 4-amino-4H-1,2,4-triazole group, namely, x,x'-(4-amino-4H-1,2,4-triazole-3,5-diyl)dianiline [x ​= ​2 (1), x ​= ​3 (2), x ​= ​4 (3)] (the formulas are C14H14N6, C14H14N6 and C14H16N6O for compounds 1–3, respectively), were obtained. The title compounds 1–3 have been characterized by IR, UV–Vis, element analysis (EA), single crystal X-ray diffraction, and powder X-ray diffraction (PXRD). In these compounds, a plenty of hydrogen bonds (C/N–H⋯O/N) and C–H … π can be obviously found. The order of the packing interactions is represented as the following: 2 ​> ​3>1. The Hirshfeld surface analyses reveal that the contribution order of the H⋯H bond contacts in compounds 1–3 is listed: 2 ​> ​3>1, which is in a good agreement with that of the stacking interactions. The solid-state luminescent spectra of 1–3 show that the emission maxima are observed at 404, 377 and 457 ​nm, respectively, where the order of the peaks is represented as 3 ​> ​1>2. The Hirshfeld surface analyses show that the contribution order of the C⋯H/H⋯C close contacts is listed: 3 ​> ​1>2, which is in a good accordance with that of the fluorescent maxima.

The Use of Hirshfeld Surface Analysis Tools to Study the Intermolecular Interactions in Single Molecule Magnets

Intermolecular interactions have proved to play an important role in properties of SMMs such as quantum tunneling of magnetization (QTM), and they also reduce the rate of magnetic relaxation, as through the influence they have on QTM, they quicken the reverse of magnetization. In addition, they are considered as the generative cause of the exchange-biased phenomenon. Using the Hirshfeld analysis tools, all the intermolecular interactions of a molecule and its neighbors are revealed, and this leads to a systematic study of the observed interactions, which could probably be helpful in other studies, such as theoretical calculations. In addition, they could be helpful to design new systems because intermolecular interactions in SMMs have been proposed as a probable tool to monitor their properties. The observation of characteristic patterns on the Hirshfeld Surfaces (HS) decorated with different properties makes easier the recognition of possible structural pathways for the different types of interactions of a molecule with its surrounding.

Supramolecular architectures in dihydropyridones: Synthesis, crystal structure, Hirshfeld analysis, cytotoxicity and in silico studies

In this study, a series of five non-aromatic dihydropyridones were synthesized, crystallized, and single-crystal X-ray diffraction was used to obtain their molecular geometries. The supramolecular assembly of the molecules through non-covalent interactions was then studied and demonstrated. The weak intermolecular interactions in the molecular packing of compounds were further validated through Hirshfeld surface analysis. The synthesized compounds were screened in vitro using lung adenocarcinoma (A549) cells to assess their cytotoxic effects. A molecular docking study has also been employed to gain insight into the binding mode of the synthesized compounds in the allosteric binding pocket of the Eg5 motor domain and survivin protein. The results showed that the title compounds have mild to moderate cytotoxic effects in these cells. Ethyl-5-cyano-4-(2,5-dimethoxyphenyl)-2-methyl-6-oxo-1,4,5,6-tetrahydropyridine-3-carb-oxylate has shown more significant cytotoxicity among all the synthesized compounds. This study has further demonstrated the importance of non-covalent intermolecular interactions of dihydropyridones for exhibiting diverse supramolecular architectures as well as for having a significant binding affinity towards the receptor.

Cyclometalated Platinum(II) β‐Diketonate Complexes with Extremely High External Quantum Efficiency for White Organic Light‐Emitting Diodes

AbstractThree cyclometalated Pt(II) β‐diketonate compounds with sky‐blue to green phosphorescence are prepared by modifying the substituents of the 2′,6′‐dimethoxy‐2,3′‐bipyridine (OMe2pypy, C^N) chelate ligand. These molecules have the general formula Pt(C^N)(O^O), where O^O = acetylacetonate; one is unsubstituted (1), one possesses a trimethylsilyl (TMS) substituent (2), and the other is substituted with dimesitylboron (BMes2) (3). The intermolecular interactions of 2 are greater than those of 1 and 3, based on color mapping and surface area results from Hirshfeld analyses. Time‐dependent density functional theory calculations reveal that the electronic transitions of monomeric 1 and 3 are predominantly intraligand or ligand‐to‐ligand charge transfer mixed with metal‐to‐ligand charge transfer transitions, while for the dimeric forms, dimeric 2, an additional strong metal–metal‐to‐ligand charge transfer transition is observed. White organic light‐emitting diode (WOLED) devices using an 1,3‐bis(N‐carbazolyl)benzene (mCP) or mCP:TSPO1(diphenyl[4‐(triphenylsilyl)phenyl]phosphine oxide) mixed host and 1–3 as dopants are fabricated. With a dopant concentration of 20 wt% in the emissive layer, compound 2 exhibited bright yellow–green emission with a maximum external quantum efficiency (EQE) of 24.9%. This result corresponds to one of the highest EQEs among the reported C^N chelated Pt(II) β‐diketonate‐based WOLEDs.

Electronic, NLO, computational and interaction analyses of DAPVMPTFB crystals for electro-optics and electronic industrial utilities

2-{2-(4-Diethylamino-phenyl)-vinyl}-1-methyl-pyridinium-tetrafluoroborate(DAPVMPTFB) organic non linear optical (NLO) crystals are grown by slow evaporation method and analyzed for XRD, carbon hydrogen nitrogen sulphur and oxygen (CHNSO) analyzer, computational, influx and dielectric studies. X-ray diffraction (XRD) analysis demonstrated the lattice parameters (a-7.8969 Å, b-20.4867 Å, c-11.1989 Å, α = γ as 90° and β as 92.407°). The chemical formula of the as-synthesized crystal is C18H23BF4N2. The presences of elements are identified theoretically and experimentally. The surface roughness of as-prepared crystal was studied by atomic force microscopy (AFM) image analysis. The NLO is 1.15 times higher than the referenced KDP specimen due to strong H atoms of 23 in the specimen. The macro influx for filters is 4.7371 µm; the structural parameters, as well as energy, interactions and Halosian with dotted effect, molecular potential, interactions, internal in addition to the external fields, shape indexing; curvedness; fragmented patching; finger print region by computational based Hirshfeld analysis (HFA), are well portrayed using the software. The dielectric utility is mainly for industries in manufacturing semiconductors. The Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram portrays the grown crystalline structural portrayal as well as the supercell effect for special volume unit cells by software.

Combined Conceptual-DFT, Quantitative MEP Analysis, and Molecular Docking Study of Benzodiazepine Analogs

In the present work, a combined approach based on conceptual-DFT formalism and molecular docking simulations were performed to investigate the chemical reactivity of six Benzodiazepine analogs. Chemical reactivity descriptors derived from the conceptual DFT were determined and discussed to explain the global and local reactivity of the six studied analogs. Also, long-range interactions were studied using the quantitative analyses of molecular electrostatic potential (MEP) on van der Waals surface to identify the nucleophilic and electrophilic sites. Moreover, a statistical analysis was performed to assess the robustness of atomic charges to the basis set. The results revealed that Hirshfeld population analysis (HPA) was the most efficient for this purpose. Molecular docking simulations were performed to predict the binding affinities of the issued molecules and estimate the binding poses into four binding sites, three of them were recently discovered, located in GABA A receptor. DOI: http://dx.doi.org/10.17807/orbital.v13i4.1607

DFT Calculation, Hirshfeld Analysis and X-Ray Crystal Structure of Some Synthesized N-alkylated(S-alkylated)-[1,2,4]triazolo[1,5-a]quinazolines

The present work aimed to synthesize 2-methylthio-triazoloquinazoline derivatives and study their X-ray, NMR, DFT and Hirshfeld characteristics. The cyclocondensation of dimethyl-N-cyanodithiocarbonate with 2-hydrazinobenzoic acid hydrochloride resulted in an intermediate, 2-methylthio-[1,2,4]triazolo[1,5-a]quinazolin-5-one (A), which upon treatment with phosphorus pentasulfide, transformed into the 2-methylthio-[1,2,4]triazolo[1,5-a]quinazolin-5-thione (B). Reaction of 2-methylthio-triazoloquinazolines (A&B) with alkyl halides (allyl bromide and ethyl iodide) in basic medium afforded 4-allyl-2-methylthio-[1,2,4]triazolo[1,5-a]quinazolin-5-one (1; N-alkylated) and 5-ethylthio-2-methylthio-[1,2,4]triazolo[1,5-a]quinazoline (2; S-alkylated), respectively. Their molecular and supramolecular structures were presented. Unambiguously, the molecular structures of 1 and 2 were confirmed via NMR and single-crystal X-ray diffraction. The resulting findings confirmed the structures of 1 and 2 and determined their crystalized system (monoclinic system; P21/n space group). Hirshfeld analysis of 1 revealed the importance of the significantly short O···H (6.7%), S···S (1.2%) and C···C (2.8%); however, the short H···H (42.6%), S···H (16.3%) and C···C (4.3%) were showed in 2 by intermolecular interactions in the molecular packing. The 1,2,4-triazoloquinzolines (1&2) were anticipated to be relatively polar compounds with net dipole moments of 2.9284 and 4.2127 Debye, respectively. The molecular electrostatic potential, atomic charge distribution maps and reactivity descriptors for 1 and 2 were also determined. The calculated nuclear magnetic resonance spectra of the targets 1 and 2 were well correlated with the experimental data.

Synthesis, crystal structures, Hirshfeld surface analysis, theoretical insight and molecular docking studies of dinuclear and triply bridged Cu(II) carboxylate complexes with 2,2′-bipyridine or 1,10-phenanthroline

Two new complexes, namely [Cu2(μ-2-nitrobenzoate)2(bpy)2(Cl)2]H2O (1) and [Cu2(μ-acetato)(phen)2(μ-OH)(μ-H2O](BF4)2 (2), where bpy = 2,2′-bipyridine and phen = 1,10-phenanthroline, were synthesized and structurally characterized by single crystal X-ray diffraction. Complex 1 crystallized in the monoclinic crystal system with the space group P 21/n, while complex 2 crystallized in the orthorhombic crystal system with the space group P212121. Compounds 1 and 2 display distorted square pyramidal coordination geometries, which are related to CuN2O2O’ and CuN2O2Cl chromophores. Hirshfeld analyses were carried out to observe the different contacts in the crystal structures. It was confirmed that van der Waals forces were behind the stacking of the molecules in the crystal lattice. Density Functional Theory (DFT) was used to understand the electronic structures of the two complexes and docking studies were carried out to examine how the complexes interacted with proteins involved in bacterial infection and with DNA.

Structural characterization, theoretical and antibacterial study of a V-shaped, cyclohexane bridged ONNO Schiff base

A tetradentate ONNO Schiff base bearing two chloro substituents, namely 6,6′-((1E,1′E)-(cyclohexane-1,2-diylbis(azanylylidene))bis(methanylylidene))bis(2-chlorophenol) (AD2C), was obtained through condensation of 3-chlorosalicyladehyde with 1,2-cyclohexanediamine. Structure elucidation was performed through physicochemical and spectroscopic analyses viz. melting point, elemental analysis, FTIR, 1H and 13C NMR, UV-Visible and single crystal X-ray diffraction. The ν(C=N) was observed at 1626 cm−1 while the azomethine proton and carbon chemical shifts appeared at 8.27 ppm and 157.56 ppm, respectively. The n‒π*(C=N) absorption band was observed at 324 nm. The crystal structure was stabilized by intramolecular hydrogen bond O˗H···N and intermolecular hydrogen bonds C˗H···O, C˗H···Cl, C˗H···π as well as π···π interactions. The existence of intermolecular interactions was confirmed through Hirshfeld analysis, showing high contribution of H⋯H contact. The B3LYP method was used to calculate the optimized structure of the molecule through density functional theory (DFT) using the 6–311++G(d, p) basis set and was found to be consistent with the X-ray diffraction value. The frontier molecular orbitals and molecular electrostatic potential of the compound investigated through DFT calculations revealed a significantly large energy gap of 4.615 eV and nucleophilic regions located at the hydroxyl groups. The compound showed no antibacterial activity against five bacterial strains namely Bacillus subtilis (ATCC 6633), Proteus vulgaris (ATCC 6380), Pseudomonas aeruginosa, Staphylococcus aureus subsp. aureus Rosenbach (ATCC 6538) and Streptococcus mutans Clarke (ATCC 700,610).

Crystal structure, powder X-Ray diffraction, Hirshfeld, thermal, Infrared-Raman studies, and symmetry analysis of the relationship between the novel tetragonal [(CH3)4N]2SiF6 and the cubic Fm3m antifluorite structure

In the present paper a novel tetragonal form of the [(CH3)4N]2SiF6 compound is investigated and compared with its already studies cubic antifluorite form (Fm3m). The single crystal and powder X-ray diffractions showed that the novel compound form crystallizes at ambient temperature in the tetragonal space group I4/m (Z = 4). The comparable space groups and parametrs obtained from single crystal and powder diffractions checked the purity of the tetragonal form. The importance of H…F/F…H (55%) and H…H (45%) intercontacts in the crystal packing are determined by the 3D Hirshfeld surfaces and the 2D fringplots analyses. Based on the Landau theory analysis, the novel tetragonal form may be derived from the antifluorite cubic form by a transition made at the Γ-Point of the Brillouin zone of the high-symmetry phase Fm3m. The lowering symmetry distortion (Fm3m→ I4/m) could be due to the anions and cations rotations around the c axis [001]. The DSC analysis showed two endothermic anomalies (12 °C/-2 °C) and (155 °C/150 °C) observed in heating/cooling, indicating that [(CH3)4N]2SiF6 exhibits two continuous reversible phase transitions of second order character. The optimal molecular geometries and thermodynamic properties of [(CH3)4N]2SiF6 have been determined by the PM3 and DFT/B3LYP 6-31G** methods. The calculated vibrational frequencies were generally closed to the experimental frequencies; besides the IR and Raman spectra are interpreted on the basis of the theoretical group analysis, considering the local symmetries S4 and C4h for the cations and anions, respectively.

X-ray Single Crystal Structure, Tautomerism Aspect, DFT, NBO, and Hirshfeld Surface Analysis of a New Schiff Bases Based on 4-Amino-5-Indol-2-yl-1,2,4-Triazole-3-Thione Hybrid

Four different new Schiff basses tethered indolyl-triazole-3-thione hybrid were designed and synthesized. X-ray single crystal structure, tautomerism, DFT, NBO and Hirshfeld analysis were explored. X-ray crystallographic investigations with the aid of Hirshfeld calculations were used to analyze the molecular packing of the studied systems. The H···H, H···C, S···H, Br···C, O···H, C···C and N···H interactions are the most important in the molecular packing of 3. In case of 4, the S···H, N···H, S···C and C···C contacts are the most significant. The results obtained from the DFT calculations indicated that the thione tautomer is energetically lower than the thiol one by 13.9545 and 13.7464 kcal/mol for 3 and 4, respectively. Hence, the thione tautomer is the most stable one which agree with the reported X-ray structure. In addition, DFT calculations were used to compute the electronic properties while natural bond orbital calculations were used to predict the stabilization energies due to conjugation effects. Both compounds are polar where 4 (3.348 Debye) has a higher dipole moment than 3 (2.430 Debye).

Diaquo{bis(p-hydroxybenzoato-κ1O1)}(1-methylimidazole- κ1N1)}copper(II)]: Synthesis, crystal structure, catalytic activity and DFT study

• Synthesis of a novel Cu(II) complex. • Single Crystal X-ray Diffraction study of the complex. • Catalytic activity of the Cu(II) complex. • Hirshfeld analysis of the complex. • DFT study of the novel Cu(II) complex Metal-organic hybrid complexes often exhibit large surface area, pore volume, fascinating structures and potential applications including catalytic applications. Hence a new metal-organic hybrid complex [Diaquo{bis( p -hydroxybenzoato- κ 1 O 1 )}(1-methylimidazole- κ 1 N 1 )}copper(II)] was synthesized using conventional method. Physico-chemical characterization of the complex was performed with FTIR spectroscopy, single crystal X-ray diffraction, TGA, EPR and FESEM. Single crystal X-ray diffraction study suggests it to be three dimensional with space group P2 1 2 1 2 1 (orthorhombic). The crystal achieves its three-dimensional structure and stability through extensive intermolecular hydrogen bonding. Hirshfeld surface analysis, catalytic activity and DFT study of the complex was also performed. The synthesized complex acts as good catalyst in benzimidazole synthesis with good recyclability as catalyst up to 5th run.

Synthesis, crystal structure, Hirshfeld surface analysis and DFT calculations of 2, 2, 2-tribromo-1-(3,5-dibromo-2-hydroxyphenyl)ethanone

A novel derivative 2, 2, 2-tribromo-1- (3,5-dibromo-2-hydroxyphenyl) ethanone was synthesis by “3-acetyl-4-hydroxycoumarin” and dibromide. The structural properties of the synthesized compound have been exploited with the aid of single-crystal X-ray crystallographic studies and infrared spectrometry. The compound crystallizes in the monoclinic system with space group P21/c. A comparative study between the novel brominated compound synthesized and the brominated coumarin derivative is presented. The optimized DFT geometries (B3PW91/6–311 G (2df, p)) and the spectral simulations of two derivatives compared agree well with the experimental data. Hirshfeld's analysis revealed the importance of Br ··· Br (40%) and Br ··· H/H ··· Br (19%) of the total surface contacts in the molecular stack. The contacts O···H/H···O have a significant contribution for the brominated coumarin (C2) of 26.1% of SH compared to the brominated cycle (C1) 9.7%.

X-ray, DFT (Chemical activity, Charge transfer and Non-linear optical properties) and Spectroscopic Studies on 2-amino-4-(4-bromophenyl)-5,6[H]quinoline-3-carbonitrile (I) and 2-amino-4-(2-bromophenyl)-5,6[H]quinoline-3-carbonitrile (II)

The title compounds of (I) and (II) have been synthesized and characterized by FT-IR and NMR spectroscopic techniques. Solid state crystal structures have been determined by X-ray diffraction technique. The Hirshfeld and 2D fingerprint analyses are used to investigate the intermolecular interactions in the crystal structure. The molecular geometries have also been optimized by using density functional theory (DFT/B3LYP) methods with the 6–31+G(d,p) basis set and geometric parameters have been compared with the experimental datas. Additionally, molecular electrostatic potential (MEP), chemical activity parameters, non-linear optical (NLO) properties, ECT analysis of the title compounds have been investigated.

Synthesis and X-ray Crystal Structure of New Substituted 3-4′-Bipyrazole Derivatives. Hirshfeld Analysis, DFT and NBO Studies

A new compounds named 3-4′-bipyrazoles 2 and 3 were synthesized in high chemical yield from a reaction of pyran-2,4-diketone 1 with aryl hydrazines under thermal conditions in MeOH. Compound 2 was unambiguously confirmed by single-crystal X-ray analysis. It crystalizes in a triclinic crystal system and space group P-1. Its crystal structure was found to be in good agreement with the spectral characterizations. With the aid of Hirshfeld calculations, the H…H (54.8–55.3%) and H…C (28.3–29.2%) intermolecular contacts are the most dominant, while the O…H (5.8–6.5%), N…H (3.8–4.6%) and C…C (3.0–4.9%) are less dominant. The compound has a polar nature with a net dipole moment of 6.388 Debye. The BD(2)C31-C32→BD*(2)N4-C34 (27.10 kcal/mol), LP(1)N5→BD*(2)C31-C32 (36.90 kcal/mol), BD(1)C32-C34→BD*(1)C18-C31 (6.78 kcal/mol) and LP(1)N4→BD*(1)N5-C31 (7.25 kcal/mol) are the strongest π→π*, n→π*, σ-σ* and n→σ* intramolecular charge transfer processes, respectively.