Hirshfeld Surface Studies Research Articles

Copper(II) complexes based on thiosemicarbazone ligand: Preparation, crystal structure, Hirshfeld surface, energy framework, antiMycobacterium activity, in silico and molecular docking studies

Considering the promising previous results on the remarkable activity exhibited by cobalt(III) and manganese(II) thiosemicarbazone compounds as antibacterial agents, the present study aimed to prepare and then evaluate the antibacterial activity of two different types of Cu(II) complexes based on a 2-acetylpyridine-N(4)-methyl-thiosemicarbazone ligand (Hatc-Me), a monomer complex [CuCl(atc-Me)] and a novel dinuclear complex [{Cu(μ-atc-Me)}2μ-SO4]. The compounds were characterized by infrared spectra, ultraviolet visible and CHN elemental analysis. In addition, the crystalline structures of the complexes were determined by single-crystal X-ray diffraction. In both cases, the Schiff base ligand coordinated in a tridentate mode via the pyridine nitrogen, imine nitrogen and sulfur atoms. The two Cu(II) atoms in the dimer are five coordinate, consisting of three NNS-donor atoms from the thiosemicarbazone ligand connected by a sulfate bridge. The Hirshfeld surface and energy framework of the complexes were additionally analyzed to verify the intermolecular interactions. The biological activity of the Cu(II) salts, the free ligand and its Cu(II) complexes was evaluated against six strains of mycobacteria including Mycobacterium tuberculosis. The complexes showed promising results as antibacterial agents for M. avium and M. tuberculosis, which ranged from 6.12 to 12.73 μM. Furthermore, molecular docking analysis was performed and the binding energy of the docked compound [{Cu(μ-atc-Me)}2μ-SO4] with M. tuberculosis and M. avium strains were extremely favorable (−11.11 and − 14.03 kcal/mol, respectively). The in silico results show that the complexes are potential candidates for the development of new antimycobacterial drugs.

Structural, Hirshfeld surface studies and computation of interaction energies of 4-Amino-N-(3-chloropyrazin-2-yl)benzene-1-Sulfonamide organic compound

Present paper reports the study of single crystal X-ray diffraction of the compound 4-Amino-N-(3-chloropyrazin-2yl)benzene-1-sulfonamide which crystallizes in an orthorhombic crystal system with the space group Pbca having precise unit cell parameters a = 11.5260(19)Å, b = 9.6270(16)Å, c = 22.099(5)Å, Z = 8 and V = 2452.1(8)Å3. The structure was solved by direct methods and was refined by full-matrix least-squares based on F2. After subsequent cycles of refinement, the structure was converges to the Goodness-of-Fit (S) = 1.33. The molecule was adopted as a non-planar structure with a dihedral angle of 89.95°. In the crystal, molecules are held together through intermolecular N–H…O and C–H…O interactions. The nitrogen (N) atom of pyrazine ring has exhibited trifurcated intramolecular relations through C–H…N, N…C, and N…O incorporating S(5), S(6), and S(7) ring motifs, respectively. The intermolecular interactions were analyzed, and their percentage of contribution towards crystal packing was computed using Hirshfeld surface analysis. Also, interaction energies between the different pairs of molecules were analyzed, visualized and estimated using the energy density model of B3LYP/6-31G(d,p).

Synthesis, structure, Hirshfeld surface, DFT, and molecular docking studies of a new organic cocrystal: creatinine:2,3‐pyridinedicarboxylic acid

AbstractA new cocrystal (CR:2,3PDCA) of creatinine (CR) with 2,3‐pyridine dicarboxylic acid (2,3PDCA) was grown by slow evaporation method, and its crystal structure was characterized by single‐crystal X‐ray diffraction (SCXRD) analysis. The cocrystal was found to be triclinic with space group P‐1 and lattice parameters a = 7.3610(7) Å, b = 8.7813(9) Å, and C = 9.4173(10) Å. The intermolecular hydrogen bonds, namely, N‐H…N and C‐O…H‐N interactions, together play a major role in stabilizing the cocrystal. Further, the molecular interactions in the crystal structure were analyzed by considering short contacts and intermolecular contactsusing Hirshfeld surface methods. Furthermore, the coordinates of cocrystal were obtained by DFT calculations using the B3LYP method with a 6‐311++G (d,p) basis set. Besides this, other molecular properties such as frontier molecular orbital, HOMO‐LUMO energies, and Mulliken charge analysis were also reported. Furthermore, a molecular docking study was performed to study the anti‐inflammatory property of the cocrystal using the Auto‐Dock vina program by investigating the binding patterns of the synthesized cocrystal into a 1R35 inhibitor. In vitro anti‐microbial activities against some bacterial and fungal strains were also investigated.

Synthesis, crystal structure, density functional theory, Hirshfeld surface analysis and molecular docking studies of 2-(2-phenylanthracen-9-yl)thiophene derivatives

Thiophene containing molecules have been distinguished as potential candidates in the largely emergent chemical world of heterocyclic compounds that show likely pharmacological characteristics. The knowledge of a mixture of synthetic pathways and the different physicochemical parameters of such compounds describe the especial interest of medicinal chemists to produce combinatorial collections and carry out in-depth efforts in the search of lead molecules. Among the various group of compounds studied, thiophene moieties stand out as unique in features due to their biological, pharmacological and medicinal properties. Synthesis, crystal structure, conformation and density functional theory of 2-(2-phenylanthracen-9-yl)thiophene derivative have been investigated in detail. Thiophene moiety are in planar conformation and having C-H…O type of hydrogen bonds and Van der Waals forces. Density functional theory has been applied to the thiophene derivative. Thiophene compounds score highly against the targeted protein and can be compared to the co-crystal ligand. Hirshfeld surface studies have been used to confirm and quantify the supramolecular features.

Study of supramolecular self-assembly of pyridone and dihydropyridone co-crystal: Synthesis, crystal structure, Hirshfeld surface, DFT and molecular docking studies

Dihydropyridone is synthesized by the multicomponent condensation reactions (MCRs), followed by three different oxidation methods to synthesize pyridone. The 3-D self-assemblies of both the compounds were determined using the single-crystal X-ray diffraction method. Dihydropyridone products are found as a racemic mixture in synthesis and crystalized as co-crystal. Similar structural conformations are observed in both the compounds but stabilized with different non-covalent interactions. Hirshfeld surface analysis is done to analyze the various intermolecular interactions in both the structure. This study gives the clue of driving force in the self-assembly of molecules in crystal lattices. The propensity of inter-molecular contacts to construct the supramolecular assembly was further studied using DFT. The geometrical optimizations of both the compounds were done by the electronic structure method using density functional theory (DFT) to identify the active sites and explore the molecules' chemically reactive parameters. Further, both compounds were docked with Survivin Protein and Kinesin Eg5 protein to analyze the binding affinity with targeted protein.

Schiff bases as possible hydrogen bond donors and acceptors

The compound (E)-N-(2,4-difluorophenyl)-1-(4-pyridinyl)methanimine monohydrate (1) was synthesized, characterized spectroscopically and by X-ray crystallography. 1 crystallizes in the non-centrosymmetric C2 space group with Z=4 (two organic molecules, 1a and 1b, and two water molecules). The crystal structure presents O–H···N, non-classical C–H···X hydrogen-bonds, and π–π stacking interactions. Hirshfeld Surface studies confirmed these interactions. The main intermolecular interactions are the π–π between the pyridine and the fluorinated ring of molecules stacking in columns (1a with 1a and 1b with 1b) and the O–H···N H-bonds. The imine acts as a H-bond-donor to the water molecules and a H-bond-acceptor of the water molecule's hydrogen atoms. The energy frameworks show significant interactions between molecules that are not easy to identify by geometric parameters, indicating the convenience of energy calculations to understand crystal structures better.

Synthesis, crystal structure, DFT calculations, Hirshfeld surface analysis, energy frameworks, molecular dynamics and docking studies of novel isoxazolequinoxaline derivative (IZQ) as anti-cancer drug

Quinoxaline derivatives with the molecular formula [C8H6N2] also named benzopyrazines, which are a valuable class of heterocyclic compounds useful for their numerous industrial and pharmaceutical applications. The new isoxazolquinoxalin (IZQ) 3-phenyl-1-((3-(p-tolyl)-4,5-dihydroisoxazol-5yl)methyl)quinoxalin-2(1H)-one (5) has been synthesized with good yield by stirring the compounds of 1-allyl-3-phenylquinoxalin-2(1H)-one (3, 3.8mmol), and (E)-4 methylbenzaldehydeoxime (4, 1.3mmol) in 20 ml of chloroform. The aqueous solution of sodium hypochlorite (10 ml of water bleach 12°) was added drop wise using bromine funnel. The mixture was stirring at 0°C temperature for 6 hours. Then it dried to obtain a crude product which on recrystallization with ethanol afforded the title compound (5) as colourless rectangular block shape crystals, and then confirmed by H NMR, LC-MS spectra. The structure of the compound has been confirmed by single crystal X-ray diffraction technique. The compound crystallizes in the monoclinic crystal system with the space group P21/c. The unit cell constants; a =15.9437(6) Å, b =16.3936(6) Å, c =7.4913(3) Å, and β =94.178(2)o. DFT calculations were carried out and HOMO-LUMO energy levels have been determined. In the structure, both Intermolecular and intramolecular hydrogen bonds of the type C-H...O were observed along with C-H...cg interactions. Hirshfeld surface studies were performed to understand the different interaction contacts of the molecule and the molecular packing strength of the crystal. Energy frameworks were constructed through different intermolecular interaction energies to investigate the stability of the compound and to know type of the dominate energy. Docking studies predicted anti-cancer activity of the title molecule against homo sapiens protein (pdb code:6HVH) and exhibited prominent interactions at active site region.

Imino-pyridyl and PPh3 mixed ligand complexes of Cu(I)X (X: I, Br, and Cl): Synthesis, structure, DFT and Hirshfeld surface studies

Three new halide bridged copper(I)complexes [Cu2(µ-L)(µ-X)2)(PPh3)2]n {X: I (1), Br (2) and Cl (3)} have been synthesized by the reaction of Cu(I)X (X: I, Br and Cl) with PPh3 and the polydentate imino-pyridyl ligand L. Interestingly, copper(I) forms coordination polymers with the ligand L and the co-ligand PPh3. These complexes 1, 2 and 3 have been characterized by elemental analysis, IR, UV-Vis, and NMR spectroscopy. The crystal structure of the complex 2 has been determined by single-crystal X-ray analysis. Crystal data for complex 2: triclinic, space group P-1 (no. 2), a = 9.471(10) Å, b = 11.043(11) Å, c = 13.215(18) Å, α = 65.853(18)°, β = 69.94(2)°, γ = 67.350(14)°, V = 1135(2) Å3, Z = 2, T = 296.15 K, μ(MoKα) = 2.806 mm-1, Dcalc = 1.535 g/cm3, 4059 reflections measured (3.462° ≤ 2Θ ≤ 44.818°), 2639 unique (Rint = 0.0637, Rsigma = 0.1621) which were used in all calculations. The final R1 was 0.0700 (I > 2σ(I)) and wR2 was 0.2207 (all data). Hirshfeld surface analysis of the complex 2 showed H···H, N···H and Br···H interactions of 55.9, 14.4 and 4.1%, respectively. MEP of ligand L reflects the whole molecule is reddish yellow in color because of equally distributed electron density over the molecule. For this reason, the ligand is supramolecularly arranged via -{CuI2-µ-X2} rhomboid core in the complex 2. The ligand L is non-emissive at room temperature in dichloromethane, whereas the complexes 1, 2 and 3 are photoluminescent. DFT and Hirshfeld surface studies have also been performed for complex 2.

Synthesis, crystal structure, Hirshfeld surface, DFT calculations, Z-scan and nonlinear optical studies of novel flourinated hexahydropyrimidine

A new fluorinated hexahydropyrimidine was synthesized and its crystal structure was elucidated using single crystal X-ray diffraction technique. This compound, C15H17F3N2O6 crystallizes in monoclinic space group P21/c with cell parameters a = 10.6345(3) Å, b = 14.7074(4) Å, c = 10.6677(4) Å, β= 101.453(2)° and V= 1635.27 (9) Å3. In this compound the hexahydropyrimidine ring (C7/C8/C12/N1/C14/N2) adopts sofa conformation. The puckering parameters are Q = 0.5117Å, Ɵ = 129.59° and φ =304.0802°. The analysis of Hirshfeld surface indicates the presence of hydrogen bonds C‒H•••F, C‒H•••O, O‒H•••O, N‒H•••O and π•••π stacking stabilizes the system. The energy optimized structure was calculated using Density Functional Theory (DFT) and were employed by hybrid functional theory (B3LYP) at 6-311++G(d,p) basis set in the Gaussian09_revision C0.1 program package. The natural bond orbital analysis results state that the highest energy transfer of 604.21 kJ/mol occur between the donor σ(O4‒H43) to acceptor σ*(C34‒H36) through carboxylate chain. Moreover, the vibrational assignments, global reactivity descriptors, energy gap and molecular electrostatic potential (MEP) also gives clear insight about chemical and biological activity of the molecule. The first hyperpolarizability value 7.2987 × 10−30 esu of the synthesized compound is twenty times greater than that of urea (0.3728 × 10−30 esu). The one electron excitation of the synthesized crystal calculated by the time dependent-density functional theory (TD-DFT) calculation and comparatively studied using recorded UV spectrum. The single beam Z-scan unit equipped with 532 nm continuous Nd:YAG wave laser with 5ns pulse width was used to measure third order nonlinear optical property reveal that the investigated molecule possess effective two photon absorption with higher effective absorption coefficient. The imaginary and real parts of the third-order susceptibility values determined as Im χ3 = 2.31 × 10−6 cm W−1 and Re χ3 = 8.74 × 10−8 cm2 W−1 respectively.

Hirshfeld surface, charge density and site selectivity studies of 1-(2-Methyl-5-nitro-1H-imidazol-1-yl)-acetone

Extensive quantum chemical calculations were carried out for the molecule with B3LYP/6311G++(d,p) level of theory. The molecular packing of the crystal is stabilized by CH…N and CH…O interactions and those interactions were investigated through Hirshfeld surface analysis. Aspherical distribution of charges was estimated using Hansen-Coppens multipole formalism and the effect of temperature on charge density was analyzed. Bader’s AIM theory was used to perform the topological analysis of electron density which disclose the strength and nature of atom-atom interaction. Stability of the molecule arising from hyper conjugative interactions and charge delocalization was examined using Natural Bond Orbital analysis and it also confirms the existence of CH…N and CH…O hydrogen bonds. Frontier Molecular Orbital analysis was carried out and the molecule is found to be a good electrophile with the electrophilicity index of 9.7349 eV. Molecular Electrostatic Potential was used to identify the possible reactive locations of the molecule.

Growth, spectral, laser damage and hirshfeld surface studies on configurationally locked 2-(3-(4-hydroxystyryl)-5,5-dimethylcyclohex-2-enylidene) malononitrile (OH1) single crystal- A potential terahertz emitter

We report on the growth, spectral, optical, laser damage and Terahertz (THz) wave generation studies and Hirshfeld analysis of the pyrrolidine-based, configurationally locked, polyene single crystals 2-(3-(4-hydroxystyryl)-5,5-dimethylcyclohex-2-enylidene) malononitrile (OH1), a potential organic material for THz generation. The laboratory synthesized OH1 was verified for its composition and crystalline phase using Carbon–Hydrogen–Nitrogen (CHN) analysis and powder X-ray diffraction method respectively. The functional groups of OH1 were confirmed through Fourier transformed infrared analysis whereas its band gap energy was calculated using the UV–Vis spectrum recorded on (100) plate of thickness of about 1 mm. The laser damage studies performed by employing Q-switched Nd:YAG laser revealed that the OH1 crystals could withstand laser fluences of the order of about 2.21 GW/ cm2.Further, the OH1 single crystals were effectively used for the generation of intense THz waves using indigenously developed setup which comprises of a Ti: Sapphire laser (with 140 fs pulses) and detection using a pyroelectric sensor. Furthermore, 3D Hirshfeld surfaces and 2D finger print plots of OH1 were supportive in decoding the intermolecular interaction behaviour and the packing structure of the crystals.

Analysis of supramolecular self-assembly of two chromene derivatives: Synthesis, crystal structure, Hirshfeld surface, quantum computational and molecular docking studies

Two 4H-chromene derivatives (1C and 1F) were synthesized by the multicomponent condensation reactions (MCRs) and spectroscopically characterized. The 3-D structures of both the compounds were determined using single crystal X-ray diffraction method. The similar structural conformations are observed in both the compounds but they are stabilized with different packing modes. The supramolecular synthons constructed by strong hydrogen bond interactions plays a major role in the supramolecular self-assembly of molecules in the solid state. Hirshfeld surface analysis is used to assess the various intermolecular interactions in both the structure that driven the self-assembly of molecules in crystal lattices. The propensity of inter-molecular contacts to construct the supramolecular assembly were analyzed using enrichment ratios. The geometrical optimization of both the structures were done by electronic structure method using density functional theory (DFT) to identify the active sites and to explore the chemically reactive parameters of the molecules. Further, novel 1C and 1F compounds were docked with DNA gyrase protein of S. aureus to analyze the binding affinity with targeted protein.

A new polymorph of six-coordinated bis(5,5′-dimethyl-2,2′-bipyridine) nitratocopper(II) nitrate and its DNA interactions

Here, we present a new polymorph of the [Cu(5mebipy)(NO3)]NO3 complex (1, Form II), where 5mebipy means 5,5′-dimethyl-2,2′-bipyridine. The copper(II) complex 1 was characterized by spectroscopic techniques and single-crystal X-ray diffraction. The Form II presents a six-coordinated structure, meanwhile the Form I, previously reported, is five-coordinated with the nitrate ligand as monodentate. The molecular structures of both crystalline forms were compared based on intramolecular aspects using Kleywegt's analysis and the intermolecular contacts evaluated by Hirshfeld surface studies. Moreover, the interaction of the complex [Cu(5mebipy)(NO3)]+ with CT-DNA was carried out using viscosity and spectrophotometric titrations, exhibiting a binding constant of 2.57 × 104 M − 1. This study contributes to explore the intra and intermolecular details of the new polymorph of the complex [Cu(5mebipy)(NO3)]NO3 and its capability to interacts with CT-DNA.

DFT calculations, Hirshfeld surface analysis and docking studies of 3-anisaldehyde thiosemicarbazone

We report herein the synthesis, quantum chemical electronic structure, Hirshfeld surface and molecular docking studies of 3-anisaldehyde thiosemicarbazone (I). The compound has been characterized by NMR (1H, 13C) and IR spectroscopy. Hirshfeld surface analysis has been performed to understand the intermolecular interactions. The quantum chemical calculations show good consistency between the predicted and experimental parameters. Molecular docking studies of I with two different cancer target enzymes exhibit higher binding energy than its ortho substituted analogue. Synthesis, spectroscopic characterization, quantum chemical calculations, Hirshfeld surface analysis and molecular docking studies have been investigated for the compound 3-anisaldehyde thiosemicarbazone (I). The theoretical results gave a better understanding of the molecular interactions and the docking results suggest I can be used for in vitro anticancer study.

Efficient Synthesis, SC-XRD, and Theoretical Studies of O-Benzenesulfonylated Pyrimidines: Role of Noncovalent Interaction Influence in Their Supramolecular Network.

Crystalline organic compounds, 2-amino-6-methylpyrimidin-4-yl benzenesulfonate (AMPBS) and 2,6-diaminopyrimidin-4-yl benzenesulfonate (DAPBS), were prepared via O-benzenesulfonylation of 2-amino-6-methylpyrimidin-4-ol 1 and 2,6-diaminopyrimidin-4-ol 2, respectively. The structural interpretations were achieved unambiguously by single-crystal X-ray diffraction (SC-XRD) analysis. The Hirshfeld surface study showed that C–H···O, N–H···N, and especially C–H···C hydrogen bond interactions are the key contributors to the intermolecular stabilization in the crystal. Density functional theory (DFT) studies were used to obtain a better understanding of natural bond orbitals (NBOs) and nonlinear optical (NLO) analysis for AMPBS and DAPBS at the B3LYP/6-311G(d,p) level. The time-dependent density functional theory (TD-DFT)/CAM-B3LYP/6-311G(d,p) level was employed for frontier molecular orbital analysis of both compounds. DFT-based vibrations for C–H, C=N, N–H, and stretching for C–C were found to be in good agreement with the experimental data. Overall, the theoretical findings were acquired in correspondence to the SC-XRD-based parameters. Intracharge transfer occurred in AMPBS and DAPBS compounds, which was evaluated through FMO activity. Global reactivity indices had been acquired utilizing energies of HOMO–LUMO orbitals. Overall, the theoretical findings related to AMPBS and DAPBS consist of promising correspondence to experimental findings. The theoretical-based study also exhibited that both AMPBS and DAPBS compounds contain promising NLO features.

Crystal Structure, Hirshfeld Surface and Frontier Molecular Orbital Analyses of N-[2-(trifluoromethyl)phenyl]succinamic Acid

The ortho-CF3 substituent and the N-H bond are in syn-conformation in N-[2-(trifluoromethyl)phenyl]succinamic acid. In amide and acid functionalities, the carbonyl groups are directed in opposite directions to each other and their related-CH2 groups. syn-Conformation is observed for the acid functionality, where the carbonyl C=O and hydroxyl O-H bonds are directed in the same direction. Three planar fragments comprise of the molecule: aromatic ring (A), core portion -Carm-N(H)-C(=O)-C(H2)-C(H2)(B) and -C(H2)-C(=O)-OH(C). The dihedral angle between a pair of fragments being 48.6(4)º (A and B), 81.6 (4)º (B and C) and 70.5 (5)º (A and C). N-H•••O hydrogen bonds bind the molecules forming C(4) chains in the crystal, and the neighbouring anti-parallel chains are bound by O-H•••O hydrogen bonds resulting in a chair shaped ribbon of one-dimensional nature. The Hirshfeld surface study was carried out, including fingerprint plots. Studies have shown that the interactions with O•••H/H•••O (27.4%), H•••H (27.3%) and H•••F/F•••H (20.2%) substantially added to the surface. Theoretically, the highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO) and various global reactivity descriptors were also computed by the density functional theory (DFT/B3LYP) approach with a 6-311G(d, p) basis set in the ground state on the geometrically optimized structure in the gas phase.

Mononuclear and binuclear dioxidomolybdenum(VI) complexes of ONO appended aroylhydrazone: Crystal structures, interaction energy calculation and cytotoxicity

Mono- and binuclear cis-MoO2 complexes (1–3) having the general formula [MoO2(ISF)D] (D = H2O (complex 1), DMSO (complex 2) and 4,4ꞌ-bipyridine (complex 3) ISF = 3,5-diiodosalicyaldehyde-2-furoichydrazone) have been synthesized and fully characterized by different physico-chemical methods. The molecular structures were confirmed unambiguously by single crystal X-ray diffraction studies. The octahedral geometry around the Mo(VI) central atom is satisfied by O, N, O donor atoms of dideprotonated dianionic hydrazone moiety, two oxido oxygens and oxygen/nitrogen atoms of the coordinated solvent molecules. The asymmetric unit of complexes 1 and 2 contains one molecule whereas complex 3 contains only half of the molecule. The 4,4ꞌ-bipyridine molecule acts as a linker that links the two asymmetric MoO2D moieties to form the binuclear dioxidomolybdenum(VI) in complex 3 with Mo⋯Mo non-bonding distance of 12.01(10) Å. The relevance of hydrogen bonding and non-bonding interactions in the construction of supramolecular architectures were investigated. The upshots of single crystal studies were reproduced with the aid Hirshfeld surface studies. The pre-eminence of dispersion energy component over other components was established by interaction energy calculations and the energy framework analysis. The average interaction energy values for complexes 2 and 3 are found to be −282.3 and −228.3 kJ mol−1 respectively. Furthermore the in vitro cytotoxicity of all the synthesized compounds was evaluated against lymphoma ascites cell line.

Growth, structural, Hirshfeld surface, optical, laser damage threshold, dielectric and chemical etching analysis of 4-dimethylaminopyridinium 4-nitrophenolate 4-nitrophenol (DMAPNP) single crystal

The organic 4-dimethylaminopyridinium 4-nitrophenolate 4-nitrophenol (DMAPNP) single crystal was grown by slow evaporation solution growth technique at 35 °C. The single crystal X-ray diffraction analysis confirms that the grown crystal belongs to the orthorhombic crystal system with the space group of P212121. Different functional groups were affirmed using FT-IR and FT-Raman analysis. The intermolecular interactions of the DMAPNP molecule were executed using Hirshfeld surface study. The Mulliken atomic charge population analysis was performed using density functional theory (DFT). The bonding interactions between two orbital atoms and groups were executed by the density of state (DOS). The optical transmittance study shows that the grown crystal has 60 to 78% transmittance in the Vis–NIR region. It has an emission peak at 482 nm in the photoluminescence (PL) spectrum. The photoconductivity analysis shows that the DMAPNP has negative photoconductive behavior. The thermal stability of the DMAPNP crystal was investigated by TG–DTA analysis. The etch pit density of the title crystal was investigated using chemical etching study. The mechanical stability of the DMAPNP crystal was tested by Vickers microhardness tester. Laser damage threshold analysis reveals that the DMAPNP is stable up to 10 mJ of laser power. The dielectric properties were assessed and the electronic polarizability of the DMAPNP was evaluated by the different empirical relations. The second harmonic generation (SHG) efficiency of DMAPNP crystal was measured by Kurtz–Perry powder technique.

Understanding the Formation of Novel Hydrated Gallic Acid-Creatinine Molecular Salt: Crystal Structure, Hirshfeld Surface and DFT Studies

Creatinine, an aliphatic hetero monocyclic compound, plays an important role in the protein metabolism and change in its physiological normal concentration leads to diabetic nephropathy, renal failure and muscle disorder. In this work, a novel molecular salt form (ionic cocrystal) of creatinine (CR) with gallic acid (GA) has been obtained and preliminarily characterized by PXRD, FTIR and the crystal structure was confirmed by X-ray diffraction method. The presence of a single C–O stretching band in the place of two stretching bands [C=O and C–O] in the infrared spectrum confirms the formation of molecular salt. The asymmetric unit of GA–CR ionic cocrystal [(C7H5O5)− (C4H8N3O)+ 3(H2O)] comprises of a molecule of gallic acid, a molecule of creatinine and three water molecules. The structural analysis reveals the strong hydrogen bond DDAA environment of water molecules which confirms the presence of different supramolecular architectures. Thermal gravimetric analysis was carried out to investigate the presence of water/solvent molecules in the molecular salt. Further, the intermolecular interactions in stabilizing the molecular salt were analyzed using Hirshfeld surfaces. Furthermore, the coordinates of molecular salt were optimized by DFT calculations using APFD hybrid functional with 6-311 + G(d,p) level basis set. Frontier molecular orbitals, energy gap and related molecular properties were also analyzed. GA–CR pharmaceutical molecular salt form is found to be more reactive than CR and therefore offers an innovative approach for the futuristic drug design. Strong hydrogen-bond DDAA environment (D: donor, A: acceptor) exhibited by the water molecules in the GA–CR molecular salt play a major role in stabilizing the crystal structure.

Solvent-free mechanochemical synthesis, hirshfeld surface analysis, crystal structure, spectroscopic characterization and NBO analysis of Bis(ammonium) Bis((4-methoxyphenyl) phosphonodithioato)-nickel (II) dihydrate with DFT studies

Abstract The green chemistry route for synthesis of dithiophosphonate nickel complex of the type, [Ni{S2P(O) (4-C6H4–OMe)}2]·2NH4·2H2O was reported1 and the structure confirmed by single crystal XRD. This work deals with FT-IR, and NMR spectral, NBO and Hirshfeld surface studies on bis(ammonium) bis((4-methoxyphenyl) phosphonodithioato)-nickel dihydrate. The molecular structure, vibrational frequencies and intensity of the vibrational bands were interpreted with the aid of structure optimizations and geometrical parameter calculations based on density functional theory (DFT) method via mixed basis set at B3LYP/GENECP level of theory. The 13C and 1H Nuclear Magnetic Resonance (NMR) of the complex were computed by gauge independent atomic orbital (GIAO) method and compared with experimental chemical shift. The reported experimental and calculated results were correlated and was further expressed with correlation plots and correlation coefficient. Matching consistency resulted between computed data on optimized geometric parameters, vibrational frequencies and NMR chemical shifts and their corresponding experimental data. Computed Natural Bond Orbital (NBO) analysis explore the interactions as well as charge transfers among different orbitals and lone pairs happening within the compound. Hirshfeld surface analyses further establish and quantify intermolecular interactions of [Ni{S2P(O)·(4-C6H4–OMe)}2]·2NH4·2H2O.