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An anhydrous nature of benzylidene derivatives of nicotin and isonicotinamides crystal structures is determined and studied for their weak intermolecular interactions. The molecular structure is non-planar in general with the pyridine ring twisted with respect to the central hydrazone moiety. The crystal structures depict various intermolecular interactions, including N–H⋯O, C–H⋯O, N–H⋯N, and C–H⋯N hydrogen bonding along with weak C–H … π and π … π contacts. Further, Hirshfeld surface and 2D-fingerprint plot analysis confirm the role of intermolecular interactions in building the crystal packing in these derivatives. The PIXELC energy calculation shows that dispersion energy plays an essential role in stabilizing the crystal packing in all six derivatives.

The effects on the physical properties of [N(CH3)4]2Zn1-xCoxBr4 (x = 0, 0.5, 0.7, and 1) crystal due to the partial substitution of Zn2+ ions with paramagnetic Co2+ ions were discussed. The crystal structures and phase transition temperature (287 K) of layered perovskite-type [N(CH3)4]2Zn1-xCoxBr4 were nearly unaffected by the partial doping of Co2+ ions, as revealed by X-ray diffraction and differential scanning calorimetry experiments. The environments surrounding the 1H and 13C in [N(CH3)4]2Zn1-xCoxBr4 mixed systems were determined from the chemical shifts and the spin-lattice relaxation time T1ρ of 1H magic angle spinning nuclear magnetic resonance (MAS NMR) and 13C cross-polarization (CP)/MAS NMR. The molecular motions by the T1ρ for 13C nuclei were nearly unaffected when Zn2+ ions were substituted with Co2+ ions, whereas those for 1H nuclei were influenced by doping Co2+ ions. A comparison of the molecular dynamics of TMA-Zn1-xCoxBr4 studied in this paper with the previously reported TMA-Zn1-xCoxCl4 was made to understand the effects of Cl and Br ions.

A new organic proton transfer compound, 2-aminothiazoliumbenzilate (2-ATB) was synthesized and single crystals of the compound were grown by solvent evaporation-solution growth method at ambient temperature. The compound was characterized by elemental analysis, UV–Vis NIR, FT-IR, 1 H and 13 C NMR spectroscopic analyses and single crystal X-ray diffraction (SXRD) structural study. Intermolecular and intramolecular N–H⋯O and O–H⋯O hydrogen bonding interactions stabilize the crystal network. The molecular structure was optimized at B3LYP/6-311G+(d,p) level using quantum chemical calculations. The natural bonding orbital (NBO) analysis was carried out to explore hyperconjugative interactions and intermolecular charge transfer. Hirshfeld surface analysis reveals that C⋯H, N⋯H and O⋯H interactions build hydrogen bond network in the molecular structure. The HOMO-LUMO energy gap value of 2-ATB is small enough for electron cloud transfer. The Z-scan technique was used to confirm 2-ATB as a third harmonic generating (THG) material for optical limiting device applications.

A series of four closely related 1,2,4-triazole-3-thione (1-4) compounds was obtained by heterocyclization of thiosemicarbazides under basic catalytic conditions. The crystal structures of the 4-alkyl-5-(substituted-phenyl)-2H-1,2,4-triazole-3(4H)-thione derivatives [4-alkyl = 4-ethyl-5-phenyl (1), 4-hexyl-5-phenyl (2), 4-hexyl-5-p-tolyl (3), and 4-ethyl-5-(2,4,6-trimethoxyphenyl) (4)] have been determined. PIXEL lattice energy calculations revealed that dispersion components make the major contributions, with the coulombic terms also contributing significantly to the total energy. Interaction energies for the inversion dimers involving N–H⋯S=C hydrogen bonds indicate a dominant contribution to packing stabilization coming from the coulombic energy component. Hirshfeld surfaces and 2D-fingerprint plots allowed us to visualize different intermolecular contacts and their relative contributions to the total surface in each compound. The comprehensive analysis of the crystal packing and the energetic features demonstrate the key role of the R 2 2 ( 8 ) supramolecular synthon of the type (···HNCS)2 in the solid state structures of these 1,2,4-triazole-3-thiones.

Synthesis of a series of 1,3-diazaheteroaromatic compounds was accomplished by the ring-opening domino reaction of cyclopropane-1,1-dicarboxylates with heterocyclic compounds. The compounds were characterized by NMR ( 1 H and 13 C) and mass spectral data. A novel single crystal 4b′ was successfully cultivated by adding a handful of Y(NO 3 ) 3 to a light yellow viscous oil 4b and organic solvent. X-ray crystal analysis of 4b′ indicated that it crystallized in p-1 space group. Additionally, 12 compounds were screened for their cytotoxic activity against the RS4; 11 leukemia cells and H3122 lung cancer cells. The preliminary biological screening results showed that several compounds could inhibit by more than 50% leukemia cell growth at 50 μM and/or 10 μM.

Molecular motion in crystals often suffer from severe limitations on their dynamic processes, and has received an extraordinary attention as artificial molecule motors and potential molecular dielectric materials. To investigated the relationship between the molecules motion in crystals and dielectric properties. Here, two hybrid crystals [1,3-bis(1-mim)C3]2[Pb4Cl12] (1) and [1,3-bis(1-mim)C3][Pb2Cl6] (2) (1,3-bis(1-mim)C3 = 1,3-bis(1-methylimidazolium)propane), which undergoes interesting dielectric relaxation and molecules motion were reported. Temperature-dependent single crystal structure shows the trans-cis transition of the carbon atoms and twisted rotation of the imidazolium ring were observed for 2. For 1, there exists thermal activating rapid motion for cation. Two compounds exhibit dielectric relaxation.The dielectric constant of 2 are much larger than 1 at the same frequency, which can be ascribed to the reorientational dynamics of guest water molecules and twisted rotation of the cation.

Optically good quality organic single crystals of imidazolium 3-nitrobenzoate (I3NB) have been grown by slow evaporation solution technique (SEST). The I3NB crystallized in monoclinic crystal system with space group P21/c, which is concluded from single crystal XRD analysis and the PXRD pattern was obtained for the crystal. The I3NB crystal was subjected to FTIR and FT-Raman spectral analyses to identify the functional groups of the I3NB compound. The optical transparency of the crystal was 80% and the cut-off wavelength was observed to be 321 nm. Thermal stability of the material was studied by TG/DTG and DSC analysis. The mechanical properties (hardness, yield strength and stiffness constant) of the crystal were analyzed by Vickers microhardness test. The electrical conductivity of the crystal was carried out by dielectric study. Z-scan method was adopted to investigate the third order nonlinear optical (NLO) properties of the crystal. Additional insight was gained from the theoretical investigation for the I3NB crystal. To achieve that, Density Functional Theory (DFT) calculations have been performed under solvation model to understand the geometrical and electronic structural features like frontier molecular orbital analysis (FMO), natural bond orbital analysis (NBO), molecular electrostatic potential (MEP) studies, dipole moment, polarizability and hyperpolarizability of the crystal. All these findings approve that the I3NB crystal is favorably suitable for NLO applications.

Two conjugated positional isomers {(2Z,2′Z)-3,3'-(1,4-phenylene)bis (2-(pyridin-2-yl)acrylonitrile), I and (2Z,2′Z)-2,2'-(1,4-phenylene)bis (3-(pyridin-2-yl)acrylonitrile), II} in which –CN group is attached to either first or second carbon atom of the C C unit, have been synthesized. One of the isomers I crystallized as a hydrated form. Single crystal X-ray analysis has been performed and a detailed quantitative analysis on the weak noncovalent interactions was presented. The results suggest that these three molecules showed different crystal packing. The positioning of the –CN group at different carbon atom of the C C unit in the isomers and the presence of a water molecule in the crystal lattice alters the distribution of electrostatic potentials. Lattice energy calculation revealed that a water molecule destabilizes the isomer I by 20.5 kcal mol−1 and the isomer II was found to be more stable. The energy frameworks displayed hexagonal packing for isomers I and II, but the variation in the magnitude of electrostatic and dispersion energies and the arrangement of molecules in the crystalline state. The Hirshfeld surface and QTAIM approaches were used to study the nature and the extent of different intermolecular interactions observed in these structures. The results indicated that intermolecular C–H⋯N interactions play a significant role in the stabilization and H–H bonding was also substantially contributing to the stabilization. UV–Vis spectral data were reported for I and II in solution and solid phases and showed similar optical properties.

A series of seven 5-aryl-1-(1,1-dimethylethyl)-3-trifluoromethyl-1H-pyrazoles [in which aryl: C6H5 (1); C6H4-4-F (2); C6H4-4-Cl (3); C6H4-4-Br (4); C6H4-4-I (5); C6H4-4-CH3 (6), C6H4-4-OCH3 (7)] and 5-aryl-1-(1,1-dimethylethyl)-1H-pyrazole [C6H4-4-NO2 (8)] was studied at the molecular and supramolecular level. X-ray diffraction, thermal analysis, sublimation enthalpy data, NMR spectroscopy, and DFT calculations were used in this systematic study. The supramolecular cluster was used as demarcation and furnished energetic and contact area data of each compound, which allowed proposals of crystallization mechanisms. Two different mechanisms were observed: (i) compounds 1–4 had 2 stages, where initially the monomers formed a 2-D block, followed by the formation of the 3-D block; (ii) compounds 5–8 also had 2 stages, where initially the monomers formed a 1-D block, followed by formation of the 3-D block. The packing observed in the crystal was corroborated by data from 1H NMR experiments. The types of interactions observed were evaluated using Hirshfeld surface and QTAIM analysis and showed slight differences in both methods. Lastly, energetic and topologic data obtained from the clusters were correlated with crystal properties such as crystal packing efficiency, sphericity, and sublimation enthalpy and presented good trends between data.

In order to understand deeply the interaction between guanidine and phosphate groups in crystal, phosphate bis-guanidinoacetate (PBGA) crystal was synthesized and grown by aqueous solvent evaporation method, which belongs to the triclinic crystallographic system, space group P-1, with unit cell parameters: a = 7.776 A, b = 8.113 A, c = 12.459 A, α = 89.591°, β = 89.146°, γ = 61.370°, Z = 1. The crystal structure studies and vibrational spectral analysis showed that the special shift of C-N stretching vibration is caused by the hydrogen bonding interaction between phosphate and guanidine groups in crystal. Through quantum chemical calculation, we investigated the Independent Gradient Model, hydrogen bond energy (EHB) from Quantum Theory of Atoms in Molecules method, the atom dipole moment corrected Hirshfeld population, the electron density difference and electron localization function difference for PBGA dimer model, which provide deeper insight into the position, type, strength and charge transfer for the interaction between phosphate and guanidine groups. Thermal stability of the title crystal was evaluated by thermogravimetric and differential scanning calorimetry. Our results indicate that the rich electrostatic interaction between phosphate and guanidine groups has great impact on the structure, charge distribution and thermal stability of PBGA.

A novel proton transfer complex, 2-methyl-8-hydroxyquinoliniumpicrate (MHQP), has been synthesized in methanol solvent using 2-methyl-8-hydroxyquinoline (MHQ) as proton acceptor and picric acid (PA) as proton donor in 1:1 M ratio, and its single crystal growth, thermal, spectroscopic, optical properties along with atomic packing of crystal have been studied. The DSC and TGA infer the thermal behavior of complex and FT-IR and proton NMR spectroscopic studies infer the charge-transfer interaction via transfer of proton. The powder XRD indicates novelty of the complex and single crystal analysis of MHQP crystal confirms the ionic interaction along with H-bonding interactions between MHQ and PA. The association constant and molar extinction coefficients were studied based on higher absorption band in UV–vis. absorption spectrum of the complex. The significant optical transmittance spectrum of grown MHQP crystal is indicative for its possible applications in opto-electronic devices.

The 1, 3, 5 - triphenylbenzene (TPB) single crystal has been grown by slow evaporation solution growth method. The lattice parameters of the grown crystal were confirmed using single crystal X-ray diffraction measurement. It shows that TPB single crystal belongs to the orthorhombic system. UV–Vis–NIR analysis reveals that grown crystal has good optical transmittance in the entire visible region. The melting and decomposition points of the grown crystal are 178 °C and 340 °C, respectively. The crystals were subjected to FT-IR and Raman analysis to confirm the various functional groups. Intermolecular interactions of the TPB crystal have been executed through Hirshfeld surface analysis. It is found that H⋯H interactions are the higher interactions (56.9%) in the total Hirshfeld surface of the molecule. Quantum chemical calculations such as optimization of the molecule structure, HOMO-LUMO, natural bond orbital analysis (NBO), Mulliken atomic charge and molecular electrostatic potential were performed using Gaussian 09W software with B3LYP function. The calculated HOMO and LUMO energy values are −6.16 eV and −1.35 eV. The molecule orbital contributions were determined using the total density of states (TDOS).

Single crystal of (E)-1-(4-ethylphenyl)-3-(4-(heptyloxy)phenyl)prop-2-en-1-one (4EPC) was grown in acetonitrile via slow evaporation solution technique. The molecular structure of 4EPC was then confirmed by single crystal X-ray diffraction analysis and the crystal exhibited monoclinic with centrosymmetric space group of C2/c. The synthesised molecule of 4EPC was fully characterized using spectroscopic techniques by Fourier-Transform infrared (FT-IR) spectroscopy, Nuclear Magnetic Resonance (1H and 13C NMR), thermal stability analysis via Thermogravimetric analysis (TGA) and electronic transitions through UV–visible analysis. In addition, the theoretical investigations on its electronic properties via UV–vis analysis of 4EPC was calculated using time-dependent TD-DFT B3LYP/6-31G (d, p) level of theory. As predicted, the experimental results were complimentary to the theoretical findings. The Hirshfeld surface analysis contributes to the study in the aspect of the nature of intermolecular interactions as well as fingerprint plots which gave the information on the percentage contribution from each individual contact. Molecular electrostatic potential (MEP) analysis provides an initial information on the charge concentration throughout the molecule 4EPC which designated the possible interaction site to occur. Moreover, the nonlinear optical (NLO) properties of 4EPC was calculated to gain further understanding on the possibility of developing this compound as NLO material. Calculated NLO results found that the polarizability and 1st order hyperpolarizability of 4EPC is −2.13 × 10−23 esu and 1.27 × 10−30 esu respectively which is greater than the value of 1st order hyperpolarizability of urea (β = 0.372 × 10−30 esu). The high values obtained from the calculated NLO were due to the dipole, molecular alignment and also from the non-covalent interaction within crystal of 4EPC which can be developed further as potential organic light emitting diode application.

The co-crystal, Mo8O26 2(C8H9N3O)·4(C2H8N) consists of Octamolybdate, (Mo8O26)−4 an anionic cluster surrounded by four dimethylammonium ions (C2H8N)+ and (E)-N'-(pyridin-2-ylmethylene)acetohydrazide 2(C8H9N3O) has been synthesized and characterized by FT-IR and UV–Vis spectroscopic methods. Single crystal X-ray diffraction analysis reveals that complex (C24H50Mo8N10O28) contains, Octamolybdate, (Mo8O26)4- an anionic cluster surrounded by four dimethylammonium ions (C2H8N)+ along with (E)-N'-(pyridin-2-ylmethylene)acetohydrazide 2(C8H9N3O), in the unit cell. Further a series of N'-[(E)-pyridin-2-ylmethylene]acetohydrazide molecules holding the octa-molybdate units forming three dimensional supramolecular networks through number of C–H⋯O and N–H ⋯ O interactions. The Hirshfeld surfaces and two-dimensional fingerprint plots were generated to visualize the intermolecular interactions quantitatively for their relative contributions.

The new organic salt of antidiabetic drug metformin, [HMet][pdtcH] (1), where pdtcH = pyridine-2,6-bis(monothiocarboxylic) acid and Met = metformin, was synthesized and characterized by FTIR, UV–Vis, 1H and 13C NMR spectroscopy. Solid-state structure of [HMet][pdtcH] (monoclinic, P21/n) was determined from low-temperature X-ray diffraction data collected at 100K. In this compound, the metformin is monoprotonated. In the crystal packing, the molecules are linked dominantly via intermolecular C–H⋯O, C–H⋯N, C–H⋯S, N–H⋯O and N–H⋯S hydrogen bond interactions, forming a three-dimensional anion-cation network and hence the stabilization of the crystal structure.

In this work reports the crystalline phase transformation of electrospinning TiO2 nanofibres by annealing at high temperatures. The nanofibres chemical stoichiometry was determined by Energy-dispersive X-ray spectroscopy (EDS), which allowed find that the TiO2 crystal phase transformation is caused by oxygen vacancy generation. The TiO2 nanofibres diameter varied from 137.0 to 115.3 nm in the temperature range of 100–1000 °C, which was estimated by Scanning Electron Microscopy. The TiO2 nanofibres structural transformation from pure anatase to pure rutile structures, including the quasi-amorphous and anatase-rutile mixed phases has been confirmed by Raman scattering and X-ray diffraction. The Raman spectroscopy exhibits the anomalous behaviour for band broadening and shifting of Raman bands with increasing crystallite size that form the nanofibres. By X-ray diffraction was found that the nanofibres crystalline phases present as preferential growth direction (101) for anatase and (110) for rutile.

A new 1:1 organic molecular adduct 2-aminopyrimidine: 3-nitrophthalic acid (APNP) was successfully synthesized and single crystals were grown by slow solvent evaporation technique at room temperature. The formation of the molecular adduct was confirmed by single crystal XRD analysis, which further reveals that the crystal belongs to the monoclinic crystal system with a centrosymmetric space group, P21/n. FT-IR spectrum was recorded to identify the functional groups present in the molecular adduct. The purity and stoichiometry of the molecular adduct were confirmed by CHN analysis. The presence of different kinds of protons and carbon atoms in the molecular adduct was confirmed by 1H and 13C NMR spectroscopic studies respectively. UV–Vis–NIR spectroscopic study was carried out to identify the transparency window of APNP crystal. The TG/DTA analyses were carried out simultaneously to establish the thermal stability of the adduct crystal. The computational studies including optimization of molecular geometry, natural bond orbital (NBO) and HOMO-LUMO analyses were performed by density functional theory at the B3LYP method at 6–21g basis set level using Gaussian 09 software. Hirshfeld surface analysis was carried out to know the influence of hydrogen bonding on the molecular properties of the adduct crystal. The third order nonlinear susceptibility of the APNP salt was established by the Z-Scan study. Moreover, the APNP crystal was subjected to antimicrobial activity against various bacterial and fungal species. In addition, the antioxidant activity of APNP adduct was evaluated by DPPH assay method.

Single crystalline hybrid framework of cadmium citrate hexahydrate has been achieved by controlled diffusion of cations in a reactive gel medium. The effect of various growth parameters and different physico-chemical characterization of these crystals were studied. The single crystal X-ray diffraction was used to identify the three dimensional molecular structure and unit cell parameters of the grown crystal. The FT-IR and micro Raman spectral studies, reported the modes of vibration of different functional groups present in the crystal. The thermogravimetric analysis supported the suggested molecular formula of the grown crystal as Cd3(C6H5O7)2·6H2O and the hydrated compound was found to be thermally stable up to a temperature of 67 °C. The thermal decomposition of the crystal in the Nitrogen atmosphere resulted in the formation of cadmium carbonate as the final product. UV–visible spectroscopic studies revealed that the grown crystal possesses high transmittance in the entire visible region. The frequency dependence of dielectric constant and dielectric loss with the applied electric field was also analysed.

The synthesis of benzothiazolium salt, N-(carboxyethyl)-2-methylbenzothiazolium bromide has been carried out by condensation of 2-methylbenzothiazole and 3-bromopropionic acid in solvent free conditions. The desired compound was obtained in excellent yield and its structural characterization was performed by FTIR, 1H NMR, 13C NMR techniques and XRD-analysis. Further the structural properties of the suitable crystal was obtained and analyzed by single crystal X-ray diffraction analysis indicates that the compound crystallizes in the triclinic space group P-1, with Z = 2 and cell parameters a = 8.6554(3) A, b = 8.9811(3) A, c = 9.3168(3) A, α = 61.237(1)°, β = 71.240(1)°, γ = 72.675(1)°. The molecular structure of the corresponding salt was optimized by Density Functional Theory (DFT) method using B3LYP/6-311G++(d,p) level. The molecular geometrical parameters (bond length. bond angle and dihedral angle) were obtained from the optimized structure. In addition, the IR frequencies were calculated using the same level of theory. The comparisons between the experimental and theoretical values of geometrical parameters and FT-IR vibrational spectra have also been discussed.

We report herein the fabrication and structural characterization of two new coordination complexes [Cu3(μ3-O)(pz)3(Hpz)(Hpdc)(H2O)2](H2O)4 (1, H2pdc = pyridine-3,5-dicarboxylic acid, Hpz = pyrazol) and [Cd(phen)(bdc)](H2O) (2, phen = 1,10-phenanthroline, H2bdc = 1,2- acidic benzenedicarboxylic) through the application of acidic carboxylic and the N-containing linkers as the co-ligands. The molecular arrangement for the constructed CPs were probed by the structural solution and refinement based on the singe crystal X-ray data and their phase purities was confirmed via a comparison between the simulated profile from the crystal data with the measured profile using the powder X-ray diffraction. Furthermore, an ultrasonic treatment method was used to produce the nano particles of CPs 1 and 2 with good water dispersibility and framework integrality. Moreover, the in vitro 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) method were administered on the breast cancer cell line BT474 with rising aggregations of the nanostructures 1 and 2, the cell apoptosis and ROS production level was also performed on BT474 cell line. This study suggested both nanostructures 1 and 2 have promising anticancer properties.

Two new 1, 8-naphthalimide-based fluorophore compounds, 4-piperazinyl-N-(4-Pyr-idinyl)-1, 8-naphthalimide (RB1) and 4-phenyl-N-(3-hydroxyphenyl)-1, 8-naphth- alimide (RB2) were synthesized via two-steps nucleophilic substitution reactions and Suzuki coupling reaction. The chemical structures of the title compounds were characterized by 1H NMR, 13C NMR, HRMS and FT-IR spectral analysis. Thermogravimetric analysis results show that the degradation temperatures of two compounds were about 300 °C. The single-crystal XRD analysis revealed that both RB1 and RB2 crystallize in the monoclinic P21/c (No. 14) space group, with lattice parameters of RB1 a = 15.3016(10), b = 15.4468(9), c = 7.1919(4) A, β = 95.384(2)°, V = 1692.38(18) A3, Z = 4 and RB2 a = 16.1990(3), b = 15.9460(3), c = 7.5870(15) A, β = 98.718(5)°, V = 1937.2(7) A3, Z = 4 respectively. Both crystals of two compounds have parallel offset stacking with extensive intermolecular interactions (hydrogen bond, C–H⋅⋅⋅π interaction), which are correspondence with the molecular packing of J-aggregation. The UV–vis and fluorescence properties of two compounds in different solvents were investigated, indicated that ICT characteristics of RB1 in organic solvents. Moreover, RB1 crystal can excite the strong green fluorescence with good thermal and optical stability qualifying it as a potential application in the fields of crystal luminescent functional materials.

A novel 3D cationic metal–organic framework, {[AgTPB]∙SbF6}n (namely 1), based on AgI and 1,2,4,5-tetra(4-pyridyl) benzene (TPB) was successfully generated under the diffusion synthesis method. The as-synthesized crystal has been investigated and characterized by physicochemical and spectroscopic methods in detail, including single crystal X-ray diffraction, powder X-ray diffraction, UV–Vis spectra, gas/liquid sorption, as well as thermogravimetric analysis. The counter anion SbF6− coming from AgSbF6 exists in the pores of MOF 1. The activated 1 can selectively adsorb CO2 over CH4, and H2O over C2H5OH. Furthermore, it also can be used as a rapid anion exchange MOF for Cr2O72− in water system at room temperature.

A new hybrid material bis(2,4,6-trihydroxy-1,3,5-triazin-1-ium) bischloride monohydrate (2C3H4N3O3+.2Cl-.H2O) as a crystal has been synthesized and its structure was identified by single-crystal X-ray diffraction and studied by UV–Vis, FT-IR, FT-Raman and 1H NMR. The crystal of 2C3H4N3O3+.2Cl-.H2O belongs to monoclinic with C2/m space group system with Z = 4, a = 12.3845 (9) A, b = 17.6236 (14) A, c = 7.0260 (5) A and β = 115.341 (2)°. The UV–Vis spectrum shows that the compound is transparent in visible and UV near visible domains. The FT-IR, FT-RAMAN and 1H NMR spectra of the crystal were discussed on the basis of crystallographic structure and the results were coherent and provides spectroscopic evidence for the crystal formation. In addition, the thermal decomposition of 2C3H4N3O3+.2Cl-.H2O has been also studied by TGA/DTG and DSC techniques and reveals that the material has a good thermal stability with the melting point about 310 °C.

The new cocrystal adducts of N-phthaloyl-β-alanine and benzimidazole (1:2) with molecular formula C18H15N3O4 (1) was synthesized by slow evaporation process of the aqueous solution containing the two said moieties. The confirmation of proposed formula can be established through crystal structure as well as FTIR analysis. The crystal structure was confirmed by single X–ray crystal analysis. The experimental and theoretical studies of photophysical properties like Fourier Transform Infrared (FTIR) and ultraviolet–visible spectroscopy (UV–Vis) have been done. The cocrystal belong to monoclinic crystallographic system with space group P21/c, Z = 4. DPPH radical scavenging activity of the title cocrystal is slightly lower than coformer with lower IC50 value, respectively. One dimensional infinite chain in direction of [010] parallel to b direction. Optimized crystalline network structure of 1 shows that conventional N−H⋯O, and O H⋯N, and the non−conventional C H⋯O hydrogen bonds (HBs) gathered the monomeric components of 1 (1−mon). The reliable calculations of the dispersion corrected density functional theory (DFT−D) display that N−H⋯O and O−H⋯N HBs more share in the stabilization of the network structure. The theoretical study of UV–Vis spectra in solvents (water, acetonitrile, methanol, and n–heptanes) confirms the experimental results as seven main bands in 180–270 nm range. They could attribute to intra-ligand charge transfer (ILCT) as benzimidazole → benzimidazole and N-phthaloyl-β-alanine → N-phthaloyl-β-alanine with π → π* character.

A new metal-organic NLO single crystal of 2-Aminopyridinium bis[hexaaqua(cobalt(II)) sulfate] monohydrate (2APCS) has been obtained by the reaction of aqueous solution of 2-Aminopyridine and cobalt(II) sulfate heptahydrate and by room temperature slow evaporation process. Single crystal X-ray diffraction study of the grown single crystal confirms the P 1 ¯ space group of a triclinic structure. The crystalline molecules are stabilized by elaborate O H⋯O and N H⋯O classical three dimensional hydrogen bonding network. The functional groups in the 2APCS were established by the FT-IR and Laser Raman spectroscopy. The obtained crystals were also characterized for thermal stability, dielectric, optical and nonlinear optical properties. Z-Scan technique was employed to observe the third order nonlinear optical susceptibility and was observed to be high. The optical limiting behaviour of the grown crystal is recognized mainly to nonlinear refraction.

In this study, reaction of 2-(5-(pyridin-3-yl)-4-(pyridin-4-yl)-4H-1,2,4-triazol-3-yl)pyridine (L) with Ni(NO3)2·6H2O or CuBr2 leads to the formation of two discrete coordination complexes [Ni(L)2(H2O)2](NO3)2 (1) and [Cu(L)Br2](H2O)(DMF)2 (2) with different metal cluster composing. Various structural characterization methods such as thermogravimetric analysis (TGA), elemental analysis (EA), powder as well as single crystal X-ray diffraction measurements were used to study the compositions along with the atom arrangement of the two as-prepared coordination complexes. Furthermore, the grinding method was used to downsize the crystal size of the complexes 1 and 2 into nano region to make them useable. In connection to these, the anticancer activities of the as-prepared two complexes have been studied via access the cell validity and the IC50 values of three human osteogenic sarcoma cells (MG-63, U2SO and Saos-2).

N, N-diethylanilinium-5-sulphosalicylate was successfully synthesized and good optical quality single crystals were grown employing slow solvent evaporation solution growth technique at ambient temperature. The CHN analysis indicates that the titled crystal is composed of stoichiometric proportion of the constituent ions, free from impurities and devoid of water molecules. The UV–Visible absorption spectrum exhibits the bands due to π-π* and n- π* transitions occurring in the salt. FT-IR spectral studies were performed to identify the different vibrational modes present in the titled crystal. The formation of salt and the molecular structure were initially confirmed by 1H and 13C NMR spectroscopic Studies. Single crystal XRD analysis indicates that the titled crystal belongs to monoclinic crystal system with centrosymmetric space group, P21/c. The hydrogen bonding parameter reveals that the salt crystal possesses N–H⋯O, O–H⋯O and C–H⋯O types of hydrogen bonding which are responsible for the stabilization of the crystal structure. TG/DTA Analyses reveal that the crystal is thermally stable up to 270 °C. The Vickers microhardness study reveals the soft nature of the titled crystal. Further, the titled salt was screened for its antimicrobial and antioxidant activities. The antimicrobial studies reveal that the synthesized salt has significant antibacterial and antifungal activities comparable to the standard compounds. The antioxidant activities of the titled salt show that the synthesized salt exhibits moderate activity against DPPH radical.

An ionic compound 4-methyl-piperidinium 4-methyl-piperidinecarbodithioate (MPMP) C6H14N+·C7H12NS2¯ has been synthesized from the one pot reaction of 4-methylpiperidine and carbon disulfide. The compound is well characterized on the basis of elemental analysis, IR, NMR, UV–visible and single crystal X-ray diffraction data. The compound introduces the concept of hydrogen bonding interactions in two ionic species and its effect on crystal packing. The asymmetric unit of the compound consists of 4-methyl-piperidinium cation and 4-methyl-piperidinecarbodithioate anion. Inter and intramolecular N H⋯S contacts link piperidinium cation and carbodithioate anion and stabilize the crystal packing in solid state. The compound crystallizes in monoclinic system with space group P 21/c. The interaction of the compound with different metal ion solutions is studied and it shows interesting red shifts with Co2+, Cu+, Cu2+ and Ni2+ ions which suggests that MPMP may be a useful probe for sensing of these ions. Cyclic voltammetric analysis of the compound exhibits quasi-reversible redox behaviour.

(C7H11N2)2[CrCl2(H2O)4]Cl3·2H2O has been obtained by slow evaporation method at room temperature. The single crystal X–ray diffraction proves that it crystallizes in the P2/c monoclinic space group with a = 8.384(2)A, b = 7.495(6)A, c = 21.868(5)A, β = 98.49(2)°, V = 1359(12)A3. The structure is built up by (C7H11N2)+ organic cation, an octahedral Cr(III) inorganic cluster [CrCl2(H2O)4], two other free chlorine anions and a water molecule. The structure exhibits an alternate organic-inorganic layered stacking along c-axis. The isolated octahedra are building a zero-dimensional anionic network. The crystal structure is stabilized by N H⋯Cl, O H⋯Cl, O H⋯O and offset cycle stacking interactions. The powder X-ray diffraction confirms the phase purity. Hirshfeld surface projections elucidate the contribution of the H⋯Cl, H⋯H, H⋯O intermolecular interactions. The UV–visible, the photoluminescence (PL), the observed/calculated infrared, the electronic transition and the crystal shape morphology as well as the thermal behaviour of the studied compound have been discussed.

1-((E)-3-(4-bromophenyl) -1-phenylallylidene)-2-(m-tolyl)hydrazine (4) was synthesized and characterized for structural elucidation by spectroscopy (FT-IR, 1H NMR, and 13C NMR) and single crystal X-ray diffraction. In the title compound, the benzene rings A, B, C were oriented at dihedral angles {A/B = 82.92 (3)°, A/C = 24.12 (3)°and B/C = 75.90 (3)°}. Crystal structure showed that intermolecular C H⋯O and C H⋯N hydrogen bonds linked the molecules, enclosing R22 (10) and R22 (16) ring motifs. The Hirshfeld surface analysis of the crystal structure indicated that the most important contributions for the crystal packing were from H⋯H (46.0%), H⋯C/C⋯H (17.6%), H⋯Br/Br⋯H (12.4%), H⋯O/O⋯H (8.5%) and C⋯C (6.6%) interactions. Hydrogen bonding and van der Waals contacts were the dominant interactions in the crystal packing. Compound's interaction with DNA was further investigated theoretically by DFT and experimentally by UV–visible spectroscopy and cyclic voltammetry. DFT analysis in terms of geometry optimization and computed parameters revealed reactive nature of 4 and the possibility of planar phenyl rings to intercalate within the DNA base pairs. Spectral and voltammetric analysis and related binding parameters suggested intercalation as a possible mode for 4 – DNA binding which was further verified by viscosity measurements.

Antiaromatic compounds have been applied in optoelectronic devices. In this paper, acenaphthoquinone bisphenylhydrazone (1a) and acenaphthoquinone bis(4-bromophenylhydrazone) (2a), were synthesized by a Schiff base reaction of acenaphthoquinone with phenylhydrazine or 4-bromophenylhydrazine. Two bisazo compounds with antiaromatic five-membered rings, 1,2-bisphenylazoacenaphthylene (1b) and 1,2-bis(4-bromophenylazo)acenaphthylene (2b) were respectively synthesized by oxidation reactions of compound 1a or 2a with PbO2. The crystal structures show that these compounds would be aggregated to H-aggregation structures, which were caused by the antiaromatic cores. Based on crystal structures of 1a, 2a, 1b and 2b, nucleus independent chemical shift (NICS) values were calculated. The obtained NICS (0) values for the five-membered rings located at cores of molecules 1a (3.64), 1b (4.64), 2a (4.42) and 2b (3.97) suggest that those core rings would exhibit antiaromatic nature. Crystal geometries and thermodynamic data of Gibbs free energies and entropies suggest that the bisazo compounds would easily accept and delocalize electrons in these crystals due to the antiaromatic cores and H-aggregation. This paper suggests a way of design of electron-accepting materials with spontaneous charge transfer nature.

Four cocrystals were obtained by using 1,4-diiodotetrafluorobenzene and four nitrogen-containing organic coformers, including pyridine, secondary and tertiary amines. The obtained cocrystals have been fully characterized with various techniques, including, single crystal and powder X-ray crystallography, TGA and DSC. Crystal structural analyses showed that halogen bond (XB) is the main driving force responsible for the cocrystallization and for the adopted architectures in the described systems. In the described cocrystals, the 1,4-diiodoperfluorobenzene has shown to be a versatile molecule for intermolecular noncovalent interactions with coformers. Its iodine atoms can serve not only as halogen bond donor, but also as halogen bond acceptor. In addition, it involves also in many non-covalent interactions, including C H⋯F and hole-π … π bondings to play a role in determining the molecular arrangement and crystal packing, which make it an ideal coformer in crystal engineering for predictable and stable supramolecular architecture for desired physicochemical properties.

The synthesis, X-ray diffraction, Hirshfeld, DSC, TGA-dTG, and Infrared spectrum of a new [C6H5NH3]3BiCl6·3H2O crystal are reported. The crystal structure of the title compound at 293 K [P212121; Z = 4; a = 7.4348(3)A, b = 16.5416(6)A, c = 22.0510(8)A] comprises units containing an isolated and distorted BiCl63−octahedron, three independent organic cations, and three independent water molecules linked together by N H⋯Cl, N H⋯O, O H⋯Cl, and O H⋯O hydrogen bonding to form organic-inorganic network. The X-rays powder diffraction pattern is satisfactory indexed and affined on the basis of an orthorhombic unit cell, with parametrs closed to those determined by single crystal X-ray diffraction. Hirshfeld surface analysis and fingerprint plots methods are used to identify and analyze the significant intermolecular interactions in the crystal network, and to determine the contribution of the component units in the crystal structure construction. DSC curves show two non reproducible and irreversible endothermic anomalies (T1 ≅ 115 °C, T2 ≅ 132 °C), which correspond to the dehydration due to removing of water species from the crystal structure. TG-dTG analyses confirm that the removed water is of crystallization in agreement with X-Ray and DSC analyses. The study of Infrared spectrum at room temperature confirms the presence of C6H5NH3+ cations, H2O molecules, which are linked to BiCl63− anions by hydrogen bonding.

In this work a metal organic single crystal, ethylenediammonium tetrachloro zinc was investigated through combining the approach of experimental and computational method. A Well transparent non-centrosymmetric single crystal (ETZ) grown from the solvent evaporation method. The crystallinity and structural parameters are investigated by X-ray diffraction analysis. The protonation of amino groups is verified from vibrational analysis. The material holds 80% optical transparency in the entire visible region, and it has lower cut off wavelength of 233 nm. Frontier molecular orbital energies and their charge transfer mechanism are carefully investigated by frontier molecular orbital analysis. The inter and intramolecular interactions are explored through the NBO analysis. The intermolecular hydrogen bond n-σ* kinds of electronic transitions are more endowment in the ETZ molecule. The solid-state molecular packing arrangement and distinct atom to atom intermolecular interactions are briefly explained via Hirshfeld surface analysis. The SHG efficiency is 0.9 times that of standard KDP material. The dipole moment, polarizability and first-order hyperpolarizability are 17.878 D, −13.40554 × 10−24 esu and 1.719 × 10−30 esu respectively are calculated from density functional theory. The obtained results concluded that titled crystal can be a decent material for nonlinear optical applications.

A novel (CuII/ReVII)-heterobimetallic complex based on l -Arginine, namely trans-[Cu( l -Arg)2(ReO4)2] (CuLARe), was successfully synthesized and fully characterized using X-ray structure analysis as well as (IR/UV–vis) spectroscopy, molar conductivity and (TG/DTA) thermal methods. The crystal structure determination reveals that CuLARe has a non-symmetrical atomic arrangement and features striking helical chains of {[Cu( l -Arg)2(ReO4)2]}n, which are further assembled into a 3D-supramolecular network through multidirectional N(C, O)-H⋯O hydrogen bonding interactions. Analysis by Hirshfeld surface generation in combination with 2D-fingerprinting was also performed to elucidate the nature of the interactions and their contributions towards the crystal packing. Moreover, a comparative antioxidant screening of CuLARe with the free ligands as well as CuCl2 has been investigated. The results emphasize that the complexation of ligands to the metal ions plays a crucial role in the improvement of the biochemical properties of CuLARe.

The title compound l -phenylalanine fumaric acid has been synthesized in slow evaporation solution growth technique. The crystallinity of the crystal is confirmed by powder X-ray diffraction studies. Complete vibrational analysis and optimized molecular structure is obtained using density functional theory calculations. The vibrational contribution of each normal mode is figured out by calculating potential energy distribution with the aid of vibrational energy distribution analysis (VEDA 4) program. Experimental FT-infrared and FT-Raman spectra are recorded and analyzed. The second harmonic generation (SHG) efficiency of the grown crystal is measured by Kurtz – Perry technique. The calculated first hyperpolarizability and the highest occupied molecular orbital (HOMO) - lowest unoccupied molecular orbital (LUMO) energies confirm the nonlinear optical activity of the compound. The theoretical and experimental cutoff wavelength corresponding to electronic transitions are obtained. The most important hyper conjugative interactions leading to the stability and intramolecular charge transfer of the system is elucidated by natural bond orbital analysis. Information regarding the charge density distribution and chemical reactivity sites of the compound has been obtained by mapping molecular electrostatic potential.

A new organic hydrazide derivative crystal, 2-(4-chlorophenoxy)-N′-[(1E)-1-(4-methylphenyl) ethylidene] acetohydrazide (4CP4MPEA) has been successfully synthesized and grown as single crystal from DMF solution. 4CP4MPEA crystallizes in triclinic crystal system with space group P-1 as revealed by single crystal X-ray diffraction (XRD). The molecule adopts an E configuration with respect to its C N double bond. The dihedral angle between the two phenyl rings is 79.29 (14)°. The synthesized compound has been characterized by UV/Vis and 1H NMR spectrum. Thermal properties and close contacts present in the crystal have also been investigated. The intermolecular interactions in the crystal structure were quantified and analyzed using Hirshfeld surface analysis. Open aperture Z-Scan data demonstrate the presence of two-photon absorption. Calculated values of σex and σg are 4.01 × 10−17cm2 and 1.33 × 10−21 cm2 respectively. The value of σex ≫> σg clearly indicates that the nonlinear absorption (NLA) process is due to the reverse saturable absorption (RSA). Observed optical limiting characteristics in 4CP4MPEA are attributed to the RSA. The Optical limiting threshold is found to be 3.13 × 1012 W/m2.

With the flourishing development of emitting materials, tremendous technological progress has been accomplished. However, they still face great challenges in convenient economical environmental-friendly large-scale commercial production. Herein we designed this hybrid lead/rare earth-free crystals with the large size of 2.7*3.0 cm, an emerging class of high-efficiency luminescent material, (PYE)[Cu2I3] (1), which emits intense photoluminescence with a high emissive quantum yields of 32.11%. In addition, the results demonstrate that it is possible to obtain regulatable fluorescence intensity by introducing free groups in material design through simple molecular design. The dielectric constant curve remains relatively smooth before melting point. Therefore, it will be an important exploration and effective way for new material design to achieve artificial intelligence luminescent molecules, in this way, the personal customized application can be realized in display and sensing.