Crystal structure and Hirshfeld surface analysis of (Z)-4-{[4-(3-methyl-3-phenyl-cyclo-but-yl)thia-zol-2-yl]amino}-4-oxobut-2-enoic acid.

The title cyclo-butyl compound, C18H18N2O3S, was synthesized by the inter-action of 4-(3-methyl-3-phenyl-cyclo-but-yl)thia-zol-2-amine and maleic anhydride, and crystallizes in the ortho-rhom-bic space group P212121 with Z' = 1. The mol-ecular geometry is partially stabilized by an intra-molecular N-H⋯O hydrogen bond forming an S 1 1(7) ring motif. The mol-ecule is non-planar with a dihedral angle of 88.29 (11)° between the thia-zole and benzene rings. In the crystal, the mol-ecules are linked by O-H⋯N hydrogen bonds, forming supra-molecular ribbons with C 1 1(9) chain motifs. To further analyze the inter-molecular inter-actions, a Hirshfeld surface analysis was performed. The results indicate that the most important contributions to the overall surface are from H⋯H (43%), C⋯H (18%), O⋯H (17%) and N⋯H (6%), inter-actions.

Structural and spectroscopic characterization of 4-(3-methyl-3-phenylcyclobutyl)-2-(2-propylidenehydrazinyl)thiazole: A combined experimental and DFT analysis.

We investigated the structural and spectroscopic properties of the title compound by means of experimental and DFT quantum chemical methods. The crystal structure of compound was brought to light by single crystal X-ray diffraction method, and were characterized spectroscopically using FT-IR and NMR spectra. FT-IR spectrum in solid state was observed in the region 4000-400 cm(-1). The (1)H and (13)C NMR spectra were recorded in CDCl3 solution. The molecular geometry were those obtained from the X-ray structure determination was optimized using density functional theory (DFT/B3LYP) method with the 6-31G(d, p) and 6-31+G(d, p) basis sets in ground state. From the optimized geometry of the molecule, geometric parameters (bond lengths, bond angles, torsion angles), vibrational assignments and chemical shifts of the title compound have been calculated theoretically and compared with the experimental data. Although theoretical calculations were carried out in gas phase, no significant differences in these values.

Structural and spectroscopic characterization of a thiosemicarbazidatodioxouranium(VI) complex: a combined experimental and DFT study.

The title thiosemicarbazidatodioxouranium(VI) compound was synthesized and characterized by FT-IR, NMR and UV-vis spectroscopies. Solid-state structure of the compound was confirmed by X-ray crystallography. Besides, the molecular geometry, vibrational frequencies and gauge-independent atomic orbital (GIAO) (1)H and (13)C NMR chemical shift values of the compound in the ground state have been calculated using the density functional theory (DFT/B3LYP) method with the 6-311++G(d,p) basis set for the C, H, Cl, N, O, S atoms and SDD pseudo-potential for the U atom, and compared with the experimental data. Using the TD-DFT method, electronic absorption spectra of the compound have been predicted at same level. As a result, a good agreement is obtained between the experimental and theoretical ones.

A novel one-pot synthesis of heterocyclic compound (4-benzoyl-5-phenyl-2-(pyridin-2-yl)-3,3a-dihydropyrazolo[1,5-c]pyrimidin-7(6H)-one): structural (X-ray and DFT) and spectroscopic (FT-IR, NMR, UV-Vis and Mass) characterization studies.

In this study, the title compound named as 4-benzoyl-5-phenyl-2-(pyridin-2-yl)-3,3a-dihydropyrazolo[1,5-c]pyrimidin-7(6H)-one (C24H18N4O2) was both experimentally and theoretically investigated. The compound was synthesized and characterized by FT-IR, NMR ((1)H NMR, (13)C NMR and HETCOR-NMR), Mass spectroscopies and single-crystal X-ray diffraction methods. The compound crystallizes in the monoclinic space group P2(1)/n with a=6.1402 (3) Å, b=21.4470 (15) Å, c=15.0049 (8) Å and ß=97.407 (4)°. The molecular geometry was obtained from the X-ray structure determination optimized using density functional theory (DFT/B3LYP) method with the 6-31+G(d, p) basis set in ground state. From the optimized structure, geometric parameters, vibrational wavenumbers and chemical shifts of molecule were obtained. Experimental measurements were compared with its corresponding the calculated data. An excellent harmony between the two data was ascertained. Besides, molecular electrostatic potential (MEP), frontier molecular orbitals (FMOs) and non-linear optical (NLO) properties of the title molecule were investigated by theoretical calculations at the B3LYP/6-31+G(d, p) level.

Synthesis, spectroscopic (FT-IR/NMR) characterization, X-ray structure and DFT studies on (E)-2-(1-phenylethylidene) hydrazinecarboximidamide nitrate hemimethanol.

The title molecular salt, (E)-2-(1-phenylethylidene) hydrazinecarboximidamide nitrate hemimethanol C9H13N4(+)·NO3(-)·0.5CH4O, was synthesized and characterized by elemental analysis, FT-IR and NMT spectroscopies, and single-crystal X-ray diffraction technique. Quantum chemical calculations were performed to study the molecular and spectroscopic properties of the title compound, and the results were compared with the experimental findings. The calculated results show that the optimized geometry can well reproduce the crystal structure parameters, and the theoretical vibrational frequencies and GIAO (1)H and (13)CNMR chemical shifts show good agreement with experimental values. The dipole moment, linear polarizability and first hyperpolarizability values were also computed. The linear polarizabilities and first hyper polarizabilities of the studied molecule indicate that the compound is a good candidate of nonlinear optical materials. On the basis of the thermodynamic properties of the title compound at different temperatures have been calculated, revealing the correlations between standard heat capacities (C) standard entropies (S), and standard enthalpy changes (H) and temperatures.

Synthesis, spectroscopic and structural characterization of 5-benzoyl-4-phenyl-2-methylthio-1H-pyrimidine with theoretical calculations using density functional theory.

In this paper, we will report a combined experimental and theoretical investigation of the molecular structure and spectroscopic parameters (FT-IR, (1)H NMR, (13)C NMR) of 5-benzoyl-4-phenyl-2-methylthio-1H-pyrimidine. The compound crystallizes in the triclinic space group P-1 with Z=2. The molecular geometry was also optimized using density functional theory (DFT/B3LYP) method with the 6-311G(d,p) and 6-311++G(d,p) basis sets in ground state and compared with the experimental data. All the assignments of the theoretical frequencies were performed by potential energy distributions using VEDA 4 program. Information about the size, shape, charge density distribution and site of chemical reactivity of the molecules has been obtained by mapping electron density isosurface with electrostatic potential (ESP). Also, non-linear optical properties of the title compound were performed at B3LYP/6-311++G(d,p) level. The theoretical results showed an excellent agreement with the experimental values.

Synthesis and characterization of SiO2-supported ruthenium complexes containing aromatic sulfonamides: as catalysts for transfer hydrogenation of acetophenone.

3-Amino-N-aryl-benzenesulfonamides (1­3) were successfully synthesized by the reaction of m-phenylenediamine and various benzenesulfonyl chlorides. Then, a series of ruthenium complexes (4­6) were prepared from the reaction of [RuCl2(p-cymene)]2 and 1­3. Finally, SiO2-supported Ru(II) complexes (7­9) were prepared by an impregnation method. The synthesized compounds and materials were characterized by different methods such as NMR, FT-IR, TG/DTA, nitrogen adsorption­desorption (BET), SEM and EDX. Also, the solid state structures of 4­6 were determined by single-crystal X-ray diffraction. 4­9 were used as catalysts for the transfer hydrogenation of acetophenone. 4­9 showed good catalytic activity and so the effects of the different groups were also examined. For the transfer hydrogenation of acetophenone, 7­9 had similar activity to 4­6. However, the longer lifetime of 7­9 makes them more advantageous than the non-supported catalysts (4­6) in terms of catalytic cycle. Therefore, the effect of SiO2 was investigated as a catalyst and the results show that excess silicon(IV) oxide was a surprisingly active catalyst for the hydrogenation of acetophenone under these conditions.

1-(3-methyl-3-mesityl)-cyclobutyl-2-(5-pyridin-4-yl-2H-[1,2,4]triazol-3-ylsulfanyl)-ethanone: X-ray structure, spectroscopic characterization and DFT studies.

The triazole compound 1-(3-Methyl-3-mesityl)-cyclobutyl-2-(5-pyridin-4-yl-2H-[1,2,4]triazol-3-ylsulfanyl)-ethanone, (C23H26N4OS), was characterized by X-ray single crystal diffraction technique, IR NMR spectroscopy and quantum chemical computational methods as both experimental and theoretically. The compound crystallizes in the monoclinic space group P2(1)/c with Z=4. The molecular geometry was also optimized using density functional theory (DFT/B3LYP) method with the 6-311G(d,p) basis set in ground state and compared with the experimental data. The computed vibrational frequencies are used to determine the types of molecular motions associated with each of the experimental bands observed. The results of the calculations were applied to simulate spectra of the title compound, which show excellent agreement with observed spectra. Data of the title compound display significant structure correlation and provide the basis for future design of efficient materials having the derivatives of 1,2,4-triazole. From the optimized geometry of the molecule, vibrational frequencies, gauge-independent atomic orbital (GIAO) 1H and 13C NMR chemical shift values, molecular electrostatic potential (MEP) distribution, non-linear optical properties and frontier molecular orbitals (FMOs) of the title compound were performed at B3LYP/6-311G(d,p). On the basis of theoretical vibrational analyses, the thermodynamic properties (standard heat capacities, standard entropies, and standard enthalpy changes) of the title compound at different temperatures have been calculated, revealing the correlations between Cp,m0, Sm0, ΔHm0 and temperatures. The predicted non-linear optical properties of the title compound are much greater than those of urea. Data of the title compound display significant structure-correlation and provide the basis for future design of efficient materials having the derivatives of 1,2,4-triazole.

Synthesis, spectroscopic characterization, X-ray structure and DFT studies on 2,6-bis(1-benzyl-1H-benzo[d]imidazol-2-yl)pyridine.

The title molecule, 2,6-bis(1-benzyl-1H-benzo[d]imidazol-2-yl)pyridine (C(33)H(25)N(5)), was synthesized and characterized by elemental analysis, FT-IR spectroscopy, one- and two-dimensional NMR spectroscopies, and single-crystal X-ray diffraction. In addition, the molecular geometry, vibrational frequencies and gauge-independent atomic orbital (GIAO) (1)H and (13)C NMR chemical shift values of the title compound in the ground state have been calculated using the density functional theory at the B3LYP/6-311G(d,p) level, and compared with the experimental data. The complete assignments of all vibrational modes were performed by potential energy distributions using VEDA 4 program. The geometrical parameters of the optimized structure are in good agreement with the X-ray crystallographic data, and the theoretical vibrational frequencies and GIAO (1)H and (13)C NMR chemical shifts show good agreement with experimental values. Besides, molecular electrostatic potential (MEP) distribution, frontier molecular orbitals (FMO) and non-linear optical properties of the title compound were investigated by theoretical calculations at the B3LYP/6-311G(d,p) level. The linear polarizabilities and first hyper polarizabilities of the molecule indicate that the compound is a good candidate of nonlinear optical materials. The thermodynamic properties of the compound at different temperatures were calculated, revealing the correlations between standard heat capacity, standard entropy, standard enthalpy changes and temperatures.

1,1'-Bis(3-methyl-3-phenyl-cyclo-but-yl)-2,2'-(aza-nedi-yl)diethanol.

The title mol-ecule, C(26)H(35)NO(2), contains two cyclo-butane rings that adopt butterfly conformations and are linked by a -CH(OH)CH(2)NHCH(2)CH(OH)- bridge. In the crystal, N-H⋯O, O-H⋯N and O-H⋯O hydrogen bonds together with C-H⋯π inter-actions link the molecules.

(Z)-1-(3-Mesityl-3-methyl-cyclo-but-yl)-2-(morpholin-4-yl)ethanone oxime.

In the title compound, C(20)H(30)N(2)O(2), the cyclo-butane ring is puckered, with a dihedral angle of 19.60 (13)° between the two planes. In the crystal, the mol-ecules are linked by inter-molecular O-H⋯N and weak C-H⋯O hydrogen bonds, as well as a C-H⋯π hydrogen-bonding association.

2-Chloro-N-[4-(3-methyl-3-phenyl-cyclo-but-yl)-1,3-thia-zol-2-yl]-N'-(naphthalen-1-yl-methyl-idene)acetohydrazide.

In the mol-ecular structure of the title hydrazide derivative, C(27)H(24)ClN(3)OS, the acetohydrazide group is approximately planar, with a maximum deviation of 0.017 (3) Å. The dihedral angle between the naphthyl-ene system and the phenyl ring is 78.91 (18)°. The crystal structure is stabilized by one weak inter-molecular C-H⋯O hydrogen bond and two aliphatic C-H⋯π hydrogen-bonding associations.

Synthesis, X-ray crystal structures, thermal and electrochemical properties of thiosemicarbazidatodioxouranium(VI) complexes.

The stable uranyl complexes, [UO(2)(L)C(9)H(19)OH], were obtained from 3,5-dichlorosalicyl-(L(I)) and salicyl-aldehyde-S-propyl-thiosemicarbazones (L(II)) with substituted-salicylaldehyde in nonyl alcohol. The structures of the complexes have been characterized by elemental analysis, IR, (1)H NMR, conductivity, magnetic moment measurements, cyclic voltammetry, thermal gravimetric analysis and single crystal X-ray diffraction technique. The U(VI) centre is seven-coordinated in a distorted pentagonal bipyramidal geometry. The relative orientations of the nonyl alcohol and S-propyl group in the title complexes are completely different due to different crystal packing. Electrochemical behaviors of the thiosemicarbazone ligands and the uranyl complexes were studied using cyclic voltammetry and square wave voltammetry. Redox processes of the compounds are significantly influenced by the central metal ions and the nature of substituents on the thiosemicarbazones, which are important factors in controlling the redox properties. In situ spectroelectrochemical studies were employed to determine the colors and spectra of electro-generated species of the complexes.

Molecular structure and vibrational bands and chemical shift assignments of 4-allyl-5-(2-hydroxyphenyl)-2,4-dihydro-3H-1,2,4-triazole-3-thione by DFT and ab initio HF calculations.

The title molecule, 4-allyl-5-(2-hydroxyphenyl)-2,4-dihydro-3H-1,2,4-triazole-3-thione (C(11)H(11)N(3)OS), was synthesized and characterized by IR-NMR spectroscopy and single-crystal X-ray diffraction. The compound crystallizes in the monoclinic space group is P2(1)/c, a=9.0907(5)A, b=9.1288(7)A, c=13.6222(7)A, alpha=90 degrees , beta=98.442 (4), gamma=90 degrees and V=2683.7(6)A(3), F(000)=488, D(x)=1.386 g/cm(3). In addition to the molecular geometry from X-ray experiment, the molecular geometry, vibrational frequencies, gauge including atomic orbital (GIAO) (1)H and (13)C chemical shift values of the title compound in the ground state have been calculated using the Hartree-Fock (HF) and density functional method (DFT/BLYP and DFT/B3LYP) with 6-31G(d) basis set. To determine conformational flexibility, molecular energy profile of the title compound was obtained by HF/6-31G(d) calculations with respect to selected degree of torsional freedom, which was varied from -180 degrees to +180 degrees in steps of 10 degrees . Besides, molecular electrostatic potential (MEP), frontier molecular orbitals (FMO), and several thermodynamic properties were performed by the HF and DFT methods.

2-Chloro-N'-[4-(dimethyl-amino)-benzyl-idene]-N-[4-(3-methyl-3-phenyl-cyclo-but-yl)-1,3-thia-zol-2-yl]acetohydrazide.

The mol-ecular conformation of the title compound, C(25)H(27)ClN(4)OS, is stabilized by an intra-molecular benzyl-idine C-H⋯N(thia-zole) hydrogen bond. The thiazole ring makes dihedral angles of 12.0 (3) and 20.4 (2)°, respectively, with the phenyl and benzene rings, while the phenyl and benzene rings make a dihedral angle of 22.6 (2)°. The crystal packing involves weak inter-molecular thia-zole C-H⋯O(carbon-yl) and methyl C-H⋯π hydrogen-bonding associations.

An experimental and theoretical approach to the molecular structure of 2-(4-[3-(2,5-dimethylphenyl)-3-methylcyclobutyl]thiazol-2-yl)isoindoline-1,3-dione.

The title compound, 2-{4-[3-(2,5-dimethylphenyl)-3-methylcyclobutyl]thiazol-2-yl}isoindoline-1,3-dione (C(24)H(22)N(2)O(2)S), was synthesized and characterized by IR-NMR spectroscopy and single-crystal X-ray diffraction. The compound crystallizes in the monoclinic space group P2(1)/c with a = 19.7799(13) A, b = 6.7473(4) A, c = 15.7259(9) A and beta = 103.416(5) degrees . In addition, the molecular geometry, vibrational frequencies and gauge including atomic orbital (GIAO) (1)H and (13)C chemical shift values of the title compound in the ground state have been calculated by using the Hartree-Fock (HF) and density functional method (DFT/B3LYP) with 6-31G(d), 6-31 + G(d,p) and LANL2DZ basis sets, and compared with the experimental data. To determine conformational flexibility, molecular energy profile of the title compound was obtained by semi-empirical (AM1) calculations with respect to two selected degrees of torsional freedom, which were varied from -180 degrees to +180 degrees in steps of 5 degrees . Besides, molecular electrostatic potential, frontier molecular orbitals (FMO) analysis and thermodynamic properties of the title compound were investigated by theoretical calculations.

Experimental and theoretical investigation of the molecular and electronic structure of 5-(4-aminophenyl)-4-(3-methyl-3-phenylcyclobutyl)thiazol-2-amine.

The title molecule, 5-(4-aminophenyl)-4-(3-methyl-3-phenylcyclobutyl)thiazol-2-amine (C(20)H(21)N(3)S), was prepared and characterized by (1)H-NMR, (13)C-NMR, IR and single-crystal X-ray diffraction. The compound crystallizes in the monoclinic space group P2(1)/c with a = 9.4350(5) A, b = 11.2796(6) A, c = 18.4170(8) A and beta = 113.378(3) degrees . In addition to the molecular geometry from X-ray experiment, the molecular geometry, vibrational frequencies, gauge including atomic orbital (GIAO) (1)H- and (13)C-NMR chemical shift values and atomic charges distribution of the title compound in the ground state have been calculated using the Hartree-Fock (HF) and density functional method (DFT) (B3LYP) with 6-31G(d) basis set. To determine conformational flexibility, molecular energy profile of the title compound was obtained by semi-empirical (AM1) calculations with respect to two selected degrees of torsional freedom, which were varied from -180 degrees to +180 degrees in steps of 10 degrees . Besides, frontier molecular orbitals (FMO) analysis was performed by the B3LYP/6-31G(d) method.

Methyl 2-methoxy-7-(4-methylbenzoyl)-4-oxo-6-p-tolyl-4H-furo[3,2-c]pyran-3-carboxylate:A combined experimental and theoretical investigation.

The title compound, methyl 2-methoxy-7-(4-methylbenzoyl)-4-oxo-6-p-tolyl-4H-furo[3,2-c]pyran-3-carboxylate (C(25)H(20)O(7)), was prepared and characterized by IR and single-crystal X-ray diffraction (XRD). The compound crystallizes in the triclinic space group P -1 with a = 8.9554(9) A, b = 10.0018(10) A, c = 12.7454(13) A, alpha = 67.678(7) degrees , beta = 89.359(8) degrees and gamma = 88.961(8) degrees . In addition to the molecular geometry from X-ray experiment, the molecular geometry and vibrational frequencies of the title compound in the ground state have been calculated using semiempirical AM1 and PM3 methods, as well as Hartree-Fock (HF) and density functional (B3LYP) levels of theory with 6-31G(d) basis set. To determine conformational flexibility, molecular energy profile of the title compound was obtained by semi-empirical (AM1) calculations with respect to two selected degrees of torsional freedom, which were varied from -180 degrees to +180 degrees in steps of 10 degrees . Besides, frontier molecular orbitals (FMO) analysis and thermodynamic properties of the title compound were performed by the B3LYP/6-31G(d) method.

Molecular structure and vibrational and chemical shift assignments of 3-(2-hydroxyphenyl)-4-phenyl-1H-1,2,4-triazole-5-(4H)-thione by DFT and ab initio HF calculations.

The molecular geometry, vibrational frequencies, gauge including atomic orbital (GIAO) 1H and 13C chemical shift values and several thermodynamic parameters of 3-(2-Hydroxyphenyl)-4-phenyl-1H-1,2,4-triazole-5-(4H)-thione in the ground state have been calculated by using the Hartree-Fock (HF) and density functional methods (BLYP and B3LYP) with 6-31G(d) basis set. The results of the optimized molecular structure are presented and compared with the experimental X-ray diffraction. The molecule contains one O-H...N and one C-H...pi (phenyl) intramolecular interactions. The computed vibrational frequencies are used to determine the types of molecular motions associated with each of the experimental bands observed. Data of the title compound display significant structure-correlation and provide the basis for future design of efficient materials having the derivatives of 1,2,4-triazole. Also, calculated 1H chemical shift values compared with the experimental ones.

(E)-5-Phenyl-N-(2-thienylmethyl-ene)-1,3,4-thia-diazole-2-amine.

In the title compound, C(13)H(9)N(3)S(2), the thio-phene and phenyl rings are oriented at dihedral angles of 8.00 (7) and 6.31 (7)°, respectively, with respect to the central thia-diazole ring. No significant C-H⋯S and π-π inter-actions exist in the crystal structure.