Crystal Structure and Density Functional Theory Studies of (p-Methoxyphenyl) Thiosemicarbazide

The title compound [CH3OC6H4NHNHCSNH2] has been characterized by ele- mental analysis, IR, electronic absorption spectra and X-ray single-crystal diffraction. It crystallizes in the monoclinic system, space group C2/c with a = 25.071(5), b = 5.9292(12), c = 14.938(3) ?, β = 118.40(3)o, Mr = 197.26 (C8H11N3OS), V = 1953.3(7) ?3, Z = 8, Dc = 1.342 g/cm3, F(000) = 832, μ = 0.296 mm-1, R = 0.0647 and wR = 0.1433. In the crystal lattice, there exist some intermolecular hydrogen bonds, π-π stacking interactions and C–H…π supramolecular interactions to stabilize the crystal structure. The density functional theory (DFT) calculations at the B3LYP/6-31G* level, charge distributions and thermodynamic properties at different temperature have been performed, showing the sulfur and nitrogen atoms have bigger negative charges because they are the potential sites reacting with the metallic ions.

Density Functional Calculations on a Double Hydrogen-bonded Dimer

Density functional theory (DFT) calculations on a double hydrogen-bonded dimer of o-hydroxybenzoic acid were carried out at the B3LYP/6-31G* level. The optimized geometry of the dimer closely resembles that of the crystal. The calculated results show that the total energy of the dimer is much lower than the sum energies of the two monomers, and the average strength of the double hydrogen bonds is about 38.37 kJ/mol. In order to probe the origin of the interactions in the dimer, natural bond orbital analyses were performed. The thermodynamic properties of the title compound at different temperatures have also been calculated on the basis of vibrational analyses and ?GT, the change of Gibbs free energy for the aggregation from monomer to the dimmer, is 26.47 kJ/mol at 298.15 K and 0.1 MPa, implying the spontaneous process of forming the dimer. The correlation graphics of S0m, H0m and temperatures is depicted.

Structure and Thermal Properties of Transition Metal Imidazole Chloride

The X-ray single-crystal structure analyses have been determined for two metal imidazole chlorides: [Fe(Im)6]Cl24H2O 1 and [CuCl(Im)4]Cl 2 (Im = imidazole). The red crystal of compound 1 is of triclinic, space group Pi with Mr = 607.31 (C18H32Cl2FeN12O4), a = 8.797(2), b = 9.068(2), c = 10.581(2) ? a = 75.35(3), ?= 83.20(3), ? = 61.85(3)o, V = 720.0(2) 3, Z = 1, Dc = 1.401 g/cm3, F(000) = 316, = 0.755 mm-1, R = 0.0353 and wR = 0.1227. The blue crystal of compound 2 belongs to monoclinic, space group P21/c with Mr = 406.77 (C12H16Cl2CuN8), a = 13.909(3), b = 8.8933(18), c = 15.086(7) ? ?= 118.32(2), V = 1642.7(9) 3, Z = 4, Dc = 1.645 g/cm3, F(000) = 828, = 1.666 mm-1, R = 0.0609 and wR = 0.1726. In solid state, both 1 and 2 form three-dimensional hydrogen bond networks to stabilize the structures which were also characterized by TG and elemental analyses. The thermal gravity (TG) data indicate that the residues are Fe and Cu for 1 and 2, respectively.

What Is Its Real Existing Form?——Theoretical and Experimental Studies on 2-Mercaptobenzothiazole

The geometry of 2-mercaptobenzothiazole （MBT） and its tautomeric form of benzothiazole-2-thione are optimized at B3LYP/6-311 G＊＊ and HF/6-311 G＊＊ levels, respectively. The crystal structure of benzothiazole-2-thione and its FFIR spectra are also obtained. From the calculated and experimental data, it can be concluded that in gas-phase and solid-state, the real existing form of 2-mercaptobenzothiazole is the thione-form of MBT.

Synthesis, Crystal Structure and Thermal Stability of (Diacetylacetone)(diimidazole)Nickel(II) Complex

The title compound, [Ni(acac)2(Im)2] (acac = acetylacetone), has been obtained by the reaction of Ni(acac)2 with imidazole ligand in the ethanol solvent. The blue crystal is of triclinic, space group Pi with a = 7.472(2), b = 9.456(2), c = 13.823(3) ? a = 85.55(3), = 89.03(3), ? = 80.63(3)o, C16H22N4NiO4, Mr = 393.09, V = 960.7(3) 3, Z = 2, Dc = 1.359 g/cm3, F(000) = 412, = 1.036 mm-1, R = 0.0549 and wR = 0.1615. The crystal structure consists of two disconnected structural units. Each Ni atom coordinated by two N atoms from two imidazole ligands and four O atoms from two acetylactone ligands adopts a slightly distorted octahedron. The structure characterization was performed by means of IR, UV, TG, elemental analysis and single-crystal X-ray analysis. The thermal gravity (TG) data indicate that thermal decomposition of the title compound takes place in two steps, and the residue is NiO.

Syntheses,Crystal Structures and Property Studies on Cu(Ⅱ) and Co(Ⅱ) Complexes with 1,8-Naphthalimid Schiff Base

The ligand of N-（2-hydroxybenzylideneamino）-1,8-naphthalimide （HL） and its metal complexes of CuL2 （1） and CoL2 （2） have been synthesized. Elemental analysis, IR and X-ray single-crystal diffraction characterizations for 1 and 2 have been carried out. In the complexes of 1 and 2, the central metallic ions of Cu^2＋ and Co^2＋ coordinate with two deprotonated ligands of L-, respectively and adopt distorted square planar geometries. The thermal analysis result shows that the two complexes undergo two similar decomposition processes because of their similar geometric configurations. For the two complexes, fluorescence spectra measurements indicate that complex CoL2 emits stronger blue fluorescence than HL and the complex CuL2 does not emit fluorescence at all.

Comparative Studies on Two 1,8-Naphthalimide Derivatives with Experimental and Theoretical Methods

Two 1,8-naphthalimide derivatives of 7H-benzimidazo[2,1,-a]benz[de] isoquino- lin-7-one（1） and 4-bromo-7H-benzimidazo[2,1,-a]benz[de]isoquinolin-7-one（2） have been synthesized and characterized by elemental analysis, IR, 1H NMR, UV-Vis and fluorescence spectra. For the two compounds, density functional theory（DFT） calculations of the structures and natural population atomic charge analysis have been performed at the B3LYP/6-311G＊＊ level of theory. Based on Onsager reaction filed model and by using TD-DFT method at the B3LYP/6-311G＊＊ level, electron spectra of 1 and 2 with solvent effect in CHCl3 solvent have been predicted, which are in agreement with the experimental ones. Comparative studies on 1 and 2 indicate that introducing an electron-withdrawing group of Br into the 4-position of naphthalene ring in 2 does not significantly make the molecular geometry of 2 different from that of 1, but evidently changes the atomic charge redistribution, moves the positive-negative charges center and then changes the dipole moment in 2. Additionally, for compound 2, the existence of Br atom has also influenced the peak intensity and peak locations in both electron and fluorescence spectra.

Crystal Structure of Chlorinate (N,N-1,3-Dibenzyl-benzimidazole) Hydrate

The structure of the title compound consisting of N,N-1,3-dibenzyl-benzimidazole ion, Cl- anion and hydrate was determined by X-ray diffraction method. It crystallizes in the triclinic system, space group P with a = 9.320(2), b = 9.850(2), c = 11.510(2) ? = 68.75(3), = 80.57(3), = 70.20(3)? C21H19ClN2H2O, Mr = 352.85, V = 925.6(3) 3, Z = 2, Dc = 1.266 g/cm3, F(000) = 372, = 0.217 mm-1, R = 0.0452 and wR = 0.1372. The total reflections were 3462 and 3244 (Rint = 0.0206) were independent, of which 1666 were observed with I > 2s(I). The planes of benzyl group are nearly perpendicular to each other. The water molecules with Cl-anions and C(8) atom are involved in hydrogen bonds and interactions, and - stacking interaction exists obviously between the adjacent phenyl and imidazole rings. The title complex forms a three-dimensional network throughout the structure through these hydrogen bonds and interactions.

Synthesis, Crystal Structure,Characterization and Quantum Chemical Studies on 1N-Acetyl-3-(2,4-dichloro-5-fluoro- phenyl)-5-(p-methyl-phenyl)-2-pyrazoline

1N-Acetyl-3-（2,4-dichloro-5-fluoro-phenyl）-5-（p-methyl-phenyl）-2-pyrazoline has been synthesized and characterized by elemental analysis, IR, UV-Vis and X-ray single-crystal diffraction. Ab intio calculations have been carded out for the compound by using both B3LYP and HF methods at the 6-31G^＊ basis set. The calculated results show that the predicted geometry can well reproduce the structural parameters. The electronic absorption spectra calculated by B3LYP/6-31G^＊ method are approximate to the experiments and the Natural Bond Orbital （NBO） analyses suggest that the above electronic transitions are mainly assigned to n→π^＊ and π→π^＊ transitions. CIS-HF/6-31G^＊ method is not suitable to predict the electronic spectra for the title compound. The calculation of the second order optical nonlinearity was carded out, giving the value of molecular hyperpolarizability equal to 2.194^＋ 10^-30 esu. On the basis of vibrational analyses, the thermodynamic properties of the compound at different temperature have been calculated, revealing the correlation between C p, m^0, S m^0, H m^0 and temperature.

Crystal Structure and Spectroscopic Studies of Diphenylcarbazide Acetonitrile Solvate,(PhNHNH)_2C=O·CH_3CN

The title compound (PhNHNH)2C=OCH3CN has been prepared and characterized by elemental analysis and IR spectrum studies. The single-crystal X-ray structure determination of the title compound was carried out. It crystallizes in the monoclinic system, space group P21/n with a = 5.7818(2), b = 15.320(1), c = 17.469(1) ? b = 97.476(1)? V = 1534.2(1) 3, Mr = 283.34 (C15H17N5O), Z = 4, Dc = 1.227 g/cm3 , F(000) = 600, ?= 0.082 mm-1, R = 0.0561 and wR = 0.1538. The total reflections were 8214 and the independent ones were 2624 (Rint = 0.0559), of which 1756 were observed with I > 2s(I). The torsion angles of the important groups (C(6)N(1) N(2)C(7) and C(7)N(3)N(4)C(8)) are 68.3(3) and 93.3(3), respectively. In the crystal lattice, the molecules form a network structure through hydrogen bonds. The crystal structure is stabilized by NH…N and NH…O hydrogen bonds. FT-IR spectra clearly show there exist acetonitrile molecules in the crystal lattice.

Synthesis and Crystal Structure of 2,2-Dimethyl-4- [1H-(1,2,4-triazolyl)]-4-[1H-benzotriazolyl]-3- butanone[t-BuCOCH(C_2H_2N_3)(C_6H_4N_3)]

The title compound, [t-BuCOCH(C2H2N3)(C6H4N3)], has been prepared and characterized by elemental analysis, IR spectrum and X-ray studies. It crystallizes in mono-clinic, space group C2/c with a = 11.563(3), b = 10.906(3), c = 23.602(5) ? b = 98.35(3)? C14H16N6O, Mr = 284.33, V = 2944.8(13) 3, Z = 8, Dc = 1.283 g/cm3, F(000) = 1200, = 0.087 mm-1, R = 0.0535 and wR = 0.1046. The crystal structure consists of discrete 2,2-dimethyl-4-[1H-(1,2,4-triazolyl)]-4-[1H-benzotriazolyl]-3-butanones. The planes of carbonyl group and benzotriazole ring form the dihedral angle of 89.14(1). The molecules of the title compound are connected to each other through extensive hydrogen bonds to form hydrogen networks. Elemen- tal analysis and IR spectra are in good agreement with the structural data.

Theoretical and Experimental Studies on the Metal Complex of Diethylenetriamino-trioxo-molybdenum(VI) [MoO_3(NH_2C_2H_4NHC_2H_4NH_2)]

For diethylenetriamino-trioxo-molybdenum（Ⅵ）, density functional theory （DFT） method calculations of the structure, atomic charge distributions, electronic spectra, natural population analyses and thermodynamic properties at different temperatures have been performed by B3LYP method using LANL2DZ, CEP-121G and CEP-31G basis sets, respectively. The calculated results show that B3LYP/LANL2DZ method can best reproduce the molecular structure. The atomic charge distribution analyses indicate that during forming the complex, the ligand of diethylenetriamine donates negative charges to MoO3 and these charges are accepted by molybdenum（Ⅵ） atom as well as three oxygen atoms. The electronic spectra calculations indicate that B3LYP/ LANL2DZ results are nearest to experimental data among the three methods and electronic transitions are mainly derived from the contribution of bands π→π^＊. The calculation of the second order optical nonlinearity was carried out, and the molecular hyperpolarizability was 0.7881^＊10^30 esu.

Quantum Chemical Calculations and Experimental Studies on 2,3-Diphenyl-tetrazole-5-thione

Diphenyl-tetrazole-5-thione has been synthesized and characterized by X-ray diffraction analysis and FTIR spectra. The extended MO calculations by using density functional theory (DFT) and self-consistent field molecular orbital Hartree-Fock theory with 6-31gG* basis set were carried out. The optimized structure and atomic charge distributions have been investi- gated, showing the exocyclic sulfur atom has the biggest negative charge value and this site is the most likely site of protonation and methylation as well as the potential coordination site with metallic ions. The predicted harmonic vibration frequencies are compared to the experimental values. On the basis of vibrational analyses, the thermodynamic properties of this compound at different temperature have been calculated, revealing the correlations between C0p, m, S0m, H0m and temperature.

Crystal Structure and Spectral Characters of 2-(4-Methylbenzoly)-3-(4-chlrolphenyl) -4-(1,2,4-triazole)-5-anilino-thiopene

The title compound 2-(4-methylbenzoly)-3-(4-chlrolphenyl)-4-(1,2,4-triazole)-5- anilino-thiopene has been prepared and characterized by IR, EA, 1H NMR, UV, MS and X-ray analysis. It crystallizes in the triclinic system, space group P1 with a = 8.061(2), b = 9.981(2), c = 15.462(3) ? a = 90.96(3), b = 103.11(3), g = 106.26(3)? Mr = 470.96 (C26H19ClN4OS), V = 1158.8(4) 3, Z = 2, Dc = 1.350 g/cm3, F(000) = 488, = 0.282 mm-1, R = 0.0482 and wR = 0.1043. In the crystal lattice, there exist some intermolecular hydrogen bonds, - stacking interactions and CH贩?supramolecular interactions. In the solid state, all of the above intermolecular interactions in the title compound can stabilize the crystal structure.

Synthesis and Crystal Structure of α-(1,2,4-Triazol-1H-yl)-ρ-chloro Acetophenone, [ClC_6H_4COCH_2(C_2H_2N_3)]

The title compound [ClC6H4COCH2(C2H2N3)] has been prepared and characterized by elemental analysis, IR spectrum and X-ray studies. It crystallizes in the monoclinic system, space group P21/c with Mr = 221.64 (C10H8ClN3O), a = 13.420(3), b = 9.720(2), c = 7.900(2) ? b = 92.00(3)? V = 1029.9(4) 3, Z = 4, Dc = 1.429 g/cm3, F(000) = 456, m = 0.345 mm-1, R = 0.0435 and wR=0.0894. The total reflections were 1949 and the independent ones were 1805 (Rint=0.0340), of which 800 were observed with I > 2s(I). The crystal structure consists of a-(1,2,4-triazol-1H- yl)-r-chloro-acetophenone. The existence of p conjugated systems in the molecule affects partly the bond lengths. The triazole and phenyl rings form the dihedral angle of 77.34. The molecules of the title compound connect to each other through extensive hydrogen bonds to form a two-dimensional structure. Elemental analysis and IR spectra are in good agreement with the structure data.

Synthesis,Characterization and Theoretical Studies on a Thiocarbamide Derivative Containing Schiff Base Group

A thiocarbamide derivative containing Schiff base groups,1,5-bis[4-（dimethylamino）benzylidene]thiocarbonohydrazide,has been synthesized and characterized by elemental analysis,IR,^1H NMR,UV and X-ray single-crystal diffraction.Density function theory（DFT） calculations at the B3LYP/6-31G＊ and PBE0/6-31G＊ levels for optimized geometries and electronic transition spectra have been performed.Comparative studies show that both B3LYP/6-31G＊ and PBE0/6-31G＊ methods can well reproduce the molecular structure,and the latter is more reliable than the former to simulate electronic spectra.NPA calculational results at the B3LYP/6-31G＊ level indicate the title compound to be a potential multidentate ligand to the metallic ions.Based on the vibrational analysis,thermodynamic properties at different temperatures have been obtained.

Hydrothermal Syntheses, Crystal Structures and Fluorescence of a Copper(I) Polymer and a Salt with H_2SO_4 Based on a Pyrimidine Building Block

Based on the building block of 2-phenyl-4,6-di（pyridin-2-yl）pyrimidine （L = C20H14N4）, a Cu（I） polymer [（CuC20H14N4）（CuCl2）]∞ and a salt with H2SO4 [（C20H16N4）（HSO4）2] have been synthesized by hydrothermal method and characterized by X-ray single-crystal diffraction. In the Cu（Ⅰ） polymer, although the central metal ions of Cu（Ⅰ） directly coordinate with the building block L, they still do not assembly expected grid-type complexes and there exists a one-dimensional chain constructed through coordinate bonds. In the salt, hydrogen bonds along with two kinds of π…π supramoleuclar interactions fabricate two-dimensional （2D） networks which further generate a 3D supramolecular architecture via interlayer π…π interactions. Fluorescent spectra show that the L emits blue fluorescence and its Cu（Ⅰ） polymer and salt decrease the fluorescent intensity.

Synthesis, Structure and Biological Activities of Novel Triazole Compounds Containing 4,6-Dimethyl-pyrimidin-2-ylthio Group

Four compounds were prepared by reacting 4,6-dimethyl-2-mercaptopyrimidine with -bromo--(1,2,4- triazol-1-yl)-substituted acetylbenzene. Their structures were identified by means of elemental analysis, IR, and 1H NMR spectra. The single crystal structure of 2-[1-(1,2,4-triazol-1-yl)-1-p-methoxyphenylcarbonylmethylthio]-4,6- dimethyl-pyrimidine was also determined. It crystallizes in monoclinic system, space group P21/c, a=0.8016(2) nm, b=1.2462(3) nm, c=1.7824(4) nm, =99.89(3), Z=4, V=1.7540(7) nm3, Dc=1.346 g/cm3, =0.205 mm-1, F(000)=744, final R1=0.0452. There is obviously potentially weak C—H…N intermolecular interaction between the molecules in the crystal lattice, which stabilizes the crystal structure. The result of the biological test showed that the four compounds all have some fungicidal and plant growth regulating activities.

Crystal Structures and Characterizations of Bis(1-benzoyl-methyl-benzotriazole-N^3)dichoro Metal(II) Complex:[MCl_2-(C_6H_4N_3CH_2COPh)_2][M=Zn(II),Co(II)]

The structures of [MCl2(C6H4N3CH2COPh)2] [M=Zn(II) (1), Co(II) (2)] have been determined by X-ray crys-tallography. They were characterized by elemental analysis, IR spectrum, electronic spectrum and thermogravimet-ric-differential thermal analysis. They all crystallize in the triclinic system, space group P? with lattice parameters a=0.9449(2) nm, b=1.1291(2) nm, c=1.3637(3) nm, a=111.70(3)o, b=94.33(3)o, =90.97(3), Z=2 for com-pound 1; a=0.9437(2) nm, b=1.1277(2) nm, c=1.3650(3) nm, =111.76(3)o, =94.50(3)o, =90.80(3)o, Z=2 for compound 2. The metal ions are all coordinated by two Cl- anions and two nitrogen atoms of 1-benzoylmethyl-benzotriazole ligands, forming the distorted tetrahedral geometry. The ZnCl and ZnN bond lengths are 0.2209(2), 0.2210(2) nm and 0.2059(4), 0.2067(4) nm, respectively. The CoCl and CoN bond lengths are 0.2215(2), 0.2222(2) nm and 0.2028(5), 0.2045(5) nm, respectively. The thermogravimetric (TG) data indicate that they are nearly similar in TG curve, and there are not structural transitions in the two compounds. They all have a high thermal stability. But, there is little difference in DTG (differential thermogravimetric) curves of those two compounds. Elemental analysis, electronic and IR spectra are in agreement with the structural data.

Synthesis, Structure and Biological Activities of Novel Triazole Compounds Containing N,N-Dialkyldithiocarbamate Moiety

The two compounds, 2,2-dimethyl-4-S-(N,N-dimethyldithiocarbamato)-5-(1,2,4-triazol-1-yl)-propione (1) and 2,2-dimethyl-4-S-(N,N-diethyldithiocarbamato)-5-(1,2,4-triazol-1-yl)-3-propione (2), were prepared by reacting N,N-dialkyldithiocarbamate sodium with 2,2-dimethyl-4-bromo-5-(1,2,4-triazol-1-yl)-propione. Their structures were identified by elemental analysis, IR and 1H NMR spectroscopy. The structure of 1 has been determined by X-ray single crystal structure analysis. It crystallizes in monoclinic system with space group P21/c, a=1.2315(3) nm, b=1.2057(2) nm, c=1.2532(3) nm, =118.55(3), Z=4, V=1.6345(6) nm3, Dc=1.221 g/cm3, =0.324 mm-1 , F(000)=640, final R1=0.0449. There is obvious potentially weak CH…N intermolecular interaction in the crystal, which stabilizes the crystal structure. The result of the biological test showed that the two compounds have fungistasis and plant growth regulating activities.