Synthesis,Crystal Structure and Properties of a New Cd(Ⅱ) Complex Based on Mixed 5-Hydroxy-isophthalic Acid and 1-(1H-imidazol-4-yl)-3-(4H-tetrazol-5-yl)benzene Ligands

A new coordination polymer [Cd2(5-IPA)(HL)2(H2O)2]·4H2O(1) was prepared under hydrothermal conditions based on 5-hydroxy-isophthalic acid(5-H2IPA) with multi-N-donor ligand 1-(1H-imidazol-4-yl)-3-(4H-tetrazol-5-yl)benzene(H2L). The complex was characterized by IR spectroscopy, TGA, X-ray powder and single-crystal diffraction. It crystallizes in the monoclinic system, space group C2/c with a = 23.6291(18), b = 9.9847(8), c = 17.7244(14) ?, β = 124.6180(10)?, V = 3441.4(5) ?3, Z = 4, C28H30N12O11Cd2, Mr = 935.44, Dc = 1.805 g/cm3, μ = 1.313 mm-1, S = 1.055, F(000) = 1864, the final R = 0.049 and w R = 0.1315 for 2985 observed reflections(I 2σ(I)). The central metal Cd(II) atoms with octahedral coordination geometry are six-coordinated by three oxygen and three nitrogen atoms. The HL- ligands from the deprotonated H2 L connect Cd(II) atoms to form two-dimensional(2D) double-layer fes networks which are further pillared by 5-IPA2- ligands into a rare binodal(3, 4)-connected three-dimensional(3D) architecture with a(4·6·8)(4·62·83) fsc-3,4-C2/c topology. Solid state luminescent property and sorption property of 1 have been investigated.     

Synthesis,Crystal Structure and Fluorescent Properties of a Cadmium(Ⅱ) Complex with 3-(Pyridin-4-yl)-5-(pyrazin-2-yl)-1H-1,2,4-triazole

Compound [Cd_(1.5)(ppt)Br_2(H_2O)]_(2n)(1),where Hppt = 3-(pyridin-4-yl)-5-(pyrazin-2-yl)-1H-1,2,4-triazole,has been synthesized under hydrothermal conditions and characterized by elemental analysis,IR spectra,powder XRD,and X-ray diffraction.Compound 1 crystallizes in the triclinic system,space group P1 with a = 7.4402(6),b = 8.0570(7),c = 12.8674(11) ?,α = 89.7300(10),β = 89.8570(10),γ = 68.3910(10)°,V = 717.13(10) ?3,Z = 1,Dc = 2.638 g/cm3,μ = 7.824 mm~(-1),F(000) = 534,the final R = 0.0324 and w R = 0.1084 for 2324 observed reflections with I 2σ(I).X-ray diffraction analyses revealed that complex 1 is a 2D layered coordination polymer constructed from the linkage of [Cd_3(μ-Br)_4] trinuclear units with ppt-spacers,and a 3D supramolecular architecture is further assembled in 1 via hydrogen-bonding contacts.Fluorescence measurements show that 1 has medium fluorescent emission at 450 nm.     

Syntheses,Structures and Characterizations of Two New Zinc(Ⅱ) Coordination Polymers Constructed from 3-(1H-Pyrazol-4-yl)-5-(pyridin-2-yl)-1,2,4-triazole and Different Carboxylate Ligands

Two new zinc(Ⅱ) coordination polymers, [Zn(ph)(H2 L)·H_2O]2 n(1) and [Zn(ip)(H2 L)-(H_2O)]n(2)(H2 ph = phthalic acid, H2 ip = isophthalic acid, H2L = 3-(1 H-pyrazol-4-yl)-5-(pyridin-2-yl)-1,2,4-triazole), have been successfully synthesized via hydrothermal reaction. It has been structurally characterized by X-ray single-crystal analysis, IR spectra, fluorescence spectroscopy and thermogravimetry analysis. The single-crystal X-ray diffraction studies reveal that compounds 1 and 2 both exhibit 1D chain structures, and assemble into 2D and 3D supermolecules through hydrogen bonds or π-π interactions. Moreover, the thermal stability and luminescent properties of compounds 1 and 2 were also studied.     

Synthesis and Antibacterial Activities of 4-Amino-3-(1-aryl-5-methyl-1,2,3-triazol-4-yl)-5-mercapto-1,2,4-triazoles/2-Amino-5-(1-aryl-5-methyl-1,2,3-triazol-4-yl)-1,3,4-thiadiazoles and Their Derivatives

ＩｎｔｒｏｄｕｃｔｉｏｎＳｃｈｉｆｆｂａｓｅｓ ,ａｍｉｄｅｓ ,ｉｍｉｄａｚｏｌｏ[2 ,1 ｂ] 1,3,4 ｔｈｉａｄｉａｚｏｌｅｓ,ａｎｄ 7Ｈ ｓ ｔｒｉａｚｏｌｏ[3,4 ｂ] 1,3,4 ｔｈｉａｄｉ ａｚｉｎｅｓｃｏｎｔａｉｎｉｎｇｈｅｔｅｒｏｃｙｃｌｅｓｈａｖｅｂｅｅｎａｔｔｒａｃｔｉｎｇｍｕｃｈａｔｔｅｎｔｉｏｎａｓｐｏｔｅｎｔｉａｌａｎｔｉｆｕｎｇａｌａｇｅｎｔｓ .1 51,2 ,3 ｔｒｉａ ｚｏｌｅ ,6 7ｍｅｒｃａｐｔｏ 1,2 ,4 ｔｒｉａｚｏｌｅ ,81,3,4 ｔｈｉａｄｉａｚｏｌｅ9 10ａｎｄｔｈｅｉｒｒｅｌａｔｅｄｃｏ…     

Synthesis and crystal structures of three new complexes derived from 3-(pyridin-3′-yl)-5-(pyridin-2′′-yl)-1,2,4-triazole

Three new coordination complexes, [Cd₂(ppt)₂(cpba)]?·?(H₂O)₂ (1), [Zn(ppt)₂]?·?(H₂O) (2), and [Zn(MoO₄)(Hppt)] (3) (H₂cpba: 3-(2′-carboxy-phenoxy)-benzoic acid; Hppt: 3-(pyridin-3′-yl)-5-(pyridin-2′′-yl)-1,2,4-triazole), were synthesized under hydrothermal conditions. Their structures have been determined by single crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric analyses. X-ray diffraction analyses revealed that Cd(II) ions are linked by ppt^? to form a ladder-shaped structure along the a-axis and further displays a 2-D supramolecular architecture with cpba^2? along the c-axis. In 2, each Zn(ppt)₂ fragment is linked by the nitrogen of pyridin-3′-yl from the neighboring Zn(ppt)₂ forming a V-shaped chain. Compound 3 consists of a ladder structure, in which each {MoO₄} unit is a bridge linking three Zn(Hppt)²⁺ fragments.     

Synthesis and transformations of 2β,3β-diacetoxy-20-(4,5-dihydroisoxazol-5-yl)-6-oxo steroids

20-Hydroxy-20-(4,5-dihydroisoxazol-5-yl) steroid was brought into reactions typical of functionalization of rings A and B in ecdysteroids. The dihydroisoxazole ring remained unchanged in reactions leading to formation of the 2,3-dihydroxy-6-oxo moiety. The isomerization of 5-bromo derivative in acetic acid in the presence of a catalytic amount of hydrobromic acid and Lewis acids is accompanied by elimination of the hydroxy group from C²⁰ and subsequent migration of the double bond to the heteroring to afford the corresponding isoxazole derivative.Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 10, 2004, pp. 1500–1505.Original Russian Text Copyright © 2004 by Litvinovskaya, Drach, Khripach.     

Syntheses and Characterizations of Cd(Ⅱ) and Pr(Ⅲ) Complexes Based on 5-(Tetrazol-5-yl) Isophthalic Acid

Hydrothermal reactions of 5-(tetrazol-5-yl) isophthalic acid with cadmium nitrate/praseodymium nitrate led to two complexes of [Cd_3(TZI)_2(H2_O)_(11)]_n(1) and [Pr(TZI)(H_2O)_5]_n(2). Their structures and properties were determined by X-ray diffraction, IR spectroscopy, fluorescence spectrum, thermal gravimetric analyses and elemental analysis. Complex 1 belongs to monoclinic system, I2/c space group, with a = 12.8688(3), b = 18.0925(3), c = 14.5190(3) ?, β = 116.054(3)°, V =3036.92(13) ?~3, Z = 4; complex 2 crystallizes in triclinic, space group P 1, with a = 7.9690(5), b =9.7665(8), c = 10.4353(9) ?, α = 116.709(9), β = 107.461(6), γ = 95.671(6)°, V = 665.54(9) ?3 and Z =2. Complex 1 is a 3D planar structure. Complex 2 is a one-dimensional double chain configuration and extends into a 3D network by hydrogen bonds and π-π interactions.     

Asymmetric Synthesis of （-）-（4R, 5R）-4-[5-（Benzo[1, 3]dioxol-5-yl）-4- hydroxyl- 1-（pyridin-2-yl）-4, 5-dihydro- 1H-pyrazol-3-yl]benzamide

For discovering novel small molecule inhibitors of transforming growth factor-β1(TGF-β1)type-I receptor(ALK5),we designed1,3,5-triaryl-4-hydroxyl-4,5-dihydro-1H-pyrazole(1)as target compound,mimic the structure of SB-431542which is a2-pyridyl substituted triarylimiazole inhibitor of ALK51.Racemic compound1showed moderate ALK5inhibitory activity in luciferase reporter assays[inhibition(%control):0.1umol/L8.79%;1umol/L19.05%].To investigate the influence of the absolute configuration of…     

Synthesis,Crystal Structure and Antifungal Activity of a New Zn(Ⅱ) Complex Based on 4-(5-(Pyridin-3-yl)-4H-1,2,4-triazol-3-yl) Benzoic Acid

A new complex[Zn(3,4-APT)2(H2 O)4]·8 H2 O(1,3,4-HAPT=4-(5-(pyridin-3-yl)-4 H-1,2,4-triazol-3-yl)benzoic acid)has been prepared and characterized by elemental analysis,X-ray single-crystal diffraction analysis,thermogravimetric analysis and infrared spectrum analysis.Theoretical calculation based on density functional theory(DFT)is also employed to explicate frontier orbitals of 3,4-HAPT.X-ray single-crystal diffraction analysis reveals that 1 belongs to the triclinic system,space group P1 with a=7.5123(3),b=8.6745(3),c=15.2074(6)?,α=78.469(1),β=87.387(1),γ=65.448(1)°,V=882.42(6)?,Z=1,D_c=1.528 g·cm^–3,μ=0.780 mm^–1,M_r=812.09,F(000)=424,the final R=0.0401 and wR=0.1136.Zn(II)ion is coordinated by two N atoms from two 3,4-HAPT as well as four O atoms from four coordinated water molecules,forming a 0D motif with distorted octahedral coordinated geometry.The adjacent 0 D units are linked into a 3 D supramolecular structure through hydrogen bonding interaction.In addition,complex 1 exhibits better antifungal activity against Colletotrichum gloeosporioides Penz than the ligand and metal salt by MIC,MBC tests and Kirby-Bauer disc diffusion method which exhibit potential application in the antifungal fields.     

Synthesis,Crystal Structure and Properties of a Zinc(Ⅱ) Complex Based on 5-(1H-Tetrazol-5-yl)isophthalic Acid Ligand

A novel polymeric zinc(II) complex {[Zn_2(TIA)(H_2O)_3]?(NO_3)}_n(1, H_3TIA = 5-(1H-tetrazol-5-yl)isophthalic acid) has been synthesized in mixed solvents under solvothermal conditions and characterized by elemental analysis, IR spectroscopy and X-ray single-crystal diffraction. Complex 1 crystallizes in orthorhombic, space group Cmcm with a = 10.4210(6), b =23.3526(14), c = 6.9214(4) ?, V = 1684.37(17) ?3, Z = 4, C_9H_4N_5O_(10)Zn_2, Mr = 472.91, Dc = 1.865g/cm~3, F(000) = 932, λ(MoK α) = 2.909 mm-1, R = 0.0423 and wR = 0.1287. The complex has good thermal stability and excellent photoluminescent property.     

Synthesis, Crystal Structure and Bioactivities of 1-（4-Chlorophenyl）-3- [ 5-（pyrid-4-yl）- 1,3,4-thiadiazol-2-yl] urea

The title compound 1-(4-chlorophenyl)-3-[5-(pyrid-4-yl)-1,3,4-thiadiazol-2-yl]urea (C14H10ClN5OS, Mr = 331.79) has been synthesized by the reaction of 2-amino-5-(pyrid-4-yl)- 1,3,4-thiadiazole with 4-chlorobenzoyl azide, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to triclinic system, space group P with a = 5.8550(8), b = 7.5668(10), c = 16.416(2) , α = 78.364(2), β = 81.204(2), γ = 84.749(2)°, V = 702.58(16) 3, Z = 2, Dc = 1.568 g/cm3, μ = 0.429 mm-1, F(000) = 340, the final R = 0.0442 and wR = 0.1092 for 2001 observed reflections (I > 2σ(I)). X-ray diffraction analysis reveals that the title molecule is nearly planar. In the crystal structure, the molecules are linked by strong intermolecular N-H…N hydrogen bonds together with weak nonclassical intermolecular (C-H…Y, Y = N, O and Cl) hydrogen bonds and stacked through π-π interactions. The preliminary bioassay shows that the title compound exhibits good fungicidal activities against Rhizoctonia solani, Botrytis cinerea and Dothiorella gregaria.     

Novel 2′-(pyridin-4-yl)-5′-(pyridin-2-yl)-1′-(pyridin-2-yl)methylpyrrolidinyl[60]fullerene-hydroxyoxo(5,10,15,20-tetraphenyl-21H,23H-porphynato) molybdenum(V) dyads

Interaction between hydroxyoxo(5,10,15,20-tetraphenylporphyrinato)molybdenum(V) and 2′-(pyridin-4-yl)-5′-(pyridin-2-yl)-1′-(pyridin-2-yl)methylpyrrolidinyl[60]fullerene in toluene has been studied by means of spectrophotometry. The reaction proceeds via two stages: rapidly established equilibrium between the reactants and their molecular complex 1: 1 [K = (1.97 ± 0.52) × 10⁴ L/mol] followed by slow irreversible displacement of hydroxy group into the second coordination sphere to form cationic outer sphere complex (k = 0.26 L s^?1 mol^?1). The effect of fullerene fragment on pyridine fragments coordination has been considered.     

Synthesis and Characterization of 4′-Bromomethyl-2-(N-trityl-1H-tetrazol-5-yl) Biphenyl

Biphenyl tetrazole ring is an important component of the Sartan family of novel drugs. 4′-Bromomethyl-2-(N-trityl-1H-tetrazol-5-yl)biphenyl was synthesized in this article from 4′-methyl-2-cyano-biphenyl through three steps. 4′-Methyl-2-cyano-biphenyl was reacted with azide ions with the help of ammonium chloride as catalyst in an autoclave with high conversion to afford the tetrazole compounds in 70.6% yield. After being protected by the trityl group with 92.6% yield, 4′-methyl-2-(N-trityl-1H-tetrazol-5-yl) biphenyl was brominated with N-bromosuccinimide (NBS) in cyclohexane with 2,2′-azo-isobutyronitrile (AIBN) acting as an initiator to provide the title compound in 83.8% yield.     

Synthesis,Crystal Structure and Fungicidal Activity of N-（4-tert-buty）-5-（1,2,4-triazol- 1-yl）thiazol-2-yl）propionamide

The title compound has been synthesized by the reaction of 4-tert-butyl-5-(1,2,4-triazol-1-yl)-2-aminothiazole with propionic anhydride, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the orthorhombic system, space group Pbca with a = 18.441(2), b = 8.3284(9), c = 19.257(2) , Z = 8, V = 2957.5(5) 3, Mr = 279.37, Dc = 1.255 mg/m3, S = 1.033, μ = 0.219 mm-1, F(000) = 1184, the final R = 0.0349 and wR = 0.0876 for 2629 observed reflections(I 2σ(I)). X-ray crystal structure presents the intermolecular N–H···N hydrogen bond, which plays an important role in stabilizing the crystal structure. The preliminary bioassay indicates that the title compound exhibits potent fungicidal activity against R. Solani(25 mg/L) with inhibition rate of 80.0%.     

Synthesis,Crystal Structure and Biological Activity of 2-（Anthracen-9-yl）-5-p-tolyl-1,3,4-oxadiazole

A novel compound,2-(anthracen-9-yl)-5-p-tolyl-1,3,4-oxadiazole(C23H16N2O),has been synthesized by the condensation of 4-methylbenzohydrazide and anthracene-9-carbaldehyde in an ethanol solution with chloramine-T.The compound was characterized by 1H-NMR,13C-NMR,MS and single-crystal X-ray diffraction.The crystal belongs to the triclinic system,space group P with a = 7.7817(4),b = 8.8544(5),c = 12.4726(8) ,β = 92.8520(10)°,Z = 2,V = 826.58(8) 3,Dc = 1.352 g/cm3,Mr = 336.38,λ(MoKα) = 0.71073 ,μ = 0.084 mm-1,F(000) = 352,R = 0.0381 and wR = 0.1099.The dihedral angle between anthracene skeleton and phenyl ring is 64.19°.A total of 6354 unique reflections were collected,of which 3172 with I > 2σ(I) were observed.X-ray analysis indicated an offset face-to-face π-π stacking interaction between anthracene skeletons and an offset face-to-face π-π stacking interaction between phenyl ring planes.The novel compound molecules are connected through the offset face-to-face π-π stacking interactions to generate a three-dimensional network.The preliminary bioassay results showed that the novel compound exhibited significant insect growth inhibitory activity against Spodoptera litura Fabricius larvae.     

Why are SiX5(-) and GeX5(-) (X = F, Cl) stable but not CF5(-) and CCl5(-)?

The possible existence of the CF(5)(-), CCl(5)(-), SiF(5)(-), SiCl(5)(-), GeF(5)(-), and GeCl(5)(-) anions has been investigated using ab initio methods. The species containing Si and Ge as central atoms were found to adopt the D(3h)-symmetry trigonal bipyramidal equilibrium structures whose thermodynamic stabilities were confirmed by examining the most probable fragmentation channels. The ab initio re-examination of the electronic stabilities of the SiF(5)(-), SiCl(5)(-), GeF(5)(-), and GeCl(5)(-) anions [using the OVGF(full) method with the 6-311+G(3df) basis set] led to the very large vertical electron detachment (VDE) energies of 9.316 eV (SiF(5)(-)) and 9.742 eV (GeF(5)(-)), whereas smaller VDEs of 6.196 and 6.452 eV were predicted for the SiCl(5)(-) and GeCl(5)(-) species, respectively. By contrast, the high-symmetry and structurally compact anionic CF(5)(-) and CCl(5)(-) systems cannot exist due to the strongly repulsive potential predicted for the X(-) (F(-) or Cl(-)) approaching the CX(4) (CF(4) or CCl(4)). The formation of weakly bound CX(4)···X(-) (CF(4)···F(-) and CCl(4)···Cl(-)) anionic complexes (consisting of pseudotetrahedral neutral CX(4) with the weakly tethered X(-)) might be expected at low temperatures (approaching 0 K), whereas neither CX(5)(-) (CF(5)(-), CCl(5)(-)) systems nor CX(4)···X(-) (CF(4)···F(-) and CCl(4)···Cl(-)) complexes can exist in the elevated temperatures (above 0K) due to their susceptibility to the fragmentation (leading to the X(-) loss).     

Synthesis,Crystal Structure and Herbicidal Activity of Methyl(E)-α-(Methoxyimino)-2-((4-(3-chloro-5-(trifluoromethyl)-pyridine-2-yl)phenoxy)methyl)benzeneacetate

The title compound methyl(E)-α-(methoxyimino)-2-((4-(3-chloro-5-(trifluoromethyl) pyridine-2-yl)phenoxy)methyl)benzeneacetate(C23 H18 ClF3 N2 O4) has been synthesized and structurally characterized by 1 H and 13 C NMR, and HRMS. Its absolute molecular configuration was investigated by X-ray crystallography. The crystal crystallizes in monoclinic system, space group P21/c with a = 15.0928(7), b = 19.6070(10), c = 7.5535(5) ?, β = 98.176(5)°, V = 2212.6(2) ?3, Z =4, Dc = 1.438 g/cm3, F(000) = 984, μ(Mo Kα) = 0.231 mm-1, the final R = 0.0619 and wR = 0.1681 with 4034 observed reflections with I 2σ(I). The title compound has significant inhibitory rate against broadleaf weeds. They are all 100% under the dose of 37.5 g.a.i/ha, which was better than mesotrione.     

Synthesis,Structure and Biological Activities of 2-(1H- 1,2,3-Benzotriazol-1-yl)-1-(4-methylphenyl)-2- (1H-1,2,4-triazol-1-yl)-1-ethanone

IntroductionTriazole derivatives have become the most rapidlyexpanding group of antifungal compounds with advanta-ges of lowtoxicity, high oral bioavailability and broad-spectrum antifungal activity, which can be used againstfungi including most yeasts an…     

Synthesis of 2-(hydroxyphenylamino)- and 2-(aminophenylamino)-4-methylquinolines and N,N′-bis(4-methylquinolin-2-yl)benzenediamines

2-(Hydroxyphenylamino)- and 2-(aminophenylamino)-4-methylquinolines and N,N′-bis(4-methylquinolin-2-yl)benzenediamines were synthesized by reactions of 2-chloro-4-methylquinolines with o-, m-, and p-aminophenols and o-, m-, and p-phenylenediamines.