One Novel 2D Co(Ⅱ) Polymer with 1,2,3-Triazole Derivative: Crystal Structure, Fluorescence and Hirshfeld Surface Analysis

One new polymer [Co（L）（H2O）2]n（1） was synthesized by 4-（ethoxycarbonyl）-5-methyl-1H-1,2,3-triazole-1-carboxylic acid（Emtc） under the in situ solvent thermal reaction（H2L = 1-（carboxymethyl）-5-methyl-1H-1,2,3-triazole-4-carboxylic acid）. The title complex performs a wave-like 2D framework and the ligand H2L demonstrates the coordination mode as μ4-η-2：η-1η-1：η-1. The crystal structure has been established by single-crystal X-ray diffraction, and characterized by FT-IR. Fluorescent property was investigated in this work. Hirshfeld surface analysis has also been carried out on 1, and obvious main intermolecular interactions are observed.

Structure and Biological Activities of 2-(1,3-Dithiolan-2-ylidene)-1-phenyl-2-(1,2,4-triazol-1-yl)ethanone

In order to find leading compounds with an excellent fungicidal activity, the title compound 2-（ 1,3-dithiolan-2- yl-idene）-1-phenyl-2-（ 1,2,4-tfiazol-1-yl） ethanone was synthesized according to the biological isosterism and its structure was confirmed by means of IR, MS, ^1 H NMR and elemental analysis. The single crystal structure of the title compound was determined by X-ray diffraction. The preliminary biological test shows that the synthesized compound exhibits some biological activities.

Synthesis and plant-growth regulatory activities of novel imine derivatives containing 1H-1,2,4-triazole and thiazole rings

Eleven new imine derivatives 6 containing 1H-1,2,4-triazole and thiazole rings were synthesized by the condensation of 5-((1H- 1,2,4-triazol-1-yl)methyl)-4-tert-butylthiazol-2-amine with various substituted benzaldehydes.The structures of the title compounds were characterized by ~1H NMR,MS and elemental analysis.The plant-growth regulatory activities of these compounds were evaluated.The primary bioassay results indicated that these target compounds exhibited promising plant-growth regulatory activities.

Syntheses, Structures, and Luminescence Properties of Two New Open-framework Zinc Phosphites Based on 1,2,4-Triazole Derivatives

With 1,2,4-triazole derivatives as structure directing agents, two new openframework zinc phosphites, [Zn（atrz）（HPO3）]n（1） and [Zn（dmatrz）（HPO3）]n（2）（atrz = 4-amino-1,2,4-triazole, dmatrz = 4-amino-3,5-dimethyl-1,2,4-triazole） have been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder and single-crystal X-ray diffractions. Both compounds are isostructure and crystallize in the P21/c space group of monoclinic system. Compound 1： a = 9.629（1）, b = 7.384（1）, c = 10.274（1） A, β = 110.729（3）°, V = 683.26（2） A^3, Z = 4, Mr = 229.44, Dc = 2.230 g/cm^3, F（000） = 456, S = 1.10, μ = 3.79 mm^（–1）, R = 0.0181 and w R = 0.0466 for 1121 observed reflections（（40） 〉 2s（（40）））. Compound 2： a = 10.786（2）, b = 8.921（1）, c = 9.749（1） A, β = 107.3°, V = 895.6（3） A^3, Z = 4, Mr = 257.49, Dc = 1.910 g/cm^3, F（000） = 520, S = 1.00, μ = 2.90 mm^（–1）, R = 0.018 and wR = 0.051 for 1581 observed reflections（（40） 〉 2s（（40）））. Both compounds are built up into 4.8-net 2D open-frameworks of vertex-linked Zn O4 and HPO3 units（3.57 × 4.53 A^2 for 1 and 4.43 × 5.90 A^2 for 2）. The structures consist of left-, right-handed helical chains that are connected through oxygen atoms to form an undulated 2D sheet stack, which can be topologically regarded as 4.8~2 nets. Solid-state luminescence properties and thermo gravimetric analyses of these two compounds were investigated, respectively.

Solid Phase Synthesis of 3,4,5-Trisubstituted-1,2,4-Triazoles Derivatives from the Resin-Bound Acylhydrazines

An extension of our methodology on solid-phase synthesis of 3,4,5-trisubstituted-1,2,4-triazoles under mild conditions has been developed. Firstly, the resin-bound acylhydrazine is reacted with orthoesters to provide resin-bound 1,3,4-oxadiazoles. Secondly, condensation of 1,3,4-oxadiazoles resin with the corresponding arylamines hydrochloride to form the the resin-bound triazoles. 3,4,5-Trisubstituted-1,2,4-triazoles derivatives were obtained from resin-bound acylhydrazines in several steps providing 78% - 87% overall yields and excellent purity. The advantages of this method include straightforward operation and high yield and purity of the products.

Synthesis and Biological Activity Study of New Schiff and Mannich Base Ligands Derived from Isatin and 3-Amino-1,2,4-triazole and Their Metal Complexes

Two new Mannich and Schiff base ligands namely： （1-（3＇-amino-methyl-1＇（H）-1＇,2＇,4＇-triazole）-3-（1＇（H）-l＇,2＇,4＇- triazole-3＇-yl） iminoisatin （Lt） and l-morpholinomethyl-3-（1＇（H）-1＇,2＇,4＇-triazolyl）iminoisatin （LII） were prepared from condensation reaction of the new Schiff base 3-（l＇（H）-l＇,2＇,4＇-triazole-3＇-yl）iminoisatin （SBH） （0.01 mol） with formaldehyde and 3-amino-l,2,4-triazole （3-At） or with formaldehyde and morpholine （0.01 mole each） respectively. Structures were characterized by tH NMR, CHN analyses, mass spectra and IR spectra. Metal complexes were synthesized by heating each ligand （0.02 mo with metal salts （0.01 moo in ethanol or ethanol： acetone mixture respectively. The formula of metal complexes were suggested depending on CHN and thermal analyses, metal and chloride contents, IR and UV-visible spectra, magnetic moments （laefr） and conductivity measurements. All complexes were of octahedral geometry except palladium （II） complexes which were square planar. The two ligands and some selected metal complexes showed various antibacterial and cytotoxic effects.

Use of Ultrasound and Microwave Irradiation for Clean and Efficient Synthesis of 3,3’-(Arylmethylene)bis (2-hydroxynaphthalene-1,4-dione) Derivatives

Nine 3,3’-(arylmethylene)bis(2-hydroxynaphthalene-1,4-dione) derivatives were synthesized through the reaction between 2-hydroxy-1,4-naphthalen-1,4-dione and different aromatic alde-hydes in water applying ultrasonic irradiation for 5 min at room temperature and microwave irradiation for 15 min at 70°;C. Two of the nine derivatives, compounds 3-e and 3-i, obtained from 3-bromo-hydroxybenzaldehyde and 5-methylfuran-2-carbaldehyde, respectively, are previously unpublished. The structures of all compounds were established on the basis of their spectral data and mass analysis. The attractive features of this synthesis protocol include mild conditions, high atom-economy and excellent yields with the elimination of water as the only by-product.

Formation of Hybrid Ring Structure of Cyanurate/Isocyanurate in the Reaction be-tween 2,4,6-Tris(4-Phenyl-Phenoxy)-1, 3,5-Triazine and Phenyl Glycidyl Ether

Reaction products of 2,4,6-tris(4-phenyl-phenoxy)-1,3,5-triazine derived from 4-phenylphenol cyanate ester and phenyl glycidyl ether were analyzed. In addition to an isocyanurate compound and an oxazolidone compound which were well known as reaction products of cyanate esters and epoxy resins, compounds with hybrid ring structure of cyanurate/isocyanurate were determined. Gibbs free energies of the compound having hybrid ring structure of cyanurate/isocyanurate with two isocyanurate moiety were found to be lower than that of the compound with cyanurate ring structure through calculations. Calculation data supported the existence of hybrid ring structure of cy-anurate/isocyanurate. It was revealed that isomerization from cyanurate to isocyanurate occurs via hybrid ring structure of cyanurate/isocyanurate in the reaction of aryl cyanurate and epoxy.

Theoretical Study on the Mechanism of a New Synthesis Reaction of 1,3,5-Substituted-1,2,4-triazoles by Carboxylic Acids,Amidines,and Hydrazines

The synthesis of 1,3,5-substituted-1,2,4-triazoles from α-imino-3-pyridine formic acid,acetamidine and anisole hydrazine as a model reaction in this paper and the synthesis mechanism of 1,3,5-substituted-1,2,4-triazole compounds from carboxylic acids,amidines and hydrazines have been first investigated with the B3 LYP/6-311＋＋G＊＊ method.According to the potential energy profile,it can be predicted that the course of the reaction consists of five reactions containing six elementary reactions.The α-imino-3-pyridine formic acid and acetamidine form first an intermediate product through a dehydration reaction; the intermediate product further combines with hydrogen ion to form a positive ion; the positive ion reacts with anisole hydrazine by a dehydration reaction to form another positive ion; then,followed by two isomerization reactions,the final reaction with the acetate ion（Ac-） produces the final product.The research results reveal the laws of synthesis reaction of 1,3,5-substituted-1,2,4-triazoles by the carboxylic acids,amidines,hydrazines and their derivatives on theoretical level.It provides the systemic theoretical basis for the synthesis,development and application of 1,3,5-substituted-1,2,4-triazole compounds.

Thermodynamic Study and Spectroscopic Analysis of a Charge-Transfer Complex between 3,5-Diamino-1,2,4-Triazole and 6-Methyl-1,3,5-Triazine-2,4-Diamine with Chloranilic Acid

Studying of charge-transfer (CT) and proton transfer interactions is essential due to their important role in many biological field and industrial applications. The current work will add more information’s about the nature of interaction between 3,5-diamino-1,2,4-triazole (DAT) and 6-methyl-1,3,5-triazine-2,4-diamine (MTDA) with 3,6-dichloro-2,5-dihydroxy-p-benzoquinone (chloranilic acid CLA) which was studied spectrophotometrically in Ethanol (EtOH) and Methanol (MeOH) solvents at different temperatures. The molecular composition of the formed complexes was studied by applying continuous variation and spectrophotometric titration methods and found to be 1:1 charge transfer complex for both Complex (DAT:CLA) and (MTDA:CLA) which are produced. Minimum-Maximum absorbance’s method has been applied to calculate the formation constant KCT and molecular extinction coefficient (ε);they recorded high values confirming high stability of the produced complexes. Oscillator strength (f), transition dipole moment (μ), ionization potential (IP) and dissociation energy (W) of the formed CT-complexes were also determined and evaluated;they showed solvent dependency. It is concluded that the formation constant (KCT) of the complexes is found to depend on the nature of both electron acceptor and donors and on the polarity of solvents.

Synthesis, Crystal Structure, Fluorescent Property and DFT Calculations of a New Zn(Ⅱ) Complex Based on 3-(2-Pyridyl)-5-(4-pyridyl)-1H-1,2,4-triazole

A new coordination compound Zn（2,4＇-bpt）2（H2O）（1） based on the versatile ligand 2,4＇-Hbpt（2,4？-Hbpt = 3-（2-pyridyl）-5-（4-pyridyl）-1H-1,2,4-triazole） was prepared by hydrothermal reactions. The structure of complex 1 has been characterized by X-ray single-crystal diffraction, elemental analysis, X-ray powder diffraction, IR spectrum analysis and thermogravimetric analysis. Single-crystal X-ray diffraction analysis indicates that the complex belongs to monoclinic system, space group C2/c with a = 23.877（3）, b = 0.7483（9）, c = 1.2492（2） A, b = 92.681（2）°, V = 2230.6（4） A^3, Z = 4, Dc = 1.572 g/cm^3, m = 1.143 mm^-1, Mr = 527.85 and F（000） = 1080. The final R = 0.0581 and wR = 0.0898 with I 〉 2s（I）. 1 is a 0D motif which is connected by hydrogen bonds to form a corrugated 1D pattern. In addition, 1 shows strong photoluminescent emissions in the solid state at room temperature which can be used as potential optical materials. Theoretical calculations based on density functional theory（DFT） were employed in order to explicate the stability and chemical reactivity of 2,4＇-Hbpt with different conformations. The results indicated that conformation I is more stable and prior to coordination in the reactions.

Catalytic Kinetic on the Thermal Decomposition of Ammonium Perchlorate with a New Energetic Complex Based on 3,5-Bis(3-pyridyl)-1H-1,2,4-triazole

A new energetic complex,[Co（3,3？-Hbpt）（Htm）]·H_2O（1,3,3？-Hbpt = 3,5-bis（3-pyridyl）-1H-1,2,4-triazole and H_3tm = trimesic acid）,has been synthesized by hydrothermal reactions and characterized by single-crystal X-ray diffraction,elementary analysis,IR spectroscopy,thermogravimetric analysis and X-ray powder diffraction. Single-crystal X-ray diffraction indicates that the complex belongs to triclinic system,space group P 1 with a = 10.0911（1）,b = 10.2573（1）,c = 10.6393（1） ？,α = 103.793（2）,β = 101.041（2）,γ = 107.918（3）o,V = 974.9（2） ？~3,Z = 2,D_c = 1.732 g·cm-3,μ = 0.941 mm^（-1）,M_r = 508.31,F（000） = 518,the final R = 0.0523 and wR = 0.0935 with I 〉 2σ（I）. In the title complex,Co（Ⅱ） ions are connected by Htm2-anions generating 1D ladder-like chains which are linked by 3,3？-Hbpt to form 1D cages. In addition,the thermal decomposition of ammonium perchlorate（AP） with complex 1 was explored by differential scanning calorimetry（DSC）. AP is completely decomposed in a shorter time in the presence of complex 1,and the decomposition heat of the mixture is 2.531 kJ·g^（-1）,significantly higher than that of pure AP. By Kissinger＇s method,the ratio of Ea/ln（A） is 11.05 for the mixture,which indicates that complex 1 shows good catalytic activity toward the AP decomposition.

Two New Metal-organic Frameworks Constructed from 3,4,5-Substituted-1,2,4-Triazole Ligands

Two new complexes,[Zn（L1）2（SCN）2]·H2O（1,L1 = 3,5-dimethyl-4-p-tolyl-4H1,2,4-triazole and [Cd3（L2）6（SCN）6]（2,L2 = 3,5-dimethyl-4-phenyl-4H-1,2,4-triazole）,have been hydrothermally prepared and characterized by single-crystal X-ray diffraction,IR spectroscopy,elemental analysis and PXRD.Complex 1 crystallizes in monoclinic,space group P21 /n with a = 11.246（13）,b = 9.640（11）,c = 26.13（3）,β = 100.97（3）,V = 1108.5（3） 3,Z = 4,C24 H28 N8 OS2 Zn,Mr = 572.02,Dc = 1.366 g/cm3,μ = 1.065 mm-1,S = 0.992,F（000） = 1184,the final R = 0.0602 and wR = 0.1700 for 2925 observed reflections（I 2σ（I））.Complex 2 crystallizes in triclinic,space group P1 with a = 11.6669（3）,b = 12.0957（2）,c = 14.3674（3）,α = 105.380（3）,β = 91.020（2）,γ = 92.4100（10）o,V = 1952.30（7）3,Z = 1,C66H66N24S6Cd3,Mr = 1725.08,Dc = 1.467 g/cm3,μ = 1.025 mm-1,S = 1.037,F（000） = 870,the final R = 0.0336 and wR = 0.0946 for 7819 observed reflections（I 2σ（I））.In the title complexes,complex 1 is a mononuclear molecule where the centre Zn（II） coordinates to two 3,4,5-substituted 1,2,4-triazole ligands（L1） and two terminal SCN-anions in a tetrahedral environment while six-coordinated centre Cd（II） atoms with octahedral geometry in complex 2 are bridged by virtue of substituted 1,2,4-triazole（L2） in N1,N2-bridging mode and μ2-N,N-SCN-anions into a trinuclear molecule.

Synthesis and Crystal Structure of Picrates of 3,5-Diamino-1,2,4-triazole

The title compound C2N5H6＋C6N3O7H2-was synthesized by the reaction of 3,5-diamino-1,2,4-triazole and picric acid in the mixture of ethanol and water solution.Single crystals suitable for X-ray measurement were obtained at room temperature.The structure was characterized by elemental analysis and IR and determined by X-ray diffraction analysis.Crystallographic data：C8N8H8O7,Mr = 328.22,monoclinic,space group C2/c with a = 22.815（2）,b = 4.8086（5）,c = 22.564（2）,β = 93.976（2）°,V = 2469.6（4）3,Dc = 1.766 g/cm3,Z = 8,μ = 0.156 mm-1,F（000） = 1344,the final R= 0.0309,wR= 0.0864.

Synthesis, Crystal Structure and Biological Activity of 4-Amino-2,4-dihydro-5-((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-3H-1,2,4-triazole-3-thione Schiff Base

The target compound 1,2,4-triazole Schiff base containing pyrazole ring was synthesized by 4-amino-2,4-dihydro-5-（（3,5-dimethyl- lH-pyrazol-1-yl）methyl）-3H-1,2,4-triazole-3-thione and 3,4,5-trimethoxy benzaldehyde.The structure was confirmed by IR,~1H NMR,H RMS,elemental analysis and single-crystal X-ray diffraction.The crystal belongs to the triclinic system,space group P1 with a = 7.8772（17）,b = 8.2986（18）,c = 15.392（3） A,α= 93.360（4）,β= 94.609（4）,γ= 93.584（4）°,C（18）H（22）N6O3S,Mr= 402.47,V= 998.9（4） A^3,Z= 2,F（000） = 422,Dc =1.335 g/cm^3,μ= 0.194 mm^（-1）,the final R = 0.0533 and wR = 0.1329 for 3517 observed reflections with I 2σ（I）.The preliminary bioassay results indicate that the target compound has good fungicidal activity against Gibberlla nicotiancola in EC50 value and F.O.f.sp.niveum in EC（95） value.

Synthesis and Crystal Structure Analysis of 4-Dibenzaldehydeamino-4H-1,2,4-triazole Diacetate

The new title compound 4-dibenzaldehydeamino-4H-1,2,4-triazole diacetate （C16H18N8O4,Mr = 386.38） has been prepared and its crystal structure was determined by single- crystal X-ray diffraction. The crystal is of monoclinic,space group P21/n with a = 8.1371（17）,b = 7.1237（12）,c = 16.325 （2）A,β = 100.366（2）°,V = 930.9（3） A^3,Z = 2,Dc = 1.378,F（000） = 404,μ = 0.104 mm^-1,MoKa radiation （λ = 0.71073 ）,R = 0.0307 and wR = 0.1196 for 4632 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that the molecule is not flat and the crystal structure is stabilized mainly by van der Waals interactions.

Synthesis and Crystal Structure of Ag_2(admtrz)_2(CF_3CO_2)_2(admtrz=4-amino-3,5-dimethyl-1,2,4-triazole)

The title compound (Ag2F6O4N8C12H16, Mr = 666.07) was synthesized and its crystal structure was determined by single-crystal X-ray diffraction method. It crystallizes in orthorhombic, space group Fddd with cell parameters: a = 12.2718(1), b = 23.3229(1), c = 29.1918(1) ? V = 8355.10(8) 3, Z = 16, Dc = 2.118 g/cm3, F(000) = 5184 and m = 1.966 mm-1. The structure was solved by direct methods and refined by full-matrix least-squares methods. The final R = 0.0624 and Rw = 0.1699 for 1584 observed reflections with I ≥ 2.0s(I). The molecular structure consists of two trigonal silver atoms bridged by double triazole ligands. The distance between the two silver atoms Ag(1)…Ag(1A) is 3.475(2) ?

Synthesis,Crystal Structure,DFT Studies and Antifungal Activity of 5-(4-Cyclopropyl-5-((3-fluorobenzyl)sulfonyl)-4H-1,2,4-triazol-3-yl)-4-methyl-1,2,3-thiadiazole

5-（4-Cyclopropyl-5-（（3-fluorobenzyl）sulfonyl）-4H-1,2,4-triazol-3-yl）-4-methyl-1,2,3-thiadiazole was synthesized and recrystallized from Et OH. The compound was characterized by ^1H NMR,MS,elemental analysis and X-ray diffraction. The structure-active relationship and the antifungal activity based on density functional theory calculation（DFT） and antifungal activities were investigated. The compound crystallizes in the monoclinic space group P121/n1 with a = 8.929（3）,b=12.715（4）,c=15.161（5） A°,β = 106.142（3）o,V = 1653.3（9） A°3,Z = 4 and R = 0.0393 for 3930 observed reflections with I 〉 2σ（I）. Theoretical calculation of the title compound was carried out with B3LYP/6-31G（d,p）. The full geometry optimization was carried out using the 6-31G（d,p） basis set.The frontier orbital energy and atomic net charges were discussed. The observed results of the compound have been compared with theoretical results and the experimental data show good agreement with the calculated values. The compound exhibits good antifungal activity.

Synthesis of Quinoxalinophenazine Derivatives and Reaction of 3,12-Dimethylbenzo[a]quinoxalino-[2,3-c]phenazine with Mercury(Ⅱ) Bromide: Spectral and Structural Characterization

A new series of quinoxalinophenazine derivatives were synthesized in good yields by the reaction of 2,3-dibromonaphthalene-1,4-dione with different aryl-1,2-diamines in DMF as solvent at 120-130℃ or under reflux conditions. 3,12-dimethylbenzo[a]quinoxalino[2,3-c] phenazine with bidentate character reacts with mercury（II） bromide to give suitable crystals. All products were confirmed by IR, ^1H and ^13C NMR, and the metal complex by single-crystal X-ray method. The crystal（C24H16Br2HgN4, Mr = 720.82） belongs to the triclinic system, space group P1 with a = 10.186（6）, b = 10.421（6）, c = 11.470（7） A, α = 98.670（7）, β = 95.069（7）, γ = 109.831（7）°, V = 1119.4（12） A3, Z = 2, Dc = 2.139 Mg/m^3, μ = 10.46 mm^-1, F（000） = 676, R = 0.043 and wR = 0.115 for 3982 observed reflections with I 〉 2σ（I）.