含硫代酰胺的新三唑类化合物的合成、结构表征及生物活性研究

由取代苯乙酮出发，经过多步反应，制得2-苯甲酰基-N-苯基-2-(1,2,4-三唑-1-基)硫代乙酰胺 (1) 和2-(4-氯苯甲酰基)-N-苯基-2-(1,2,4-三唑-1-基)硫代乙酰胺 (2), 通过元素分析、核磁共振氢谱、红外光谱和质谱进行表征。并利用单晶X射线衍射法测定化合物1。晶体属单斜晶系, P2₁/c空间群, a = 0.8806(2) nm, b = 1.2097(2) nm, c = 1.4809(3) nm, β=105.88˚, Z=4, V=1.5173(6) nm³, D_c=1.411 Mg/m³, μ=0.22 mm^-1, F(000)=672, R₁=0.040. 采用离体平皿法对它们的杀菌活性进行了比较，同时测定了它们的植物生长调节活性。测定结果表明化合物2对黄瓜子叶生根具有较强的促进作用，促进率达131％。     

新型含吡啶酰胺基希夫碱多齿配体的合成,光谱,晶体结构及抑菌活性研究

采用稀释法与胺5倍过量合成了一种新型的含吡啶环的开链二胺1a（N，N′-双(2-氨基乙基)－2，6-吡啶二甲酰胺）。此外，合成了六个新型多齿希夫碱配体N，N′－双(β－R－苯甲醛亚胺基乙基)－2，6－吡啶二甲酰胺[其中，R=H(2a)，o-OH(2b)，p-OH(2c)，m-NO₂(2d)，p- N(CH₃)₂(2e)]及N，N′-双[γ-水杨醛亚胺基正丙基]－2，6－吡啶二甲酰胺2f。通过元素分析,紫外－可见光谱，红外光谱，氢核磁共振谱及质谱对化合物进行了表征。通过化合物2e的单晶结构X－射线单晶衍射分析表明该晶体属于立方晶系P－1空间群，其晶胞参数为：a=11.010(2) nm，b=13.865(3) nm，c=9.6537(19) nm，α=102.77(2)º，β=92.07(3)º，γ=87.98(3)º，V=1435.7(5) nm³，Z=2，D_c=1.230 mg•cm^-3，M_r=531.66。微量热法检测了化合物对大肠杆菌的抑制作用，并初步分析了化合物结构与抗菌活性之间的关系。实验结果表明，所有化合物都对大肠杆菌有抑制作用，其中水杨醛希夫碱的抑菌活性最好。     

Syntheses,Structures and Characterizations of Two Vanadium(V) Complexes:[2-MePyH][V^vO2(C14H9N2O3Br)] and [2-EtPyH][V^VO2(C14H9N2O3Br)]

Two new oxovanadium(V) complexes, [2‐MePyH][V^vO₂(L)] (3) and[2‐EtPyH][V^vO₂,(L)] (4) (salicylaldehyde 5‐bromo salicyloylhydrazone is abbreviated as H₂L; 2‐MePyH is protonated 2‐Mepyridine; 2‐EtPyH presents protonated 2‐Et‐pyridine) were obtained from a reaction of VOSO₄ and H₂L in acetonitrile‐methanol with small quantity of 2‐Me‐pyridine or 2‐Et‐pyridine, and characterized by X‐ray diffraction and spectroscopic methods. Crystal data: [2‐MePyH][VO₂(L)] (3), C₂₀H₁₇N₃O₅BrV, M_r = 510.2, monoclinic, P2₁/n, a = 0.7363(1) nm, 6 = 0.9514(1) nm, c = 2.8594(2) nm, β = 95.305(2)°, Z = 4 and V=1.9946(3) nm³, μ(Mo Kα) = 2.539 mm^?1; [2‐EtPyH][VO₂(L)] (4), C₂₁H₁₉N₃ O₃BrV, M_r = 524.2, triclinic, P1 , a = 0.8051(1) nm, b = 0.9413(1) nm, c = 1.4648(2) nm, α=99.1900(10)°, α = 99.4530(10)°, γ = 104.6670(10)°, Z = 2 and V= 1.0355(2) nm³, μ(Mo Kα) = 2.448 mm^?1, X‐Ray analyses revealed that the crystal structures of 3 and 4 have similar packing modes.     

Synthesis and Structural Characterization of Three New Inorganic ＂Host-gues＂ Polyoxomolybdates

Since two interesting inorganic “host‐guest” polyoxomolybdates 1 and 2 have been reported previously, we have now succeeded in selectively isolating three new acetated “host‐guest” polyoxomolybdates 3–5, which considerably extend the range of structures in the cyclic polyoxomolybdate catalogue. 3 crystallizes in the triclinic space group P‐1 with a = 1.22235(1) nm, b = 1.52977(2) nm, c = 1.54022(1) nm, a = 113.746(1)°, β = 96.742(1)°, γ = 101.564(1)°, V = 2.51892(4) nm³, Z =1, D_c = 2.568 g. cm^?3. 4 and 5 crystallize in the monoclinic system: P2(1)/n, a = 1.08298(2) nm, b = 1.54029(1) nm, c = 2.78893(5) nm, β =94.2730(10)°, V = 4.63929(12) nm³, Z = 2 and D_c = 2.671 g. cm^?3 for 4, and C2/c, a =2.59907(8) nm, b = 1.65992(3) nm, c = 2.28473(7) nm, β‐93.4370(10)°, V = 9.8392(5) nm³, Z = 4 and D_c = 2.556 g. cm^?3 for 5. The structures of 3, 4 and 5 consist of 18‐membered “host‐guest” polyoxoanions [ Na (X)₂| ∈ |(μ_3‐OH)₄Mo^y₈Mo^VI₁₀52(μ₂‐CH₃COO)₂]^?(R+9 (X = CH₃COO^?for 3, DMF for 4 and H₂O for 5), which are connected via Na* ions or hydrogen bonds into infinite extended frameworks.     

Molecular Structure,Theoretical Calculation and Thermal Behavior of DAG(NTO)

A new compound, [DAG(NTO)], was prepared by mixing the NaNTO•H2O aqueous solution and diaminogaunidine hydrochloride aqueous solution. Single crystals suitable for X-ray measurement were obtained by recrystallization from water at room temperature. The crystal belongs to triclinic, space group P-1 with crystal parameters of a＝0.6732(3) nm, b＝0.6745(3) nm, c＝0.9840(4) nm, α＝88.309(7)°, β＝77.255(6)°, γ＝86.520(7)°, V＝4.349(3) nm3, Z＝2, μ＝0.144 mm－1, F(000)＝228, and Dc＝1.674 g/cm3. The theoretical investigation on DAG(NTO) as a structural unit was carried out by B3LYP, MP2 and HF methods with 6-31＋G(d) basis set. The apparent activation energy and pre-exponential constant of the exothermic decomposition reaction of DAG(NTO) are 112.15 kJ•mol－1 and 109.603 s－1, respectively. The critical temperature of thermal explosion is 208.6 ℃.     

Synthesis and Crystal Structure of Two One—dimensional Chain Copper Complexes [Cu（TTA）2（4,4‘’—azpy）] and [Cu（TTA）2（3,3‘’—azpy）

Two copper complexes [Cu(TTA)₂(4,4′‐azpy)] (1) and [Cu‐(TTA)₂(3,3′‐azpy)] (2) (HTTA = 1,1,1‐trifluoro‐3‐(2‐thenoyl)‐acetone, 4,4′‐azpy = 4,4′‐azobispyridine, 3,3′‐azpy = 3,3′‐azobispyridine) were synthesized and characterized. The crystal structures were determined by X‐ray diffraction analysis. The crystal 1 belongs to triclinic with space group P1 , a = 0.8515(2) nm, b = 0.9259(2) nm, c = 0.9468(2) nm, a = 66.126(9)°, β = 79.667(9)°, γ = 90.13(1)°, Z = 1, V = 0.6692(2) nm³, D_c = 3.425 g/cm³, γ = 2.113 mm^?1, F(000) = 694, R₁ = 0.0594, wR₂ = 0.1499. The crystal 2 belongs to monoclinic with space group P2₁/c, a = 1.0661(2) nm, b = 1.4296(3) ran, c = 1.0041(3) nm, β = 114.50(3)°, V = 1.3926(5) nm³, Z = 2, D_c = 1.646 g/ cm³, μ = 1.015 mm^?1, F(000) = 694, R₁, = 0.0535, wR₂ = 0.1113. In the crystals of complexes 1 and 2, the copper atoms have distorted octahedral symmetry. The two compounds possess very similar one‐dimensional linear chains linked through the rodlike 4,4′‐azpy ligands or 3,3′‐azpy ligands.     

Non‐Planar Lithium‐Phthalocyanine in the Double Salt (nBu4N)2[Lipc]PF6

We report the synthesis of the diamagnetic double salt bis(tetra(n‐butyl)ammonium) phthalocyanato(2‐)lithate hexafluorophosphate (nBu₄N)₂[Lipc]PF₆ [pc = phthalocyanine, nBu₄N⁺ = tetra(n‐butyl)ammonium] in dme (dme = dimethoxyethane). According to single‐crystal X‐ray diffraction structure analysis [P$\bar{1}$ , a = 8.642(2) Å, b = 12.820(3) Å, c = 15.019(3) Å, α = 83.01(3)°, β = 87.87(3)°, γ = 74.45(3)°, Z = 1, R₁ = 6.4 %], the phthalocyanine building bloc shows a substantial distortion of the macrocyclic ring from planarity. The deviation from D_4h symmetry originates from packing effects induced by the two tetra(n‐butyl)ammonium cations located above and below the macrocycle. DFT structure optimization starting from the experimental non‐planar configuration produces a fully planar complex anion [Lipc]^–.     

新颖有机/无机杂化配位聚合物[(DBU-H)(PbI3)]n的合成、晶体结构和量子化学研究

The coordination polymer [（DBU-H）（PbI3）]n（DBU=catena-（1,8-diazabicyclo[5,4,0]-undec-7-ene） was synthesized by self-assembly reaction of DBU and PbI2 at room temperature with pH=6.0 and structurally characterized by means of X-ray single crystal diffraction. It crystallizes in monoclinic system with space group P21/c and crystal parameters a = 1.1940（2） nm, b = 1.7409（4） nm, c = 0.81347（16） nm, β= 100.32（3）°, chemical formula C9H17N213Pb and Mr=741.15, V= 1.6635（6） nm^3, Z=4, Dc=2.959 g/cm^3, F（000）= 1304,μ（Mo Kα）= 15.687 mm^-1, the final R=0.0389 and wR=0.0635 for 2279 observed reflections with 1〉2σ（I）. Structure analysis shows that the inorganic anion chain consists of distorted PbI6 octahedra, which shares the same faces with adjacent PbI6 units to form one-dimensional infinite chains along the c-axis. Anion chains are surrounded by protonated （DBU-H）^＋ cations. Anion chains and cations are in combination with each other by static attracting forces in the crystal to form so-called organic-inorganic hybrid structure. According to the crystal structure data, quantum chemical calculation with DFT at B3LYP level was used to reveal the electronic structure of title compound.     

Syntheses and Crystal Structures of Cadmium Complexes with Thiophenedicarboxylate and Bipyridine‐like Ligands

Two new coordination polymers [Cd(tdc)(bpy)(H₂O)]_n ( 1 ) and [Cd(tdc)(phen)]_n ( 2 ) (H₂tdc = thiophene‐2,5‐dicarboxylic acid, bpy = 2,2′‐bipyridine and phen = 1,10‐phenanthroline) have been synthesized under hydrothermal condition. Their crystal structures have been established by X‐ray single‐crystal diffraction. Complex 1 crystallizes in the orthorhombic space group Fdd2 with a = 14.757(7), b = 45.38(2), c = 10.518(5) Å, V = 7044(6) ų, Z = 16; 2 in the monoclinic space group P2₁/c with a = 7.262(1), b = 21.970(2), c = 10.051(1) Å, β = 105.01(1)°, V = 1548.8(2) ų, Z = 4. Both of them are double‐stranded chains and further assembled into three‐dimensional networks by π‐π stacking interactions. 1 and 2 are stable in air, and show blue photoluminescence at 415 nm and 410 nm, respectively.     

Synthesis, Structure and Biological Activities of S-[α-（ 4-Methoxyphenylcarbonyl ）-2-（1,2,4-triazole-l-yl） ethyl-N, N-dime-thyldithiocarbamate

The title compound was prepared by reaction of N, N‐dimethyldithiocarbamate sodium with l‐bromo‐l‐(4‐methoxyphenylcarbonyl)‐2‐(1, 2, 4‐triazole‐l‐yl) ethane. Its crystal structure has been determined by X‐ray diffraction analysis. The crystal belongs to triclinic with space group Pī, a = 0.7339(2) nm, b = 1.1032(2) nm, c = 1.1203(2) nm, a = 90.27(3)°, β = 102.03(3)°, γ = 104.91(3)°, Z=2, V = 0.8556(3) nm³, D_c = 1.360 g/cm³, μ =0.325 mm^?1, F(000)=368, final R₁ =0.0475. The planes of 4‐methoxybenzyl group and triazole ring are nearly perpendicular to each other. The dihedral angle is 83.97°. There is an obvious π‐π stacking interaction between the molecules in the crystal lattice. The results of biological test show that the title compound has fungicidal and plant growth regulating activities.     

G(FOX-7)的合成、晶体结构及量子化学研究

用1,1-二氨基-2,2-二硝基乙烯（FOX-7）和盐酸胍在KOH水溶液中合成了[HN=C(NH₂)₂]⁺(FOX-7)^---G(FOX-7),并培养出淡黄色单晶。化合物属正交晶系,空间群为P-bca,晶体结构参数为: a=1.0428(3)nm, b=0.73099(18)nm,c=2.2253(5)nm,V=1.6963(7) nm³,D_c=1.542 g/cm³,μ＝0.333 mm^-1,F(000)=864, Z=8。在分析分子晶体结构的基础上,采用B3LYP、HF和MP2三种方法在6-31+G(d)基组水平上对标题化合物进行几何全优化,并对其成键情况、原子电荷分布、分子轨道能量进行了分析。     

Bismuth(III) Complexes with N,N‐Di(2‐hydroxylethyl)aminodithiocarboxylate: Synthesis and Crystal Structure of {Bi[S2CN(C2H4OH)2]2[1, 10‐Phen]2(NO3)}·3H2O and (Bi[S2CN(C2H4OH)2]3}2

Two novel one‐ and two‐dimensional network structure bismuth(III) complexes with N, N‐di(2‐hydroxylethyl)‐aminodithiocarboxylate, {Bi[S₂CN(C₂H₄OH)₂]₂[1, 10‐Phen]₂(NO₃)}·3H₂O (1) and (Bi[S₂CN(C₂H₄OH)₂]₃)₂ (2) were synthesized. Their crystal and molecular structures were determined by X‐ray single crystal diffraction analysis. The crystal 1 belongs to monoclinic system with space group C2/c, a=1.6431(7) nm, b=2.4323(10) nm, c= 1.2646(5) nm, β=126. 237(5), Z=4, V=4.076(3) nm³, D_c=1.757 Mg/m^3, μ=4.598 mm^?1, F(000)=2156, R= 0.0211, wR=0.0369. The structure shows a distorted square antiprism configuration with eight‐coordination for the central Bi atom. The one‐dimensional chain structure was formed by H‐bonding interaction between hydroxyl group of N, N‐di(2‐hydroxylethyl)aminodithiocarboxylate ligands and crystal water. The crystal 2 belongs to monoclinic system with space group p2(1)/c, a= 1.1149(4) nm, b=2.1274(8) nrn, c=2.2107(8) nm, β=98.325(8)°, 2=4, V=5. 188(3) nm³, Dc=1.920 Mg/m³, μ=7.315 mm^?1, F(000)=2944, R=0.0565, wR=0.0772. The structure shows a distorted square antiprism configuration with eight‐coordination for the central Bi atoms. The two‐dimensional network structure was formed by H‐bonding interaction between adjacent molecules.     

Synthesis and Crystal Structure of a New Oxovanadium（V） Multicomponent Complex with Acylhydrazone and Benzoylhydrazine

A new oxovanadium（V） complex with the mixed ligand of 2-oxopropionic acid benzoylhydrazone （C10H10N2O3） and benzoylhydrazine （C7H8N2O）, VO（C7H7N2O）（C10H9N2O3）, has been synthesized. Its structure was determined by single crystal X-ray diffraction analysis. The crystal belongs to monoclinic system with space group P21/n and cell parameters： a=1.1136（4） nm, b=0.6217（2） nm, c=2.6038（9） nm, β=97.182（6）°, V= 1.7887（11） nm^3, Z=4, F（000）=836, Mr=407.28, Dc= 1.512 g/cm^3,μ （Mo Kα） =0.592 mm^-1, R1 =0.0445, wR2= 0.1203. Vanadium atom is 6-coordinated by carboxyl and carbonyl O atoms and N atom of one tridentate C10H10N2O3 to form two stable five-membered rings with the same edge, and the other coordinated atoms of N and O come from one bidentate benzoylhydrazine C7H8N2O. The title complex has a six-coordinated V center [VO（N2O3）] with a distorted octahedral arrangement. In the crystal lattice, there are hydrogen bonding interactions between two molecules.     

Synthesis and Characterization of Monomeric Salicylaldiminato Lanthanide Complexes and Their Catalytic Behavior for Polymerization of ε—Caprolactone

IntroductionSchiffbaseligandscanbeusedtoprovideastereochem icallyrigidligandframeworkinhomogenousprecatalystsofsomemetals,suchassalenCrcatalystsinasymmetricring openingreactionofepoxide1andsalenAlinring openingpolymerizationoflactideandrelatedcyclicesters .2 Recently ,itwasreportedthatthebidentateSchiffbasecomplexesofearlyandlatetransitionmetalscanserveaspromisingalterna tivestometallocenecatalystsforthepolymerizationofα olefins.3Therefore ,theapplicationsofSchiffbaseligandsinorganometallic…     

斯蒂芬酸氢铷的制备，晶体结构和热分解机理

A new compound,[RbHTNR]_∞[HTNR:C_6H(NO_2)_3(OH)O],was synthesized by the reaction of rubidium ni-trate and styphnic acid.The molecular structure was characterized using X-ray diffraction analysis,elementalanalysis and FTIR spectroscopy.The crystalline is monoclinic with space group P2_1/n and the empirical formulaC_6H_2N_3O_8Rb.The unit cell parameters are:a=0.4525 nm,b=1.0777 nm,c=1.9834 nm,β=90.47(2)°,V=0.96725 nm~3,Z=4,D_c=2.263 g/cm~3,Mr=329.58,F(000)=640,μ(Mo Kα)=5.165 mm~(-1).The thermal decompo-sition mechanism of the complex was studied by differential scanning calorimetry(DSC),thermogravimetry-derivative thermogravimetry(TG-DTG)and FTIR techniques.At the linear rate of 10 ℃/min,the thermaldecomposition of the complex showed three mass reducing processes between 60 and 500 ℃,and finally evolvedRbCN and some gaseous products.     

A New Dinuclear Copper (II) Complex of a Bis‐macrocyclic Ligand: Synthesis,Characterization, Crystal Structure and Magnetic Properties

A new dinuclear Cu(II) complex, [Cu₂L(N₃)₂](ClO₄)₁.₅ (OH)_4.5 · 2H₂O 0.5C₂H₅OH (1), of a bis‐macrocyclic ligand, 2,6‐bis(l,4,7,10‐tetraazacyclododecan‐10‐ylmethyl)‐methoxybenzene (L), has been synthesized, characterized and structurally determined by X‐ray diffraction analysis. Complex 1 crystallizes in orthorhombic crystal system, Pca2(l) space group with a = 1.5371(3), b = 1.6641(3), c = 3.0950(6) nm, V = 7.917(3) nm³, F_w = 904.62, Z=8, D_c= 1.529 g/cm³ and final R = 0.0568, wR = 0.1406 for 10410 observed reflections with I≥2σ (I). Both Cu(II) centers in the structure are coordinated by four nitrogen atoms of 1,4,7, 10‐tetraazacyclododecane (cyclen) and a nitrogen donor of the axial azide anion. Each Cu(II) center is in a square‐pyramidal coordination environment, and the intra‐and nearest inter‐molecular Cu? Cu nonbonding distances are 0.9855 and 0.7298 nm, respectively. Variable temperature magnetic susceptibility measurements in the range of 4.2–300 K indicate mat there exists weak intra‐ and inter‐molecular antiferromagnetic coupling between the Cu(II) centers with 27= ?4.2 cm^?1 and Θ = ?0.47 K.     

四（对叔丁基）硫杂杯[4]芳烃选择性包合四氟硼酸分子：晶体结构和理论研究

X－射线晶体衍射测定了4－(对叔丁基)硫杂杯[4]芳烃选择性地包合四氟硼酸分子。晶体学数据为：C₄₀H₄₉O₄S₄BF₄，M_r=808.88， 四方锥， 空间群 P4/nmm，a=1.5887(2), b=1.5887(2), c=0.8428(0) nm, V=2.127(2) nm³, Z=2, D_c=1.263 g·cm^-3, R₁=0.0405, _WR[I>2σ(I)]=0.1218. ¹⁹F NMR谱中，在-151.4 ppm处出现的峰，证实了四氟硼酸的存在。用Bader的分子中的原子理论方法计算了分子结构中的非共价键相互作用。结果显示，在四氟硼酸包合物中，除了F…H－C氢键作用和阳离子－阴离子的静电作用外，F^δ--C^δ+静电作用的存在也对4－(对叔丁基)硫杂杯[4]芳烃憎水空腔包合氟硼酸分子起到了稳定作用。     

Crystal Structures and Magnetic Studies of Naphthalene Derivatives Containing Nitronly Nitroxides

Crystal structures of new nitronyl nitroxide derivatives 1, 2 and 3 were determined with X‐ray diffraction analysis: 1, monoclinic, C₂/c, a = 1.2404(5) nm, b = 0.9730(5) um, c = 2.7049(10) ran, β = 98.189(15)°, V = 3.2315(24) nm³, Z = 8; 2, or‐thorhombic, Pbca, a = 0.61262(2) nm, b = 1.11426(6) nm, c = 2.30543(13) nm, V = 1.57373(13) nm³, Z = 4; 3, monoclinic, P2(1)/n, a=0.64253(4) nm, b=2.55003(17) nm, c = 1.15497(6) nm, β = 95.000(3)°, V = 1.8852(2) nm³, Z = 4. Their magnetic properties were measured with SQUID and analyzed based on their crystal structures with simple singlet‐triplet, modified one dimensional antiferromagnetic chain and modified singlet‐triplet models respectively: 1, J/k_b= ?2.5 K; 2, J/k_b = 7.8 K, θ = 2.8 K; 3, J/k_b = ?0.96 K, θ = 0.21 K.     

Investigation of Copper Halide:Hydrothermal Syntheses and Characterization of CuBr2(C12H8N2) and Cu3Br3(C12H8N2)2

The reaction of CuBr₂ with 1,10‐phen‐H₂O (1,10‐phen = 1,10‐phenanthroline) gave two compounds: CuBr₂(C₁₂H₈N₂) and Cu₃Br₃(C₁₂H₈N₂)₂. Their structures have been characterized by single‐crystal X‐ray diffraction analysis, elemental analyses, thermogravimetric analyses (TGA) and measurement of variable temperature magnetic susceptibility. Crystal data for CuBr₂(C₁₂‐H₈N₂): monoclinic, space group P2₁/n, a = 0.9977(3) nm, b = 0.65138(14) nm, c = 1.8207(4) nm, β = 91.624(18)°, V = 1.1828(5) nm³, Z = 2. Crystal data for Cu₃Br₃(C₁₂H₈N₂)₂: monoclinic, space group C2/c, a = 1.00167(11) nm, b = 1.4523(4) nm, c = 1.6295(3) nm, β = 94.386(14)°, V = 2.3635(8) nm³, Z = 3.     

Synthesis and Crystal Structure of Drum Organooxotin Clusters from Heteroaromatic Carboxylic Acid [PhCH2Sn（O）（O2CC5H4N）]6 and[PhCh2Sn）（O）（O2CC4H3O）]6

IntroductionRecentlywehaveinvestigatedthestructuralchemistryofanumberofdi ortri organotinheteroaromaticcarboxyl ates.1 5Thesestudieshaveshownthatthestructureoforgan otinheteroaromaticcarboxylatesisdependentonboththena tureofthealkylorarylsubstituentboundtothetinatomandthetypeofcarboxylateligand .Inparticular,majorstructuralvariationsareobservedwhencarboxylateligandcontainsanadditionaldonoratom ,suchasapyridineNatom ,availableforcoordinationtotheSnatom .1 3,5 8Wehavenowturnedtothemonoorganotin…