香豆素衍生物的合成及结构表征

合成了11个香豆素衍生物,产率53%—79%,利用元素分析、MS和¹HNMR对其结构进行了表征.同时,由2-氨基苯并噻唑(ABT)和8-甲氧基香豆素-3-甲酸乙酯(MCC)合成了给体-受体加合物ABT-MCC,通过X射线单晶衍射法测定了其晶体结构,晶体属三斜晶系,P1空间群,晶胞参数为:a=9.5978(19)Å,b=10.686(2)Å,c=10.693(2)Å,α=71.30(3)°,β=70.43(3)°,γ=88.99(3)°,V=973.9(3)ų,Z=2,D_x=1.359 mg/m³,μ=0.200 mm^-1,F(000)=416,R=0.0463,wR=0.0992.结果表明,在ABT-MCC晶体中,分子间通过N—H…N和N—H…O氢键作用形成对称的A…D…D′…A′氢键四聚体,并通过弱的C—H…O氢键连接成为一维超分子链状结构,进而分子间通过π-π堆积作用形成层状结构.     

一种新型钼钒多酸化合物的合成、结构与荧光性能

采用水热技术,合成了一种新型四帽Keggin结构多酸化合物[H₃Mo₈^ⅥV₈^ⅣO₄₀(AsO₄)](en)₂(4,4-bipy)₇·9H₂O(en:乙二胺;bipy:联吡啶)(1),并对化合物进行了元素分析、红外光谱、X射线光电子能谱和X射线单晶结构分析。 晶体结构分析表明, 化合物属三斜晶系,P1空间群,晶胞参数a=1.47395(5) nm,b=1.48172(6) nm,c=1.62881(7) nm,α=66.16(3)°,β=87.15(2)°,γ=63.42(1)°,V=2.8723(2) nm³,Z=1,R₁=0.0728,wR₂=0.2014。 化合物由四帽Keggin多酸阴离子、4,4'-联吡啶、乙二胺和结晶水分子构成,化合物分子间存在大量的氢键,使化合物1形成3-D超分子结构。 荧光测试表明,化合物1能发出较强的荧光,有可能成为潜在的光活性材料。     

2-氯甲基苯并咪唑硝酸盐的晶体结构、质子化特征及量子化学理论研究

制备了2-氯甲基苯并咪唑硝酸盐(C₈H₈N₂Cl⁺·NO₃^-)化合物,采用元素分析,IR, ¹H NMR和TG-DTA对产物进行了表征,并采用X射线单晶衍射仪测定了该化合物的晶体结构,该化合物属单斜晶系,空间群P21/n, a=0.74189(3) nm, b=1.53064(6) nm, c=1.05478(3) nm, β=120.930(2)º, V=1.02744 nm³, D_c=1.484 g/cm³, Z=4, F(000)=472, μ=0.363 mm^-1, R=0.0659, wR=0.1498, GOF=0.840.在此基础上,采用量子化学方法,在MP2/6-311G^**, B3LYP/6-311G^**和HF/6-311G^**水平上计算了2-氯甲基苯并咪唑及其质子化阳离子的优化构型、电荷分布、振动光谱、热力学函数及总能量.计算结果显示2-氯甲基苯并咪唑环具有较强质子化能力,这与晶体结构结果相一致.     

芴衍生物的合成、结构与蓝色(λmax=418nm)双光子荧光

分别以二苯胺和咔唑为端基,以芴为共轭桥, 合成了两个对称型芴衍生物:2,7-二-(N,N-二苯胺基)-9,9-二乙基芴[2,7-bis(N,N-diphenylamino)-9,9-diethyl-fluorene,简称DPDEF]和2,7-二咔唑基-9,9-二乙基芴(2,7-dicarbazol-9'-yl-9,9-diethyl-fluorene,简称DCDEF).用四圆X射线衍射方法测定了其晶体结构.DPDEF单晶属于单斜晶系,C2/c空间群.晶胞参数:a=2.8649(4) nm, b=0.85111(9) nm, c=2.7012(4) nm, β=100.982(11)º, V=6.4657(14) nm³, Z=8, D_c=1.144 g·cm^-3, R=0.0581. DCDEF单晶属于单斜晶系,P2₁/c空间群.晶胞参数:a=0.92794(12) nm, b=0.88561(9) nm, c=3.7236(4) nm, β=96.914(9)º, V=3.0378(6) nm³, Z=4, D_c=1.208 g*cm^-3, R=0.0652.晶体中DPDEF和DCDEF的芴桥具有很好的平面性,构成芴桥的两个苯环平面之间的夹角分别仅为3.0º和5.8º.在波长为730 nm的飞秒脉冲激光激发下,化合物DPDEF在THF中发出强的蓝色双光子上转换荧光(λ_max=418 nm),测得双光子吸收截面为15 GM.     

混合配体配合物镉(Ⅱ)-邻菲罗啉-丙二酸根异构体的结构特征研究

由硝酸镉、邻菲罗啉和丙二酸混合反应,得到无色透明单晶.经X射线单晶衍射法测定了该晶体的分子结构,在1个晶胞中存在两个混合配体配合物异构体,其组成为C₂₇H₁₈O₄N₄Cd.晶体学数据为:三斜晶系,P-1空间群.a=0.14432(5)m,b=0.15517(5)nm,c=0.16098(6)nm,α=107.048(6)°,β=98.989(6)°,γ=116.481(6)°,Z=2,F(000)=1287,D_c=1.453g/cm3,μ=0.802mm^-1,R₁=0.0645,wR₂=0.1756.该异构体的差别在于丙二酸根中2个羧基中各1个氧原子配位(1)或1个羧基中2个氧原子同时配位(2).1和2之间靠氢键和π-π堆积等弱相互作用形成超分子结构.     

三环已基锡L-扁桃酸酯配合物的合成、结构及性质

三环己基氢氧化锡与L-扁桃酸(物质的量比1:1)在苯和乙醇混合溶剂中反应合成了三环己基锡L-扁桃酸酯。 经X射线衍射方法测定了其晶体结构,配合物属斜方晶系,空间群为P2₁2₁2₁,晶体学参数a=0.80825(4) nm,b=1.77151(8) nm,c=1.8385(2) nm,α=β=γ=90°,V=2.6324(2) nm³,Z=4,D_c=1.310 g/nm³,μ(MoKα)=9.92 cm^-1,F(000)=1080,R₁=0.0472,wR₂=0.1341。 中心锡原子与环己基碳原子和氧原子构成畸型四面体。 对其结构进行量子化学从头计算,探讨了配合物的稳定性、分子轨道能量以及一些前沿分子轨道的组成特征。 研究了配合物的热稳定性、电化学性能、圆二色谱和体外抗癌活性。     

合成黑索今中副产物3, 5-二硝基-1-氧-3, 5-二氮杂环己烷的晶体结构及热分解动力学

直接法硝解乌洛托品制备黑索今的过程中合成了一种新型的环形副产物,采用硅胶柱层析法分离得到3, 5-二硝基-1-氧-3, 5-二氮杂环己烷,洗脱剂为:丙酮/二氯甲烷,梯度洗脱.以丙酮为溶剂培养得到了3, 5-二硝基-1-氧-3, 5-二氮杂环己烷单晶,用元素分析、傅里叶变换红外(FTIR)光谱、核磁共振氢谱(NMR)以及质谱(MS)对其结构进行了表征,用X射线单晶衍射仪测定了其晶体结构.结果表明,晶体C₃H₆N₄O₅分子量为178.12,属于单斜晶系,空间群P121/n1,晶胞参数: a = 0.58128(13) nm, b = 1.72389(14) nm, c = 0.71072(6) nm, β =112.056°, V = 0.66006(16) nm³, Z = 4, D_C= 1.792 g·cm^-3, μ = 0.17 mm^-1, F(000) = 368.0,最终偏差因子R =0.0397.用同步热分析仪技术研究了3, 5-二硝基-1-氧-3, 5-二氮杂环己烷的热行为, DSC曲线上在383.15和519.05 K分别有一个尖锐的熔化吸热峰和分解放热峰.另外,根据Kissinger方程及Flynn-Wall-Ozawa方程和不同升温速率下的TG曲线计算得到了该化合物的热分解动力学参数(活化能和指前因子),利用Coats-Redfern法研究了该物质的热分解机理.结果表明: 3, 5-二硝基-1-氧-3, 5-二氮杂环己烷是一种低熔点、热稳定性好的化合物. Kissinger方程计算其活化能为212.32 kJ·mol^-1,指前因子为6.20×10²⁰ s^-1, Flynn-Wall-Ozawa方程计算其活化能为210.39 kJ·mol^-1,该物质的热分解动力学方程为G(α) = (1-α)^-1-1,反应级数为2.     

二价铥三元碘化物研究

用一步法合成了ATmI₃(A=K,Rb,Cs)和A₄TmI₆(A=Rb,Cs)两类化合物.用X射线粉末衍射法确定其晶体结构.CsTmI₃、RbTmI₃和KTmI₃都属正交晶系,Z=4.CsTmI₃:a=0.8689(3)nm,b=1.2339(4)nm,c=0.8565(3)nm,空间群Pnma;RbTmI₃:a=1.0381(3)nm,b=0.4686(3)nm,c=1.7256(9)nm,空间群Pnma;KTmI₃:a=0.4576(2)nm,b=1.5133(20)nm,c=1.1679(6)nm,空间群Pmcm;3种结构中八面体结构单元[TmI₆]的连接方式不同,分别为共顶点、共棱和共顶点同时共棱方式连接.Cs、Rb和K原子的配位数依次下降,分别为10、9和8.Cs₄TmI₆和Rb₄TmI₆的结构属于K₄CdCl₆型,三方晶系,空间群R3 c,Z=6.Cs₄TmI₆:a=1.4516(1)nm,C=1.8292(2)nm,Rb₄TmI₆:a=1.41714(9)nm,c=1.7473(1)nm.     

基于一维双螺旋链的锌配合物的合成与荧光性能

选择配体N,N'-双(3-吡啶)丙二酰胺(3-bpma)、1,4-对苯二乙酸(H₂pda)和硝酸锌在水热条件下,自组装制备了一个基于双螺旋链的三维超分子锌配合物[Zn(3-bpma)(pda)]_n(1),并通过红外光谱、元素分析、热重分析和X射线单晶衍射分析进行了晶体结构表征。 单晶结构分析表明标题锌配合物是正交晶系,Pna21空间群,晶胞参数a=1.62512(11) nm,b=1.15947(8) nm,c=1.19282(8) nm,α=90°,β=90°,γ=90°,V=2.2476(3) nm³,M_r=513.80,D_c=1.518 g/cm³,Z=4,F(000)=1056,R₁=0.0381,wR₂=0.0669。 金属锌离子被两种桥连配体3-bpma和pda连接形成一种一维双螺旋链状结构,相邻的链间进一步通过氢键作用拓展成为三维超分子网络结构。 标题锌配合物具有强荧光发射特性,而且其对不同的有机溶剂分子和金属离子有显著的荧光传感特性,可以作为检测硝基苯的高灵敏性荧光传感材料。 CCDC:1811967     

[Co(aipamp或apamp)(amp)Cl][ZnCl4]两体系中四个几何异构体的合成、结构解析以及量子化学计算

利用单晶X射线衍射解析了[Co(aipamp)(amp)Cl][ZnCl₄] (aipamp=2-[(2-氨基异丙基)氨基甲基]呲啶,amp=2-(氨基甲基)吡啶)体系中两个异构体Ⅱ的结构和[Co(apamp)(amp)Cl][ZnCl₄](apamp=2-[(2-氨基丙基)氨基甲基]呲啶)体系中一异构体Ⅲ的结构.晶体Ⅰ属单斜晶系,空间群P2₁/n,a=1.08028(10) nm,b=1.84843(18) nm,c=1.25582(12) nm,α=90.00°,β=97.150(2)°,γ=90.00°,V=2.4881(4) nm³,D_c=1.620 g·cm^-3,Z=6,F(000)=582,R=0.0361,wR=0.0974,晶胞中含4个配合物阳离子,4个[ZnCl₄]^2-阴离子;晶体Ⅱ 属三斜晶系,空间群 P1,a=0.9957(2) nm,b=1.0207(3) nm,c=1.1478(3) nm,α= 102.584(5)°,β=91.559(5)°,γ=98.462(5)°,V=1.1240(5) nm³,D_c=1.699 g·cm^-3,Z=2,F(000)=580.00,R=0.0449,wR=0.0984,晶胞中含2个配合物阳离子,2个[ZnCl₄]^2-阴离子.晶体Ⅲ属三斜晶系,空间群P1,a=0.82423(7) nm,b=1.7199(8) nm,c=1.36399(1) nm,α=86.6350(10)°,β=81.7140(10)°,γ=67.6230(10)°,V=1.10278(15) nm³,D_c=1.734 g·cm^-3,Z=2,F(000)=582.00,R=0.0332,wR=0.0823,晶胞中含4个配合物阳离子,4个[ZnCl₄]^2-阴离子.三异构体中Co³⁺为六配位,且配合物阳离子中具有C-H…π 结构.用一、二维核磁共振技术解析了第四个配合物在溶液中的结构,论证了该异构体属于[Co(apamp)(amp)Cl][ZnCl₄]体系.4个异构体具有共同的结构特征--分子内C-H…π结构.     

配合物[1-(4′-bromo-2′-fluorobenzyl)pyridinium]2[Ni(mnt)2]和[1-(4′-bromo-2′-fluorobenzyl)pyrazinium]2[Ni(mnt)2](mnt2-=maleonitriledithiolate dianion)的合成及晶体结构

本文报道两个含双(马来二氰基二硫烯)镍(Ⅱ)配合物阴离子的离子对化合物。对阳离子为1-(4′-溴-2′-氟苄基)吡啶 盐时,生成配合物1。晶体数据:三斜晶系,空间P1群,a=0.7086(2)nm,b=1.0968(3)nm,c=1.1775(3)nm,α=69.914(5)°,β=89.495(5)°,γ=74.765(5)°,V=0.8259(4)nm³,Z=1。对阳离子为1-(4′-溴-2′-氟苄基)吡嗪鎓盐时,生成配合物2。晶体数据:单斜晶系,空间群P2₁/n,a=0.71554(17)nm,b=1.4262(3)nm,c=1.6725(4)nm,β=100.396(4)°,V=1.6788(7)nm³,Z=4。两个配合物中,阴离子为拟平面结构,镍原子均位于对称中心。变换对阳离子上的芳环种类对晶体的堆积结构产生影响。     

Crystal Structure of 3- (4-Methoxyphenyl )- 1-methylpyrrolo [2, 1-b] benzothiazole

lINTR0DUCTI0NSincebiologicalandpharmacol0gicalactivitieshavebeenwellknownfornumer-ousheterocyc1icar0matictricyc1es""',muchattenti0nhasbeenpaidtothesynthesisoftheheterocycliccompoundswithnovelringsystem(').Inrecentyears,ourwork-inggr0uphassynthesizedaseries0f1,5-benzothiazepineandl,5-benz0diazepinetri-cyclicderivativesandstudiedtheirstructurest4~10i.l,3-Disubstituded-pyrr0l0F2,1-bjbenz0thiazo1eshavebeenobtainedasmainbyproductsinthecycloadditionreactionofl,5-benzothiazepineswithdichl0rocarbe…     

Synthesis, Crystal Structure and Biological Activity of N-(2,6-Difiuorobenzoyl)-N'-[5-(4-trifiuoromethylphenyl)-1,3,4-thiadiazol-2-yl] ure

The title compound N-(2,6-difluorobenzoyl)-N'-[5-(4-trifluoromethylphenyl)-1,3,4-thiadiazol-2-yl]urea(C17H9F5N4O2S, Mr = 428.34) has been synthesized by the reaction of 2-amino-5-(4-trifluoromethylphenyl)-l,3,4-thiadiazole with 2,6-difluorobenzoyl isocyanate, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/n with a = 10.7316(13), b = 10.5617(13), c = 16.037(2) (A), β =106.408(2)°, V= 1743.6(4) (A)3, Z = 4, Dc = 1.632 g/cm3, μ = 0.260 mm-1, F(000) = 864, the final R = 0.0599 and wR = 0.1420 for 3467 observed reflections with I ＞ 2o(Ⅰ). The urea group, which adopts a planar configuration mediated by the intramolecular N-H…O hydrogen bond, is nearly coplanar with the thiadiazole and 4-trifluoromethylbenzene rings. The title compound was found to exhibit good fungicidal activity against Rhizoctonia solani and Botrytis cinerea.     

Synthesis,Crystal Structure and Biological Activity of N-（2,6-Difluorobenzoyl）-N＇-[5-（4-trifluoromethyl-phenyl）-1,3,4-thiadiazol-2-yl]ure

The title compound N-(2,6-difluorobenzoyl)-N'-[5-(4-trifluoromethylphenyl)-1,3,4-thiadiazol-2-yl]urea(C17H9F5N4O2S,Mr = 428.34) has been synthesized by the reaction of 2-amino-5-(4-trifluoromethylphenyl)-1,3,4-thiadiazole with 2,6-difluorobenzoyl isocyanate,and its crystal structure was determined by single-crystal X-ray diffraction.The crystal belongs to monoclinic,space group P21/n with a = 10.7316(13),b = 10.5617(13),c = 16.037(2) ,β = 106.408(2)°,V = 1743.6(4) 3,Z = 4,Dc = 1.632 g/cm3,μ = 0.260 mm-1,F(000) = 864,the final R = 0.0599 and wR = 0.1420 for 3467 observed reflections with I > 2σ(I).The urea group,which adopts a planar configuration mediated by the intramolecular N-H...O hydrogen bond,is nearly coplanar with the thiadiazole and 4-trifluoromethylbenzene rings.The title compound was found to exhibit good fungicidal activity against Rhizoctonia solani and Botrytis cinerea.     

化合物[2,6-bis(benzo[1,2-d:4,5-d′]diimidazole-2′-yl)pyridine] 的合成、晶体结构和光物理性质

A new tridentate benzimidazole derivative, 2,6-bis (benzo[1,2-d:4,5-d′]diimidazole-2′-yl) -pyridine (Bzdiimpy),was prepared from o-phenylenediamine in five steps with improved methods according to the literature in good yield.The crystal structure was determined by X-ray diffraction analysis. It crystallized in monoclinic, space group P21/c,with a=1.1708(4) nm, b=2.4796(9) nm, c=1.215 9(4) nm,β=114.641(7)°, Z=1, R=0.035 0, wR2=0.0890. The bzdiimp molecule displayed an almost planar structure and formed a zig-zag chain through weak interactions between imidazole-N and [SnCl6]2--Cl. Its electronic absorption and emission spectra were measured and compared with the reported analogue 2,6-bis (benz[1,2-d:4,5-d′]imidazole-2′-yl)-pyridine (Bzp).     

Synthesis and Crystal Structure of N-[1-(4-Chlorophenyl)- 1,4-dihydro-4-oxe-6-methylpyridazine-3-carbonyl]- N''''-benzoylhydrazine

1 INTRODUCTION Pyridazinone derivatives represent one of the most active classes of compounds possessing a wide spectrum of biological activity. It was widely used in pharmaceuticals and agrochemicals[1, 2]. Rohm Haas Company had reported that pyridazinones exhibit useful plant growth regulating effects [3,4]. It was also reported that diacylhydrazines exhibit excellent insecticides [5~7]. In view of these facts, it was contemplated to synthesize compounds con- taining both pyridazinone …     

四氯合钯(Ⅱ)酸双{[4-溴-2，6-二(N，N-二乙基氨基亚甲基)吡啶基]氯化钯(Ⅱ)}的合成及晶体结构

A palladium（Ⅱ） complex, [PdLCl]2· [PdCl4], [L=4-bromo-2,6-bis（N,N-diethylaminomethylene）pyridine], was synthesized and its crystal structure was determined by X-ray analysis. The complex crystallizes in monoclinic system with space group Cc, a=0.845 1（17） nm, b=1.836 5（4） nm, c=2.715 8（5） nm,β=93.99（3）°, V=4.204 8（15） nm^3, Z=4, R,=0.037 7 and wR2=0.076 9. The coordination geometry of the Pd atom in the cation is a slightly distorted square planar, with one pyridyl N and two N atoms of the diethylamine ligand, together with one Cl atom. The dihedral angle between the square planar （N3PdCl） and the pyridyl ring is 10.3（4）°. CCDC： 623421.     

2-[1-(2,6-Dibenzhydryl-4-methylphenylimino)ethyl]-6-[1-(arylimino)ethyl]pyridylcobalt(II) dichlorides: synthesis, characterization and ethylene polymerization behavior

A series of unsymmetrical 2,6-bis(imino)pyridylcobalt(II) complexes, {2-[2,6-(CH(C(6)H(5))(2))(2)-4-Me-C(6)H(2)N==C(CH(3))]-6-(2,6-R(1)(2)-4-R(2)-C(6)H(2)N==CCH(3))-C(5)H(3)NCoCl(2)} where R(1) = Me, Et or (i)Pr, R(2) = H or Me, together with the new symmetrical complex 2,6-[2,6-(CH(C(6)H(5))(2))(2)-4-Me-C(6)H(2)N==C(CH(3))](2)-C(5)H(3)NCoCl(2), were synthesized. All of the compounds were fully characterized by (1)H NMR and IR spectroscopy, as well as by elemental analysis. The molecular structures of Co1 (R(1) = Me, R(2) = H) and Co5 (R(1) = Et, R(2) = Me) were further confirmed by single crystal X-ray diffraction, which indicated that the cobalt centres were penta-coordinate with a pseudo square-pyramidal geometry. Upon treatment with MAO or MMAO, these cobalt pre-catalysts exhibited higher activities than any previously reported cobalt pre-catalysts, with values as high as 4.64 × 10(6) g PE mol(-1)(Co) h(-1) for ethylene polymerization at atmospheric pressure. The polyethylenes obtained were of high molecular weight and narrow molecular weight distribution.     

Synthesis and Crystal Structure of Spiro[1-bromo(S)-4-(R)-hydroxy- 5-oxa-6-oxo-bicyclo[3.1.0]hexane-2,2''-(3''-diethyl-(-(S)-4''-Cl-benzyloxyphosphonyl-4''-(1R,2S,5R)-menthyloxybutyrolactone)]

The title compound, spiro[1-bromo(S)-4-(R)-hydroxy-5-oxa-6-oxo-bicyclo[3.1.0]-hxane-2,2'-(3'-diethyl-α-(S)-4'-Cl-benzyloxyphosphonyl-4'-(1R,2S,5R)-menthyloxybutyrolactone)] has been synthesized via the tandem asymmetric reaction and it crystallizes in a monoclinic system, space group P21 with a = 11.067(3), b = 12.484(2), c = 12.356(2)(A), β = 101.95°,C29H39BrC1O10P, Mr = 693.93, V= 1670.2(6) (A)3, Z= 2, Dc= 1.380 g/cm3, λ(MoKα) = 0.071073nm, μ = 1.410 mm-1, F(000) = 720, the final R = 0.0570 and wR = 0.0758 for 6190 observed reflections with I ＞ 2σ(I). The structure is characterized by the special combination of biologic phosphonyl group and one cyclopropane as well as two butyrolactones. The intermolecular hydrogen bond between O(3)-H(3A)…O(10) in the crystal lattice has been observed.     

Synthesis and Crystal Structure of 1-（4-Fluorophenyl）-2-hexylthiobenzo[4,5]-furo[3,2-d]-1,2,4-triazolo[1,5-a]pyrimidin-5（1H）-one

The crystal structure of the title compound 1-(4-fluorophenyl) -2-hexylthio-benzo [4,5]furo[3,2-d]-1,2,4-triazolo[1,5-a]pyrimidin-5(1H) -one(C23H21FN4O2S,Mr = 436.5) has been prepared and determined by single-crystal X-ray diffraction. The crystal is of monoclinic,space group P21/n with a = 13.9854(3) ,b = 17.2678(4) ,c = 18.1828(5) ,β = 99.364(2) °,V = 4332.58(18) 3,Z = 4,Dc = 1.338,F(000) =1824,μ = 0.185 mm-1,MoKa radiation(λ = 0.71073) ,R = 0.0538 and wR = 0.1162 for 4728 observed reflections with I > 2σ(I) . X-ray diffraction analysis reveals the fused rings of benzo[4,5]furo[3,2-d]-1,2,4-triazolo[1,5-a] pyrimidin-5(1H) -one system are nearly coplanar. The crystal packing is mainly stabilized by weak intermolecular C-H···O hydrogen bond and π-π interactions.