2-吡咯类酰腙的合成、晶体结构及与小牛胸腺DNA的相互作用

以2-吡咯甲酰肼与2,4-二羟基苯甲醛和2-羟基-3-甲氧基苯甲醛经缩合反应合成2,4-二羟基苯甲醛-2-吡咯甲酰腙C₁₂H₁₁N₃O₃(Ⅰ)和2-羟基-3-甲氧基苯甲醛-2-吡咯甲酰腙C₁₃H₁₅N₃O₄(Ⅱ),并利用红外光谱、元素分析、¹H NMR、X射线单晶衍射和热重分析进行表征,结果表明晶体Ⅰ属单斜晶系,空间群为P2₁/c,Z=4,晶胞参数为a=1.2586(4) nm,b=0.8050(3) nm,c=1.1914(4) nm;晶体Ⅱ为正交晶系,空间群为P2₁2₁2₁,Z=4,晶胞参数为a=0.4756(2) nm,b=1.2491(6) nm,c=2.2145(11) nm。 热重结果显示,化合物Ⅰ和Ⅱ最大热分解峰分别出现在267.59和284.79 ℃,表观活化能分别为176.6和122.9 kJ/mol,表明化合物Ⅰ和Ⅱ具有较高的热稳定性。 利用粘度实验和微量热实验研究了化合物Ⅰ和Ⅱ与CT-DNA的相互作用,均显示两种化合物均与CT-DNA发生了插入作用,且相互作用过程放热,焓变值分别为ΔH(Ⅰ)=4.67 kJ/mol和ΔH(Ⅱ)=4.40 kJ/mol。     

配合物Cu(C14H9NO3)(C3H4N2)的合成、晶体结构及性质研究

合成了配合物Cu(C₁₄H₉NO₃)(C₃H₄N₂)[C₁₄H₉NO₃^2- 为N-(2-羧基苯基)-水杨醛亚胺,C₃H₄N₂为咪唑].晶体属正交晶系,空间群Pca2₁,晶胞参数a=0.94453(12)nm,b=1.12278(9)nm,c=2.9123(4)nm,V=3.0885(6)nm³,Mr=370.84,Z=8,最终的偏离因子R=0.036,wR=0.087,GOF=0.975.三齿Schiff碱配体中的二个氧原子、一个氮原子和咪唑的一个氮原子与铜原子配位,形成扭曲的平面正方形结构.通过元素分析,IR,UV,CV和TG表征了配合物的结构.     

有机锡9-芴酮-4-甲酸酯的合成、结构及抗癌活性

合成了3个有机锡9-芴酮-4-甲酸酯:三苯基锡9-芴酮-4-甲酸酯[(C₆H₅)₃Sn(C₁₄H₇O₃)](1)、三环己基锡9-芴酮-4-甲酸酯[(C₆H₁₁)₃Sn(C₁₄H₇O₃)](2)和三(2-甲基-2-苯基丙基)锡9-芴酮-4-甲酸酯[(C₆H₅C(CH₃)₂CH₂)₃Sn(C₁₄H₇O₃)](3)。通过元素分析、红外光谱、核磁共振谱(¹H、¹³C和¹¹⁹Sn)、热重分析进行了表征;用单晶X射线衍射方法测定了化合物的晶体结构,并对其进行了量子化学计算和体外抗...     

一维链状卤化亚铜化合物的溶剂热原位合成、 结构及性质

采用溶剂热原位反应合成了一例具有一维铜卤链结构的化合物(C₁₀H₂₂N₂)₃[Cu₉I₁₄Br](C₁₀H₂₂N₂=N,N'-二乙基三乙烯二胺阳离子). 利用X射线单晶衍射、 元素分析、 粉末X射线衍射及红外光谱等测试手段对化合物进行了表征. 测试结果表明, 化合物属于单斜晶系, C2/c空间群, a=2.6233(5)nm, b=1.6299(3)nm, c=1.6707(3)nm, β=117.31(3)°, V=6.347(2) nm³. 化合物的结构由一维的铜卤链和有机模板剂构成, 其中有机模板剂是通过三乙烯二胺和乙醇烷基化反应得到的有机季铵盐阳离子. 该化合物在室温下表现出较好的光致发光性质.     

(C26H40N2O4)[Ln(NO3)5H2O]的合成及其铕缔合物的晶体结构

合成了4个新型的稀土化合物(C₂₆H₄₀N₂O₄)[Ln(NO₃)₅H₂O](Ln=Pr,Nd,Sm,Eu),采用元素分析和红外光谱表征,用四圆衍射仪测定了其中(C₂₆H₄₀N₂O₄)[Eu(NO₃)₅H₂O]的晶体结构,属三斜晶系,P1空间群,晶胞参数:α=0.9100(4)nm,b=1.3560(3)nm,c=1.6463(4)nm;α=68.62(2)°,β=74.84(3)°,γ=87.50(2)°;Z=2.中心铕离子由5个硝酸根的10个氧原子和1个水分子中的氧原子配位,配位数是11.1,7,10,16-四氧-4,13-二氮杂-N,N'-二苄基环十八烷(N,N'-二苄基穴醚(2,2))未参与配位.     

C4H6O,C4H6S与XF (X＝F,Cl, Br)分子间卤键的电子密度拓扑研究

运用MP2/aug-cc-pVDZ方法对2,5-二氢呋喃, 2,5-二氢噻吩与XF (X＝F, Cl, Br)之间的卤键作用进行了理论研究. 研究发现: C₄H₆O, C₄H₆S与XF之间不仅存在O(S)…XF n型卤键, C＝C双键与XF分子亦可形成π型卤键|对于C₄H₆O与XF之间的n型和π型卤键以及C₄H₆S与XF之间的π型卤键, 卤键键能ΔE、键鞍点处的电子密度ρ(r_c)以及电子给体到受体之间的电子转移数Δq(XF)均按B…F₂＜B…ClF＜B…BrF (B＝C₄H₆O, C₄H₆S)的顺序依次增大|对于卤键键能较大的体系C₄H₆O…BrF(n), C₄H₆O…BrF(π), C₄H₆S…F₂(n), C₄H₆S…ClF(n), C₄H₆S…BrF(n), C₄H₆S…BrF(π), 卤键作用介于离子键和共价键之间|而对于其它的卤键键能较小的体系, 卤键作用为闭壳层静电作用.     

两种具有氢键网络的Ni(Ⅱ)-咪唑配合物的晶体结构和磁性

合成了两种配合物晶体[Ni(im)₆](NO₃)(OH)(H₂O)₄(Ⅰ)和[Ni(im)₄(H₂O)₂][C₆H₄(COO)₂](Ⅱ)(im=C₃H₄N₂).晶体结构测定表明,晶体(Ⅰ)属于六方晶系,空间群P6₃/m,a=0.8985(10)nm,c=2.1002(4)nm,V=1.4685(4)nm₃,Z=2,R=0.043,R_w=0.045.晶体(Ⅱ)属单斜晶系,空间群C2/c,a=2.2207(4)nm,b=0.7665(2)nm,c=1.6043(3)nm,β=120.60(3)°,V=2.3503(9)nm₃,Z=4,R=0.056,R_w=0.079.两种配合物在结构上的突出特点是通过氢键形成了三维无限伸展的氢键电荷传递体系,对分子间电子传递有调节和促进作用,从而对晶体的磁性质产生了一定影响。     

带有吸电子-Cl基团的供体-受体氮化碳的构建及其光催化性能

聚合物氮化碳(C₃N₄)因具有可见光响应特性、良好的化学稳定性、无毒性等优点而成为一类极具吸引力的光催化剂.遗憾的是,由于本征库仑相互作用,C₃N₄中的光生电子和空穴通常以激子的形式存在,导致迁移到表面的光生电子和空穴数量减少,从而降低了光催化活性,因此人们做了大量的研究工作来促进激子解离成自由电子和空穴.D-A体系可以诱导内部电场的产生,从而促进激子解离成自由电子和空穴,因此,构建供体-受体(D-A)体系是一种有效地促进激子解离的方法.然后在内电场作用下,自由电子和空穴也能够更加容易地转移到共聚物表面,从而发生相应的光催化还原和氧化反应.本文选择了2-氨基-4,6-二氯嘧啶(C₄H₃Cl₂N₃)作为单体,与三聚氰胺共聚形成分子内共聚物(CNCl_x)来构建D-A体系.由于分子结构相似,C₄H₃Cl₂N₃与C₃N₃(NH₂)₃分子具有良好的化学相容性.在共聚过程中,C₄H₃Cl₂N₃在219~222℃升华,三聚氰胺在300℃升华,在温度继续升高到550oC的过程中,气相混合物充分混合并发生共聚反应.在共聚过程中,如果C₄H₃Cl₂N₃分子与C₃N₃(NH₂)₃反应,那么三聚氰胺沿着这个方向的聚合将终止,因此吸电子-Cl基团将全部位于共聚分子的末端.相较于体相C₃N₄,CNCl_x样品活性均有所提高,且随着-Cl基团数量的增加,CNCl_x样品活性先提高后降低,其中CNCl_0.15样品活性最高.CNCl_0.15在可见光下的析氢速率是体相C₃N₄的15.3倍,在420 nm处的表观量子效率为13.6%.对RhB,MO和苯酚的降解速率分别为体相C₃N₄的5.82,7.93和9.53倍.构建分子内D-A体系以后,C₃N₄活性提高主要是因为随着末端-Cl基团的增加,材料的吸光能力和激子解离效率提高.而且-Cl基团也可以充当电子的俘获位点,浓度进一步升高会降低电荷转移的效率使活性降低.EIS的奈奎斯特图和i-t曲线结果表明,CNCl_0.15的电弧半径最小,光电流最大,说明其具有最低的电阻和最高的载流子传输效率.紫外光电子能谱测试结果表明,CNCl_x功函数值较小,电子更容易在内部电场的作用下移动到表面,而过量的-Cl基团增加了CNCl_0.2的功函数值,导致CNCl_0.2样品的光催化活性降低.     

三种六氯铈(Ⅳ)酸有机盐的研究

合成了2,6-二甲基-γ-吡喃酮、咪唑和吡啶铈(Ⅳ)的氯化物,化学式为(C₇H₈O₂H)₂CeCl₆、(C₃H₄N₂H)₂CeCl₆和(C₄H₉NH)₄CeCl₈.采用差热、热重分析法比较了上述三种化合物的热稳定性,并配合以电导、红外、紫外光谱等手段进行了结构分析.     

基于2-氨基吡啶的两个簇基超分子化合物的合成、 结构及催化性能

以磷钼酸、 2-氨基吡啶、 五氧化二钒、 氯化锌和氯化镍等为主要原料, 采用水热方法合成了2个簇基超分子化合物[H₃PMo₁₂O₄₀]₂[C₅H₆N₂]₆(1)和[H₂PMo₁₂V₂O₄₂][C₅H₆N₂]₅·3H₂O(2)(C₅H₆N₂=2-氨基吡啶). 通过元素分析、 红外光谱、 紫外-可见光谱、 X射线光电子能谱、 热重分析、 X射线单晶衍射及X射线粉末衍射等手段对化合物进行了结构表征. 结构分析显示, 簇单元不同的2个超分子化合物以各自独特的堆积方式形成三维超分子网络. 利用苯乙烯的环氧化反应研究了2个化合物的催化性能.     

新型氮杂环卡宾银(I)配合物的合成及其晶体结构

以取代苄氯(1a~1c)为起始原料,与咪唑经氮烷基化反应制得苄基咪唑氯盐(2a~2c); 2a~2c与氧化银经原位去质子化反应合成了3种新型的氮杂环卡宾银配合物--(NHC)AgCl［NHC: 1,3-二(4-甲氧基苄基)咪唑-2-亚基(3a), 1,3-二(3-甲氧基苄基)咪唑-2-亚基(3b)］和［(NHC)AgCl]₂［NHC=1,3-二(4-氯苄基)咪唑-2-亚基(3c)］,其结构经¹H NMR, ¹³C NMR, IR,元素分析和X-射线单晶衍射表征。3a~3c单晶结构均属单斜晶系,3a为P2₁/n空间群,3b和3c为P2₁/c空间群,3a和3b为单核银配合物,3c为双核银配合物。     

6,7-二氧亚甲基-3-氮杂(硫杂)-1(2H,4H)吖啶酮及其衍生物的合成

氮杂吖啶酮;硫杂吖啶酮;杂环化合物;6;7-二氧亚甲基-3-氮杂(硫杂)-1(2H;4H)吖啶酮及其衍生物的合成     

Oxygen atom transfer from nitrogenous ReVO reagents to diphosphines and subsequent transformations. Rhenium(III) products and reaction models

The concerned diphosphines are Ph2P(CH2)nPPh2 (1), abbreviated PnP, and the ReVO reagents are ReOCl3L (2) and ReOCl3L' (3), where L and L' are the azopyridine and pyridine-imine ligands p-ClC6H4N=NC5H4N and p-MeC6H4N=CHC5H4N, respectively. One atom transfer from 2 to 1 has afforded Re(OPnP)Cl3L (4a, n = 1; 4b, n = 2; 4c, n = 3). Of these 4b and 4c are stable, but 4a undergoes spontaneous isomerization to Re(PlPO)Cl3L (5) in solution. Two-atom transfer studied with both 2 and 3 has afforded binuclear LCl3Re(OPnPO)ReCl3L (8a, n = 2; 8b, n = 3) and L'Cl3Re(OPnPO)ReCl3L' (9a, n = 2; 9b, n = 3) for n = 2, 3 and mononuclear Re(OP1PO)Cl3L (11) and Re(OP1PO)Cl3L' (12) for n = 1. The mixed system L'Cl3Re(OP2PO)ReCl3L (10) has been prepared from 3 and 4b. The complex Re(PPh3)Cl3L (7a) is furnished by the reaction of Re(OPPh3)Cl3L (6a) or 4b or 11 with PPh3. The species have been characterized with the help of spectral, electrochemical, and X-ray structural data. All the complexes have mer geometry except 5 and 7a, which have fac geometry. The latter is best suited for concurrent Re-N and Re-P back-bonding. Variable-temperature rate data of the reaction 4a-->5 are consistent with an intramolecular strongly associative transition state (delta S++, -22.6 eu) in which the dangling phosphine function lies close to the metal. Two-atom transfer to P1P is believed to proceed via a transient binuclear intermediate which undergoes cleavage at one end due to steric crowding, affording 11 and 12. Crystal data for the complexes are as follows: 5.1.5 C6H6, empirical formula C45H39Cl4N3OP2Re, crystal system triclinic, space group P1, a = 10.034(2) A, b = 10.737(2) A, c = 20.357(4) A, alpha = 89.38(3) degrees, beta = 87.79(3) degrees, gamma = 80.22(3) degrees, V = 2159.7(7) A3, Z = 2; 7a.CH2Cl2, empirical formula C30H25Cl6N3PRe, crystal system monoclinic, space group P2(1)/n, a = 11.695(6) A, b = 17.745(7) A, c = 15.459(9) A, beta = 100.94(5) degrees, V = 3150(3) A3, Z = 4; 9a, empirical formula C52H48Cl6N4O2P2Re2, crystal system monoclinic, space group C2/c, a = 19.769(12) A, b = 12.864(6) A, c = 22.20(2) A, beta = 101.76(6) degrees, V = 5530(6) A3, Z = 4; 11, empirical formula C36H30Cl4N3O2P2Re, crystal system monoclinic, space group I2/a, a = 16.866(6) A, b = 12.583(6) A, c = 34.78(2) A, beta = 99.22(4) degrees, V = 7285(7) A3, Z = 8.     

新型6-氯-4(3H)-喹唑啉酮类Schiff碱的合成及其抑菌活性

以6-氯邻氨基苯甲酸为起始原料,与醋酐酰化关环制得6-氯-2-甲基噁嗪-4-酮(1);1在80%水合肼中回流反应制得6-氯-2-甲基-3-氨基-4(3H)-喹唑啉酮(2);2与羟基芳醛反应合成了4种新型的6-氯-4(3H)-喹唑啉酮类Schiff碱(4a~4d),其结构经1H NMR,13C NMR,IR和元素分析表征。采用琼脂扩散法研究了4a~4d对金黄色葡萄球菌(A)、大肠杆菌(B)和枯草杆菌(C)的抑制活性。结果表明:用药浓度为300 mg·m L~(-1)时,4a~4d对A~C均有一定的抑制活性,其中6-氯-2-甲基-3-(5-甲基-2-羟基苯亚甲氨基)-4(3H)-喹唑啉酮(4c)抑菌活性最强,对A~C的抑菌圈直径分别为8.8 mm,11.9 mm和9.6 mm。     

吡嗪类碳酰肼化合物与CT-DNA相互作用及体外抑菌

以5-氯吡嗪-2-羧酸甲酯和水合肼为原料,经亲核取代和脱水缩合反应合成了3种新型吡嗪类碳酰肼化合物C13H14N6O(a)、C13H14N6O2(b)和C12H12N6O2(c)。采用元素分析与核磁共振氢谱对化合物a~c进行了表征,结果表明合成的产物即为目标化合物。通过溶剂挥发法培养得到了化合物a的单晶并利用X-射线单晶衍射测定化合物a的晶体结构为单斜晶系。根据紫外-可见光谱可知,化合物a~c均以插入模式与CT-DNA作用。利用微量热实验测定了化合物a~c与CT-DNA的相互作用,发现反应过程放热,热效应ΔH依次为-5.77×103、 -5.50×103和-5.96×103 kJ·moL-1,反应时间均小于40 min。通过分子对接模拟计算明确了化合物a和b与DNA的具体结合位点包括A链DC4和DG5以及B链DC4、 DG5和DA6,化合物c与DNA的具体结合位点包括A链DC4和DG5以及B链DC4和DG5。采用牛津杯法测定了化合物a~c对枯草芽孢杆菌、金黄色葡萄球菌、铜绿假单胞菌以及大肠杆菌四种细菌的抑菌活性,结果表明化合物a~c均对铜绿假单胞菌表现出优于阳性对照组四环素的抑菌活性。     

Eight- and 16-membered cyanuric-sulfanuric ring systems: C2N4S2-->C2N3S ring contraction

Eight- and 16-membered cyanuric-sulfanuric ring systems of the type Ar2C2N4S2(O)2Ar'2 (3a, Ar = 4-BrC6H4, Ar' = Ph; 3b, Ar = 4-CF3C6H4, Ar' = Ph; 3c, Ar = 4-CF3C6H4, Ar' = 4-CH3C6H4) and Ar4C4N8S4(O)4Ar'4 (4b, Ar = 4-CF3C6H4, Ar' = Ph; 4c, Ar = 4-CH3C6H4, Ar' = Ph; 4d, Ar = 4-CF3C6H4, Ar' = 4-CH3C6H4), respectively, were prepared in good yields by the reaction of the corresponding sulfur(IV) systems with m-chloroperbenzoic acid. The X-ray structures of 3b, 3c.C7H14, 4b.CH2Cl2, 4c, and the S(IV) system Ar4C4N8S4Ar'4 (2c, Ar = 4-CH3C6H4, Ar' = Ph) were determined. Upon oxidation the two oxygen atoms in 3b and 3c.C7H14 adopt endo positions leading to a twist boat conformation for the C2N4S2 ring. The 16-membered C4N8S4 rings in 4b and 4c retain a cradle conformation upon oxidation. The S-N bond distances are ca. 0.06 A shorter in all the S(VI) systems compared to those in the corresponding S(IV) rings. The thermolysis of 3b at ca. 220 degrees C occurs primarily via loss of a sulfanuric group, NS(O)Ph, to give the six-membered ring (4-CF3C6H4)2C2N3S(O)Ph (6). The structure of 6 was confirmed by X-ray crystallography. Crystal data: 2c, triclinic, space group P1 with a = 13.917(2) A, b = 15.610(4) A, c = 13.491(3) A, alpha = 95.77(2) degrees, beta = 114.82(1) degrees, gamma = 76.21(2) degrees, V = 2583(1) A3, and Z = 2; 3b, monoclinic, space group P2(1)/a with a = 7.316(2) A, b = 29.508(5) A, c = 12.910(2) A, beta = 101.30(2) degrees, V = 2733(1) A3, and Z = 4; 3c.C7H14, triclinic, space group P1 with a = 12.849(4) A, b = 12.863(4) A, c = 12.610(7) A, alpha = 110.61(3) degrees, beta = 105.77(3) degrees, gamma = 62.77(2) degrees, V = 1719(1) A3, and Z = 2; 4b.CH2Cl2, triclinic, space group P1 with a = 12.647(3) A, b = 19.137(3) A, c = 12.550(2) A, alpha = 105.765(11) degrees, beta = 93.610(15) degrees, gamma = 88.877(16) degrees, V = 2917.2(9) A3, and Z = 2; 4c, orthorhombic, space group Pba2 with a = 22.657(2) A, b = 10.570(2) A, c = 10.664(3) A, alpha = beta = gamma = 90 degrees, V = 2554(1) A3, and Z = 2; 6, triclinic, space group P1 with a = 7.4667(8) A, b = 11.3406(12) A, c = 13.5470(14) A, alpha = 108.000(2) degrees, beta = 105.796(2) degrees, gamma = 94.300(2) degrees, V = 1033.8(2) A3, and Z = 2.     

Synthesis and characterization of zirconogermanates

Six new zirconogermanates have been prepared under hydrothermal conditions using amines as bases. There are four new structure types (ASU-n) with a common motif of ZrGe(5). ASU-23 is a layered structure: ZrGe(3)O(8)(OH)F.[C(10)H(26)N(4)].H(2)O, space group P2(1)/n, a = 6.7957(8) A, b = 12.700(1) A, c = 24.293(3) A, beta = 97.936(2) degrees, V = 2076.4(4) A(3). ASU-24 is a pillared layered structure: Zr(3)Ge(6)O(18)(OH(2),F)(4)F(2).[C(6)H(18)N(2)].[C(6)H(17)N(2)](2).2H(2)O, space group P2(1)/n, a = 7.4249(3) A, b = 25.198(1) A, c = 11.3483(5) A, beta = 90.995(1) degrees, V = 2122.9(2) A(3). This material has the lowest framework density (FD) of any oxide material that we are aware of (FD = 8.48 metal atoms/nm(3)). Two other materials form three-dimensional open-frameworks, ASU-25: ZrGe(3)O(9).[C(3)H(12)N(2)], space group P112(1)/a, a = 13.1994(4) A, b = 7.6828(2) A, c = 11.2373(3) A, gamma = 91.233(3) degrees, V = 1139.29(5) A(3). The other is ASU-26: ZrGe(3)O(9).[C(2)H(10)N(2)], space group Pn, a = 13.7611(3) A, b = 7.7294(2) A, c = 11.2331(3) A, beta = 104.793(1) degrees, V = 1155.21(4) A(3). ASU-25 is related to the mineral umbite K(2)ZrSi(3)O(9).H(2)O. The germanium equivalent has been prepared through the inorganic route: K(2)ZrGe(3)O(9).H(2)O, space group P2(1)2(1)2(1), a = 13.6432(6) A, b = 7.4256(3) A, c = 10.3973(4) A, V = 1053.33(8) A(3). The structural relationships between ASU-25 and its inorganic counterpart are described. The thermal decomposition of the germanium umbite generated the cyclic trigermanate K(2)ZrGe(3)O(9), analogue of the mineral wadeite, crystallizing in the orthorhombic system, a = 7.076 A, b = 12.123 A, c = 10.451 A, V = 904.5 A(3).     

Polynuclear bismuth-oxo clusters: insight into the formation process of a metal oxide

The reaction of the bismuth silanolates [Bi(OSiR2R')3] (R = R' = Me, Et, iPr; R = Me, R' = tBu) with water has been studied. Partial hydrolysis gave polynuclear bismuth-oxo clusters whereas amorphous bismuth-oxo(hydroxy) silanolates were obtained when an excess of water was used in the hydrolysis reaction. The metathesis reaction of BiCl3 with NaOSiMe3 provided mixtures of heterobimetallic silanolates. The molecular structures of [Bi18Na4O20(OSiMe3)18] (2), [Bi33NaO38(OSiMe3)24].3 C7H8 (3.3 C7H8), [Bi50Na2O64(OH)2(OSiMe3)22].2 C7H8.2H2O (4.2 C7H8.2 H2O), [Bi4O2(OSiEt3)8] (5), [Bi9O7(OSiMe3)13].0.5 C7H8 (6. 0.5C7H8), [Bi18O18(OSiMe3)18)].2C7H8 (7. 2C7H8) and [Bi20O18(OSiMe3)24].3C7H8 (8.3C7H8) are presented and compared with the solid-state structures of [Bi22O26(OSiMe2tBu)14] (9) and beta-Bi2O3. Compound 2 crystallises in the triclinic space group P1 with the lattice constants a = 17.0337(9), b = 19.5750(14), c = 26.6799(16) A, alpha = 72.691(4), beta = 73.113(4) and gamma = 70.985(4) degrees ; compound 3.3C7H8 crystallises in the monoclinic space group P2(1)/n with the lattice constants a = 20.488(4), b = 22.539(5), c = 26.154(5) A and beta = 100.79(3) degrees ; compound 4.2C7H82 H2O crystallises in the monoclinic space group P2(1)/n with the lattice constants a = 20.0518(12), b = 24.1010(15), c = 27.4976(14) A and beta = 103.973(3) degrees ; compound 5 crystallises in the monoclinic space group P2(1)/c with the lattice constants a = 25.256(5), b = 15.372(3), c = 21.306(4) A and beta = 113.96(3) degrees ; compound 6.0.5C7H8 crystallises in the triclinic space group P1 with the lattice constants a = 15.1916(9), b = 15.2439(13), c = 22.487(5) A, alpha = 79.686(3), beta = 74.540(5) and gamma = 66.020(4) degrees ; compound 7.2C7H8 crystallises in the triclinic space group P1 with the lattice constants a = 14.8295(12), b = 16.1523(13), c = 18.4166(17) A, alpha = 75.960(4), beta = 79.112(4) and gamma = 63.789(4) degrees ; and compound 8.3C7H8 crystallises in the triclinic space group P1 with the lattice constants a = 17.2915(14), b = 18.383(2), c = 18.4014(18) A, alpha = 95.120(5), beta = 115.995(5) and gamma = 106.813(5) degrees . The molecular structures of the bismuth-rich compounds are related to the CaF2-type structure. Formally, the hexanuclear [Bi6O8]2+ fragment might be described as the central building unit, which is composed of bismuth atoms placed at the vertices of an octahedron and oxygen atoms capping the trigonal faces. Depending on the reaction conditions and the identity of R, the thermal decomposition of the hydrolysis products [Bi(n)O(l)(OH)(m-)(OSiR3)(3n-(2l-m))] gives alpha-Bi2O3, beta-Bi2O3, Bi12SiO20 or Bi4Si3O12.     

新型氮杂异香豆素化合物的合成

以4-氯烟酸和芳基乙腈为原料,经取代和环合反应合成了3个新型的氮杂异香豆素化合物（3a~3c）,收率32.1%~89.0%,其结构经¹H NMR, IR, ESI-MS和元素分析表征。用X-单晶衍射研究了3a的亚甲基衍生物（4a）的晶体结构。4a(CCDC: 935 919)属三斜晶系,空间群P ī, 晶胞参数a=6.881(2) , b=9.768(2) , c=11.809(2) , β=104.125(10)°, V=732.1³, Dc=1.331 mg·cm^-3 , Z=2, F(000)=308, μ=0.090 mm^-1。并对环合反应机理进行了研究。     

Syntheses, Spectroscopic Properties and Crystal Structures of （2-Cl-C6H4CH2）3SnS2CN（C5H10） and （2-Cl-C6H4CH2）3SnS2CN（C4H9N）

1 INTRODUCTION The chemistry of organotin(IV) complexes was extensively studied due to their biological activity and coordination chemistry[1～7]. More recently, phar- maceutical properties of alkyltin(IV) complexes with dithiocarbamate ligands have bee…