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1.
用X射线晶体结构分析法测定了氯代羟基六氢茚二酮(1)和环氧十氢萘二酮(2)的晶体结构和分子构型.化合物1属正交晶系,空间群为Pbca,晶胞参数α=10.439(1),b=19.950(2),c=9.455(1)A,Z=8;化合物2属单斜晶系,空间群为P2_1/c,晶胞参数α=8.355(2),b=9.221(2),c=25.801(4)A,β=294.19(1)°,Z=8.在RASA-IIS型四圆衍射仪上收集了这两个化合物的衍射数据,用直接法解晶体结构,经块对角矩阵最小二乘修正,对化合物1的1810个独立的可观察反射,R=0.043;对化合物2的1804个独立的可观察反射,R=0.064.化合物l带有α-Cl,β-CH_3和β-OH.由此推断环氧六氢茚二酮(3)的分子构型带有β-CH_3和β-环氧.化合物2中的甲基和环氧基均为β构型,与3相似.因此Danishefsky等由核磁共振所推断的关于2的分子构型中的α环氧应校正为β环氧.  相似文献   

2.
郝亚暾  杨媛  杨云霞  李奇 《化学学报》2009,67(11):1177-1181
合成了2,2’-二(4-羟基苯基)丙烷为主体分子的四丁基铵包合物, [(n-C4H9)4N]+•[(C15H15O2)2H]-, 并通过单晶X射线衍射法对其进行了晶体结构测定, 发现该包合物的晶体存在两种同质异晶体. 结果表明, 晶型1属单斜晶系, C2/c空间群, 晶胞参数a=2.8199(2) nm, b=0.92730(8) nm, c=2.1450(3) nm, β=130.050(1)°, Z=4, R1=0.0771, wR2=0.2452; 晶型2属三斜晶系, P`1空间群, 晶胞参数a=1.0895(1) nm, b=1.2331(2) nm, c=1.7244(2) nm, α=108.137(2)°, β=94.458(2)°, γ=100.172(2)°, Z=2, R1=0.0697, wR2=0.2176. 晶型1中2,2’-二(4-羟基苯基)丙烷阴离子的氢键链构成管道式主体晶格, 正四丁基铵阳离子被包合在这些管道中; 晶型2中2个独立的2,2’-二(4-羟基苯基)丙烷阴离子分别形成氢键主体层, 它们交替排列并与夹在其间的正四丁基铵阳离子形成类三明治层状包合物.  相似文献   

3.
聚丙烯合金PP-c的晶相结构及形态   总被引:1,自引:0,他引:1  
用偏光显微镜和广角X射线衍射研究了聚丙烯合金PP c的结晶形态.发现PP -c的晶相结构中不仅存在α-晶型聚丙烯(α- PP ) ,也存在着β-晶型聚丙烯(β-PP) .计算了不同乙烯含量PP c的结晶度和β- PP含量.表明随着乙烯含量的增加,β- PP的含量增加,而PP- c的结晶度下降.通过与同等熔融结晶条件下等规聚丙烯(iPP)的结晶形态相比较,发现乙烯组分含量的增加,改变了球晶的生长状况,降低了PP- c晶相的晶体完整性.  相似文献   

4.
用X射线晶体结构分析法测定了氯代羟基六氢茚二酮(1)和环氧十氢萘二酮(2)的晶体结构和分子构型。化合物1属正交晶系,空间群为Pbca,晶胞参数a=10.439(1),b=19.950(2),c=9.455(1)A,Z=8;化合物2属单斜晶系,空间群为P2~1/c,晶胞参数a=8.355(2),b=9.221(2),c=25.801(4)A,β=94.19(1)`,Z=8。在RASA-IIS型四圆衍射仪上收集了这两个化合物的衍射数据,用直接法解晶体结构,经块对角矩阵最小二乘修正,对化合物1的1810个独立的可观察反射,R=0.043;对化合物2的1804个独立的可观察反射,R=0.064。化合物1带有a-Cl,β-CH~3和β-OH。由此推断环氧六氢茚二酮(3)的分子构型带有β-CH~3和β-环氧。化合物2中的甲基和环氧基均为β构型,与3相似,因此Danishefsky等由核磁共振所推断的关于2的分子构型中的α环氧应校正为β环氧。  相似文献   

5.
用小角X-射线散射法(SAXS),广角X-射线衍射法(WXAD)和差示扫描量热法(DSC)对由N-催化剂催化聚合的聚丙烯结晶行为进行探讨。发现这种聚丙烯结晶中有β晶型存在,且其含量随结晶时间增加而增加随结晶温度升高而降低;β晶含量增加,聚合物的长周期也会增加,β晶对长周期的影响比α晶更大。乙烯共聚改性后的聚丙烯因分子链规整性下降而阻止了β晶的形成。在熔融状态下结晶时,β晶的形成要求聚丙烯的分子链具有更高的规整性。这些实验结果均从分子链段结晶机理得到了解释。  相似文献   

6.
成核剂含量对β晶相聚丙烯结晶与熔融行为的影响   总被引:13,自引:2,他引:13  
用DSC研究了β成核剂含量对β聚丙烯在等温与非等温结晶条件下的结晶与熔融行为的影响,发现当成核剂含量为0.005%时,结晶焓△H_c、β晶的熔融焓△H_(mβ)及熔点T_(mβ)均为最大,而α晶的相对含量最小.广角X-衍射数据表明,成核剂含量高的试样的(301)衍射峰的相对强度下降,反映分子链排列的纵向有序性降低.根据聚丙烯分子在β成核剂上附生结晶的成核机理解释了上述结果.  相似文献   

7.
以粉末X射线衍射技术(PXRD)表征有机物晶体结构为目的,选取我国第1个全新药物青蒿素(Artemisinin)验证粉晶解析有机物晶体结构方法的合理性。粉晶解析结果为正交晶系,P212121空间群,a=23.98223±0.01624,b=9.42480±0.00645,c=6.34589±0.00439,α=β=γ=90°,Z=4,V=1434.693;单晶解析结果为正交晶系,P212121空间群,a=23.9564(9),b=9.3224(5),c=6.3205(3),α=β=γ=90°,P212121,Z=4,V=1411.55(17)3;两者所确定分子非氢结构键长、键角、二面角的相关系数分别为0.9921、0.9833和0.9997,晶胞参数基本吻合,分子构型相似。结果表明,粉晶X射线衍射技术可以求得较为准确的青蒿素晶胞参数及晶胞内分子构型。  相似文献   

8.
用单晶X射线衍射分析方法测得1,4-二苯氧基苯(Ⅰ)和1,4-双(4-甲氧基苯氧基)苯(Ⅱ)的晶体结构。它们的晶胞参数分别为:(Ⅰ)α=5.876(2),b=7.832(2),c=15.455(6),β=95.33(3)°;空间群为P2_1/c,Z=2。(Ⅱ)α=6.017(1),b=7.577(1),c=36.404(5);空间群为Pcab,Z=4.(Ⅰ),(Ⅱ)的分子构象、键长和键角数据表明氧桥两边的苯环的共轭极化效应不能贯通,而苯氧基只是分子中的一个独立片断。从而也阐明了此类聚苯醚体系的电子吸收光谱的同系直线斜率小的原因。  相似文献   

9.
用恒电流电化学结晶法合成了一种新的基于BEDT-TTF的电荷转移盐α′-(BEDT-TTF)2C6H4(SO3)2[BEDT-TTF=双亚乙基二硫四硫富瓦烯,C6H4(SO3)2 2 -=对苯二磺酸根].通过四圆X射线衍射方法测定了α′@(BEDT-TTF)2C6H4-(SO3)2的结构.晶体属于单斜晶系,P2/n空间群;晶胞参数:α=0.77937(17)nm,b=0.66989(11)nm,c=3.4422(7)nm,β=91.135(12)°,V=1.7968(6)nm3.该晶体中BEDT-TTF+自由基沿α轴方向形成具有二聚体结构的交错排列型柱状堆积,沿b轴方向由肩并肩强分子间相互作用形成一维分子链.电荷补偿阴离子C6H4(SO3)2 2 -则在α方向存在较强的作用.沿c轴方向,BEDT-TTF+自由基层和阴离子层交替排列形成夹心式结构.α′-(BEDT-TTF)2C6H4-(SO3)2在ab面的某方向的室温电导率为0.5913 Q-1@m-1,电阻率-温度测定曲线表明它具有半导体导电行为.在150K附近,晶体发生了某种相变.  相似文献   

10.
β晶型聚丙烯的力学性质   总被引:2,自引:0,他引:2  
研究了主要含β晶型的聚丙烯在不同温度下的应力-应变性质,并与同一商品牌号得到的α晶型聚丙烯作了对比。发现,β晶型试样的屈服强度低于α晶型,而抗冲击强度则比α晶型试样高1—2倍。结合X射线衍射法对β晶型试样在拉伸过程中发生的晶型转变的研究及形变的分子机制解释了二种晶型试样在力学性质上的差异。  相似文献   

11.
1 INTRODUCTION4,4' bipyridine( bipy) is a good candidate for building open framework struc ture because of their rodlike rigidity and length.Framework structures formed bytransition metalsbridged by bipy vary with metaland anion.The structures of Zn bipy system include interpenetrating square grid sheets〔 Zn( bipy) 2 ( H2 O) 2 〕Si F6〔1〕,two dimensionallayer〔 Zn( bipy) ( H2 O) 4 〕( NO3) 2 · bipy〔2〕,〔 Zn( bipy) ( H2 O) 4 〕 ( NO3) 2 · 2 bipy· 3 H2 O〔2〕 and〔 Zn( bipy)…  相似文献   

12.
The surface reaction of isotactic and syndiotactic polypropylene (I-PP and S-PP) films with ozone was studied with FT-IR spectroscopy with differential scanning calorimetry (DSC) and making use of 2,2,4-trimethylpentane as a model compound of PP chain segment. I-PP and S-PP were found reactive toward ozone, and it was found that I-PP being more crystalline than S-PP, reacts more slowly with O3. In fact, the pseudo first rate constant of I-PP with ozone was k’I-PP = 8.0 × 10?6 s?1 while that of S-PP with ozone k’S-PP = 1.3 × 10?5 s?1. However, the DSC study has shown that the ozone attack on I-PP or S-PP films is not selective and simultaneously destroys the amorphous and the crystalline phases. The ozone treated I-PP and S-PP films are much less resistant to the combined thermal and oxidative degradation reaction than the unexposed films. Thus, ozone is a naturally occurring pollutant at the soil level which accelerates the ageing of I-PP and S-PP materials.  相似文献   

13.
The molecular conformation and the crystal structure of α-form poly-p-xylylene has been determined by x-ray diffraction. The polymer has a monoclinic unit cell with a = 5.92, b = 10.64, c (fiber axis) = 6.55 Å, and β = 134.7°. Two chains pass through the unit cell, and the space groups is C2/m. The packing fraction is 0.705. One monomer unit makes up the fiber identity period and the internal rotation angles are 0° and 90° for the ? CH2? CH2? and ? CH2? ?? bonds, respectively. All benzene rings are in parallel orientation, perpendicular to the ac plane.  相似文献   

14.
Propene-hexene copolymers crystallize in a new polymorphic form of isotactic polypropylene when the concentration of hexene is higher than nearly 10-15 mol %. The hexene units are included in the crystals, inducing an increase of density that allows crystallization of 3-fold helical chains in a trigonal unit cell according to the space group R3c or Rc, where the helical symmetry of the chains is maintained in the crystal lattice. The structure of this new form is similar to those of isotactic polybutene and polystyrene and does not crystallize in polypropylene homopolymer because it would have too low density. The crystal structure of isotactic polypropylene is therefore no longer an exception to the principles of polymer crystallography, but the new structure represents the fulfillment of these principles and indicates that the packing of polymer molecules is mainly driven by density.  相似文献   

15.
The crystal of the title compound (C10H18N2O9SZn Mr= 407. 69) belongs to the hexagonal system, space group P65 with cell parameters: a= 11. 411(2), c=20. 908(4) A, V=2357.7(7)A 3, Z=6, Dc=1. 723g/cm3, F(000)=1260,μ(MoKα) =1. 743mm-1. The final R and wR factors are 0. 072 and 0. 178 respectively for 1335 observed reflections. In the structure, zinc ions are bridged by 4,4'-bipyridine to form infinite chains. The sheets containing parallel chains stack along a 65 screw axis to give a helical staircase motif. The helical structure is mainly controlled by the hydrogen bonds.  相似文献   

16.
A novel two-dimensional layered vanadate complex 1 [Ni(phen)H2O][V2O6] has been hydrothermally synthesized and characterized by elemental analyses, i.r., x.p.s., t.g. and single crystal X-ray diffraction. The single crystal X-ray diffraction analysis reveals that compound 1 consists of the chains covalently linked by [Ni(phen)H2O]2+ subunits to form two-dimensional layered polyoxovanadate. It is interesting that the compound 1 consists of left-handed and right-handed helical chains, which are further interconnected to produce the double helical chains. The adjacent two-dimensional layers interact with each other via extensive hydrogen bonds and π–π stacking interactions to form a three-dimensional supramolecular framework.  相似文献   

17.
Packing energy calculations for isotactic polypropylene chains have been performed with the purpose: (a) to predict the most stable kind of monoclinic lattice for the α-modification; (b) to contribute to the understanding of the structural disorder which is commonly found in the α-modification; (c) to evaluate the order of magnitude of the differences in energies among the three modifications (α, β, γ) experimentally observed. The results for the α-form show that the best packing of the chains is achievable for the ordered P21/c space group, while more or less disordered structures may exist, which only slightly differ in energy from the most stable structure. In connection with point (c), our results are in agreement with the possibility of polymorphism in isotactic polypropylene.  相似文献   

18.
The thermal transition behavior of poly(bis(p-fluorophenoxy)phosphazene) was studied as a representative aryloxy-substituted poly(organophosphazene) using X-ray diffraction, differential thermal analysis and density measurements. The crystal structure of-form contained in as-cast film had marked paracrystalline disorder. The crystal phase transformed into the mesophase atT(1) (110 140 °C). The structure of the-form observed in the mesophase was a representative hexagonal-packing of macromolecular chains which rotate around the chain axes. When the mesophase was cooled to room temperature, a more ordered crystal phase of the-form could appear. The most ordered crystal structure of the-form has a monoclinic unit cell with the following lattice parameters: a=18.9, b=13.2, c=4.90 Å, and=77°. The chain conformation is nearly planar cis-trans, which has been observed commonly in poly(organophosphazenes). The macroscopic deformation of the film sample was also examined, taking into account the microscopic deformation of the lamellar crystal due to the crystal-mesophase transition.  相似文献   

19.
Polymorphic behavior and γ-ray-initiated postpolymerization of the even-numbered long-chain Methacrylates (C18-C12) have been investigated. Phase transition behaviors of octadecyl, hexadecyl, tetradecyl, and dodecyl methacrylates are respectively, which become simpler with shortening of the chain length. The methacrylate monomers with sufficiently long hydrocarbon chains, such as octadecyl and hexadecyl, can be polymerized rapidly in the α-form crystal (hexagonal packing) by a fully two-dimensional mechanism, whereas in the β-form crystal (triclinic packing), polymerization can hardly occur. In the case of dodecyl methacrylate, however, an accelerated polymerization in the β form occurs after an induction period of several hours and the resultant polymer is gel-like. This can be interpreted by the propagation reaction across the polymer chain already formed. It has been found that the solid-state post-polymerization of n-alkyl methacrylates is affected by the chain length through the packing mode of the monomer molecules and also by the aggregation state of side chains in the resultant comblike polymer.  相似文献   

20.
醚类会被广泛用来改性Ziegler-Natta催化剂,如著名的Solvay型催化剂就是用异戊醚处理β-TiCl_3,国内研制的所谓络合Ⅰ型,或络合Ⅱ型催化剂则是用异戊醚或正丁醚作为络合剂。乙醚与四氯化钛的反应物对3TiCl_3·AlCl_3催化剂有显著的改进,给电子体醚可使铝在催化剂表面富集。因而研究醚与四氯化钛或三氯化钛络合物的结构是一个基本的问题。已知四氯化钛和醚可生成多种络合物,但其分子结构及晶体结构测定甚少,本  相似文献   

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