1,2-二甲基-3-吲哚甲叉(异丙叉)丁二酸酐(1)和1,2-二甲基-3-吲哚乙叉(异丙叉)丁二酸酐(2)的晶体结构

The crystal structures of 1,2-dimethyl-3-indolylmethylidene succinic fulgide anhydride (1) and 1,2-dimethyl-3-indolylethylidene succinic fulgide anhydride(2) were determined by singe crystal X-ray diffraction analysis. The crystal data are C_(18)H_(17)NO_3(1), orthogonal space group Pbca, with a=1.0084(3) nm, b=1.3966(4) nm, c=2.0945(6) nm, V=2.9498(15) nm, Z=8; C_(19)H_(19)NO_3 (2), orthogonal space group Pbca, with a=0.7988(3) nm, b=2.5782(10) nm, c=1.5664(5) nm, V=3.2259(22) nm, Z=8. R values are 0. 047 for (1) and 0.059 for (2) respectively.The photochemical properties of (1) and (2) were reported. Compound (1) is nonphotochromic, compound (2) changed from pale yellow to blue or green on irradiation at 365 nm or on exposure to indoor UV light either in crystal state or in solution (liquid or rigid plastic matrix).The differences in photochromic properties of compound (1) and (2) were discussed.     

1-甲基-3-吲哚甲叉(异丙叉)琥珀酸酐(I)和1-甲基-3-吲哚乙叉(异丙叉)琥珀酸酐(II)的晶体结构

The crystal structures of the title compound (Ⅰ) and (Ⅱ) have been determined by X-ray diffraction. Crystal data are: C_(17)H_(15)NO_3(Ⅰ), triclinic, α=0.7308(2) nm, b=0.8845(3) nm, c=1.1323(3) nm, α=100.03(2)°, β=104.81(2)°, γ=97.20(2)°, V=0.6856(3) nm, Z=2, R=0.047 and C_(18)H_(17)NO_3(Ⅱ), monoclinic, a=1.1006(3) nm, b=1.1172(2) nm, c=1.4046(3) nm, β=102.78(2)°, V=1.5337(6) nm, Z=4, R=0.055. The molecular conformation is cis form for compound Ⅰ and trans form for compound(Ⅱ).     

1,2,5—三甲基吡咯—3—甲叉（异丙叉）—丁二酸酐的合成与晶体结构

近年来,在光致变色材料研究领域中,人们的注意力从无机材料转移到有机材料。O-杂环俘精酸酐衍生物就是其中一类,但N-杂环俘精酸酐还没有引起人们注意。N-杂环俘精酸酐也能象O-杂环俘精酸酐一样在紫外光照射下环合成双氢吲哚的衍生物,N的给电子能力比O强,因此其双氢吲哚衍生物的吸收波长会出现红移。O-杂环俘精酸酐存     

1-甲基-3-吲哚甲叉(异丙叉)琥珀酸酐(Ⅰ)和1-甲基-3-吲哚乙叉(异丙叉)琥珀酸酐(Ⅱ)的晶体结构

氮杂俘精酸酐作为光致变色材料近年来已引起人们的极大兴趣,但其晶体结构数据还未见报导.测定它们的晶体结构,研究其结构与性能的关系,有着非常重要的意义.本文测定了标题化合物(Ⅰ)和(Ⅱ)的结构。实验1.从氯仿和石油醚的混合溶剂中培养出黄色单晶.在Nicolet R 3m/E 四圆衍射仪上收集衍射强度数据.用石墨单色器单色化的Mo Kα射线作辐射光源,以θ/2θ扫描方式收集2θ3～50°范围的数据.强度数据没有进行吸收校正.有关晶体数据列于表1中。     

2-(1-苄基-3-甲基-2-吲哚亚甲基)-3-亚异丙基丁二酸酐的合成及其光致变色性能研究

在氢化钠和甲苯存在下, 1-苄基-3-甲基吲哚-2-甲醛与亚异丙基丁二酸二乙酯发生Stobbe缩合反应, 经过碱性水解和酸化得到二酸化合物, 接着在乙酰氯存在下脱水, 合成2-(1-苄基-3-甲基-2-吲哚亚甲基)-3-亚异丙基丁二酸酐. 研究了该俘精酸酐在不同溶剂中的光致变色性能.     

(E)-2,5-二甲基-3-呋喃乙叉(异丙叉)-丁二酸酐的光发色和光消色反应过程

淡黄色的(E)-2,5-二甲基-3-呋喃乙叉(异丙叉)-丁二酸酐,1,在紫外光作用下同旋闭环生成深红色的闭环体,7,7,a-二氢苯骈呋喃-5,6-二羧酸酐,2,在Ar⁺激光(515nm)作用下,2同旋开环成1,由于在2的分子中无1-位氢,因此不发生与光消色反应相竞争的1,5氢迁移反应。用Fischer的方法测定了光化学反应1→2的光化学转化率,发现转化率是100%,证明光发色反应是定量的。对于用Ar⁺激光引起的光消色反应进行稳态的光化学分析处理,结果揭示在2的激发态和1的基态之间的某一个能级处有一个过渡态X,X分别以22.43ms^-1和1.11ms^-1的速率常数转变成化合物2和1,提出一个一般性的反应能量座标以解释俘精酸酐的光致色变过程,化合物1的光发色和光消色反应遵循两条不同的反应路线。     

5-二氰亚甲基-4-二环丙亚甲基-3-[1-(2,5-二甲基-3-呋喃基)亚乙基]四氢呋喃-2-酮的合成

报道俘精酸酐类化合物(E/Z)4-二环丙亚甲基-3-[1-(2,5-二甲基-3-呋喃基)亚乙基]四氢呋喃-2,5-酮的拆分,及(E)和(Z)-5-二氰亚甲基-4-二环丙亚甲基-3-[1-(2,5-二甲基-3-呋喃基)亚乙基]四氢呋喃-2-酮4(E)和4(Z)的合成,并对它们的光致变色特性进行了初步研究。     

1-(4-(1H-吲哚-3-基)-2-甲基-5-苯基-1-对甲苯基-1H-吡咯-3-基)乙酮的简便合成和结构表征

标题化合物(C28H24N2O)以N-对甲苯基烯胺酮,2,2-二羟基-1-苯基乙酮和吲哚为原料,在醋酸溶剂中,经微波辐射合成得到.其结构通过单晶X射线衍射法确定,晶体属单斜晶系,空间群P21/n,相对分子质量Mr=404.49,晶胞参数a=0.806 93(8)nm,b=1.473 70(13)nm,c=1.865 12(18)nm,V=2.213 5(4)nm3,Z=4,晶胞密度Dc=1.214g/cm3,吸收系数μ=0.074mm-1,单胞中电子的数目F(000)=856.晶体结构用直接法解出,经全矩阵最小二乘法对原子参数进行修正,最终的偏离因子为R=0.0491,ωR=0.115 4.在晶体结构中新形成的吡咯杂环近似于平面结构.     

三苯基锡-2-(1，2-亚乙二硫)亚甲基-3-羰基-5-芳基-4-戊烯酸酯的合成及晶体结构

由2-(1,2-亚乙二硫)亚甲基-3-羰基-5-芳基-4-戊烯酸与三苯基氢氧化锡反应,合成了九个标题化合物3。用X射线衍射法测定了3b的晶体结构。该晶体属三斜晶系,空间群P1,a=0.9074(2)nm,b=1.6809(3)nm,c=2.1834(4)nm,α=77.57(3)ⅲ,β=88.04(3)ⅲ,γ=89.47(3)ⅲ,V=3.2503nm^3,Z=2;R=0.0592。由锡氧原子间距离可推测,该晶体中羧酸根作为双齿配体与锡原子形成了分子内五配位结构。     

1,2-双(4-溴苯基)-6,7-二氢-3-甲氧基-6,6-二甲基-1H-吲哚-4(5H)-酮的简便合成和结构表征

以1-(4-溴苯基)-2,2-二羟基-乙酮、3-((4-溴苯基)氨基)-5,5-二甲基环己-2-烯酮为原料,甲醇既为醚化试剂也是反应介质,采用对-甲基苯磺酸(p-TsOH)为催化剂,通过多组分的多米诺反应微波辐射下合成多取代的四氢吲哚类衍生物--1,2-双(4-溴苯基)-6,7-二氢-3-甲氧基-6,6-二甲基-1H-吲哚-4(5H)-酮.其结构通过单晶X射线衍射法确定,晶体属三斜晶系,空间群P-1,相对分子质量Mr=503.23,晶胞参数a=0.884 19(9)nm,b=0.969 36(11)nm,c=1.348 97(13)nm,V=1.070 96(19)nm3,Z=2,晶胞密度Dc=1.561g/cm3,吸收系数μ=3.803mm-1,单胞中电子的数目F(000)=504.晶体结构用直接法解出,经全矩阵最小二乘法对原子参数进行修正,最终的偏离因子为.R=0.058 4,wR=0.107 8.在晶体结构中新形成的吡咯杂环近似于平面结构.     

低分子量聚噻吩结晶结构研究

用Ruland方法计算了氯仿可溶级分低分子量聚噻吩(PT_1)热处理前后的结晶度。热处理后结晶度及微晶尺寸均有明显提高。测量及计算晶胞参数证明,PT_1在晶态下具有近似平面伸展构象,提出了初步的结构模型。热处理前后的PT_1给出了明确可归属的红外吸收谱带。     

反丁烯二酸稀土配合物的合成及晶体结构

合成了反丁烯二酸C_4H_4O_4与六种稀土(Eu, Gd, Tb, Y, Er, Lu)的配合物M_2F_3·12H_2O(H_2F=C_4H_4O_4). 用X射线衍射法测定了它们的晶体学参数, 并测定了其中五种配合物的结构. 指出存在两类不同的结构, 其中铕配合物为三斜晶系, 空间群P(1), 铕离子配位数为10. 铽、钇、铒、镥配合物为单斜晶系, 空间群为P2_1/c, 配位数为8. 配合物均具有三维网状结构.     

全同立构聚丙烯晶体结构的对称性研究

本文利用对称理论,研究了全同立构聚丙烯的α(型)晶及β(型)晶的可能的晶体结构.1.推导了与C2/c空间群有关的有色空间群,研究了聚丙烯分子链在它们中的排布,得出其中5种是聚丙烯α(型)晶晶体结构可能存在的空间群;2.从晶畴理论出发,得出具有Cc空间群与P2_(1/c)空间群的两种晶畴共存于一个体系中,3.聚丙烯β(型)晶的晶体结构的可能排列方式是聚丙烯分子链按R型晶胞的半无规排列。     

THE CRYSTAL STRUCTURES OF AMMONIUM AND SODIUM 2-AMINO-3,5-DICHLOROBENZOATES

Abstract

The crystal structures of ammonium and sodium 2-amino-3,5-dichlorobenzoates were determined by the X-ray diffraction method. The ammonium salt crystallizes in the monoclinic system (space group P2₁/c) with a = 13.941(3), b = 9.128(3), c = 7.349(2) Å, β = 90.80(3)° and Z = 4. The structure consists of an ammonium cation hydrogen bonded to a carboxylate oxygen of the 2-amino-3,5-dichlorobenzoate anion. The sodium salt of 2-amino-3,5-dichlorobenzoic acid crystallizes in the triclinic system (space group P 1) with a = 8.033(2), 6 = 8.944(2), c = 17.350(3) Å, α = 76.72(3)°, β = 79.69(3)°, γ = 72.54(3)° and Z = 4. The compound is a polymer in which the sodium ions are coordinated by carboxylate oxygen atoms of the organic ligand and water molecules in an octahedral arrangement. IR spectra of the salts are discussed.     

PHASE STRUCTURES AND TRANSITION BEHAVIORS OF A TRIPHENYLENE DISCOTIC LIQUID CRYSTAL

The phase behaviors and structures of a triphenylene-derived discotic liquid crystal (LC) hexa-n-octoxyl-triphenylene (C8HET) were studied using the combined techniques of differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD), selected area electron diffraction (SAED) and polarized light microscopy (PLM). Onedimensional (1D) powder WAXD results at different temperatures coupled with DSC and PLM observations revealed that the C8HET compound possessed an LC phase and three different crystalline (K3, K2 and K1) phases below the isotropic (Ⅰ)melt. The I (←→) LC phase transition was thermodynamically reversible and independent of the heating and cooling rates. The development and experimental observation of the three crystalline phases relied on different thermal histories. Among the three crystalline phases in C8HET, the K3 phase is the most stable phase, while the K2 and K1 phases are metastable. Note that the K1 phase only formed via a quenching process. On the basis of structure sensitive diffraction experiments such as 2D WAXD of oriented samples and SAED of single crystals, detailed structures and molecular packings of these four ordered phases were identified. The LC phase exhibited a hexagonal columnar phase with 2D lattice dimensions of a = b = 2.38 nm and γ= 120°. All the three crystalline phases possess monoclinic unit cells, yet the γ angle is not 90° in the cases of the K2 and the K3 phases, while in the case of the K1 phase the α angle is not 90°.     

EFFECT OF PAN-MILLING STRESS ON CRYSTAL STRUCTURES OF HIGH DENSITY POLYETHYLENE

A detailed study was performed on the crystal structures of pan-milled high-density polyethylene (HDPE) usingdifferential scanning calorimetry (DSC) and X-ray diffraction. The crystallinity of HDPE first decreased slightly, followed bya gradual increase with increasing milling times. Monoclinic crystals appeared after 4 cycles of milling. With increasingtimes of milling, the proportion of monoclinic crystals increased significantly while the proportion of orthorhombic crystalsdecreased gradually. With increasing times of milling, the crystallite size of orthorhombic form decreased greatly, while thesize of monoclinic crystallites kept almost constant during milling.     

CRYSTAL STRUCTURES OF TWO 1:1 COMPLEXES OF MANGANESE(II) WITH 1,10-PHENANTHROLINE,CONTAINING COORDINATED AND UNCOORDINATED SULFATE ANIONS

Abstract

The crystal structures of fac-triaqua-(1,10-phenanthroline-N,N′)-sulfato-manganese(II) (1) and tetraaqua-(1,10-phenanthroline-N,N′)-manganese(II) sulfate dihydrate (2) are described. The coordination polyhedron around the Mn(II) ion displays a distorted octahedral shape and contains the N,N′-chelating phen ligand. In the first complex the coordination sphere is completed by three water molecules and a monodentate O-sulfato ligand (C _3v), whereas in the second one, an uncoordinated sulfate ion (T_d ) and four coordinated water molecules have been found. In both structures, the molecular units are extensively 2-D hydrogen bonded, with the 1,10-phenanthroline ligands arranged roughly perpendicular to the sheets; the bidimensional sheets are piled up giving rise to polar layers made by the hydrogen bonded species, the aqua-ions, sulfate anions, and water molecules, alternated with apolar layers formed by the 1,10-phenanthroline ligands.     

热拉伸的超高分子量聚乙烯的晶体结构和力学性能

讨论了超高分子量聚乙烯（ＵＨＭＷ－ＰＥ）的熔融一次拉伸和二次拉伸的晶体结构和力学性能．利用ＷＡＸＤ和ＳＡＸＤ测定了拉伸片的晶体取向因子和极图，晶粒尺寸，晶体畸变，长周期等晶体结构．用ＤＳＣ和ＶＥＳ测定热性能和动态力学性能．应力－应变实验测定拉伸片的杨氏模量，断裂强度和伸长．这些实验结果说明ＵＨＭＷ－ＰＥ经二次拉伸能产生正交晶系的伸直链晶体．二次拉伸片由折叠链片晶和伸直链晶体两元结构组成．二次拉伸片的杨氏模量比一次拉伸片有大幅度提高．二次拉伸片的晶体结构和力学性能是在一次拉伸的基础上形成的．