Inclusion complexes of the natural product gossypol. Crystal structure of the 2:1 complex of gossypol with amyl acrylate

The crystal structure of the 2: 1 inclusion complex of gossypol with amyl acrylate has been determined by X-ray structure analysis. The crystals of (C₃₀H₃₀O₈)₂C₈H₁₄O₂ are triclinic, space group P ,a = 14.425(2),b = 15.519(1),c = 16.409(2) Å, =97.89(1), = 117.80(1), =67.01(1)° (reduced cell:a = 14.425(2),b = 15.519(2),c = 16.017(2)Å, = 92.19(1), = 115.01(l), =67.01(1)°],V = 2986.7(5) ų,Z = 2,D _x = 1.31 g cm^–3, (CuK ) = 7.40 cm^–1,T = 292 K. The structure has been solved by direct methods and refined to the final R value of 0.059 for 5155 observed reflections. The gossypol molecules bonded via several hydrogen bonds form centrosymmetric tetramers. The two independent gossypol molecules, A and B, are related within the tetramer by a local noncrystallographic 2-fold axis. The host molecules in the crystal form cavities in which two guest molecules are placed. The ester molecule interacts via a pair of C-...H-O hydrogen bonds with two gossypol molecules of the same chirality and belonging to the same tetramer unit. The amyloxy group of the ester molecule shows a very large thermal motion. It adopts a non-extended conformation in which it can be fitted into the cavity formed by the host molecules.     

Synthesis and structural studies of hydrazino-crown ethers and thermodynamic studies of their interaction with transition,and post-transition metal ions and methyl ammonium ion

Hydrazino-crown ethers have been synthesized in only 3 or 4 steps starting from 1,2-diacetylhydrazine. The X-ray crystal structure of protonated hydrazino-19-crown-7 (2) showed that one of the hydrazino nitrogen atoms was directed outside the ring cavity. A solvent methanol molecule is held in the cavity of the host ligand by three hydrogen bonds involving two hydrogen atoms bonded to nitrogens of the ligand and the alcohol hydrogen of the methanol. The logK values for the interaction of2 with CH₃NH ₊ ³ , Ag⁺, Pb²⁺, and Cd²⁺ were much less than those for the interaction of symmetrical triaza-l8-crown-6 (5) with the same cations. Hydrazino-crown2 reduced silver ions to silver metal when a solution of2 and silver ions in DMSO was allowed to stand for several days.     

Characterization of tension and normally lignified wood cellulose inPopulus maximowiczii

We have investigated unlignified tension wood and normally lignified wood celluloses inPopulus maximowiczii with particular reference to the composition of two crystalline phases I/I (triclinic/ monoclinic). Four independent techniques, which enable us to detect the two phases, CP/MAS¹³C NMR, Fourier transform infrared microscopy, selected-area electron diffraction, and X-ray diffraction were applied. Because of the low crystallinity of wood celluloses, particularly in the case of celluloses in the lignified cell wall, no single method was decisive enough to be able to determine the composition of the two phases as one can with highly crystalline materials. The I dominant structure (monoclinic crystal type) was, however, preferred for both tension and normal wood celluloses.     

CuCl2/NaY体系表面分散态研究

铜负载分子筛作为催化剂或吸附剂，在石油化工、环境保护等方面有许多用途[1，2]．已有研究发现，铜交换的Y型分子筛对NO分解等反应具有较高活性及稳定性［3-5］．因此研究铜负载Y型分子筛对有关吸附剂和催化剂的制备有重要意义．我们实验室在研究活性组分在载体表面分散现象时     

Study on Phase-Formation Mechanism and Intergrowth for Bi(Pb)-Sr-Ca-Cu-O System

In this paper, the phase-formation mechanism of Bi-based superconductors was systematically investigated by using high-temperature X-ray diffraction, differential thermal analysis (DTA) and crystallization of amorphous state. The transformations among Bi-based 2201, 2212 and 2223 phases were observed, and the intergrown phenomenon of the 2201, 2212 and 2223 phases was explained. It was proposed that there exist a composition equilibrium between 2212 phase and Ca2CuO3 and a competition of thermody-namic stability among Ca2CuO3, 2212 and 2223 phases. This is why it is difficult to prepare the 2223 phase. After Pb was doped in Bi-Sr-Ca-Cu-O system, Ca2CuO3 phase in the Bi-Sr-Ca-Cu-O system was replaced by Ca2PbO4, so that the composition equilibrium and competition of thermodynamic stability mentioned above were avoided.     

Das Pyren und der Einfluß von Substitution oder Komplexie-rung auf seine Geometrie und Packung im kristallinen Zustand

The crystal structures of pyrene and substituted and complexed derivatives of pyrene have been investigated by X-ray and neutron diffraction. The geometry of the pyrene skeleton has been determined experimentally with high accuracy and calculated by quantum chemical methods. In the cases reported in the literature and cited here the pyrene skeleton has the molecular symmetry mmm or mm2 with values for the bond lengths of the six symmetrically independent bondsa, b, c, d, e, f differing significantly in the limits of error. Mean values of a number of experimental and theoretical bond lengths are given and can be considered as standard values for the mm2 symmetric pyrene skeleton. In the case of substitution of the pyrene in 3-position with a polar heterocyclic molecule of the azomethine-imine type the mm2 symmetry vanishes, a C–H ... N intramolecular hydrogen bond arises and the directly neighbouring pyrene units are not packed parallel with their planes to each other, but they are considerably tilted. Relatively narrow intermolekular C-C contacts, 3.314 and 3.368 Å, have been observed. The conclusion is drawn that the asymmetry of the pyrene molecule and a tilt of directly neighbouring pyrene units in the crystal packing can be induced by substitution e. g. with suitable polar heterocycles.

Juli 1985.     

Synthesis,structure, and physico-chemical properties of 3-methyl and 3,3-dimethyl derivatives of l-(4′,4′-dimethyl-2′,6′-dioxocyclohex-1′-yl)-3,4-dihydroisoquinoline

3,3-Dimethyl- and 3-methyl-1-(4,4-dimethyl-2,6-dioxocyclohex-1-yl)-3,4-dihydroisoquinolines have been synthesized. Crystal and molecular structures of the 3,3-dimethyl derivative have been determined. In the crystalline state this compound exists as a tautomeric form where a hydrogen atom is located at the N atom of the dihydroisoquinoline fragment of the molecule. The tautomeric equilibrium does not shift noticeably in solutions, as shown by IR, UV, and NMR spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 331–336, February, 1993.     

小角X射线散射法研究CH2Cl2,CHCl3和CCl4对PE液晶结构的影响

采用小角X射线散射法研究了CH_2Cl_2、CHCl_3和CCl_4对磷脂酰乙醇胺(PE)液晶结构影响的机理.CH_3Cl_2、CHCl_3和CCl_4对PE液晶结构影响的差别主要是其空间旋转电子云密度分布形状不同所致.空间旋转电子云密度分布呈椭球状的物质有使PE液晶形成六角形H_1相的趋向;呈圆锥状的物质有诱发PE液晶形成立方六角相的趋向;呈球状的物质有使PE液晶形成片层立方相的趋向.     

Citrate - Nitrate route for the synthesis and characterization of TAG using sol-gel techniques

Terbium Aluminum Garnet (TAG) is an important optically active material and is one of the best materials known for the fabrication of optical isolators. TAG has a large Verdet constant and has good transmission in the region of 350–1500 nm of the electromagnetic spectrum. It is also known that TAG melts incongruently at 1840°C. This makes efficient synthesis of TAG important and challenging and forms the motivation of the present work to develop techniques for the synthesis of TAG at lower temperatures. In the present work we report the synthesis of TAG using sol-gel techniques following the citrate-nitrate route. The prepared sample is sintered at various temperatures in presence of air and characterized using X-ray diffraction, FT-IR spectroscopy, energy dispersive X-ray Analysis and the morphology is observed using the scanning electron microscopy.