The Chair–Envelope Conformation of Two Derivatives of Triethylammonium 3-Oxo-8,9-Dinitro-Bicyclo [3.3.1] Non-7-En-6-Nitronate [I] and [II]

Abstract  

The title compounds C₁₉H₁₈N₃O₉ ⁻·C₆H₁₆N⁺ (I) [triethylammonium 2-benzyl-2-ethoxycarbonyl-3-oxo-8,9-dinitro-bicyclo [3.3.1] non-7-en-6-nitronate] and C₁₉H₁₇N₄O₁₁ ⁻·C₆H₁₆N⁺ (II) [triethylammonium 2(4-nitrophenylmethyl)-2-ethoxycarbonyl-3-oxo-8,9-dinitro-bicyclo [3.3.1] non-7-en-6-nitronate] crystallize in monoclinic crystal system with P2 ₁ /c space group. In compounds I and II, the bicyclo [3.3.1] nonane has chair–envelope conformation. The crystal structure of compound (I) is stabilized by N–H⋯O, N–H⋯N hydrogen bonds. In both the crystal structures weak C–H⋯O hydrogen bond is observed. Both compounds adopt chair–envelope conformation. An examination of puckering parameters, torsion angles and model (Dreiding) of the title compounds clearly indicates that the ring A has slightly distorted chair conformation and ring B has slightly distorted envelope conformation.     

X-ray structure of 6-phenyldiquino[3,2-b;5,6-b′] [1,4]thiazine

The title compound (C₂₄H₁₅N₃S) is monoclinic, with a = 10.816(1), b = 8.193(1), c = 10.892(1), = 104.20(1)° and space group P2₁. The molecule is folded with the central ring in a boat conformation. It can also be considered as folded around the C—C axis between the thiazine and pyridine rings. The butterfly folding angle between the two quinoline planes is 20.5(1)° and between the planes of the two halves of the thiazine ring is 30.6(1)°. The phenyl substituent is in an equatorial location with respect to the thiazine ring with the C—N···S angle of 163.0(2)°. The phenyl plane nearly bisects the pentacyclic ring system and is nearly perpendicular to the C(2), C(3), C(12), C(13) plane.     

沿[1 ■00]方向升华法生长6H-SiC单晶

本文采用升华法沿着垂直于c轴方向的[1 ■00]方向生长6H-SiC单晶。利用光学显微镜对晶体表面及腐蚀后的晶片进行观察,发现沿[1 ■00]方向生长出的单晶与传统方法沿[0001]方向生长单晶有很多的不同之处,多型对于籽晶的继承性非常强,但是在生长过程中多型夹杂不会发生,该方法生长的晶体中没有发现螺位错(微管)缺陷。     

沿[1-100]方向升华法生长6H-SiC单晶

本文采用升华法沿着垂直于c轴方向的[1-100]方向生长6H-SiC单晶.利用光学显微镜对晶体表面及腐蚀后的晶片进行观察,发现沿[1-100]方向生长出的单晶与传统方法沿[0001]方向生长单晶有很多的不同之处,多型对于籽晶的继承性非常强,但是在生长过程中多型夹杂不会发生,该方法生长的晶体中没有发现螺位错(微管)缺陷.     

有机模板硼酸盐[C6N2H18]0.5[B5O6(OH)4]的合成、晶体结构及变温荧光性质

以硼酸和有机胺为原料在水溶液体系中合成了一种有机模板硼酸盐[C6N2H18]0.5[B5O6(OH)4](1a),通过X射线单晶衍射仪对其晶体结构进行了检测.此外,对其进行了元素分析、X射线粉末衍射、红外光谱、热重差热分析及固态荧光光谱等表征.结果表明,该化合物属单斜晶系,空间群为P21/n,晶胞参数为a=0.8593(2) nm,b=1.4015(4) nm,c=1.0293(3) nm,β=104.723(3)°,V=1.1989(6) nm3,Z=4.阴离子基团[B506 (OH)4]-通过强的氢键连接形成具有三种不同形状孔道的新颖三维超分子骨架结构.该化合物在波长为248 nm的激发光下,发射出最大发射波长为375 nm的紫外光.对化合物进行不同温度的热处理后,其荧光性质发生了明显的变化.     

一种新络合盐晶体——K3[InCl6]的合成

在采用本实验室提出的络盐法制备氧化铟锡(Indium-tin-oxide,简称ITO)纳米粉末的试验过程中发现和制备了一种新络合盐晶体--K3[InCl6].通过XRD、SEM和CCD等测试手段对其物相、形貌、元素成份和结构进行了表征.结果表明:该晶体属单斜晶系,空间群为P21/c,分子式为K3[InCl6],Z=4,其晶胞参数为:a=1.2188nm,b=0.7553nm,c=1.2703nm,α=90.00°,β=108.96°,γ= 90.00°,V=110.598nm3.     

Air-stable liquid clathrates. 1. Crystal structure of [NBu4][Br3] and reactivity of the [NBu4][Br3]·5 C6H6 liquid clathrate

[NBu₄][Br₃] interacts with C₆H₆ to form an air-stable liquid clathrate. The tribromide anion reacts with phenol to give para-bromophenol in>95% yield. The HBr which is generated in the reaction combines with the Br^– anion to form [Br-H-Br]^–. The latter forms the basis for a new liquid clathrate, [NBu₄][Br-H-Br]·n C₆H₆. The parent salt, [NBu₄][Br₃], crystallizes in the monoclinic space group C2/c witha=12.983(5),b=10.380(7),c=16.222(6) Å,=93.93(3)°, andD _c =1.47 g cm^–3 forZ=4. The final R value is 0.068 based on 787 observed reflections.     

Hydrothermal crystallization and X-ray structure determination of a new decavanadate with mixed cations [Mn(H2O)6]2[N(CH3)4]2[V10O28]·2H2O

A new decavanadate with mixed cations, [Mn(H₂O)₆]₂[N(CH₃)₄]₂[V₁₀O₂₈]·2H₂O (1), was crystallized from a hydrothermal reaction between MnCO₃ and V₂O₅ in the presence of N(CH₃)₄Br at 100°C. The structure of 1, as determined by x-ray single crystal analysis, consists of cations and anions of hexa-aqua manganese [Mn(H₂O)₆]²⁺, tetramethyl ammonium [N(CH₃)₄]⁺ and decavanadate [V₁₀O₂₈]^6–. The extended H-bonding between the [Mn(H₂O)₆]²⁺ and [V₁₀O₂₈]^6– ions gives rise to a pseudo- two-dimensional network in the crystal lattice x-ray crystallographic data for 1: monoclinic P2₁/n, a = 9.1499(5), b = 12.8725(7), c = 18.625(1) Å, = 92.252(1)°, V = 2192.0(2) ų, MZ = 2, and D _calcd = 2.22 g cm^–3.     

Potassium bromo-borate K3[B6O10]Br—A new nonlinear optical material

A new polar hexaborate, K₃[B₆O₁₀]Br (space group R3m), is synthesized under hydrothermal conditions. The radical anion is composed of macallisterite hexaborate blocks 6[3Δ + 3T] formed by boron triangles and boron tetrahedra. The blocks are joined together through vertices into a [B₆O₁₀] _∞∞∞ ^2? zeolite-like framework of a new type. Large K⁺ cations and Br^? anions are located in extended channels that are aligned parallel to rhombohedral translations of the crystal lattice. The structure of the sublattice formed by large ions consists of BrK₆ bromo-centered octahedra, which are linked together through vertices into a hexagonally distorted perovskite framework. The perovskite framework is inserted into the boron-oxygen framework so that these two frameworks do not intersect. The nonlinear optical properties of powdered samples of the K₃[B₆O₁₀]Br compound are investigated using the second harmonic generation method. It is found that the K₃[B₆O₁₀]Br compound exhibits a high nonlinear optical activity that exceeds the activities of the majority of borate compounds and is characteristic of haloid borates of the hilgardite family.     

Crystal structure of 9,12-ethano-12a-methoxycarbonyl-5, 8a,9,12,12a,12b-hexahydro-6H-[1,2]dioxino[4′,5′:4,5] isoxazolo[3,2-a]isoquinoline, C17H19NO5

The title compound crystallizes in the space group P2₁/n, with a = 18.423(3), b = 9.628(3), c = 19.243(2) Å, = 116.208(8)°, with two independent molecules in the asymmetric unit, which are not enantiomers. The chiral centers C8a, C9, C12, C12a, C12b are either S,R,S,R,R or R,S,R,S,S, respectively, because of the centric space group.     

Crystal structure of tetrachlorobisd[μ-imidocarbonylchloridato]diboron

Boron trichloride and mercuric cyanide react slowly to form the title compound, B₂N₂C₂Cl₈, which contains a four-membered B₂N₂ ring with alternating BCl₂ and N—CCl₂. Crystals are triclinic, space group P , a = 6.1198(1), b = 7.4457(3), c = 7.9186(3) Å, = 117.064(2), = 106.923, = 93.712(2)°, Z = 1, and V = 299.07(2) ų. The compound has a crystallographic center of symmetry but the metric symmetry is close to the expected mmm.     

Crystal structure of cesium sodium hexathiocyanatobismuthate Cs2Na[Bi(SCN)6] and characterization of Cs2Na[Bi(SCN)6−x Cl x ] and Cs2Na[Bi2(SCN)9−x Cl x ] complexes by X-ray powder diffraction

Cs₂Na[Bi(SCN)₆] crystallizes in the trigonal space group with one formal molecule per unit cell.M=846.25,a=7.189(1),c=10.580(2) ,V=473.5(1) ,D _x =2.967 g cm^–3, (MoK)=13.70 mm^–1,F(000)=378. FinalR=0.029 for 917 absorption-corrected reflections. The structure consists of infinite[Bi(SCN)₆Na] ^2– anionic chains along thec axis with slightly distorted octahedral Bi–6S and Na–6N coordination and Cs⁺ ions surrounded by three anionic chains with irregular coordination by six N and three S atoms. X-ray powder diffractograms of three complexes, Cs₂Na[Bi(SCN)_6–x Cl _x ] withx=2, 3 and 4, indicate that the mixed complexes are not isostructural and can be indexed in different orthorombic unit cells witha=14.617(8),b=12.32(1),c=10.769(6) forx=2;a=15.37(1),b=10.81(1),c=10.287(6) forx=3 anda=14.662(7),b=14.366(7),c=7.932(4) forx=4. The two dinuclear complexes Cs₂Na[Bi₂(SCN)_9–x Cl _x ] withx=2 and 3, despite the large similarity of their diffractograms, are not isostructural and can be indexed in different orthorombic unit cells witha=14.79(1),b=13.72(1),c=10.591(5) forx=2 anda=18.423(8),b=15.657(7),c=7.410(7) forx=3.     

Refined crystal structure of lovozerite Na2CaZr[Si6O12(OH,O)6] · H2O

The structure of Na,Ca,Zr-silicate lovozerite, Na₂CaZr[Si₆O₁₂(OH,O)₆] · H₂O, from the Khibiny alkaline massif (the Kola Peninsula) was refined by single-crystal X-ray diffraction analysis (Syntex $P\bar 1$ diffractometer, λMoK _α radiation, 2θ/θ scanning technique). The refinement (R _hkl = 0.077, 1531 independent reflections; anisotropic thermal parameters) confirmed the trigonal system proposed for the mineral earlier (sp. gr. R3; a = 10.18(1) Å, c = 13.13(2) Å, Z = 3) and revealed the presence of two additional positions (C and B) statistically occupied by Ca and Na atoms (and partly by Mn) and H₂O molecules, respectively.     

Li离子浓度对铌酸钾锂晶体[NbO6]7-八面体畸变的影响

用顶部籽晶法生长了一批不同组成的铌酸钾锂晶,用同步辐射X射线分析了晶体结晶特性,用Philips PW2400 X射线荧光光谱法测量了晶体的组成.对三种组成的晶体样品测量了红外拉曼光谱,分析了晶体中组分离子浓度对晶体红外拉曼光谱特征的影响,结果表明,晶体中位于C格位的Li离子浓度对晶体拉曼光谱产生了强烈的影响,影响的本质在于晶体中Li含量的提高导致晶体中[NbO6]7-八面体畸变程度加大,对八面体晶格振动产生了强烈的影响.     

Crystal and molecular structure of complex compound [Fe3O(CH3COO)6(H2O)3]2[ZnCl4] ⋅ 2H2O

The X-ray crystal structure of trinuclear iron acetate [Fe₃O(CH₃COO)₆(H₂O)₃]₂ [ZnCl₄] ? 2H₂O was determined. The crystal has a ionic structure. It is monoclinic, a = 25.363(7), b = 14.533(4), c = 15.692(4) Å, β = 103.11(2)°, space group _C2/c, and R = 0.0685. The structure of the cationic complex [Fe₃O(CH₃COO)₆(H₂O)₃]⁺ is typical of trinuclear iron(III) compounds containing a μ₃-O bridge: the iron atoms are situated at the vertices of an almost equilateral triangle with the O atom at the center. Each Fe atom is coordinated by four O atoms of bridging carboxy groups, the μ₃-bridging O atom, and the water molecule in the trans position to the latter O atom. Mössbauer spectroscopy evidence indicates the high-spin state (_S = 5/2) of the iron(III) ions.     

[100]金刚石薄膜的辐照响应特性研究

采用热丝辅助化学气相沉积(HFCVD)方法生长得到25μm厚的[100]取向金刚石膜,用以制备辐射探测器.在100 V偏压下,测得暗电流为16.1 nA,55Fe X射线(5.9 keV)和241Am α粒子(5.5 MeV)辐照下的净光电流分别为15.9nA和7.0nA.光电流随时间的变化先快速增加随后由于"pumping"效应逐渐达到稳定.X射线和α粒子辐照下的平均电荷收集效率分别为45;和19;,并由Hecht理论计算得到对应的电荷收集距离为11.25μm和4.75μm.     

Crystal structure of syn-1-acetyl-9′aH-8′- methoxyspiro[indole-3,2′-oxeto[3′,2′:4,5]furo[3,2-g][1] benzopyran]2,6′-dione

The crystal structure of syn-1-acetyl-9a-hydro-8-methoxyspiro[3H-indole-3,2(2aH) oxeto[3,2-g]furo[3,2-g]benzo[ b]pyran-2,6-dione 1 was determined by X-ray diffraction analysis. It possesses P2(1)/c space group symmetry, with a = 12.391(3), b = 15.035(3), c = 9.5435(19) Å, = 93.66(3), and D _calc. = 1.517 Mg/m³ for Z = 4.     

[Co（amghCl2]3·[Co（amg）2Cl（OH）]·[Co（amg）（phen）]·（R2O）4的合成和晶体结构

本文合成了一个复杂的单核配合物 [Co(H2dmg)2Cl2]3·[Co(H2dmg)2Cl(OH)]·[Co(Hdmg)(phen)]·(H2O)4 (H2dmg＝dimethylglyoxime, phen＝1,10-Phenanthroline).通过X射线衍射技术获得其单晶结构.在单晶结构中,每五个单核钴(II)的配位结构形成一个重复单元,是一个较为复杂的单晶.其空间群为P-1,晶胞参数为a＝1.3738nm;b＝1.4396nm;c＝1.8656nm.本文中我们将讨论该化合物的分子结构及相关光谱性质.     

Annulated bicyclo[2.2.2]octenones: 9-hydroxy-9-chloromethyl-endo-tricyclo[5.2.2.02,6]undeca-4,10-diene-3-spiro(1′-cyclopropane)-8-one and 12-hydroxy-12-chloromethyl-endo-tricyclo [8.2.2.02,9]tetradeca-13-en-11-one

A single crystal X-ray diffraction study of two annulated bicyclo[2.2.2]octenones has been carried out to establish their precise stereostructures. The compounds, with their crystal data, are:1, 9-hydroxy-9-chloromethyl-endo-tricyclo[5.2.2.0^2,6]undeca-4,10-diene-3-spiro(1-cyclopropane)-8-one, C₁₄H₁₅O₂Cl, space group P2₁/c,a=10.540(2),b=9.668(1),c=11.841(4)Å, =95.67(2)°,Z=4, and2, 12-hydroxy-12-chloromethyl-endo-tricyclo[8.2.2.0^2,9]tetradeca-13-en-11-one, C₁₅H₂₁O₂Cl, space group C2/c,a=20.747(8),b=6.498(1),c=20.525(3)Å, =93.04(3)°,Z=8. The molecule of1 has endo stereochemistry at the ring junction and the spirocyclopropane ring is proximal to the hydroxyl group. In2, the eight membered ring deviates from a chair conformation and one ring atom is disordered. Crystals of1 and2 contain centrosymmetric dimers formed by C=O...O–H hydrogen bonds.     

X-ray crystal structure ofcis-H(Ph3Si)Pt[Ph2P(CH2)4PPh2] ·0.5 C6H6

The title compound, cis-hydrido(triphenylsilyl)-1,4-butanediyl-bis-(diphenylphosphine)platinum(II) (I), crystallizes in the monoclinic space groupP2 ₁/n (No. 14) witha=9.472(4),b=16.924(5),c=25.799(4) Å, β=91.29(3)° andZ=4. The structure was solved using the direct methods and refined by the full-matrix least-squares procedure to yield residuals ofR=0.024 andR _w =0.025 based on 4160 unique reflections. The square-planar geometry about the Pt atom is angularly distorted with P(1)?Pt?P(2) and Si?Pt?P(2) angles of 103.5(1) and 102.1(1)°, respectively. The Pt?P(1) bond is longer than the Pt?P(2) bond due to thetrans influence of the SiPh₃ group. Distortion due to steric bulk of the ligands is accommodated by the opening of the tetrahedral angles at the silicon and phosphorous atoms.