THE CRYSTAL STRUCTURES OF ALKALOIDS FROM KOPSIA OFFICINALIS

<正> Kopsamine(I): Mr=456.50, orthorhombic, P212121, a=ll.245(3), b=12.547(2), c=15.043(3)A, Z=4, Dc=1.429g.cm-3, V=2122.5A3, final R=0.041 for 2008 observed reflections.N-carbomethoxy-11-methoxy-12-hydroxy-kopsinaline(Ⅱ): Mr=458.52, mono-clinic, P21,a=8.424(2), b=13.037(1), c=9.883(1)A,β=90.14(2)°, Z=2, Dc= 1.403g·cm-3, V=1085.4 A3, final R=0.039 for 1687 observed reflections.In the structures: The rings A,B and E(I) take envelop conformations. The ring C takes chair conformation and the ring D boat conformation. There are intramolecular hydrogen bonds 0(5)-HO(5)...0(1) both in molecule(I) and molecule(Ⅱ), which formed the distorted seven-membered ring with atoms C(22), N(1), C(2), and C(18).     

THE CTYSTAL STRUCTURE OF m—FERROCENYLACETOOHENONE

<正> The title compound C18H16FeO (Mr=304. 17) crystallizes in the mono-clinic system,space group P21/c with cell constants a= 14. 428(3),b=9. 939(8),c = 10. 027(5) A .B=93. 73(1),Z=4,Dc=1.41 gcm-3 and V= 1435. 0A 3.The structure is solved by direct methods and refined by least-squares technique to final R=0. 038 and Rw=0.051 based on 2413 independent reflections with I>3o(I). Result shows that both the Cp rings are approximately parallel with dihedral angle of 1. 2 ,The phenyl ring is somewhat tilted from the Cp ring linked to it with a dihedral angle of 8. 36 . The oxygen and carbon atoms of the aceto group are almost co-planar with the phenyl ring.     

Crystal Structure of 8-Demethoxyrunanine

A new hasubanane-type alkaloid, 8-demethoxyrunanine, was isolated from Sino- menium acutum and characterized by melting point, HREIMS, 1H NMR, and X-ray diffraction analysis. X-ray diffraction reveals that the title compound crystallizes in the orthorhombic system, space group P212121 with a = 7.308（1）, b = 21.742（5）, c = 22.893（4）A, V = 3637.5（11） A^3, Z = 8, Dx = 1.254 g/cm^3, F（000） = 1472, μ（MoKα） = 0.087 mm^-1, the final R = 0.0438 and wR = 0.0575 for 4497 independent reflections with Rint = 0.0192 and 2091 observed reflections with I 〉 2σ（I）. Four rings （ring A： one benzene ring, ring B： one hexagon carbon ring in a half-chair conformation, ring C： one hexagon carbon ring with α,β-unsaturated ketone segment （-CR2=CR1-C=O） in a screw-boat conformation, and ring D： one nonplanar tetrahydropyrrole） form a hasubanane-type alkaloid.     

CRYSTAL STRUCTURE OF {Mo_3(μ_3-S)(μ-S)_3 [S_2P(OEt}_2]_4·PhCH_2CN}

<正> Mr=2548.12, Triclinic, P1, a=15.941(5), b=15.957(2),c=20.240(6)A, α=76.41(2),β=83.87(2),γ=74.41(2)°,V=4814.6A3, Z=4, Dc=1.757g.cm-3, Final R=0.053 for 11867 reflections. There are two crystallographically independent M1 type trinuclear Mo cluster molecules with 'loose coordination site', A and B, in an asymmetric unit of the title crystal. They are formulated as {Mo3S4(u-dtp)(dtp)3.PhCH2CN}(dtp=[S2P(OEt)2]-) and have essentially identical cluster molecular configuration, but differ from each other in the conformations for the phenyl rings of the ligands PhCH2CN. The lengths of the Mo-Mo bonds are 2.750(1), 2.753(1),and 2.768(1)A for molecule A and 2.742(1), 2.756(1), and 2.764(1)A for molecule B, while the dihedral angles betweem the phenyl ring and the {Mo3} triangle are 25.0° and 94.9° for A and B respectively.     

冬凌草甲素的晶体结构

冬凌草甲素,C_(20)H_(28)O_6,Mr=364.44,是一种从中药中提取的抗癌药,它的晶体结构分析表明晶体属正交晶系的空间群P2_12_12_1,晶胞参数为α=13.316(9),b=21.302(2),c=13.015(1),V=3697(9)~3。Z=8,D_c=1.31g/cm~3,D_o=1.30g/cm~3,F(000)=1568。该分子是四环二萜类化合物,A环和C环是椅型结构,B环是船型结构;D环是部分共轭五员环,为半椅型结构,环上相邻的两个双重键侧基组成一个六原子的共轭平面。     

2,11,14-三氮-5,8-二氧-3,4,9,10-双(4,4'-三氟甲苯并)-13,15-(2’,6’)吡啶环十五-1,12-二烯酮的合成和晶体结构

合成并测定了2，11，14-三氯-5，8-二氧-3，4，9，10－双（4，4’-三氟甲苯并）-13，15－（2’，6’）吡啶环十五-1，12-二烯酮的单晶结构。晶体分子式C23H15F6N3O4，Mr=511．38，晶体属单斜晶系，空间群P21/c，晶胞参数a=6.732（2），b=15.751（4），c=20．420（8）A，β=96．54（3）°，V=2151．6A3，Z=4，Dc=1．579g／cm3，μ（MOKO）=1．360cm－1，F（000）=1040。分子含有A、B、C、D四个环，D、C苯环对称连有2个三氟甲基，中间A环为含氧、氮的十五员王冠大杂环，整个分子为近平面结构。     

CRYSTAL STRUCTURE OF A NEW STEROIDAL ALKALOID FROM PEIMINE,C_(27)H_(43)NO_2·H_2O

<正> Mr = 431,.6 orthorhombic,P212121,a = 8.526(2), b = 9.970(2), c= 29.787(6)X,Z=4,V=2532.0A3,Dc=1.132g.cm-3,λ(MoKα)=0.71073A,μ=0.67cm-1, F(000) = 952, final R= 0.069 for 1733 observed reflections with I>1σ(I). All six-membered rings in this free base are in the chair form and the five-membered ring C takes the envelope conformation, with the ring fusions A/B traps, B/C trans, C/D cis, D/E trans and E/F trans. There is one crystal water whose oxygen atom joins the adjacent alkaloid molecules by the inter-molecular hydrogen bonds O(1)-H... 0(3)-H(31)...0(2)=C(6). Pertinent parameters for the hydrogen bonding system are: .0(1)...0(3) 2.878(6), 0(2)...O(3) 2.917(6)A,O(1)-H...O(3) 178.3(3)°,and 0(3)-H(31)...0(2) 165.6(3)°.     

Extraction and Crystal Structure of Pedunculoside

The title compound of pedunculoside (C36H58O10), a main active triterpenoid saponin of Ilicis Rotundae Cortex, was isolated from the dried bark of Ilex rotunda Thunb., and characterized by X-ray diffraction analysis. It crystallizes in the orthorhombic system, space group P212121 with C36H58O10, a=13.046(3), b=21.038(4), c=28.413(6) , V=7798.28(3) ·3, Z=8, Dc=1.109 g/cm3, Mr=650.82, F(000)=2832, and μ=0.080 mm-1. The final R=0.0765 and wR=0.1736 for 15117 observed reflections (I > 2σ(I)). The molecular crystal structure of pedunculoside shows relative stereochemistry of 3β,19α,23-trihydroxy-urs-12-en-28-oic acid-28-O-β-D-glucopy- ranosyl ester. The molecule is composed of one glucopyranosyl ring and five six-membered rings with ring junctures of A/B trans, B/C trans, and D/E cis. There are two C36H58O10 molecules in an asymmetric unit, and the title compound is stacked into a 2D layer structure through hydrogen bonds.     

Total Synthesis of 1‐Hydroxytaxinine

1‐Hydroxytaxinine ( 1 ) is a cytotoxic taxane diterpenoid. Its central eight‐membered B‐ring possesses four oxygen‐functionalized centers (C1, C2, C9, and C10) and two quaternary carbon centers (C8 and C15), and is fused with six‐membered A‐ and C‐rings. The densely functionalized and intricately fused structure of 1 makes it a highly challenging synthetic target. Reported here is an efficient radical‐based strategy for assembling 1 from A‐ and C‐ring fragments. The A‐ring bearing an α‐alkoxyacyl telluride moiety underwent intermolecular coupling with the C‐ring fragment by a Et₃B/O₂‐promoted decarbonylative radical formation. After construction of the C8‐quaternary stereocenter, a pinacol coupling reaction using a low‐valent titanium reagent formed the B‐ring with stereoselective installation of the C1,C2‐diol. Subsequent manipulations at the A‐ and C‐rings furnished 1 in 26 total steps.     

Single-conformation ultraviolet and infrared spectroscopy of model synthetic foldamers: beta-peptides Ac-beta3-hPhe-beta3-hAla-NHMe and Ac-beta3-hAla-beta3-hPhe-NHMe

The conformational preferences and infrared and ultraviolet spectral signatures of two model beta-peptides, Ac-beta3-hPhe-beta3-hAla-NHMe (1) and Ac-beta3-hAla-beta3-hPhe-NHMe (2), have been explored under jet-cooled, isolated-molecule conditions. The mass-resolved, resonant two-photon ionization spectra of the two molecules were recorded in the region of the S0-S1 origin of the phenyl substituents (37,200-37,800 cm(-1)). UV-UV hole-burning spectroscopy was used to determine the ultraviolet spectral signatures of five conformational isomers of both 1 and 2. Transitions due to two conformers (labeled A and B) dominate the R2PI spectra of each molecule, while the other three are minor conformers (C-E) with transitions a factor of 3-5 smaller. Resonant ion-dip infrared spectroscopy was used to obtain single-conformation infrared spectra in the 3300-3700 cm(-1) region. The infrared spectra showed patterns of NH stretch transitions characteristic of the number and type of intramolecular H-bonds present in the beta-peptide backbone. For comparison with experiment, full optimizations of low-lying minima of both molecules were carried out at DFT B3LYP/6-31+G*, followed by single point MP2/6-31+G* and selected MP2/aug-cc-pVDZ calculations at the DFT optimized geometries. Calculated harmonic vibrational frequencies and infrared intensities for the amide NH stretch vibrations were used to determine the beta-peptide backbone structures for nine of the ten observed conformers. Conformers 1B, 1D, and 2A were assigned to double ring structures containing two C6 H-bonded rings (C6a/C6a), conformers 1A and 2B are C10 single H-bonded rings, conformers 1C and 2D are double ring structures composed of two C8 H-bonded rings (C8/C8), and conformers 1E and 2E are double ring/double acceptor structures in which two NH groups H-bond to the same C=O group, thereby weakening both H-bonds. Both 1E and 2E are tentatively assigned to C6/C8 double ring/double acceptor structures, although C8/C12 structures cannot be ruled out unequivocally. Finally, no firm conformational assignment has been made for conformer 2C whose unusual infrared spectrum contains one very strong H-bond with NH stretch frequency at 3309 cm(-1), a second H-bonded NH stretch fundamental of more typical value (3399 cm(-1)), and a third fundamental at 3440 cm(-1), below that typical of a branched-chain free NH. The single conformation spectra provide characteristic wavenumber ranges for the amide NH stretch fundamentals ascribed to C6 (3378-3415 cm(-1)), C8 (3339-3369 cm(-1)), and C10 (3381-3390 cm(-1)) H-bonded rings.     

CRYSTAL AND MOLECULAR STRUCTURE OF 2-PHBNYLQUINOXALINE

<正> C14H10N2,Mr =206.24, space group P21/n, a =5.861(3), b =10.230 (5), c =17.440(11) A,β=92.07(5)°,V= 1045(1) A3,Z=4, Dx=1.31 g.cm-3, MoKa radiation,u=0.73 cm-1,F(000)=432,R=0.063 for 1054 observed reflections. 2-Phenylquinoxaline molecule is approximately planar. The dihedral angle between the quinoxaline ring and the substituted phenyl ring is 7.0°. The C-C bond distance connecting these two rings is 1.495(4) A. The whole molecule is a conjugation system.     

Extraction and Crystal Structure of Karounidiol

1 INTRODUCTION Karounidiol is a natural pentacyclic triterpene compound, which was identified as a novel compound initially from the Japanese commercial seeds of Trichosanthes kirilowii Maxim. (Fam. Cucurbitaceae)[1], and then isolated from the Chinese commercial seeds of T. kirilowii Maxim. and T. rosthornii Harms[2, 3] and the Japanese wild plant seeds of T. cucumeroides (Ser.) Maxim.[4]. It has not been isolated from other plants up to now, so we are thinking about how to use th…     

Synthesis of double-armed lariat ethers with pyrene moieties at each end of two sidearms and their fluorescence properties in the presence of alkali metal and alkaline earth metal cations

Two types of double-armed lariat ether derivatives having pyrene moieties at each end of two sidearms, (3x + 1)-crown-x derivatives 1 (x = 5), 2 (x = 6), and 3 (x = 4) (type A) and 3y-crown-y derivatives, 6 (y = 5) and 7 (y = 6) (type B), were synthesized, and their complexation behavior toward alkali metal and alkaline earth metal cations was examined by fluorescence spectroscopy. Pyrene excimer emission decreased accompanied by an increase in monomer emission upon metal ion complexation. This finding is ascribed to the change of the spatial distance of two pyrene rings by movement suppression of both the crown ring and one of the two sidearms based on complexation with the metal cation. The selectivity for alkaline earth metal cations was highly dependent on the fitness of the host cavity and the guest size. Although most of the fluorophores did not respond to alkali metal cations, only trans-7a containing an 18-crown-6 ring showed K(+) selectivity.     

Inter- and intramolecular pi-stacking interactions in cis-bis[1-(9-anthracene)]phosphirane complexes of platinum(II)

The bis[1-(9-anthracene)phosphirane]dithiolatoplatinum(II) complexes, Pt[1-(9-anthracene)phosphirane](2)(dithiolate), where dithiolate = 1,1-dimethoxycarbonyl-ethylene-2,2-dithiolate (dmdt) (2), 1,1-diethoxycarbonyl-ethylene-2,2-dithiolate (dedt) (3), 1-ethoxycarbonyl-1-cyano-ethylene-2, 2-dithiolate (ecdt) (4), and 1,1-dicyano-ethylene-2,2-dithiolate (dcdt) (5), were prepared from cis-dichlorobis[1-(9-anthracene)phosphirane]platinum(II) (1). Complexes 3 and 5 were characterized by X-ray crystallography and were found to have vastly different crystal and molecular structures. The crystal and molecular structure of 3 is dominated by intramolecular pi-stacking between the anthracene rings of the cis-bis(anthracene)phosphiranes with a ring...ring separation of 3.48(6) A. The molecular structure of 5 does not exhibit an intramolecular interaction between the anthracene rings. Instead, the crystal structure of 5shows significant intermolecular pi-stacking between the anthracene rings of the phosphirane ligands of adjacent molecules packed in the crystal lattice. The intermolecular stacking interaction results in a ring...ring separation of 3.33(4) A. Complexes 2-5 were found to emit at 530 nm at low temperatures in the solid state. Complex 5 emits strongly in fluid THF or benzene solution at 430 nm.     

硼氢二茂铁铵盐的结构化学研究——Ⅲ.十二硼十二氢双(二茂铁甲基二甲基)铵晶体结构

标题的化合物晶体属斜方晶系,空间群为Pcnb,晶胞参数为:a=12.975(26),b=16.342(28),c=17.582(48),Z=4。晶体结构用直接法,三维Patterson函数和差值Fourier方法解出,经全矩阵最小二乘法修正,对1674个独立衍射点[I≥3σ(I)],最后偏离因子R=0.054。 该化合物属于离子型,阴离子和阳离子分别以六面体和四面体配位。     

Synthesis and Crystal Structure of N-methyl- 9- （4-bromophenyl）-1,2,3,4,5,6,7,8,9,10- decahydroacridine- 1,8-dione under Microwave Irradiation

1 INTRODUCTION Since the discovery of pharmacological effectsof 1,4-dihydropyridine (1,4-DHPs) as calcium mo-dulators[1], a great deal of work has been directedtowards the synthesis of 1,4-DHPs acting as cal-cium antagonists[2]. The chemical modifications onthe DHP ring, such as the introduction of differentsubstituents on heteroatoms[3], have allowed theexpansion of researches on structure-activity rela-tionship to have new insight into the molecularinteractions at the receptor l…     

Synthesis and Crystal Structure of N-[(3aR,4R,4aR,5aS,6S,6aS)-1,3-Dioxooctahydro-4,6-ethenocyclopropa[f]lisoindol-2(1H)-yl]-3-(trifluoromethyl)phenylmethanimine

The crystal structure of the title compound (C19H15F3N2O2, Mr= 360.33) was determined by single-crystal X-ray diffraction. The crystal belongs to triclinic, space group P(1), with a = 6.5604(7), b = 13.9614(16), c = 18.1790(18) (A), α = 102.749(7),β = 97.542(6), γ = 94.355(4)°, V= 1600.5(3) (A)3, Z = 4, Dc = 1.495 g/cm3, λ(MoKα) = 0.71070, F(000) = 744, μ(MoKα) = 0.122mm-1, R = 0.0434 and wR = 0.1051. A total of 7590 unique reflections were collected, of which 5429 with |F|2 ≥ 2σ|F|2 were observed. The two cyclohexene rings in the molecule adopt boat-boat conformations with the deviations of ring atoms C(9) and C10 from the C(5)/C(6)/C(7)/C(8) plane (Ⅰ) by 1.1204 (0.0023) and 1.1132 (0.0023) (A), respectively, whereas from the C(2)/C(3)/C(5)/C(8)plane (Ⅱ) by 1.1627 (0.0022) and 1.1818 (0.0021) (A), respectively. In the cyclopropane and lactam rings, atoms C(11) and N(1) point towards the double bond of C(9)-C(10) and the dihedral angle between the ring plane (Ⅲ) containing C(1), C(2), C(3) and C(4) and plane (Ⅳ) consisting of C(6),C(7) and C(11) is 55.76 (0.07)°. The dihedral angles between planes Ⅳ and Ⅰ and Ⅱ and Ⅲ are 63.58 (0.07)° and 58.10 (0.06)°, respectively. The dihedral angle between the benzene ring C(13)～C(18) and plane Ⅳ is 42.41 (0.06)°.     

Synthesis,Crystal Structure and Prosperities of 10-（4,5-Dibenzylthio- 1,3-dithiol-2-ylidene）anthracen-9（10H）-one

The title compound 10-（4,5-dibenzylthio-1,3-dithiol-2-ylidene）anthracen-9（10H）- one （C31H22OS4） has been synthesized, and its crystal structure was prepared by crystallization from CH2Cl2-MeOH. The crystal belongs to the triclinic system, space group Pi with a = 10.9758（3）, b = 11.4241（4）, c = 11.7460（2）A^°, α = 62.379（2）, β = 81.227（3）, γ = 80.321（2）°, Mr = 538.73, V = 1281.69（7） A^°^3, Z = 2, Dc = 1.396 g/cm^3, F（000） = 560,μ = 0.395 mm^-1, the final R = 0.0291 and wR = 0.0739. The molecular structure is severely distorted from planarity. The central ring of anthraquinone moiety adopts a boat conformation, while the two outer benzene rings are tilted in the opposite direction to form a dihedral angle of 23.65°. The photocurrent generation was measured and an anodic photocurrent response was obtained. The electronic spectrum was studied by using TDDFr method on the basis of optimized geometries with B3LYP method. The obtained results are in good agreement with the experimental values.     

Synthesis and Crystal Structure of 2-（ 4-Decarboxydehydroabietyl）- 5-p-tolyl-[ 1,3,4 ]-oxadiazole

2-（4-Decarboxydehydroabietyl）-5-p-toyl-[1,3,4]-oxadiazole, C28H34N2O, has been synthesized and characterized by IR, NMR, elemental analysis and single-crystal X-ray diffraction method. The crystal belongs to the orthorhombic system, space group P212121 with a = 6.1351（5）, b = 14.8495（19）, c = 25.9050（2） A, V = 2360.0（4） A3, Z = 4, Mr = 414.57, Dc = 1.167 Mg/m^3, 2 = 0.71073 A,μ（MoKa） = 0.070 mm^-1, F（000） = 896, the final R = 0.0452 and wR = 0.1076 for 1647 observed reflections with I 〉 2σ（I）. There are five rings in the crystal structure of the title compound, but the oxadiazole ring is non-coplanar with the benzene ring D.     

Synthesis,Crystal Structure,Vibrational Spectroscopy,and Thermal Behavior of Y[B_2O_3（OH）]_3

The hydroxy yttrium hexaborate,Y[B2O3(OH)]3,has been synthesized under mild hydrothermal conditions at 458 K.The crystal structure was solved and refined from single-crystal X-ray diffraction.It adopts a trigonal space group R3c(No.161) with a = 8.3942(4),c = 20.6484(12) ,V = 1260.03(12) 3,YB6H3O12,Mr = 348.79,Z = 6,Dc = 2.758 g/cm3,F(000) = 1008,μ = 7.015 mm-1,R = 0.0321 and wR = 0.0772.Its crystal structure is made up of six-membered rings,alternating three-connected [BO3(OH)] tetrahedra and planar [BO3] trigonal groups,which are interconnected with each other by sharing their common oxygen corners to form a three-dimensional framework structure with six-membered ring channels that are occupied by the yttrium atoms and run along the c axis.FT-IR,Raman,and TG-DTA results are also presented.