Synthesis and structure ofexo-11-cyano-endo-11-(trimethylsilyloxy)pentacyclo[5.4.0.02,6.03,10.05,9]undecan-8-one

The crystal structure of an asymmetric pentacyclo[5.4.0.0^2,6.0^3,10.0^5,9]undecan-8,11-dione derivative is reported, in which Me₃SiCN has been added across one of the keto groups. The cage structure demonstrates the expected effects of this addition.     

Structure of a PCU-derived pinacol formed via sodiumpromoted reductive dimerization of pentacyclo[5.4.0.02,6.03,10.05,9]undecane-8,11-dione monoethylene ketal

The pinacol resulting from sodium promoted reductive coupling of pentacyclo[5.4.0.0^2,6.-0^3,10.0^5,9]undecane-8,11-dione monoethylene ketal possesses a conformation, dictated by intramolecular hydrogen bonding, that lies midway between eclipsed and staggered. The C–C and C–O distances in the pinacol unit are, respectively, longer and shorter than usual, and all parameters are as expected.     

Stereospecific solid-state NaBH4-promoted reduction of 1-methylpentacyclo[5.4.0.02,6.03,10.05,9]undecane-8,11-dione

NaBH₄ reduction of a cage dione proceeds in a stereospecific fashion to give theendo,endo-diol. This reactivity is related to the crystal structure.     

Tetracyclo[6.3.0.04,11.05,9]undecane-2,7-dione

The compound crystallizes in the triclinic space group, , witha=6.7702(4),b=7.0180(4),c=9.1960(7) Å, =92.457(6), =96.150(6), =93.444(5)°, andZ=2. The structure contains a rather short intramolecular H...H contact of 2.26(4) Å.     

Crystal structures of three substituted pentacyclo[5.4.0.02,6.03,10.05,9]undecanes

The crystal structures of three compounds formed via ultimate nucleophilic attack of unsaturated hydrocarbon fragments are reported. Geometries of the bis(vinyl)-, mono(vinyl), and bis(ethynyl)-substituted PCU species are unexceptional. The crystal structures are dictated by the availability of intermolecular hydrogen bonding.     

Stereospecific solid-state NaBH4-promoted reduction of 1-methylpentacyclo[5.4.0.02,6.03,10.05,9]undecane-8,11-dione

NaBH₄ reduction of a cage dione proceeds in a stereospecific fashion to give theendo,endo-diol. This reactivity is related to the crystal structure.     

Reaction of vinylmagnesium bromide with hexacyclo[10.2.1.02,11.04,9.04,14.09,13]pentadeca-5,7-diene-3,10-dione: Transannular hemiketal formation

Reaction between vinylmagnesium bromide and the cage dione leads to attack of only one equivalent of Grignard and intramolecular nucleophilic attack on the second ketone. The product compound crystallizes in the monoclinic space group, P2₁/a, witha=9.509(1),b=11.071(2),c=12.492(4) Å, =104.32(2)°, andZ=4.     

Structure of de-oxy corticosterone (4-pregnen-21-ol-3,20-dione)

Synthetic steroid de-oxy corticosterone (4-pregnen-21-ol-3,20-dione) crystallizes in the monoclinic space group P2₁, with a = 11.706(2); b = 11.171(3), c = 13.966(3) Å, and = 100.94(2)°, Z = 4. Ring A tends to acquire the conformation of a half-boat, rings B and C are in the chair configuration, and ring D is a 13, 14-half-chair. The ring junctions B/C and C/D are both trans, whereas the ring junction A/B is quasi-trans. The molecule as a whole is slightly convex toward the -side, with an angle of 16.01(0.36)° between the C10--C19 and C13--C18 vectors. Molecular packing and stacking interactions play the major role in structural association. Cohesion of the crystal is due to van der Waals interactions.     

Crystal structure of 4-methyl-2-phenylbenzo[de]cyclobut[i] isoquinoline-3,5(2H)-dione

4-Methyl-2-phenylbenzo[de]cyclobut[i]isoquinoline-3,5(2H)-dione, C₂₁H₁₅NO₂, resulted from the photochemical reaction of N-methyl-1,8-naphthalenedicarboximide with phenylacetylene, has been characterized by ¹H NMR, IR, and MS spectra and established by single-crystal X-ray crystallography. The crystal structure belongs to the monoclinic space group P2₁/n with cell parameters a = 12.530(2) Å, b = 9.324(2) Å, c = 13.296(2) Å, = 96.85(1), V = 1542.3(4) ų, and Z = 4.     

全取代环戊基六元瓜环晶体制备及其晶体结构研究

研究了对全取代环戊基六元瓜环(CyP6Q6)与结构诱导剂ZnCl2在稀盐酸条件下长的晶体进行X-射线单晶衍射分析.通过实验得到一个新的晶体,其结构表明,晶体属于斜方晶系,空间群为P21/n,a=27.599(7)(A),6=17.393(7)(A),c=18.265(5)(A),α=90.00°,β=93.369(6)°,γ=90.00°,Z=4,R=0.046,其中结构中出现了蜂巢效应并且形成了较大的孔道.     

Structure of 2-{2-[3-methyl-3-(2,4,6-trimethylphenyl) cyclobutyl]-2-oxoethyl}isoindole-1,3-dione

2-{2-[3-Methyl-3-(2,4,6-trimethylphenyl)cyclobutyl]-2-oxoethyl}isoindole-1,3-dione (C₂₄ H₂₅NO₃) was synthesized, and its crystal structure was determined by X-ray crystallographic techniques. The compound crystallizes in the triclinic space group P-1, with unit cell parameters: a = 14.109(9) Å, b = 14.130(8) Å, c = 12.152(6) Å, = 105.62(5)°, = 113.75(4)°, = 98.78(5)°, V = 2039.8(19) ų, D _c= 1.223 g/cm³, and Z = 4. The crystal structure has two crystallographically independent molecules, I and II. These molecules are held together by weak intermolecular C—H···O interactions, forming a continuous chain. The dihedral angles between the N-substituted phthalimide moiety and cyclobutane ring in molecules I and II are 60.37(14) and 68.18(18)°, respectively.     

Syntheses and structures of dihydrocalix[4]arenes bearing O-benzonitrile and O-acetonyl substituents

Three 25,27-dihydrocalix[4]arene derivatives, bearing benzonitrile and acetone groups on the oxygens, were prepared and structurally characterized. All three structures crystallize in , with cell dimensions: bis(benzonitrile)calix[4]arene·toluene, a = 11.530(2) Å, b = 12.013(2) Å, c = 14.089(4) Å, = 103.555(18)°, = 94.341(18)°, = 104.704(16)°, and V = 1815.9(7) ų; anti-bis-acetone-calix[4]arene, a = 7.5847(8) Å, b = 12.0948(17) Å, c = 15.3375(16) Å, = 78.982(10)°, = 76.932(9)°, = 73.129(10)°, and V = 1299.6(3) ų; syn-bis-acetone-calix[4]arene, a = 9.080(3) Å, b = 10.391(3) Å, c = 14.816(3) Å, = 96.998(19)°, = 100.02(2)°, = 103.93(3)°, and V = 1299.6(3) ų.     

Structure determination of [tetraethylammonium]-[(1,3-dithiole-2-one-4,5-dithiolato)diphenyl-(thiocyanato-N)stannate]

The title compound (3) has been synthesised and its molecular structure has been elucidated by single crystal X-ray diffraction. Refinement of the complex in space groupP2₁/c witha=11.535(4),b=9.831(2),c=25.217(1) and β=94.23(5)° converged atR=0.064. The geometry at the tin center in the anion is trigonal bipyramidal, with the thiocyanato N atom and a dithiolato S atom in the axial sites. The tetraethylammonium cation exhibtis normal geometry.     

Synthesis and crystal structure of 3,5,9,11-tetraacetyl-14-oxo-1,3,5,7,9,11-hexaazapentacyclo[5.5.3.02,6.04,10.08,12]pentadecane

Crystals of 3,5,9,11-tetraacetyl-14-oxo-1,3,5,7,9,11-hexaazapentacyclo[5.5.3.0^2,6.0^4,10 .0^8,12]pentadecane, a new hexaazaisowurtzitane derivative, were obtained from a condensation reaction of 2,6,8,12-tetraacetyl-2,4,6,8,10,12-hexaazatetracyclo[5.5.0.0^5,9.0^3,11] dodecane with aqueous formaldehyde and subsequent crystallization of the product from aqueous acetone. X-ray diffraction analysis at room temperature indicates that the compound crystallizes in monoclinic system, space group P2₁/n with a = 9.4564(15), b = 14.184(2), c = 13.334(2) ?, β = 107.671(4)°, V = 1704.1(5) ?³, Z = 4, D _calc = 1.475 g/cm³, F(000) = 800, μ(MoK) = 0.112 mm⁻¹, and final R ₁ = 0.0505, wR ₂ = 0.1215 for observed reflections 2641 (I > 2σ(I)). The ether link (C–O–C) forms two heptacyclic rings with the N, C atoms in the cage respectively. The results of elemental analysis, IR and NMR spectroscopy are included.     

Structure of 4,6-dimethylisothiazolo[5,4-b]pyridin-3(2H)-one and its 2-[4-(2-methylphenyl) piperazin-1-ylmethyl] derivative

The crystal and molecular structures of 4,6-dimethylisothiazolo[5,4-b]pyridin-3(2H)-one, C₈H₈N₂OS, 1, and its 2-[4-(2-methylphenyl)piperazin-1-ylmethyl] derivative, C₂₀H₂₄N₄OS, 2c, are described. These compounds crystallize in the monoclinic system in the space group P2 ₁/c. The cell constants for compound 1 are a = 5.049(1), b = 14.897(1), c = 11.330(1) Å, = 98.07(1)°, Z = 4, T = 293 K, and D _cal = 1.419 g cm^–3, and for compound 2c are a = 15.525(1), b = 12.021(1), c = 10.911(1) Å, = 106.42(1)°, Z = 4, T = 293 K, and D _cal = 1.253 g cm^–3 The structures were solved by direct methods and refined to R values of 0.0411 and 0.0380 for 1640 and 3504 reflections for 1 and 2c, respectively. The analysis of the geometry and difference electron density map reveal that the dimethylisothiazolopyridine 1 exists in the amino tautomeric form in the crystalline state. The conformation of the o-methylphenylpiperazine part of the molecule 2c strongly depends on the substituents effect in the phenyl ring and is very similar to those observed in crystals for other investigated arylopiperazine derivatives of the isothiazolopyridine.     

Crystal structure of 2,8,14,20-tetranaphthylpyrogallol[4]arene

The aromatic derivative 2,8,14,20-tetranaphthylpyrogallol[4]arene was synthesized by the acid catalyzed condensation of 2-naphthaldehyde and pyrogallol in refluxing aqueous ethanol. Single crystal X-ray analysis revealed that the molecule crystallizes in a triclinic space group P1(bar) No. 2, with a = 11.3396(7) Å, b = 15.9942(10) Å, c = 26.3653(17) Å, α = 94.309(2)°, β = 91.765(2)°, γ = 93.892(2)°, D _calc = 1.298 g/m³ for Z = 1. Within the unit cell, six methanol molecules of crystallization plus one molecule of pyrazine were found to accompany the pyrogallol macrocycle. In the solid state, the macrocycle is found to adopt the chair conformation.     

Synthesis and Crystal Structure of 5,7,12,13b,13c,14-Hexahydro-1,4,-dibromo-8,11-dimethoxy-13b,13c-bis(ethoxycarbonyl)-6H,13H-5a,6a,12a,13a-tetra azbenz[5,6]azuleno[2,1,8-ija]benz[f]azulene-6,13-dione

The title compound has been synthesized by the reaction of 4 with 1,4-dimethoxybenzene. The yielded product 5 was investigated with X-ray crystallographic, NMR, EI-MS, and IR techniques. The crystal belongs to a monoclinic system, space group P2₁/c with unit cell parameters a = 12.7790(17) Å, b = 21.565(3) Å, c = 12.2544(16) Å, α = 90°, β = 107.014(2)°, γ = 90°, V = 3229.3(7) Å³, Z = 4, D_c = 1.661, M_r = 807.32, μ = 2.732 mm^?1, F(000) = 1632, R₁ = 0.0540 and wR₂ = 0.0989.     

Crystal structure of 25,27-bis[(2-cyanophenyl)methoxy] calix[4]arene

The crystal structure of 25,27-bis[(2-cyanophenyl)methoxy] calix[4]arene (C₄₄H₃₄N₂O₄) was determined by X-ray crystallographic analysis. It possesses space group R , with a = b = 35.993(8) Å, c = 13.842(3) Å, = = 90°, = 120°, and D _calc = 1.260 mg/cm³ for Z = 18. Crystal data indicate that Compound 1 exists in a pinched-cone conformation with intramolecular hydrogen bonds.     

Crystal structure and electrochemical behavior of a novel polyoxometalate [Ni(bpy)3]2[W4V2O19] with Lindqvist‐type structure

A novel polyoxometalate [Ni(bpy)₃]₂[W₄V₂O₁₉] (Ni₂V₂W₄) has been synthesized by the hydrothermal method and the structure determined by X‐ray crystallography. Ni₂V₂W₄ crystallizes in a trigonal system with space group R ‐3c (a = 15.8984 (5) Å, b = 15.8984 (5) Å, c = 43.855 (3) Å). In the structure of the compound, terminal and bridging oxygen atoms are bond to the metal centers by σ or π bonds. The W⁶⁺ and V⁵⁺ ions in isopolyanion [W₄V₂O₁₉]^4‐ statistically distribute over the six metal centers. Using cathodic adsorptive voltammetric method with a carbon paste electrode, the redox property and the electron transferring process were studied. The results show that electrochemical behavior about W(VI) and V(V) atoms give one‐electron, three‐electron and two‐electron reduction waves. Three successive oxidation waves are observed too. The compound was also characterized by thermal gravimetric analysis and IR spectra. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)