Synthesis of hexacyclo[7.4.0.02,8.03,7.06,11]Tridecane-10,13-dione(“homosecohexaprismane-10,13-dione”)

HEXACYCLO[7.4.0.0^2,8.0^3,7.0^6,11]tridecane-10,13-dione (“homosecohexaprismane-10,13-dione”, 8) has been prepared via a six-step sequence that results in homologation of two of the cyclopentane rings in pentacyclo[5.4.0.0^2,6.0^3,10.0^5,9]-undecane-8,11-dione, 1. The structure of 8 has been established unequivocally via single crystal X-ray structural analysis.     

Synthesis of 5′-amino- and 5′-azido-2′,5′-dideoxy nucleosides from thieno[2,3-d]pyrimidine-2,4(1H,3H)-dione

Summary Thieno[2,3-d]pyrimidine-2,4(1H,3H)-dione (4) was silylated and condensed with methyl 5-azido-2,5-dideoxy-3-O-(4-methylbenzoyl)-D-erythro-pentofuranoside (2) in the presence ofTMS triflate to afford the corresponding protected nucleoside6 and acyclic nucleoside7. Deprotection of6 with MeONa/MeOH at room temperature gave 1-(5-azido-2,5-dideoxy--D-erythro-pentofuranosyl)-thieno[2,3-d]pyrimidine-2,4(1H,3H)-dione (8) and the corresponding anomer9, whereas compound7 yielded 5-azido-2,5-dideoxy-1-(2,4-dioxo-1,2,3,4-tetrahydrothieno[2,3-d]pyrimidin-1-yl)-1-O-methyl-D-erythro-pentitol (10) under the same reaction conditions. 1-(5-Amino-2,5-dideoxy--D-erythro-pentofuranosyl)thieno[2,3-d]pyrimidine-2,4(1H,3H)-dione (11) was obtained on treating9 with Ph₃P in pyridine followed by hyrolysis with NH₄OH. The anomeric nucleosides14 and15 and the corresponding acyclic nucleoside16 were obtained when4 was trimethylsilylated and condensed with methyl 2-deoxy-3,5-di-O-(4-methylbenzoyl)-D-erythro-pentofuranoside (3) followed by deprotection with MeONa in MeOH. Compounds8 and9 were also obtained when the anomeric mixture14/15 was treated with a mixture of NaN₃, Ph₃P, and CBr₄ in dryDMF at room temperature.On leave from Chemistry Department, Faculty of Science, Tanta University, Tanta, Egypt     

Calixarenes as second-sphere ligands for transition metal ions. Synthesis and crystal structure of [(H2O)5 Ni(NC5H5)]2(Na)[calix[4]arene sulfonate] · 3.5 H2O and [(H2O)4Cu(NC5H5)2]-(H3O)3 [calix[4]arene sulfonate] · 10 H2O

The title compounds crystallize such that bilayers of calixarenes are separated by hydrophilic layers. In each case the transition metal has, in addition to a primary sphere of ligands, a second-sphere coordination by a calixarene. [(H₂O)₅Ni(NC₅H₅)]₂(Na)[calix[4]arene sulfonate]·3.5 H₂O,1, crystallizes in the triclinic space groupP \(\bar 1\) witha = 12.487(4),b = 14.281(2),c = 15.055(5) Å, α = 85.66(2), β = 80.07(2), γ = 80.48(2)°, andD _c = 1.64 g cm^?3 forZ = 2. Refinement based on 2441 observed reflections led to a finalR value of 0.066. There are two different environments for the nickel-containing cations: one is positioned within the hydrophilic layer with the pyridine ligand intercalated into the hydrophobic calixarene bilayer and the other is also positioned within the hydrophilic layer, but the pyridine ligand is inserted into the hydrophobic cavity of the calix[4]arene. [(H₂O)₄Cu(NC₅HS)₂](H₃O)₃[calix[4]arene sulfonate]·10 H₂O,2, crystallizes in the triclinic space groupP \(\bar 1\) witha = 15.438(4),b = 15.727(6),c = 12.121(9) Å, α = 112.74(4), β = 102.02(4), γ = 85.34(4)°, andD _c = 1.57 g cm^?3 forZ = 2. Refinement based on 3925 observed reflections led to a finalR value of 0.107. The structure is similar to that of 1 except that the one copper-containing cation spans the hydrophilic layer and is intercalated into the bilayer of calixarenes on one side and positioned into the calixarene cavity on the other.     

Molecular structure of two dicyclopentadienylmolybdenum derivatives containing a four-membered ring [Mo(η5-C5H5)2(2-NHNC5H4)][PF6] and [Mo(η5C5H5)2(2-ONC5H4)][PF6]

The structure of the new compound [Mo(η⁵-C₅H₅)₂(2-NHNC₅H₄)][PF₆] (1) has been determined. The crystals are orthorhombic, space group Pca2₁ with a 20.807(1), b 8.0030(8), c 10.056(3) Å, V 1674.5 ų, Z = 4. The structure of [Mo(η⁵-C₅H₅)₂(2-ONC₅H₄)][PF₆] (2) has also been determined. The crystals are orthorhombic, space group Pnma with a 12.727(3), b 10.174(2), c 12.918(1) Å, V 1672.8 ų, Z = 4. The structures were solved by Patterson and difference electron density syntheses and refined by least-squares to R of 0.028 for 1287 reflections for 1 and 0.059 for 1178 reflections for 2.Although not isostructural the two cationic complexes have equivalent geometries with the normal bent bismetallocene structure. For 1 the MoN bond lengths are 2.160(8) and 2.142(9) Å, with a NMoN bond angle of 59.8(3)°, whereas for 2 MoO is 2.142(10), MoN is 2.138(11) Å, the NMoO angle is 61.2(4)°. These parameters are discussed and compared with the corresponding data for similar biscyclopentadienyl complexes of molybdenum(IV). Extended Hückel molecular orbital calculations have been carried out to throw light on the nature of the bonding between the metal and the bidentate ligand.     

Preparation and crystal structures of [μ-SbPh2]2[Mo(CO)2(η5-C5H5)]2·CHCl3 and SbPh[Fe(CO)2(η5-C5H5)]2

Antimony is reduced when [SbPh₂BrO]₂ is treated with Na[Mo(CO)₃(η⁵-C₅H₅)] to produce [μ-SbPh₂]₂[Mo(CO)₂(η⁵-C₅H₅)]₂. A structure determination shows diphenylstibido groups bridging between two Mo(CO)₂(η⁵-C₅H₅) moieties giving a central ‘butterfly’ shaped Sb₂Mo₂ ring. The cyclopentadiene rings are trans to each other and Mo–Sb and Sb–Sb separations are both short. An iron analogue could not be obtained from [SbPh₂BrO]₂ and Na[Fe(CO)₂(η⁵-C₅H₅)] but a mixture of SbPh[Fe(CO)₂(η⁵-C₅H₅)]₂ and SbPh₂[Fe(CO)₂(η⁵-C₅H₅)] was obtained using SbPh₂Cl. An X-ray structure for SbPh[Fe(CO)₂(η⁵-C₅H₅)]₂ shows an open stibinidine structure.     

Syntheses,crystal structures and antibacterial activities of [Cu2(C11H11NO5S)2(H2O)4] · 5H2O and [Ni2(C11H11NO5S)2(H2O)4] · 2H2O

The binuclear complexes [Cu₂L₂(H₂O)₄] · 5H₂O (1) and [Ni₂L₂(H₂O)₄] · 2H₂O (2) (where L = C₁₁H₁₁NO₅S, H ₂ L = 2-[(3-formyl-5-methyl-2-hydroxy-benzylidene)-amino]ethanesulfonic acid) have been synthesized and characterized by IR, elemental analysis and X-ray diffraction. The crystals belong to the monoclinic system, space group P2₁/c. Complex 1: a = 16.8902(12), b = 11.2829(6), c = 17.4249(11) Å; β = 106.709(4)°; S = 1.131; V = 3180.5(3) ų; Z = 4; D _Calcd = 1.729 g cm^?3; F(000) = 1712; μ = 1.554 mm^?1; R ₁ = 0.0519, wR ₂ = 0.1349; complex 2: a = 11.399(2), b = 19.985(3), c = 7.3694(10) Å; β = 108.664(7)°; S = 1.157; V = 1590.6(4) ų; Z = 2; D _Calcd = 1.604 g cm^?3; F(000) = 800; μ = 1.388 mm^?1; R ₁ = 0.1859, wR ₂ = 0.4346. The geometry around each metal(II) center can be described as slightly distorted octahedral. Water-sulfonic clusters and (H₂O)₄ water clusters can be observed for 1 from the crystal packing diagram, while cavity and offset face-to-face π–π stacking can be observed for 2. The complexes have been tested for the antibacterial activities which show antibacterial activities of 1 for β-hemolytic streptococcus, Staphylococcus aureus and Escherichia coli, and the antibacterial activity of 2 only for β-hemolytic streptococcus.     

Synthesis and structure of bismuth-containing complexes [Ph3PMe] 2 + [BiI5]2− and [Ph3PMe] 2 + [BiI5 · C5H5N]2− · C5H5N

The complexes [Ph₃PMe] ₂ ⁺ [BiI₅]^2? (I) and [Ph₃PMe] ₂ ⁺ [BiI₅ · C ₅H₅N]^2? · C ₅H₅N (II) were synthesized by the reaction of bismuth triiodide with triphenylmethylphosphonium iodide, and their structures were determined by X-ray diffraction analysis. The P atom in cation I has slightly distorted tetragonal coordination polyhedron (the CPC angles 109.42(4)° and 109.52(4)°, the bond lengths P-C_Ph 1.779(2), P-C_Me 1.793(1) Å. The Bi atom in the anion of complex I has an ideal trigonal-bipyramidal coordination polyhedron (Bi-I_eq 3.0031(4), Bi-I_eq 3.0485(5) Å). The crystal of complex II consists of the anions [BiI₅ · C ₅H₅N]^2?, solvated pyridine molecules, and two types of crystallographically independent tetrahedral triphenylmethylphosphonium cations (the angles CPC 106.9(1)°–111.7(1)°, the distances P-C_Ph 1.785(3)–1.792(3), P-C_Me 1.793(3), 1.786(3) Å). The Bi atoms in the anion of complex II have a distorted octahedral coordination polyhedron (Bi-I 3.0878(4)–3.1240(3), Bi-N(1) 2.628(3) Å).     

5′,5′,6,6-Tetramethyl-6,7-dihydro-3′H-spiro[1,3-benzodithiole-2,1′-cyclohexane]-3′,4(5H)-dione

Russian Journal of Organic Chemistry -     

Comparative studies of the photochemical and thermal reactivities of the molybdenum-molybdenum single bond in [Mo2(η5-C5H5)2(CO)6] and triple bond in [Mo2(η5-C5H5)2(CO)4] towards nitrite and nitrate

Irradiation at λ = 507 and 391 nm of [Mo₂(η⁵-C₅H₅)₂(CO)₆] in a degassed tetrahydrofuran (THF) or THF-MeOH solution containing nitrite gives [Mo(η⁵-C₅H₅)₂NO] and several oxo complexes including [{Mo(η⁵-C₅H₅)(O)₂}₂O] in good yields. The quantum yields for the disappearance of [Mo₂(η⁵-C₅H₅)₂(CO)₆] in the reaction with NO₂⁻ depend on the nitrite concentration, thus suggesting participation of the metal-radical intermediate in the reduction of nitrite. Reactions of [Mo₂(η⁵-C₅H₅)₂(CO)₄] with nitrite or nitrate in the dark give the same nitrosyl and oxo complexes as above. An oxygen atom in nitrite or nitrate is mainly transferred onto the molybdenum atom both in the photochemical and the dark reactions.     

Electron transfer in organometallic clusters: XIV. Crystal and electronic structures of the tricobalt carbon cluster (η5-C5H5)Fe[η5-C5H4-CCo3(CO)9] and the biscarbyne cluster (η5-C5H5)Fe[η5-C5H4CCo3(η5-C5H5)3CH]

The crystal and molecular structures of (η⁵-C₅H₅)Fe[η⁵--C₅H₄CCo₃(CO)₉] (1), Pna2₁, α 17.354, b 11.463, c 11.207 Å Z = 4, R = 0.053, R_w = 0.056 for 939 reflections (I>3σ(I)) at 293 K, and (η⁵-C₅H₅Fe[η⁵--C₅H₄CCo₃(η⁵C₅H₅)₃CH] (2), P2₁/n, a 13.807(9), b 11.254(4), c 13.991(9) Å, β 99.98(5)°, Z = 4, R = 0.033 and R_w = 0.033 for 3051 observed reflections (I>3σ(I)) at 180 K, have been determined by X-ray methods.The results provide a detailed characterisation of related tricobalt-carbon complexes directly bound to ferrocene residues. In 1 the ferrocenyl moiety tops the pyramidal CCo₃ cluster core, while in 2 the CCo₃C core is bipyramidal with a ferrocenyl substituent on one capping carbon atom and a hydrogen atom at the other. In both cases the ferrocenyl group is tilted towards one cobalt atom of the cluster core, a distortion believed to be the consequence of the non-degeneracy of the carbyne p(π) orbitals resulting from a cooperative π-interaction between the clusters and the ferrocenyl substituents.     

Syntheses and Crystal Structures of Two Ion Pair Complexes, [Ru(bpy)3]2[Fe(CN)6]I · 7H2O and [Ru(bpy)3]- [Fe(CN)5NO]CH3OH · H2O

Two ion pair complexes, [Ru(bpy)₃]₂[Fe(CN)₆]I [sdot] 7H₃O (1) and [Ru(bpy)₃][Fe(CN)₅NO](CH₃OH) [sdot] H₂O (2) (bpy = 2,2-bipyridine) have been synthesized and structurally characterized. X-Ray crystallographic structures of 1 and 2 both show Fe(III) and Ru(II) in distorted octahedral environments. In both complexes, H-bonding interactions between an uncoordinated water molecule and the nitrogen atom of a cyano group exist.     

4[CuCl(C5H5N)4]·[W10O32]·2(C5H5N)·3H2O的合成及晶体结构

标题化合物是通过(NH_4)_2WS_4, CuCl_2·2H_2O在吡咤溶液中反应制得。晶体呈蓝色, 属三斜晶系, 空间群P1, 晶胞参数为:a=1.3555(7), b=1.3666(5), c=1.7860(13) nm, α=69.08(4)°, β=87.39(5)°, γ=70.72(4)。V=2.907(3) nm, Z=1, D_m=2.56 g cm~(-3)。结构由Patterson法和Fourier法测出。对5692个收集到的独立衍射数据进行计算, 最后R=0.046。结构测定表明, 晶体由W_(10)O_(32)~(4-), [CuCl(C_5H_5N)_4]~+, C_5H_5N和H_2O所组成。W_(10)O_(32)~(4-)的结构见图1, W原子处在O原子的八面体配位中, 彼此共边和共顶点相连。[CuCl(C_5H_5N)_4]~+的结构见图2, Cu原子由1个Cl和4个N原子配位, 呈略有变形的四方锥形, 这种离子是首次报导。C_5H_5N和H_2O填入正负离子堆积的空隙中。     

Spiro[1,3-benzoxathiepin-4(5H),1′-cyclohexa[2,4]dien]-2,2′-dione,a Novel Heterocyclic Ring System

Abstract

Besides the common cyclisation reactions between divalent electrophiles such as Soc1₂, SC1₂, etc. and 2,2′-alkylidene-bisphenols 1 with selective attack by the two oxygens yielding dibenzo[d,g][1,3,2]dioxathiocines [1] we observed previously an unusual cyclisation of 1 with S₂CI₂ with a nucleophilic attack by the ortho- and para-carbon atoms (C(2) and C(4)) of bisphenol 1 [2]. We now report a new type of cyclocondensation reaction of 4,4′,6,6′-tetrasubstituted 2,2′-alkylidene-bisphenols 1 with ClSCOCl affording spiro[1,3-benzoxathiepin-4(5H),1′-cyclohexa[2,4]dien]-2,2′-diones 2 together with the cyclic carbonates 3. The structures of the products were elucidated mainly by ^l3C-NMR- and ¹H-NMR-spectroscopy. The mode of formation of the novel spiro thiocarbonates 2 resp. the known carbonates 3 [3] is discussed.     

Synthesis,Structure and Antimicrobial Activity of 9,9-Dimethyl-9,10-dihydrospiro[benzo[a]-xanthene-12,3?-indoline]-2?,11(8H)-dione

One novel spiro-compound(C_(26)H_(21)NO_3) has been synthesized and characterized by means of NMR spectroscopy,elemental analyses and X-ray diffraction. The single crystal belongs to the monoclinic system,space group P21/c with a = 8.8039(7),b = 24.123(2),c = 10.0751(9) ?,β = 108.403(3)°,M3r = 395.44,V = 2030.3(3) ?~3,Z = 4,D_c = 1.294 g/cm,F(000) = 832.0,μ = 0.085 mm~(-1),R = 0.0801 and wR = 0.2228. The title compound shows good activities against Micrococcus tetragenus,Bacillus cereus,Bacillus subtilis,Staphylococcus aureus,S.albus and Escherichia coli.     

N,N′-methylenedipyridinium Pt(II) and Pt(IV) hybrid salts: synthesis, crystal and molecular structures of [(C5H5N)2CH2] · [PtCl4] and [(C5H5N)2CH2] · [PtCl6]

The highly insoluble organic-inorganic hybrid ionic compounds N,N??-methylenedipyridinium tetrachloroplatinate(II) [(C₅H₅N)₂CH₂] · [PtCl₄] and N,N??-methylenedipyridinium hexachloroplatinate(IV) [(C₅H₅N)₂CH₂] · [PtCl₆] were obtained by the treatment of N,N??-methylenedipyridinium dichloride monohydrate [(C₅H₅N)₂CH₂]Cl₂ · H₂O with K₂[PtCl₄] or (NH₄)₂[PtCl₆], respectively, in an aqueous solution. Both complexes were isolated, purified, characterised by elemental analysis, and their molecular structures were confirmed by powder X-ray diffraction. The crystal structure of both compounds consists of separated discrete dications [(C₅H₅N)₂CH₂]²⁺ and anions [PtCl _n ]^2? (n = 4 or 6). As anticipated, the dications formed a butterfly shape consisting of two pyridine rings bound to the methylene group via their N atoms, while the Pt centre had a square planar geometry in [(C₅H₅N)₂CH₂] · [PtCl₄] and an octahedral coordination in [(C₅H₅N)₂CH₂] · [PtCl₆]. Interestingly, both crystal structures are stabilised by intermolecular C-H??Cl non-standard hydrogen bonds, ??-?? ring interactions between two pyridine rings of adjacent dications, and also by Cl-?? interactions.     

Alkylation of 3-tert-Butylpyrimido[4′,5′:3,4]pyrazolo[5,1-c]-[1,2,4]triazine-4,10(1H,9H)-diones and -dithiones

Russian Journal of Organic Chemistry - The condensation of 7-amino-1-benzyl-3-tert-butyl-4-oxo-1,4-dihydropyrazolo[5,1-c][1,2,4]triazine-8-carbonitrile with formic acid afforded...     

Synthesis and Crystal Structure of [CpRu(η5-C5H5)(dppc)Cl][PF6]

The title complex [Ru(η5-C5H5)(dppc)Cl][PF6] has been synthesized by the reaction of [Ru(η5-C5H5)(PPh3)2Cl] with [dppc][PF6] (1,1'-bis(diphenylphosphino)cobaltocenium hexaflurophospate) in CH2Cl2, and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/n with a = 15.754(8), b =13.704(7), c=19.120(10) (A),β=106.148(9)°, V=3965(4) (A)3, Z=4, C40H35Cl3CoF6P3Ru, Mr=988.94, Dc=1.657 g/cm3, F(000) = 1984 and μ(MoKα) = 1.181 mm-1. The final R = 0.0425 and wR = 0.1001 for 7002 independent reflections. The title complex shows a mononuclear Ru(Ⅱ)capped by an η5-Cp ring, a chelating η2-dppc and a terminal chloride to assume a three-legged piano-stool configuration.     

The crystal and molecular structures of aqua(1,4,7,10,13-pentaazacyclopentadecane)nickel(II) nitrate perchlorate [Ni[15]aneN5·H H2O](NO3)(ClO4) and (1,5,9,13,17-pentaazacycloeicosane)-nikel(II) nitrate hydrate [Ni[20]aneN5](NO3)2·H2O

Summary The structures of Ni^II complexes of the macrocyclic ligands 1,4,7,10,13-pentaazacyclopentadecane, [15]aneN₅ and 1,5,9,13,17-pentaazacycloeicosane, [20]aneN₅ have been determined. [Ni(C₁₀H₂₅N₅)H₂O]-(NO₃)(ClO₄) monoclinic, space group P2₁/n,a=8.265(3)Å,b=6.201(6)Å,c=13.672(4)Å, =93.35(3)°· 2394 unique reflections were used in the structure determination and the refinement proceeded to an R value of 0.045. The ligand is coordinated to the metalvia all five nitrogens in theracemic conformation and a water molecule completes the coordination sphere of the metal ion. The complex cation shows considerable distortion from octahedral geometry which may rationalise the unusual spectroscopic properties and the low enthalpy of formation of the complex cation. [Ni(C₁₅H₃₅N₅)](NO₃)₂·H₂O monoclinic, space group P2₁/n,a=15.437(9)Å,b=9.573(6)Å,c=15.942(8)Å, =109.24(4)°. 2715 unique observed reflections were used in the structure refinement which proceeded to an R value of 0.035. The five nitrogens of the macrocycle are bound to Ni(II) in a distorted square pyramidal coordination geometry. The Ni^II lies 0.35Å above the basal plane of the four nitrogen atoms.     

Heterocyclizations of Di- and Tricarbonyl Indole Derivatives. Synthesis of β-Carbolines, 3H-[1,2,5]Triazepino-[5,4-a]indol-4(5H)-one,and 5,10-Dihydro[1,2]diazepino-[4,5-b]indol-4(3H)-one

Russian Journal of Organic Chemistry - A synthetic approach to β-carbolines has been proposed on the basis of heterocyclization of ethyl 2-(2-benzoyl-1H-indol-3-yl)acetate with...     

Synthesis and Crystal Structure of an Ionic Compound [Fe(CN)6(phCH2NC5H5)3]·(H2O)4

A novel ionic compound [Fe(CN)6(phCH2NC5H5)3]·(H2O)4(Mr = 794.71) has been synthesized and its structure was characterized by IR, elemental analysis and X-ray diffraction. The compound crystallizes in monoclinic, space group P21/c with a = 10.837(2), b = 16.551(3), c = 23.402(5) (A), β = 97.531(4)°V = 4161.0(15)(A)3, Z = 4, Dc = 1.269 g/cm3, F(000) = 1668, μ = 0.414 mm-1, R = 0.0479 and wR = 0.1232. The building unit of the title compound consists of three (phCH2N C5H5) ions, one [Fe(CN)6]3- anion and four water molecules. According to the structural analysis, [Fe(CN)6]3- are linked together by O-H…N and O-H…O hydrogen bonds, but [Fe(CN)6]3- and [(phCH2N C5H5)3] ions are bound by electrostatic force to form an ionic compound.Keywords: N-benzyl-pyridine, ferricyanic anion, crystal structure, supramolecular, ionic compound.