A Conformational Study of the Semisynthetic Ergot Alkaloid - Terguride

1993 ◽  
Vol 58 (12) ◽  
pp. 2944-2954 ◽  
Author(s):  
Michal Hušák ◽  
Bohumil Kratochvíl ◽  
Petr Sedmera ◽  
Josef Stuchlík ◽  
Alexandr Jegorov
Keyword(s):  
Solid State ◽  
Ergot Alkaloid ◽  
Direct Methods ◽  
2D Nmr ◽  
Free Base ◽  
Conformational Study ◽  
X Ray Diffraction ◽  
Triclinic Space Group ◽  
X Ray ◽  
Nmr Techniques

Conformational analysis studied by 2D NMR techniques and X-ray diffraction methods are reported for the semisynthetic ergot alkaloid - terguride, in the form of free base and as the protonated species. The structure of terguride hydrogen maleate monohydrate (C20H29N4O)+(C4H3O4)- . H2O (II) was solved by direct methods and refined anisotropically to an Rvalue of 0.068 for 1 991 unique observed reflections. The title compound crystallizes in the triclinic space group P1 with lattice parameters a = 7.061(2), b = 9.205(1), c = 12.223(4) Å, α = 96.36(2), β = 107.15(2), γ = 106.67(1)°. Studies revealed that terguride monohydrate (I) and its protonized form (terguride hydrogen maleate monohydrate) possesses the identical conformations both in solutions and in the solid state - an envelope for C and Chair for D ergoline rings.

Structural studies of organoboron compounds. LVI. 1-Benzyl-7-methyl-3,5-diphenyl-2,4,6-trioxa-1-azonia-3-bora-5-boratabicyclo[3.3.0]octane and 1,4,6,9-tetramethyl-2,7-diphenyl-3,8,11,12-tetraoxa-1,6-diazonia-2,7-diboratatricyclo[5.3.1.12,6]dodecane

1992 ◽  
Vol 70 (11) ◽  
pp. 2809-2817 ◽  
Author(s):  
Wolfgang Kliegel ◽  
Gottfried Lubkowitz ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Solid State ◽  
Gas Phase ◽  
Phenylboronic Acid ◽  
Direct Methods ◽  
Structural Studies ◽  
Triclinic Space Group ◽  
Full Matrix ◽  
X Ray ◽  
Molar Ratios ◽  
New Type

The preparation of the N-(2-hydroxypropyl)-N-alkylhydroxylamines, 6a (R = CH3) and 6b (R = CH2Ph), and their reactions with phenylboronic acid are described. Regardless of the molar ratios of reactants employed, the reaction with 6b leads to the 1:2 condensate 1-benzyl-7-methyl-3,5-diphenyl-2,4,6-trioxa-1-azonia-3-bora-5-boratabicyclo[3.3.0]octane, 7, while that with 6a gives rise to the 1:1 condensate 1,4,6,9-tetramethyl-2,7-diphenyl-3,8,11,12-tetraoxa-1,6-diazonia-2,7-diboratatricyclo[5.3.1. 12,6]dodecane, 11 (the cyclic BONBON dimer of 4,6-dimethyl-2-phenyl-1,3-dioxa-4-aza-2-boracyclohexane, 9). Compounds 7 and 11 both crystallize in the triclinic space group [Formula: see text]: for 7; a = 13.126(1), b = 15.337(1), c = 10.9469(5) Å, α = 91.727(5), β = 104.647(5), γ = 72.922(7)°, Z = 4; and for 11; a = 9.0807(4), b = 9.1653(3), c = 6.4876(2) Å, α = 97.708(3), β = 108.830(3), γ = 89.188(4)°, Z = 1. The structures were solved by direct methods and were refined by full-matrix least-squares procedures to R = 0.038 and 0.032 for 5879 and 1827 reflections with I ≥ 3σ(F2), respectively. Compound 7 has the expected bicyclic pyroboronate structure, but represents the first reported N-substituted example of this type of compound. Bond lengths involving boron in 7 are (C) O—B(sp3) = 1.428(2) and 1.420(2), (B)O—B(sp3) = 1.472(2) and 1.468(2), N—B(sp3) = 1.737(2) and 1.762(2), C(phenyl)—B(sp3) = 1.588(2) and 1.584(2), (N)O—B(sp2) = 1.402(2) and 1.404(2), (B)O—B(sp2) = 1.331(2) and 1.329(2), C(phenyl)—B(sp2) = 1.555(3) and 1.553(2) Å. The X-ray analysis establishes a centrosymmetric, twofold N → B coordinated, dimeric structure in the solid state for 11 in which each B—O—N segment of a central six-membered BONBON ring is bridged by an O—C—C moiety. Compound 11 represents the first fully characterized example of a new type of "BONBON" compound. Bond distances involving the boron atom are (N)O—B = 1.465(1), (C)O—B = 1.428(1), N—B = 1.695(2), and C(phenyl)—B = 1.607(2) Å. Spectroscopic evidence indicates that in solution and in the gas phase this material exists predominantly as the monomer 9.

Synthesis, reactivity and property of 5,15-dithiaporphyrin copper(II) complex

2014 ◽  
Vol 18 (08n09) ◽  
pp. 675-678 ◽  
Author(s):  
Naruhiko Wachi ◽  
Takeshi Kondo ◽  
Satoru Ito ◽  
Satoru Hiroto ◽  
Ji-Young Shin ◽  
...  
Keyword(s):  
Magnetic Susceptibility ◽  
Solid State ◽  
Sulfur Atom ◽  
Good Yield ◽  
Axial Ligand ◽  
Antiferromagnetic Interaction ◽  
Free Base ◽  
X Ray Diffraction ◽  
Temperature Dependent ◽  
X Ray

Preparation of 5,15-dithiaporphyrin copper(II) complex was carried out by treatment of 5,15-dithiaporphyrin free-base with copper(II) acetate. X-ray diffraction analysis elucidated its dimeric structure in the solid state, in which the meso-sulfur atom served as an axial ligand to each pentacoordinated Cu ( II ) center. Temperature dependent magnetic susceptibility of the complex was measured to reveal the weak antiferromagnetic interaction between two Cu ( II ) centers in the solid state. 5,15-dithiaporphyrin Cu ( II ) complex was converted into 10-thiacorrole Cu ( II ) complex in good yield upon heating with triphenylphosphine in refluxing toluene.

Synthesis and structural characterization of BaSr2Ge3O9

2016 ◽  
Vol 71 (12) ◽  
pp. 1225-1232
Author(s):  
Sebastian Bräuchle ◽  
Clivia Hejny ◽  
Hubert Huppertz
Keyword(s):  
High Temperature ◽  
Solid State ◽  
Structural Characterization ◽  
Diffraction Data ◽  
Barium Carbonate ◽  
Strontium Carbonate ◽  
X Ray Diffraction ◽  
Triclinic Space Group ◽  
X Ray

AbstractBaSr2Ge3O9 was prepared by high-temperature solid-state synthesis at 1100°C in a platinum crucible from barium carbonate, strontium carbonate, and germanium(IV) oxide. The compound crystallizes in the triclinic space group P1̅ (no. 2) isotypically to walstromite BaCa2Si3O9. The structure was refined from single-crystal X-ray diffraction data: a=7.104(5), b=10.060(7), c=7.099(5) Å, α=83.0(2), β=77.0(2), γ=70.2(2)°, V=464.3(6) Å3, R1=0.0230, and wR2=0.0602 for all data. BaSr2Ge3O9 is characterized by three-membered rings of germanate tetrahedra. There are three crystallographically different Ge sites (Ge1, Ge2, and Ge3) in each [Ge3O9]6− ring. The rings occur in layers with the apices of alternating rings pointing in opposite directions. The Sr2+ and Ba2+ ions are located in between. The Sr1 cation is eight-fold coordinated, while Sr2 is octahedrally surrounded by oxide anions, and the Ba cation again eight-fold coordinated.

The preparation and the crystal and molecular structure of S3N2NH2+BF4−; a molecular orbital study of the protonation of the trisulphur trinitride anion

1984 ◽  
Vol 62 (9) ◽  
pp. 1822-1827 ◽  
Author(s):  
Clifford G. Marcellus ◽  
Richard T. Oakley ◽  
A. Wallace Cordes ◽  
William T. Pennington
Keyword(s):  
Molecular Structure ◽  
Molecular Orbital ◽  
Crystal And Molecular Structure ◽  
Direct Methods ◽  
Membered Ring ◽  
Molecular Orbital Calculations ◽  
X Ray Diffraction ◽  
Triclinic Space Group ◽  
X Ray ◽  
Molecular Orbital Study

Protonation of the trisulphur trinitride ion, S3N3−, with tetrafluoroboric acid yields the ring-contracted S-amino thiodithiazyl salt, S3N2NH2+BF4−. The crystal and molecular structure of this salt has been determined by X-ray diffraction. The crystals are triclinic, space group P1, with a = 5.445(2), b = 7.346(3), c = 9.473(5) Å, α = 85.89(4), β = 83.92(3), γ = 82.13(3)°, V = 372.6(4) Å3, Dc = 2.02 g cm−3, and Z = 2. The structure was solved by direct methods and refined by full-matrix least-squares procedures to give a final R = 0.060. The structure of the five-membered ring with a single exocyclic NH2 group bonded to sulphur is discussed in relation to other S3N2NR derivatives. The reasons for the instability of six-membered rings of the type S3N3R are discussed in the light of MNDO molecular orbital calculations on an S3N3H model.

Synthesis, conformational analysis, and molecular structure of 5-ethyl-5,6-dihydro-11H-dibenzo[b,e]azepine-6-thione

1994 ◽  
Vol 72 (2) ◽  
pp. 334-338 ◽  
Author(s):  
J. Irurre ◽  
F. Marquillas ◽  
A. Alvarez-Larena ◽  
J.F. Piniella
Keyword(s):  
Molecular Structure ◽  
Solid State ◽  
Conformational Analysis ◽  
Activation Barrier ◽  
Direct Methods ◽  
Membered Ring ◽  
Boat Conformation ◽  
X Ray Diffraction ◽  
X Ray ◽  
R Value

5-Ethyl-5,6-dihydro-11H-dibenzo[b,e]azepine-6-thione has been synthesized and studied in the solid state and in solution by X-ray diffraction and 1H DNMR, respectively. The crystals are monoclinic, P21/n, a = 9.642(1), b = 13.757(2), c = 9.889((2) Å, β = 98.57(1)°, Z = 4. The structure has been solved by direct methods and refined to an R value of 0.040 for 1771 reflections with I > 2.5σ(I). The seven-membered ring has a slightly deformed boat conformation. The activation barrier associated with the inversion ring has been determined, being ΔG≠ = 21.6 kcal/mol.

scholarly journals Halogenated Diazabutadiene Dyes: Synthesis, Structures, Supramolecular Features, and Theoretical Studies

Molecules ◽  
2020 ◽  
Vol 25 (21) ◽  
pp. 5013
Author(s):  
Valentine G. Nenajdenko ◽  
Namiq G. Shikhaliyev ◽  
Abel M. Maharramov ◽  
Khanim N. Bagirova ◽  
Gulnar T. Suleymanova ◽  
...  
Keyword(s):  
Solid State ◽  
Self Assembly ◽  
Topological Analysis ◽  
Halogen Bonding ◽  
Fine Tuning ◽  
Theoretical Studies ◽  
X Ray Diffraction ◽  
1H And 13C Nmr ◽  
X Ray ◽  
Nmr Techniques

Novel halogenated aromatic dichlorodiazadienes were prepared via copper-mediated oxidative coupling between the corresponding hydrazones and CCl4. These rare azo-dyes were characterized using 1H and 13C NMR techniques and X-ray diffraction analysis for five halogenated dichlorodiazadienes. Multiple non-covalent halogen···halogen interactions were detected in the solid state and studied by DFT calculations and topological analysis of the electron density distribution within the framework of Bader’s theory (QTAIM method). Theoretical studies demonstrated that non-covalent halogen···halogen interactions play crucial role in self-assembly of highly polarizable dichlorodiazadienes. Thus, halogen bonding can dictate a packing preference in the solid state for this class of dichloro-substituted heterodienes, which could be a convenient tool for a fine tuning of the properties of this novel class of dyes.

Synthesis and Characterization of Hybrid Dimeric Steroid Spiroketals

Synthesis ◽  
2021 ◽  
Author(s):  
Martha C. Mayorquín-Torres ◽  
Mauricio Maldonado-Domínguez ◽  
MARCOS FLORES-ALAMOS ◽  
Martín A. Iglesias-Arteaga
Keyword(s):  
Dft Calculations ◽  
Structural Characterization ◽  
2D Nmr ◽  
Synthesis And Characterization ◽  
Sonogashira Coupling ◽  
X Ray Diffraction ◽  
X Ray ◽  
Synthetic Procedure ◽  
Nmr Techniques

The synthesis of six dimeric spiroketals bearing an estradiol half fused to the 5-or 5-epimers of androstane, cholestane and spirostane nuclei is described. The synthetic procedure comprises the Sonogashira coupling of different steroid alkynes with 2-iodoestradiol 17-monoacetate, followed by Pd-catalyzed spiroketalization. The structural characterization of the obtained hybrid dimers was performed using a combination of 1D and 2D NMR techniques, and was assisted by DFT calculations. Single crystal X-ray diffraction of one of the obtained compounds confirmed the proposed structures.

Synthesis and structure of the λ 6Si-silicate [Cs(18-crown-6)]2[Si(OSO2CH3)6]

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Isabelle Georg ◽  
Michael Bolte ◽  
Matthias Wagner ◽  
Hans-Wolfram Lerner
Keyword(s):  
Solid State ◽  
Nmr Spectroscopy ◽  
Single Crystal ◽  
State Structure ◽  
X Ray Diffraction ◽  
Triclinic Space Group ◽  
Space Group ◽  
Solid State Structure ◽  
X Ray

Abstract The λ 6Si-silicate [Cs(18-crown-6)]2[Si(OSO2CH3)6] (1) was synthesized by treatment of Si2Cl6 with Cs[OSO2CH3] in the presence of 18-crown-6. Compound 1 is the first example of a λ 6Si-silicate with a methanesulfonate ligand. It was characterized by NMR spectroscopy and by single-crystal X-ray diffraction. The solid-state structure of 1 consists of discrete [Si(OSO2CH3)6]2– anions and two [Cs(18-crown-6)]+ cations (triclinic space group, P 1 ¯ $P\overline{1}$ , Z = 1).

Physical and structural studies of N-substituted-3-hydroxy-2-methyl-4(1H)-pyridinones

1988 ◽  
Vol 66 (1) ◽  
pp. 123-131 ◽  
Author(s):  
William O. Nelson ◽  
Timothy B. Karpishin ◽  
Steven J. Rettig ◽  
Chris Orvig
Keyword(s):  
Mass Spectrometry ◽  
Hydrogen Bonding ◽  
Solid State ◽  
Single Crystal ◽  
Direct Methods ◽  
Structural Studies ◽  
X Ray Diffraction ◽  
Full Matrix ◽  
Space Group ◽  
X Ray

A series of 3-hydroxy-2-methyl-4(1H)-pyridinones has been prepared with the substituents H, CH3, n-C6H11, and CH2CH2NH2 at the ring N. The dipyridinone 1,6-bis(3-hydroxy-2-methyl-4(1H)-pyridinon-1-yl)hexane has also been synthesized. The products with H and CH3 substituents have been studied by single crystal X-ray diffraction. Crystals of 3-hydroxy-2-methyl-4-pyridinone are monoclinic, a = 6.8351(4), b = 10.2249(4), c = 8.6525(4) Å, β = 105.215(4)°, Z = 4, space group P21/n and those of 3-hydroxy-1,2-dimethyl-4-pyridinone are orthorhombic, a = 7.3036(4), b = 13.0490(6), c = 13.7681(7) Å, Z = 8, space group Pbca. Both structures were solved by direct methods and were refined by full-matrix least-squares procedures to R = 0.037 and 0.044 for 914 and 857 reflections with I ≥ 3σ(I), respectively. Bond lengths and angles in the two compounds were normal. All the compounds have been studied by mass spectrometry, and by infrared and proton nmr spectroscopies. The importance of hydrogen bonding to both the solution and solid state properties of these compounds has been confirmed by these techniques.

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