Synthesis and crystal structure of 17-deaza-17-methyl thionium isomorphinan (isosulforphanol) perchlorate, an isostere of the opiate isolevorphanol

1985 ◽  
Vol 63 (6) ◽  
pp. 1268-1274 ◽  
Author(s):  
Bernard Belleau ◽  
Ugo Gulini ◽  
Barbara Gour-Salin ◽  
F. R. Ahmed
Keyword(s):  
Ring Closure ◽  
Monoclinic Space Group ◽  
Orthorhombic Space Group ◽  
Synthesis And Crystal Structure ◽  
Space Group ◽  
X Ray ◽  
The Central Nervous System ◽  
Potent Agonist ◽  
Potent Antagonist ◽  
Sulfur Analog

No morphinan analog carrying a heteroatom other than nitrogen at position 17 has yet been synthesized. The synthesis of the position 17 sulfur analog of the perchlorate salt of (±)-isolevorphanol is described. The strategy adopted is based on the classical Grewe synthesis of morphinans and, under narrowly defined conditions, the title compound isosulforphanol (3a) and an intermediate by-product 13 resulting from an unusual non-bridged head ring closure of 11a were obtained. The X-ray structures of both 3a and 13 were determined. Crystals of 13 (C17H22OS) are monoclinic, space group P21/a, a = 17.080(2), b = 9.372(1), c = 9.327(1) Å, β = 108.67(1), V = 1414.4 Å3, Z = 4. Final R = 0.034 for 2545 reflections. The crystals of 3a(C17H23OS+•ClO4−)are orthorhombic, space group Pna21,a = 10.934(1), b = 9.219(1), c = 17.131(2) Å, V = 1726.8 Å3, Z = 4. Final R = 0.053 for 1018 reflections. The C17H23OS+ molecule has been identified by this X-ray analysis as S-methyl isosulforphanol (Fig. 2). The structure of 13 is shown in Fig. 1. The stereochemical outcome of the Grewe-like synthesis is thus established as proceeding in a reversed manner when sulfur replaces the nitrogen in the final cyclization step. Preliminary pharmacological studies showed that 3a is a potent agonist in the central nervous system but a potent antagonist on the guinea-pig ileum.

scholarly journals Synthese und Kristallstruktur von (S4N3)2Se2Cl10, (S4N3)2Se2Cl6 und [(S4Ν3)SeSeCl5]n / Synthesis and Crystal Structure of (S4N3)2Se2Cl10, (S4N3)2Se2Cl6, and [(S4N3)SeCl5]n

1989 ◽  
Vol 44 (12) ◽  
pp. 1483-1487 ◽  
Author(s):  
Hans Georg Stammler ◽  
Johannes Weiss
Keyword(s):  
Crystal Structure ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
Synthesis And Crystal Structure ◽  
Space Group ◽  
X Ray ◽  
Octahedral Environment ◽  
Square Planar ◽  
Distorted Octahedra

(S4N3)2Se2Cl10, (S4N3)2Se2Cl6 and [(S4N3)SeCl5]n are formed by the reaction of S4N4, Se2Cl2, and SOCl2. The structures of the three compounds where determined by X-ray diffraction. The yellow crystals of (S4N3)2Se2Cl,10 are monoclinic, space group P21/a, a = 817.5(2) pm, b = 1790.4(5) pm, c = 843.1(6) pm, β = 104.31(4)°, Z = 2. The Se2Cl,102- anion consists of 2 Cl-bridged distorted octahedra. (S4N3)2Se2Cl6 forms red monoclinic crystals, space group P21/c, a = 1036.5(3) pm, b = 1376.5(5) pm, c = 1400.4(4) pm, β = 100.65(2)°, Ζ = 4. In the Se2Cl62- anion the Se atoms have a square planar environment. The yellow crystals of (S4N3)SeCl5 are orthorhombic, space group P212121, a = 734.2(3) pm, b = 989.4(4) pm, c = 1627.4(6) pm, Z = 4. In the SeCl5- anion the Se atom has an octahedral environment of chlorine atoms, thus forming a polymeric structure.

Synthesis and Crystal Structure of K3AsSe4 and K4As2Se5 Containing [AsSe4]3- Anions and a Novel [As2Se5]4- Isomer Featuring an As–As Bond

2012 ◽  
Vol 67 (7) ◽  
pp. 651-656 ◽  
Author(s):  
Prashanth W. Menezes ◽  
Thomas F. Fässler
Keyword(s):  
Oxidation States ◽  
Solvothermal Reaction ◽  
Monoclinic Space Group ◽  
Prominent Feature ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
Synthesis And Crystal Structure ◽  
Space Group ◽  
X Ray ◽  
Pentavalent Arsenic

Two novel selenoarsenates, K3AsSe4 and K4As2Se5, were synthesized by the mild solvothermal reaction of potassium carbonate and arsenic and selenium powder in the presence of superheated ethylenediamine and structurally characterized by single-crystal X-ray diffraction. K3AsSe4 crystallizes in the orthorhombic space group Pnma (no. 62) with a = 9:4169(4), b = 10:9695(5), c = 9:7568(8) Å, Z = 4 and V = 1007:86(10) Å3 and contains [AsSe4]3- anions with pentavalent arsenic. K4As2Se5 crystallizes in the monoclinic space group P21/n (no. 14) with a = 7:6167(2), b = 22:8733(4), c = 8:4687(2) Å, b = 107:241(2)°, Z = 4 and V = 1409:14(5) Å3, and shows isolated [As2Se5]4- anions. The most prominent feature of the latter anions is the presence of arsenic in two different formal oxidation states (+4/+2) due to the presence of an As-As bond.

Strukturuntersuchungen an Diaryldichalkogeniden: Die Molekülstrukturen von [2,4,6-(CF3)3C6H2S]2,[2,4,6-Me3C6H2Te]2 und [2-Me2N-4,6-(CF3)2C6H2Te]2 / Structural Investigations of Diaryl Dichalcogenides: The Molecular Structures of [2,4,6-(CF3)3C6H2S]2, [2,4,6-Me3C6H2Te]2 and [2-Me2N-4,6-(CF3)2C6H2Te]2

1992 ◽  
Vol 47 (3) ◽  
pp. 305-309 ◽  
Author(s):  
Anja Edelmann ◽  
Sally Brooker ◽  
Norbert Bertel ◽  
Mathias Noltemeyer ◽  
Herbert W. Roesky ◽  
...  
Keyword(s):  
Molecular Structures ◽  
Monoclinic Space Group ◽  
Crystal Data ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
Structural Investigations ◽  
Space Group ◽  
X Ray

Abstract The Molecular Structures of [2,4,6-(CF3)3C6H2S]2 (1) [2,4,6-Me3C6H2Te]2 and [2-Me2N-4,6-(CF3)2C6H2Te]2 (3) have been determined by X-ray diffraction. Crystal data: 1: orthorhombic, space group P212121, Z = 4, a = 822.3(2), b = 1029.2(2), c = 2526.6(5) pm (2343 observed independent reflexions, R = 0.042); 2: orthorhombic, space group Iba 2, Z = 8, a = 1546.5(2), b = 1578.4(2), c = 1483.9(1) pm (2051 observed independent reflexions, R = 0.030); 3: monoclinic, space group P 21/c, Z = 4, a = 1118.7(1), b = 1536.5(2), c = 1492.6(2) pm, β = 98.97(1)° (3033 observed independent reflexions, R = 0.025).

The Crystal and Molecular Structures of Two Modifications of cis-Dichloro-mer-tris-(dimethylphenylphosphine)hydridoiridium(III)

1988 ◽  
Vol 41 (3) ◽  
pp. 283 ◽  
Author(s):  
GB Robertson ◽  
PA Tucker
Keyword(s):  
Heavy Atom ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
X Ray ◽  
Bond Lengths ◽  
Metal Ligand ◽  
Ligand Bond

The structures of two crystalline modifications of mer -(Pme2Ph)3H-cis-Cl2IrIII, (1), have been determined from single-crystal X-ray diffraction data. Modification (A) is monoclinic, space group P21/c with a 12.635(1), b 30.605(3), c 14.992(2)Ǻ, β 110.01(2)° and Z = 8. Modification (B) is orthorhombic, space group Pbca with a 27.646(3), b 11.366(1), c 17.252(2)Ǻ and Z = 8. The structures were solved by conventional heavy atom techniques and refined by full-matrix least- squares analyses to conventional R values of 0.037 [(A), 8845 independent reflections] and 0.028 [(B), 5291 independent reflections]. Important bond lengths [Ǻ] are Ir -P(trans to Cl ) 2.249(1) av. (A) and 2.234(1) (B), Ir -P(trans to PMe2Ph) 2.339(2) av. (A) and 2.344(1), 2.352(1) (B), Ir-Cl (trans to H) 2.492(2), 2.518(2) (A) and 2.503(1) (B) and Ir-Cl (trans to PMe2Ph)2.452(2) av. (A) and 2.449(1)(B). Differences in chemically equivalent metal- ligand bond lengths emphasize the importance of non-bonded contacts in determining those lengths.

The Constituents of Marine Sponges. IX New Norditerpenoids from Aplysilla pallida

1997 ◽  
Vol 50 (9) ◽  
pp. 903 ◽  
Author(s):  
Trevor W. Hambley ◽  
Walter C. Taylor ◽  
Stephen Toth
Keyword(s):  
Crystal Structures ◽  
Spectroscopic Studies ◽  
Marine Sponges ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
X Ray

Four novel norditerpenoids were isolated from a new encrusting sponge, conveniently labelled Aplysilla pallida. The structures of aplypallidenone (1), aplypallidoxone (2), aplypallidione (3) and aplypallidioxone (4) were elucidated by spectroscopic studies and the crystal structures of aplypallidenone and aplypallidoxone have been determined by X-ray diffraction methods. The structure of (1) was refined to a residual of 0·040 for 1665 independent observed reflections and the structure of (2) was refined to a residual of 0·031 for 1699 independent observed reflections. The crystals of (1) are orthorhombic, space group P212121, a 7·728(2), b 10·838(4), c 24·880(5) Å, Z 4. Those of (2) are monoclinic, space group C 2, a 23·927(7), b 6·674(2), c 14·033(3) Å, Z 4.

Notizen: Eine neue bicyclische Zinn-Selen-Verbindung. Synthese und Kristallstruktur von [{Cp(CO)2Fe}3ClSn3Se4] / A New Bicyclic Tin Selenium Compound. Synthesis and Crystal Structure of [{Cp(CO)2Fe}3ClSn3Se4]

1993 ◽  
Vol 48 (7) ◽  
pp. 1009-1012 ◽  
Author(s):  
Kurt Merzweiler ◽  
Harald Kraus
Keyword(s):  
Crystal Structure ◽  
Structure Determination ◽  
Unit Cell ◽  
Monoclinic Space Group ◽  
Synthesis And Crystal Structure ◽  
Selenium Compound ◽  
Space Group ◽  
X Ray ◽  
Lattice Constants ◽  
Compound Synthesis

[{Cp(CO)2Fe}SnCl3] reacts with Na2Se in THF to form the compound [{Cp(CO)2Fe}3ClSn3Se4] 1. 1 crystallizes in the monoclinic space group P21/n with 4 formula units per unit cell. The lattice constants are α = 1435.2(7), b = 1124.4(4), c = 1972.7(12) pm, β = 94.59(4)°. According to the X-ray structure determination 1 contains a bicyclic Sn3Se4 framework.

Crystal and molecular structure of Z- and E-1,2-dichloro-1,2-bis(2-chlorophenyl)ethylene. An X-ray and NMR study

1995 ◽  
Vol 73 (9) ◽  
pp. 1520-1525
Author(s):  
Luciano Antolini ◽  
Ugo Folli ◽  
Dario Iarossi ◽  
Adele Mucci ◽  
Silvia Sbardellati ◽  
...  
Keyword(s):  
Chemical Shifts ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
X Ray ◽  
Nmr Study ◽  
Phenyl Rings ◽  
A Cell ◽  
C Nmr

The crystal structures of the title compounds were determined by single crystal X-ray diffraction techniques. The molecule of the Z isomer, which crystallizes in the monoclinic space group C2/c with Z = 4 in a cell of dimensions a = 14.891 (2), b = 10.780(2), c = 8.769(1) Å, β = 97.47(2)°, V = 1395.7(7) Å3 has crystallographic twofold symmetry. The E form crystallizes in the orthorhombic space group Pbca with a = 11.730(1), b = 6.932(1), c = 16.841(1) Å, V = 1369.4(2) Å3 and Z = 4. Its molecules have crystallographically dictated [Formula: see text] symmetry. In both isomers the phenyl rings are roughly perpendicular to the average ethylene plane. The atoms characterizing this plane show significant deviations from planarity in the Z isomer. Marked bond-angle distortions at the ethene carbons of both structures are observed. The 1H and 13C NMR spectra of the compounds were measured and, particularly in the case of the 1H chemical shifts, fall into two quite separate spectral regions. At low temperature, two conformational isomers, those with different relative orientation of the C—Cl bonds of the phenyl rings, are observed in the spectrum of each compound. Keywords: chlorostilbenes, overcrowded molecules. X-ray structure, conformations, NMR spectroscopy.

Quinoxaline-1,2,3-dithiazolyls — Synthesis, EPR characterization, and redox chemistry

2001 ◽  
Vol 79 (9) ◽  
pp. 1352-1359
Author(s):  
A Wallace Cordes ◽  
James R Mingie ◽  
Richard T Oakley ◽  
Robert W Reed ◽  
Hongzhou Zhang
Keyword(s):  
Epr Spectroscopy ◽  
Ring Closure ◽  
Coupling Constants ◽  
Monoclinic Space Group ◽  
Orthorhombic Space Group ◽  
Molecular Conductors ◽  
Vacuum Sublimation ◽  
Space Group ◽  
X Ray Crystallography ◽  
Sulfenyl Chlorides

Oxidation of quinoxalineaminothiol with SCl2 or S2Cl2/Cl2 affords a series of compounds based on the quinoxaline-1,2,3-dithiazole framework QDTA. Under highly oxidizing conditions, the 1,2,3-dithiazolyl ring is opened to afford the acyclic dichlorosulfimino-sulfenyl chlorides Clx-QDTA-Cl3 (x = 0, 1, 2). Reduction of these "trichloro" compounds leads to ring closure. For x = 2, reduction using S2Cl2 affords the dithiazolylium chloride [Cl2-QDTA][Cl]. For all values of x, reduction with iodide ion (3 mol equiv) affords the corresponding dithiazolyl radical [Clx-QDTA]. The radicals can be isolated in good yield in crude form, but attempts to purify them by vacuum sublimation lead to thermal degradation. The radicals have nonetheless been fully characterized by EPR spectroscopy, and the assignments of the observed hyperfine coupling constants cross-matched with those obtained by computation at the B3LYP/6-31G** level. The structures of the trichloro compounds Clx-QDTA-Cl3 (x = 1, 2) have been confirmed by X-ray crystallography. Crystal data: Cl-QDTA-Cl3, monoclinic, space group C2/c, a = 30.561(5) Å, b = 4.9764(9) Å, c = 22.247(4) Å, β = 131.822(14)°, V = 2521.4(8) Å3, Z = 8, R(F) = 0.043, and Rw(F) [I [Formula: see text] σ (I)] = 0.049; Cl2-QDTA-Cl3, orthorhombic, space group Pnma, a = 18.627(12) Å, b = 6.848(4) Å, c = 10.926(7) Å, V = 1393.7(15) Å3, Z = 4, R(F) = 0.047, and Rw(F) [I [Formula: see text] 3σ(I)] = 0.060.Key words: thiazyl radicals, molecular conductors, EPR spectroscopy, quinoxaline, DFT calculations.

Kristallstrukturen der iodierten closo-Hexaborate trans-(Ph4P)2[B6H4I2], mer-(Ph4P)2[B6H3I3] · 2 CH2Cl2, trans-(Ph4P)2[B6H2I4] · 2 CH3CN und (CH2Py2)[B6HI5]/Crystal Structures of the Iodized closo-Hexaborates trans-(Ph4P)2[B6H4I2], mer-(Ph4P)2[B6H3I3] · 2 CH2Cl2, trans-(Ph4P )2[B6H2I4] · 2 CH3CN and (CH2Py2)[B6HI5]

1998 ◽  
Vol 53 (2) ◽  
pp. 206-210 ◽  
Author(s):  
D. Sonnak ◽  
W. Preetz
Keyword(s):  
Single Crystals ◽  
Crystal Structures ◽  
Monoclinic Space Group ◽  
Orthorhombic Space Group ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Structure Determinations

Abstract X-ray structure determinations have been performed on single crystals of trans-(Ph4P)2-[B6H4I2] (1) (triclinic, space group P1̄, a = 9.9680(12), b = 10.9690(11), c = 11.0470(14) Å,α = 88.167(9), β = 80.466(12), γ = 68.839(11)°, Z = 1), mer-(Ph4P)2[B6H3I3] · 2 CH2Cl2 (2)(triclinic, space group P1̄, a = 11.8694(11), b = 15.1699(13), c = 17.051(2) Å, α = 75.118(9), β = 71.953(10), γ = 69.331(8)°, Z = 2), trans-(Ph4P )2[B6H2I4] · 2 CH3CN (3) (monoclinic, space group P21/n, a = 14.9665(10), b = 7.6783(10), c = 23.385(3) Å, β = 95.78(9)°, Z = 2), and (CH2Py2)[B6HI5] (4) (orthorhombic, space group Pnma, a = 13.660(2), b = 11.8711(13), c = 13.839(2) Å, Z = 4). The B6 octahedra are compressed in the direction of the B-I bonds, resulting in shortened diagonal B ··· B distances with average values of the groups I-B ··· B-I = 2.37 and I-B ··· B-H = 2.43 Å as compared with H-B ··· B-H = 2.49 Å.

Molecular Motions in (CH3)3XCl, X = Sn and Pb. NMR Investigations and Crystal Structure Study of (CH3)3PbCl and CH3SnBr3

1991 ◽  
Vol 46 (4) ◽  
pp. 337-343 ◽  
Author(s):  
Da Zhang ◽  
Shi-Qi Dou ◽  
Alarich Weiss
Keyword(s):  
Molecular Motion ◽  
Structure Study ◽  
Methyl Groups ◽  
Monoclinic Space Group ◽  
Molecular Motions ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
X Ray ◽  
Group D

Abstract The molecular motion in (CH3)3XCl, X = Sn and Pb has been investigated by measurement of the second moment M2(1H) as function of temperature in the range 95 < T,/K<345. The methyl groups in both compounds rotate freely over the whole temperature range studied. In (CH3)3SnCl the C'3-rotation of (CH3)3Sn-group about the Sn CI axis sets in above 273 K. To explain the NMR and INS results, the crystal structures of (CH3)3PbCl and CH3SnBr3 were determined by single X-ray diffraction. (CH3)3PbCl crystallizes in a monoclinic space group C32-C2, a = 1276.7(3) pm, b = 982.3(3) pm, c = 547.0(2) pm, ß = 91.12(1)°; Z = 4, R = 0.035. CH3SnBr3 crystallizes in an orthorhombic space group D162h-Pnma, a = 643.0(3) pm, b= 1005.3(4) pm, c= 1148.0(4) pm; Z = 4, R =0.057

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