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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of chemical crystallography 10 (1980), S. 75-81 
    ISSN: 1572-8854
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The formula of the title compound is C16H27ClN2O5,P21/a = 8.348(1),b = 10.127(1),c = 11.264(2) Å, β = 116.42(1) °,Z = 2,D x = 1.41 g cm−3,V c = 852.8(2) Å3,MW = 362.9, μ (CuKα) = 2.25 mm−1. The structure was solved by direct methods and refined by full-matrix least squares to anR value of 0.055 for 1197 reflections. The cation consists of twotrans quinolizidine systems. RingA is a distorted half-chair, and the remaining rings are chairs. The CH3 group attached to C(17) is in the axial position. There is a weak hydrogen bond between N(16) and O(2) of the ClO 4 − group with N(16) ... O(2) distance 2.968(7) Å.
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  • 2
    ISSN: 1572-8854
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Δ1(6)-Dehydrosparteinium monoperchlorate, [C15H25N2]+·ClO 4 − , is orthorhombic∶P212121,a=12.473(2),b=24.292(3),c=10.835(1) Å,V c =3353.7(9) Å3,Z=8,D x =1.32,D m =1.32 g cm−3, μ(CuKα)=20.7 cm−1. The finalR was 0.097 for 2091 observed counter reflections. A partial disorder of the crystal structure has been observed. The two independent perchlorate anions are orientationally disordered, and the peripheral atoms in the cation skeletons have large temperature factors due both to conformational disorder of ringsA and to disordered orientations of the whole cations alike. In ringsA, atoms C(3) and C(4), trans-annular to the immonium bond, are disordered to a different extent in each of the two independent cations. RingsB,C, andD have sofa (distorted towards half-chair), chair, and chair conformations, respectively. The quinolizidinium and quinolizidine moieties have planar and cis configurations, respectively. The title compound was obtained from Δ5-dehydrosparteine, the product of mercuric acetate dehydrogenation of sparteine at room temperature. From13C NMR measurements in2H2O and in DMSO-2H6 it is evident that, in solution, the molecular geometry with chair/chair cis-ring fusion within the quinolizidine moiety is present, as was found in the crystalline state by X-ray analysis.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Journal of chemical crystallography 17 (1987), S. 259-265 
    ISSN: 1572-8854
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
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  • 4
    ISSN: 1572-8854
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Both of the title compounds crystallize in the monoclinic system: C23H17NO2 (Ib),P21/c,a = 8.970(1),b = 22.629(5),c = 9.101(1) Å, β = 106.08(1) °,Z = 4,D x = 1.27 Mg m−3; C19H17NO2 (Ic),P21/a,a = 15.225(2),b = 6.429(1),c = 17.190(1) Å, β = 112.99(1) °,Z = 4,D x = 1.25 Mg m−3. The structures were solved and refined by standard methods, both toR ≈ 0.04. In compound Ib, a weak intramolecular interaction is observed between the nitrogen atom from the isoquinoline ring and the carbon atom from the carbonyl group, with the N(2) ⋯. C(18)distance being 2.98 Å. In compound Ic, the PhCO2 -fragment is twisted in the opposite direction to that in compound Ib, without hydrogen bonding. The pK′ a and IR data were considered in the light of the results of the X-ray investigation.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Journal of chemical crystallography 18 (1988), S. 353-364 
    ISSN: 1572-8854
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The crystal structure; determined by X rays, and the13C-NMR spectra ofβ-isosparteine perchlorate are presented. The quinolizidine moieties are present in acis ring-juncture; all piperidine rings are in a chair conformation. The two nitrogen atoms are linked by a hydrogen bond of 2.704(5) Å. The proton at N(16) is also involved in a weak hydrogen bond with the O(2) of the perchlorate anion. The two quinolizidine moieties-protonated and unprotonated-differ only slightly in conformation; the protonation caused small but significant changes in the length of the bonds about the nitrogen atoms. The title compound was obtained by chemical transformations of 17-oxosparteine and protonation with an equimolar amount of HClO4 in methanol.13C-NMR spectra in DMSO-2H6 revealed the presence of the symmetricalcis-cis bis-quinolizidine structure of the salt in solution.
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  • 6
    ISSN: 1572-8854
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Δ1(6)-Dehydro-17-oxosparteinium perchlorate, [C15H23N2O]+·C10 4 − , is monoclinic:P21,a=8.620(1),b=14.406(2),c=6.825(1) Å, β=101.97(1)°,Z=2,V c=829.1(1)Å3,D x=1.52g cm−3, μ (Cukα)=21.7cm−1. The finalR was 0.051 for 1159 observed counterreflections. Carbon atoms C(3) and C(4) are highly disordered. This is probably due to conformational properties of the ringA, which are caused by the group situated between ringsA andB. RingsB,C, andD have sofa, sofa, and chair conformations, respectively. The bond distances and valency angles of the quinolizidone moiety (ringsC andD) are in good agreement with those obtained previously for 17-oxosparteine (free base) and its perchlorate salt. The title compound was obtained from Δ5-dehydro-17-oxosparteine, the product of mercuric acetate dehydrogenation of 17-oxosparteine. From IR spectra in the condensed phase and13C-NMR measurements in DMSO-2H6 solution, it is evident that, in the crystalline state as well as in solution, the immoniumlactam molecular structure is present in the compound studied.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Journal of chemical crystallography 16 (1986), S. 687-694 
    ISSN: 1572-8854
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The formula of the title compound is C22H30N2,M T =322.5; monoclinic:P21,a=7.569(3),b=9.381(1),c=13.684(4) Å,β=105.81(2)°,Z=2,V c =933.7 Å3,D x =1.15 g cm−3,μ(CuKα)=5.1 cm−1. The sparteine skeleton (bis-quinolizidine system) has atrans-trans configuration. RingA has an intermediate form between the sofa and half-chair conformations, ringsB andD-chair, and ringC-boat conformations, respectively. The double bond C(2)=C(3) is equal to 1.343(9) Å. The phenyl ring is planar and makes an angle with a plane through N(1), C(2), C(3), and C(4) atoms equal to 43.9°.
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  • 8
    ISSN: 1572-8854
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Δ1(6)-Dehydrosparteinium diperchlorate, [C15H26N2]2+·2ClO 4 − , is tetragonal; space groupP43,a=9.368(1),c=21.719(3) Å,Z=4,V c =1906.1(5) Å3,D x =1.51g cm−3,μ(CuKα)=35.0 cm−1. The finalR=0.055 for 1259 independent reflections. Atoms C(3) and C(4), which are trans-annular to the immonium bond in ringA, are disordered, as was observed for other bis-quinolizidine immonium salts. RingsB, C, andD have sofa, chair and chair conformations, respectively. The quinolizidinium and quinolizidine moieties have planar and cis configurations. The title compound was obtained by mercuric acetate dehydrogenation of sparteine to Δ5-dehydrosparteine and protonation of the latter with methanolic solution of perchloric acid to pH=2.0. From13C NMR measurements in DMSO-2H6 and in2H2O it is evident that in solution the chair/chair cis-ring fusion is present within the protonated quinolizidine moiety-identical to that found in the crystalline state by X-ray analysis.
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  • 9
    ISSN: 1572-8854
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Δ1(6),11(16)-Didehydrosparteinium diperchlorate,M r =431.27, (C15H24N2)2+ ·2C1O 4 − , orthorhombic, C2221,a=9.295(1),b=12.447(1),c=16.834(2) Å,V c =1947.5(4) Å3,Z=4,D m =1.47 g cm−3,D c =1.47 g cm−3,μ(CuKα)=31.7 cm−1. The finalR=0.052 for 733 counter reflections. The dication and the perchlorate anions lie on two-fold axes, and one perchlorate anion is disordered in two symmetrically equivalent positions. The two independent rings of the dication have conformations intermediate between half-chair and sofa, and the quinolizidine moiety (AB system) has a planar configuration. The title compound was obtained by mercuric acetate dehydrogenation of sparteine to Δ5,11-didehydrosparteine and protonation of the latter in methanol with perchloric acid.13C-NMR spectra in DMSO-2H6 and in2H2O revealed the presence of the symmetrical diimmonium structure of the salt in solution.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Journal of chemical crystallography 10 (1980), S. 67-74 
    ISSN: 1572-8854
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The formula of the title compound is C16H27ClN2O5,MW = 362.9 orthorhombic,P212121,a = 8.403(1),b= 13.133(1),c= 15.972(2) Å,Z = 4,D x = 1.37 g cm−3, μ (CuKα) = 2.2 mm-1. The lupanine skeleton has atrans-trans configuration. The ringA has a half-chair conformation, theB andD rings adopt a chair form, and theC ring forms a boat. The lupanine cations are linked together by the intermolecular hydrogen bonds forming infinite chains alongb. The N(16) ... O(C2) distance is 2.763(7) Å.
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