organic compounds
6,6-[Ethylenebis(sulfanediyl)]-2-(2-methoxyethyl)-1,2,3,4,5,6-hexahydro-1,5-methano-1H-azocino[4,3-b]indol-3-one
aDepartment of Physics, Karabük University, 78050 Karabük, Turkey, bDepartment of Chemistry, Gebze High Technology Institute, 41400 Gebze, Kocaeli, Turkey, cDepartment of Chemistry Education, Faculty of Education, Hacettepe University, 06800 Beytepe, Ankara, Turkey, and dDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey
*Correspondence e-mail: merzifon@hacettepe.edu.tr
The title compound, C19H22N2O2S2, consists of a tetracyclic ring system containing an azocine skeleton with methoxyethyl and dithiolane groups as substituents. The benzene and five-membered N-heterocyclic rings are nearly coplanar, making a dihedral angle of 0.81 (12)°. The dithiolane ring adopts an Intermolecular N—H⋯O hydrogen-bonding and weak C—H⋯π interactions are present in the crystal structure.
Related literature
For general background to the hexahydro-1,5-methano-azocino[4,3-b]indole core structure, a synthetic precursor for most of the pentacyclic and tetracyclic indole of biological interest, see: Hesse (2002); Bosch & Bonjoch (1988); Saxton (1983). For related structures, see: Hökelek et al. (2004, 2006, 2007); Tercan et al. (2010); Uludağ et al. (2006).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
Supporting information
https://doi.org/10.1107/S1600536810015941/xu2755sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810015941/xu2755Isup2.hkl
The title compound, (I), was prepared from 2,3-dichloro-5,6-dicyano-p -benzoquinone (0.68 g, 3.00 mmol) and N-(methoxyethyl)-(2,3,4,9-tetra -hydrospiro-[1H-carbazole-1,2'-(1,3)dithiolane]-2-yl)-2-acetamide (1.00 g, 2.68 mmol) in THF (35 ml). The mixture was stirred at room temperature for 4 h under nitrogen atmosphere, and then poured into sodium hydroxide solution (100 ml, 10%). After extraction with dichloromethane (50 ml), the organic layer was dried with Na2SO4 and the solvent was evaporated. The residue was purified by silicagel
using triethylamine, acetone and ethyl acetate (7:25:75) and crystallized from ethyl acetate/diethyl ether (2:1) (yield; 0.87 g, 88%), m.p. 445 K.The hexahydro-1,5-methano-azocino[4,3-b]indole core structure can be considered to be synthetic precursor for most of the pentacyclic and tetracyclic indole
of biological interests (Hesse, 2002; Bosch & Bonjoch, 1988; Saxton, 1983), such as akuminicine and uleine. Most of them have the pentacyclic ring system as a common element and include a large group of naturally occuring compounds such as strychnine, a consulvant poison, and uleine alkaloids.The structures of tricyclic, tetracyclic and pentacyclic ring systems with different substituents of azocino[4,3-b]indole core have been determined, previously. These include N-(2-benzyloxyethyl)-4,7-dimethyl-6-(1,3-dithiolan- 2yl)-1,2,3,4,5,6-hexahydro-1,5-methano-2-azocino[4,3-b]indole-2-one, (II) (Hökelek et al., 2004), 12-ethyl-2-methyl-6,6-ethylenedithio-1,2,3,4,5,6 -hexahydro-1,5-methano-2-azocino[4,3-b]indole-3-one, (III) (Uludağ et al., 2006), 4-ethyl-6,6-ethylenedithio-2-(2-methoxymethyl)-7-methoxymethylene-2, 3,4,5,6,7-hexahydro-1,5-methano-1H-azocino[4,3-b]indole-3-one, (IV) (Hökelek et al., 2006), 2-(2,2-dimethoxyethyl)-3-oxo-1,2,3,4,5,6 -hexahydro-1,5-methano-7H-azocino[4,3-b]indole, (V) (Hökelek et al., 2007) and 2-ethyl-6,6-ethylenedisulfanediyl-7-methoxymethyl-1,2,3,4,5,6-hexahydro -1,5-methanoazocino[4,3-b]indol-3-one, (VI) (Tercan et al., 2010). The present study was undertaken to ascertain the
of the title compound, (I).The molecule of the title compound, (I), (Fig. 1) consists of a tetracyclic ring system containing an azocino skeleton with methoxyethyl and dithiolane groups as substituents at positions N2 and 6, respectively. The bonds N7—C6a [1.368 (4) Å] and N7—C7a [1.374 (4) Å] agree well with those in compounds (II) [1.392 (8) and 1.370 (8) Å], (IV) [1.393 (4) and 1.386 (5) Å], (V) [1.377 (3) and 1.376 (3) Å] and (VI) [1.398 (3) and 1.387 (3) Å]. The absolute configurations of C1 and C5 are S and S (Fig. 1). The S atoms of the dithiolane ring have electron-releasing properties, but the N atom at position 7 and the O atom attached to C3 have electron-withdrawing properties, leading to some changes in the bond lengths and angles of the carbazole skeleton.
An examination of the deviations from the least-squares planes through individual rings shows that rings A (C7a/C8/C9/C10/C11/C11a) and B (N7/C7a/C11a/C11b/C6a) are planar. They are also coplanar with a dihedral angle of A/B = 0.81 (12)°. Rings C (C1/C11b/C6a/C6/C5/C14), D (C1/N2/C3/C4/C5/C14) and E (C6/S1/S2/C12/C13) are, of course, not planar. Atom C14 deviates from the planes of F(C1/C5/C6/C6a/C11b) and G (C1/N2/C3/C4/C5) by 0.705 (4) Å and 0.737 (4) Å, respectively where the dihedral angle between planes of F and G is F/G = 69.64 (12)°. On the other hand, the dihedral angles between the plane of H (C1/C5/C14) and the planes of F and G are 54.18 (24)° and 56.47 (21)°, respectively. The conformation of ring E is an envelope, with atom C13 at the flap position, 0.583 (6) Å from the mean plane through the other four atoms.
In the π interaction also occurs (Table 1).
intermolecular N—H···O hydrogen bonds (Table 1) link the molecules into chains nearly parallel to b-axis (Fig. 2), in which they may be effective in the stabilization of the structure. A weak C—H···For general background to the hexahydro-1,5-methano-azocino[4,3-b]indole core structure, a synthetic precursor for most of the pentacyclic and tetracyclic indole
alkaloids of biological interest, see: Hesse (2002); Bosch & Bonjoch (1988); Saxton (1983). For related structures, see: Hökelek et al. (2004, 2006, 2007); Tercan et al. (2010); Uludağ et al. (2006).
Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).C19H22N2O2S2 | F(000) = 792 |
Mr = 374.53 | Dx = 1.367 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6662 reflections |
a = 11.2233 (3) Å | θ = 2.5–25.0° |
b = 15.4228 (5) Å | µ = 0.31 mm−1 |
c = 12.3027 (4) Å | T = 294 K |
β = 121.267 (2)° | Block, colourless |
V = 1820.23 (10) Å3 | 0.11 × 0.11 × 0.09 mm |
Z = 4 |
Bruker Kappa APEXII CCD area-detector diffractometer | 3203 independent reflections |
Radiation source: fine-focus sealed tube | 2765 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
φ and ω scans | θmax = 25.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −13→13 |
Tmin = 0.85, Tmax = 0.97 | k = −15→18 |
13979 measured reflections | l = −14→14 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.159 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.073P)2 + 2.6218P] where P = (Fo2 + 2Fc2)/3 |
3203 reflections | (Δ/σ)max < 0.001 |
279 parameters | Δρmax = 1.10 e Å−3 |
1 restraint | Δρmin = −0.56 e Å−3 |
C19H22N2O2S2 | V = 1820.23 (10) Å3 |
Mr = 374.53 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.2233 (3) Å | µ = 0.31 mm−1 |
b = 15.4228 (5) Å | T = 294 K |
c = 12.3027 (4) Å | 0.11 × 0.11 × 0.09 mm |
β = 121.267 (2)° |
Bruker Kappa APEXII CCD area-detector diffractometer | 3203 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 2765 reflections with I > 2σ(I) |
Tmin = 0.85, Tmax = 0.97 | Rint = 0.029 |
13979 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | 1 restraint |
wR(F2) = 0.159 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 1.10 e Å−3 |
3203 reflections | Δρmin = −0.56 e Å−3 |
279 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
S1 | −0.00713 (10) | 0.85797 (6) | 0.42981 (9) | 0.0531 (3) | |
S2 | −0.17536 (8) | 0.82283 (6) | 0.54739 (8) | 0.0505 (3) | |
O1 | −0.0128 (3) | 0.51573 (16) | 0.7174 (3) | 0.0610 (7) | |
O2 | 0.4150 (5) | 0.4833 (2) | 0.7731 (4) | 0.1090 (14) | |
C1 | 0.2094 (3) | 0.6542 (2) | 0.6617 (3) | 0.0415 (7) | |
H1 | 0.304 (4) | 0.639 (2) | 0.679 (3) | 0.043 (9)* | |
N2 | 0.1631 (3) | 0.58379 (16) | 0.7142 (3) | 0.0431 (6) | |
C3 | 0.0280 (4) | 0.57123 (19) | 0.6714 (3) | 0.0443 (7) | |
C4 | −0.0805 (4) | 0.6256 (3) | 0.5630 (4) | 0.0564 (9) | |
H41 | −0.142 (4) | 0.587 (3) | 0.502 (4) | 0.068 (12)* | |
H42 | −0.141 (5) | 0.653 (3) | 0.592 (4) | 0.077 (13)* | |
C5 | −0.0340 (3) | 0.6908 (2) | 0.4983 (3) | 0.0430 (7) | |
H5 | −0.104 (3) | 0.691 (2) | 0.408 (3) | 0.044 (9)* | |
C6 | −0.0220 (3) | 0.7862 (2) | 0.5439 (3) | 0.0380 (7) | |
C6A | 0.1071 (3) | 0.79611 (18) | 0.6714 (3) | 0.0339 (6) | |
N7 | 0.1383 (3) | 0.86796 (17) | 0.7466 (2) | 0.0366 (6) | |
H7 | 0.087 (4) | 0.909 (2) | 0.735 (3) | 0.042 (9)* | |
C7A | 0.2701 (3) | 0.85823 (19) | 0.8510 (3) | 0.0356 (6) | |
C8 | 0.3469 (3) | 0.9135 (2) | 0.9544 (3) | 0.0447 (7) | |
H8 | 0.307 (4) | 0.965 (3) | 0.963 (4) | 0.065 (11)* | |
C9 | 0.4779 (4) | 0.8870 (3) | 1.0455 (3) | 0.0527 (9) | |
H9 | 0.531 (4) | 0.923 (2) | 1.112 (4) | 0.058 (11)* | |
C10 | 0.5337 (4) | 0.8091 (3) | 1.0358 (4) | 0.0577 (10) | |
H10 | 0.617 (5) | 0.798 (3) | 1.094 (4) | 0.070 (13)* | |
C11 | 0.4588 (3) | 0.7542 (2) | 0.9344 (4) | 0.0500 (8) | |
H11 | 0.493 (4) | 0.699 (3) | 0.925 (3) | 0.053 (10)* | |
C11A | 0.3232 (3) | 0.77788 (19) | 0.8398 (3) | 0.0371 (7) | |
C11B | 0.2155 (3) | 0.73953 (18) | 0.7235 (3) | 0.0362 (6) | |
C12 | −0.1673 (5) | 0.9159 (3) | 0.3688 (5) | 0.0906 (17) | |
H12A | −0.1475 | 0.9741 | 0.4036 | 0.109* | |
H12B | −0.2121 | 0.9205 | 0.2771 | 0.109* | |
C13 | −0.2624 (5) | 0.8740 (4) | 0.3995 (6) | 0.106 (2) | |
H13A | −0.3178 | 0.8314 | 0.3344 | 0.127* | |
H13B | −0.3256 | 0.9171 | 0.3991 | 0.127* | |
C14 | 0.1063 (4) | 0.6613 (2) | 0.5194 (3) | 0.0470 (8) | |
H141 | 0.096 (3) | 0.608 (2) | 0.482 (3) | 0.046 (9)* | |
H142 | 0.145 (4) | 0.704 (2) | 0.483 (3) | 0.056 (10)* | |
C15 | 0.2666 (4) | 0.5408 (2) | 0.8317 (4) | 0.0575 (9) | |
H151 | 0.216 (6) | 0.523 (4) | 0.884 (5) | 0.114 (18)* | |
H152 | 0.346 (5) | 0.582 (3) | 0.883 (4) | 0.076 (13)* | |
C16 | 0.3309 (5) | 0.4618 (3) | 0.8156 (5) | 0.0704 (11) | |
H16A | 0.3840 | 0.4319 | 0.8964 | 0.084* | |
H16B | 0.2586 | 0.4230 | 0.7556 | 0.084* | |
C17 | 0.4859 (8) | 0.4086 (4) | 0.7611 (8) | 0.126 (2) | |
H17A | 0.5444 | 0.4269 | 0.7298 | 0.189* | |
H17B | 0.4182 | 0.3679 | 0.7027 | 0.189* | |
H17C | 0.5419 | 0.3817 | 0.8427 | 0.189* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0634 (6) | 0.0513 (5) | 0.0516 (5) | 0.0028 (4) | 0.0346 (5) | 0.0135 (4) |
S2 | 0.0386 (4) | 0.0590 (6) | 0.0533 (5) | 0.0041 (4) | 0.0234 (4) | 0.0035 (4) |
O1 | 0.0779 (17) | 0.0414 (13) | 0.0728 (17) | −0.0145 (12) | 0.0456 (15) | 0.0025 (12) |
O2 | 0.152 (3) | 0.066 (2) | 0.175 (4) | 0.025 (2) | 0.131 (3) | 0.019 (2) |
C1 | 0.0471 (18) | 0.0336 (16) | 0.0529 (19) | 0.0004 (13) | 0.0324 (16) | −0.0034 (13) |
N2 | 0.0523 (16) | 0.0296 (13) | 0.0498 (15) | 0.0011 (11) | 0.0281 (13) | 0.0007 (11) |
C3 | 0.059 (2) | 0.0292 (15) | 0.0503 (18) | −0.0081 (14) | 0.0327 (16) | −0.0075 (13) |
C4 | 0.049 (2) | 0.047 (2) | 0.067 (2) | −0.0100 (17) | 0.0265 (19) | 0.0050 (18) |
C5 | 0.0479 (18) | 0.0403 (17) | 0.0371 (17) | −0.0057 (14) | 0.0196 (15) | −0.0025 (13) |
C6 | 0.0407 (16) | 0.0380 (16) | 0.0379 (16) | −0.0017 (13) | 0.0222 (14) | 0.0014 (13) |
C6A | 0.0361 (14) | 0.0338 (15) | 0.0364 (15) | −0.0018 (12) | 0.0220 (13) | −0.0006 (12) |
N7 | 0.0375 (13) | 0.0321 (13) | 0.0402 (14) | 0.0028 (11) | 0.0200 (12) | −0.0024 (11) |
C7A | 0.0358 (15) | 0.0349 (15) | 0.0410 (16) | −0.0031 (12) | 0.0234 (13) | −0.0005 (12) |
C8 | 0.0470 (18) | 0.0393 (17) | 0.0503 (19) | −0.0047 (14) | 0.0270 (16) | −0.0069 (14) |
C9 | 0.0441 (18) | 0.060 (2) | 0.0455 (19) | −0.0104 (17) | 0.0168 (16) | −0.0123 (17) |
C10 | 0.0369 (18) | 0.065 (2) | 0.054 (2) | 0.0004 (17) | 0.0109 (17) | −0.0014 (18) |
C11 | 0.0393 (17) | 0.0452 (19) | 0.061 (2) | 0.0052 (15) | 0.0234 (16) | 0.0017 (16) |
C11A | 0.0349 (14) | 0.0364 (15) | 0.0432 (16) | −0.0015 (12) | 0.0225 (13) | −0.0001 (13) |
C11B | 0.0383 (15) | 0.0312 (14) | 0.0436 (16) | −0.0016 (12) | 0.0245 (13) | −0.0015 (12) |
C12 | 0.056 (2) | 0.091 (3) | 0.100 (4) | 0.008 (2) | 0.023 (2) | 0.050 (3) |
C13 | 0.076 (3) | 0.148 (5) | 0.099 (4) | 0.050 (3) | 0.049 (3) | 0.062 (4) |
C14 | 0.065 (2) | 0.0384 (18) | 0.0494 (19) | −0.0033 (16) | 0.0383 (18) | −0.0078 (15) |
C15 | 0.063 (2) | 0.0424 (19) | 0.054 (2) | 0.0027 (17) | 0.0210 (19) | 0.0035 (16) |
C16 | 0.071 (3) | 0.053 (2) | 0.085 (3) | 0.007 (2) | 0.039 (2) | 0.007 (2) |
C17 | 0.165 (6) | 0.097 (4) | 0.188 (7) | 0.030 (4) | 0.141 (6) | 0.002 (4) |
S1—C6 | 1.862 (3) | C9—C10 | 1.388 (5) |
S1—C12 | 1.787 (5) | C9—H9 | 0.91 (4) |
S2—C6 | 1.833 (3) | C10—C11 | 1.374 (5) |
S2—C13 | 1.744 (5) | C10—H10 | 0.85 (4) |
O1—C3 | 1.238 (4) | C11—C11A | 1.401 (4) |
O2—C16 | 1.337 (5) | C11—H11 | 0.96 (4) |
O2—C17 | 1.450 (6) | C11A—C11B | 1.437 (4) |
C1—H1 | 0.99 (3) | C11B—C6A | 1.358 (4) |
N2—C1 | 1.487 (4) | C11B—C1 | 1.503 (4) |
N2—C3 | 1.337 (4) | C12—C13 | 1.456 (7) |
N2—C15 | 1.462 (5) | C12—H12A | 0.9700 |
C4—C3 | 1.510 (5) | C12—H12B | 0.9700 |
C4—H41 | 0.92 (4) | C13—H13A | 0.9700 |
C4—H42 | 1.01 (5) | C13—H13B | 0.9700 |
C5—C4 | 1.531 (5) | C14—C1 | 1.521 (5) |
C5—C14 | 1.525 (5) | C14—H141 | 0.92 (4) |
C5—H5 | 0.97 (3) | C14—H142 | 1.01 (4) |
C6—C5 | 1.556 (4) | C15—C16 | 1.480 (6) |
C6A—C6 | 1.492 (4) | C15—H152 | 1.00 (5) |
N7—C6A | 1.368 (4) | C15—H151 | 1.09 (6) |
N7—C7A | 1.374 (4) | C16—H16A | 0.9700 |
N7—H7 | 0.81 (4) | C16—H16B | 0.9700 |
C7A—C8 | 1.397 (4) | C17—H17A | 0.9600 |
C7A—C11A | 1.412 (4) | C17—H17B | 0.9600 |
C8—C9 | 1.369 (5) | C17—H17C | 0.9600 |
C8—H8 | 0.95 (4) | ||
C12—S1—C6 | 98.61 (18) | C9—C10—H10 | 117 (3) |
C13—S2—C6 | 98.0 (2) | C11—C10—C9 | 121.4 (3) |
C16—O2—C17 | 112.3 (4) | C11—C10—H10 | 121 (3) |
N2—C1—C11B | 110.8 (2) | C10—C11—C11A | 118.8 (3) |
N2—C1—C14 | 108.9 (3) | C10—C11—H11 | 124 (2) |
N2—C1—H1 | 108.1 (19) | C11A—C11—H11 | 117 (2) |
C11B—C1—C14 | 109.1 (3) | C7A—C11A—C11B | 106.2 (2) |
C11B—C1—H1 | 109.3 (19) | C11—C11A—C7A | 118.6 (3) |
C14—C1—H1 | 110.7 (19) | C11—C11A—C11B | 135.2 (3) |
C3—N2—C15 | 118.7 (3) | C6A—C11B—C1 | 122.0 (3) |
C3—N2—C1 | 121.0 (3) | C6A—C11B—C11A | 106.9 (3) |
C15—N2—C1 | 118.9 (3) | C11A—C11B—C1 | 131.2 (3) |
O1—C3—N2 | 122.3 (3) | S1—C12—H12A | 109.1 |
O1—C3—C4 | 117.9 (3) | S1—C12—H12B | 109.1 |
N2—C3—C4 | 119.8 (3) | C13—C12—S1 | 112.5 (3) |
C3—C4—C5 | 119.2 (3) | C13—C12—H12A | 109.1 |
C3—C4—H41 | 106 (3) | C13—C12—H12B | 109.1 |
C3—C4—H42 | 107 (3) | H12A—C12—H12B | 107.8 |
C5—C4—H41 | 108 (3) | C12—C13—S2 | 112.5 (4) |
C5—C4—H42 | 113 (3) | C12—C13—H13A | 109.1 |
H41—C4—H42 | 101 (4) | C12—C13—H13B | 109.1 |
C4—C5—C6 | 114.9 (3) | S2—C13—H13A | 109.1 |
C4—C5—H5 | 108 (2) | S2—C13—H13B | 109.1 |
C6—C5—H5 | 106 (2) | H13A—C13—H13B | 107.8 |
C14—C5—C4 | 108.4 (3) | C1—C14—C5 | 108.6 (3) |
C14—C5—C6 | 109.4 (3) | C1—C14—H141 | 109 (2) |
C14—C5—H5 | 110.6 (19) | C1—C14—H142 | 108 (2) |
C5—C6—S1 | 108.4 (2) | C5—C14—H141 | 110 (2) |
C5—C6—S2 | 113.2 (2) | C5—C14—H142 | 112 (2) |
C6A—C6—C5 | 109.3 (3) | H141—C14—H142 | 109 (3) |
C6A—C6—S1 | 108.3 (2) | N2—C15—C16 | 115.7 (3) |
C6A—C6—S2 | 110.8 (2) | N2—C15—H151 | 108 (3) |
S2—C6—S1 | 106.67 (16) | N2—C15—H152 | 109 (2) |
N7—C6A—C6 | 124.2 (3) | C16—C15—H151 | 108 (3) |
C11B—C6A—N7 | 110.5 (3) | C16—C15—H152 | 105 (2) |
C11B—C6A—C6 | 125.0 (3) | H152—C15—H151 | 111 (4) |
C6A—N7—C7A | 108.5 (3) | O2—C16—C15 | 109.9 (4) |
C6A—N7—H7 | 127 (2) | O2—C16—H16A | 109.7 |
C7A—N7—H7 | 124 (2) | O2—C16—H16B | 109.7 |
N7—C7A—C8 | 129.8 (3) | C15—C16—H16A | 109.7 |
N7—C7A—C11A | 108.0 (3) | C15—C16—H16B | 109.7 |
C8—C7A—C11A | 122.1 (3) | H16A—C16—H16B | 108.2 |
C7A—C8—H8 | 121 (2) | O2—C17—H17A | 109.5 |
C9—C8—C7A | 117.1 (3) | O2—C17—H17B | 109.5 |
C9—C8—H8 | 122 (2) | O2—C17—H17C | 109.5 |
C8—C9—C10 | 121.9 (3) | H17A—C17—H17B | 109.5 |
C8—C9—H9 | 118 (2) | H17A—C17—H17C | 109.5 |
C10—C9—H9 | 120 (2) | H17B—C17—H17C | 109.5 |
C12—S1—C6—S2 | −7.3 (3) | C11B—C6A—C6—S1 | −101.0 (3) |
C12—S1—C6—C5 | 114.9 (3) | C11B—C6A—C6—S2 | 142.3 (3) |
C12—S1—C6—C6A | −126.6 (3) | C11B—C6A—C6—C5 | 16.8 (4) |
C6—S1—C12—C13 | −15.1 (5) | C7A—N7—C6A—C6 | −174.4 (3) |
C13—S2—C6—C6A | 140.4 (3) | C7A—N7—C6A—C11B | −0.3 (3) |
C13—S2—C6—C5 | −96.3 (3) | C6A—N7—C7A—C8 | −179.4 (3) |
C13—S2—C6—S1 | 22.8 (3) | C6A—N7—C7A—C11A | 0.4 (3) |
C6—S2—C13—C12 | −35.3 (5) | N7—C7A—C8—C9 | −179.6 (3) |
C17—O2—C16—C15 | 177.4 (5) | C11A—C7A—C8—C9 | 0.6 (5) |
C3—N2—C1—C11B | 82.0 (4) | N7—C7A—C11A—C11 | 178.5 (3) |
C3—N2—C1—C14 | −38.0 (4) | N7—C7A—C11A—C11B | −0.4 (3) |
C15—N2—C1—C11B | −84.5 (3) | C8—C7A—C11A—C11 | −1.7 (4) |
C15—N2—C1—C14 | 155.6 (3) | C8—C7A—C11A—C11B | 179.4 (3) |
C1—N2—C3—O1 | −176.6 (3) | C7A—C8—C9—C10 | 0.7 (5) |
C1—N2—C3—C4 | 3.6 (5) | C8—C9—C10—C11 | −0.8 (6) |
C15—N2—C3—O1 | −10.1 (5) | C9—C10—C11—C11A | −0.4 (6) |
C15—N2—C3—C4 | 170.1 (3) | C10—C11—C11A—C7A | 1.6 (5) |
C1—N2—C15—C16 | −92.1 (4) | C10—C11—C11A—C11B | −179.9 (3) |
C3—N2—C15—C16 | 101.1 (4) | C7A—C11A—C11B—C1 | −178.8 (3) |
C5—C4—C3—O1 | −176.1 (3) | C7A—C11A—C11B—C6A | 0.3 (3) |
C5—C4—C3—N2 | 3.7 (5) | C11—C11A—C11B—C1 | 2.5 (6) |
C6—C5—C4—C3 | −98.9 (4) | C11—C11A—C11B—C6A | −178.4 (4) |
C14—C5—C4—C3 | 23.9 (5) | C6A—C11B—C1—N2 | −94.1 (3) |
C4—C5—C14—C1 | −57.4 (4) | C6A—C11B—C1—C14 | 25.7 (4) |
C6—C5—C14—C1 | 68.7 (3) | C11A—C11B—C1—N2 | 84.9 (4) |
S1—C6—C5—C4 | −166.5 (2) | C11A—C11B—C1—C14 | −155.3 (3) |
S1—C6—C5—C14 | 71.2 (3) | C1—C11B—C6A—N7 | 179.2 (3) |
S2—C6—C5—C4 | −48.4 (3) | C11A—C11B—C6A—N7 | 0.0 (3) |
S2—C6—C5—C14 | −170.6 (2) | C1—C11B—C6A—C6 | −6.7 (4) |
C6A—C6—C5—C4 | 75.7 (3) | C11A—C11B—C6A—C6 | 174.1 (3) |
C6A—C6—C5—C14 | −46.6 (3) | S1—C12—C13—S2 | 34.0 (7) |
N7—C6A—C6—S1 | 72.2 (3) | C5—C14—C1—N2 | 65.4 (3) |
N7—C6A—C6—S2 | −44.4 (3) | C5—C14—C1—C11B | −55.6 (3) |
N7—C6A—C6—C5 | −169.9 (3) | N2—C15—C16—O2 | 70.2 (5) |
Cg1 is the centroid of the C7a/C8/C9/C10/C11/C11a ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N7—H7···O1i | 0.82 (4) | 2.06 (4) | 2.832 (4) | 157 (3) |
C17—H17A···Cg1ii | 0.96 | 2.89 | 3.545 (9) | 127 |
Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) −x+1, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C19H22N2O2S2 |
Mr | 374.53 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 294 |
a, b, c (Å) | 11.2233 (3), 15.4228 (5), 12.3027 (4) |
β (°) | 121.267 (2) |
V (Å3) | 1820.23 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.31 |
Crystal size (mm) | 0.11 × 0.11 × 0.09 |
Data collection | |
Diffractometer | Bruker Kappa APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.85, 0.97 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13979, 3203, 2765 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.159, 1.04 |
No. of reflections | 3203 |
No. of parameters | 279 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.10, −0.56 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
Cg1 is the centroid of the C7a/C8/C9/C10/C11/C11a ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N7—H7···O1i | 0.82 (4) | 2.06 (4) | 2.832 (4) | 157 (3) |
C17—H17A···Cg1ii | 0.96 | 2.89 | 3.545 (9) | 127 |
Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) −x+1, y−1/2, −z+3/2. |
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The hexahydro-1,5-methano-azocino[4,3-b]indole core structure can be considered to be synthetic precursor for most of the pentacyclic and tetracyclic indole alkaloids of biological interests (Hesse, 2002; Bosch & Bonjoch, 1988; Saxton, 1983), such as akuminicine and uleine. Most of them have the pentacyclic ring system as a common element and include a large group of naturally occuring compounds such as strychnine, a consulvant poison, and uleine alkaloids.
The structures of tricyclic, tetracyclic and pentacyclic ring systems with different substituents of azocino[4,3-b]indole core have been determined, previously. These include N-(2-benzyloxyethyl)-4,7-dimethyl-6-(1,3-dithiolan- 2yl)-1,2,3,4,5,6-hexahydro-1,5-methano-2-azocino[4,3-b]indole-2-one, (II) (Hökelek et al., 2004), 12-ethyl-2-methyl-6,6-ethylenedithio-1,2,3,4,5,6 -hexahydro-1,5-methano-2-azocino[4,3-b]indole-3-one, (III) (Uludağ et al., 2006), 4-ethyl-6,6-ethylenedithio-2-(2-methoxymethyl)-7-methoxymethylene-2, 3,4,5,6,7-hexahydro-1,5-methano-1H-azocino[4,3-b]indole-3-one, (IV) (Hökelek et al., 2006), 2-(2,2-dimethoxyethyl)-3-oxo-1,2,3,4,5,6 -hexahydro-1,5-methano-7H-azocino[4,3-b]indole, (V) (Hökelek et al., 2007) and 2-ethyl-6,6-ethylenedisulfanediyl-7-methoxymethyl-1,2,3,4,5,6-hexahydro -1,5-methanoazocino[4,3-b]indol-3-one, (VI) (Tercan et al., 2010). The present study was undertaken to ascertain the crystal structure of the title compound, (I).
The molecule of the title compound, (I), (Fig. 1) consists of a tetracyclic ring system containing an azocino skeleton with methoxyethyl and dithiolane groups as substituents at positions N2 and 6, respectively. The bonds N7—C6a [1.368 (4) Å] and N7—C7a [1.374 (4) Å] agree well with those in compounds (II) [1.392 (8) and 1.370 (8) Å], (IV) [1.393 (4) and 1.386 (5) Å], (V) [1.377 (3) and 1.376 (3) Å] and (VI) [1.398 (3) and 1.387 (3) Å]. The absolute configurations of C1 and C5 are S and S (Fig. 1). The S atoms of the dithiolane ring have electron-releasing properties, but the N atom at position 7 and the O atom attached to C3 have electron-withdrawing properties, leading to some changes in the bond lengths and angles of the carbazole skeleton.
An examination of the deviations from the least-squares planes through individual rings shows that rings A (C7a/C8/C9/C10/C11/C11a) and B (N7/C7a/C11a/C11b/C6a) are planar. They are also coplanar with a dihedral angle of A/B = 0.81 (12)°. Rings C (C1/C11b/C6a/C6/C5/C14), D (C1/N2/C3/C4/C5/C14) and E (C6/S1/S2/C12/C13) are, of course, not planar. Atom C14 deviates from the planes of F(C1/C5/C6/C6a/C11b) and G (C1/N2/C3/C4/C5) by 0.705 (4) Å and 0.737 (4) Å, respectively where the dihedral angle between planes of F and G is F/G = 69.64 (12)°. On the other hand, the dihedral angles between the plane of H (C1/C5/C14) and the planes of F and G are 54.18 (24)° and 56.47 (21)°, respectively. The conformation of ring E is an envelope, with atom C13 at the flap position, 0.583 (6) Å from the mean plane through the other four atoms.
In the crystal structure, intermolecular N—H···O hydrogen bonds (Table 1) link the molecules into chains nearly parallel to b-axis (Fig. 2), in which they may be effective in the stabilization of the structure. A weak C—H···π interaction also occurs (Table 1).