Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807029480/rk2017sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807029480/rk2017Isup2.hkl |
CCDC reference: 655002
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.003 Å
- R factor = 0.067
- wR factor = 0.231
- Data-to-parameter ratio = 23.8
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C14
Alert level G PLAT793_ALERT_1_G Check the Absolute Configuration of C1 = ... R PLAT793_ALERT_1_G Check the Absolute Configuration of C5 = ... S
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For general backgroud, see: Hesse (2002); Bosch & Bonjoch (1988); Saxton (1983); Allen et al. (1987). For related literature, see: Hökelek et al. (2004, 2006); Uludağ et al. (2006).
The title compound, (I), was prepared from N-(2',2'-Dimethoxyethyl)-6- (1,2-dithiolane-2-yl)-1,2,3,4,5,6-hexahydro-1,5-methano-3-oxo-1H- azocino[4,3-b]indole (1.0 g, 2.47 mmol) and Raney nickel (1.0 g) in ethanol (50 ml). The mixture was refluxed for 22 h, and then filtered and evaporated. The residue was purified by silica gel chromatography using ethyl acetate and crystallized from diethyl ether (yield; 0.42 g, 54%, m.p. 453 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 indol 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 structural element and include a large group of naturally occurring compounds such as strychnine, a covulsant poison.
The structures of tricyclic, tetracyclic and pentacyclic ring systems with different substituent of azocino[4,3-b]indole core, have been the subject of much interest in our laboratory. These include N-(2-benzyloxyethyl)-4,7- dimethyl-6-(1,3-dithiolan-2-yl)-1,2,3,4,5,6-hexahydro-1,5-methano-2- azocino[4,3-b]indol-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) and 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]indol-3-one, (IV), (Hökelek et al., 2006). 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 system containing an azocino skeleton with dimethoxyethyl group as substituent at position N2, in which the bond lengths and angles are within normal ranges (Allen et al., 1987). The bonds N7—C6a [1.377 (3) Å] and N7—C7a [1.376 (3) Å] agree well with those in compounds (II) [1.392 (8) and 1.370 (8) Å] and (IV) [1.393 (4) and 1.386 (5) Å]. In all three structures atom N7 is substituted. The absolute configurations of C1 and C5 are R and S (Fig. 1), respectively.
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 nearly co-planar with a dihedral angle of A/B = 1.25 (7)°. Rings C (C1/C11b/C6a/C6/C5/C12) and D (C1/N2/C3/C4/C5/C12) are, of course, not planar. Atom C12 deviates from the planes of E (C1/C5/C6/C6a/C11b) and F (C1/N2/C3/C4/C5) by -0.710 (2) Å and 0.7445 (2) Å, respectively, where the dihedral angle between the planes of E and F is E/F = 69.72 (6)°. On the other hand, the dihedral angles between the plane of G (C1/C5/C12) and planes of E and F are 53.93 (7)° and 69.84 (6)°, respectively.
In the crystal structure, intermolecular N–H···O hydrogen bonds (see Table) link the molecules into chains nearly parallel to b axis (Fig. 2), in which they may be effective in the stabilization of the structure; van der Waals interactions are also effective in the molecular packing.
For general backgroud, see: Hesse (2002); Bosch & Bonjoch (1988); Saxton (1983); Allen et al. (1987). For related literature, see: Hökelek et al. (2004, 2006); Uludağ et al. (2006).
Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
C18H22N2O3 | F(000) = 672 |
Mr = 314.38 | Dx = 1.259 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 6164 reflections |
a = 10.0347 (4) Å | θ = 2.1–30.6° |
b = 8.4616 (7) Å | µ = 0.09 mm−1 |
c = 20.1168 (9) Å | T = 294 K |
β = 103.750 (3)° | Prism, colorless |
V = 1659.16 (17) Å3 | 0.35 × 0.20 × 0.15 mm |
Z = 4 |
Rigaku R-AXIS RAPID-S diffractometer | 5094 independent reflections |
Radiation source: fine-focus sealed tube | 2625 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.076 |
ω scans | θmax = 30.7°, θmin = 2.1° |
Absorption correction: multi-scan (Blessing, 1995) | h = −14→14 |
Tmin = 0.971, Tmax = 0.987 | k = −10→12 |
47331 measured reflections | l = −28→28 |
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)] = 0.067 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.231 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.1052P)2 + 0.0611P] where P = (Fo2 + 2Fc2)/3 |
5094 reflections | (Δ/σ)max < 0.001 |
214 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
C18H22N2O3 | V = 1659.16 (17) Å3 |
Mr = 314.38 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.0347 (4) Å | µ = 0.09 mm−1 |
b = 8.4616 (7) Å | T = 294 K |
c = 20.1168 (9) Å | 0.35 × 0.20 × 0.15 mm |
β = 103.750 (3)° |
Rigaku R-AXIS RAPID-S diffractometer | 5094 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 2625 reflections with I > 2σ(I) |
Tmin = 0.971, Tmax = 0.987 | Rint = 0.076 |
47331 measured reflections |
R[F2 > 2σ(F2)] = 0.067 | 0 restraints |
wR(F2) = 0.231 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.32 e Å−3 |
5094 reflections | Δρmin = −0.32 e Å−3 |
214 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 | ||
O1 | 0.05988 (15) | 0.19313 (18) | 0.09564 (7) | 0.0701 (4) | |
O2 | −0.31895 (16) | 0.1229 (2) | 0.14450 (8) | 0.0794 (5) | |
O3 | −0.2405 (2) | −0.12092 (19) | 0.12128 (10) | 0.0944 (6) | |
C1 | −0.0680 (2) | 0.3424 (2) | 0.23627 (10) | 0.0594 (5) | |
H1 | −0.1476 | 0.3034 | 0.2516 | 0.071* | |
N2 | −0.04095 (17) | 0.2356 (2) | 0.18262 (8) | 0.0595 (4) | |
C3 | 0.03154 (19) | 0.2844 (2) | 0.13862 (10) | 0.0581 (5) | |
C4 | 0.0769 (2) | 0.4547 (3) | 0.14005 (12) | 0.0715 (6) | |
H4A | 0.0477 | 0.4955 | 0.0938 | 0.086* | |
H4B | 0.1764 | 0.4556 | 0.1519 | 0.086* | |
C5 | 0.0288 (2) | 0.5715 (3) | 0.18762 (11) | 0.0702 (6) | |
H5 | 0.0053 | 0.6712 | 0.1629 | 0.084* | |
C6 | 0.1378 (3) | 0.6059 (3) | 0.25340 (12) | 0.0768 (6) | |
H6A | 0.2262 | 0.6213 | 0.2427 | 0.092* | |
H6B | 0.1144 | 0.7019 | 0.2743 | 0.092* | |
C6A | 0.1460 (2) | 0.4708 (2) | 0.30211 (10) | 0.0626 (5) | |
C7A | 0.2202 (2) | 0.3180 (2) | 0.39445 (10) | 0.0590 (5) | |
N7 | 0.24803 (18) | 0.4512 (2) | 0.36095 (9) | 0.0663 (5) | |
H7 | 0.315 (2) | 0.529 (3) | 0.3798 (12) | 0.077 (7)* | |
C8 | 0.2921 (2) | 0.2521 (3) | 0.45622 (10) | 0.0677 (6) | |
H8 | 0.3729 | 0.2974 | 0.4813 | 0.081* | |
C9 | 0.2393 (3) | 0.1185 (3) | 0.47851 (11) | 0.0756 (6) | |
H9 | 0.2848 | 0.0724 | 0.5196 | 0.091* | |
C10 | 0.1190 (3) | 0.0506 (3) | 0.44087 (12) | 0.0792 (7) | |
H10 | 0.0856 | −0.0401 | 0.4574 | 0.095* | |
C11 | 0.0475 (2) | 0.1142 (3) | 0.37944 (11) | 0.0673 (6) | |
H11 | −0.0328 | 0.0669 | 0.3549 | 0.081* | |
C11A | 0.0979 (2) | 0.2506 (2) | 0.35487 (9) | 0.0560 (5) | |
C11B | 0.0528 (2) | 0.3514 (2) | 0.29624 (10) | 0.0570 (5) | |
C12 | −0.1000 (2) | 0.5072 (3) | 0.20518 (12) | 0.0705 (6) | |
H12A | −0.1739 | 0.5011 | 0.1642 | 0.085* | |
H12B | −0.1285 | 0.5765 | 0.2376 | 0.085* | |
C13 | −0.0850 (2) | 0.0703 (2) | 0.18074 (10) | 0.0644 (5) | |
H13A | −0.1020 | 0.0420 | 0.2247 | 0.077* | |
H13B | −0.0121 | 0.0030 | 0.1728 | 0.077* | |
C14 | −0.2129 (2) | 0.0419 (2) | 0.12555 (11) | 0.0636 (5) | |
H14 | −0.2009 | 0.0815 | 0.0816 | 0.076* | |
C15 | −0.4422 (3) | 0.1293 (4) | 0.09197 (15) | 0.0976 (9) | |
H15A | −0.4230 | 0.1734 | 0.0513 | 0.146* | |
H15B | −0.5081 | 0.1943 | 0.1067 | 0.146* | |
H15C | −0.4784 | 0.0245 | 0.0825 | 0.146* | |
C16 | −0.2419 (5) | −0.1910 (4) | 0.05865 (17) | 0.1358 (15) | |
H16A | −0.3086 | −0.1393 | 0.0232 | 0.204* | |
H16B | −0.2651 | −0.3008 | 0.0602 | 0.204* | |
H16C | −0.1528 | −0.1814 | 0.0493 | 0.204* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0713 (9) | 0.0756 (10) | 0.0610 (9) | 0.0142 (7) | 0.0112 (7) | 0.0032 (7) |
O2 | 0.0630 (9) | 0.0999 (12) | 0.0721 (10) | −0.0028 (8) | 0.0097 (8) | 0.0025 (8) |
O3 | 0.1162 (15) | 0.0666 (10) | 0.0902 (12) | −0.0259 (9) | 0.0043 (11) | −0.0006 (9) |
C1 | 0.0540 (10) | 0.0674 (12) | 0.0553 (11) | −0.0031 (9) | 0.0100 (8) | 0.0005 (9) |
N2 | 0.0593 (9) | 0.0623 (10) | 0.0542 (9) | −0.0065 (7) | 0.0080 (7) | −0.0011 (7) |
C3 | 0.0506 (10) | 0.0666 (12) | 0.0526 (10) | 0.0055 (9) | 0.0037 (8) | 0.0049 (9) |
C4 | 0.0750 (14) | 0.0717 (14) | 0.0679 (13) | −0.0088 (11) | 0.0176 (11) | 0.0050 (11) |
C5 | 0.0802 (14) | 0.0586 (12) | 0.0681 (13) | 0.0022 (10) | 0.0104 (11) | 0.0093 (10) |
C6 | 0.0919 (16) | 0.0639 (13) | 0.0710 (14) | −0.0125 (12) | 0.0122 (12) | 0.0034 (11) |
C6A | 0.0646 (12) | 0.0637 (12) | 0.0573 (11) | −0.0051 (9) | 0.0101 (9) | −0.0005 (9) |
C7A | 0.0596 (11) | 0.0642 (12) | 0.0527 (10) | −0.0001 (9) | 0.0122 (9) | −0.0055 (8) |
N7 | 0.0625 (10) | 0.0699 (11) | 0.0622 (10) | −0.0150 (9) | 0.0064 (8) | −0.0034 (8) |
C8 | 0.0651 (12) | 0.0834 (15) | 0.0506 (10) | 0.0062 (11) | 0.0059 (9) | −0.0073 (10) |
C9 | 0.0920 (17) | 0.0815 (15) | 0.0501 (11) | 0.0105 (13) | 0.0105 (11) | 0.0059 (10) |
C10 | 0.1020 (18) | 0.0760 (15) | 0.0607 (13) | −0.0012 (13) | 0.0218 (13) | 0.0082 (11) |
C11 | 0.0739 (13) | 0.0700 (13) | 0.0579 (12) | −0.0117 (10) | 0.0158 (10) | 0.0005 (9) |
C11A | 0.0568 (11) | 0.0605 (11) | 0.0509 (10) | −0.0019 (8) | 0.0132 (8) | −0.0023 (8) |
C11B | 0.0549 (10) | 0.0619 (11) | 0.0534 (10) | −0.0039 (9) | 0.0115 (8) | −0.0005 (8) |
C12 | 0.0682 (13) | 0.0753 (14) | 0.0652 (12) | 0.0135 (11) | 0.0101 (10) | 0.0026 (10) |
C13 | 0.0670 (12) | 0.0633 (12) | 0.0574 (11) | −0.0056 (10) | 0.0037 (9) | 0.0057 (9) |
C14 | 0.0692 (12) | 0.0615 (12) | 0.0564 (11) | −0.0103 (10) | 0.0074 (9) | 0.0035 (9) |
C15 | 0.0691 (15) | 0.119 (2) | 0.096 (2) | −0.0027 (14) | 0.0021 (14) | 0.0302 (16) |
C16 | 0.190 (4) | 0.087 (2) | 0.098 (2) | 0.014 (2) | −0.030 (2) | −0.0281 (18) |
O1—C3 | 1.242 (2) | C6A—C6 | 1.495 (3) |
O2—C14 | 1.393 (3) | C7A—C8 | 1.396 (3) |
O2—C15 | 1.424 (3) | C7A—C11A | 1.414 (3) |
O3—C14 | 1.404 (2) | C8—C9 | 1.368 (3) |
O3—C16 | 1.390 (4) | C8—H8 | 0.9300 |
N2—C3 | 1.338 (3) | C9—C10 | 1.388 (3) |
N2—C13 | 1.464 (3) | C9—H9 | 0.9300 |
N2—C1 | 1.482 (2) | C10—H10 | 0.9300 |
N7—C7A | 1.376 (3) | C11—C10 | 1.382 (3) |
N7—C6A | 1.378 (2) | C11—H11 | 0.9300 |
N7—H7 | 0.95 (2) | C11A—C11 | 1.397 (3) |
C1—C11B | 1.495 (3) | C11A—C11B | 1.439 (3) |
C1—C12 | 1.530 (3) | C12—H12A | 0.9700 |
C1—H1 | 0.9800 | C12—H12B | 0.9700 |
C3—C4 | 1.509 (3) | C13—C14 | 1.503 (3) |
C4—H4A | 0.9700 | C13—H13A | 0.9700 |
C4—H4B | 0.9700 | C13—H13B | 0.9700 |
C5—C4 | 1.532 (3) | C14—H14 | 0.9800 |
C5—H5 | 0.9800 | C15—H15A | 0.9600 |
C5—C6 | 1.531 (3) | C15—H15B | 0.9600 |
C5—C12 | 1.519 (3) | C15—H15C | 0.9600 |
C6—H6A | 0.9700 | C16—H16A | 0.9600 |
C6—H6B | 0.9700 | C16—H16B | 0.9600 |
C6A—C11B | 1.362 (3) | C16—H16C | 0.9600 |
C14—O2—C15 | 113.62 (19) | C9—C8—H8 | 121.2 |
C16—O3—C14 | 115.7 (2) | C7A—C8—H8 | 121.2 |
C3—N2—C13 | 119.09 (18) | C8—C9—C10 | 121.2 (2) |
C3—N2—C1 | 121.07 (16) | C8—C9—H9 | 119.4 |
C13—N2—C1 | 119.67 (16) | C10—C9—H9 | 119.4 |
C7A—N7—C6A | 108.88 (17) | C11—C10—C9 | 121.7 (2) |
C7A—N7—H7 | 125.2 (14) | C11—C10—H10 | 119.1 |
C6A—N7—H7 | 124.6 (14) | C9—C10—H10 | 119.1 |
N7—C7A—C8 | 129.9 (2) | C10—C11—C11A | 118.9 (2) |
N7—C7A—C11A | 107.72 (17) | C10—C11—H11 | 120.5 |
C8—C7A—C11A | 122.4 (2) | C11A—C11—H11 | 120.5 |
C11—C11A—C7A | 118.18 (19) | C6A—C11B—C11A | 107.04 (17) |
C11—C11A—C11B | 135.28 (19) | C6A—C11B—C1 | 121.07 (17) |
C7A—C11A—C11B | 106.52 (17) | C11A—C11B—C1 | 131.89 (17) |
N2—C1—C11B | 111.41 (16) | C5—C12—C1 | 108.28 (17) |
N2—C1—C12 | 108.36 (16) | C5—C12—H12A | 110.0 |
C11B—C1—C12 | 109.54 (17) | C1—C12—H12A | 110.0 |
N2—C1—H1 | 109.2 | C5—C12—H12B | 110.0 |
C11B—C1—H1 | 109.2 | C1—C12—H12B | 110.0 |
C12—C1—H1 | 109.2 | H12A—C12—H12B | 108.4 |
O1—C3—N2 | 121.26 (19) | N2—C13—C14 | 111.79 (16) |
O1—C3—C4 | 119.29 (18) | N2—C13—H13A | 109.3 |
N2—C3—C4 | 119.43 (18) | C14—C13—H13A | 109.3 |
C3—C4—C5 | 119.29 (18) | N2—C13—H13B | 109.3 |
C3—C4—H4A | 107.5 | C14—C13—H13B | 109.3 |
C5—C4—H4A | 107.5 | H13A—C13—H13B | 107.9 |
C3—C4—H4B | 107.5 | O2—C14—O3 | 110.32 (18) |
C5—C4—H4B | 107.5 | O2—C14—C13 | 107.03 (17) |
H4A—C4—H4B | 107.0 | O3—C14—C13 | 108.87 (17) |
C12—C5—C6 | 109.86 (19) | O2—C14—H14 | 110.2 |
C12—C5—C4 | 109.05 (18) | O3—C14—H14 | 110.2 |
C6—C5—C4 | 113.3 (2) | C13—C14—H14 | 110.2 |
C12—C5—H5 | 108.2 | O2—C15—H15A | 109.5 |
C6—C5—H5 | 108.2 | O2—C15—H15B | 109.5 |
C4—C5—H5 | 108.2 | H15A—C15—H15B | 109.5 |
C6A—C6—C5 | 109.75 (18) | O2—C15—H15C | 109.5 |
C6A—C6—H6A | 109.7 | H15A—C15—H15C | 109.5 |
C5—C6—H6A | 109.7 | H15B—C15—H15C | 109.5 |
C6A—C6—H6B | 109.7 | O3—C16—H16A | 109.5 |
C5—C6—H6B | 109.7 | O3—C16—H16B | 109.5 |
H6A—C6—H6B | 108.2 | H16A—C16—H16B | 109.5 |
C11B—C6A—N7 | 109.84 (18) | O3—C16—H16C | 109.5 |
C11B—C6A—C6 | 125.46 (19) | H16A—C16—H16C | 109.5 |
N7—C6A—C6 | 124.68 (19) | H16B—C16—H16C | 109.5 |
C9—C8—C7A | 117.6 (2) | ||
C15—O2—C14—O3 | −71.6 (2) | C12—C5—C6—C6A | 45.2 (3) |
C15—O2—C14—C13 | 170.10 (19) | C4—C5—C6—C6A | −77.0 (2) |
C16—O3—C14—O2 | 123.3 (3) | C6—C5—C12—C1 | −68.7 (2) |
C16—O3—C14—C13 | −119.5 (3) | C4—C5—C12—C1 | 56.0 (2) |
C13—N2—C3—O1 | 1.3 (3) | C11B—C6A—C6—C5 | −13.1 (3) |
C1—N2—C3—O1 | 176.60 (17) | N7—C6A—C6—C5 | 168.7 (2) |
C13—N2—C3—C4 | 179.79 (17) | N7—C6A—C11B—C11A | 0.3 (2) |
C1—N2—C3—C4 | −4.9 (3) | C6—C6A—C11B—C11A | −178.1 (2) |
C3—N2—C1—C11B | −80.3 (2) | N7—C6A—C11B—C1 | −179.11 (18) |
C13—N2—C1—C11B | 95.02 (19) | C6—C6A—C11B—C1 | 2.5 (3) |
C3—N2—C1—C12 | 40.3 (2) | N7—C7A—C8—C9 | 178.9 (2) |
C13—N2—C1—C12 | −144.41 (18) | C11A—C7A—C8—C9 | −0.7 (3) |
C3—N2—C13—C14 | −81.7 (2) | N7—C7A—C11A—C11 | −179.01 (18) |
C1—N2—C13—C14 | 102.9 (2) | C8—C7A—C11A—C11 | 0.7 (3) |
C6A—N7—C7A—C8 | −178.8 (2) | N7—C7A—C11A—C11B | −0.7 (2) |
C6A—N7—C7A—C11A | 0.8 (2) | C8—C7A—C11A—C11B | 179.03 (18) |
C7A—N7—C6A—C11B | −0.7 (2) | C7A—C8—C9—C10 | 0.3 (3) |
C7A—N7—C6A—C6 | 177.7 (2) | C8—C9—C10—C11 | 0.1 (4) |
N2—C1—C11B—C6A | 96.2 (2) | C11A—C11—C10—C9 | −0.2 (3) |
C12—C1—C11B—C6A | −23.7 (3) | C7A—C11A—C11—C10 | −0.2 (3) |
N2—C1—C11B—C11A | −83.0 (3) | C11B—C11A—C11—C10 | −178.0 (2) |
C12—C1—C11B—C11A | 157.1 (2) | C11—C11A—C11B—C6A | 178.2 (2) |
N2—C1—C12—C5 | −66.2 (2) | C7A—C11A—C11B—C6A | 0.2 (2) |
C11B—C1—C12—C5 | 55.5 (2) | C11—C11A—C11B—C1 | −2.5 (4) |
O1—C3—C4—C5 | 173.37 (19) | C7A—C11A—C11B—C1 | 179.5 (2) |
N2—C3—C4—C5 | −5.2 (3) | N2—C13—C14—O2 | −67.5 (2) |
C12—C5—C4—C3 | −21.6 (3) | N2—C13—C14—O3 | 173.28 (18) |
C6—C5—C4—C3 | 101.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N7—H7···O1i | 0.95 (2) | 1.86 (2) | 2.805 (2) | 172 (2) |
Symmetry code: (i) −x+1/2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C18H22N2O3 |
Mr | 314.38 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 294 |
a, b, c (Å) | 10.0347 (4), 8.4616 (7), 20.1168 (9) |
β (°) | 103.750 (3) |
V (Å3) | 1659.16 (17) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.35 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID-S |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.971, 0.987 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 47331, 5094, 2625 |
Rint | 0.076 |
(sin θ/λ)max (Å−1) | 0.717 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.067, 0.231, 1.06 |
No. of reflections | 5094 |
No. of parameters | 214 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.32, −0.32 |
Computer programs: CrystalClear (Rigaku/MSC, 2005), CrystalClear, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
N7—H7···O1i | 0.95 (2) | 1.86 (2) | 2.805 (2) | 172 (2) |
Symmetry code: (i) −x+1/2, y+1/2, −z+1/2. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
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 indol 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 structural element and include a large group of naturally occurring compounds such as strychnine, a covulsant poison.
The structures of tricyclic, tetracyclic and pentacyclic ring systems with different substituent of azocino[4,3-b]indole core, have been the subject of much interest in our laboratory. These include N-(2-benzyloxyethyl)-4,7- dimethyl-6-(1,3-dithiolan-2-yl)-1,2,3,4,5,6-hexahydro-1,5-methano-2- azocino[4,3-b]indol-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) and 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]indol-3-one, (IV), (Hökelek et al., 2006). 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 system containing an azocino skeleton with dimethoxyethyl group as substituent at position N2, in which the bond lengths and angles are within normal ranges (Allen et al., 1987). The bonds N7—C6a [1.377 (3) Å] and N7—C7a [1.376 (3) Å] agree well with those in compounds (II) [1.392 (8) and 1.370 (8) Å] and (IV) [1.393 (4) and 1.386 (5) Å]. In all three structures atom N7 is substituted. The absolute configurations of C1 and C5 are R and S (Fig. 1), respectively.
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 nearly co-planar with a dihedral angle of A/B = 1.25 (7)°. Rings C (C1/C11b/C6a/C6/C5/C12) and D (C1/N2/C3/C4/C5/C12) are, of course, not planar. Atom C12 deviates from the planes of E (C1/C5/C6/C6a/C11b) and F (C1/N2/C3/C4/C5) by -0.710 (2) Å and 0.7445 (2) Å, respectively, where the dihedral angle between the planes of E and F is E/F = 69.72 (6)°. On the other hand, the dihedral angles between the plane of G (C1/C5/C12) and planes of E and F are 53.93 (7)° and 69.84 (6)°, respectively.
In the crystal structure, intermolecular N–H···O hydrogen bonds (see Table) link the molecules into chains nearly parallel to b axis (Fig. 2), in which they may be effective in the stabilization of the structure; van der Waals interactions are also effective in the molecular packing.