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Tetrahydroberberine (systematic name: 9,10-dimethoxy-5,8,13,13a-tetrahydro-6
H-benzo[
g][1,3]benzodioxolo[5,6-
a]quinolizine), C
20H
21NO
4, a widely distributed naturally occurring alkaloid, has been crystallized as a racemic mixture about an inversion center. A bent conformation of the molecule is observed, with an angle of 24.72 (5)° between the arene rings at the two ends of the reduced quinolizinium core. The intermolecular hydrogen bonds that play an apparent role in crystal packing are 1,3-benzodioxole –CH
2OCH
3 and –OCH
3OCH
3 interactions between neighboring molecules.
Supporting information
CCDC reference: 1051389
Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Bruker, 2008); software used to prepare material for publication: SHELXTL (Bruker, 2008).
9,10-Dimethoxy-5,8,13,13a-tetrahydro-6
H-benzo[
g][1,3]benzodioxolo[5,6-
a]quinolizine
top
Crystal data top
C20H21NO4 | F(000) = 720 |
Mr = 339.38 | Dx = 1.395 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 10.516 (3) Å | Cell parameters from 7019 reflections |
b = 14.796 (5) Å | θ = 2.4–28.8° |
c = 10.620 (3) Å | µ = 0.10 mm−1 |
β = 101.986 (4)° | T = 150 K |
V = 1616.3 (9) Å3 | Needle, pale yellow |
Z = 4 | 0.39 × 0.17 × 0.03 mm |
Data collection top
Bruker SMART APEX CCD diffractometer | 3306 independent reflections |
Radiation source: fine-focus sealed tube | 2468 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.069 |
φ and ω scans | θmax = 26.4°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2009) | h = −13→13 |
Tmin = 0.650, Tmax = 0.997 | k = −18→18 |
23937 measured reflections | l = −13→13 |
Refinement top
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)] = 0.050 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.132 | All H-atom parameters refined |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0723P)2 + 0.074P] where P = (Fo2 + 2Fc2)/3 |
3306 reflections | (Δ/σ)max < 0.001 |
310 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
Special details top
Experimental. The diffraction data were obtained from 3 sets of 400 frames, each of width
0.5° in ω, collected at φ = 0.00, 90.00 and 180.00° and 2 sets of
800 frames, each of width 0.45° in φ, collected at ω = -30.00 and
210.00°. The scan time was 60 sec per frame. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.01598 (13) | 0.06160 (9) | 0.36706 (14) | 0.0336 (4) | |
O3 | 0.22930 (14) | 0.01051 (9) | 0.41434 (14) | 0.0354 (4) | |
O9 | 0.17222 (12) | 0.72123 (8) | 0.45030 (11) | 0.0239 (3) | |
O10 | −0.04453 (12) | 0.79326 (8) | 0.30532 (13) | 0.0280 (3) | |
N7 | 0.25961 (14) | 0.44323 (10) | 0.43049 (14) | 0.0221 (4) | |
C2 | 0.0985 (2) | −0.01444 (14) | 0.3572 (2) | 0.0343 (5) | |
H2A | 0.0936 (18) | −0.0300 (14) | 0.259 (2) | 0.031 (5)* | |
H2B | 0.073 (2) | −0.0622 (16) | 0.405 (2) | 0.042 (6)* | |
C3A | 0.22800 (19) | 0.10373 (12) | 0.41602 (18) | 0.0268 (4) | |
C4 | 0.33017 (19) | 0.16167 (13) | 0.44905 (18) | 0.0272 (4) | |
H4 | 0.425 (2) | 0.1429 (13) | 0.4669 (19) | 0.035 (6)* | |
C4A | 0.30206 (18) | 0.25497 (13) | 0.45153 (17) | 0.0238 (4) | |
C5 | 0.41270 (19) | 0.32064 (14) | 0.4927 (2) | 0.0287 (5) | |
H5A | 0.461 (2) | 0.3298 (15) | 0.426 (2) | 0.039 (6)* | |
H5B | 0.479 (2) | 0.2963 (13) | 0.563 (2) | 0.033 (6)* | |
C6 | 0.36381 (18) | 0.40983 (13) | 0.5335 (2) | 0.0262 (4) | |
H6A | 0.4355 (16) | 0.4541 (12) | 0.5470 (17) | 0.017 (5)* | |
H6B | 0.3344 (18) | 0.4026 (13) | 0.617 (2) | 0.026 (5)* | |
C8 | 0.22941 (18) | 0.53680 (12) | 0.4588 (2) | 0.0242 (4) | |
H8A | 0.3083 (19) | 0.5739 (15) | 0.452 (2) | 0.036 (6)* | |
H8B | 0.2145 (17) | 0.5424 (13) | 0.5490 (19) | 0.024 (5)* | |
C8A | 0.10988 (16) | 0.57312 (12) | 0.37059 (17) | 0.0212 (4) | |
C9 | 0.08419 (17) | 0.66546 (12) | 0.37020 (17) | 0.0219 (4) | |
C10 | −0.02979 (18) | 0.70131 (12) | 0.29698 (17) | 0.0226 (4) | |
C11 | −0.11958 (18) | 0.64397 (13) | 0.22179 (18) | 0.0255 (4) | |
H11 | −0.2030 (19) | 0.6661 (13) | 0.1691 (19) | 0.028 (5)* | |
C12 | −0.09305 (18) | 0.55190 (13) | 0.22067 (18) | 0.0251 (4) | |
H12 | −0.1505 (19) | 0.5118 (13) | 0.1677 (19) | 0.029 (5)* | |
C12A | 0.01994 (17) | 0.51544 (12) | 0.29443 (17) | 0.0223 (4) | |
C13 | 0.04806 (19) | 0.41507 (12) | 0.29529 (19) | 0.0254 (4) | |
H13A | 0.0904 (17) | 0.3990 (13) | 0.216 (2) | 0.028 (5)* | |
H13B | −0.0306 (19) | 0.3836 (13) | 0.2815 (19) | 0.029 (5)* | |
C13A | 0.14229 (17) | 0.38655 (12) | 0.41905 (18) | 0.0225 (4) | |
H13C | 0.1002 (19) | 0.3994 (14) | 0.499 (2) | 0.039 (6)* | |
C13B | 0.17429 (17) | 0.28614 (12) | 0.41996 (17) | 0.0215 (4) | |
C14 | 0.07047 (18) | 0.22417 (12) | 0.38865 (18) | 0.0244 (4) | |
H14 | −0.023 (2) | 0.2423 (14) | 0.3727 (19) | 0.033 (6)* | |
C14A | 0.10102 (18) | 0.13438 (12) | 0.38828 (18) | 0.0257 (4) | |
C15 | 0.2498 (2) | 0.77260 (14) | 0.3804 (2) | 0.0272 (5) | |
H15A | 0.3058 (19) | 0.7324 (14) | 0.3347 (19) | 0.030 (5)* | |
H15B | 0.313 (2) | 0.8061 (16) | 0.440 (2) | 0.049 (7)* | |
H15C | 0.1959 (18) | 0.8084 (13) | 0.3141 (19) | 0.024 (5)* | |
C16 | −0.1724 (2) | 0.82776 (15) | 0.2625 (2) | 0.0320 (5) | |
H16A | −0.199 (2) | 0.8207 (15) | 0.172 (2) | 0.040 (6)* | |
H16B | −0.234 (2) | 0.7982 (15) | 0.311 (2) | 0.046 (7)* | |
H16C | −0.167 (2) | 0.8946 (16) | 0.283 (2) | 0.038 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0357 (8) | 0.0156 (7) | 0.0466 (9) | −0.0020 (6) | 0.0016 (7) | −0.0014 (6) |
O3 | 0.0438 (9) | 0.0155 (7) | 0.0424 (9) | 0.0039 (6) | −0.0016 (7) | 0.0015 (6) |
O9 | 0.0281 (7) | 0.0195 (7) | 0.0224 (7) | −0.0054 (5) | 0.0010 (5) | −0.0020 (5) |
O10 | 0.0313 (7) | 0.0163 (7) | 0.0340 (8) | 0.0037 (5) | 0.0010 (6) | 0.0012 (6) |
N7 | 0.0207 (8) | 0.0176 (8) | 0.0252 (8) | 0.0000 (6) | −0.0014 (6) | 0.0002 (6) |
C2 | 0.0428 (12) | 0.0173 (10) | 0.0401 (13) | 0.0012 (9) | 0.0021 (10) | −0.0018 (9) |
C3A | 0.0382 (11) | 0.0154 (9) | 0.0249 (10) | 0.0035 (8) | 0.0019 (8) | 0.0020 (8) |
C4 | 0.0284 (10) | 0.0256 (10) | 0.0258 (10) | 0.0050 (8) | 0.0015 (8) | 0.0037 (9) |
C4A | 0.0271 (10) | 0.0212 (10) | 0.0221 (10) | 0.0029 (8) | 0.0027 (8) | 0.0020 (8) |
C5 | 0.0239 (10) | 0.0251 (11) | 0.0341 (12) | 0.0017 (8) | −0.0012 (9) | 0.0039 (9) |
C6 | 0.0247 (10) | 0.0220 (10) | 0.0288 (11) | −0.0003 (8) | −0.0014 (8) | 0.0018 (8) |
C8 | 0.0248 (10) | 0.0174 (9) | 0.0276 (11) | −0.0018 (8) | −0.0012 (8) | −0.0024 (8) |
C8A | 0.0224 (9) | 0.0201 (9) | 0.0202 (9) | −0.0003 (7) | 0.0025 (7) | 0.0008 (8) |
C9 | 0.0235 (9) | 0.0198 (9) | 0.0214 (9) | −0.0039 (7) | 0.0022 (7) | −0.0010 (8) |
C10 | 0.0290 (10) | 0.0171 (9) | 0.0219 (9) | 0.0023 (7) | 0.0057 (8) | 0.0023 (7) |
C11 | 0.0252 (10) | 0.0242 (10) | 0.0251 (10) | 0.0015 (8) | 0.0004 (8) | 0.0046 (8) |
C12 | 0.0256 (10) | 0.0231 (10) | 0.0237 (10) | −0.0029 (8) | −0.0015 (8) | −0.0010 (8) |
C12A | 0.0253 (9) | 0.0189 (9) | 0.0216 (9) | −0.0003 (7) | 0.0025 (7) | 0.0001 (8) |
C13 | 0.0254 (10) | 0.0167 (9) | 0.0296 (11) | 0.0004 (8) | −0.0047 (8) | −0.0020 (8) |
C13A | 0.0220 (9) | 0.0173 (9) | 0.0268 (10) | −0.0012 (7) | 0.0016 (8) | −0.0011 (8) |
C13B | 0.0253 (9) | 0.0195 (9) | 0.0186 (9) | 0.0014 (7) | 0.0019 (7) | 0.0004 (7) |
C14 | 0.0251 (10) | 0.0204 (10) | 0.0264 (10) | 0.0015 (8) | 0.0022 (8) | 0.0017 (8) |
C14A | 0.0306 (10) | 0.0206 (10) | 0.0243 (10) | −0.0039 (8) | 0.0019 (8) | −0.0006 (8) |
C15 | 0.0289 (11) | 0.0236 (11) | 0.0270 (11) | −0.0054 (9) | 0.0014 (9) | 0.0016 (9) |
C16 | 0.0360 (12) | 0.0234 (11) | 0.0323 (12) | 0.0096 (9) | −0.0031 (9) | 0.0030 (9) |
Geometric parameters (Å, º) top
O1—C14A | 1.388 (2) | C8—H8A | 1.01 (2) |
O1—C2 | 1.438 (2) | C8—H8B | 1.005 (19) |
O3—C3A | 1.379 (2) | C8A—C9 | 1.393 (3) |
O3—C2 | 1.431 (3) | C8A—C12A | 1.400 (2) |
O9—C9 | 1.391 (2) | C9—C10 | 1.391 (2) |
O9—C15 | 1.430 (2) | C10—C11 | 1.391 (3) |
O10—C10 | 1.374 (2) | C11—C12 | 1.391 (3) |
O10—C16 | 1.422 (2) | C11—H11 | 0.99 (2) |
N7—C6 | 1.464 (2) | C12—C12A | 1.389 (3) |
N7—C8 | 1.466 (2) | C12—H12 | 0.94 (2) |
N7—C13A | 1.476 (2) | C12A—C13 | 1.514 (2) |
C2—H2A | 1.06 (2) | C13—C13A | 1.532 (3) |
C2—H2B | 0.94 (2) | C13—H13A | 1.06 (2) |
C3A—C4 | 1.362 (3) | C13—H13B | 0.93 (2) |
C3A—C14A | 1.383 (3) | C13A—C13B | 1.523 (2) |
C4—C4A | 1.413 (3) | C13A—H13C | 1.05 (2) |
C4—H4 | 1.01 (2) | C13B—C14 | 1.411 (3) |
C4A—C13B | 1.394 (3) | C14—C14A | 1.367 (3) |
C4A—C5 | 1.509 (3) | C14—H14 | 1.00 (2) |
C5—C6 | 1.512 (3) | C15—H15A | 1.03 (2) |
C5—H5A | 0.96 (2) | C15—H15B | 0.96 (2) |
C5—H5B | 0.98 (2) | C15—H15C | 0.97 (2) |
C6—H6A | 0.987 (18) | C16—H16A | 0.95 (2) |
C6—H6B | 1.00 (2) | C16—H16B | 1.01 (2) |
C8—C8A | 1.503 (2) | C16—H16C | 1.01 (2) |
| | | |
C14A—O1—C2 | 103.91 (15) | O10—C10—C9 | 115.91 (16) |
C3A—O3—C2 | 104.61 (14) | O10—C10—C11 | 124.64 (16) |
C9—O9—C15 | 112.13 (14) | C9—C10—C11 | 119.45 (17) |
C10—O10—C16 | 116.53 (15) | C12—C11—C10 | 119.25 (17) |
C6—N7—C8 | 109.01 (14) | C12—C11—H11 | 118.2 (12) |
C6—N7—C13A | 110.66 (14) | C10—C11—H11 | 122.5 (12) |
C8—N7—C13A | 109.92 (14) | C12A—C12—C11 | 121.67 (17) |
O3—C2—O1 | 107.99 (16) | C12A—C12—H12 | 117.3 (12) |
O3—C2—H2A | 108.7 (11) | C11—C12—H12 | 121.0 (12) |
O1—C2—H2A | 109.6 (11) | C12—C12A—C8A | 119.03 (17) |
O3—C2—H2B | 108.7 (13) | C12—C12A—C13 | 121.83 (16) |
O1—C2—H2B | 107.9 (14) | C8A—C12A—C13 | 119.14 (16) |
H2A—C2—H2B | 113.9 (18) | C12A—C13—C13A | 111.48 (15) |
C4—C3A—O3 | 128.55 (17) | C12A—C13—H13A | 109.2 (11) |
C4—C3A—C14A | 121.57 (17) | C13A—C13—H13A | 108.5 (10) |
O3—C3A—C14A | 109.69 (16) | C12A—C13—H13B | 108.8 (12) |
C3A—C4—C4A | 117.56 (17) | C13A—C13—H13B | 113.0 (12) |
C3A—C4—H4 | 124.6 (11) | H13A—C13—H13B | 105.6 (16) |
C4A—C4—H4 | 117.8 (11) | N7—C13A—C13B | 111.97 (15) |
C13B—C4A—C4 | 120.90 (17) | N7—C13A—C13 | 107.14 (15) |
C13B—C4A—C5 | 120.22 (17) | C13B—C13A—C13 | 112.15 (15) |
C4—C4A—C5 | 118.86 (16) | N7—C13A—H13C | 108.4 (11) |
C4A—C5—C6 | 110.94 (16) | C13B—C13A—H13C | 107.5 (12) |
C4A—C5—H5A | 111.9 (13) | C13—C13A—H13C | 109.6 (11) |
C6—C5—H5A | 110.6 (13) | C4A—C13B—C14 | 120.10 (17) |
C4A—C5—H5B | 111.7 (12) | C4A—C13B—C13A | 121.66 (16) |
C6—C5—H5B | 109.3 (12) | C14—C13B—C13A | 118.23 (16) |
H5A—C5—H5B | 102.0 (17) | C14A—C14—C13B | 117.47 (17) |
N7—C6—C5 | 109.04 (16) | C14A—C14—H14 | 119.0 (12) |
N7—C6—H6A | 108.4 (10) | C13B—C14—H14 | 123.4 (12) |
C5—C6—H6A | 109.0 (10) | C14—C14A—C3A | 122.36 (17) |
N7—C6—H6B | 112.1 (11) | C14—C14A—O1 | 127.64 (17) |
C5—C6—H6B | 110.2 (11) | C3A—C14A—O1 | 109.95 (16) |
H6A—C6—H6B | 108.1 (15) | O9—C15—H15A | 112.4 (11) |
N7—C8—C8A | 113.50 (15) | O9—C15—H15B | 108.8 (14) |
N7—C8—H8A | 106.5 (12) | H15A—C15—H15B | 103.1 (17) |
C8A—C8—H8A | 110.9 (12) | O9—C15—H15C | 111.0 (11) |
N7—C8—H8B | 110.9 (11) | H15A—C15—H15C | 106.3 (16) |
C8A—C8—H8B | 106.8 (10) | H15B—C15—H15C | 114.9 (18) |
H8A—C8—H8B | 108.2 (16) | O10—C16—H16A | 110.4 (13) |
C9—C8A—C12A | 119.28 (16) | O10—C16—H16B | 110.4 (13) |
C9—C8A—C8 | 119.31 (15) | H16A—C16—H16B | 112.3 (19) |
C12A—C8A—C8 | 121.31 (16) | O10—C16—H16C | 105.8 (12) |
O9—C9—C10 | 120.16 (16) | H16A—C16—H16C | 108.3 (19) |
O9—C9—C8A | 118.43 (15) | H16B—C16—H16C | 109.3 (18) |
C10—C9—C8A | 121.32 (16) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2B···O10i | 0.94 (2) | 2.58 (2) | 3.212 (3) | 124.5 (17) |
C16—H16A···O9ii | 0.95 (2) | 2.53 (2) | 3.455 (3) | 162.9 (18) |
Symmetry codes: (i) x, y−1, z; (ii) x−1/2, −y+3/2, z−1/2. |
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