organic papers
o1764
Xiao-Ling Wang C20H19NO5 doi:10.1107/S1600536806010324 Acta Cryst.(2006). E62, o1764–o1765 Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368
8-Oxocanadine
Xiao-Ling Wang
Department of Chemistry, Baoji College of Arts and Sciences, Baoji 721007, People’s Republic of China
Correspondence e-mail: [email protected]
Key indicators
Single-crystal X-ray study
T= 286 K
Mean(C–C) = 0.005 A˚
Rfactor = 0.040
wRfactor = 0.076 Data-to-parameter ratio = 6.9
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
Received 18 March 2006 Accepted 21 March 2006
#2006 International Union of Crystallography
All rights reserved
The title compound, C20H19NO5, a protoberberine-type
alkaloid, was isolated from the roots of the plantSinomenium acutum. The piperidine ring adopts a screw-boat conformation and the pyridinone ring is in an envelope conformation.
Comment
Sinomenium acutum is distributed mainly in hilly regions of southwest, northwest and southeast China. The roots and stems of the plant are used as folk medicine to cure rheuma-tism, dropsy and dermatophytosis. A number of alkaloids with different kinds of skeletons have been isolated from the plant
(Jiangsu New Medical College, 1985; Chen et al., 1991;
Moriyasuet al., 1993, 1994). In the course of our systematic search for bioactive substances from Chinese traditional herbal medicines, we have studied the roots ofS. acutumand obtained several compounds, including the title compound, (I), which is reported here. Compound (I) was first isolated from the stem and roots ofAnamirta cocculusand identified on the basis of its mass, UV, and NMR spectra (Zhanget al., 1991). Previously, we have reported the crystal structures of cheilanthifoline (Wanget al., 2006), 8-oxotetrahydropalmatine (Wang, 2006a) and tetrahydroepiberberine (Wang, 2006b).
The piperidine ring adopts a screw-boat conformation whereas the pyridinone ring is in an envelope conformation (Fig. 1). The methoxy group attached at atom C10 is essen-tially coplanar with the C9–C12/C8A/C12Abenzene ring with
a torsion angle C20—O5—C10—C9 of 164.9 (3), but that at
atom C9 is twisted away from the benzene ring with a torsion
angle C19—O4—C9—C10 of 84.5 (4). The
1,3-benzo-dioxole ring system is essentially planar with a C18—O2— C3—C4 torsion angle of 170.6 (4).
Experimental
Sinomenine was produced from the powder of the roots ofS. acutum
Baoji, People’s Republic of China. It was obtained from a benzene extract of the powder in vacuo(Chenet al., 1995). The remaining benzene mother liquor (3 kg), after the extraction of sinomenine, was obtained from the company. It was subjected to repeated chroma-tography on a silica gel column and eluted with petroleum ether/ acetone (from 3:1 to 2:1) to afford compound (I) (0.01 g). Single crystals of (I) were obtained after repeated recrystalization from methanol.
Crystal data
C20H19NO5
Mr= 353.36
Monoclinic,P21
a= 5.132 (2) A˚ b= 7.203 (2) A˚ c= 22.767 (8) A˚
= 95.59 (3)
V= 837.5 (5) A˚3
Z= 2
Dx= 1.401 Mg m
3
MoKradiation Cell parameters from 33
reflections
= 3.9–15.5
= 0.10 mm1
T= 286 (2) K Needle, yellow 0.560.240.20 mm
Data collection
Siemens P4 diffractometer
!scans
Absorption correction: none 2412 measured reflections 1651 independent reflections 1165 reflections withI> 2(I) Rint= 0.016
max= 25.2
h= 0!6 k= 0!8 l=27!27 3 standard reflections
every 97 reflections intensity decay: 3.5%
Refinement
Refinement onF2 R[F2> 2(F2)] = 0.040
wR(F2) = 0.076 S= 1.00 1651 reflections 238 parameters
H-atom parameters constrained
w= 1/[2
(Fo2) + (0.0306P)2]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001 max= 0.14 e A˚
3 min=0.16 e A˚
3
Extinction correction:SHELXL Extinction coefficient: 0.0134 (19)
H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.98 A˚ . TheUisovalues were constrained to be 1.5Ueqof the carrier atom for
methyl H atoms and 1.2Ueqfor the remaining H atoms. A
rotating-group model was used for the methyl rotating-groups. In the absence of any significant anomalous dispersion, Friedel pairs were merged before the final refinement.
Data collection: XSCANS (Siemens, 1994); cell refinement:
XSCANS; data reduction:SHELXTL(Sheldrick, 1997b); program(s)
used to solve structure:SHELXS97(Sheldrick, 1997a); program(s) used to refine structure:SHELXL97(Sheldrick, 1997a); molecular graphics:SHELXTL; software used to prepare material for publi-cation:SHELXTL.
The author thanks the Phytochemistry Key Laboratory of Shaanxi province for the research grant (No. 05js43) and Professor Kai-Bei Yu, Chengdu Institute of Organic Chem-istry, Chinese Academy of Sciences, for diffraction measure-ments.
References
Chen, C., Sun, L. J. & Xu, H. Q. (1995). Chinese Patent No. 1125724. Chen, Y. Y., Qiu, C. C. & Shen, L. (1991).Beijing Yike Daxue Xuebao,23, 235–
237. (In Chinese.)
Jiangsu New Medical College (1985).The Dictionary of Chinese Medicine, pp. 1234–1236. Shanghai: Shanghai Science and Technology Press.
Moriyasu, M., Ichimaru, M. & Nishiyama, Y. (1993).Bunseki Kagaku,42, 659– 665. (In Japanese.)
Moriyasu, M., Ichimaru, M. & Nishiyama, Y. (1994).Nat. Med. 48, 287– 290.
Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.
Sheldrick, G. M. (1997b).SHELXTL(Version 5.0). Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
Siemens (1994). XSCANS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
Wang, X. L. (2006a).Acta Cryst.E62, o498–o499. Wang, X. L. (2006b).Acta Cryst.E62, o1271–o1272.
[image:2.610.316.565.74.186.2]Wang, X. L., Li, Z. X. & Qin, G. W. (2006).Acta Cryst.E62, o81–o82. Zhang, J. S. & Chen, Z. L. (1991).Planta Med.57, 457–459.
Figure 1
supporting information
sup-1 Acta Cryst. (2006). E62, o1764–o1765
supporting information
Acta Cryst. (2006). E62, o1764–o1765 [https://doi.org/10.1107/S1600536806010324]
8-Oxocanadine
Xiao-Ling Wang
(I)
Crystal data C20H19NO5
Mr = 353.36
Monoclinic, P21
a = 5.132 (2) Å b = 7.203 (2) Å c = 22.767 (8) Å β = 95.59 (3)° V = 837.5 (5) Å3
Z = 2
F(000) = 372 Dx = 1.401 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 33 reflections θ = 3.9–15.5°
µ = 0.10 mm−1
T = 286 K Needle, yellow 0.56 × 0.24 × 0.20 mm
Data collection Siemens P4
diffractometer
Radiation source: normal-focus sealed tube Graphite monochromator
ω scans
2412 measured reflections 1651 independent reflections 1165 reflections with I > 2σ(I)
Rint = 0.016
θmax = 25.2°, θmin = 1.8°
h = 0→6 k = 0→8 l = −27→27
3 standard reflections every 97 reflections intensity decay: 3.5%
Refinement Refinement on F2
Least-squares matrix: full R[F2 > 2σ(F2)] = 0.040
wR(F2) = 0.076
S = 1.00 1651 reflections 238 parameters 1 restraint
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained w = 1/[σ2(F
o2) + (0.0306P)2]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.14 e Å−3
Δρmin = −0.16 e Å−3
Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Extinction coefficient: 0.0134 (19)
Special details
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.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
O1 0.8939 (5) 0.1808 (4) 0.11412 (10) 0.0671 (8)
O2 0.8235 (5) 0.3580 (4) 0.02937 (9) 0.0647 (8)
O3 0.0356 (5) 1.0173 (3) 0.26661 (10) 0.0609 (8)
O4 −0.0769 (5) 0.9773 (3) 0.38007 (10) 0.0484 (7)
O5 −0.2044 (5) 0.7366 (4) 0.45937 (9) 0.0668 (8)
N7 0.3033 (5) 0.8033 (3) 0.23256 (11) 0.0426 (8)
C1 0.6743 (6) 0.3960 (5) 0.17792 (14) 0.0447 (9)
H1 0.7042 0.3232 0.2116 0.054*
C2 0.7615 (7) 0.3428 (5) 0.12622 (14) 0.0467 (9)
C3 0.7162 (7) 0.4473 (6) 0.07549 (14) 0.0511 (10)
C4 0.5849 (8) 0.6090 (5) 0.07458 (15) 0.0540 (10)
H4 0.5561 0.6784 0.0401 0.065*
C4A 0.4926 (7) 0.6697 (5) 0.12751 (14) 0.0458 (9)
C5 0.3507 (8) 0.8535 (5) 0.12886 (13) 0.0563 (10)
H5A 0.4170 0.9381 0.1007 0.068*
H5B 0.1653 0.8349 0.1177 0.068*
C6 0.3897 (7) 0.9364 (5) 0.18976 (13) 0.0536 (10)
H6A 0.5731 0.9659 0.1996 0.064*
H6B 0.2895 1.0503 0.1910 0.064*
C8 0.1376 (7) 0.8630 (5) 0.27118 (14) 0.0440 (9)
C8A 0.0878 (6) 0.7324 (5) 0.32014 (13) 0.0375 (8)
C9 −0.0297 (7) 0.7909 (5) 0.36971 (15) 0.0416 (9)
C10 −0.0895 (8) 0.6643 (5) 0.41240 (15) 0.0488 (10)
C11 −0.0319 (7) 0.4787 (5) 0.40589 (15) 0.0562 (10)
H11 −0.0743 0.3935 0.4341 0.067*
C12 0.0893 (7) 0.4185 (5) 0.35715 (15) 0.0554 (10)
H12 0.1299 0.2935 0.3534 0.066*
C12A 0.1497 (6) 0.5429 (5) 0.31430 (14) 0.0421 (9)
C13 0.2703 (7) 0.4810 (5) 0.26095 (14) 0.0476 (9)
H13A 0.1325 0.4495 0.2304 0.057*
H13B 0.3721 0.3696 0.2704 0.057*
C13A 0.4449 (7) 0.6256 (4) 0.23752 (14) 0.0409 (9)
H13C 0.5992 0.6409 0.2660 0.049*
C14 0.5364 (7) 0.5658 (5) 0.17897 (14) 0.0398 (8)
C18 0.9758 (9) 0.2101 (6) 0.05727 (15) 0.0748 (13)
H18A 0.9511 0.0977 0.0339 0.090*
H18B 1.1602 0.2423 0.0605 0.090*
C19 −0.3406 (7) 1.0315 (5) 0.36281 (15) 0.0596 (10)
H19A −0.3763 1.0194 0.3208 0.071*
supporting information
sup-3 Acta Cryst. (2006). E62, o1764–o1765
H19C −0.4578 0.9533 0.3820 0.071*
C20 −0.3266 (8) 0.6116 (6) 0.49627 (16) 0.0703 (12)
H20A −0.4562 0.5403 0.4729 0.084*
H20B −0.4089 0.6804 0.5255 0.084*
H20C −0.1974 0.5297 0.5154 0.084*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
O1 0.099 (2) 0.0483 (16) 0.0579 (15) 0.0243 (16) 0.0276 (15) 0.0074 (13)
O2 0.096 (2) 0.0543 (16) 0.0453 (13) 0.0210 (18) 0.0168 (14) 0.0018 (14)
O3 0.086 (2) 0.0387 (16) 0.0610 (15) 0.0150 (16) 0.0254 (14) 0.0109 (14)
O4 0.0625 (17) 0.0340 (15) 0.0490 (14) −0.0072 (14) 0.0073 (12) −0.0054 (12)
O5 0.108 (2) 0.0506 (17) 0.0472 (13) −0.0143 (17) 0.0333 (15) −0.0050 (14)
N7 0.057 (2) 0.0300 (16) 0.0430 (16) 0.0035 (15) 0.0160 (15) 0.0039 (14)
C1 0.053 (2) 0.038 (2) 0.0436 (19) 0.0036 (19) 0.0078 (17) 0.0067 (16)
C2 0.060 (2) 0.034 (2) 0.047 (2) 0.004 (2) 0.0082 (18) 0.0038 (17)
C3 0.063 (3) 0.047 (2) 0.043 (2) 0.008 (2) 0.0065 (18) −0.0047 (19)
C4 0.075 (3) 0.049 (2) 0.037 (2) 0.010 (2) 0.003 (2) 0.0087 (18)
C4A 0.054 (2) 0.037 (2) 0.046 (2) 0.0091 (19) 0.0079 (18) 0.0016 (18)
C5 0.081 (3) 0.047 (2) 0.0415 (19) 0.019 (2) 0.0093 (18) 0.0105 (19)
C6 0.078 (3) 0.035 (2) 0.049 (2) 0.000 (2) 0.0160 (19) 0.0071 (18)
C8 0.054 (2) 0.035 (2) 0.043 (2) −0.004 (2) 0.0046 (18) 0.0017 (18)
C8A 0.043 (2) 0.0319 (18) 0.0381 (18) −0.0025 (17) 0.0064 (17) 0.0006 (15)
C9 0.046 (2) 0.036 (2) 0.042 (2) −0.0066 (18) 0.0000 (17) −0.0018 (17)
C10 0.069 (3) 0.037 (2) 0.041 (2) −0.004 (2) 0.009 (2) −0.0024 (17)
C11 0.072 (3) 0.047 (2) 0.051 (2) −0.004 (2) 0.014 (2) 0.015 (2)
C12 0.073 (3) 0.034 (2) 0.062 (2) 0.000 (2) 0.022 (2) 0.0057 (19)
C12A 0.045 (2) 0.034 (2) 0.047 (2) −0.0024 (18) 0.0055 (17) −0.0012 (17)
C13 0.055 (2) 0.033 (2) 0.056 (2) −0.0018 (19) 0.0078 (18) 0.0021 (18)
C13A 0.049 (2) 0.033 (2) 0.0410 (19) 0.0003 (18) 0.0034 (16) −0.0023 (17)
C14 0.046 (2) 0.036 (2) 0.0378 (18) 0.0025 (18) 0.0057 (16) −0.0012 (16)
C18 0.104 (4) 0.063 (3) 0.061 (2) 0.032 (3) 0.028 (2) 0.006 (2)
C19 0.066 (3) 0.048 (2) 0.067 (2) 0.000 (2) 0.014 (2) −0.012 (2)
C20 0.097 (3) 0.063 (3) 0.056 (2) −0.006 (3) 0.030 (2) 0.005 (2)
Geometric parameters (Å, º)
O1—C2 1.392 (4) C6—H6B 0.9700
O1—C18 1.415 (4) C8—C8A 1.499 (5)
O2—C3 1.390 (4) C8A—C9 1.395 (4)
O2—C18 1.433 (4) C8A—C12A 1.411 (5)
O3—C8 1.229 (4) C9—C10 1.389 (5)
O4—C9 1.389 (4) C10—C11 1.380 (5)
O4—C19 1.426 (4) C11—C12 1.393 (4)
O5—C10 1.373 (4) C11—H11 0.9300
O5—C20 1.418 (4) C12—C12A 1.382 (4)
N7—C6 1.466 (4) C12A—C13 1.484 (4)
N7—C13A 1.471 (4) C13—C13A 1.505 (4)
C1—C2 1.355 (4) C13—H13A 0.9700
C1—C14 1.415 (5) C13—H13B 0.9700
C1—H1 0.9300 C13A—C14 1.518 (4)
C2—C3 1.379 (4) C13A—H13C 0.9800
C3—C4 1.345 (5) C18—H18A 0.9700
C4—C4A 1.407 (5) C18—H18B 0.9700
C4—H4 0.9300 C19—H19A 0.9600
C4A—C14 1.390 (4) C19—H19B 0.9600
C4A—C5 1.513 (5) C19—H19C 0.9600
C5—C6 1.505 (4) C20—H20A 0.9600
C5—H5A 0.9700 C20—H20B 0.9600
C5—H5B 0.9700 C20—H20C 0.9600
C6—H6A 0.9700
C2—O1—C18 104.5 (3) O5—C10—C9 115.9 (3)
C3—O2—C18 104.4 (2) C11—C10—C9 119.8 (3)
C9—O4—C19 113.2 (3) C10—C11—C12 120.3 (3)
C10—O5—C20 118.0 (3) C10—C11—H11 119.9
C8—N7—C6 118.3 (3) C12—C11—H11 119.9
C8—N7—C13A 124.4 (3) C12A—C12—C11 120.6 (3)
C6—N7—C13A 116.2 (3) C12A—C12—H12 119.7
C2—C1—C14 117.9 (3) C11—C12—H12 119.7
C2—C1—H1 121.1 C12—C12A—C8A 119.5 (3)
C14—C1—H1 121.1 C12—C12A—C13 121.5 (3)
C1—C2—C3 122.0 (3) C8A—C12A—C13 118.9 (3)
C1—C2—O1 128.2 (3) C12A—C13—C13A 113.1 (3)
C3—C2—O1 109.7 (3) C12A—C13—H13A 109.0
C4—C3—C2 121.9 (3) C13A—C13—H13A 109.0
C4—C3—O2 128.6 (3) C12A—C13—H13B 109.0
C2—C3—O2 109.5 (3) C13A—C13—H13B 109.0
C3—C4—C4A 117.8 (3) H13A—C13—H13B 107.8
C3—C4—H4 121.1 N7—C13A—C13 108.8 (3)
C4A—C4—H4 121.1 N7—C13A—C14 111.9 (3)
C14—C4A—C4 121.0 (3) C13—C13A—C14 111.1 (3)
C14—C4A—C5 119.5 (3) N7—C13A—H13C 108.3
C4—C4A—C5 119.5 (3) C13—C13A—H13C 108.3
C6—C5—C4A 110.2 (3) C14—C13A—H13C 108.3
C6—C5—H5A 109.6 C4A—C14—C1 119.4 (3)
C4A—C5—H5A 109.6 C4A—C14—C13A 123.3 (3)
C6—C5—H5B 109.6 C1—C14—C13A 117.3 (3)
C4A—C5—H5B 109.6 O1—C18—O2 108.6 (3)
H5A—C5—H5B 108.1 O1—C18—H18A 110.0
N7—C6—C5 109.3 (3) O2—C18—H18A 110.0
N7—C6—H6A 109.8 O1—C18—H18B 110.0
C5—C6—H6A 109.8 O2—C18—H18B 110.0
supporting information
sup-5 Acta Cryst. (2006). E62, o1764–o1765
C5—C6—H6B 109.8 O4—C19—H19A 109.5
H6A—C6—H6B 108.3 O4—C19—H19B 109.5
O3—C8—N7 121.5 (3) H19A—C19—H19B 109.5
O3—C8—C8A 121.9 (3) O4—C19—H19C 109.5
N7—C8—C8A 116.6 (3) H19A—C19—H19C 109.5
C9—C8A—C12A 119.1 (3) H19B—C19—H19C 109.5
C9—C8A—C8 122.0 (3) O5—C20—H20A 109.5
C12A—C8A—C8 118.7 (3) O5—C20—H20B 109.5
C10—C9—O4 117.5 (3) H20A—C20—H20B 109.5
C10—C9—C8A 120.7 (3) O5—C20—H20C 109.5
O4—C9—C8A 121.7 (3) H20A—C20—H20C 109.5
O5—C10—C11 124.3 (3) H20B—C20—H20C 109.5
C14—C1—C2—C3 −0.9 (5) C20—O5—C10—C9 164.9 (3)
C14—C1—C2—O1 −178.0 (3) O4—C9—C10—O5 3.6 (5)
C18—O1—C2—C1 −170.5 (4) C8A—C9—C10—O5 179.9 (3)
C18—O1—C2—C3 12.1 (4) O4—C9—C10—C11 −176.2 (4)
C1—C2—C3—C4 0.7 (6) C8A—C9—C10—C11 0.1 (6)
O1—C2—C3—C4 178.3 (3) O5—C10—C11—C12 −178.8 (3)
C1—C2—C3—O2 −179.0 (3) C9—C10—C11—C12 1.0 (6)
O1—C2—C3—O2 −1.4 (4) C10—C11—C12—C12A −1.0 (6)
C18—O2—C3—C4 170.6 (4) C11—C12—C12A—C8A 0.0 (5)
C18—O2—C3—C2 −9.8 (4) C11—C12—C12A—C13 −177.8 (3)
C2—C3—C4—C4A −0.2 (6) C9—C8A—C12A—C12 1.0 (5)
O2—C3—C4—C4A 179.4 (3) C8—C8A—C12A—C12 −175.8 (3)
C3—C4—C4A—C14 0.1 (6) C9—C8A—C12A—C13 178.9 (3)
C3—C4—C4A—C5 178.3 (3) C8—C8A—C12A—C13 2.1 (5)
C14—C4A—C5—C6 26.8 (5) C12—C12A—C13—C13A −149.6 (3)
C4—C4A—C5—C6 −151.4 (3) C8A—C12A—C13—C13A 32.6 (5)
C8—N7—C6—C5 −129.9 (3) C8—N7—C13A—C13 36.7 (4)
C13A—N7—C6—C5 61.8 (4) C6—N7—C13A—C13 −155.8 (3)
C4A—C5—C6—N7 −56.0 (4) C8—N7—C13A—C14 159.9 (3)
C6—N7—C8—O3 8.7 (5) C6—N7—C13A—C14 −32.6 (4)
C13A—N7—C8—O3 175.9 (3) C12A—C13—C13A—N7 −49.3 (4)
C6—N7—C8—C8A −170.5 (3) C12A—C13—C13A—C14 −172.9 (3)
C13A—N7—C8—C8A −3.3 (4) C4—C4A—C14—C1 −0.4 (5)
O3—C8—C8A—C9 −13.8 (5) C5—C4A—C14—C1 −178.6 (3)
N7—C8—C8A—C9 165.4 (3) C4—C4A—C14—C13A 179.1 (3)
O3—C8—C8A—C12A 162.9 (3) C5—C4A—C14—C13A 0.9 (5)
N7—C8—C8A—C12A −17.9 (5) C2—C1—C14—C4A 0.8 (5)
C19—O4—C9—C10 −84.5 (4) C2—C1—C14—C13A −178.7 (3)
C19—O4—C9—C8A 99.2 (4) N7—C13A—C14—C4A 0.8 (4)
C12A—C8A—C9—C10 −1.1 (5) C13—C13A—C14—C4A 122.6 (4)
C8—C8A—C9—C10 175.6 (3) N7—C13A—C14—C1 −179.7 (3)
C12A—C8A—C9—O4 175.0 (3) C13—C13A—C14—C1 −57.8 (4)
C8—C8A—C9—O4 −8.3 (5) C2—O1—C18—O2 −18.3 (4)
