Epibisde-hydro-neotuberostemonine J.

The title compound, C22H29NO4, a stemona alkaloid, is composed of two lactone rings (A and E), a six-membered ring (B), a pyrrole ring (C) and a seven-membered ring (D). The five-membered rings A and E exhibit envelope conformations (C atoms as flaps) while ring C is planar. Ring B exhibits a twist-chair conformation due to fusion with pyrrole ring C while ring D adopts a chair conformation. The junction between rings A and B is cis. In the crystal, weak C-H⋯O inter-actions involving the two carbonyl groups, a methyl-ene and a methyl group give rise to a three-dimensional network.

Related literature

For general background to the structures and biological activity of stemona alkaloids, see: Pilli et al. (2010 ▶). For the anti­tussive activity of epibisde­hydro­neotuberostemonine J and other stemona alkaloids, see: Chung et al. (2003 ▶); Xu et al. (2010 ▶). For other properties of and studies on Stemona alkaloids, see: Chung et al. (2003 ▶); Frankowski et al. (2008 ▶, 2011 ▶); Jiang et al. (2006 ▶); Zhang et al. (2011 ▶). For an absolute structure reference, see: Jiang et al. (2010 ▶). For related isomers, see: Pham et al. (2002 ▶).

Experimental

Crystal data

C22H29NO4

M = 371.46

Monoclinic,

a = 6.3596 (19) Å

b = 18.495 (3) Å

c = 8.3875 (15) Å

β = 92.521 (18)°

V = 985.6 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 291 K

0.43 × 0.28 × 0.20 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.831, T max = 1.000

2449 measured reflections

1914 independent reflections

1383 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.093

S = 1.05

1914 reflections

245 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.13 e Å−3

Δρmin = −0.13 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SMART and SAINT (Bruker, 1998 ▶); data reduction: SAINT and XPREP (Bruker, 1998 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813021077/zl2558sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813021077/zl2558Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813021077/zl2558Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C22H29NO4	F(000) = 400
Mr = 371.46	Dx = 1.252 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 6.3596 (19) Å	Cell parameters from 2449 reflections
b = 18.495 (3) Å	θ = 2.2–24.0°
c = 8.3875 (15) Å	µ = 0.09 mm−1
β = 92.521 (18)°	T = 291 K
V = 985.6 (4) Å3	Prism, colorless
Z = 2	0.43 × 0.28 × 0.20 mm

Bruker SMART 1000 CCD diffractometer	1383 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.022
ω scan	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −1→7
Tmin = 0.831, Tmax = 1.000	k = −1→21
2449 measured reflections	l = −9→9
1914 independent reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045	H-atom parameters constrained
wR(F2) = 0.093	w = 1/[σ2(Fo2) + (0.0368P)2 + 0.0285P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
1914 reflections	Δρmax = 0.13 e Å−3
245 parameters	Δρmin = −0.13 e Å−3
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.013 (2)

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	0.5763 (4)	0.32620 (15)	0.2326 (4)	0.0552 (8)
O2	0.6531 (5)	0.36723 (17)	−0.0073 (4)	0.0716 (9)
O3	0.4293 (4)	0.02284 (15)	−0.1869 (3)	0.0472 (7)
O4	0.5576 (4)	−0.01361 (17)	−0.4150 (3)	0.0611 (9)
C1	0.2603 (6)	0.2093 (2)	0.1225 (5)	0.0451 (11)
C2	0.1727 (6)	0.1714 (2)	−0.0118 (5)	0.0469 (10)
H2A	0.0781	0.1903	−0.0886	0.056*
C3	0.2514 (6)	0.1021 (2)	−0.0095 (5)	0.0418 (10)
N4	0.3821 (5)	0.09614 (16)	0.1254 (4)	0.0404 (8)
C5	0.5164 (6)	0.0346 (2)	0.1696 (5)	0.0449 (10)
H5A	0.4792	−0.0063	0.1015	0.054*
H5B	0.4929	0.0208	0.2790	0.054*
C6	0.7464 (6)	0.0528 (2)	0.1536 (5)	0.0483 (11)
H6A	0.8247	0.0079	0.1468	0.058*
H6B	0.7611	0.0785	0.0540	0.058*
C7	0.8456 (6)	0.0977 (2)	0.2873 (5)	0.0505 (11)
H7A	0.9952	0.1014	0.2707	0.061*
H7B	0.8298	0.0720	0.3868	0.061*
C8	0.7586 (6)	0.1742 (2)	0.3066 (5)	0.0472 (10)
H8A	0.7729	0.2005	0.2076	0.057*
H8B	0.8419	0.1991	0.3892	0.057*
C9A	0.3875 (6)	0.1609 (2)	0.2037 (5)	0.0426 (10)
C9	0.5259 (6)	0.1751 (2)	0.3501 (4)	0.0440 (10)
H9A	0.5059	0.1348	0.4236	0.053*
C10	0.4468 (7)	0.2435 (2)	0.4320 (5)	0.0501 (11)
H10A	0.3150	0.2295	0.4798	0.060*
C11	0.3881 (7)	0.3036 (2)	0.3145 (5)	0.0557 (12)
H11A	0.3360	0.3449	0.3742	0.067*
C12	0.2296 (6)	0.2868 (2)	0.1766 (5)	0.0493 (11)
H12A	0.0855	0.2939	0.2102	0.059*
C13	0.2864 (7)	0.3445 (2)	0.0563 (5)	0.0561 (12)
H13A	0.2310	0.3903	0.0954	0.067*
C14	0.5207 (8)	0.3479 (2)	0.0821 (6)	0.0556 (12)
C15	0.2115 (7)	0.3382 (3)	−0.1162 (6)	0.0708 (14)
H15A	0.2599	0.3792	−0.1745	0.106*
H15B	0.0605	0.3368	−0.1232	0.106*
H15C	0.2665	0.2947	−0.1608	0.106*
C16	0.5885 (7)	0.2711 (3)	0.5694 (5)	0.0615 (13)
H16A	0.5235	0.3133	0.6154	0.074*
H16B	0.7215	0.2863	0.5279	0.074*
C17	0.6320 (8)	0.2152 (3)	0.7012 (6)	0.0754 (15)
H17A	0.7226	0.2360	0.7836	0.113*
H17B	0.6990	0.1736	0.6573	0.113*
H17C	0.5016	0.2009	0.7454	0.113*
C18	0.2231 (5)	0.0417 (2)	−0.1246 (5)	0.0438 (10)
H18A	0.1681	−0.0004	−0.0688	0.053*
C19	0.0829 (7)	0.0565 (2)	−0.2721 (5)	0.0574 (12)
H19A	−0.0591	0.0393	−0.2578	0.069*
H19B	0.0778	0.1078	−0.2957	0.069*
C20	0.1851 (6)	0.0151 (3)	−0.4045 (5)	0.0504 (11)
H20A	0.1825	0.0449	−0.5011	0.060*
C21	0.4088 (6)	0.0065 (2)	−0.3421 (5)	0.0457 (10)
C22	0.0893 (7)	−0.0577 (3)	−0.4437 (7)	0.0806 (16)
H22A	0.1641	−0.0799	−0.5278	0.121*
H22B	−0.0558	−0.0516	−0.4776	0.121*
H22C	0.0985	−0.0879	−0.3507	0.121*

	U11	U22	U33	U12	U13	U23
O1	0.0521 (19)	0.0380 (17)	0.076 (2)	−0.0075 (15)	0.0086 (17)	0.0000 (16)
O2	0.072 (2)	0.051 (2)	0.093 (2)	−0.0096 (18)	0.0255 (19)	0.0111 (19)
O3	0.0362 (15)	0.0522 (17)	0.0528 (17)	0.0054 (14)	−0.0032 (13)	−0.0032 (16)
O4	0.0454 (18)	0.079 (2)	0.0597 (18)	0.0066 (18)	0.0107 (16)	0.0065 (18)
C1	0.038 (2)	0.036 (2)	0.062 (3)	−0.001 (2)	0.009 (2)	0.002 (2)
C2	0.032 (2)	0.041 (2)	0.068 (3)	0.003 (2)	−0.001 (2)	0.005 (2)
C3	0.034 (2)	0.034 (2)	0.057 (3)	−0.0011 (19)	0.002 (2)	−0.001 (2)
N4	0.0352 (17)	0.0295 (18)	0.056 (2)	0.0002 (16)	0.0012 (16)	−0.0011 (17)
C5	0.047 (2)	0.036 (2)	0.052 (2)	0.005 (2)	−0.001 (2)	0.001 (2)
C6	0.042 (2)	0.042 (2)	0.061 (3)	0.006 (2)	−0.002 (2)	0.000 (2)
C7	0.038 (2)	0.053 (3)	0.060 (3)	0.002 (2)	0.002 (2)	0.008 (2)
C8	0.038 (2)	0.046 (2)	0.058 (3)	−0.008 (2)	0.0031 (19)	−0.004 (2)
C9A	0.035 (2)	0.036 (2)	0.058 (3)	−0.0071 (19)	0.006 (2)	−0.002 (2)
C9	0.044 (2)	0.036 (2)	0.052 (2)	−0.007 (2)	0.0098 (19)	−0.005 (2)
C10	0.048 (3)	0.037 (2)	0.066 (3)	−0.008 (2)	0.013 (2)	−0.004 (2)
C11	0.054 (3)	0.040 (3)	0.074 (3)	0.002 (2)	0.018 (3)	−0.015 (2)
C12	0.041 (2)	0.038 (2)	0.070 (3)	0.004 (2)	0.010 (2)	0.001 (2)
C13	0.059 (3)	0.033 (2)	0.076 (3)	0.009 (2)	0.009 (3)	0.002 (2)
C14	0.071 (3)	0.024 (2)	0.074 (3)	−0.004 (2)	0.015 (3)	0.001 (2)
C15	0.074 (3)	0.047 (3)	0.092 (4)	0.006 (3)	0.009 (3)	0.008 (3)
C16	0.072 (3)	0.053 (3)	0.061 (3)	−0.009 (3)	0.010 (3)	−0.012 (3)
C17	0.083 (4)	0.077 (4)	0.066 (3)	0.000 (3)	0.003 (3)	−0.008 (3)
C18	0.029 (2)	0.044 (3)	0.059 (2)	−0.001 (2)	0.0064 (19)	−0.006 (2)
C19	0.042 (2)	0.054 (3)	0.076 (3)	0.008 (2)	−0.012 (2)	−0.008 (3)
C20	0.045 (2)	0.051 (3)	0.055 (2)	0.008 (2)	−0.008 (2)	0.004 (2)
C21	0.042 (2)	0.043 (2)	0.052 (3)	0.002 (2)	−0.001 (2)	0.007 (2)
C22	0.055 (3)	0.062 (3)	0.123 (4)	0.008 (3)	−0.020 (3)	−0.022 (3)

O1—C14	1.356 (5)	C10—C16	1.519 (5)
O1—C11	1.467 (5)	C10—C11	1.520 (6)
O2—C14	1.207 (5)	C10—H10A	0.9800
O3—C21	1.337 (4)	C11—C12	1.533 (6)
O3—C18	1.475 (4)	C11—H11A	0.9800
O4—C21	1.207 (4)	C12—C13	1.523 (6)
C1—C9A	1.368 (5)	C12—H12A	0.9800
C1—C2	1.420 (5)	C13—C14	1.498 (6)
C1—C12	1.518 (6)	C13—C15	1.507 (6)
C2—C3	1.375 (5)	C13—H13A	0.9800
C2—H2A	0.9300	C15—H15A	0.9600
C3—N4	1.378 (5)	C15—H15B	0.9600
C3—C18	1.483 (5)	C15—H15C	0.9600
N4—C9A	1.366 (5)	C16—C17	1.530 (6)
N4—C5	1.462 (5)	C16—H16A	0.9700
C5—C6	1.513 (5)	C16—H16B	0.9700
C5—H5A	0.9700	C17—H17A	0.9600
C5—H5B	0.9700	C17—H17B	0.9600
C6—C7	1.512 (5)	C17—H17C	0.9600
C6—H6A	0.9700	C18—C19	1.518 (5)
C6—H6B	0.9700	C18—H18A	0.9800
C7—C8	1.529 (6)	C19—C20	1.518 (6)
C7—H7A	0.9700	C19—H19A	0.9700
C7—H7B	0.9700	C19—H19B	0.9700
C8—C9	1.540 (5)	C20—C21	1.503 (5)
C8—H8A	0.9700	C20—C22	1.508 (6)
C8—H8B	0.9700	C20—H20A	0.9800
C9A—C9	1.502 (5)	C22—H22A	0.9600
C9—C10	1.534 (6)	C22—H22B	0.9600
C9—H9A	0.9800	C22—H22C	0.9600
C14—O1—C11	109.6 (3)	C1—C12—C11	109.1 (3)
C21—O3—C18	110.4 (3)	C13—C12—C11	101.0 (3)
C9A—C1—C2	106.0 (3)	C1—C12—H12A	110.3
C9A—C1—C12	123.3 (4)	C13—C12—H12A	110.3
C2—C1—C12	130.7 (4)	C11—C12—H12A	110.3
C3—C2—C1	108.6 (4)	C14—C13—C15	114.4 (4)
C3—C2—H2A	125.7	C14—C13—C12	101.3 (4)
C1—C2—H2A	125.7	C15—C13—C12	120.5 (4)
C2—C3—N4	107.0 (4)	C14—C13—H13A	106.6
C2—C3—C18	131.3 (4)	C15—C13—H13A	106.6
N4—C3—C18	121.7 (3)	C12—C13—H13A	106.6
C9A—N4—C3	109.1 (3)	O2—C14—O1	120.4 (4)
C9A—N4—C5	124.0 (3)	O2—C14—C13	129.8 (5)
C3—N4—C5	126.5 (3)	O1—C14—C13	109.9 (4)
N4—C5—C6	111.1 (3)	C13—C15—H15A	109.5
N4—C5—H5A	109.4	C13—C15—H15B	109.5
C6—C5—H5A	109.4	H15A—C15—H15B	109.5
N4—C5—H5B	109.4	C13—C15—H15C	109.5
C6—C5—H5B	109.4	H15A—C15—H15C	109.5
H5A—C5—H5B	108.0	H15B—C15—H15C	109.5
C7—C6—C5	115.5 (3)	C10—C16—C17	113.8 (4)
C7—C6—H6A	108.4	C10—C16—H16A	108.8
C5—C6—H6A	108.4	C17—C16—H16A	108.8
C7—C6—H6B	108.4	C10—C16—H16B	108.8
C5—C6—H6B	108.4	C17—C16—H16B	108.8
H6A—C6—H6B	107.5	H16A—C16—H16B	107.7
C6—C7—C8	116.5 (3)	C16—C17—H17A	109.5
C6—C7—H7A	108.2	C16—C17—H17B	109.5
C8—C7—H7A	108.2	H17A—C17—H17B	109.5
C6—C7—H7B	108.2	C16—C17—H17C	109.5
C8—C7—H7B	108.2	H17A—C17—H17C	109.5
H7A—C7—H7B	107.3	H17B—C17—H17C	109.5
C7—C8—C9	113.1 (3)	O3—C18—C3	108.9 (3)
C7—C8—H8A	109.0	O3—C18—C19	104.7 (3)
C9—C8—H8A	109.0	C3—C18—C19	116.4 (3)
C7—C8—H8B	109.0	O3—C18—H18A	108.9
C9—C8—H8B	109.0	C3—C18—H18A	108.9
H8A—C8—H8B	107.8	C19—C18—H18A	108.9
N4—C9A—C1	109.4 (3)	C20—C19—C18	104.5 (3)
N4—C9A—C9	123.3 (3)	C20—C19—H19A	110.9
C1—C9A—C9	127.2 (4)	C18—C19—H19A	110.9
C9A—C9—C10	108.6 (3)	C20—C19—H19B	110.9
C9A—C9—C8	109.8 (3)	C18—C19—H19B	110.9
C10—C9—C8	116.9 (3)	H19A—C19—H19B	108.9
C9A—C9—H9A	107.0	C21—C20—C22	110.4 (4)
C10—C9—H9A	107.0	C21—C20—C19	103.2 (3)
C8—C9—H9A	107.0	C22—C20—C19	115.3 (4)
C16—C10—C11	111.5 (3)	C21—C20—H20A	109.2
C16—C10—C9	114.9 (4)	C22—C20—H20A	109.2
C11—C10—C9	112.8 (3)	C19—C20—H20A	109.2
C16—C10—H10A	105.6	O4—C21—O3	121.2 (3)
C11—C10—H10A	105.6	O4—C21—C20	127.4 (4)
C9—C10—H10A	105.6	O3—C21—C20	111.4 (4)
O1—C11—C10	109.3 (3)	C20—C22—H22A	109.5
O1—C11—C12	103.1 (3)	C20—C22—H22B	109.5
C10—C11—C12	118.4 (3)	H22A—C22—H22B	109.5
O1—C11—H11A	108.5	C20—C22—H22C	109.5
C10—C11—H11A	108.5	H22A—C22—H22C	109.5
C12—C11—H11A	108.5	H22B—C22—H22C	109.5
C1—C12—C13	115.3 (3)
C9A—C1—C2—C3	−0.9 (5)	C9A—C1—C12—C13	122.1 (4)
C12—C1—C2—C3	179.3 (4)	C2—C1—C12—C13	−58.1 (6)
C1—C2—C3—N4	1.2 (4)	C9A—C1—C12—C11	9.3 (5)
C1—C2—C3—C18	−175.9 (4)	C2—C1—C12—C11	−170.9 (4)
C2—C3—N4—C9A	−1.1 (4)	O1—C11—C12—C1	86.1 (4)
C18—C3—N4—C9A	176.4 (3)	C10—C11—C12—C1	−34.7 (5)
C2—C3—N4—C5	−173.7 (3)	O1—C11—C12—C13	−35.8 (4)
C18—C3—N4—C5	3.8 (6)	C10—C11—C12—C13	−156.5 (4)
C9A—N4—C5—C6	−62.4 (5)	C1—C12—C13—C14	−80.9 (4)
C3—N4—C5—C6	109.1 (4)	C11—C12—C13—C14	36.6 (4)
N4—C5—C6—C7	78.0 (4)	C1—C12—C13—C15	46.5 (5)
C5—C6—C7—C8	−64.2 (5)	C11—C12—C13—C15	163.9 (4)
C6—C7—C8—C9	63.6 (5)	C11—O1—C14—O2	−178.3 (4)
C3—N4—C9A—C1	0.5 (4)	C11—O1—C14—C13	2.8 (4)
C5—N4—C9A—C1	173.3 (3)	C15—C13—C14—O2	24.3 (7)
C3—N4—C9A—C9	−175.8 (3)	C12—C13—C14—O2	155.6 (4)
C5—N4—C9A—C9	−3.0 (6)	C15—C13—C14—O1	−157.0 (3)
C2—C1—C9A—N4	0.2 (4)	C12—C13—C14—O1	−25.7 (4)
C12—C1—C9A—N4	−180.0 (4)	C11—C10—C16—C17	173.3 (4)
C2—C1—C9A—C9	176.4 (4)	C9—C10—C16—C17	−56.7 (5)
C12—C1—C9A—C9	−3.8 (6)	C21—O3—C18—C3	−141.6 (3)
N4—C9A—C9—C10	−163.9 (4)	C21—O3—C18—C19	−16.5 (4)
C1—C9A—C9—C10	20.4 (6)	C2—C3—C18—O3	117.6 (4)
N4—C9A—C9—C8	67.1 (5)	N4—C3—C18—O3	−59.2 (4)
C1—C9A—C9—C8	−108.6 (5)	C2—C3—C18—C19	−0.4 (6)
C7—C8—C9—C9A	−78.1 (4)	N4—C3—C18—C19	−177.2 (3)
C7—C8—C9—C10	157.7 (4)	O3—C18—C19—C20	23.7 (4)
C9A—C9—C10—C16	−171.9 (3)	C3—C18—C19—C20	144.0 (3)
C8—C9—C10—C16	−47.0 (5)	C18—C19—C20—C21	−22.1 (4)
C9A—C9—C10—C11	−42.5 (4)	C18—C19—C20—C22	98.3 (4)
C8—C9—C10—C11	82.3 (5)	C18—O3—C21—O4	−176.7 (4)
C14—O1—C11—C10	148.1 (3)	C18—O3—C21—C20	2.1 (5)
C14—O1—C11—C12	21.3 (4)	C22—C20—C21—O4	68.0 (6)
C16—C10—C11—O1	67.9 (4)	C19—C20—C21—O4	−168.2 (4)
C9—C10—C11—O1	−63.2 (4)	C22—C20—C21—O3	−110.7 (4)
C16—C10—C11—C12	−174.5 (3)	C19—C20—C21—O3	13.1 (5)
C9—C10—C11—C12	54.4 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···O2i	0.97	2.60	3.531 (4)	161
C5—H5B···O4ii	0.97	2.66	3.595 (3)	162
C22—H22B···O4iii	0.96	2.63	3.496 (4)	150

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯O2i	0.97	2.60	3.531 (4)	161
C5—H5B⋯O4ii	0.97	2.66	3.595 (3)	162
C22—H22B⋯O4iii	0.96	2.63	3.496 (4)	150

Symmetry codes: (i) ; (ii) ; (iii) .