(9S,13R,14R)-7,8-Didehydro-3,4,7-trimeth-oxy-17-methyl-morphinan-6-one.

The title compound, C(20)H(25)NO(4), was synthesized by a Mitsunobu reaction of sinomenine [(9S,13R,14R)-7,8-didehydro-4-hydroxy-3,7-dimethoxy-17-methylmorphinan-6-one] with methanol. The chiral centers were unchanged during the reaction. Intra-molecular C-H⋯O hydrogen bonds result in the formation of six-membered rings.

Related literature

For the anti-inflammatory, anti­tussive and anti­arrgythmic activities of sinomenine, see: Wang & Li (1965 ▶).

Experimental

Crystal data

C20H25NO4

M = 343.41

Trigonal,

a = 10.9590 (15) Å

c = 12.726 (3) Å

V = 1323.6 (4) Å3

Z = 3

Mo Kα radiation

μ = 0.09 mm−1

T = 298 K

0.40 × 0.30 × 0.30 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.965, T max = 0.974

2008 measured reflections

1728 independent reflections

1281 reflections with I > 2σ(I)

R int = 0.037

3 standard reflections every 200 reflections intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.070

wR(F 2) = 0.208

S = 1.06

1728 reflections

226 parameters

44 restraints

H-atom parameters constrained

Δρmax = 0.45 e Å−3

Δρmin = −0.22 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808040749/hk2561sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808040749/hk2561Isup2.hkl

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

C20H25NO4	Dx = 1.292 Mg m−3
Mr = 343.41	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P32	Cell parameters from 25 reflections
Hall symbol: P 32	θ = 10–13°
a = 10.9590 (15) Å	µ = 0.09 mm−1
c = 12.726 (3) Å	T = 298 K
V = 1323.6 (4) Å3	Block, colorless
Z = 3	0.40 × 0.30 × 0.30 mm
F(000) = 552

Enraf–Nonius CAD-4 diffractometer	1281 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.037
graphite	θmax = 26.0°, θmin = 2.2°
ω/2θ scans	h = −13→6
Absorption correction: ψ scan (North et al., 1968)	k = 0→11
Tmin = 0.965, Tmax = 0.974	l = −15→15
2008 measured reflections	3 standard reflections every 200 reflections
1728 independent reflections	intensity decay: none

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)] = 0.070	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.208	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.1178P)2 + 0.4849P] where P = (Fo2 + 2Fc2)/3
1728 reflections	(Δ/σ)max = 0.005
226 parameters	Δρmax = 0.45 e Å−3
44 restraints	Δρmin = −0.22 e Å−3

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	0.7890 (7)	0.2303 (6)	0.0383 (5)	0.0855 (17)
O2	0.8937 (7)	0.0744 (5)	0.1262 (6)	0.093 (2)
O3	1.2532 (6)	0.7232 (5)	−0.1456 (4)	0.0719 (13)
O4	1.0260 (6)	0.4750 (6)	−0.1870 (4)	0.0765 (15)
N	0.9014 (7)	0.6779 (6)	0.2458 (4)	0.0607 (14)
C18	0.7882 (16)	0.1603 (14)	−0.0423 (8)	0.123 (4)
H18A	0.6976	0.1188	−0.0757	0.185*
H18B	0.8071	0.0873	−0.0210	0.185*
H18C	0.8595	0.2222	−0.0909	0.185*
C17	0.9251 (11)	−0.0152 (9)	0.1821 (8)	0.093 (3)
H17A	0.8722	−0.1088	0.1540	0.139*
H17B	0.9009	−0.0159	0.2547	0.139*
H17C	1.0240	0.0172	0.1763	0.139*
C3	0.9567 (7)	0.2137 (7)	0.1507 (5)	0.0592 (16)
C4	0.9072 (7)	0.2945 (7)	0.0963 (5)	0.0563 (15)
C12	0.9634 (6)	0.4366 (6)	0.1177 (4)	0.0436 (12)
C11	1.0594 (6)	0.4957 (7)	0.1981 (4)	0.0470 (13)
C1	1.1056 (8)	0.4155 (8)	0.2521 (5)	0.0590 (17)
H1A	1.1723	0.4579	0.3051	0.071*
C2	1.0563 (8)	0.2771 (8)	0.2294 (6)	0.0653 (19)
H2A	1.0890	0.2259	0.2663	0.078*
C19	1.3723 (8)	0.8546 (9)	−0.1173 (7)	0.082 (2)
H19A	1.4485	0.8759	−0.1646	0.123*
H19B	1.4005	0.8490	−0.0468	0.123*
H19C	1.3480	0.9274	−0.1212	0.123*
C20	0.9242 (11)	0.7233 (10)	0.3554 (6)	0.085 (2)
H20A	0.9976	0.8201	0.3594	0.127*
H20B	0.9511	0.6659	0.3949	0.127*
H20C	0.8388	0.7138	0.3840	0.127*
C15	0.7923 (7)	0.5297 (7)	0.2337 (5)	0.0569 (16)
H15A	0.7056	0.5152	0.2655	0.068*
H15B	0.8213	0.4711	0.2709	0.068*
C16	0.7647 (6)	0.4843 (7)	0.1193 (5)	0.0531 (15)
H16A	0.7221	0.5323	0.0842	0.064*
H16B	0.6994	0.3837	0.1154	0.064*
C13	0.9034 (6)	0.5194 (6)	0.0638 (5)	0.0461 (13)
C5	0.8825 (7)	0.4990 (7)	−0.0559 (5)	0.0533 (14)
H5A	0.8155	0.4009	−0.0706	0.064*
H5B	0.8429	0.5550	−0.0819	0.064*
C6	1.0162 (7)	0.5401 (7)	−0.1131 (5)	0.0557 (15)
C7	1.1414 (7)	0.6762 (7)	−0.0771 (5)	0.0541 (14)
C8	1.1330 (7)	0.7371 (6)	0.0109 (5)	0.0532 (15)
H8A	1.2119	0.8200	0.0328	0.064*
C14	1.0026 (7)	0.6780 (6)	0.0759 (4)	0.0470 (13)
H14A	0.9502	0.7236	0.0519	0.056*
C9	1.0334 (7)	0.7134 (7)	0.1920 (5)	0.0549 (15)
H9A	1.0938	0.8159	0.1966	0.066*
C10	1.1204 (8)	0.6499 (7)	0.2307 (5)	0.0593 (16)
H10A	1.1262	0.6562	0.3067	0.071*
H10B	1.2153	0.7046	0.2031	0.071*

	U11	U22	U33	U12	U13	U23
O1	0.090 (4)	0.069 (3)	0.099 (4)	0.040 (3)	−0.017 (3)	−0.012 (3)
O2	0.101 (4)	0.042 (3)	0.140 (5)	0.039 (3)	−0.018 (4)	0.016 (3)
O3	0.071 (3)	0.068 (3)	0.071 (3)	0.030 (3)	0.023 (2)	0.011 (2)
O4	0.077 (3)	0.081 (3)	0.075 (3)	0.042 (3)	−0.001 (3)	−0.024 (3)
N	0.077 (4)	0.066 (3)	0.053 (3)	0.046 (3)	0.007 (3)	0.001 (2)
C18	0.207 (13)	0.138 (9)	0.090 (7)	0.135 (10)	−0.005 (7)	−0.001 (7)
C17	0.112 (7)	0.062 (5)	0.126 (7)	0.060 (5)	0.041 (6)	0.043 (5)
C3	0.059 (4)	0.051 (3)	0.072 (4)	0.031 (3)	0.010 (3)	0.020 (3)
C4	0.058 (4)	0.041 (3)	0.069 (4)	0.024 (3)	0.001 (3)	0.014 (3)
C12	0.048 (3)	0.046 (3)	0.045 (3)	0.030 (3)	0.002 (2)	0.010 (2)
C11	0.056 (3)	0.055 (3)	0.042 (3)	0.037 (3)	−0.001 (3)	0.002 (2)
C1	0.067 (4)	0.085 (5)	0.049 (3)	0.056 (4)	−0.002 (3)	0.009 (3)
C2	0.069 (4)	0.073 (5)	0.077 (4)	0.053 (4)	0.006 (4)	0.021 (4)
C19	0.062 (5)	0.086 (6)	0.078 (5)	0.023 (4)	0.012 (4)	−0.008 (4)
C20	0.124 (7)	0.101 (6)	0.054 (4)	0.074 (6)	0.010 (4)	0.001 (4)
C15	0.061 (4)	0.062 (4)	0.064 (4)	0.042 (3)	0.010 (3)	0.009 (3)
C16	0.045 (3)	0.053 (3)	0.066 (4)	0.028 (3)	0.002 (3)	0.013 (3)
C13	0.047 (3)	0.043 (3)	0.054 (3)	0.027 (3)	−0.004 (3)	0.006 (2)
C5	0.062 (3)	0.046 (3)	0.060 (3)	0.034 (3)	−0.010 (3)	−0.002 (3)
C6	0.064 (4)	0.050 (3)	0.059 (3)	0.032 (3)	−0.002 (3)	0.000 (3)
C7	0.060 (3)	0.054 (3)	0.046 (3)	0.027 (3)	0.004 (3)	0.003 (3)
C8	0.058 (3)	0.045 (3)	0.054 (3)	0.024 (3)	0.003 (3)	0.003 (2)
C14	0.060 (4)	0.042 (3)	0.045 (3)	0.030 (3)	0.004 (3)	0.007 (2)
C9	0.065 (4)	0.052 (3)	0.052 (4)	0.033 (3)	−0.008 (3)	−0.003 (3)
C10	0.069 (4)	0.069 (4)	0.048 (3)	0.041 (4)	−0.019 (3)	−0.008 (3)

O1—C18	1.278 (11)	C19—H19B	0.9600
O1—C4	1.344 (9)	C19—H19C	0.9600
O2—C3	1.360 (8)	C20—H20A	0.9600
O2—C17	1.388 (9)	C20—H20B	0.9600
O3—C7	1.377 (8)	C20—H20C	0.9600
O3—C19	1.424 (9)	C15—C16	1.520 (7)
O4—C6	1.217 (8)	C15—H15A	0.9700
N—C20	1.461 (10)	C15—H15B	0.9700
N—C9	1.466 (9)	C16—C13	1.541 (8)
N—C15	1.466 (9)	C16—H16A	0.9700
C18—H18A	0.9600	C16—H16B	0.9700
C18—H18B	0.9600	C13—C14	1.528 (8)
C18—H18C	0.9600	C13—C5	1.540 (9)
C17—H17A	0.9600	C5—C6	1.490 (10)
C17—H17B	0.9600	C5—H5A	0.9700
C17—H17C	0.9600	C5—H5B	0.9700
C3—C2	1.386 (10)	C6—C7	1.507 (9)
C3—C4	1.428 (8)	C7—C8	1.330 (9)
C4—C12	1.385 (9)	C8—C14	1.491 (9)
C12—C11	1.376 (8)	C8—H8A	0.9300
C12—C13	1.524 (7)	C14—C9	1.523 (8)
C11—C1	1.395 (8)	C14—H14A	0.9800
C11—C10	1.531 (9)	C9—C10	1.516 (9)
C1—C2	1.363 (10)	C9—H9A	0.9800
C1—H1A	0.9300	C10—H10A	0.9700
C2—H2A	0.9300	C10—H10B	0.9700
C19—H19A	0.9600
C18—O1—C4	118.1 (9)	C16—C15—H15A	109.1
C3—O2—C17	120.6 (7)	N—C15—H15B	109.1
C7—O3—C19	114.3 (6)	C16—C15—H15B	109.1
C20—N—C9	112.2 (6)	H15A—C15—H15B	107.9
C20—N—C15	112.5 (6)	C15—C16—C13	110.4 (5)
C9—N—C15	113.3 (5)	C15—C16—H16A	109.6
O1—C18—H18A	109.5	C13—C16—H16A	109.6
O1—C18—H18B	109.5	C15—C16—H16B	109.6
H18A—C18—H18B	109.5	C13—C16—H16B	109.6
O1—C18—H18C	109.5	H16A—C16—H16B	108.1
H18A—C18—H18C	109.5	C12—C13—C14	111.0 (5)
H18B—C18—H18C	109.5	C12—C13—C5	115.9 (5)
O2—C17—H17A	109.5	C14—C13—C5	103.5 (4)
O2—C17—H17B	109.5	C12—C13—C16	108.0 (5)
H17A—C17—H17B	109.5	C14—C13—C16	106.8 (5)
O2—C17—H17C	109.5	C5—C13—C16	111.2 (5)
H17A—C17—H17C	109.5	C6—C5—C13	112.7 (5)
H17B—C17—H17C	109.5	C6—C5—H5A	109.0
O2—C3—C2	124.0 (6)	C13—C5—H5A	109.0
O2—C3—C4	116.6 (6)	C6—C5—H5B	109.0
C2—C3—C4	119.2 (6)	C13—C5—H5B	109.0
O1—C4—C12	117.9 (5)	H5A—C5—H5B	107.8
O1—C4—C3	120.5 (6)	O4—C6—C5	124.2 (6)
C12—C4—C3	120.6 (6)	O4—C6—C7	120.8 (6)
C11—C12—C4	118.8 (5)	C5—C6—C7	115.0 (5)
C11—C12—C13	120.7 (5)	C8—C7—O3	128.1 (6)
C4—C12—C13	119.9 (5)	C8—C7—C6	119.7 (6)
C12—C11—C1	120.2 (6)	O3—C7—C6	112.2 (5)
C12—C11—C10	122.0 (5)	C7—C8—C14	122.8 (6)
C1—C11—C10	117.8 (5)	C7—C8—H8A	118.6
C2—C1—C11	122.1 (6)	C14—C8—H8A	118.6
C2—C1—H1A	119.0	C8—C14—C9	112.7 (5)
C11—C1—H1A	119.0	C8—C14—C13	114.8 (5)
C1—C2—C3	119.1 (6)	C9—C14—C13	109.2 (5)
C1—C2—H2A	120.5	C8—C14—H14A	106.5
C3—C2—H2A	120.5	C9—C14—H14A	106.5
O3—C19—H19A	109.5	C13—C14—H14A	106.5
O3—C19—H19B	109.5	N—C9—C10	119.4 (5)
H19A—C19—H19B	109.5	N—C9—C14	108.8 (5)
O3—C19—H19C	109.5	C10—C9—C14	108.0 (5)
H19A—C19—H19C	109.5	N—C9—H9A	106.7
H19B—C19—H19C	109.5	C10—C9—H9A	106.7
N—C20—H20A	109.5	C14—C9—H9A	106.7
N—C20—H20B	109.5	C9—C10—C11	113.0 (5)
H20A—C20—H20B	109.5	C9—C10—H10A	109.0
N—C20—H20C	109.5	C11—C10—H10A	109.0
H20A—C20—H20C	109.5	C9—C10—H10B	109.0
H20B—C20—H20C	109.5	C11—C10—H10B	109.0
N—C15—C16	112.4 (5)	H10A—C10—H10B	107.8
N—C15—H15A	109.1
C17—O2—C3—C2	1.2 (12)	C12—C13—C5—C6	−59.6 (7)
C17—O2—C3—C4	−173.7 (7)	C14—C13—C5—C6	62.2 (6)
C18—O1—C4—C12	127.8 (8)	C16—C13—C5—C6	176.6 (5)
C18—O1—C4—C3	−64.2 (11)	C13—C5—C6—O4	139.7 (7)
O2—C3—C4—O1	11.0 (10)	C13—C5—C6—C7	−43.8 (7)
C2—C3—C4—O1	−164.1 (7)	C19—O3—C7—C8	−1.0 (11)
O2—C3—C4—C12	178.7 (6)	C19—O3—C7—C6	177.5 (6)
C2—C3—C4—C12	3.6 (9)	O4—C6—C7—C8	−172.3 (7)
O1—C4—C12—C11	162.8 (6)	C5—C6—C7—C8	11.0 (8)
C3—C4—C12—C11	−5.2 (9)	O4—C6—C7—O3	9.1 (9)
O1—C4—C12—C13	−8.4 (9)	C5—C6—C7—O3	−167.6 (6)
C3—C4—C12—C13	−176.4 (6)	O3—C7—C8—C14	177.1 (6)
C4—C12—C11—C1	4.2 (9)	C6—C7—C8—C14	−1.3 (9)
C13—C12—C11—C1	175.3 (6)	C7—C8—C14—C9	150.3 (6)
C4—C12—C11—C10	−176.7 (6)	C7—C8—C14—C13	24.5 (9)
C13—C12—C11—C10	−5.6 (9)	C12—C13—C14—C8	73.0 (6)
C12—C11—C1—C2	−1.5 (10)	C5—C13—C14—C8	−52.0 (6)
C10—C11—C1—C2	179.3 (6)	C16—C13—C14—C8	−169.4 (5)
C11—C1—C2—C3	−0.2 (10)	C12—C13—C14—C9	−54.6 (6)
O2—C3—C2—C1	−175.6 (7)	C5—C13—C14—C9	−179.6 (5)
C4—C3—C2—C1	−0.8 (10)	C16—C13—C14—C9	62.9 (6)
C20—N—C15—C16	177.7 (6)	C20—N—C9—C10	62.0 (8)
C9—N—C15—C16	−53.7 (7)	C15—N—C9—C10	−66.7 (7)
N—C15—C16—C13	53.3 (6)	C20—N—C9—C14	−173.6 (5)
C11—C12—C13—C14	23.7 (7)	C15—N—C9—C14	57.7 (6)
C4—C12—C13—C14	−165.3 (5)	C8—C14—C9—N	168.2 (5)
C11—C12—C13—C5	141.4 (6)	C13—C14—C9—N	−63.0 (6)
C4—C12—C13—C5	−47.6 (8)	C8—C14—C9—C10	−61.0 (7)
C11—C12—C13—C16	−93.2 (6)	C13—C14—C9—C10	67.9 (7)
C4—C12—C13—C16	77.8 (7)	N—C9—C10—C11	76.5 (7)
C15—C16—C13—C12	62.0 (6)	C14—C9—C10—C11	−48.2 (7)
C15—C16—C13—C14	−57.5 (6)	C12—C11—C10—C9	18.3 (9)
C15—C16—C13—C5	−169.8 (5)	C1—C11—C10—C9	−162.5 (6)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···O1	0.97	2.23	2.853 (9)	121
C16—H16B···O1	0.97	2.53	3.102 (10)	118
C18—H18B···O2	0.96	2.14	2.812 (16)	126

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯O1	0.97	2.23	2.853 (9)	121
C16—H16B⋯O1	0.97	2.53	3.102 (10)	118
C18—H18B⋯O2	0.96	2.14	2.812 (16)	126