10α-Hy-droxy-4,9-dimethyl-13-(morph-o-lin-4-ylmeth-yl)-3,8,15-trioxatetra-cyclo-[10.3.0.0.0]penta-decan-14-one.

The title compound, C(19)H(29)NO(6), was synthesized from 9α-hy-droxy-parthenolide (9α-hy-droxy-4,8-dimethyl-12-methyl-ene-3,14-dioxatricyclo-[9.3.0.0(2,4)]tetra-dec-7-en-13-one), which was isolated from the chloro-form extract of the aerial parts of Anvillea radiata. The mol-ecule contains a fused five- and ten-membered ring system. The ten-membered ring adopts an approximate chair-chair conformation, while the five-membered ring is in an envelope conformation, with the C atom closest to the hy-droxy group forming the flap. In the crystal, weak C-H⋯O hydrogen bonds connect the mol-ecules into layers parallel to (001). An intra-molecular O-H⋯N hydrogen bond is also present.

Related literature

For background to the medicinal uses of the plant Anvillea radiata, see: El Hassany et al. (2004 ▶); Qureshi et al. (1990 ▶). For the reactivity of this sesquiterpene, see: Hwang et al. (2006 ▶); Neukirch et al. (2003 ▶); Neelakantan et al. (2009 ▶). For ring puckering parameters, see: Cremer & Pople (1975 ▶). For the synthesis see: Moumou et al. (2010 ▶).

Experimental

Crystal data

C19H29NO6

M = 367.43

Monoclinic,

a = 11.6772 (9) Å

b = 6.9524 (4) Å

c = 11.8244 (9) Å

β = 102.160 (2)°

V = 938.42 (12) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 296 K

0.65 × 0.45 × 0.26 mm

Data collection

Bruker X8 APEXII CCD diffractometer

7793 measured reflections

2069 independent reflections

1661 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.110

S = 1.07

2069 reflections

239 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.20 e Å−3

Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick,2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick,2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia,1997 ▶)and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811053207/lh5393sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811053207/lh5393Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811053207/lh5393Isup3.cml

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

C19H29NO6	F(000) = 396
Mr = 367.43	Dx = 1.300 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2070 reflections
a = 11.6772 (9) Å	θ = 3.6–26.4°
b = 6.9524 (4) Å	µ = 0.10 mm−1
c = 11.8244 (9) Å	T = 296 K
β = 102.160 (2)°	Prism, colourless
V = 938.42 (12) Å3	0.65 × 0.45 × 0.26 mm
Z = 2

Bruker X8 APEXII CCD diffractometer	1661 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.032
graphite	θmax = 26.4°, θmin = 3.6°
φ and ω scans	h = −14→14
7793 measured reflections	k = −6→8
2069 independent reflections	l = −14→13

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)] = 0.044	H-atom parameters constrained
wR(F2) = 0.110	w = 1/[σ2(Fo2) + (0.0604P)2 + 0.079P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
2069 reflections	Δρmax = 0.20 e Å−3
239 parameters	Δρmin = −0.23 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: 0.047 (7)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
C1	0.2787 (2)	0.2053 (4)	0.3279 (2)	0.0354 (6)
H1	0.2200	0.1396	0.2692	0.042*
C2	0.2207 (2)	0.3348 (5)	0.3984 (2)	0.0410 (7)
H2	0.2724	0.4347	0.4397	0.049*
C3	0.0963 (2)	0.3897 (5)	0.3702 (3)	0.0481 (8)
C4	0.0687 (3)	0.5894 (6)	0.4046 (3)	0.0631 (10)
H4A	0.1265	0.6277	0.4724	0.076*
H4B	−0.0073	0.5888	0.4256	0.076*
C5	0.0673 (3)	0.7374 (5)	0.3081 (4)	0.0659 (10)
H5A	−0.0014	0.7161	0.2472	0.079*
H5B	0.0615	0.8655	0.3389	0.079*
C6	0.1748 (3)	0.7262 (4)	0.2578 (3)	0.0525 (8)
H6	0.2486	0.7177	0.3153	0.063*
C7	0.1814 (3)	0.6562 (4)	0.1444 (3)	0.0503 (8)
C8	0.2969 (3)	0.5873 (5)	0.1194 (3)	0.0468 (7)
H8	0.2923	0.6064	0.0365	0.056*
C9	0.3194 (3)	0.3721 (5)	0.1433 (2)	0.0419 (7)
H9A	0.3758	0.3287	0.0993	0.050*
H9B	0.2469	0.3033	0.1145	0.050*
C10	0.3649 (2)	0.3155 (4)	0.2708 (2)	0.0323 (6)
H10	0.3866	0.4339	0.3151	0.039*
C11	0.4738 (2)	0.1839 (4)	0.2903 (2)	0.0378 (6)
H11	0.4747	0.1113	0.2195	0.045*
C12	0.4563 (2)	0.0491 (4)	0.3832 (2)	0.0439 (7)
C13	0.5891 (2)	0.2916 (5)	0.3277 (2)	0.0455 (7)
H13A	0.5919	0.3489	0.4030	0.055*
H13B	0.6533	0.2006	0.3355	0.055*
C14	0.0086 (3)	0.2978 (6)	0.2748 (3)	0.0673 (11)
H14A	0.0412	0.1824	0.2501	0.101*
H14B	−0.0109	0.3854	0.2109	0.101*
H14C	−0.0609	0.2666	0.3024	0.101*
C15	0.0772 (3)	0.5911 (7)	0.0548 (3)	0.0753 (11)
H15A	0.0068	0.6419	0.0731	0.113*
H15B	0.0737	0.4531	0.0540	0.113*
H15C	0.0845	0.6368	−0.0200	0.113*
C16	0.6476 (3)	0.3626 (5)	0.1469 (3)	0.0481 (7)
H16A	0.5893	0.2747	0.1048	0.058*
H16B	0.7193	0.2908	0.1745	0.058*
C17	0.6915 (3)	0.5830 (6)	0.3049 (3)	0.0568 (9)
H17A	0.7644	0.5178	0.3374	0.068*
H17B	0.6628	0.6422	0.3678	0.068*
C18	0.6700 (3)	0.5208 (5)	0.0673 (3)	0.0610 (9)
H18A	0.6983	0.4652	0.0031	0.073*
H18B	0.5970	0.5870	0.0361	0.073*
C19	0.7136 (3)	0.7371 (6)	0.2215 (3)	0.0697 (10)
H19A	0.6419	0.8085	0.1934	0.084*
H19B	0.7721	0.8263	0.2617	0.084*
N	0.60588 (19)	0.4434 (4)	0.24620 (18)	0.0419 (6)
O1	0.39115 (18)	0.7008 (3)	0.1779 (2)	0.0641 (7)
H1A	0.4495	0.6332	0.1973	0.096*
O2	0.1778 (3)	0.8609 (4)	0.1609 (3)	0.0845 (9)
O3	0.14029 (17)	0.2566 (4)	0.46360 (19)	0.0613 (7)
O4	0.34823 (15)	0.0656 (3)	0.40522 (16)	0.0440 (5)
O5	0.5259 (2)	−0.0639 (4)	0.4365 (2)	0.0649 (7)
O6	0.7532 (2)	0.6551 (4)	0.1254 (2)	0.0678 (7)

	U11	U22	U33	U12	U13	U23
C1	0.0331 (13)	0.0335 (14)	0.0376 (14)	0.0022 (11)	0.0032 (10)	0.0047 (12)
C2	0.0336 (13)	0.0482 (17)	0.0435 (16)	−0.0015 (12)	0.0135 (12)	0.0037 (14)
C3	0.0325 (14)	0.0540 (19)	0.0604 (19)	0.0025 (14)	0.0156 (13)	0.0134 (17)
C4	0.0520 (19)	0.073 (2)	0.072 (2)	0.0145 (18)	0.0297 (17)	−0.003 (2)
C5	0.070 (2)	0.0451 (19)	0.089 (3)	0.0156 (18)	0.0315 (19)	−0.004 (2)
C6	0.0608 (18)	0.0330 (17)	0.064 (2)	−0.0023 (14)	0.0126 (15)	−0.0011 (15)
C7	0.0543 (17)	0.0281 (15)	0.066 (2)	0.0054 (13)	0.0064 (15)	0.0079 (14)
C8	0.0523 (17)	0.0445 (17)	0.0430 (16)	0.0003 (14)	0.0084 (13)	0.0106 (14)
C9	0.0461 (15)	0.0467 (16)	0.0324 (14)	0.0087 (13)	0.0071 (12)	0.0003 (13)
C10	0.0349 (13)	0.0317 (14)	0.0306 (13)	0.0050 (11)	0.0074 (10)	0.0016 (11)
C11	0.0388 (14)	0.0434 (16)	0.0328 (14)	0.0095 (12)	0.0115 (11)	0.0020 (12)
C12	0.0424 (15)	0.0452 (17)	0.0443 (16)	0.0096 (14)	0.0098 (13)	0.0037 (14)
C13	0.0366 (14)	0.065 (2)	0.0364 (15)	0.0050 (14)	0.0110 (11)	0.0041 (15)
C14	0.0379 (16)	0.060 (2)	0.096 (3)	0.0009 (16)	−0.0017 (17)	0.015 (2)
C15	0.058 (2)	0.084 (3)	0.071 (2)	0.012 (2)	−0.0148 (17)	0.008 (2)
C16	0.0527 (16)	0.0531 (18)	0.0422 (16)	0.0025 (15)	0.0182 (13)	−0.0040 (15)
C17	0.0459 (16)	0.073 (2)	0.0537 (18)	−0.0100 (17)	0.0146 (14)	−0.0156 (19)
C18	0.071 (2)	0.063 (2)	0.0545 (19)	−0.0047 (18)	0.0258 (17)	0.0017 (18)
C19	0.066 (2)	0.062 (2)	0.083 (3)	−0.0115 (19)	0.0228 (19)	−0.017 (2)
N	0.0367 (12)	0.0561 (15)	0.0351 (12)	0.0013 (11)	0.0122 (10)	−0.0053 (12)
O1	0.0548 (13)	0.0511 (14)	0.0851 (17)	−0.0106 (11)	0.0121 (12)	0.0156 (13)
O2	0.114 (2)	0.0458 (15)	0.095 (2)	0.0084 (15)	0.0268 (18)	0.0058 (15)
O3	0.0436 (11)	0.0799 (17)	0.0678 (14)	0.0123 (11)	0.0285 (10)	0.0279 (14)
O4	0.0425 (11)	0.0441 (11)	0.0470 (11)	0.0054 (9)	0.0135 (9)	0.0138 (9)
O5	0.0584 (13)	0.0708 (17)	0.0663 (14)	0.0282 (13)	0.0148 (11)	0.0282 (13)
O6	0.0679 (14)	0.0695 (16)	0.0750 (15)	−0.0158 (13)	0.0351 (12)	−0.0037 (14)

C1—O4	1.458 (3)	C11—C12	1.490 (4)
C1—C2	1.484 (4)	C11—C13	1.523 (4)
C1—C10	1.530 (3)	C11—H11	0.9800
C1—H1	0.9800	C12—O5	1.208 (3)
C2—O3	1.441 (3)	C12—O4	1.346 (3)
C2—C3	1.471 (4)	C13—N	1.470 (4)
C2—H2	0.9800	C13—H13A	0.9700
C3—O3	1.449 (4)	C13—H13B	0.9700
C3—C14	1.498 (5)	C14—H14A	0.9600
C3—C4	1.500 (5)	C14—H14B	0.9600
C4—C5	1.535 (5)	C14—H14C	0.9600
C4—H4A	0.9700	C15—H15A	0.9600
C4—H4B	0.9700	C15—H15B	0.9600
C5—C6	1.500 (5)	C15—H15C	0.9600
C5—H5A	0.9700	C16—N	1.474 (4)
C5—H5B	0.9700	C16—C18	1.506 (5)
C6—C7	1.443 (5)	C16—H16A	0.9700
C6—O2	1.486 (4)	C16—H16B	0.9700
C6—H6	0.9800	C17—N	1.460 (4)
C7—O2	1.438 (4)	C17—C19	1.514 (5)
C7—C15	1.505 (5)	C17—H17A	0.9700
C7—C8	1.518 (4)	C17—H17B	0.9700
C8—O1	1.411 (4)	C18—O6	1.417 (4)
C8—C9	1.535 (4)	C18—H18A	0.9700
C8—H8	0.9800	C18—H18B	0.9700
C9—C10	1.540 (4)	C19—O6	1.432 (4)
C9—H9A	0.9700	C19—H19A	0.9700
C9—H9B	0.9700	C19—H19B	0.9700
C10—C11	1.544 (3)	O1—H1A	0.8200
C10—H10	0.9800
O4—C1—C2	108.2 (2)	C12—C11—C13	110.2 (2)
O4—C1—C10	106.18 (18)	C12—C11—C10	104.2 (2)
C2—C1—C10	111.4 (2)	C13—C11—C10	113.7 (2)
O4—C1—H1	110.3	C12—C11—H11	109.5
C2—C1—H1	110.3	C13—C11—H11	109.5
C10—C1—H1	110.3	C10—C11—H11	109.5
O3—C2—C3	59.70 (17)	O5—C12—O4	120.6 (3)
O3—C2—C1	119.8 (3)	O5—C12—C11	127.7 (3)
C3—C2—C1	125.2 (3)	O4—C12—C11	111.6 (2)
O3—C2—H2	113.8	N—C13—C11	113.2 (2)
C3—C2—H2	113.8	N—C13—H13A	108.9
C1—C2—H2	113.8	C11—C13—H13A	108.9
O3—C3—C2	59.13 (17)	N—C13—H13B	108.9
O3—C3—C14	112.2 (3)	C11—C13—H13B	108.9
C2—C3—C14	123.1 (3)	H13A—C13—H13B	107.7
O3—C3—C4	116.5 (3)	C3—C14—H14A	109.5
C2—C3—C4	115.9 (3)	C3—C14—H14B	109.5
C14—C3—C4	116.5 (3)	H14A—C14—H14B	109.5
C3—C4—C5	112.8 (3)	C3—C14—H14C	109.5
C3—C4—H4A	109.0	H14A—C14—H14C	109.5
C5—C4—H4A	109.0	H14B—C14—H14C	109.5
C3—C4—H4B	109.0	C7—C15—H15A	109.5
C5—C4—H4B	109.0	C7—C15—H15B	109.5
H4A—C4—H4B	107.8	H15A—C15—H15B	109.5
C6—C5—C4	112.5 (3)	C7—C15—H15C	109.5
C6—C5—H5A	109.1	H15A—C15—H15C	109.5
C4—C5—H5A	109.1	H15B—C15—H15C	109.5
C6—C5—H5B	109.1	N—C16—C18	110.4 (3)
C4—C5—H5B	109.1	N—C16—H16A	109.6
H5A—C5—H5B	107.8	C18—C16—H16A	109.6
C7—C6—O2	58.8 (2)	N—C16—H16B	109.6
C7—C6—C5	126.8 (3)	C18—C16—H16B	109.6
O2—C6—C5	115.5 (3)	H16A—C16—H16B	108.1
C7—C6—H6	114.4	N—C17—C19	110.8 (3)
O2—C6—H6	114.4	N—C17—H17A	109.5
C5—C6—H6	114.4	C19—C17—H17A	109.5
O2—C7—C6	62.1 (2)	N—C17—H17B	109.5
O2—C7—C15	110.5 (3)	C19—C17—H17B	109.5
C6—C7—C15	124.2 (3)	H17A—C17—H17B	108.1
O2—C7—C8	113.0 (3)	O6—C18—C16	111.7 (3)
C6—C7—C8	120.7 (3)	O6—C18—H18A	109.3
C15—C7—C8	112.8 (3)	C16—C18—H18A	109.3
O1—C8—C7	111.2 (3)	O6—C18—H18B	109.3
O1—C8—C9	111.7 (2)	C16—C18—H18B	109.3
C7—C8—C9	113.3 (3)	H18A—C18—H18B	107.9
O1—C8—H8	106.7	O6—C19—C17	111.3 (3)
C7—C8—H8	106.7	O6—C19—H19A	109.4
C9—C8—H8	106.7	C17—C19—H19A	109.4
C8—C9—C10	116.1 (2)	O6—C19—H19B	109.4
C8—C9—H9A	108.3	C17—C19—H19B	109.4
C10—C9—H9A	108.3	H19A—C19—H19B	108.0
C8—C9—H9B	108.3	C17—N—C13	109.8 (2)
C10—C9—H9B	108.3	C17—N—C16	108.9 (2)
H9A—C9—H9B	107.4	C13—N—C16	111.1 (2)
C1—C10—C9	115.9 (2)	C8—O1—H1A	109.5
C1—C10—C11	103.6 (2)	C7—O2—C6	59.1 (2)
C9—C10—C11	113.6 (2)	C2—O3—C3	61.17 (18)
C1—C10—H10	107.8	C12—O4—C1	110.9 (2)
C9—C10—H10	107.8	C18—O6—C19	110.1 (2)
C11—C10—H10	107.8

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N	0.82	2.23	3.048 (3)	178
C1—H1···O2i	0.98	2.32	3.169 (4)	145
C2—H2···O5ii	0.98	2.50	3.260 (3)	134
C4—H4B···O3iii	0.97	2.52	3.367 (4)	146

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N	0.82	2.23	3.048 (3)	178
C1—H1⋯O2i	0.98	2.32	3.169 (4)	145
C2—H2⋯O5ii	0.98	2.50	3.260 (3)	134
C4—H4B⋯O3iii	0.97	2.52	3.367 (4)	146

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