10α-Hy-droxy-4,9-dimethyl-13-[(pyrrol-idin-1-yl)meth-yl]-3,8,15-trioxatetra-cyclo-[10.3.0.0.0]penta-decan-14-one.

The title compound, C(19)H(29)NO(5), 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 is built up from two fused five- and ten-membered rings with the (pyrrolidin-4-yl)methyl group as a substituent. The two five-membered ring display the same envelope conformations, whereas the ten-membered ring adopts an approximate chair-chair conformation. The dihedral angle between the ten-membered ring and the lactone ring is 21.81 (9)°. An intra-molecular O-H⋯N hydrogen bond stabilizes the mol-ecular conformation. In the crystal, inter-molecular C-H⋯O inter-actions link the mol-ecules into chains parallel to the c axis.

Related literature

For background to the medicinal uses of the plant Anvillea radiata, see: El Hassany et al. (2004 ▶). For reactivity of this sesquiterpene see: Der-Ren et al. (2006 ▶); Neelakantan et al. (2009 ▶); Neukirch et al. (2003 ▶). For ring puckering parameters, see: Cremer & Pople (1975 ▶). For conformations of ten-membered rings, see: Castaneda-Acosta et al. (1997 ▶). For related structures, see: Moumou et al. (2010 ▶); Watson & Zabel (1982 ▶).

Experimental

Crystal data

C19H29NO5

M = 351.43

Orthorhombic,

a = 8.0714 (2) Å

b = 10.4571 (3) Å

c = 21.5816 (8) Å

V = 1821.56 (10) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 298 K

0.89 × 0.46 × 0.21 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

8707 measured reflections

2122 independent reflections

1660 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.098

S = 1.03

2122 reflections

229 parameters

H-atom parameters constrained

Δρmax = 0.17 e Å−3

Δρmin = −0.15 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2 and 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/S1600536811024688/om2443sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811024688/om2443Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811024688/om2443Isup3.cml

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

C19H29NO5	F(000) = 760
Mr = 351.43	Dx = 1.281 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3417 reflections
a = 8.0714 (2) Å	θ = 2.7–26.4°
b = 10.4571 (3) Å	µ = 0.09 mm−1
c = 21.5816 (8) Å	T = 298 K
V = 1821.56 (10) Å3	Prism, colourless
Z = 4	0.89 × 0.46 × 0.21 mm

Bruker APEXII CCD area-detector diffractometer	1660 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.034
graphite	θmax = 26.4°, θmin = 2.7°
φ and ω scans	h = −7→10
8707 measured reflections	k = −13→10
2122 independent reflections	l = −26→25

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0589P)2] where P = (Fo2 + 2Fc2)/3
2122 reflections	(Δ/σ)max < 0.001
229 parameters	Δρmax = 0.17 e Å−3
0 restraints	Δρmin = −0.15 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.2294 (3)	0.5169 (2)	0.08783 (11)	0.0361 (6)
H1	0.1851	0.5945	0.0685	0.043*
C2	0.3205 (3)	0.5410 (2)	0.14572 (11)	0.0399 (6)
C3	0.3293 (3)	0.6785 (2)	0.16551 (12)	0.0483 (7)
H3A	0.3354	0.6820	0.2104	0.058*
H3B	0.2280	0.7212	0.1530	0.058*
C4	0.4776 (3)	0.7513 (3)	0.13836 (13)	0.0491 (7)
H4A	0.4573	0.8423	0.1424	0.059*
H4B	0.5754	0.7311	0.1626	0.059*
C5	0.5120 (3)	0.7213 (2)	0.07148 (12)	0.0377 (6)
H5	0.4129	0.7113	0.0457	0.045*
C6	0.6598 (3)	0.6526 (2)	0.04855 (11)	0.0361 (5)
C7	0.6555 (3)	0.5740 (2)	−0.01081 (10)	0.0336 (5)
H7	0.7700	0.5517	−0.0214	0.040*
C8	0.5592 (3)	0.4481 (2)	−0.00134 (11)	0.0351 (5)
H8A	0.6027	0.3845	−0.0297	0.042*
H8B	0.5792	0.4177	0.0405	0.042*
C9	0.3708 (3)	0.4590 (2)	−0.01138 (10)	0.0325 (5)
H9	0.3454	0.5497	−0.0179	0.039*
C10	0.2637 (3)	0.4126 (2)	0.04320 (12)	0.0367 (6)
H10	0.3146	0.3389	0.0639	0.044*
C11	0.2981 (3)	0.3852 (2)	−0.06591 (12)	0.0410 (6)
H11	0.3523	0.3016	−0.0685	0.049*
C12	0.1199 (3)	0.3663 (2)	−0.04627 (14)	0.0491 (7)
C13	0.7995 (3)	0.6124 (3)	0.09028 (13)	0.0549 (8)
H13A	0.9032	0.6363	0.0718	0.082*
H13B	0.7963	0.5214	0.0959	0.082*
H13C	0.7881	0.6539	0.1297	0.082*
C14	0.4501 (3)	0.4522 (3)	0.17126 (13)	0.0557 (7)
H14A	0.4431	0.4509	0.2157	0.084*
H14B	0.5580	0.4814	0.1590	0.084*
H14C	0.4321	0.3675	0.1554	0.084*
C15	0.3068 (3)	0.4494 (3)	−0.12859 (12)	0.0469 (6)
H15A	0.2480	0.3971	−0.1585	0.056*
H15B	0.2506	0.5312	−0.1262	0.056*
C16	0.5619 (4)	0.3520 (3)	−0.16867 (15)	0.0686 (9)
H16A	0.4884	0.2950	−0.1910	0.082*
H16B	0.6043	0.3079	−0.1324	0.082*
C17	0.7000 (5)	0.3955 (4)	−0.2091 (2)	0.0935 (13)
H17A	0.7218	0.3332	−0.2414	0.112*
H17B	0.8003	0.4078	−0.1851	0.112*
C18	0.6423 (4)	0.5219 (3)	−0.23718 (14)	0.0664 (9)
H18A	0.7210	0.5895	−0.2283	0.080*
H18B	0.6301	0.5143	−0.2817	0.080*
C19	0.4779 (4)	0.5494 (3)	−0.20714 (12)	0.0553 (7)
H19A	0.4686	0.6394	−0.1968	0.066*
H19B	0.3875	0.5265	−0.2346	0.066*
N	0.4750 (3)	0.47021 (19)	−0.15073 (9)	0.0435 (5)
O1	0.1047 (2)	0.37802 (16)	0.01525 (9)	0.0474 (5)
O2	0.0011 (3)	0.3449 (2)	−0.07852 (11)	0.0696 (6)
O3	0.5907 (2)	0.64734 (16)	−0.06008 (8)	0.0415 (4)
H3	0.5656	0.5999	−0.0888	0.062*
O4	0.6462 (2)	0.78993 (16)	0.04219 (8)	0.0460 (5)
O5	0.1545 (2)	0.48703 (17)	0.14653 (8)	0.0503 (5)

	U11	U22	U33	U12	U13	U23
C1	0.0278 (11)	0.0437 (13)	0.0369 (13)	−0.0005 (11)	0.0061 (10)	0.0094 (10)
C2	0.0353 (13)	0.0507 (14)	0.0338 (13)	−0.0003 (12)	0.0068 (10)	0.0073 (12)
C3	0.0521 (15)	0.0586 (16)	0.0340 (14)	0.0070 (13)	0.0051 (12)	−0.0027 (12)
C4	0.0538 (16)	0.0513 (15)	0.0423 (16)	−0.0036 (13)	0.0025 (13)	−0.0083 (12)
C5	0.0378 (13)	0.0365 (12)	0.0389 (14)	−0.0073 (12)	0.0015 (11)	0.0009 (11)
C6	0.0270 (11)	0.0401 (13)	0.0411 (14)	−0.0065 (11)	−0.0007 (10)	0.0050 (11)
C7	0.0269 (11)	0.0398 (12)	0.0341 (13)	0.0029 (11)	0.0037 (10)	0.0065 (10)
C8	0.0352 (12)	0.0341 (11)	0.0359 (13)	0.0025 (11)	0.0024 (10)	0.0030 (10)
C9	0.0337 (11)	0.0284 (10)	0.0354 (12)	0.0000 (10)	−0.0004 (10)	0.0027 (10)
C10	0.0304 (12)	0.0348 (12)	0.0450 (15)	−0.0028 (10)	−0.0001 (11)	0.0096 (11)
C11	0.0444 (14)	0.0343 (12)	0.0442 (15)	0.0005 (12)	−0.0029 (12)	−0.0032 (11)
C12	0.0517 (17)	0.0366 (13)	0.0591 (19)	−0.0096 (14)	−0.0047 (15)	0.0015 (13)
C13	0.0385 (15)	0.077 (2)	0.0487 (17)	−0.0019 (14)	−0.0071 (13)	0.0033 (14)
C14	0.0566 (16)	0.0671 (17)	0.0434 (16)	0.0044 (16)	−0.0038 (13)	0.0116 (15)
C15	0.0485 (15)	0.0516 (14)	0.0405 (15)	0.0041 (14)	−0.0047 (12)	−0.0067 (12)
C16	0.079 (2)	0.0623 (18)	0.064 (2)	0.0231 (18)	0.0107 (19)	−0.0128 (16)
C17	0.083 (3)	0.116 (3)	0.082 (3)	0.026 (2)	0.027 (2)	−0.008 (2)
C18	0.070 (2)	0.081 (2)	0.0476 (18)	−0.0066 (19)	0.0082 (16)	−0.0081 (16)
C19	0.0636 (17)	0.0695 (18)	0.0327 (14)	0.0029 (17)	−0.0035 (13)	−0.0014 (14)
N	0.0512 (13)	0.0459 (12)	0.0333 (11)	0.0082 (11)	−0.0027 (10)	−0.0041 (9)
O1	0.0366 (10)	0.0480 (10)	0.0576 (12)	−0.0131 (8)	0.0013 (9)	0.0040 (9)
O2	0.0568 (13)	0.0737 (14)	0.0784 (16)	−0.0238 (12)	−0.0205 (12)	−0.0018 (12)
O3	0.0507 (10)	0.0409 (8)	0.0327 (10)	−0.0062 (9)	−0.0004 (8)	0.0074 (7)
O4	0.0488 (10)	0.0406 (9)	0.0485 (11)	−0.0146 (8)	0.0053 (9)	0.0000 (8)
O5	0.0399 (9)	0.0666 (12)	0.0445 (11)	−0.0044 (9)	0.0147 (8)	0.0106 (9)

C1—O5	1.438 (3)	C10—H10	0.9800
C1—C2	1.472 (3)	C11—C15	1.512 (4)
C1—C10	1.481 (3)	C11—C12	1.512 (4)
C1—H1	0.9800	C11—H11	0.9800
C2—O5	1.454 (3)	C12—O2	1.206 (3)
C2—C3	1.501 (4)	C12—O1	1.339 (3)
C2—C14	1.504 (4)	C13—H13A	0.9600
C3—C4	1.535 (4)	C13—H13B	0.9600
C3—H3A	0.9700	C13—H13C	0.9600
C3—H3B	0.9700	C14—H14A	0.9600
C4—C5	1.503 (4)	C14—H14B	0.9600
C4—H4A	0.9700	C14—H14C	0.9600
C4—H4B	0.9700	C15—N	1.455 (3)
C5—O4	1.445 (3)	C15—H15A	0.9700
C5—C6	1.478 (3)	C15—H15B	0.9700
C5—H5	0.9800	C16—N	1.473 (3)
C6—O4	1.446 (3)	C16—C17	1.487 (5)
C6—C13	1.503 (3)	C16—H16A	0.9700
C6—C7	1.523 (3)	C16—H16B	0.9700
C7—O3	1.412 (3)	C17—C18	1.526 (5)
C7—C8	1.543 (3)	C17—H17A	0.9700
C7—H7	0.9800	C17—H17B	0.9700
C8—C9	1.540 (3)	C18—C19	1.504 (4)
C8—H8A	0.9700	C18—H18A	0.9700
C8—H8B	0.9700	C18—H18B	0.9700
C9—C11	1.525 (3)	C19—N	1.473 (3)
C9—C10	1.540 (3)	C19—H19A	0.9700
C9—H9	0.9800	C19—H19B	0.9700
C10—O1	1.464 (3)	O3—H3	0.8200
O5—C1—C2	59.96 (15)	C9—C10—H10	111.2
O5—C1—C10	119.5 (2)	C15—C11—C12	110.7 (2)
C2—C1—C10	125.8 (2)	C15—C11—C9	116.62 (19)
O5—C1—H1	113.7	C12—C11—C9	102.5 (2)
C2—C1—H1	113.7	C15—C11—H11	108.9
C10—C1—H1	113.7	C12—C11—H11	108.9
O5—C2—C1	58.87 (15)	C9—C11—H11	108.9
O5—C2—C3	114.3 (2)	O2—C12—O1	121.1 (3)
C1—C2—C3	115.4 (2)	O2—C12—C11	128.2 (3)
O5—C2—C14	113.4 (2)	O1—C12—C11	110.7 (2)
C1—C2—C14	123.6 (2)	C6—C13—H13A	109.5
C3—C2—C14	117.0 (2)	C6—C13—H13B	109.5
C2—C3—C4	113.8 (2)	H13A—C13—H13B	109.5
C2—C3—H3A	108.8	C6—C13—H13C	109.5
C4—C3—H3A	108.8	H13A—C13—H13C	109.5
C2—C3—H3B	108.8	H13B—C13—H13C	109.5
C4—C3—H3B	108.8	C2—C14—H14A	109.5
H3A—C3—H3B	107.7	C2—C14—H14B	109.5
C5—C4—C3	114.0 (2)	H14A—C14—H14B	109.5
C5—C4—H4A	108.7	C2—C14—H14C	109.5
C3—C4—H4A	108.7	H14A—C14—H14C	109.5
C5—C4—H4B	108.7	H14B—C14—H14C	109.5
C3—C4—H4B	108.7	N—C15—C11	113.8 (2)
H4A—C4—H4B	107.6	N—C15—H15A	108.8
O4—C5—C6	59.31 (14)	C11—C15—H15A	108.8
O4—C5—C4	117.1 (2)	N—C15—H15B	108.8
C6—C5—C4	124.9 (2)	C11—C15—H15B	108.8
O4—C5—H5	114.6	H15A—C15—H15B	107.7
C6—C5—H5	114.6	N—C16—C17	104.8 (3)
C4—C5—H5	114.6	N—C16—H16A	110.8
O4—C6—C5	59.20 (15)	C17—C16—H16A	110.8
O4—C6—C13	113.1 (2)	N—C16—H16B	110.8
C5—C6—C13	122.7 (2)	C17—C16—H16B	110.8
O4—C6—C7	117.0 (2)	H16A—C16—H16B	108.9
C5—C6—C7	121.7 (2)	C16—C17—C18	105.6 (3)
C13—C6—C7	111.7 (2)	C16—C17—H17A	110.6
O3—C7—C6	110.42 (18)	C18—C17—H17A	110.6
O3—C7—C8	112.11 (19)	C16—C17—H17B	110.6
C6—C7—C8	111.14 (18)	C18—C17—H17B	110.6
O3—C7—H7	107.7	H17A—C17—H17B	108.7
C6—C7—H7	107.7	C19—C18—C17	105.3 (3)
C8—C7—H7	107.7	C19—C18—H18A	110.7
C9—C8—C7	114.57 (19)	C17—C18—H18A	110.7
C9—C8—H8A	108.6	C19—C18—H18B	110.7
C7—C8—H8A	108.6	C17—C18—H18B	110.7
C9—C8—H8B	108.6	H18A—C18—H18B	108.8
C7—C8—H8B	108.6	N—C19—C18	105.2 (2)
H8A—C8—H8B	107.6	N—C19—H19A	110.7
C11—C9—C10	102.40 (17)	C18—C19—H19A	110.7
C11—C9—C8	116.8 (2)	N—C19—H19B	110.7
C10—C9—C8	115.03 (19)	C18—C19—H19B	110.7
C11—C9—H9	107.3	H19A—C19—H19B	108.8
C10—C9—H9	107.3	C15—N—C19	111.7 (2)
C8—C9—H9	107.3	C15—N—C16	113.9 (2)
O1—C10—C1	106.59 (19)	C19—N—C16	104.3 (2)
O1—C10—C9	104.76 (18)	C12—O1—C10	110.54 (19)
C1—C10—C9	111.73 (18)	C7—O3—H3	109.5
O1—C10—H10	111.2	C5—O4—C6	61.49 (14)
C1—C10—H10	111.2	C1—O5—C2	61.17 (15)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···N	0.82	2.04	2.851 (2)	172
C9—H9···O4i	0.98	2.38	3.260 (2)	149
C10—H10···O2ii	0.98	2.46	3.392 (3)	158
C19—H19B···O5iii	0.97	2.59	3.357 (3)	136

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯N	0.82	2.04	2.851 (2)	172
C9—H9⋯O4i	0.98	2.38	3.260 (2)	149
C10—H10⋯O2ii	0.98	2.46	3.392 (3)	158
C19—H19B⋯O5iii	0.97	2.59	3.357 (3)	136

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