(E)-13-(2-Bromo-phen-yl)micheliolide.

The title compound, C21H23BrO3 [systematic name: (3E,3aS,6Z,9R,9aS,9bS)-3-(2-bromo-benzyl-idene)-9-hy-droxy-6,9-dimethyl-3,3a,4,5,7,8,9,9a-octa-hydro-azuleno[4,5-b]furan-2(9bH)-one] was prepared by the reaction of 1-bromo-2-iodo-benzene with micheliolide [systematic name: (3aS,R,9aS,9bS,Z)-9-hy-droxy-6,9-dimethyl-3-methyl-ene-3,3a,4,5,7,8,9,9a-octa-hydro-azuleno[4,5-b]furan-2(9bH)-one] under Heck reaction conditions. The title compound exhibits intra-molecular O-H⋯O hydrogen bonding between the hy-droxy group and the lactone ring O atom, forming a ring of graph-set motif S(6). The 2-bromo-phenyl group is trans to the lactone ring, indicating that this is the E isomer (geometry of the exocyclic C=C bond). The dihedral angle between the benzene ring of the 2-bromo-phenyl moiety and the mean plane of the lactone ring is 51.68 (7)°.

Related literature

For the biological activity of micheliolide Michael addition compounds, see: Rodriguez et al. (1976 ▶); Sethi et al. (1984 ▶); Neelakantan et al. (2009 ▶); Zhang et al. (2012 ▶). For details of the Heck chemistry, see: Han et al. (2009 ▶). For the crystal structure of micheliolide, see: Acosta et al. (1991 ▶). For the crystal structure of a similar compound, see: Penthala et al. (2013 ▶).

Experimental

Crystal data

C21H23BrO3

M = 403.30

Orthorhombic,

a = 7.1617 (1) Å

b = 13.1615 (2) Å

c = 19.2306 (3) Å

V = 1812.65 (5) Å3

Z = 4

Mo Kα radiation

μ = 2.29 mm−1

T = 90 K

0.20 × 0.20 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ▶) T min = 0.550, T max = 0.714

48139 measured reflections

4148 independent reflections

3871 reflections with I > 2σ(I)

R int = 0.047

Refinement

R[F 2 > 2σ(F 2)] = 0.025

wR(F 2) = 0.064

S = 1.04

4148 reflections

231 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.41 e Å−3

Δρmin = −0.34 e Å−3

Absolute structure: Flack parameter determined using 1569 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▶)

Absolute structure parameter: 0.032 (3)

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 2006 ▶); data reduction: DENZO-SMN (Otwinowski & Minor, 2006 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008b ▶); molecular graphics: XP in (Sheldrick, 2008b ▶); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008b ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814002177/sj5372sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814002177/sj5372Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814002177/sj5372Isup3.cml

CCDC reference:

Additional supporting information: crystallographic information; 3D view; checkCIF report

C21H23BrO3	Dx = 1.478 Mg m−3
Mr = 403.30	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 127083 reflections
a = 7.1617 (1) Å	θ = 1.0–27.5°
b = 13.1615 (2) Å	µ = 2.29 mm−1
c = 19.2306 (3) Å	T = 90 K
V = 1812.65 (5) Å3	Block, cut from needle, colourless
Z = 4	0.20 × 0.20 × 0.15 mm
F(000) = 832

Nonius KappaCCD diffractometer	4148 independent reflections
Radiation source: fine-focus sealed-tube	3871 reflections with I > 2σ(I)
Detector resolution: 9.1 pixels mm-1	Rint = 0.047
φ and ω scans at fixed χ = 55°	θmax = 27.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −9→9
Tmin = 0.550, Tmax = 0.714	k = −17→17
48139 measured reflections	l = −24→24

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.064	w = 1/[σ2(Fo2) + (0.0352P)2 + 0.4253P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
4148 reflections	Δρmax = 0.41 e Å−3
231 parameters	Δρmin = −0.34 e Å−3
0 restraints	Absolute structure: Flack parameter determined using 1569 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.032 (3)

Experimental. The crystal was mounted with polyisobutene oil on the tip of a fine glass fibre, fastened in a copper mounting pin with electrical solder. It was placed directly into the cold stream of a liquid nitrogen based cryostat.Diffraction data were collected with the crystal at 90 K, which is standard practice in this laboratory for the majority of flash-cooled crystals.

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.

	x	y	z	Uiso*/Ueq
Br1	0.79983 (4)	−0.11654 (2)	0.35920 (2)	0.03215 (9)
O1	0.7715 (3)	0.26157 (14)	0.45446 (10)	0.0248 (4)
O2	0.5251 (3)	0.34175 (14)	0.40803 (9)	0.0215 (4)
O3	0.3499 (3)	0.53339 (15)	0.43985 (11)	0.0285 (5)
H3	0.434 (6)	0.498 (3)	0.444 (2)	0.043*
C1	0.0338 (3)	0.3743 (2)	0.33548 (13)	0.0202 (5)
C2	−0.0575 (4)	0.4794 (2)	0.33076 (16)	0.0252 (6)
H2A	−0.0553	0.5046	0.2823	0.030*
H2B	−0.1887	0.4765	0.3468	0.030*
C3	0.0577 (4)	0.5486 (2)	0.37792 (14)	0.0243 (6)
H3A	0.0633	0.6184	0.3589	0.029*
H3B	0.0037	0.5512	0.4253	0.029*
C4	0.2513 (4)	0.50008 (19)	0.37900 (13)	0.0208 (5)
C5	0.2022 (3)	0.38520 (18)	0.38337 (12)	0.0185 (4)
H5	0.1602	0.3704	0.4319	0.022*
C6	0.3602 (3)	0.31433 (18)	0.36651 (14)	0.0192 (5)
H6	0.3917	0.3211	0.3161	0.023*
C7	0.3212 (4)	0.20208 (18)	0.38266 (13)	0.0198 (5)
H7	0.2314	0.1984	0.4224	0.024*
C8	0.2325 (4)	0.1511 (2)	0.31966 (14)	0.0237 (6)
H8A	0.2408	0.0764	0.3251	0.028*
H8B	0.3031	0.1702	0.2774	0.028*
C9	0.0275 (4)	0.1814 (2)	0.31045 (16)	0.0259 (6)
H9A	−0.0413	0.1538	0.3509	0.031*
H9B	−0.0193	0.1449	0.2690	0.031*
C10	−0.0321 (4)	0.2927 (2)	0.30252 (14)	0.0212 (5)
C11	0.5102 (4)	0.1654 (2)	0.40740 (13)	0.0201 (5)
C12	0.6223 (4)	0.2566 (2)	0.42595 (13)	0.0204 (5)
C13	0.5791 (4)	0.07309 (19)	0.42009 (13)	0.0210 (5)
H13	0.7092	0.0697	0.4295	0.025*
C14	−0.2025 (4)	0.3016 (2)	0.25629 (14)	0.0257 (5)
H14A	−0.2471	0.3720	0.2565	0.039*
H14B	−0.3011	0.2567	0.2738	0.039*
H14C	−0.1695	0.2817	0.2087	0.039*
C15	0.3630 (4)	0.5270 (2)	0.31404 (15)	0.0255 (6)
H15A	0.3776	0.6010	0.3111	0.038*
H15B	0.2969	0.5024	0.2727	0.038*
H15C	0.4864	0.4951	0.3165	0.038*
C16	0.4774 (4)	−0.0247 (2)	0.42131 (13)	0.0204 (5)
C17	0.5616 (4)	−0.1163 (2)	0.40254 (13)	0.0220 (5)
C18	0.4756 (4)	−0.2095 (2)	0.41364 (14)	0.0252 (6)
H18	0.5356	−0.2707	0.3999	0.030*
C19	0.3015 (5)	−0.21243 (19)	0.44500 (14)	0.0261 (6)
H19	0.2434	−0.2759	0.4542	0.031*
C20	0.2116 (4)	−0.1224 (2)	0.46308 (13)	0.0251 (5)
H20	0.0909	−0.1244	0.4835	0.030*
C21	0.2988 (4)	−0.02945 (19)	0.45117 (13)	0.0228 (5)
H21	0.2364	0.0317	0.4634	0.027*

	U11	U22	U33	U12	U13	U23
Br1	0.03169 (14)	0.02821 (14)	0.03656 (15)	0.00934 (12)	0.00802 (12)	0.00322 (13)
O1	0.0264 (10)	0.0225 (9)	0.0254 (9)	−0.0003 (8)	−0.0026 (8)	0.0020 (8)
O2	0.0249 (9)	0.0140 (8)	0.0256 (9)	−0.0014 (7)	−0.0045 (7)	0.0001 (7)
O3	0.0383 (12)	0.0152 (9)	0.0319 (11)	0.0016 (8)	−0.0109 (9)	−0.0040 (8)
C1	0.0231 (11)	0.0163 (12)	0.0212 (11)	−0.0009 (10)	0.0027 (9)	0.0025 (10)
C2	0.0257 (13)	0.0145 (12)	0.0355 (15)	0.0004 (10)	−0.0034 (11)	0.0028 (11)
C3	0.0301 (13)	0.0148 (12)	0.0281 (14)	0.0020 (10)	0.0017 (11)	0.0004 (10)
C4	0.0289 (12)	0.0112 (11)	0.0224 (13)	−0.0009 (9)	−0.0046 (10)	−0.0001 (9)
C5	0.0231 (11)	0.0120 (10)	0.0204 (10)	−0.0016 (12)	0.0008 (9)	0.0005 (9)
C6	0.0242 (11)	0.0148 (11)	0.0185 (12)	−0.0012 (9)	−0.0028 (10)	−0.0006 (10)
C7	0.0258 (12)	0.0119 (11)	0.0218 (12)	−0.0010 (10)	0.0007 (10)	−0.0009 (9)
C8	0.0304 (14)	0.0162 (12)	0.0246 (13)	0.0016 (10)	−0.0023 (11)	−0.0038 (10)
C9	0.0290 (13)	0.0172 (13)	0.0316 (14)	0.0001 (11)	−0.0044 (11)	−0.0055 (11)
C10	0.0229 (12)	0.0187 (13)	0.0221 (13)	0.0003 (10)	0.0010 (10)	0.0000 (10)
C11	0.0261 (13)	0.0175 (13)	0.0168 (12)	0.0002 (10)	0.0008 (10)	0.0004 (10)
C12	0.0254 (13)	0.0176 (12)	0.0182 (12)	−0.0011 (10)	0.0006 (10)	0.0013 (10)
C13	0.0255 (13)	0.0184 (12)	0.0191 (12)	−0.0010 (10)	0.0022 (10)	0.0006 (10)
C14	0.0236 (12)	0.0222 (13)	0.0312 (14)	−0.0014 (12)	−0.0005 (12)	−0.0016 (11)
C15	0.0262 (13)	0.0179 (13)	0.0323 (15)	−0.0013 (10)	−0.0030 (11)	0.0043 (11)
C16	0.0277 (13)	0.0157 (12)	0.0179 (12)	0.0002 (10)	−0.0028 (11)	0.0009 (10)
C17	0.0243 (12)	0.0205 (12)	0.0211 (12)	0.0033 (12)	−0.0017 (9)	0.0009 (11)
C18	0.0360 (15)	0.0148 (13)	0.0247 (14)	0.0045 (11)	−0.0032 (12)	−0.0021 (11)
C19	0.0361 (14)	0.0163 (12)	0.0259 (13)	−0.0040 (13)	−0.0051 (14)	0.0014 (10)
C20	0.0275 (12)	0.0214 (12)	0.0264 (12)	−0.0042 (13)	−0.0001 (11)	0.0025 (11)
C21	0.0279 (12)	0.0155 (12)	0.0251 (12)	0.0024 (12)	−0.0004 (13)	0.0019 (10)

Br1—C17	1.899 (3)	C8—H8B	0.9900
O1—C12	1.203 (3)	C9—C10	1.533 (4)
O2—C12	1.364 (3)	C9—H9A	0.9900
O2—C6	1.470 (3)	C9—H9B	0.9900
O3—C4	1.435 (3)	C10—C14	1.514 (4)
O3—H3	0.77 (4)	C11—C13	1.335 (4)
C1—C10	1.333 (4)	C11—C12	1.487 (4)
C1—C5	1.525 (3)	C13—C16	1.479 (4)
C1—C2	1.532 (4)	C13—H13	0.9500
C2—C3	1.527 (4)	C14—H14A	0.9800
C2—H2A	0.9900	C14—H14B	0.9800
C2—H2B	0.9900	C14—H14C	0.9800
C3—C4	1.527 (4)	C15—H15A	0.9800
C3—H3A	0.9900	C15—H15B	0.9800
C3—H3B	0.9900	C15—H15C	0.9800
C4—C15	1.525 (4)	C16—C17	1.396 (4)
C4—C5	1.555 (3)	C16—C21	1.403 (4)
C5—C6	1.502 (3)	C17—C18	1.389 (4)
C5—H5	1.0000	C18—C19	1.386 (4)
C6—C7	1.535 (3)	C18—H18	0.9500
C6—H6	1.0000	C19—C20	1.393 (4)
C7—C11	1.514 (4)	C19—H19	0.9500
C7—C8	1.524 (4)	C20—C21	1.392 (4)
C7—H7	1.0000	C20—H20	0.9500
C8—C9	1.532 (4)	C21—H21	0.9500
C8—H8A	0.9900
C12—O2—C6	110.22 (19)	C8—C9—H9A	106.9
C4—O3—H3	106 (3)	C10—C9—H9A	106.9
C10—C1—C5	130.0 (2)	C8—C9—H9B	106.9
C10—C1—C2	123.2 (2)	C10—C9—H9B	106.9
C5—C1—C2	106.8 (2)	H9A—C9—H9B	106.7
C3—C2—C1	105.8 (2)	C1—C10—C14	120.2 (2)
C3—C2—H2A	110.6	C1—C10—C9	128.6 (2)
C1—C2—H2A	110.6	C14—C10—C9	110.8 (2)
C3—C2—H2B	110.6	C13—C11—C12	119.4 (2)
C1—C2—H2B	110.6	C13—C11—C7	132.7 (2)
H2A—C2—H2B	108.7	C12—C11—C7	107.5 (2)
C4—C3—C2	104.4 (2)	O1—C12—O2	121.6 (2)
C4—C3—H3A	110.9	O1—C12—C11	129.3 (2)
C2—C3—H3A	110.9	O2—C12—C11	109.1 (2)
C4—C3—H3B	110.9	C11—C13—C16	127.8 (2)
C2—C3—H3B	110.9	C11—C13—H13	116.1
H3A—C3—H3B	108.9	C16—C13—H13	116.1
O3—C4—C15	109.8 (2)	C10—C14—H14A	109.5
O3—C4—C3	109.3 (2)	C10—C14—H14B	109.5
C15—C4—C3	111.6 (2)	H14A—C14—H14B	109.5
O3—C4—C5	111.4 (2)	C10—C14—H14C	109.5
C15—C4—C5	112.9 (2)	H14A—C14—H14C	109.5
C3—C4—C5	101.7 (2)	H14B—C14—H14C	109.5
C6—C5—C1	114.0 (2)	C4—C15—H15A	109.5
C6—C5—C4	115.0 (2)	C4—C15—H15B	109.5
C1—C5—C4	103.7 (2)	H15A—C15—H15B	109.5
C6—C5—H5	107.9	C4—C15—H15C	109.5
C1—C5—H5	107.9	H15A—C15—H15C	109.5
C4—C5—H5	107.9	H15B—C15—H15C	109.5
O2—C6—C5	109.59 (19)	C17—C16—C21	117.4 (2)
O2—C6—C7	105.82 (19)	C17—C16—C13	122.3 (2)
C5—C6—C7	114.6 (2)	C21—C16—C13	119.7 (2)
O2—C6—H6	108.9	C18—C17—C16	122.1 (2)
C5—C6—H6	108.9	C18—C17—Br1	117.7 (2)
C7—C6—H6	108.9	C16—C17—Br1	120.2 (2)
C11—C7—C8	118.8 (2)	C19—C18—C17	119.3 (3)
C11—C7—C6	102.0 (2)	C19—C18—H18	120.3
C8—C7—C6	109.8 (2)	C17—C18—H18	120.3
C11—C7—H7	108.6	C18—C19—C20	120.1 (2)
C8—C7—H7	108.6	C18—C19—H19	120.0
C6—C7—H7	108.6	C20—C19—H19	120.0
C7—C8—C9	112.1 (2)	C21—C20—C19	119.9 (2)
C7—C8—H8A	109.2	C21—C20—H20	120.0
C9—C8—H8A	109.2	C19—C20—H20	120.0
C7—C8—H8B	109.2	C20—C21—C16	121.0 (3)
C9—C8—H8B	109.2	C20—C21—H21	119.5
H8A—C8—H8B	107.9	C16—C21—H21	119.5
C8—C9—C10	121.8 (2)
C10—C1—C2—C3	178.0 (2)	C2—C1—C10—C14	1.5 (4)
C5—C1—C2—C3	−1.5 (3)	C5—C1—C10—C9	8.9 (5)
C1—C2—C3—C4	26.5 (3)	C2—C1—C10—C9	−170.6 (3)
C2—C3—C4—O3	−158.4 (2)	C8—C9—C10—C1	−39.4 (4)
C2—C3—C4—C15	80.0 (3)	C8—C9—C10—C14	147.9 (3)
C2—C3—C4—C5	−40.6 (3)	C8—C7—C11—C13	−48.2 (4)
C10—C1—C5—C6	31.2 (4)	C6—C7—C11—C13	−169.0 (3)
C2—C1—C5—C6	−149.3 (2)	C8—C7—C11—C12	138.5 (2)
C10—C1—C5—C4	157.0 (3)	C6—C7—C11—C12	17.7 (3)
C2—C1—C5—C4	−23.5 (3)	C6—O2—C12—O1	173.0 (2)
O3—C4—C5—C6	−79.2 (3)	C6—O2—C12—C11	−9.5 (3)
C15—C4—C5—C6	44.9 (3)	C13—C11—C12—O1	−3.0 (4)
C3—C4—C5—C6	164.5 (2)	C7—C11—C12—O1	171.3 (3)
O3—C4—C5—C1	155.6 (2)	C13—C11—C12—O2	179.7 (2)
C15—C4—C5—C1	−80.3 (2)	C7—C11—C12—O2	−6.0 (3)
C3—C4—C5—C1	39.3 (2)	C12—C11—C13—C16	164.5 (2)
C12—O2—C6—C5	145.0 (2)	C7—C11—C13—C16	−8.2 (5)
C12—O2—C6—C7	21.0 (3)	C11—C13—C16—C17	148.9 (3)
C1—C5—C6—O2	171.08 (19)	C11—C13—C16—C21	−40.2 (4)
C4—C5—C6—O2	51.4 (3)	C21—C16—C17—C18	−1.1 (4)
C1—C5—C6—C7	−70.1 (3)	C13—C16—C17—C18	170.0 (3)
C4—C5—C6—C7	170.2 (2)	C21—C16—C17—Br1	178.06 (18)
O2—C6—C7—C11	−22.9 (2)	C13—C16—C17—Br1	−10.8 (3)
C5—C6—C7—C11	−143.8 (2)	C16—C17—C18—C19	−0.7 (4)
O2—C6—C7—C8	−149.8 (2)	Br1—C17—C18—C19	−179.9 (2)
C5—C6—C7—C8	89.3 (3)	C17—C18—C19—C20	2.0 (4)
C11—C7—C8—C9	168.4 (2)	C18—C19—C20—C21	−1.6 (4)
C6—C7—C8—C9	−74.9 (3)	C19—C20—C21—C16	−0.3 (4)
C7—C8—C9—C10	57.4 (4)	C17—C16—C21—C20	1.6 (4)
C5—C1—C10—C14	−179.1 (2)	C13—C16—C21—C20	−169.8 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.77 (4)	2.26 (4)	2.883 (3)	139 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2	0.77 (4)	2.26 (4)	2.883 (3)	139 (4)