2-Bromo-1,6,6-trimethyl-6,7,8,9-tetra-hydro-phenanthro[1,2-b]furan-10,11-dione.

In the title compound, C19H17BrO3, the ring skeleton is located on a crystallographic mirror plane; two C atoms of the cyclo-hexene ring are disordered over the two locations to satisfy the preferred ring conformation. In the crystal, C-H⋯O hydrogen bonds link the mol-ecules into chains along the a axis. π-π stacking inter-actions between benzo-quinone rings, with a centroid-centroid distance of 3.7225 (4) Å, are also observed, which connect the chains into a two-dimensional networkparallel to the ab plane.

Related literature

The title compound is a derivative of Tanshinone IIA, the major active component isolated from the Chinese herbal medicine danshen, which is used in the treatment of coronary heart disease (Chang et al., 1991 ▶; Wang et al., 2005 ▶), myocard­ial infarction and angina pectoris (Xue et al., 1999 ▶) and has anti­tumour activity (Ryu et al., 1997 ▶). For the structure of 1,6,6-trimethyl-6,7,8,9-tetra­hydro­phenanthro[1,2-b]furan-10,11-dione, see: Liu & Gao (2007 ▶).

Experimental

Crystal data

C19H17BrO3

M = 373.24

Monoclinic,

a = 9.6063 (12) Å

b = 7.0457 (9) Å

c = 11.9688 (15) Å

β = 96.723 (1)°

V = 804.52 (18) Å3

Z = 2

Mo Kα radiation

μ = 2.57 mm−1

T = 296 K

0.48 × 0.15 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.372, T max = 0.748

6178 measured reflections

1634 independent reflections

1177 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.087

S = 1.02

1634 reflections

144 parameters

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.41 e Å−3

Data collection: SMART (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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813011483/kp2449sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813011483/kp2449Isup2.hkl

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

C19H17BrO3	F(000) = 380
Mr = 373.24	Dx = 1.541 Mg m−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 2150 reflections
a = 9.6063 (12) Å	θ = 2.6–23.0°
b = 7.0457 (9) Å	µ = 2.57 mm−1
c = 11.9688 (15) Å	T = 296 K
β = 96.723 (1)°	Block, brown
V = 804.52 (18) Å3	0.48 × 0.15 × 0.12 mm
Z = 2

Bruker SMART CCD area-detector diffractometer	1634 independent reflections
Radiation source: fine-focus sealed tube	1177 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
phi and ω scans	θmax = 25.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −11→11
Tmin = 0.372, Tmax = 0.748	k = −8→8
6178 measured reflections	l = −14→14

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0469P)2] where P = (Fo2 + 2Fc2)/3
1634 reflections	(Δ/σ)max < 0.001
144 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.41 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	Occ. (<1)
Br1	0.50666 (4)	0.7500	−0.40805 (3)	0.0774 (2)
C1	0.9138 (3)	0.7500	0.2002 (2)	0.0392 (7)
C2	0.7711 (3)	0.7500	0.2173 (2)	0.0365 (7)
C3	0.6680 (3)	0.7500	0.1229 (2)	0.0354 (7)
C4	0.7082 (3)	0.7500	0.0134 (2)	0.0371 (7)
C5	0.8494 (3)	0.7500	−0.0014 (3)	0.0462 (8)
H5	0.8766	0.7500	−0.0734	0.055*
C6	0.9483 (3)	0.7500	0.0909 (3)	0.0471 (8)
H6	1.0425	0.7500	0.0798	0.057*
C7	0.5146 (3)	0.7500	0.1357 (3)	0.0456 (8)
C8	0.4040 (3)	0.7500	0.0286 (3)	0.0440 (8)
C9	0.4585 (3)	0.7500	−0.0783 (3)	0.0405 (8)
C10	0.5998 (3)	0.7500	−0.0809 (3)	0.0387 (7)
C11	0.3933 (3)	0.7500	−0.1926 (3)	0.0435 (8)
C12	0.5002 (4)	0.7500	−0.2540 (3)	0.0490 (8)
C13	0.2392 (4)	0.7500	−0.2319 (3)	0.0590 (10)
H13A	0.2017	0.8744	−0.2222	0.088*	0.50
H13B	0.1930	0.6601	−0.1886	0.088*	0.50
H13C	0.2244	0.7155	−0.3100	0.088*	0.50
C14	0.7287 (4)	0.7500	0.3362 (3)	0.0513 (9)
H14A	0.7133	0.6252	0.3353	0.062*	0.50
H14B	0.6436	0.8237	0.3530	0.062*	0.50
C15	0.8496 (5)	0.8191 (7)	0.4235 (4)	0.0587 (15)	0.50
H15B	0.8751	0.9509	0.4144	0.070*	0.50
H15A	0.8219	0.8036	0.4983	0.070*	0.50
C16	0.9772 (5)	0.7020 (8)	0.4095 (3)	0.058 (2)	0.50
H16A	0.9494	0.5696	0.4079	0.070*	0.50
H16B	1.0497	0.7207	0.4721	0.070*	0.50
C17	1.0334 (3)	0.7500	0.2971 (3)	0.0495 (8)
C18	1.1253 (3)	0.5741 (4)	0.2885 (2)	0.0726 (8)
H18A	1.1998	0.5740	0.3494	0.109*
H18B	1.1641	0.5760	0.2182	0.109*
H18C	1.0694	0.4619	0.2925	0.109*
O1	0.4673 (3)	0.7500	0.2239 (2)	0.0881 (10)
O2	0.2812 (3)	0.7500	0.0408 (2)	0.0763 (8)
O3	0.6299 (2)	0.7500	−0.18897 (17)	0.0468 (6)

	U11	U22	U33	U12	U13	U23
Br1	0.0776 (4)	0.1056 (4)	0.0470 (3)	0.000	−0.0020 (2)	0.000
C1	0.0356 (18)	0.0377 (18)	0.0443 (18)	0.000	0.0051 (14)	0.000
C2	0.0394 (18)	0.0273 (16)	0.0436 (18)	0.000	0.0093 (14)	0.000
C3	0.0328 (17)	0.0327 (16)	0.0422 (17)	0.000	0.0107 (14)	0.000
C4	0.0293 (17)	0.0391 (17)	0.0435 (17)	0.000	0.0072 (14)	0.000
C5	0.0348 (19)	0.063 (2)	0.0420 (18)	0.000	0.0106 (15)	0.000
C6	0.0283 (17)	0.064 (2)	0.050 (2)	0.000	0.0080 (14)	0.000
C7	0.0374 (19)	0.0464 (19)	0.0548 (19)	0.000	0.0126 (16)	0.000
C8	0.0323 (19)	0.0402 (18)	0.060 (2)	0.000	0.0093 (16)	0.000
C9	0.0304 (18)	0.0346 (17)	0.056 (2)	0.000	0.0041 (15)	0.000
C10	0.0386 (19)	0.0378 (17)	0.0401 (18)	0.000	0.0062 (14)	0.000
C11	0.0397 (19)	0.0343 (18)	0.055 (2)	0.000	−0.0023 (16)	0.000
C12	0.046 (2)	0.051 (2)	0.048 (2)	0.000	−0.0043 (17)	0.000
C13	0.045 (2)	0.047 (2)	0.080 (3)	0.000	−0.0106 (19)	0.000
C14	0.048 (2)	0.061 (2)	0.0461 (19)	0.000	0.0119 (16)	0.000
C15	0.069 (3)	0.066 (4)	0.042 (3)	0.001 (2)	0.012 (2)	−0.005 (2)
C16	0.060 (3)	0.069 (8)	0.042 (2)	−0.004 (3)	−0.008 (2)	0.006 (2)
C17	0.0395 (19)	0.059 (2)	0.049 (2)	0.000	0.0007 (15)	0.000
C18	0.0569 (17)	0.0664 (19)	0.089 (2)	0.0088 (14)	−0.0157 (14)	0.0102 (15)
O1	0.0423 (15)	0.174 (3)	0.0517 (16)	0.000	0.0206 (13)	0.000
O2	0.0311 (15)	0.124 (2)	0.0759 (18)	0.000	0.0144 (13)	0.000
O3	0.0378 (13)	0.0616 (15)	0.0409 (13)	0.000	0.0045 (10)	0.000

Br1—C12	1.852 (3)	C13—H13A	0.9600
C1—C6	1.386 (4)	C13—H13B	0.9600
C1—C2	1.410 (4)	C13—H13C	0.9600
C1—C17	1.534 (4)	C14—C15i	1.547 (5)
C2—C3	1.412 (4)	C14—C15	1.547 (5)
C2—C14	1.526 (4)	C14—H14A	0.8918
C3—C4	1.409 (4)	C14—H14B	1.0084
C3—C7	1.499 (4)	C15—C15i	0.973 (9)
C4—C5	1.388 (4)	C15—C16i	1.265 (6)
C4—C10	1.444 (4)	C15—C16	1.503 (6)
C5—C6	1.371 (4)	C15—H15B	0.9700
C5—H5	0.9300	C15—H15A	0.9700
C6—H6	0.9300	C16—C16i	0.677 (12)
C7—O1	1.197 (4)	C16—C15i	1.265 (6)
C7—C8	1.566 (5)	C16—C17	1.545 (5)
C8—O2	1.205 (4)	C16—H16A	0.9700
C8—C9	1.439 (4)	C16—H16B	0.9700
C9—C10	1.361 (4)	C17—C18i	1.532 (3)
C9—C11	1.436 (4)	C17—C18	1.532 (3)
C10—O3	1.358 (3)	C17—C16i	1.545 (5)
C11—C12	1.331 (5)	C18—H18A	0.9600
C11—C13	1.499 (4)	C18—H18B	0.9600
C12—O3	1.389 (4)	C18—H18C	0.9600
C6—C1—C2	118.7 (3)	C15—C14—H14B	105.4
C6—C1—C17	118.2 (3)	H14A—C14—H14B	111.9
C2—C1—C17	123.1 (3)	C15i—C15—C16i	83.3 (3)
C1—C2—C3	119.2 (3)	C15i—C15—C16	56.7 (3)
C1—C2—C14	120.3 (3)	C16i—C15—C16	26.6 (5)
C3—C2—C14	120.5 (3)	C15i—C15—C14	71.66 (18)
C4—C3—C2	120.0 (3)	C16i—C15—C14	122.4 (4)
C4—C3—C7	118.4 (3)	C16—C15—C14	108.0 (3)
C2—C3—C7	121.6 (3)	C15i—C15—H15B	163.3
C5—C4—C3	119.8 (3)	C16i—C15—H15B	80.6
C5—C4—C10	121.8 (3)	C16—C15—H15B	107.0
C3—C4—C10	118.4 (3)	C14—C15—H15B	113.9
C6—C5—C4	119.5 (3)	C15i—C15—H15A	83.5
C6—C5—H5	120.2	C16i—C15—H15A	118.9
C4—C5—H5	120.2	C16—C15—H15A	110.9
C5—C6—C1	122.7 (3)	C14—C15—H15A	108.8
C5—C6—H6	118.6	H15B—C15—H15A	108.2
C1—C6—H6	118.6	C16i—C16—C15i	96.7 (3)
O1—C7—C3	124.7 (3)	C16i—C16—C15	56.7 (3)
O1—C7—C8	115.5 (3)	C15i—C16—C15	40.0 (4)
C3—C7—C8	119.8 (3)	C16i—C16—C17	77.4 (2)
O2—C8—C9	124.8 (3)	C15i—C16—C17	125.7 (4)
O2—C8—C7	118.7 (3)	C15—C16—C17	110.5 (4)
C9—C8—C7	116.4 (3)	C16i—C16—H16A	164.1
C10—C9—C11	107.7 (3)	C15i—C16—H16A	67.7
C10—C9—C8	119.2 (3)	C15—C16—H16A	107.7
C11—C9—C8	133.1 (3)	C17—C16—H16A	108.5
O3—C10—C9	110.2 (3)	C16i—C16—H16B	82.2
O3—C10—C4	122.0 (3)	C15i—C16—H16B	122.2
C9—C10—C4	127.8 (3)	C15—C16—H16B	111.1
C12—C11—C9	104.3 (3)	C17—C16—H16B	110.5
C12—C11—C13	128.6 (3)	H16A—C16—H16B	108.5
C9—C11—C13	127.1 (3)	C18i—C17—C18	108.0 (3)
C11—C12—O3	112.9 (3)	C18i—C17—C1	109.60 (18)
C11—C12—Br1	131.9 (3)	C18—C17—C1	109.60 (18)
O3—C12—Br1	115.2 (2)	C18i—C17—C16i	98.3 (3)
C11—C13—H13A	109.5	C18—C17—C16i	119.9 (3)
C11—C13—H13B	109.5	C1—C17—C16i	110.6 (3)
H13A—C13—H13B	109.5	C18i—C17—C16	119.9 (3)
C11—C13—H13C	109.5	C18—C17—C16	98.3 (3)
H13A—C13—H13C	109.5	C1—C17—C16	110.6 (3)
H13B—C13—H13C	109.5	C16i—C17—C16	25.3 (4)
C2—C14—C15i	111.7 (3)	C17—C18—H18A	109.5
C2—C14—C15	111.7 (3)	C17—C18—H18B	109.5
C15i—C14—C15	36.7 (4)	H18A—C18—H18B	109.5
C2—C14—H14A	92.9	C17—C18—H18C	109.5
C15i—C14—H14A	79.0	H18A—C18—H18C	109.5
C15—C14—H14A	115.4	H18B—C18—H18C	109.5
C2—C14—H14B	119.8	C10—O3—C12	104.9 (2)
C15i—C14—H14B	126.1
C6—C1—C2—C3	0.0	C13—C11—C12—O3	180.0
C17—C1—C2—C3	180.0	C9—C11—C12—Br1	180.0
C6—C1—C2—C14	180.0	C13—C11—C12—Br1	0.0
C17—C1—C2—C14	0.0	C1—C2—C14—C15i	−19.8 (2)
C1—C2—C3—C4	0.0	C3—C2—C14—C15i	160.2 (2)
C14—C2—C3—C4	180.0	C1—C2—C14—C15	19.8 (2)
C1—C2—C3—C7	180.0	C3—C2—C14—C15	−160.2 (2)
C14—C2—C3—C7	0.0	C2—C14—C15—C15i	−97.56 (14)
C2—C3—C4—C5	0.000 (1)	C2—C14—C15—C16i	−28.5 (5)
C7—C3—C4—C5	180.0	C15i—C14—C15—C16i	69.1 (5)
C2—C3—C4—C10	180.0	C2—C14—C15—C16	−53.3 (4)
C7—C3—C4—C10	0.0	C15i—C14—C15—C16	44.3 (3)
C3—C4—C5—C6	0.000 (1)	C15i—C15—C16—C16i	180.000 (2)
C10—C4—C5—C6	180.0	C14—C15—C16—C16i	127.6 (4)
C4—C5—C6—C1	0.0	C16i—C15—C16—C15i	180.000 (1)
C2—C1—C6—C5	0.0	C14—C15—C16—C15i	−52.4 (4)
C17—C1—C6—C5	180.0	C15i—C15—C16—C17	121.6 (4)
C4—C3—C7—O1	180.0	C16i—C15—C16—C17	−58.4 (4)
C2—C3—C7—O1	0.0	C14—C15—C16—C17	69.2 (4)
C4—C3—C7—C8	0.0	C6—C1—C17—C18i	59.21 (19)
C2—C3—C7—C8	180.0	C2—C1—C17—C18i	−120.79 (19)
O1—C7—C8—O2	0.0	C6—C1—C17—C18	−59.21 (19)
C3—C7—C8—O2	180.0	C2—C1—C17—C18	120.79 (19)
O1—C7—C8—C9	180.0	C6—C1—C17—C16i	166.5 (2)
C3—C7—C8—C9	0.0	C2—C1—C17—C16i	−13.5 (2)
O2—C8—C9—C10	180.0	C6—C1—C17—C16	−166.5 (2)
C7—C8—C9—C10	0.0	C2—C1—C17—C16	13.5 (2)
O2—C8—C9—C11	0.0	C16i—C16—C17—C18i	34.1 (2)
C7—C8—C9—C11	180.0	C15i—C16—C17—C18i	123.4 (5)
C11—C9—C10—O3	0.0	C15—C16—C17—C18i	81.0 (4)
C8—C9—C10—O3	180.0	C16i—C16—C17—C18	150.55 (19)
C11—C9—C10—C4	180.0	C15i—C16—C17—C18	−120.2 (6)
C8—C9—C10—C4	0.0	C15—C16—C17—C18	−162.6 (3)
C5—C4—C10—O3	0.0	C16i—C16—C17—C1	−94.83 (11)
C3—C4—C10—O3	180.0	C15i—C16—C17—C1	−5.6 (6)
C5—C4—C10—C9	180.0	C15—C16—C17—C1	−48.0 (4)
C3—C4—C10—C9	0.0	C15i—C16—C17—C16i	89.2 (6)
C10—C9—C11—C12	0.0	C15—C16—C17—C16i	46.8 (4)
C8—C9—C11—C12	180.0	C9—C10—O3—C12	0.0
C10—C9—C11—C13	180.0	C4—C10—O3—C12	180.0
C8—C9—C11—C13	0.0	C11—C12—O3—C10	0.0
C9—C11—C12—O3	0.0	Br1—C12—O3—C10	180.0

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O2ii	0.93	2.39	3.322 (4)	177

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O2i	0.93	2.39	3.322 (4)	177

Symmetry code: (i) .