Ethyl (2S,4R)-4-(4-bromo-phen-yl)-2-hydr-oxy-5,10-dioxo-3,4,5,10-tetra-hydro-2H-benzo[g]chromene-2-carboxyl-ate.

In the crystal structure of the title compound, C(22)H(17)BrO(6), the quinone ring makes a dihedral angle of 81.84 (3)° with the benzene ring. The chiral C atoms, viz. the ring C atoms bearing the hydr-oxy and bromo-phenyl substituents, exhibit R and S configurations, respectively. The terminal ethyl group of the -CO(2)CH(2)CH(3) group is disordered over two sets of sites with site-occupancy factors of 0.64 (1) and 0.36 (1). Inter-molecular O-H⋯O inter-actions further stabilize the crystal packing.

Related literature

For general background to the modification of hydroxyquinone, see: Rueping et al. (2008 ▶); Zhou et al. (2008 ▶). For related structures, see: Peng (2006 ▶); Nasiri et al. (2008 ▶).

Experimental

Crystal data

C22H17BrO6

M = 457.27

Monoclinic,

a = 8.2993 (6) Å

b = 9.9445 (7) Å

c = 12.4884 (10) Å

β = 96.323 (2)°

V = 1024.43 (13) Å3

Z = 2

Mo Kα radiation

μ = 2.04 mm−1

T = 296 K

0.32 × 0.30 × 0.28 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.520, T max = 0.565

9887 measured reflections

4549 independent reflections

2257 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.122

S = 1.00

4549 reflections

273 parameters

3 restraints

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.37 e Å−3

Absolute structure: Flack (1983 ▶), 2082 Friedel pairs

Flack parameter: −0.008 (11)

Data collection: PROCESS-AUTO (Rigaku, 2006 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2007 ▶); 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 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810001315/zq2026sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810001315/zq2026Isup2.hkl

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

C22H17BrO6	F(000) = 464
Mr = 457.27	Dx = 1.482 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 6026 reflections
a = 8.2993 (6) Å	θ = 3.1–27.4°
b = 9.9445 (7) Å	µ = 2.04 mm−1
c = 12.4884 (10) Å	T = 296 K
β = 96.323 (2)°	Block, yellow
V = 1024.43 (13) Å3	0.32 × 0.30 × 0.28 mm
Z = 2

Rigaku R-AXIS RAPID diffractometer	4549 independent reflections
Radiation source: rolling anode	2257 reflections with I > 2σ(I)
graphite	Rint = 0.036
Detector resolution: 10.00 pixels mm-1	θmax = 27.4°, θmin = 3.1°
ω scans	h = −10→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −12→12
Tmin = 0.520, Tmax = 0.565	l = −16→16
9887 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.037	w = 1/[σ2(Fo2) + (0.0455P)2 + 0.125P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.122	(Δ/σ)max < 0.001
S = 1.00	Δρmax = 0.30 e Å−3
4549 reflections	Δρmin = −0.37 e Å−3
273 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
3 restraints	Extinction coefficient: 0.032 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 2082 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: −0.008 (11)

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	Occ. (<1)
Br1	0.33160 (10)	0.08140 (7)	0.99547 (5)	0.1284 (4)
O2	0.4425 (4)	0.3938 (3)	0.2686 (3)	0.0777 (8)
O3	0.5431 (3)	0.4731 (3)	0.4648 (2)	0.0672 (7)
O1	0.0040 (4)	0.4443 (3)	0.5476 (3)	0.0859 (10)
O5	0.6613 (4)	0.2659 (3)	0.5810 (3)	0.0889 (10)
C9	0.1656 (5)	0.3695 (4)	0.2984 (4)	0.0611 (10)
O4	0.7341 (3)	0.5933 (3)	0.5658 (3)	0.0775 (8)
H4	0.8167	0.5502	0.5593	0.093*
C1	0.3205 (5)	0.5027 (4)	0.6295 (3)	0.0570 (10)
H1	0.2390	0.5695	0.6443	0.068*
O6	0.7358 (5)	0.3924 (4)	0.7236 (3)	0.1036 (12)
C11	0.3827 (5)	0.4427 (4)	0.4456 (3)	0.0538 (10)
C12	0.6071 (5)	0.5058 (4)	0.5745 (4)	0.0606 (10)
C4	0.0525 (5)	0.3817 (4)	0.3718 (3)	0.0590 (10)
C2	0.2738 (5)	0.4529 (4)	0.5170 (3)	0.0531 (9)
C14	0.3196 (4)	0.3945 (4)	0.7159 (3)	0.0569 (10)
C15	0.3232 (6)	0.4341 (4)	0.8218 (4)	0.0771 (13)
H15	0.3219	0.5255	0.8375	0.093*
C13	0.4825 (4)	0.5773 (5)	0.6336 (3)	0.0615 (9)
H13A	0.4633	0.6660	0.6025	0.074*
H13B	0.5261	0.5890	0.7083	0.074*
C8	0.1163 (7)	0.3247 (5)	0.1949 (4)	0.0797 (13)
H8	0.1922	0.3135	0.1461	0.096*
C7	−0.0437 (7)	0.2971 (5)	0.1644 (4)	0.0874 (15)
H7	−0.0758	0.2688	0.0943	0.105*
C19	0.3191 (5)	0.2591 (4)	0.6952 (4)	0.0629 (11)
H19	0.3151	0.2295	0.6243	0.076*
C3	0.1041 (5)	0.4276 (4)	0.4823 (4)	0.0630 (11)
C10	0.3394 (5)	0.4014 (4)	0.3315 (4)	0.0618 (11)
C20	0.6695 (5)	0.3722 (5)	0.6254 (4)	0.0685 (11)
C5	−0.1090 (5)	0.3531 (4)	0.3391 (4)	0.0707 (11)
H5	−0.1852	0.3627	0.3879	0.085*
C6	−0.1585 (6)	0.3107 (5)	0.2360 (4)	0.0795 (14)
H6	−0.2670	0.2915	0.2148	0.095*
C16	0.3287 (6)	0.3430 (5)	0.9056 (4)	0.0887 (14)
H16	0.3334	0.3723	0.9766	0.106*
C18	0.3245 (5)	0.1658 (4)	0.7774 (4)	0.0755 (13)
H18	0.3264	0.0744	0.7616	0.091*
C17	0.3270 (6)	0.2071 (5)	0.8817 (4)	0.0789 (13)
C21A	0.8604 (17)	0.2834 (14)	0.7646 (12)	0.132 (5)	0.640 (10)
H21A	0.8698	0.2138	0.7112	0.159*	0.640 (10)
H21B	0.9665	0.3215	0.7868	0.159*	0.640 (10)
C22A	0.7845 (17)	0.2353 (15)	0.8537 (12)	0.147 (4)	0.640 (10)
H22A	0.8593	0.1800	0.8983	0.221*	0.640 (10)
H22B	0.6907	0.1833	0.8280	0.221*	0.640 (10)
H22C	0.7523	0.3101	0.8950	0.221*	0.640 (10)
C21B	0.763 (3)	0.2550 (18)	0.780 (3)	0.132 (5)	0.360 (10)
H21C	0.6731	0.2300	0.8194	0.159*	0.360 (10)
H21D	0.7829	0.1840	0.7297	0.159*	0.360 (10)
C22B	0.903 (3)	0.289 (3)	0.849 (2)	0.147 (4)	0.360 (10)
H22D	0.8842	0.2739	0.9224	0.221*	0.360 (10)
H22E	0.9294	0.3819	0.8392	0.221*	0.360 (10)
H22F	0.9924	0.2339	0.8322	0.221*	0.360 (10)

	U11	U22	U33	U12	U13	U23
Br1	0.2086 (8)	0.0939 (4)	0.0809 (4)	0.0050 (5)	0.0071 (4)	0.0256 (3)
O2	0.0728 (19)	0.096 (2)	0.068 (2)	−0.0024 (17)	0.0246 (16)	−0.0008 (16)
O3	0.0554 (17)	0.0802 (18)	0.067 (2)	−0.0018 (14)	0.0092 (14)	0.0006 (15)
O1	0.0552 (17)	0.128 (3)	0.075 (2)	0.0008 (16)	0.0111 (17)	−0.0089 (19)
O5	0.094 (2)	0.0616 (19)	0.109 (3)	0.0086 (17)	0.005 (2)	−0.0157 (18)
C9	0.063 (3)	0.062 (2)	0.057 (3)	−0.002 (2)	0.002 (2)	0.0062 (19)
O4	0.0591 (16)	0.0631 (16)	0.110 (2)	−0.0151 (15)	0.0098 (17)	0.004 (2)
C1	0.060 (2)	0.051 (2)	0.061 (3)	0.0031 (18)	0.011 (2)	−0.0041 (18)
O6	0.132 (3)	0.079 (2)	0.091 (3)	0.025 (2)	−0.027 (2)	0.006 (2)
C11	0.054 (2)	0.052 (2)	0.056 (3)	0.0022 (16)	0.006 (2)	0.0052 (17)
C12	0.055 (2)	0.058 (2)	0.067 (3)	−0.0071 (19)	0.002 (2)	−0.0010 (19)
C4	0.051 (2)	0.062 (2)	0.062 (3)	−0.0003 (18)	0.000 (2)	0.0078 (19)
C2	0.042 (2)	0.055 (2)	0.062 (3)	0.0040 (16)	0.0023 (19)	0.0026 (17)
C14	0.062 (2)	0.053 (2)	0.055 (3)	−0.0003 (19)	0.0055 (19)	−0.0066 (18)
C15	0.118 (4)	0.053 (2)	0.062 (3)	−0.006 (2)	0.016 (3)	−0.004 (2)
C13	0.063 (2)	0.0481 (18)	0.073 (3)	−0.001 (2)	0.0057 (19)	0.001 (2)
C8	0.092 (4)	0.094 (3)	0.053 (3)	−0.003 (3)	0.009 (3)	0.001 (2)
C7	0.091 (4)	0.103 (4)	0.063 (3)	−0.008 (3)	−0.013 (3)	−0.005 (3)
C19	0.071 (3)	0.058 (2)	0.060 (3)	−0.0003 (19)	0.009 (2)	−0.0053 (19)
C3	0.060 (3)	0.064 (2)	0.066 (3)	0.0035 (18)	0.010 (2)	−0.0004 (19)
C10	0.063 (3)	0.057 (2)	0.066 (3)	−0.002 (2)	0.013 (2)	0.010 (2)
C20	0.062 (3)	0.065 (3)	0.077 (3)	0.004 (2)	0.002 (2)	0.000 (2)
C5	0.062 (3)	0.077 (3)	0.073 (3)	−0.006 (2)	0.007 (2)	0.002 (2)
C6	0.077 (3)	0.082 (3)	0.076 (4)	−0.007 (2)	−0.006 (3)	0.003 (3)
C16	0.126 (4)	0.085 (3)	0.056 (3)	0.002 (3)	0.014 (3)	−0.012 (2)
C18	0.093 (4)	0.057 (3)	0.075 (3)	−0.003 (2)	0.005 (3)	−0.001 (2)
C17	0.097 (4)	0.073 (3)	0.065 (3)	0.004 (2)	0.004 (3)	−0.005 (2)
C21A	0.160 (14)	0.136 (8)	0.092 (7)	−0.003 (9)	−0.021 (10)	0.026 (7)
C22A	0.133 (10)	0.180 (12)	0.129 (9)	−0.002 (9)	0.013 (9)	0.027 (9)
C21B	0.160 (14)	0.136 (8)	0.092 (7)	−0.003 (9)	−0.021 (10)	0.026 (7)
C22B	0.133 (10)	0.180 (12)	0.129 (9)	−0.002 (9)	0.013 (9)	0.027 (9)

Br1—C17	1.889 (5)	C15—H15	0.9300
O2—C10	1.226 (5)	C13—H13A	0.9700
O3—C11	1.360 (5)	C13—H13B	0.9700
O3—C12	1.451 (5)	C8—C7	1.368 (7)
O1—C3	1.238 (5)	C8—H8	0.9300
O5—C20	1.192 (5)	C7—C6	1.384 (7)
C9—C8	1.386 (6)	C7—H7	0.9300
C9—C4	1.387 (6)	C19—C18	1.381 (6)
C9—C10	1.490 (6)	C19—H19	0.9300
O4—C12	1.380 (5)	C5—C6	1.374 (7)
O4—H4	0.8200	C5—H5	0.9300
C1—C2	1.500 (5)	C6—H6	0.9300
C1—C14	1.524 (6)	C16—C17	1.383 (6)
C1—C13	1.531 (5)	C16—H16	0.9300
C1—H1	0.9800	C18—C17	1.364 (6)
O6—C20	1.304 (5)	C18—H18	0.9300
O6—C21B	1.541 (12)	C21A—C22A	1.420 (13)
O6—C21A	1.546 (11)	C21A—H21A	0.9700
C11—C2	1.341 (6)	C21A—H21B	0.9700
C11—C10	1.489 (6)	C22A—H22A	0.9600
C12—C13	1.513 (6)	C22A—H22B	0.9600
C12—C20	1.538 (6)	C22A—H22C	0.9600
C4—C5	1.387 (6)	C21B—C22B	1.415 (14)
C4—C3	1.472 (6)	C21B—H21C	0.9700
C2—C3	1.450 (6)	C21B—H21D	0.9700
C14—C19	1.371 (5)	C22B—H22D	0.9600
C14—C15	1.377 (6)	C22B—H22E	0.9600
C15—C16	1.381 (6)	C22B—H22F	0.9600
C11—O3—C12	117.8 (3)	C14—C19—C18	121.4 (4)
C8—C9—C4	119.5 (4)	C14—C19—H19	119.3
C8—C9—C10	120.3 (4)	C18—C19—H19	119.3
C4—C9—C10	120.2 (4)	O1—C3—C2	118.7 (4)
C12—O4—H4	109.5	O1—C3—C4	120.9 (4)
C2—C1—C14	114.1 (3)	C2—C3—C4	120.5 (4)
C2—C1—C13	109.0 (3)	O2—C10—C11	121.2 (4)
C14—C1—C13	113.0 (3)	O2—C10—C9	122.1 (4)
C2—C1—H1	106.7	C11—C10—C9	116.6 (4)
C14—C1—H1	106.7	O5—C20—O6	124.8 (4)
C13—C1—H1	106.7	O5—C20—C12	125.1 (4)
C20—O6—C21B	108.5 (11)	O6—C20—C12	110.1 (4)
C20—O6—C21A	113.7 (7)	C6—C5—C4	121.2 (4)
C2—C11—O3	125.7 (4)	C6—C5—H5	119.4
C2—C11—C10	123.2 (4)	C4—C5—H5	119.4
O3—C11—C10	111.0 (3)	C5—C6—C7	118.7 (5)
O4—C12—O3	105.7 (3)	C5—C6—H6	120.7
O4—C12—C13	108.1 (3)	C7—C6—H6	120.7
O3—C12—C13	111.6 (3)	C15—C16—C17	118.6 (4)
O4—C12—C20	110.6 (3)	C15—C16—H16	120.7
O3—C12—C20	105.5 (3)	C17—C16—H16	120.7
C13—C12—C20	114.9 (4)	C17—C18—C19	120.2 (4)
C9—C4—C5	119.4 (4)	C17—C18—H18	119.9
C9—C4—C3	119.9 (4)	C19—C18—H18	119.9
C5—C4—C3	120.8 (4)	C18—C17—C16	119.9 (4)
C11—C2—C3	119.4 (4)	C18—C17—Br1	121.0 (4)
C11—C2—C1	121.6 (3)	C16—C17—Br1	119.0 (4)
C3—C2—C1	118.7 (4)	C22A—C21A—O6	99.0 (10)
C19—C14—C15	117.5 (4)	C22A—C21A—H21A	112.0
C19—C14—C1	124.0 (4)	O6—C21A—H21A	112.0
C15—C14—C1	118.5 (3)	C22A—C21A—H21B	112.0
C14—C15—C16	122.4 (4)	O6—C21A—H21B	112.0
C14—C15—H15	118.8	H21A—C21A—H21B	109.6
C16—C15—H15	118.8	C22B—C21B—O6	97.8 (16)
C12—C13—C1	113.6 (3)	C22B—C21B—H21C	112.2
C12—C13—H13A	108.8	O6—C21B—H21C	112.2
C1—C13—H13A	108.8	C22B—C21B—H21D	112.2
C12—C13—H13B	108.8	O6—C21B—H21D	112.2
C1—C13—H13B	108.8	H21C—C21B—H21D	109.8
H13A—C13—H13B	107.7	C21B—C22B—H22D	109.5
C7—C8—C9	120.1 (5)	C21B—C22B—H22E	109.5
C7—C8—H8	120.0	H22D—C22B—H22E	109.5
C9—C8—H8	120.0	C21B—C22B—H22F	109.5
C8—C7—C6	121.1 (5)	H22D—C22B—H22F	109.5
C8—C7—H7	119.4	H22E—C22B—H22F	109.5
C6—C7—H7	119.4
C12—O3—C11—C2	7.0 (5)	C9—C4—C3—O1	177.1 (4)
C12—O3—C11—C10	−175.6 (3)	C5—C4—C3—O1	−1.6 (6)
C11—O3—C12—O4	−150.5 (3)	C9—C4—C3—C2	−3.5 (5)
C11—O3—C12—C13	−33.2 (4)	C5—C4—C3—C2	177.9 (4)
C11—O3—C12—C20	92.3 (4)	C2—C11—C10—O2	179.7 (4)
C8—C9—C4—C5	−2.1 (6)	O3—C11—C10—O2	2.2 (5)
C10—C9—C4—C5	179.3 (4)	C2—C11—C10—C9	−0.5 (5)
C8—C9—C4—C3	179.2 (4)	O3—C11—C10—C9	−178.1 (3)
C10—C9—C4—C3	0.6 (5)	C8—C9—C10—O2	2.5 (6)
O3—C11—C2—C3	174.9 (3)	C4—C9—C10—O2	−178.8 (4)
C10—C11—C2—C3	−2.3 (5)	C8—C9—C10—C11	−177.3 (4)
O3—C11—C2—C1	0.8 (6)	C4—C9—C10—C11	1.4 (5)
C10—C11—C2—C1	−176.3 (3)	C21B—O6—C20—O5	−13.4 (15)
C14—C1—C2—C11	−109.5 (4)	C21A—O6—C20—O5	22.5 (9)
C13—C1—C2—C11	18.0 (5)	C21B—O6—C20—C12	167.8 (14)
C14—C1—C2—C3	76.5 (4)	C21A—O6—C20—C12	−156.2 (7)
C13—C1—C2—C3	−156.1 (3)	O4—C12—C20—O5	−115.1 (5)
C2—C1—C14—C19	16.4 (5)	O3—C12—C20—O5	−1.3 (5)
C13—C1—C14—C19	−108.9 (4)	C13—C12—C20—O5	122.1 (5)
C2—C1—C14—C15	−165.1 (4)	O4—C12—C20—O6	63.6 (5)
C13—C1—C14—C15	69.5 (5)	O3—C12—C20—O6	177.5 (4)
C19—C14—C15—C16	1.0 (7)	C13—C12—C20—O6	−59.2 (5)
C1—C14—C15—C16	−177.6 (4)	C9—C4—C5—C6	1.1 (6)
O4—C12—C13—C1	168.5 (3)	C3—C4—C5—C6	179.8 (4)
O3—C12—C13—C1	52.7 (4)	C4—C5—C6—C7	−0.2 (7)
C20—C12—C13—C1	−67.4 (4)	C8—C7—C6—C5	0.2 (8)
C2—C1—C13—C12	−44.0 (4)	C14—C15—C16—C17	−1.4 (8)
C14—C1—C13—C12	84.1 (4)	C14—C19—C18—C17	1.4 (7)
C4—C9—C8—C7	2.1 (7)	C19—C18—C17—C16	−1.8 (7)
C10—C9—C8—C7	−179.2 (4)	C19—C18—C17—Br1	179.2 (3)
C9—C8—C7—C6	−1.2 (8)	C15—C16—C17—C18	1.8 (8)
C15—C14—C19—C18	−0.9 (6)	C15—C16—C17—Br1	−179.2 (4)
C1—C14—C19—C18	177.5 (4)	C20—O6—C21A—C22A	−119.4 (11)
C11—C2—C3—O1	−176.2 (4)	C21B—O6—C21A—C22A	−31 (2)
C1—C2—C3—O1	−2.0 (5)	C20—O6—C21B—C22B	149 (2)
C11—C2—C3—C4	4.3 (5)	C21A—O6—C21B—C22B	43.5 (16)
C1—C2—C3—C4	178.5 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O1i	0.82	1.90	2.716 (4)	177

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O1i	0.82	1.90	2.716 (4)	177

Symmetry code: (i) .