Ethyl (2S,4R)-4-(4-bromo­phen­yl)-2-hydr­oxy-5,10-dioxo-3,4,5,10-tetra­hydro-2H-benzo[g]chromene-2-carboxyl­ate

Zhang, W.; Wang, Y.; Zhang, G.; Xu, X.

doi:10.1107/S1600536810001315

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page o388

https://doi.org/10.1107/S1600536810001315

Open

access

Ethyl (2S,4R)-4-(4-bromophenyl)-2-hydroxy-5,10-dioxo-3,4,5,10-tetrahydro-2H-benzo[g]chromene-2-carboxylate

Wei Zhang,^a Yifeng Wang,^a ^* Guangcun Zhang ^a and Xiangsheng Xu ^a

^aState Key Laboratory Breeding Base of Green Chemistry–Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: yifengwang108@gmail.com

(Received 23 December 2009; accepted 11 January 2010; online 16 January 2010)

In the crystal structure of the title compound, C₂₂H₁₇BrO₆, 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 hydroxy and bromophenyl substituents, exhibit R and S configurations, respectively. The terminal ethyl group of the –CO₂CH₂CH₃ group is disordered over two sets of sites with site-occupancy factors of 0.64 (1) and 0.36 (1). Intermolecular O—H⋯O interactions 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_r = 457.27
Monoclinic, P 2₁
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[F² > 2σ(F²)] = 0.037
wR(F²) = 0.122
S = 1.00
4549 reflections
273 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.37 e Å⁻³
Absolute structure: Flack (1983 ), 2082 Friedel pairs
Flack parameter: −0.008 (11)

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) x+1, y, z.

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 ).

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810001315/zq2026Isup2.hkl

checkCIF report

Comment top

The Michael addition to α, β-unsaturated systems is an important carbon-carbon bond-forming reaction in organic synthesis. Hydroxyquinones, quinones bearing a hydroxy group on the quinone ring, are an important class of the naturally occurring quinones with diverse biological activity. The title compound, ethyl (2S,4R)-4-(4-bromophenyl)-2-hydroxy-5,10-dioxo-3,4,5,10-tetrahydro-2H-benzo[g]chromene-2-carboxylate, was synthesized from a Michael Addition of 2-hydroxy-1,4-naphthoquinone to β,γ-unsaturated α-keto esters. The crystal structure of the title compound (Fig. 1) contains a tricyclic ring system with two chiral centers, which is consisting of a quinone ring and a tetrahydropyrane. One carbon atom of the tetrahydropyrane structure is not coplanar with the backbone, lying 0.554 (4) Å from the mean plane of the rest backbone. The terminal ethyl group of CO₂CH₂CH₃ is disordered over two sites with site occupancy factors of 0.64 (1) and 0.36 (1). Moreover, weak O-H···O and C-H···O intermolecular interactions further stabilize the crystal structure.

Related literature top

For general background, see: Rueping et al. (2008); Zhou et al. (2008). For related structures, see: Peng (2006); Nasiri et al. (2008).

Experimental top

To a solution of (E)-ethyl 4-(4-bromophenyl)-2-oxobut-3-enoate (1 mmol) and 2-hydroxy-1,4-naphthoquinone (1 mmol) in 1,4-dioxane (3 ml) was added 3-((1S)-(6-methoxyquinolin-4-yl) (8-vinylquinuclidin-2-yl)methylamino)-4- ((S)-1-phenylethylamino)cyclobut -3-ene-1,2-dione (0.025 mmol) as catalyst, and the mixture was stirred at room temperature for 12 h (monitored by TLC). Then the solvent was distilled under vacuum, and the residue was purified by flash column chromatography (silica gel, Hex/AcOEt, v/v, 3:1) giving the title compound. Single crystals were obtained by slow evaporation of an ethyl acetate solution.

Structure description top

For general background, see: Rueping et al. (2008); Zhou et al. (2008). For related structures, see: Peng (2006); Nasiri et al. (2008).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 2006); 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).

Figures top

	Fig. 1. Molecular structure of the title compound, with the atomic labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Crystal packing of the title compound showing O—H···O interactions (symmetry code i = x+1, y, z).

Ethyl (2S,4R)-4-(4-bromophenyl)-2-hydroxy-5,10-dioxo-3,4,5,10- tetrahydro-2H-benzo[g]chromene-2-carboxylate top

Crystal data top

C₂₂H₁₇BrO₆	F(000) = 464
M_r = 457.27	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0455P)² + 0.125P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.122	(Δ/σ)_max < 0.001
S = 1.00	Δρ_max = 0.30 e Å⁻³
4549 reflections	Δρ_min = −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	Absolute structure parameter: −0.008 (11)

Crystal data top

C₂₂H₁₇BrO₆	V = 1024.43 (13) Å³
M_r = 457.27	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 8.2993 (6) Å	µ = 2.04 mm⁻¹
b = 9.9445 (7) Å	T = 296 K
c = 12.4884 (10) Å	0.32 × 0.30 × 0.28 mm
β = 96.323 (2)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	4549 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2257 reflections with I > 2σ(I)
T_min = 0.520, T_max = 0.565	R_int = 0.036
9887 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.122	Δρ_max = 0.30 e Å⁻³
S = 1.00	Δρ_min = −0.37 e Å⁻³
4549 reflections	Absolute structure: Flack (1983), 2082 Friedel pairs
273 parameters	Absolute structure parameter: −0.008 (11)
3 restraints

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₂₂H₁₇BrO₆
M_r	457.27
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	296
a, b, c (Å)	8.2993 (6), 9.9445 (7), 12.4884 (10)
β (°)	96.323 (2)
V (Å³)	1024.43 (13)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.04
Crystal size (mm)	0.32 × 0.30 × 0.28

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.520, 0.565
No. of measured, independent and observed [I > 2σ(I)] reflections	9887, 4549, 2257
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.122, 1.00
No. of reflections	4549
No. of parameters	273
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.37
Absolute structure	Flack (1983), 2082 Friedel pairs
Absolute structure parameter	−0.008 (11)

Computer programs: PROCESS-AUTO (Rigaku, 2006), CrystalStructure (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

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) x+1, y, z.

Acknowledgements

We thank Professor Jian-Ming Gu, Zhejiang University, for his help.

References

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Nasiri, H., Bolte, M. & Schwalbe, H. (2008). Nat. Prod. Res. 22, 1225–1230. Web of Science CSD CrossRef PubMed CAS Google Scholar
Peng, D.-Q. (2006). Acta Cryst. E62, o4706–o4707. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (2006). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2007). CrystalStructure. Rigaku Americas Corporation, The Woodlands, Texas, USA. Google Scholar
Rueping, M., Sugiono, E. & Merino, E. (2008). Angew. Chem. Int. Ed. 47, 3046–3049. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhou, W. M., Liu, H. & Du, D. M. (2008). Org. Lett. 10, 2817–2820. Web of Science CSD CrossRef PubMed CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page o388

https://doi.org/10.1107/S1600536810001315

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Ethyl (2S,4R)-4-(4-bromo­phen­yl)-2-hydr­­oxy-5,10-dioxo-3,4,5,10-tetra­hydro-2H-benzo[g]chromene-2-carboxyl­ate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Ethyl (2S,4R)-4-(4-bromophenyl)-2-hydroxy-5,10-dioxo-3,4,5,10-tetrahydro-2H-benzo[g]chromene-2-carboxylate