6-Bromo-3-(dibromo­acet­yl)-2H-chromen-2-one

Chopra, D.; Venugopala, K.N.; Rao, G.K.

doi:10.1107/S1600536807060886

6-Bromo-3-(dibromoacetyl)-2H-chromen-2-one

D. Chopra, K. N. Venugopala and G. K. Rao

In the title compound, C₁₁H₅Br₃O₃, the coumarin group is planar [maximum deviation from the mean plane is 0.032 (3) Å] and makes a dihedral angle of 19.9 (3)° with the dibromoacetyl group. The crystal structure is stabilized by C—H

O hydrogen bonds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807060886/bi2256sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807060886/bi2256Isup2.hkl Contains datablock I

CCDC reference: 673063

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Key indicators

Single-crystal X-ray study
T = 290 K
Mean (C-C) = 0.012 Å
R factor = 0.068
wR factor = 0.173
Data-to-parameter ratio = 15.5

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No syntax errors found



Alert level C
PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct...          1
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         12

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Coumarins are an important class of organic compounds having vast structural diversity and useful applications in several areas of synthetic chemistry, medicinal chemistry and photochemistry (Vishnumurthy et al., 1996, 1997, 1999). The formation of [2 + 2] cycloaddition products upon irradiation (Vishnumurthy et al., 2001) of coumarin and its derivatives has demonstrated the importance of preorganization of molecules in the crystalline solid state.

In the title compound (Fig. 1), the coumarin group is planar with a maximum deviation of -0.032 (3) Å from the weighted least squares plane for atom C8. C—H···O hydrogen bonds involving H1, H7 and O3, are observed between molecules, forming bifurcated R²₂(14) and R²₂(10) dimeric units. Furthermore, H11, O1 and O2 are involved in formation of a trimeric motif R²₁(4), forming chains along the b axis (Fig. 2, Table. 1).

Related literature top

For related literature concerning coumarin derivatives, see: Vishnumurthy et al. (1996, 1997, 1999, 2001). For synthesis details, see: Venugopala et al. (2004).

Experimental top

The title compound was synthesized in accordance with the procedure reported in the literature (Venugopala et al., 2004). Single crystals were grown from a solution in glacial acetic acid.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1999) and CAMERON (Watkin et al., 1993); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top

	Fig. 1. Molecular structure of the title compound drawn with displacement ellipsoids at 50% probability for non-H atoms.
	Fig. 2. Packing diagram highlighting C—H···O hydrogen bonds.

6-Bromo-3-(dibromoacetyl)-2H-chromen-2-one top

Crystal data top

C₁₁H₅Br₃O₃	F(000) = 800
M_r = 424.85	D_x = 2.326 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 765 reflections
a = 7.999 (6) Å	θ = 1.4–25.8°
b = 6.794 (5) Å	µ = 9.96 mm⁻¹
c = 22.442 (17) Å	T = 290 K
β = 95.819 (12)°	Needle, yellow
V = 1213.4 (16) Å³	0.23 × 0.04 × 0.03 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	2443 independent reflections
Radiation source: fine-focus sealed tube	1585 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.066
ϕ and ω scans	θ_max = 26.4°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.595, T_max = 0.742	k = −8→8
8820 measured reflections	l = −27→27

Refinement top

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.173	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0977P)²] where P = (F_o² + 2F_c²)/3
2443 reflections	(Δ/σ)_max < 0.000
158 parameters	Δρ_max = 1.20 e Å⁻³
0 restraints	Δρ_min = −1.26 e Å⁻³

Crystal data top

C₁₁H₅Br₃O₃	V = 1213.4 (16) Å³
M_r = 424.85	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.999 (6) Å	µ = 9.96 mm⁻¹
b = 6.794 (5) Å	T = 290 K
c = 22.442 (17) Å	0.23 × 0.04 × 0.03 mm
β = 95.819 (12)°

Data collection top

Bruker SMART CCD diffractometer	2443 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1585 reflections with I > 2σ(I)
T_min = 0.595, T_max = 0.742	R_int = 0.066
8820 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	0 restraints
wR(F²) = 0.173	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 1.20 e Å⁻³
2443 reflections	Δρ_min = −1.26 e Å⁻³
158 parameters

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
Br1	−0.09220 (13)	1.46570 (14)	0.16134 (5)	0.0483 (3)
Br2	0.32441 (12)	0.18266 (14)	−0.04363 (5)	0.0513 (4)
Br3	−0.16865 (16)	1.03307 (18)	0.20405 (5)	0.0654 (4)
O1	0.3421 (8)	0.7006 (9)	0.1727 (3)	0.0430 (15)
O2	0.2656 (11)	0.9552 (11)	0.2223 (3)	0.075 (3)
O3	−0.0060 (8)	1.1803 (9)	0.0700 (2)	0.0438 (16)
C1	0.2423 (10)	0.5207 (12)	0.0200 (4)	0.0328 (19)
C2	0.3320 (11)	0.3498 (12)	0.0239 (4)	0.037 (2)
C3	0.4266 (11)	0.2942 (14)	0.0771 (4)	0.046 (2)
C4	0.4265 (11)	0.4105 (13)	0.1262 (4)	0.045 (2)
C5	0.3374 (11)	0.5832 (12)	0.1224 (4)	0.037 (2)
C6	0.2424 (10)	0.6429 (11)	0.0695 (4)	0.0293 (18)
C7	0.1510 (10)	0.8219 (12)	0.0713 (3)	0.0295 (18)
C8	0.1489 (10)	0.9319 (12)	0.1208 (4)	0.0304 (18)
C9	0.2510 (13)	0.8716 (13)	0.1758 (4)	0.042 (2)
C10	0.0453 (10)	1.1136 (12)	0.1172 (4)	0.0308 (18)
C11	−0.0027 (11)	1.2063 (13)	0.1754 (4)	0.037 (2)
H1	0.1811	0.5554	−0.0159	0.039*
H3	0.4889	0.1785	0.0788	0.055*
H7	0.0896	0.8649	0.0363	0.035*
H11	0.075 (12)	1.188 (13)	0.213 (4)	0.05 (3)*
H4	0.4865	0.3735	0.1621	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0425 (6)	0.0451 (6)	0.0587 (6)	0.0118 (4)	0.0125 (5)	−0.0063 (4)
Br2	0.0372 (6)	0.0460 (6)	0.0712 (7)	0.0105 (4)	0.0073 (5)	−0.0152 (5)
Br3	0.0631 (8)	0.0721 (8)	0.0660 (7)	−0.0104 (6)	0.0312 (6)	0.0105 (5)
O1	0.034 (4)	0.052 (4)	0.041 (3)	0.015 (3)	−0.007 (3)	0.003 (3)
O2	0.096 (7)	0.077 (5)	0.045 (4)	0.042 (5)	−0.030 (4)	−0.017 (4)
O3	0.055 (4)	0.047 (4)	0.030 (3)	0.015 (3)	0.005 (3)	0.001 (3)
C1	0.018 (4)	0.039 (5)	0.040 (5)	0.004 (3)	0.001 (4)	−0.001 (4)
C2	0.022 (5)	0.039 (5)	0.050 (5)	0.003 (4)	0.008 (4)	−0.005 (4)
C3	0.028 (5)	0.043 (6)	0.065 (6)	0.010 (4)	0.001 (5)	−0.004 (5)
C4	0.027 (5)	0.047 (5)	0.057 (6)	0.012 (4)	−0.009 (4)	0.008 (5)
C5	0.030 (5)	0.032 (5)	0.048 (5)	0.003 (4)	0.003 (4)	0.004 (4)
C6	0.018 (4)	0.032 (5)	0.039 (5)	0.001 (3)	0.005 (4)	0.003 (3)
C7	0.019 (4)	0.040 (5)	0.028 (4)	0.005 (3)	0.000 (3)	0.004 (3)
C8	0.022 (5)	0.035 (5)	0.033 (4)	0.002 (3)	0.001 (4)	0.005 (3)
C9	0.043 (6)	0.044 (6)	0.038 (5)	0.007 (4)	−0.005 (4)	−0.003 (4)
C10	0.024 (5)	0.035 (4)	0.033 (5)	−0.004 (3)	0.003 (4)	−0.002 (4)
C11	0.030 (5)	0.040 (5)	0.041 (5)	0.006 (4)	0.005 (4)	0.003 (4)

Geometric parameters (Å, º) top

Br1—C11	1.917 (9)	C7—C8	1.341 (11)
Br2—C2	1.890 (9)	C7—H7	0.930
Br3—C11	1.932 (9)	C3—C4	1.355 (13)
O3—C10	1.187 (10)	C3—C2	1.399 (13)
O1—C9	1.377 (10)	C3—H3	0.930
O1—C5	1.378 (10)	C8—C9	1.467 (12)
C6—C1	1.387 (11)	C8—C10	1.484 (11)
C6—C5	1.403 (12)	O2—C9	1.183 (10)
C6—C7	1.422 (11)	C10—C11	1.534 (11)
C1—C2	1.363 (11)	C11—H11	1.00 (9)
C1—H1	0.930	C4—H4	0.930
C5—C4	1.371 (12)

C9—O1—C5	124.0 (7)	O2—C9—O1	116.4 (8)
C1—C6—C5	117.5 (7)	O2—C9—C8	127.1 (9)
C1—C6—C7	125.2 (8)	O1—C9—C8	116.4 (7)
C5—C6—C7	117.4 (7)	O3—C10—C8	120.4 (7)
C2—C1—C6	120.1 (8)	O3—C10—C11	120.7 (8)
C2—C1—H1	120.0	C8—C10—C11	118.8 (7)
C6—C1—H1	120.0	C1—C2—C3	121.3 (8)
C4—C5—O1	118.3 (8)	C1—C2—Br2	119.1 (7)
C4—C5—C6	122.2 (8)	C3—C2—Br2	119.6 (6)
O1—C5—C6	119.5 (7)	C10—C11—Br1	111.0 (6)
C8—C7—C6	123.4 (7)	C10—C11—Br3	105.8 (6)
C8—C7—H7	118.3	Br1—C11—Br3	110.9 (4)
C6—C7—H7	118.3	C10—C11—H11	118 (5)
C4—C3—C2	119.4 (8)	Br1—C11—H11	116 (5)
C4—C3—H3	120.3	Br3—C11—H11	92 (5)
C2—C3—H3	120.3	C3—C4—C5	119.5 (9)
C7—C8—C9	119.2 (7)	C3—C4—H4	120.2
C7—C8—C10	118.2 (7)	C5—C4—H4	120.2
C9—C8—C10	122.6 (7)

C5—C6—C1—C2	0.1 (12)	C10—C8—C9—O1	−179.4 (8)
C7—C6—C1—C2	−178.5 (8)	C7—C8—C10—O3	−15.0 (12)
C9—O1—C5—C4	−176.2 (8)	C9—C8—C10—O3	163.7 (8)
C9—O1—C5—C6	3.8 (13)	C7—C8—C10—C11	161.5 (8)
C1—C6—C5—C4	−0.5 (13)	C9—C8—C10—C11	−19.8 (12)
C7—C6—C5—C4	178.2 (8)	C6—C1—C2—C3	−0.5 (13)
C1—C6—C5—O1	179.5 (7)	C6—C1—C2—Br2	178.2 (6)
C7—C6—C5—O1	−1.7 (12)	C4—C3—C2—C1	1.3 (14)
C1—C6—C7—C8	177.2 (8)	C4—C3—C2—Br2	−177.4 (7)
C5—C6—C7—C8	−1.5 (12)	O3—C10—C11—Br1	−16.2 (10)
C6—C7—C8—C9	2.7 (13)	C8—C10—C11—Br1	167.3 (6)
C6—C7—C8—C10	−178.6 (7)	O3—C10—C11—Br3	104.3 (8)
C5—O1—C9—O2	178.7 (9)	C8—C10—C11—Br3	−72.2 (8)
C5—O1—C9—C8	−2.5 (13)	C2—C3—C4—C5	−1.7 (15)
C7—C8—C9—O2	177.9 (11)	O1—C5—C4—C3	−178.7 (8)
C10—C8—C9—O2	−0.7 (16)	C6—C5—C4—C3	1.3 (15)
C7—C8—C9—O1	−0.8 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O3ⁱ	0.93	2.43	3.264 (9)	149
C1—H1···O3ⁱ	0.93	2.51	3.317 (10)	145
C11—H11···O1ⁱⁱ	1.00 (9)	2.59 (9)	3.519 (11)	154 (1)
C11—H11···O2ⁱⁱ	1.00 (9)	2.58 (9)	3.293 (12)	128 (1)

Symmetry codes: (i) −x, −y+2, −z; (ii) −x+1/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₅Br₃O₃
M_r	424.85
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	290
a, b, c (Å)	7.999 (6), 6.794 (5), 22.442 (17)
β (°)	95.819 (12)
V (Å³)	1213.4 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	9.96
Crystal size (mm)	0.23 × 0.04 × 0.03

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.595, 0.742
No. of measured, independent and observed [I > 2σ(I)] reflections	8820, 2443, 1585
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.068, 0.173, 1.05
No. of reflections	2443
No. of parameters	158
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.20, −1.26

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1999) and CAMERON (Watkin et al., 1993), PLATON (Spek, 2003).