3-(2-Bromo­acet­yl)-6-fluoro-2H-chromen-2-one

HarishKumar, H.N.; Mahapatra, S.; Venugopala, K.N.; Mahadevan, K.M.

doi:10.1107/S1600536811030960

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2264

doi:10.1107/S1600536811030960

Open

access

3-(2-Bromoacetyl)-6-fluoro-2H-chromen-2-one

H. N. HarishKumar,^a Sudarshan Mahapatra,^b ^* K. N. Venugopala ^b and Kittappa Mariswamy Mahadevan ^a

^aDepartment of Post Graduate Studies and Research in Chemistry, School of Chemical Sciences Kuvempu University, Shankaraghatta, Karnataka 577 451, India, and ^bSolid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, India
^*Correspondence e-mail: sudarshan@sscu.iisc.ernet.in

(Received 24 July 2011; accepted 1 August 2011; online 6 August 2011)

The non-H atoms of the title compound, C₁₁H₆BrFO₃, are essentially coplanar (r.m.s. deviation for all non-H atoms = 0.074 Å). In the crystal, the molecules are linked by C—H⋯O and C—H⋯Br interactions.

Related literature

For background to coumarins, see: Hooper et al.,(1982 ); Morris et al. (1971 ); Khalfan et al. (1987 ); Domagala et al. (1996 ); Eid et al. (1994 ).

Experimental

Crystal data

C₁₁H₆BrFO₃
M_r = 285.06
Monoclinic, P 2₁ /n
a = 4.0590 (5) Å
b = 11.7719 (13) Å
c = 21.608 (2) Å
β = 94.318 (10)°
V = 1029.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 3.99 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Bruker SMART CCD area-detector
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.201, T_max = 0.506
10491 measured reflections
2007 independent reflections
1438 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.065
S = 0.95
2007 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O3ⁱ	0.93	2.45	3.296 (3)	152
C7—H7⋯O2ⁱⁱ	0.93	2.52	3.425 (3)	164
C11—H11A⋯Br1ⁱⁱⁱ	0.97	2.89	3.747 (3)	148
Symmetry codes: (i) -x+1, -y+1, -z; (ii) $[-x-{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x-1, y, z.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Window (Farrugia, 1997 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811030960/bt5592sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811030960/bt5592Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811030960/bt5592Isup3.cml

checkCIF report

Comment top

Coumarine derivatives have potential application in the dye industry (Hooper et al.,1982 & Morris et al., 1971), developing LASER dyes(Khalfan et al.,1987) and pharmaceutical industry for their antiviral activity (Domagala et al.,1996) and antimicrobial activity (Eid et al., 1994). 3-Acetyl coumarins is found to be a major compound in the coumarine series and the title compound is a member of this family. The molecule forms well defined dimer via C—H···O intermolecular interaction through the center of inversion. The three dimensional packing motif in the title compound is built up of C—H···O and C—H···Br intermolecular interaction.

Related literature top

For background to coumarins, see: Hooper et al.,(1982); Morris et al. (1971); Khalfan et al. (1987); Domagala et al. (1996); Eid et al. (1994).

Experimental top

Synthesis of 3-Bromoacetyl-6-fluoro-2H-1-benzopyran-2-one: To a solution of compound 3-acetyl-6-fluoro-2H-1-benzopyran-2-one (206 mg, 1 mmol) in alcohol free chloroform (5 ml), bromine (173.8 mg, 1.1 mmol) in chloroform (2 ml) was added with intermittent shaking and warming. The mixture was heated for fifteen minutes on a water bath, cooled and filtered. The solid was washed with ether and crystallized from glacial acetic acid to yield 3-bromoacetyl-6-fluoro-2H-1-benzopyran-2-one.

Crystallization: Needle shape crsytals of 3-acetyl-6-fluoro-2H-1-benzopyran-2-one was obtained by dissolving in glacial aceic acid and warmed for few minutes in a 5 ml beaker. Then the total content was covered by paraffin film with few punches and kept for crystallization at room temperature.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Window (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

Fig. 1. View of the title compound with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.

3-(2-Bromoacetyl)-6-fluoro-2H-chromen-2-one top

Crystal data top

C₁₁H₆BrFO₃	F(000) = 560
M_r = 285.06	D_x = 1.839 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2007 reflections
a = 4.0590 (5) Å	θ = 3.3–26.0°
b = 11.7719 (13) Å	µ = 3.99 mm⁻¹
c = 21.608 (2) Å	T = 293 K
β = 94.318 (10)°	Needle, yellow
V = 1029.6 (2) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2007 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1438 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
Detector resolution: 16.0839 pixels mm^-1	θ_max = 26.0°, θ_min = 3.3°
ω scans	h = −5→4
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −14→14
T_min = 0.201, T_max = 0.506	l = −26→26
10491 measured reflections

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.065	H-atom parameters constrained
S = 0.95	w = 1/[σ²(F_o²) + (0.0335P)²] where P = (F_o² + 2F_c²)/3
2007 reflections	(Δ/σ)_max = 0.001
145 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

C₁₁H₆BrFO₃	V = 1029.6 (2) Å³
M_r = 285.06	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.0590 (5) Å	µ = 3.99 mm⁻¹
b = 11.7719 (13) Å	T = 293 K
c = 21.608 (2) Å	0.30 × 0.20 × 0.10 mm
β = 94.318 (10)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2007 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1438 reflections with I > 2σ(I)
T_min = 0.201, T_max = 0.506	R_int = 0.036
10491 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.065	H-atom parameters constrained
S = 0.95	Δρ_max = 0.21 e Å⁻³
2007 reflections	Δρ_min = −0.37 e Å⁻³
145 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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.

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

	x	y	z	U_iso*/U_eq
Br1	0.29450 (7)	0.10699 (2)	−0.07092 (1)	0.0553 (1)
F1	0.1896 (5)	0.78595 (14)	0.21546 (8)	0.0728 (7)
O1	−0.1428 (4)	0.34429 (15)	0.16976 (8)	0.0450 (6)
O2	−0.1904 (5)	0.19171 (16)	0.11181 (9)	0.0630 (8)
O3	0.3915 (5)	0.34027 (16)	−0.01840 (9)	0.0606 (8)
C1	−0.0789 (7)	0.2860 (2)	0.11695 (12)	0.0405 (9)
C2	0.1133 (6)	0.3458 (2)	0.07253 (11)	0.0320 (8)
C3	0.1926 (6)	0.4562 (2)	0.08252 (11)	0.0351 (9)
C4	0.1121 (6)	0.5154 (2)	0.13648 (11)	0.0338 (8)
C5	0.1933 (7)	0.6296 (2)	0.14854 (13)	0.0428 (10)
C6	0.1139 (7)	0.6754 (2)	0.20335 (14)	0.0478 (10)
C7	−0.0399 (7)	0.6145 (3)	0.24778 (13)	0.0531 (11)
C8	−0.1208 (7)	0.5031 (3)	0.23639 (12)	0.0487 (10)
C9	−0.0485 (6)	0.4551 (2)	0.18082 (11)	0.0372 (9)
C10	0.2260 (6)	0.2882 (2)	0.01622 (12)	0.0362 (9)
C11	0.1383 (7)	0.1654 (2)	0.00482 (12)	0.0417 (9)
H3	0.30428	0.49474	0.05289	0.0421*
H5	0.29859	0.67285	0.11987	0.0514*
H7	−0.08758	0.64873	0.28485	0.0637*
H8	−0.22291	0.46050	0.26572	0.0585*
H11A	−0.10000	0.15723	0.00318	0.0500*
H11B	0.23180	0.12039	0.03940	0.0500*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0651 (2)	0.0464 (2)	0.0556 (2)	−0.0025 (2)	0.0125 (2)	−0.0186 (2)
F1	0.1021 (14)	0.0435 (11)	0.0734 (12)	−0.0040 (10)	0.0097 (10)	−0.0273 (9)
O1	0.0634 (12)	0.0387 (11)	0.0351 (10)	−0.0073 (10)	0.0176 (9)	−0.0014 (9)
O2	0.0971 (16)	0.0386 (13)	0.0576 (13)	−0.0262 (12)	0.0342 (12)	−0.0060 (10)
O3	0.0977 (16)	0.0382 (11)	0.0506 (12)	−0.0227 (12)	0.0377 (12)	−0.0104 (10)
C1	0.0487 (17)	0.0389 (17)	0.0346 (15)	−0.0033 (14)	0.0086 (13)	0.0010 (13)
C2	0.0372 (15)	0.0297 (14)	0.0297 (14)	−0.0041 (12)	0.0070 (12)	0.0004 (11)
C3	0.0406 (15)	0.0320 (16)	0.0331 (15)	−0.0054 (12)	0.0065 (12)	0.0017 (11)
C4	0.0361 (14)	0.0329 (15)	0.0324 (14)	0.0025 (12)	0.0027 (12)	−0.0025 (12)
C5	0.0499 (17)	0.0359 (17)	0.0433 (16)	−0.0014 (13)	0.0075 (13)	−0.0040 (12)
C6	0.0550 (18)	0.0336 (17)	0.0540 (19)	0.0068 (15)	−0.0013 (16)	−0.0144 (14)
C7	0.063 (2)	0.055 (2)	0.0413 (17)	0.0138 (17)	0.0044 (15)	−0.0154 (15)
C8	0.0570 (19)	0.0529 (19)	0.0376 (16)	0.0047 (16)	0.0123 (14)	−0.0051 (14)
C9	0.0416 (16)	0.0338 (16)	0.0363 (15)	0.0039 (13)	0.0037 (13)	−0.0037 (12)
C10	0.0407 (15)	0.0321 (16)	0.0361 (15)	−0.0031 (12)	0.0053 (12)	−0.0013 (12)
C11	0.0477 (16)	0.0343 (16)	0.0446 (16)	−0.0053 (14)	0.0142 (13)	−0.0095 (12)

Geometric parameters (Å, º) top

Br1—C11	1.926 (3)	C5—C6	1.362 (4)
F1—C6	1.358 (3)	C6—C7	1.384 (4)
O1—C1	1.373 (3)	C7—C8	1.370 (5)
O1—C9	1.375 (3)	C8—C9	1.379 (4)
O2—C1	1.201 (3)	C10—C11	1.505 (3)
O3—C10	1.209 (3)	C3—H3	0.9300
C1—C2	1.462 (4)	C5—H5	0.9300
C2—C3	1.352 (3)	C7—H7	0.9300
C2—C10	1.494 (3)	C8—H8	0.9300
C3—C4	1.418 (3)	C11—H11A	0.9700
C4—C5	1.404 (3)	C11—H11B	0.9700
C4—C9	1.393 (3)

Br1···O3	2.9861 (19)	C5···O3^vi	3.404 (3)
Br1···C11ⁱ	3.747 (3)	C6···C7ⁱ	3.569 (4)
Br1···H11Aⁱ	2.8900	C7···C6^v	3.569 (4)
F1···O1ⁱⁱ	3.053 (3)	C8···C5^v	3.574 (4)
F1···C8ⁱⁱ	3.226 (4)	C8···F1^iv	3.226 (4)
F1···C9ⁱⁱ	3.259 (3)	C9···C4^v	3.541 (3)
F1···H8ⁱⁱⁱ	2.8400	C9···F1^iv	3.259 (3)
O1···F1^iv	3.053 (3)	C10···C1ⁱ	3.431 (4)
O2···C11	2.772 (3)	C10···O2ⁱ	3.230 (3)
O2···C2^v	3.411 (3)	C11···Br1^v	3.747 (3)
O2···C10^v	3.230 (3)	C11···O2	2.772 (3)
O3···C2ⁱ	3.403 (3)	C1···H7^vii	3.0600
O3···C3^vi	3.296 (3)	C1···H11A	2.8800
O3···C5^vi	3.404 (3)	C1···H11B	2.9200
O3···Br1	2.9861 (19)	C11···H11Aⁱ	3.1000
O1···H7^vii	2.7600	H3···O3	2.4300
O2···H7^vii	2.5200	H3···H5	2.5500
O2···H11B	2.5500	H3···O3^vi	2.4500
O2···H11A	2.4400	H5···H3	2.5500
O2···H11B^v	2.8500	H5···O3^vi	2.6100
O3···H3	2.4300	H7···O1ⁱⁱⁱ	2.7600
O3···H3^vi	2.4500	H7···O2ⁱⁱⁱ	2.5200
O3···H5^vi	2.6100	H7···C1ⁱⁱⁱ	3.0600
C1···C2^v	3.420 (4)	H8···F1^vii	2.8400
C1···C10^v	3.431 (4)	H11A···Br1^v	2.8900
C2···O2ⁱ	3.411 (3)	H11A···O2	2.4400
C2···O3^v	3.403 (3)	H11A···C1	2.8800
C2···C1ⁱ	3.420 (4)	H11A···C11^v	3.1000
C3···O3^vi	3.296 (3)	H11B···O2	2.5500
C4···C9ⁱ	3.541 (3)	H11B···O2ⁱ	2.8500
C5···C8ⁱ	3.574 (4)	H11B···C1	2.9200

C1—O1—C9	123.43 (19)	C4—C9—C8	122.1 (2)
O1—C1—O2	116.5 (2)	O3—C10—C2	119.5 (2)
O1—C1—C2	116.7 (2)	O3—C10—C11	121.4 (2)
O2—C1—C2	126.9 (2)	C2—C10—C11	119.1 (2)
C1—C2—C3	119.4 (2)	Br1—C11—C10	113.15 (18)
C1—C2—C10	121.8 (2)	C2—C3—H3	119.00
C3—C2—C10	118.8 (2)	C4—C3—H3	119.00
C2—C3—C4	122.5 (2)	C4—C5—H5	121.00
C3—C4—C5	123.9 (2)	C6—C5—H5	121.00
C3—C4—C9	117.6 (2)	C6—C7—H7	120.00
C5—C4—C9	118.4 (2)	C8—C7—H7	120.00
C4—C5—C6	118.2 (2)	C7—C8—H8	120.00
F1—C6—C5	118.8 (2)	C9—C8—H8	121.00
F1—C6—C7	118.0 (3)	Br1—C11—H11A	109.00
C5—C6—C7	123.2 (2)	Br1—C11—H11B	109.00
C6—C7—C8	119.1 (3)	C10—C11—H11A	109.00
C7—C8—C9	119.0 (3)	C10—C11—H11B	109.00
O1—C9—C4	120.2 (2)	H11A—C11—H11B	108.00
O1—C9—C8	117.7 (2)

C9—O1—C1—O2	−176.2 (2)	C3—C4—C5—C6	−177.3 (3)
C9—O1—C1—C2	2.9 (3)	C9—C4—C5—C6	0.7 (4)
C1—O1—C9—C4	2.0 (3)	C3—C4—C9—O1	−4.2 (3)
C1—O1—C9—C8	−178.5 (2)	C3—C4—C9—C8	176.3 (2)
O1—C1—C2—C3	−5.6 (4)	C5—C4—C9—O1	177.7 (2)
O1—C1—C2—C10	174.2 (2)	C5—C4—C9—C8	−1.8 (4)
O2—C1—C2—C3	173.4 (3)	C4—C5—C6—F1	−179.7 (2)
O2—C1—C2—C10	−6.8 (4)	C4—C5—C6—C7	0.6 (4)
C1—C2—C3—C4	3.6 (4)	F1—C6—C7—C8	179.5 (3)
C10—C2—C3—C4	−176.3 (2)	C5—C6—C7—C8	−0.8 (4)
C1—C2—C10—O3	−178.2 (2)	C6—C7—C8—C9	−0.4 (4)
C1—C2—C10—C11	0.2 (4)	C7—C8—C9—O1	−177.8 (2)
C3—C2—C10—O3	1.7 (4)	C7—C8—C9—C4	1.7 (4)
C3—C2—C10—C11	−179.9 (2)	O3—C10—C11—Br1	−3.2 (3)
C2—C3—C4—C5	179.4 (3)	C2—C10—C11—Br1	178.48 (18)
C2—C3—C4—C9	1.4 (4)

Symmetry codes: (i) x+1, y, z; (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x−1/2, y+1/2, −z+1/2; (iv) −x+1/2, y−1/2, −z+1/2; (v) x−1, y, z; (vi) −x+1, −y+1, −z; (vii) −x−1/2, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O3^vi	0.93	2.45	3.296 (3)	152
C7—H7···O2ⁱⁱⁱ	0.93	2.52	3.425 (3)	164
C11—H11A···Br1^v	0.97	2.89	3.747 (3)	148

Symmetry codes: (iii) −x−1/2, y+1/2, −z+1/2; (v) x−1, y, z; (vi) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₁H₆BrFO₃
M_r	285.06
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	4.0590 (5), 11.7719 (13), 21.608 (2)
β (°)	94.318 (10)
V (Å³)	1029.6 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.99
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.201, 0.506
No. of measured, independent and observed [I > 2σ(I)] reflections	10491, 2007, 1438
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.065, 0.95
No. of reflections	2007
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.37

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Window (Farrugia, 1997), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O3ⁱ	0.93	2.45	3.296 (3)	152
C7—H7···O2ⁱⁱ	0.93	2.52	3.425 (3)	164
C11—H11A···Br1ⁱⁱⁱ	0.97	2.89	3.747 (3)	148

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

Acknowledgements

SM thanks the CSIR, India, for providing a Research Associateship. The authors thank Professor T. N. Guru Row for scientific discussions and the data collection.

References

Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Domagala, J. M., Hagen, S. E., Lunney, E. T. & Bradly, D. (1996). Warner-Lambert Co. USA, US Patent No. 5510375, A23. Google Scholar
Eid, A. I., Ragab, F. A., El-Ansary, S. L., El-Gazayerly, S. M. & Mourad, F. E. (1994). Arch. Pharm. 327, 211–213. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Hooper, D. C., Wolfson, J. S., McHugh, G. L., Winters, M. B. & Swartz, M. N. (1982). Antimicrob. Agents Chemother. 22, 662–671. CrossRef CAS PubMed Web of Science Google Scholar
Khalfan, H., Abuknesha, R., Rond-Weaver, M., Price, R. G. & Robinson, R. (1987). Chem. Abstr. 106, 63932. Google Scholar
Morris, A. & Russell, A. D. (1971). Prog. Med. Chem. 8, 39–59. CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar