6-Chloro-3-(2,2-di­bromo­acet­yl)-2H-chromen-2-one

Yarbagi, K.; Chennuru, R.; Mahapatra, S.; Venkateswara Rao, B.; Sanasi, P.D.

doi:10.1107/S241431461700356X

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 3| March 2017| x170356

https://doi.org/10.1107/S241431461700356X

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6-Chloro-3-(2,2-dibromoacetyl)-2H-chromen-2-one

Kaviraj Yarbagi,^a,^b Ramanaiah Chennuru,^c Sudarshan Mahapatra,^c ^* B. Venkateswara Rao ^b and Paul Douglas Sanasi ^b

^aDr. Reddys Laboratories Ltd, Custom Pharmaceutical Services, Bollaram Road, Miyapur, Hyderabad 500 049, India, ^bDepartment of Engineering Chemistry, Andhra University, Visakhapatnam 530 003, India, and ^cDr. Reddys Laboratories Ltd, IPDO, Bachupally, Hyderabad, 500 090, India
^*Correspondence e-mail: smahapatra@drreddys.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 2 March 2017; accepted 6 March 2017; online 10 March 2017)

In the title compound, C₁₁H₅Br₂ClO₃, the benzopyran ring system is essentially planar (r.m.s. deviation = 0.023 Å) and one of the bromine atoms is almost coplanar with it [deviation = 0.091 (1) Å]. In the crystal, inversion dimers linked by pairs of double-acceptor (C—H)₂⋯O hydrogen bonds are seen. Further C—H⋯O interactions link the dimers into (010) sheets.

Keywords: crystal structure; coumarin; hydrogen bonding.

CCDC reference: 739323

Structure description

Two polymorphic forms of 3-acetyl coumarin have been reported in the literature (Munshi et al., 2004 ; Munshi & Guru Row, 2006 ). In both cases, weak C—H⋯O hydrogen bonds are the structure-directing interactions. Halogen-substituted 3-acetyl coumarin derivatives (Chopra et al., 2006 , 2007a ,b ) have also been described.

In the title compound, the benzopyran ring system is essentially planar (r.m.s. deviation = 0.023 Å) and one of the bromine atoms is almost coplanar with it [deviation = 0.091 (1) Å] (Fig. 1). In the crystal, inversion dimers linked by pairs of double-acceptor (C—H)₂⋯O hydrogen bonds are seen (Table 1). Further C—H⋯O interactions link the dimers into (010) sheets.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O3ⁱ	0.94 (2)	2.41 (2)	3.238 (3)	147.9 (19)
C5—H5⋯O3ⁱ	0.85 (2)	2.59 (2)	3.299 (3)	142.0 (19)
C11—H11⋯O2ⁱⁱ	0.94 (2)	2.46 (2)	3.283 (4)	147.0 (17)
Symmetry codes: (i) -x+1, -y, -z; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound, with displacement ellipsoids for non-H atoms drawn at the 50% probability level.

Synthesis and crystallization

3-Acetyl-6-chloro-2H-1-benzopyran-2-one (222 mg, 1 mmol) was dissolved in chloroform (5 ml) and 4.0 ml chloroform containing 347.6 mg bromine was added to it with intermittent shaking and warming. The mixture was heated for 15 min on a water bath, cooled and filtered. The solid was washed with ether and recrystallized from glacial acetic acid solution at room temperature to yield yellow plates of the title compound.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₁H₅Br₂ClO₃
M_r	380.42
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	7.9086 (16), 6.7115 (10), 22.640 (3)
β (°)	96.744 (16)
V (Å³)	1193.4 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	7.01
Crystal size (mm)	0.51 × 0.15 × 0.09

Data collection
Diffractometer	Oxford Diffraction Xcalibur, Eos, Nova
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ )
T_min, T_max	0.124, 0.571
No. of measured, independent and observed [I > 2σ(I)] reflections	19365, 4065, 1989
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.765

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.074, 0.82
No. of reflections	4065
No. of parameters	174
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.86
Computer programs: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ), SHELXL (Sheldrick, 2008 ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 739323

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S241431461700356X/hb4128sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461700356X/hb4128Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S241431461700356X/hb4128Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: CrysAlis PRO (Oxford Diffraction, 2009; program(s) used to refine structure: SHELXL (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

6-Chloro-3-(2,2-dibromoacetyl)-2H-chromen-2-one top

Crystal data top

C₁₁H₅Br₂ClO₃	F(000) = 728
M_r = 380.42	D_x = 2.117 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.9086 (16) Å	Cell parameters from 2350 reflections
b = 6.7115 (10) Å	θ = 3.2–26.0°
c = 22.640 (3) Å	µ = 7.01 mm⁻¹
β = 96.744 (16)°	T = 293 K
V = 1193.4 (3) Å³	Plate, metallic light yellow
Z = 4	0.51 × 0.15 × 0.09 mm

Data collection top

Oxford Diffraction Xcalibur, Eos, Nova diffractometer	4065 independent reflections
Radiation source: sealed tube, Incoatec Iµs	1989 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
Detector resolution: 8 pixels mm^-1	θ_max = 33.0°, θ_min = 3.2°
ω and φ scans	h = −11→11
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −10→10
T_min = 0.124, T_max = 0.571	l = −33→33
19365 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.035	All H-atom parameters refined
wR(F²) = 0.074	w = 1/[σ²(F_o²) + (0.0354P)²] where P = (F_o² + 2F_c²)/3
S = 0.82	(Δ/σ)_max < 0.001
4065 reflections	Δρ_max = 0.48 e Å⁻³
174 parameters	Δρ_min = −0.86 e Å⁻³
0 restraints

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Br1	0.40623 (4)	−0.46632 (4)	0.16129 (2)	0.04633 (10)
Br2	0.32549 (5)	−0.02781 (5)	0.20266 (2)	0.06416 (12)
Cl1	0.82997 (11)	0.81238 (11)	−0.03885 (4)	0.0587 (2)
O1	0.8448 (2)	0.3098 (3)	0.17211 (7)	0.0434 (5)
O2	0.7652 (3)	0.0538 (3)	0.22160 (9)	0.0742 (8)
O3	0.4892 (3)	−0.1777 (2)	0.06963 (7)	0.0450 (5)
C1	0.7507 (4)	0.1378 (4)	0.17503 (12)	0.0415 (7)
C2	0.6475 (3)	0.0758 (3)	0.12046 (10)	0.0300 (6)
C3	0.6492 (3)	0.1857 (3)	0.07073 (11)	0.0312 (6)
C4	0.7432 (3)	0.3664 (3)	0.06950 (10)	0.0304 (6)
C5	0.7427 (3)	0.4869 (4)	0.01960 (12)	0.0370 (6)
C6	0.8356 (3)	0.6603 (4)	0.02339 (12)	0.0393 (7)
C7	0.9292 (4)	0.7169 (4)	0.07625 (13)	0.0470 (8)
C8	0.9309 (4)	0.5995 (4)	0.12582 (14)	0.0460 (7)
C9	0.8380 (3)	0.4255 (4)	0.12192 (11)	0.0364 (6)
C10	0.5405 (3)	−0.1082 (4)	0.11729 (11)	0.0321 (6)
C11	0.4948 (4)	−0.2029 (4)	0.17427 (11)	0.0350 (6)
H3	0.578 (3)	0.149 (3)	0.0364 (11)	0.039 (7)*
H5	0.685 (3)	0.460 (3)	−0.0136 (11)	0.037 (8)*
H7	0.992 (3)	0.830 (4)	0.0772 (10)	0.038 (7)*
H8	0.988 (3)	0.629 (3)	0.1616 (11)	0.034 (7)*
H11	0.585 (3)	−0.220 (3)	0.2045 (11)	0.044 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.05146 (19)	0.04012 (15)	0.04839 (17)	−0.00928 (13)	0.00999 (14)	0.00593 (12)
Br2	0.0737 (3)	0.0622 (2)	0.0621 (2)	0.00668 (17)	0.03098 (18)	−0.01290 (16)
Cl1	0.0587 (5)	0.0499 (4)	0.0673 (5)	−0.0148 (4)	0.0059 (4)	0.0200 (4)
O1	0.0493 (13)	0.0465 (10)	0.0314 (10)	−0.0138 (9)	−0.0086 (9)	−0.0023 (8)
O2	0.102 (2)	0.0750 (15)	0.0362 (12)	−0.0414 (14)	−0.0306 (13)	0.0174 (11)
O3	0.0661 (14)	0.0427 (10)	0.0245 (10)	−0.0197 (9)	−0.0024 (9)	−0.0030 (8)
C1	0.0472 (18)	0.0416 (15)	0.0326 (15)	−0.0095 (13)	−0.0077 (13)	−0.0001 (12)
C2	0.0347 (15)	0.0317 (13)	0.0226 (12)	−0.0016 (11)	−0.0011 (11)	−0.0021 (10)
C3	0.0323 (15)	0.0357 (13)	0.0247 (13)	−0.0040 (11)	−0.0005 (11)	−0.0051 (11)
C4	0.0294 (14)	0.0338 (13)	0.0275 (13)	−0.0029 (11)	0.0010 (11)	−0.0032 (10)
C5	0.0346 (15)	0.0396 (15)	0.0359 (15)	−0.0046 (12)	0.0007 (12)	0.0000 (12)
C6	0.0355 (17)	0.0361 (14)	0.0482 (17)	−0.0040 (12)	0.0122 (13)	0.0047 (12)
C7	0.0395 (18)	0.0386 (16)	0.062 (2)	−0.0150 (13)	0.0029 (15)	−0.0036 (14)
C8	0.0425 (19)	0.0425 (15)	0.0498 (19)	−0.0116 (13)	−0.0076 (15)	−0.0057 (14)
C9	0.0321 (15)	0.0381 (14)	0.0384 (15)	−0.0038 (11)	0.0020 (12)	−0.0024 (12)
C10	0.0348 (15)	0.0354 (13)	0.0258 (13)	−0.0017 (11)	0.0018 (11)	0.0013 (11)
C11	0.0386 (17)	0.0380 (14)	0.0278 (13)	−0.0045 (12)	0.0007 (12)	0.0022 (11)

Geometric parameters (Å, º) top

Br1—C11	1.912 (2)	C4—C5	1.389 (3)
Br2—C11	1.947 (3)	C4—C9	1.385 (3)
Cl1—C6	1.736 (3)	C5—C6	1.374 (3)
O1—C1	1.379 (3)	C5—H5	0.85 (2)
O1—C9	1.372 (3)	C6—C7	1.385 (4)
O2—C1	1.189 (3)	C7—C8	1.370 (4)
O3—C10	1.202 (3)	C7—H7	0.90 (2)
C1—C2	1.459 (3)	C8—C9	1.377 (4)
C2—C3	1.347 (3)	C8—H8	0.90 (2)
C2—C10	1.494 (3)	C10—C11	1.519 (3)
C3—C4	1.424 (3)	C11—H11	0.93 (3)
C3—H3	0.94 (2)

C9—O1—C1	122.99 (19)	C6—C7—H7	119.0 (15)
O1—C1—C2	116.7 (2)	C8—C7—C6	120.2 (3)
O2—C1—O1	116.3 (2)	C8—C7—H7	120.8 (15)
O2—C1—C2	127.0 (2)	C7—C8—C9	118.8 (3)
C1—C2—C10	122.3 (2)	C7—C8—H8	124.3 (15)
C3—C2—C1	119.5 (2)	C9—C8—H8	116.9 (15)
C3—C2—C10	118.3 (2)	O1—C9—C4	120.8 (2)
C2—C3—C4	122.6 (2)	O1—C9—C8	117.3 (2)
C2—C3—H3	119.0 (15)	C8—C9—C4	121.9 (3)
C4—C3—H3	118.1 (15)	O3—C10—C2	119.6 (2)
C5—C4—C3	124.1 (2)	O3—C10—C11	120.8 (2)
C9—C4—C3	117.3 (2)	C2—C10—C11	119.7 (2)
C9—C4—C5	118.7 (2)	Br1—C11—Br2	110.81 (14)
C4—C5—H5	122.8 (17)	Br1—C11—H11	103.7 (14)
C6—C5—C4	119.5 (2)	Br2—C11—H11	109.0 (15)
C6—C5—H5	117.7 (17)	C10—C11—Br1	112.07 (17)
C5—C6—Cl1	119.0 (2)	C10—C11—Br2	105.61 (16)
C5—C6—C7	120.9 (2)	C10—C11—H11	115.8 (16)
C7—C6—Cl1	120.0 (2)

Cl1—C6—C7—C8	178.6 (2)	C3—C2—C10—C11	−162.8 (2)
O1—C1—C2—C3	0.4 (4)	C3—C4—C5—C6	178.8 (3)
O1—C1—C2—C10	179.6 (2)	C3—C4—C9—O1	2.2 (4)
O2—C1—C2—C3	−178.0 (3)	C3—C4—C9—C8	−178.8 (3)
O2—C1—C2—C10	1.2 (5)	C4—C5—C6—Cl1	−178.5 (2)
O3—C10—C11—Br1	15.3 (3)	C4—C5—C6—C7	−0.1 (4)
O3—C10—C11—Br2	−105.4 (2)	C5—C4—C9—O1	−178.9 (2)
C1—O1—C9—C4	−4.5 (4)	C5—C4—C9—C8	0.1 (4)
C1—O1—C9—C8	176.4 (3)	C5—C6—C7—C8	0.2 (4)
C1—C2—C3—C4	−2.6 (4)	C6—C7—C8—C9	−0.1 (4)
C1—C2—C10—O3	−163.2 (3)	C7—C8—C9—O1	179.0 (3)
C1—C2—C10—C11	18.0 (4)	C7—C8—C9—C4	−0.1 (4)
C2—C3—C4—C5	−177.5 (3)	C9—O1—C1—O2	−178.3 (3)
C2—C3—C4—C9	1.4 (4)	C9—O1—C1—C2	3.2 (4)
C2—C10—C11—Br1	−165.94 (19)	C9—C4—C5—C6	0.0 (4)
C2—C10—C11—Br2	73.3 (3)	C10—C2—C3—C4	178.2 (2)
C3—C2—C10—O3	16.0 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O3ⁱ	0.94 (2)	2.41 (2)	3.238 (3)	147.9 (19)
C5—H5···O3ⁱ	0.85 (2)	2.59 (2)	3.299 (3)	142.0 (19)
C11—H11···O2ⁱⁱ	0.94 (2)	2.46 (2)	3.283 (4)	147.0 (17)

Symmetry codes: (i) −x+1, −y, −z; (ii) −x+3/2, y−1/2, −z+1/2.

Acknowledgements

The authors thank Professor T. N. Guru Row, Indian Institute of Science, Bangalore, for scientific discussions and the data collection.

References

Chopra, D., Venugopala, K. N. & Rao, G. K. (2007a). Acta Cryst. E63, o4872. Web of Science CSD CrossRef IUCr Journals Google Scholar
Chopra, D., Venugopala, K. N., Rao, G. K. & Guru Row, T. N. (2007b). Acta Cryst. E63, o2826. Web of Science CSD CrossRef IUCr Journals Google Scholar
Chopra, D., Venugopala, K. N., Jayashree, B. S. & Guru Row, T. N. (2006). Acta Cryst. E62, o2310–o2312. Web of Science CSD CrossRef IUCr Journals Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Munshi, P. & Guru Row, T. N. (2006). Cryst. Growth Des. 6, 708–718. Web of Science CSD CrossRef CAS Google Scholar
Munshi, P., Venugopala, K. N., Jayashree, B. S. & Guru Row, T. N. (2004). Cryst. Growth Des. 4, 1105–1107. Web of Science CSD CrossRef CAS Google Scholar
Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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