organic compounds
6-Chloro-3-(2,2-dibromoacetyl)-2H-chromen-2-one
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
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.
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 .
details are summarized in Table 2Structural data
CCDC reference: 739323
https://doi.org/10.1107/S241431461700356X/hb4128sup1.cif
contains datablock I. DOI: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
Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell
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).C11H5Br2ClO3 | F(000) = 728 |
Mr = 380.42 | Dx = 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 |
Oxford Diffraction Xcalibur, Eos, Nova diffractometer | 4065 independent reflections |
Radiation source: sealed tube, Incoatec Iµs | 1989 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
Detector resolution: 8 pixels mm-1 | θmax = 33.0°, θmin = 3.2° |
ω and φ scans | h = −11→11 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | k = −10→10 |
Tmin = 0.124, Tmax = 0.571 | l = −33→33 |
19365 measured reflections |
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(Fo2) + (0.0354P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.82 | (Δ/σ)max < 0.001 |
4065 reflections | Δρmax = 0.48 e Å−3 |
174 parameters | Δρmin = −0.86 e Å−3 |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
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)* |
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) |
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) |
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
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