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The molecular structure of the title compound, C11H6Br2O3, contains a planar coumarin ring system which makes a dihedral angle of 18.5 (1)° with the bromo­acetyl group. The structure is stabilized by inter­molecular C—H...O hydrogen bonds and π–π aromatic stacking inter­actions, with centroid–centroid distances of 3.567 (2) (symmetry code: −x, −y, −z) and 3.642 (2) Å (−x + 1, −y, −z). A short Br...Br [3.4605 (8) Å] contact also stabilizes the crystal structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807021472/sj2309sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807021472/sj2309Isup2.hkl
Contains datablock I

CCDC reference: 651393

Key indicators

  • Single-crystal X-ray study
  • T = 2930 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.029
  • wR factor = 0.076
  • Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct... 6 PLAT431_ALERT_2_C Short Inter HL..A Contact Br2 .. Br2 .. 3.46 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 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 with vast structural diversity and find useful applications in 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, (I) (Fig. 1, Table 1), the coumarin system is planar, with maximum deviations of 0.012 (4)Å and 0.018 (3)Å for atoms C1 and C9 respectively.

The molecules are held by C—H···O intermolecular hydrogen bonds forming dimeric units. A pair of such dimers are stabilized by Br2···Br2 short contacts [d = 3.4605 Å, symmetry code: -x - 1, -y + 1, -z + 1], [Fig. 2]. Furthermore, π···π stacking interactions link Cg1..Cg2, (the centroids of the pyanone O, C4···C9 and benzene C1···C6 rings) with separations of 3.567 (2), [Symmetry code: -x, -y, -z] and 3.642 (2)Å -x + 1, -y, -z] respectively between the centroids, Fig. 2.

Related literature top

For applications and photochemical reactivity of coumarins, see: Vishnumurthy et al. (1996, 1997, 1999, 2001).

Experimental top

To a solution of compound (I) (4.7 g, 0.025 mol) in 20 ml of alcohol free chloroform, bromine (7.9 g, 0.05 mol) was added in 25 ml of chloroform, with intermittent shaking. The mixture was warmed to decompose an addition product. heated for 15 min on a water bath to expel most of the hydrogen bromide, cooled and filtered. The solid on washing with ether gave 6.98 g (81%) of almost pure product, which on crystallization from acetic acid gave colorless crystals of (I).

Refinement top

All the H atoms were located in a difference Fourier map and refined isotropically with C—H bond lengths in the range 0.89 (4)–0.94 (3) Å.

Structure description top

Coumarins are an important class of organic compounds with vast structural diversity and find useful applications in 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, (I) (Fig. 1, Table 1), the coumarin system is planar, with maximum deviations of 0.012 (4)Å and 0.018 (3)Å for atoms C1 and C9 respectively.

The molecules are held by C—H···O intermolecular hydrogen bonds forming dimeric units. A pair of such dimers are stabilized by Br2···Br2 short contacts [d = 3.4605 Å, symmetry code: -x - 1, -y + 1, -z + 1], [Fig. 2]. Furthermore, π···π stacking interactions link Cg1..Cg2, (the centroids of the pyanone O, C4···C9 and benzene C1···C6 rings) with separations of 3.567 (2), [Symmetry code: -x, -y, -z] and 3.642 (2)Å -x + 1, -y, -z] respectively between the centroids, Fig. 2.

For applications and photochemical reactivity of coumarins, see: Vishnumurthy et al. (1996, 1997, 1999, 2001).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; 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
[Figure 1] Fig. 1. The structure of (I) drawn with 50% ellipsoidal probability.
[Figure 2] Fig. 2. Packing diagram of compound (I) highlighting the C—H···O and π···π contacts. Cg1 and Cg2 are the centroids of the pyranone O1/C7 and benzene C1/C6 rings. Hydrogen bonds are drawn and ring centroids are joined by dotted lines.
3-Dibromoacetyl-2H-chromen-2-one top
Crystal data top
C11H6Br2O3Z = 2
Mr = 345.98F(000) = 332
Triclinic, P1Dx = 2.073 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.1998 (17) ÅCell parameters from 565 reflections
b = 8.969 (2) Åθ = 1.6–26.4°
c = 9.722 (2) ŵ = 7.30 mm1
α = 69.094 (5)°T = 2930 K
β = 85.974 (6)°Block, yellow
γ = 71.177 (4)°0.25 × 0.20 × 0.20 mm
V = 554.4 (2) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer
2184 independent reflections
Radiation source: fine-focus sealed tube1885 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
φ and ω scansθmax = 26.4°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 88
Tmin = 0.189, Tmax = 0.232k = 1111
5722 measured reflectionsl = 1212
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029All H-atom parameters refined
wR(F2) = 0.076 w = 1/[σ2(Fo2) + (0.0344P)2 + 0.543P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
2184 reflectionsΔρmax = 0.57 e Å3
170 parametersΔρmin = 0.88 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.027 (2)
Crystal data top
C11H6Br2O3γ = 71.177 (4)°
Mr = 345.98V = 554.4 (2) Å3
Triclinic, P1Z = 2
a = 7.1998 (17) ÅMo Kα radiation
b = 8.969 (2) ŵ = 7.30 mm1
c = 9.722 (2) ÅT = 2930 K
α = 69.094 (5)°0.25 × 0.20 × 0.20 mm
β = 85.974 (6)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2184 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1885 reflections with I > 2σ(I)
Tmin = 0.189, Tmax = 0.232Rint = 0.030
5722 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.076All H-atom parameters refined
S = 1.05Δρmax = 0.57 e Å3
2184 reflectionsΔρmin = 0.88 e Å3
170 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
xyzUiso*/Ueq
Br10.13625 (5)0.36757 (5)0.37268 (4)0.04873 (15)
Br20.32868 (6)0.45590 (5)0.37414 (4)0.05603 (16)
O10.2817 (3)0.0994 (2)0.1884 (2)0.0345 (5)
O20.1724 (4)0.0165 (3)0.3736 (2)0.0468 (6)
O30.1836 (3)0.4487 (3)0.0802 (2)0.0395 (5)
C40.1934 (4)0.0809 (4)0.0648 (3)0.0282 (6)
C10.4394 (5)0.1793 (5)0.1471 (4)0.0453 (8)
C20.3357 (5)0.0283 (5)0.2541 (4)0.0461 (9)
C30.2151 (5)0.1004 (4)0.2145 (4)0.0381 (7)
C50.2981 (4)0.0728 (4)0.0405 (3)0.0289 (6)
C60.4211 (5)0.2033 (4)0.0004 (4)0.0386 (7)
C70.0709 (4)0.2073 (4)0.0126 (3)0.0262 (6)
C80.0564 (4)0.1833 (3)0.1321 (3)0.0245 (5)
C90.1687 (4)0.0216 (3)0.2422 (3)0.0296 (6)
C100.0809 (4)0.3233 (3)0.1739 (3)0.0283 (6)
C110.0879 (5)0.3081 (4)0.3347 (3)0.0345 (7)
H10.517 (5)0.277 (4)0.164 (3)0.035 (8)*
H20.350 (6)0.018 (5)0.348 (5)0.053 (11)*
H30.157 (5)0.203 (5)0.283 (4)0.043 (10)*
H60.484 (6)0.300 (5)0.072 (4)0.054 (11)*
H70.002 (5)0.307 (5)0.078 (4)0.039 (9)*
H110.078 (5)0.200 (5)0.397 (4)0.043 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0557 (2)0.0580 (3)0.0382 (2)0.01529 (18)0.00347 (15)0.02506 (17)
Br20.0527 (3)0.0579 (3)0.0504 (2)0.00193 (18)0.01973 (17)0.02811 (19)
O10.0362 (11)0.0262 (10)0.0330 (11)0.0015 (9)0.0035 (9)0.0104 (9)
O30.0463 (13)0.0281 (11)0.0339 (11)0.0012 (10)0.0012 (10)0.0102 (9)
C100.0317 (15)0.0268 (14)0.0282 (14)0.0116 (12)0.0053 (11)0.0108 (12)
C80.0267 (14)0.0221 (13)0.0244 (13)0.0080 (11)0.0018 (10)0.0080 (11)
C40.0292 (14)0.0297 (14)0.0297 (15)0.0133 (12)0.0058 (11)0.0125 (12)
C110.0388 (17)0.0306 (16)0.0299 (15)0.0056 (13)0.0095 (12)0.0121 (13)
C70.0284 (14)0.0221 (13)0.0270 (14)0.0095 (11)0.0013 (11)0.0061 (11)
C90.0311 (15)0.0263 (14)0.0295 (15)0.0076 (12)0.0015 (11)0.0092 (12)
C50.0232 (13)0.0326 (15)0.0347 (15)0.0088 (11)0.0025 (11)0.0165 (12)
O20.0617 (16)0.0375 (12)0.0249 (12)0.0004 (11)0.0004 (10)0.0055 (9)
C30.0438 (18)0.0430 (19)0.0318 (17)0.0180 (15)0.0075 (14)0.0156 (15)
C10.0332 (17)0.056 (2)0.064 (2)0.0149 (16)0.0159 (16)0.0424 (19)
C20.050 (2)0.062 (2)0.041 (2)0.0258 (18)0.0204 (16)0.0328 (18)
C60.0262 (15)0.0370 (17)0.055 (2)0.0039 (13)0.0006 (14)0.0248 (16)
Geometric parameters (Å, º) top
Br1—C111.951 (3)C11—H110.92 (4)
Br2—C111.922 (3)C7—H70.90 (4)
O1—C51.374 (4)C9—O21.199 (4)
O1—C91.375 (3)C5—C61.384 (4)
O3—C101.212 (3)C3—C21.363 (5)
C10—C81.492 (4)C3—H30.90 (4)
C10—C111.519 (4)C1—C61.375 (5)
C8—C71.347 (4)C1—C21.387 (6)
C8—C91.470 (4)C1—H10.94 (3)
C4—C51.395 (4)C2—H20.89 (4)
C4—C31.407 (4)C6—H60.90 (4)
C4—C71.422 (4)
C5—O1—C9123.3 (2)O2—C9—O1116.4 (3)
O3—C10—C8120.2 (3)O2—C9—C8127.2 (3)
O3—C10—C11120.5 (3)O1—C9—C8116.3 (2)
C8—C10—C11119.3 (2)O1—C5—C6117.7 (3)
C7—C8—C9119.9 (2)O1—C5—C4120.7 (2)
C7—C8—C10117.6 (2)C6—C5—C4121.6 (3)
C9—C8—C10122.5 (2)C2—C3—C4120.3 (3)
C5—C4—C3118.2 (3)C2—C3—H3121 (2)
C5—C4—C7117.4 (3)C4—C3—H3118 (2)
C3—C4—C7124.5 (3)C6—C1—C2121.0 (3)
C10—C11—Br2111.9 (2)C6—C1—H1113 (2)
C10—C11—Br1105.6 (2)C2—C1—H1126 (2)
Br2—C11—Br1110.47 (15)C3—C2—C1120.3 (3)
C10—C11—H11112 (2)C3—C2—H2121 (3)
Br2—C11—H11107 (2)C1—C2—H2119 (3)
Br1—C11—H11110 (2)C1—C6—C5118.6 (3)
C8—C7—C4122.3 (3)C1—C6—H6123 (3)
C8—C7—H7118 (2)C5—C6—H6118 (3)
C4—C7—H7119 (2)
O3—C10—C8—C74.5 (4)C7—C8—C9—O11.3 (4)
C11—C10—C8—C7174.4 (3)C10—C8—C9—O1176.6 (2)
O3—C10—C8—C9173.4 (3)C9—O1—C5—C6178.2 (3)
C11—C10—C8—C97.6 (4)C9—O1—C5—C42.0 (4)
O3—C10—C11—Br221.6 (4)C3—C4—C5—O1179.6 (3)
C8—C10—C11—Br2159.5 (2)C7—C4—C5—O10.1 (4)
O3—C10—C11—Br198.7 (3)C3—C4—C5—C60.3 (4)
C8—C10—C11—Br180.3 (3)C7—C4—C5—C6180.0 (3)
C9—C8—C7—C40.4 (4)C5—C4—C3—C20.1 (5)
C10—C8—C7—C4178.4 (2)C7—C4—C3—C2179.7 (3)
C5—C4—C7—C81.0 (4)C4—C3—C2—C10.5 (5)
C3—C4—C7—C8179.3 (3)C6—C1—C2—C30.9 (5)
C5—O1—C9—O2177.7 (3)C2—C1—C6—C50.7 (5)
C5—O1—C9—C82.5 (4)O1—C5—C6—C1179.9 (3)
C7—C8—C9—O2178.9 (3)C4—C5—C6—C10.1 (5)
C10—C8—C9—O23.2 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C11—H11···O2i0.92 (4)2.46 (4)3.278 (4)148 (3)
Symmetry code: (i) x, y, z+1.

Experimental details

Crystal data
Chemical formulaC11H6Br2O3
Mr345.98
Crystal system, space groupTriclinic, P1
Temperature (K)2930
a, b, c (Å)7.1998 (17), 8.969 (2), 9.722 (2)
α, β, γ (°)69.094 (5), 85.974 (6), 71.177 (4)
V3)554.4 (2)
Z2
Radiation typeMo Kα
µ (mm1)7.30
Crystal size (mm)0.25 × 0.20 × 0.20
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.189, 0.232
No. of measured, independent and
observed [I > 2σ(I)] reflections
5722, 2184, 1885
Rint0.030
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.076, 1.05
No. of reflections2184
No. of parameters170
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.57, 0.88

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

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C11—H11···O2i0.92 (4)2.46 (4)3.278 (4)148 (3)
Symmetry code: (i) x, y, z+1.
 

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