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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 2| February 2015| Pages 121-123

Crystal structure of 3-(2,2-di­bromo­acet­yl)-4-hy­dr­oxy-2H-chromen-2-one

aUnité de Chimie des Matériaux et de l'Environnement UR11ES25, ISSBAT, Université de Tunis-El Manar, 9, Avenue Dr. Zoheir SAFI, 1006 Tunis, Tunisia
*Correspondence e-mail: rached.benhassen@fss.rnu.tn

Edited by V. V. Chernyshev, Moscow State University, Russia (Received 27 November 2014; accepted 22 December 2014; online 3 January 2015)

The title compound, C11H6Br2O4, is a new coumarin derivative obtained from the reaction of 3-acetyl-4-hy­droxy-2H-chromen-2-one with bromine in acetic acid. The hy­droxyl group in involved in an intra­molecular O—H⋯O hydrogen bond. In the crystal, ππ inter­actions between the rings of the bicycle [inter­centroid distances = 3.498 (2) and 3.539 (2) Å] pack mol­ecules into stacks along the b axis, and weak inter­molecular C—H⋯O hydrogen bonds further link these stacks into layers parallel to the ab plane.

1. Chemical context

3-Acetyl-4-hy­droxy-2H-chromen-2-one is one of the well-known 3-substituted-4-hy­droxy­coumarins, which form a class of fused-ring heterocycles and occur widely among natural products. Several natural products with the coumarinic moiety exhibit inter­esting biological properties such as anti-oxidant and anti­bacterial (Kayser & Kolodziej, 1997[Kayser, O. & Kolodziej, H. (1997). Planta Med. 63, 508-510.]). They also possess pharmacological activities including anti-inflammatory (Mahidol et al., 2004[Ploypradith, P., Mahidol, C., Sahakitpichan, P., Wongbundit, S. & Ruchirawat, S. (2004). Angew. Chem. Int. Ed. 43, 866-868.]), anti­cancer (Wang et al., 2002[Wang, C. J., Hsieh, Y. J., Chu, C. Y., Lin, Y. L. & Tseng, T. H. (2002). Cancer Lett. 183, 163-168.]) and inhibition of platelet aggregation (Cravotto et al., 2001[Cravotto, G., Nano, G. M., Palmisano, G. & Tagliapietra, S. (2001). Tetrahedron Asymmetry, 12, 707-709.]). These derivatives are very susceptible to electrophilic substitutions (Dou et al., 1969[Dou, H. J. M., Vernin, G. & Metzger, J. (1969). J. Heterocycl. Chem. 6, 575-576.]); their reaction with bromine can give rise to several compounds used as inter­mediate products which are susceptible to inter­esting substitutions (Takase et al., 1971[Takase, K., Sasaki, K., Shimizu, K. & Nozoe, T. (1971). Bull. Chem. Soc. Jpn, 44, 2460-2464.]) in a wide range of organic syntheses. The bromination of these compounds increases their anti­convulsant activity (Dimmock et al., 2000[Dimmock, J. R., Vashishtha, S. C. & Stables, J. P. (2000). Eur. J. Med. Chem. 35, 241-248.]), which gives them pharmacological importance. Thus, as part of a study of the effects of substituents on the crystal structures of 3-acetyl-4-hy­droxy­coumarins (Traven et al., 2000[Traven, V. F., Manaev, A. V., Safronova, O. B., Chibisova, T. A., Lyssenko, K. A. & Antipin, M. Yu. (2000). Russ. J. Gen. Chem. 70, 798-808.]), the structure of 3-(2,2-di­bromo­acet­yl)-4-hy­droxy-2H-chromen-2-one, (I)[link], has been determined.

[Scheme 1]

2. Structural commentary

In the title compound (Fig. 1[link]), the hy­droxy group is involved in formation of an intra­molecular O—H⋯O hydrogen bond (Table 1[link]). In fact, the O3—H5 distance of 0.94 (7) Å has decreased from 1.02 (3) Å, observed in the starting reagent 3-acetyl-4-hy­droxy-2H-chromen-2-one (Lyssenko & Anti­pin, 2001[Lyssenko, K. A. & Antipin, M. Yu. (2001). Russ. Chem. Bull. 50, 418-431.]). The H5⋯O4 distance of 1.65 (7) Å is elongated compared with its value in the parent compound [1.45 (3) Å], and the O3—H5⋯O4 angle of 147 (6)° is significantly smaller than that found for the starting reagent [161 (2)°]. This trend has already been observed in the fluorinated compound 2-di­fluoro­acetyl-1,3-cyclo­hexa­dione (Grieco et al., 2011[Grieco, L. M., Halliday, G. A., Junk, C. P., Lustig, S. R., Marshall, W. J. & Petrov, V. A. (2011). J. Fluor. Chem. 132, 1198-1206.]), in which the O3—H5 and H5⋯O4 distances are even more affected (0.908 and 1.658 Å respectively). These observations can be easily understood from the point of view of the strong attractive effect of the halogen atoms due to their high electronegativities. All these geometrical parameters are in good agreement with the significant attractor effect of the halogen atoms, which affects the lone pairs of the oxygen atom O4, leading to a decrease of the attractor effect of O4 in the H5⋯O4 hydrogen bond and, consequently, an increase in the H5⋯O4 distance.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O3—H5⋯O4 0.94 (7) 1.65 (7) 2.489 (6) 147 (6)
C11—H11⋯O2 0.98 2.12 2.793 (7) 125
C11—H11⋯O2i 0.98 2.51 3.362 (8) 146
C2—H2⋯O2ii 0.93 2.62 3.458 (8) 151
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x-1, y, z.
[Figure 1]
Figure 1
The mol­ecular structure of (I)[link], showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Intra­molecular hydrogen bonds are shown as dashed lines.

The C—C and C—O bond lengths in (I)[link] correspond well to those observed in the parent compound, so they are not affected by the α-ketodibromation except for C10—C11 [1.523 (9) Å] which is elongated compared to the distance in the starting reagent [1.485 (2) Å; Lyssenko & Anti­pin, 2001[Lyssenko, K. A. & Antipin, M. Yu. (2001). Russ. Chem. Bull. 50, 418-431.]). This trend had previously been observed in the similar structure of 2-di­fluoro­acetyl-1,3-cyclo­hexa­dione (Grieco et al., 2011[Grieco, L. M., Halliday, G. A., Junk, C. P., Lustig, S. R., Marshall, W. J. & Petrov, V. A. (2011). J. Fluor. Chem. 132, 1198-1206.]), in which the difluoration reaction affects the C10—C11 distance [1.529 (2) Å].

3. Supra­molecular features

In the crystal structure of (I)[link], the mol­ecules are assembled in a head-to-tail overlapping manner as a result of the ππ inter­actions between the benzene and lactone rings of neighbouring mol­ecules (Table 2[link]) into stacks along the b-axis direction (Fig. 2[link]). The observed stacking arrangement can be considered as a balance between van der Waals dispersion and repulsion inter­actions, and electrostatic inter­actions between two rings of opposed polarity – the benzene ring (high electron density) and the lactone ring (low electron density) (Hunter & Sanders, 1990[Hunter, C. A. & Sanders, J. K. M. (1990). J. Am. Chem. Soc. 112, 5525-5534.]). Weak inter­molecular C—H⋯O hydrogen bonds (Table 2[link]) further link these stacks into layers parallel to the ab plane (Fig. 3[link]).

Table 2
Details of π–π inter­actions: inter­centroid distances (Å)

Cg1 and Cg2 are centroids of the C1–C6 and O1/C5–C9 rings, respectively.

Cg1⋯Cg2i 3.498 (7)
Cg1⋯Cg2ii 3.539 (7)
Symmetry codes: (i) −x, −y + 2, −z; (ii) −x, −y + 1, −z.
[Figure 2]
Figure 2
A portion of the crystal packing showing one stack of mol­ecules parallel to the b axis.
[Figure 3]
Figure 3
The crystal packing, viewed down the b axis, showing the inter­molecular C—H⋯O hydrogen bonds as thin blue lines.

4. Synthesis and crystallization

An excess amount of bromine dissolved in acetic acid was added dropwise to a solution of 3-acetyl-4-hy­droxy-2H-chromen-2-one in acetic acid (Fig. 4[link]). During the reaction, the dropwise addition was made after every disappearance of the brown colour of the bromine. The reaction mixture was maintained under stirring at 373 K until the bromine colour persisted. The resulting solution was left to crystallize at room temperature to obtain transparent crystals of a light-yellow colour. Yield: 70%; m.p. = 375 K.

[Figure 4]
Figure 4
The synthetic route for (I)[link].

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3[link]. The hy­droxy atom H5 was located from an electron density difference map and freely refined. C-bound H atoms were fixed geometrically (C—H = 0.93 or 0.98 Å) and refined as riding, with Uiso(H) set to 1.2Ueq of the parent atom.

Table 3
Experimental details

Crystal data
Chemical formula C11H6Br2O4
Mr 361.98
Crystal system, space group Monoclinic, P21/n
Temperature (K) 296
a, b, c (Å) 9.399 (4), 6.916 (3), 17.967 (7)
β (°) 97.37 (3)
V3) 1158.4 (8)
Z 4
Radiation type Mo Kα
μ (mm−1) 7.00
Crystal size (mm) 0.15 × 0.12 × 0.10
 
Data collection
Diffractometer Bruker SMART CCD area detector
Absorption correction For a sphere (WinGX; Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.])
Tmin, Tmax 0.58, 0.75
No. of measured, independent and observed [I > 2σ(I)] reflections 11685, 3234, 1094
Rint 0.089
(sin θ/λ)max−1) 0.712
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.057, 0.133, 0.96
No. of reflections 3234
No. of parameters 158
H-atom treatment H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.43, −0.48
Computer programs: SMART and SAINT (Bruker, 2001[Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 and SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), ORTEP-3 for Windows and WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]).

Supporting information


Chemical context top

3-Acetyl-4-hy­droxy-2H-chromen-2-one is one of the well-known 3-substituted-4-hy­droxy­coumarins, which form a class of fused-ring heterocycles and occur widely among natural products. Several natural products with the coumarinic moiety exhibit inter­esting biological properties such as anti-oxidant and anti­bacterial (Kayser & Kolodziej, 1997). They possess also pharmacological activities: anti-inflammatory (Mahidol et al., 2004), anti­cancer (Wang et al., 2002) and inhibition of platelet aggregation (Cravotto et al., 2001). These derivatives are very susceptible to electrophilic substitutions (Dou et al., 1969); their reaction with bromine can give rise to several compounds used as inter­mediate products susceptible to inter­esting substitutions (Takase et al., 1971) in a wide range of organic syntheses. The bromination of these compounds increases their anti­convulsant activity (Dimmock et al., 2000), which gives them pharmacological importance. Thus, as part of a study of the effects of substituents on the crystal structures of 3-acetyl-4-hy­droxy­coumarins (Traven et al., 2000), the structure of 3-(2,2-di­bromo­acetyl)-4-hy­droxy-2H-chromen-2-one, (I), has been determined.

Structural commentary top

In the title compound (Fig. 1), the hy­droxy group is involved in formation of an intra­molecular O—H···O hydrogen bond (Table 1). In fact, the O3—H5 distance of 0.94 (7) Å has decreased from 1.02 (3) Å, observed in the starting reagent 3-acetyl-4-hy­droxy-2H-chromen-2-one (Lyssenko & Anti­pin, 2001). The H5···O4 distance of 1.65 (7) Å is elongated compared with its value in the parent compound [1.45 (3) Å], and the O3—H5···O4 angle of 147 (6)° is significantly smaller than that found for the starting reagent [161 (2)°]. This trend has already been observed in the fluorinated compound 2-di­fluoro­acetyl-1,3-cyclo­hexadione (Grieco et al., 2011), in which the O3—H5 and H5···O4 distances are even more affected (0.908 and 1.658 Å respectively). These observations can be easily understood from the point of view of the strong attractive effect of the halogen atoms due to their high electronegativities. All these geometrical parameters are in good agreement with the significant attractor effect of the halogen atoms, which affects the lone pairs of the oxygen atom O4, leading to a decrease of the attractor effect of O4 in the H5···O4 hydrogen bond and, consequently, an increase in the H5···O4 distance.

The C—C and C—O bond lengths in (I) correspond well to those observed in the parent compound, so they are not affected by the α-ketodibromation except for C10—C11 [1.523 (9) Å] which is elongated as compared to that in the starting reagent [1.485 (2) Å; Lyssenko & Anti­pin, 2001). This trend had previously been observed in the similar structure of 2-di­fluoro­acetyl-1,3-cyclo­hexadione (Grieco et al., 2011), in which the difluoration reaction affects the C10—C11 distance [1.529 (2) Å].

Supra­molecular features top

In the crystal structure of (I), the molecules are assembled in a head-to-tail overlapping manner as a result of the ππ inter­actions between the benzene and lactone rings of neighbouring molecules (Table 2) into stacks along the b-axis direction (Fig. 2). The observed stacking arrangement can be considered as a balance between van der Waals dispersion and repulsion inter­actions, and electrostatic inter­actions between two rings of opposed polarity – the benzene ring (high electron density) and the lactone ring (low electron density) (Hunter & Sanders, 1990). Weak inter­molecular C—H···O hydrogen bonds (Table 2) further link these stacks into layers parallel to the ab plane (Fig. 3).

Synthesis and crystallization top

An excess amount of bromine dissolved in acetic acid was added dropwise to a solution of 3-acetyl-4-hy­droxy-2H-chromen-2-one in acetic acid (Fig. 4). During the reaction, the drop addition was made after every disappearance of the brown colour of the bromine. The reaction mixture was maintained under stirring at 373 K until the bromine colour persisted. The resulting solution was left to crystallize at room temperature to obtain transparent crystals of a light-yellow colour. Yield: 70%; m.p. = 375 K.

Refinement top

The hy­droxy atom H5 was located from an electron density difference map and freely refined. C-bound H atoms were fixed geometrically (C—H = 0.93 or 0.98 Å) and refined as riding, with Uiso(H) set to 1.2Ueq of the parent atom.

Related literature top

For related literature, see: Cravotto et al. (2001); Dimmock et al. (2000); Dou et al. (1969); Grieco et al. (2011); Hunter & Sanders (1990); Kayser & Kolodziej (1997); Lyssenko & Antipin (2001); Mahidol et al. (2004); Takase et al. (1971); Traven et al. (2000); Wang et al. (2002).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Intramolecular hydrogen bonds are shown as dashed lines.
[Figure 2] Fig. 2. A portion of the crystal packing showing one stack of molecules parallel to the b axis.
[Figure 3] Fig. 3. The crystal packing, viewed down the b axis, showing the intermolecular C—H···O hydrogen bonds as thin blue lines.
[Figure 4] Fig. 4. The synthetic route for (I).
3-(2,2-Dibromoacetyl)-4-hydroxy-2H-chromen-2-one top
Crystal data top
C11H6Br2O4Z = 4
Mr = 361.98F(000) = 696
Monoclinic, P21/nDx = 2.076 Mg m3
Hall symbol: -P 2ynMelting point: 375 K
a = 9.399 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 6.916 (3) ŵ = 7.00 mm1
c = 17.967 (7) ÅT = 296 K
β = 97.37 (3)°Needle, yellow
V = 1158.4 (8) Å30.15 × 0.12 × 0.10 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
3234 independent reflections
Radiation source: fine-focus sealed tube1094 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.089
ϕ and ω scansθmax = 30.4°, θmin = 2.3°
Absorption correction: for a sphere
(WinGX; Farrugia, 2012)
h = 1013
Tmin = 0.58, Tmax = 0.75k = 68
11685 measured reflectionsl = 2525
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.057Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133H atoms treated by a mixture of independent and constrained refinement
S = 0.96 w = 1/[σ2(Fo2) + (0.0409P)2 + 0.259P]
where P = (Fo2 + 2Fc2)/3
3234 reflections(Δ/σ)max < 0.001
158 parametersΔρmax = 0.43 e Å3
0 restraintsΔρmin = 0.48 e Å3
Crystal data top
C11H6Br2O4V = 1158.4 (8) Å3
Mr = 361.98Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.399 (4) ŵ = 7.00 mm1
b = 6.916 (3) ÅT = 296 K
c = 17.967 (7) Å0.15 × 0.12 × 0.10 mm
β = 97.37 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3234 independent reflections
Absorption correction: for a sphere
(WinGX; Farrugia, 2012)
1094 reflections with I > 2σ(I)
Tmin = 0.58, Tmax = 0.75Rint = 0.089
11685 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0570 restraints
wR(F2) = 0.133H atoms treated by a mixture of independent and constrained refinement
S = 0.96Δρmax = 0.43 e Å3
3234 reflectionsΔρmin = 0.48 e Å3
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
xyzUiso*/Ueq
Br10.56249 (8)0.89000 (12)0.15244 (5)0.0906 (3)
Br20.58984 (10)0.45607 (13)0.21230 (4)0.1029 (4)
O10.1772 (4)0.7341 (5)0.05777 (19)0.0525 (10)
O20.4010 (5)0.6891 (6)0.0136 (2)0.0637 (12)
O30.0411 (5)0.6852 (6)0.1484 (2)0.0639 (12)
O40.2923 (5)0.6171 (7)0.2042 (2)0.0782 (14)
C10.1597 (7)0.7718 (8)0.0249 (3)0.0552 (16)
H10.19410.76560.07110.066*
C20.2515 (7)0.8099 (8)0.0390 (4)0.0609 (17)
H20.34900.82670.03650.073*
C30.1981 (8)0.8233 (8)0.1075 (3)0.0590 (17)
H30.26120.85070.15040.071*
C40.0559 (7)0.7973 (8)0.1138 (3)0.0533 (16)
H40.02190.80610.16010.064*
C50.0358 (7)0.7576 (7)0.0489 (3)0.0453 (15)
C60.0123 (6)0.7421 (7)0.0202 (3)0.0426 (14)
C70.0922 (7)0.7009 (8)0.0839 (3)0.0476 (15)
C80.2351 (7)0.6807 (8)0.0762 (3)0.0448 (14)
C90.2804 (8)0.7008 (8)0.0022 (3)0.0489 (15)
C100.3352 (7)0.6382 (8)0.1427 (3)0.0576 (17)
C110.4958 (7)0.6271 (9)0.1383 (3)0.0637 (18)
H110.51170.58250.08830.076*
H50.117 (8)0.628 (9)0.180 (3)0.08 (2)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0551 (5)0.1001 (6)0.1139 (7)0.0050 (4)0.0000 (4)0.0223 (5)
Br20.1112 (8)0.1317 (8)0.0614 (5)0.0584 (6)0.0057 (4)0.0091 (4)
O10.044 (3)0.071 (3)0.042 (2)0.005 (2)0.004 (2)0.0054 (18)
O20.044 (3)0.093 (3)0.055 (3)0.010 (2)0.008 (2)0.006 (2)
O30.061 (3)0.088 (3)0.044 (3)0.006 (3)0.012 (2)0.003 (2)
O40.066 (3)0.130 (4)0.037 (2)0.005 (3)0.003 (2)0.001 (2)
C10.052 (5)0.054 (4)0.062 (4)0.001 (3)0.017 (4)0.007 (3)
C20.048 (4)0.054 (4)0.078 (5)0.003 (3)0.005 (4)0.002 (3)
C30.062 (5)0.053 (4)0.058 (4)0.002 (3)0.006 (4)0.006 (3)
C40.046 (5)0.054 (4)0.058 (4)0.000 (3)0.001 (3)0.004 (3)
C50.045 (4)0.035 (4)0.055 (4)0.001 (3)0.003 (3)0.004 (3)
C60.048 (4)0.036 (4)0.043 (4)0.003 (3)0.006 (3)0.003 (2)
C70.059 (5)0.046 (4)0.040 (4)0.008 (3)0.016 (3)0.004 (3)
C80.050 (4)0.054 (4)0.031 (3)0.001 (3)0.007 (3)0.000 (3)
C90.054 (5)0.045 (4)0.048 (4)0.005 (3)0.007 (4)0.000 (3)
C100.062 (5)0.064 (4)0.045 (4)0.005 (3)0.002 (4)0.001 (3)
C110.058 (5)0.086 (5)0.044 (4)0.011 (4)0.006 (3)0.004 (3)
Geometric parameters (Å, º) top
Br1—C111.930 (6)C2—H20.9300
Br2—C111.910 (6)C3—C41.368 (8)
O1—C51.368 (6)C3—H30.9300
O1—C91.374 (6)C4—C51.386 (7)
O2—C91.206 (7)C4—H40.9300
O3—C71.315 (6)C5—C61.379 (7)
O3—H50.94 (7)C6—C71.438 (7)
O4—C101.233 (7)C7—C81.375 (8)
C1—C21.370 (7)C8—C101.453 (7)
C1—C61.413 (8)C8—C91.454 (8)
C1—H10.9300C10—C111.523 (9)
C2—C31.391 (8)C11—H110.9800
C5—O1—C9121.8 (5)C1—C6—C7123.8 (5)
C7—O3—H5103 (4)O3—C7—C8123.5 (5)
C2—C1—C6119.7 (6)O3—C7—C6115.4 (6)
C2—C1—H1120.2C8—C7—C6121.1 (5)
C6—C1—H1120.2C7—C8—C10118.4 (5)
C1—C2—C3119.6 (6)C7—C8—C9119.1 (5)
C1—C2—H2120.2C10—C8—C9122.5 (6)
C3—C2—H2120.2O2—C9—O1114.7 (5)
C4—C3—C2122.2 (6)O2—C9—C8127.1 (6)
C4—C3—H3118.9O1—C9—C8118.2 (6)
C2—C3—H3118.9O4—C10—C8120.7 (6)
C3—C4—C5117.7 (6)O4—C10—C11118.7 (5)
C3—C4—H4121.1C8—C10—C11120.6 (6)
C5—C4—H4121.1C10—C11—Br2111.6 (4)
O1—C5—C6122.1 (5)C10—C11—Br1104.7 (4)
O1—C5—C4115.7 (5)Br2—C11—Br1112.2 (3)
C6—C5—C4122.2 (6)C10—C11—H11109.4
C5—C6—C1118.7 (5)Br2—C11—H11109.4
C5—C6—C7117.5 (6)Br1—C11—H11109.4
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H5···O40.94 (7)1.65 (7)2.489 (6)147 (6)
C11—H11···O20.982.122.793 (7)125
C11—H11···O2i0.982.513.362 (8)146
C2—H2···O2ii0.932.623.458 (8)151
Symmetry codes: (i) x+1, y+1, z; (ii) x1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H5···O40.94 (7)1.65 (7)2.489 (6)147 (6)
C11—H11···O20.982.122.793 (7)125
C11—H11···O2i0.982.513.362 (8)146
C2—H2···O2ii0.932.623.458 (8)151
Symmetry codes: (i) x+1, y+1, z; (ii) x1, y, z.
Details of ππ interactions: intercentroid distances (Å) top
Cg1 and Cg2 are centroids of the C1–C6 and O1/C5–C9 rings, respectively.
Cg1···Cg2i3.498 (7)
Cg1···Cg2ii3.539 (7)
Symmetry codes: (i) -x, -y + 2, -z; (ii) -x, -y + 1, -z.

Experimental details

Crystal data
Chemical formulaC11H6Br2O4
Mr361.98
Crystal system, space groupMonoclinic, P21/n
Temperature (K)296
a, b, c (Å)9.399 (4), 6.916 (3), 17.967 (7)
β (°) 97.37 (3)
V3)1158.4 (8)
Z4
Radiation typeMo Kα
µ (mm1)7.00
Crystal size (mm)0.15 × 0.12 × 0.10
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionFor a sphere
(WinGX; Farrugia, 2012)
Tmin, Tmax0.58, 0.75
No. of measured, independent and
observed [I > 2σ(I)] reflections
11685, 3234, 1094
Rint0.089
(sin θ/λ)max1)0.712
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.057, 0.133, 0.96
No. of reflections3234
No. of parameters158
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.43, 0.48

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012).

 

Acknowledgements

Professor A. Ben Salah is acknowledged for his contribution to the X-ray diffraction data collection at the Laboratory of Materials Science and the Environment, University of Sfax, Tunisia.

References

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Volume 71| Part 2| February 2015| Pages 121-123
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