Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807021472/sj2309sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807021472/sj2309Isup2.hkl |
CCDC reference: 651393
Key indicators
- Single-crystal X-ray study
- T = 2930 K
- Mean (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
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).
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.
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).
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).
C11H6Br2O3 | Z = 2 |
Mr = 345.98 | F(000) = 332 |
Triclinic, P1 | Dx = 2.073 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.1998 (17) Å | Cell parameters from 565 reflections |
b = 8.969 (2) Å | θ = 1.6–26.4° |
c = 9.722 (2) Å | µ = 7.30 mm−1 |
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 |
Bruker SMART CCD area-detector diffractometer | 2184 independent reflections |
Radiation source: fine-focus sealed tube | 1885 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
φ and ω scans | θmax = 26.4°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
Tmin = 0.189, Tmax = 0.232 | k = −11→11 |
5722 measured reflections | l = −12→12 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.029 | All 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 reflections | Δρmax = 0.57 e Å−3 |
170 parameters | Δρmin = −0.88 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.027 (2) |
C11H6Br2O3 | γ = 71.177 (4)° |
Mr = 345.98 | V = 554.4 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.1998 (17) Å | Mo Kα radiation |
b = 8.969 (2) Å | µ = 7.30 mm−1 |
c = 9.722 (2) Å | T = 2930 K |
α = 69.094 (5)° | 0.25 × 0.20 × 0.20 mm |
β = 85.974 (6)° |
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 = 0.232 | Rint = 0.030 |
5722 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.076 | All H-atom parameters refined |
S = 1.05 | Δρmax = 0.57 e Å−3 |
2184 reflections | Δρmin = −0.88 e Å−3 |
170 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.13625 (5) | 0.36757 (5) | 0.37268 (4) | 0.04873 (15) | |
Br2 | −0.32868 (6) | 0.45590 (5) | 0.37414 (4) | 0.05603 (16) | |
O1 | 0.2817 (3) | −0.0994 (2) | 0.1884 (2) | 0.0345 (5) | |
O2 | 0.1724 (4) | −0.0165 (3) | 0.3736 (2) | 0.0468 (6) | |
O3 | −0.1836 (3) | 0.4487 (3) | 0.0802 (2) | 0.0395 (5) | |
C4 | 0.1934 (4) | 0.0809 (4) | −0.0648 (3) | 0.0282 (6) | |
C1 | 0.4394 (5) | −0.1793 (5) | −0.1471 (4) | 0.0453 (8) | |
C2 | 0.3357 (5) | −0.0283 (5) | −0.2541 (4) | 0.0461 (9) | |
C3 | 0.2151 (5) | 0.1004 (4) | −0.2145 (4) | 0.0381 (7) | |
C5 | 0.2981 (4) | −0.0728 (4) | 0.0405 (3) | 0.0289 (6) | |
C6 | 0.4211 (5) | −0.2033 (4) | 0.0004 (4) | 0.0386 (7) | |
C7 | 0.0709 (4) | 0.2073 (4) | −0.0126 (3) | 0.0262 (6) | |
C8 | 0.0564 (4) | 0.1833 (3) | 0.1321 (3) | 0.0245 (5) | |
C9 | 0.1687 (4) | 0.0216 (3) | 0.2422 (3) | 0.0296 (6) | |
C10 | −0.0809 (4) | 0.3233 (3) | 0.1739 (3) | 0.0283 (6) | |
C11 | −0.0879 (5) | 0.3081 (4) | 0.3347 (3) | 0.0345 (7) | |
H1 | 0.517 (5) | −0.277 (4) | −0.164 (3) | 0.035 (8)* | |
H2 | 0.350 (6) | −0.018 (5) | −0.348 (5) | 0.053 (11)* | |
H3 | 0.157 (5) | 0.203 (5) | −0.283 (4) | 0.043 (10)* | |
H6 | 0.484 (6) | −0.300 (5) | 0.072 (4) | 0.054 (11)* | |
H7 | 0.002 (5) | 0.307 (5) | −0.078 (4) | 0.039 (9)* | |
H11 | −0.078 (5) | 0.200 (5) | 0.397 (4) | 0.043 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0557 (2) | 0.0580 (3) | 0.0382 (2) | −0.01529 (18) | −0.00347 (15) | −0.02506 (17) |
Br2 | 0.0527 (3) | 0.0579 (3) | 0.0504 (2) | −0.00193 (18) | 0.01973 (17) | −0.02811 (19) |
O1 | 0.0362 (11) | 0.0262 (10) | 0.0330 (11) | 0.0015 (9) | −0.0035 (9) | −0.0104 (9) |
O3 | 0.0463 (13) | 0.0281 (11) | 0.0339 (11) | 0.0012 (10) | −0.0012 (10) | −0.0102 (9) |
C10 | 0.0317 (15) | 0.0268 (14) | 0.0282 (14) | −0.0116 (12) | 0.0053 (11) | −0.0108 (12) |
C8 | 0.0267 (14) | 0.0221 (13) | 0.0244 (13) | −0.0080 (11) | 0.0018 (10) | −0.0080 (11) |
C4 | 0.0292 (14) | 0.0297 (14) | 0.0297 (15) | −0.0133 (12) | 0.0058 (11) | −0.0125 (12) |
C11 | 0.0388 (17) | 0.0306 (16) | 0.0299 (15) | −0.0056 (13) | 0.0095 (12) | −0.0121 (13) |
C7 | 0.0284 (14) | 0.0221 (13) | 0.0270 (14) | −0.0095 (11) | 0.0013 (11) | −0.0061 (11) |
C9 | 0.0311 (15) | 0.0263 (14) | 0.0295 (15) | −0.0076 (12) | 0.0015 (11) | −0.0092 (12) |
C5 | 0.0232 (13) | 0.0326 (15) | 0.0347 (15) | −0.0088 (11) | 0.0025 (11) | −0.0165 (12) |
O2 | 0.0617 (16) | 0.0375 (12) | 0.0249 (12) | −0.0004 (11) | 0.0004 (10) | −0.0055 (9) |
C3 | 0.0438 (18) | 0.0430 (19) | 0.0318 (17) | −0.0180 (15) | 0.0075 (14) | −0.0156 (15) |
C1 | 0.0332 (17) | 0.056 (2) | 0.064 (2) | −0.0149 (16) | 0.0159 (16) | −0.0424 (19) |
C2 | 0.050 (2) | 0.062 (2) | 0.041 (2) | −0.0258 (18) | 0.0204 (16) | −0.0328 (18) |
C6 | 0.0262 (15) | 0.0370 (17) | 0.055 (2) | −0.0039 (13) | 0.0006 (14) | −0.0248 (16) |
Br1—C11 | 1.951 (3) | C11—H11 | 0.92 (4) |
Br2—C11 | 1.922 (3) | C7—H7 | 0.90 (4) |
O1—C5 | 1.374 (4) | C9—O2 | 1.199 (4) |
O1—C9 | 1.375 (3) | C5—C6 | 1.384 (4) |
O3—C10 | 1.212 (3) | C3—C2 | 1.363 (5) |
C10—C8 | 1.492 (4) | C3—H3 | 0.90 (4) |
C10—C11 | 1.519 (4) | C1—C6 | 1.375 (5) |
C8—C7 | 1.347 (4) | C1—C2 | 1.387 (6) |
C8—C9 | 1.470 (4) | C1—H1 | 0.94 (3) |
C4—C5 | 1.395 (4) | C2—H2 | 0.89 (4) |
C4—C3 | 1.407 (4) | C6—H6 | 0.90 (4) |
C4—C7 | 1.422 (4) | ||
C5—O1—C9 | 123.3 (2) | O2—C9—O1 | 116.4 (3) |
O3—C10—C8 | 120.2 (3) | O2—C9—C8 | 127.2 (3) |
O3—C10—C11 | 120.5 (3) | O1—C9—C8 | 116.3 (2) |
C8—C10—C11 | 119.3 (2) | O1—C5—C6 | 117.7 (3) |
C7—C8—C9 | 119.9 (2) | O1—C5—C4 | 120.7 (2) |
C7—C8—C10 | 117.6 (2) | C6—C5—C4 | 121.6 (3) |
C9—C8—C10 | 122.5 (2) | C2—C3—C4 | 120.3 (3) |
C5—C4—C3 | 118.2 (3) | C2—C3—H3 | 121 (2) |
C5—C4—C7 | 117.4 (3) | C4—C3—H3 | 118 (2) |
C3—C4—C7 | 124.5 (3) | C6—C1—C2 | 121.0 (3) |
C10—C11—Br2 | 111.9 (2) | C6—C1—H1 | 113 (2) |
C10—C11—Br1 | 105.6 (2) | C2—C1—H1 | 126 (2) |
Br2—C11—Br1 | 110.47 (15) | C3—C2—C1 | 120.3 (3) |
C10—C11—H11 | 112 (2) | C3—C2—H2 | 121 (3) |
Br2—C11—H11 | 107 (2) | C1—C2—H2 | 119 (3) |
Br1—C11—H11 | 110 (2) | C1—C6—C5 | 118.6 (3) |
C8—C7—C4 | 122.3 (3) | C1—C6—H6 | 123 (3) |
C8—C7—H7 | 118 (2) | C5—C6—H6 | 118 (3) |
C4—C7—H7 | 119 (2) | ||
O3—C10—C8—C7 | 4.5 (4) | C7—C8—C9—O1 | −1.3 (4) |
C11—C10—C8—C7 | −174.4 (3) | C10—C8—C9—O1 | 176.6 (2) |
O3—C10—C8—C9 | −173.4 (3) | C9—O1—C5—C6 | 178.2 (3) |
C11—C10—C8—C9 | 7.6 (4) | C9—O1—C5—C4 | −2.0 (4) |
O3—C10—C11—Br2 | 21.6 (4) | C3—C4—C5—O1 | −179.6 (3) |
C8—C10—C11—Br2 | −159.5 (2) | C7—C4—C5—O1 | 0.1 (4) |
O3—C10—C11—Br1 | −98.7 (3) | C3—C4—C5—C6 | 0.3 (4) |
C8—C10—C11—Br1 | 80.3 (3) | C7—C4—C5—C6 | 180.0 (3) |
C9—C8—C7—C4 | −0.4 (4) | C5—C4—C3—C2 | −0.1 (5) |
C10—C8—C7—C4 | −178.4 (2) | C7—C4—C3—C2 | −179.7 (3) |
C5—C4—C7—C8 | 1.0 (4) | C4—C3—C2—C1 | −0.5 (5) |
C3—C4—C7—C8 | −179.3 (3) | C6—C1—C2—C3 | 0.9 (5) |
C5—O1—C9—O2 | −177.7 (3) | C2—C1—C6—C5 | −0.7 (5) |
C5—O1—C9—C8 | 2.5 (4) | O1—C5—C6—C1 | 179.9 (3) |
C7—C8—C9—O2 | 178.9 (3) | C4—C5—C6—C1 | 0.1 (5) |
C10—C8—C9—O2 | −3.2 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···O2i | 0.92 (4) | 2.46 (4) | 3.278 (4) | 148 (3) |
Symmetry code: (i) −x, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C11H6Br2O3 |
Mr | 345.98 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 554.4 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 7.30 |
Crystal size (mm) | 0.25 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.189, 0.232 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5722, 2184, 1885 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.076, 1.05 |
No. of reflections | 2184 |
No. of parameters | 170 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 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).
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···O2i | 0.92 (4) | 2.46 (4) | 3.278 (4) | 148 (3) |
Symmetry code: (i) −x, −y, −z+1. |
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.