


Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810042005/bh2314sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536810042005/bh2314Isup2.hkl |
CCDC reference: 799667
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean
(C-C) = 0.005 Å
- R factor = 0.044
- wR factor = 0.101
- Data-to-parameter ratio = 15.5
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT480_ALERT_4_B Long H...A H-Bond Reported H10A .. O1 .. 2.98 Ang.
Alert level C PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 3.59 PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 1 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 3
Alert level G PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c ....... P21/n PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature 293 K
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 2 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 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
To a mixture of equimolar quantity of 4-methoxy phenol (0.1 mol) and 4-bromoethylacetoacetate (0.1 mol) was added drop wise sulfuric acid (30 ml) with stirring and maintaining the temperature between 0-5 °C. The reaction mixture was allowed to stand in ice chest overnight and deep red coloured solution was poured into the stream of crushed ice. Solid separated was filtered and washed with water and then with cold ethanol so as to get a colourless compound. Finally, it is recrystallized from acetic acid.
All the H atoms were positioned geometrically and refined using a riding model with bond lengths 0.97 (methylene), 0.96 (methyl) or 0.93 Å (aromatic). Isotropic displacement parameters were calculated as Uĩso~(H) = 1.5U~eq~(C) for methyl group C11 and Uĩso~(H) = 1.2U~eq~(C) for all other H atoms.
Coumarins are a class of naturally occurring oxygen heterocycles which have been found to exhibit wide ranging biological activities (Kulkarni et al., 2006; Fylaktakidou et al., 2004; Neyts et al., 2009) through its innumerable derivatives. Structural studies on coumarins have been focused on their solid state photochemical dimerization (Gnanaguru et al., 1985), hydrogen bonding (Munshi et al., 2005), mode of packing (Gavuzzo et al., 1974), molecular self assembling (Moorthy et al., 2003) and photophysical properties (Katerinopoulos et al., 2004). Introduction of bromine has resulted in formation of hydrates, intermolecular hydrogen bonds, and eclipsed conformation, as observed in 3-bromocoumarin (Gaultier et al., 1965), 6-bromo-3-acetylcoumarin (Kokila et al., 1996), and 3-bromoacetylcoumarin (Vasudevan et al., 1991), respectively. 3-Bromophenyl-6-acetoxymethyl-coumarin-3-carboxylates have been found to exhibit potential anticancer and antitumour activity (Kempen et al., 2003).
The title compound is cyclic, planar and aromatic in nature due to the continuous delocalization of electrons over the coumarin rings system. There is a significant deviation from trigonality in bond angle at O1—C1—C2 [117.0 (3)°], due to the electronic repulsion of atom O2 which is bonded to C1. This is also reflected at C9—C4—C5 [117.9 (3)°] and C9—C4—C3 [117.6 (3)°] but these are due to fused benzene and α pyrone rings. Another significant deviation in bond angle is observed at C6—O3—C11 [118.0 (3)°] due to the repulsion between lone pair electrons of atom O3 with valence electrons of C6—O3 and O3—C11 bonds.
For the properties of coumarins, see: Kulkarni et al. (2006); Fylaktakidou et al. (2004); Neyts et al. (2009); Kempen et al. (2003). For structural analysis of coumarins, see: Gnanaguru et al. (1985); Munshi & Guru Row (2005); Gavuzzo et al. (1974); Moorthy et al. (2003); Katerinopoulos (2004). For Br-containing coumarins, see: Gaultier & Hauw (1965); Kokila et al. (1996); Vasudevan et al. (1991).
Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![]() | Fig. 1. ORTEP diagram of the title molecule with 50% probability displacement ellipsoids for non-H atoms. |
C11H9BrO3 | F(000) = 536 |
Mr = 269.09 | Dx = 1.749 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3217 reflections |
a = 4.3573 (3) Å | θ = 2.3–25.4° |
b = 9.2859 (6) Å | µ = 4.01 mm−1 |
c = 25.2677 (17) Å | T = 293 K |
β = 91.927 (3)° | Needle, colourless |
V = 1021.79 (12) Å3 | 0.25 × 0.15 × 0.1 mm |
Z = 4 |
Bruker Kappa APEXII CCD diffractometer | 2128 independent reflections |
Radiation source: fine-focus sealed tube | 1501 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
ω and φ scans | θmax = 26.6°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −5→3 |
Tmin = 0.434, Tmax = 0.501 | k = −11→11 |
9950 measured reflections | l = −31→31 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 0.96 | w = 1/[σ2(Fo2) + (0.0467P)2 + 1.203P] where P = (Fo2 + 2Fc2)/3 |
2128 reflections | (Δ/σ)max = 0.008 |
137 parameters | Δρmax = 0.93 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
0 constraints |
C11H9BrO3 | V = 1021.79 (12) Å3 |
Mr = 269.09 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 4.3573 (3) Å | µ = 4.01 mm−1 |
b = 9.2859 (6) Å | T = 293 K |
c = 25.2677 (17) Å | 0.25 × 0.15 × 0.1 mm |
β = 91.927 (3)° |
Bruker Kappa APEXII CCD diffractometer | 2128 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 1501 reflections with I > 2σ(I) |
Tmin = 0.434, Tmax = 0.501 | Rint = 0.037 |
9950 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 0.96 | Δρmax = 0.93 e Å−3 |
2128 reflections | Δρmin = −0.26 e Å−3 |
137 parameters |
x | y | z | Uiso*/Ueq | ||
C1 | 0.3658 (8) | 0.2636 (4) | 0.73840 (14) | 0.0406 (9) | |
C2 | 0.4641 (8) | 0.1339 (4) | 0.71330 (13) | 0.0375 (8) | |
H2 | 0.3944 | 0.0462 | 0.7260 | 0.045* | |
C3 | 0.6518 (7) | 0.1332 (4) | 0.67239 (13) | 0.0321 (7) | |
C4 | 0.7577 (7) | 0.2706 (4) | 0.65171 (12) | 0.0318 (7) | |
C5 | 0.9489 (7) | 0.2851 (4) | 0.60828 (13) | 0.0348 (8) | |
H5 | 1.0139 | 0.2035 | 0.5905 | 0.042* | |
C6 | 1.0401 (7) | 0.4188 (4) | 0.59198 (13) | 0.0378 (9) | |
C7 | 0.9456 (8) | 0.5407 (4) | 0.61872 (14) | 0.0429 (9) | |
H7 | 1.0121 | 0.6311 | 0.6081 | 0.051* | |
C8 | 0.7556 (8) | 0.5293 (4) | 0.66048 (14) | 0.0401 (9) | |
H8 | 0.6889 | 0.6113 | 0.6778 | 0.048* | |
C9 | 0.6642 (7) | 0.3941 (4) | 0.67652 (13) | 0.0345 (8) | |
C10 | 0.7530 (9) | −0.0074 (4) | 0.65024 (14) | 0.0421 (9) | |
H10A | 0.7086 | −0.0837 | 0.6751 | 0.050* | |
H10B | 0.9733 | −0.0052 | 0.6460 | 0.050* | |
C11 | 1.2815 (9) | 0.3270 (5) | 0.51587 (15) | 0.0535 (11) | |
H11A | 1.4005 | 0.2554 | 0.5347 | 0.080* | |
H11B | 1.3939 | 0.3612 | 0.4863 | 0.080* | |
H11C | 1.0908 | 0.2856 | 0.5033 | 0.080* | |
O1 | 0.4744 (5) | 0.3905 (3) | 0.71899 (9) | 0.0397 (6) | |
O2 | 0.1939 (7) | 0.2719 (3) | 0.77495 (11) | 0.0569 (7) | |
O3 | 1.2213 (6) | 0.4438 (3) | 0.55030 (10) | 0.0500 (7) | |
Br1 | 0.54925 (10) | −0.04981 (5) | 0.582134 (17) | 0.0612 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0437 (19) | 0.039 (2) | 0.039 (2) | −0.0003 (18) | 0.0059 (16) | −0.0004 (17) |
C2 | 0.0442 (19) | 0.029 (2) | 0.0390 (19) | −0.0025 (16) | 0.0024 (16) | 0.0004 (16) |
C3 | 0.0345 (17) | 0.027 (2) | 0.0344 (18) | 0.0024 (15) | 0.0010 (14) | −0.0003 (14) |
C4 | 0.0310 (16) | 0.034 (2) | 0.0301 (17) | 0.0032 (15) | −0.0022 (13) | 0.0012 (15) |
C5 | 0.0338 (17) | 0.036 (2) | 0.0350 (18) | 0.0037 (16) | 0.0031 (14) | −0.0014 (16) |
C6 | 0.0371 (18) | 0.042 (2) | 0.0343 (19) | −0.0030 (16) | 0.0050 (15) | 0.0044 (15) |
C7 | 0.051 (2) | 0.030 (2) | 0.048 (2) | −0.0055 (18) | 0.0027 (17) | 0.0076 (17) |
C8 | 0.050 (2) | 0.029 (2) | 0.042 (2) | 0.0018 (17) | 0.0008 (16) | −0.0045 (16) |
C9 | 0.0335 (17) | 0.037 (2) | 0.0333 (18) | −0.0008 (15) | 0.0020 (14) | −0.0007 (15) |
C10 | 0.048 (2) | 0.032 (2) | 0.046 (2) | 0.0050 (17) | 0.0039 (17) | 0.0013 (17) |
C11 | 0.063 (3) | 0.053 (3) | 0.045 (2) | 0.000 (2) | 0.0162 (19) | 0.002 (2) |
O1 | 0.0483 (14) | 0.0339 (15) | 0.0376 (13) | 0.0013 (12) | 0.0117 (11) | −0.0024 (11) |
O2 | 0.0759 (19) | 0.0461 (18) | 0.0508 (16) | 0.0039 (15) | 0.0305 (15) | −0.0005 (13) |
O3 | 0.0618 (16) | 0.0435 (17) | 0.0460 (15) | −0.0072 (13) | 0.0208 (13) | 0.0030 (13) |
Br1 | 0.0732 (3) | 0.0518 (3) | 0.0587 (3) | 0.0043 (2) | 0.0017 (2) | −0.0214 (2) |
C1—O2 | 1.211 (4) | C7—C8 | 1.367 (5) |
C1—O1 | 1.367 (4) | C7—H7 | 0.9300 |
C1—C2 | 1.434 (5) | C8—C9 | 1.382 (5) |
C2—C3 | 1.340 (5) | C8—H8 | 0.9300 |
C2—H2 | 0.9300 | C9—O1 | 1.377 (4) |
C3—C4 | 1.459 (5) | C10—Br1 | 1.950 (4) |
C3—C10 | 1.493 (5) | C10—H10A | 0.9700 |
C4—C9 | 1.375 (5) | C10—H10B | 0.9700 |
C4—C5 | 1.406 (5) | C11—O3 | 1.420 (5) |
C5—C6 | 1.371 (5) | C11—H11A | 0.9600 |
C5—H5 | 0.9300 | C11—H11B | 0.9600 |
C6—O3 | 1.357 (4) | C11—H11C | 0.9600 |
C6—C7 | 1.388 (5) | ||
O2—C1—O1 | 116.7 (3) | C7—C8—C9 | 119.0 (3) |
O2—C1—C2 | 126.3 (4) | C7—C8—H8 | 120.5 |
O1—C1—C2 | 117.0 (3) | C9—C8—H8 | 120.5 |
C3—C2—C1 | 123.0 (3) | C4—C9—C8 | 122.1 (3) |
C3—C2—H2 | 118.5 | C4—C9—O1 | 122.0 (3) |
C1—C2—H2 | 118.5 | C8—C9—O1 | 115.9 (3) |
C2—C3—C4 | 118.7 (3) | C3—C10—Br1 | 112.1 (2) |
C2—C3—C10 | 119.3 (3) | C3—C10—H10A | 109.2 |
C4—C3—C10 | 122.0 (3) | Br1—C10—H10A | 109.2 |
C9—C4—C5 | 117.9 (3) | C3—C10—H10B | 109.2 |
C9—C4—C3 | 117.6 (3) | Br1—C10—H10B | 109.2 |
C5—C4—C3 | 124.5 (3) | H10A—C10—H10B | 107.9 |
C6—C5—C4 | 120.4 (3) | O3—C11—H11A | 109.5 |
C6—C5—H5 | 119.8 | O3—C11—H11B | 109.5 |
C4—C5—H5 | 119.8 | H11A—C11—H11B | 109.5 |
O3—C6—C5 | 124.7 (3) | O3—C11—H11C | 109.5 |
O3—C6—C7 | 115.4 (3) | H11A—C11—H11C | 109.5 |
C5—C6—C7 | 119.9 (3) | H11B—C11—H11C | 109.5 |
C8—C7—C6 | 120.7 (3) | C1—O1—C9 | 121.6 (3) |
C8—C7—H7 | 119.7 | C6—O3—C11 | 118.0 (3) |
C6—C7—H7 | 119.7 | ||
O2—C1—C2—C3 | 179.0 (3) | C5—C4—C9—C8 | −0.9 (5) |
O1—C1—C2—C3 | −0.5 (5) | C3—C4—C9—C8 | 179.0 (3) |
C1—C2—C3—C4 | −1.0 (5) | C5—C4—C9—O1 | 179.3 (3) |
C1—C2—C3—C10 | 177.4 (3) | C3—C4—C9—O1 | −0.8 (4) |
C2—C3—C4—C9 | 1.6 (4) | C7—C8—C9—C4 | −0.2 (5) |
C10—C3—C4—C9 | −176.7 (3) | C7—C8—C9—O1 | 179.6 (3) |
C2—C3—C4—C5 | −178.5 (3) | C2—C3—C10—Br1 | 106.3 (3) |
C10—C3—C4—C5 | 3.2 (5) | C4—C3—C10—Br1 | −75.4 (3) |
C9—C4—C5—C6 | 0.7 (5) | O2—C1—O1—C9 | −178.1 (3) |
C3—C4—C5—C6 | −179.2 (3) | C2—C1—O1—C9 | 1.4 (5) |
C4—C5—C6—O3 | −179.3 (3) | C4—C9—O1—C1 | −0.8 (5) |
C4—C5—C6—C7 | 0.5 (5) | C8—C9—O1—C1 | 179.4 (3) |
O3—C6—C7—C8 | 178.2 (3) | C5—C6—O3—C11 | 10.6 (5) |
C5—C6—C7—C8 | −1.6 (5) | C7—C6—O3—C11 | −169.2 (3) |
C6—C7—C8—C9 | 1.4 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O1i | 0.93 | 2.60 | 3.451 (4) | 152 |
C2—H2···O2i | 0.93 | 2.58 | 3.446 (5) | 155 |
C10—H10A···O2i | 0.97 | 2.57 | 3.437 (5) | 148 |
C8—H8···O2ii | 0.93 | 2.56 | 3.433 (5) | 156 |
C10—H10A···O1iii | 0.97 | 2.98 | 3.601 (4) | 122 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) −x+1/2, y+1/2, −z+3/2; (iii) −x+3/2, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C11H9BrO3 |
Mr | 269.09 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 4.3573 (3), 9.2859 (6), 25.2677 (17) |
β (°) | 91.927 (3) |
V (Å3) | 1021.79 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.01 |
Crystal size (mm) | 0.25 × 0.15 × 0.1 |
Data collection | |
Diffractometer | Bruker Kappa APEXII CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.434, 0.501 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9950, 2128, 1501 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.630 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.101, 0.96 |
No. of reflections | 2128 |
No. of parameters | 137 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.93, −0.26 |
Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT (Bruker, 2004), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006).
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O1i | 0.93 | 2.60 | 3.451 (4) | 152 |
C2—H2···O2i | 0.93 | 2.58 | 3.446 (5) | 155 |
C10—H10A···O2i | 0.97 | 2.57 | 3.437 (5) | 148 |
C8—H8···O2ii | 0.93 | 2.56 | 3.433 (5) | 156 |
C10—H10A···O1iii | 0.97 | 2.98 | 3.601 (4) | 122 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) −x+1/2, y+1/2, −z+3/2; (iii) −x+3/2, y−1/2, −z+3/2. |
Coumarins are a class of naturally occurring oxygen heterocycles which have been found to exhibit wide ranging biological activities (Kulkarni et al., 2006; Fylaktakidou et al., 2004; Neyts et al., 2009) through its innumerable derivatives. Structural studies on coumarins have been focused on their solid state photochemical dimerization (Gnanaguru et al., 1985), hydrogen bonding (Munshi et al., 2005), mode of packing (Gavuzzo et al., 1974), molecular self assembling (Moorthy et al., 2003) and photophysical properties (Katerinopoulos et al., 2004). Introduction of bromine has resulted in formation of hydrates, intermolecular hydrogen bonds, and eclipsed conformation, as observed in 3-bromocoumarin (Gaultier et al., 1965), 6-bromo-3-acetylcoumarin (Kokila et al., 1996), and 3-bromoacetylcoumarin (Vasudevan et al., 1991), respectively. 3-Bromophenyl-6-acetoxymethyl-coumarin-3-carboxylates have been found to exhibit potential anticancer and antitumour activity (Kempen et al., 2003).
The title compound is cyclic, planar and aromatic in nature due to the continuous delocalization of electrons over the coumarin rings system. There is a significant deviation from trigonality in bond angle at O1—C1—C2 [117.0 (3)°], due to the electronic repulsion of atom O2 which is bonded to C1. This is also reflected at C9—C4—C5 [117.9 (3)°] and C9—C4—C3 [117.6 (3)°] but these are due to fused benzene and α pyrone rings. Another significant deviation in bond angle is observed at C6—O3—C11 [118.0 (3)°] due to the repulsion between lone pair electrons of atom O3 with valence electrons of C6—O3 and O3—C11 bonds.