4-Bromo­methyl-7,8-dimethyl­coumarin

Gowda, R.; Gowda, K.V.A.; Basanagouda, M.; Kulkarni, M.V.

doi:10.1107/S1600536810049135

organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3352

https://doi.org/10.1107/S1600536810049135

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4-Bromomethyl-7,8-dimethylcoumarin

Ramakrishna Gowda,^a ^*‡ K.V. Arjuna Gowda,^b Mahantesha Basanagouda ^c and Manohar V. Kulkarni ^c

^aDepartment of Physics, Govt. College for Women, Kolar 563 101, Karnataka, India, ^bDepartment of Physics, Govt. College for Women, Mandya 571 401, Karnataka, India, and ^cDepartment of Chemistry, Karnatak University, Dharwad 580 003, Karnataka, India
^*Correspondence e-mail: kvarjunagowda@gmail.com

(Received 14 November 2010; accepted 24 November 2010; online 30 November 2010)

In the title molecule, C₁₂H₁₁BrO₂, all non-H atoms with the exception of the Br atom are essentially coplanar (r.m.s. deviation = 0.018 Å). The C—Br bond is inclined by 80.17 (12)° to this plane. The crystal structure is stabilized by weak C—H⋯O hydrogen bonds.

Related literature

For potential synthetic applications of the title compound, see: Cui et al. (2007 ); Zhao et al. (2008 ). For related structures, see: Gowda et al. (2009 , 2010 ).

Experimental

Crystal data

C₁₂H₁₁BrO₂
M_r = 267.12
Monoclinic, C 2/c
a = 18.5025 (14) Å
b = 9.8785 (7) Å
c = 13.1639 (10) Å
β = 118.908 (2)°
V = 2106.3 (3) Å³
Z = 8
Mo Kα radiation
μ = 3.88 mm⁻¹
T = 292 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker 2004 ) T_min = 0.432, T_max = 0.571
14710 measured reflections
3610 independent reflections
2516 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.116
S = 1.05
3610 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 1.78 e Å⁻³
Δρ_min = −0.73 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12B⋯O2ⁱ	0.97	2.40	3.342 (3)	163
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT; 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 PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810049135/lh5165sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810049135/lh5165Isup2.hkl

checkCIF report

Comment top

The title compound has potential use in Heck and Suzuki cross coupling reactions (Cui et al., 2007) and Negishi coupling reactions (Zhao et al., 2008). In continuation of our work on the crystal structures of halogenated coumarin derivatives (Gowda et al., 2009; 2010) herein we report crystal structure of title compound.

The molecular structure of the title compound is shown in Fig. 1. In the molecule, with the exception of the Br atom, all non-hydrogen atoms [C1-C12/O1/O2] are essentially planar [r.m.s. = 0.018Å]]. The C-Br bond is inclined [defined by the C7/C12/Br1 plane] by 80.17 (12)° to this plane. The crystal structure is stabilized by weak C-H···O hydrogen bonds (Fig. 2).

Related literature top

For potential synthetic applications of the title compound, see: Cui et al. (2007); Zhao et al. (2008). For related structures, see: Gowda et al. (2009, 2010).

Experimental top

To a mixture of equimolar quantities of 2,3-dimethylphenol (0.1 mol) and 4-bromoethylacetoacetate (0.1 mol), sulfuric acid (30 ml) was added dropwise with stirring while maintaining the temperature between 273-278K. The reaction mixture was allowed to stand in ice chest overnight and the deep red coloured solution was poured into a stream of crushed ice. The solid which separated was filtered and washed with water and then with cold ethanol to yield a colourless compound which was recrystallized from acetic acid.

Structure description top

For potential synthetic applications of the title compound, see: Cui et al. (2007); Zhao et al. (2008). For related structures, see: Gowda et al. (2009, 2010).

Computing details top

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 PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound shown with 50% probability displacement ellipsoids.
	Fig. 2. Part of the crystal structure showing weak C-H···O hydrogen bonds as dashed lines.

4-Bromomethyl-7,8-dimethylcoumarin top

Crystal data top

C₁₂H₁₁BrO₂	F(000) = 1072
M_r = 267.12	D_x = 1.685 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5018 reflections
a = 18.5025 (14) Å	θ = 2.4–28.6°
b = 9.8785 (7) Å	µ = 3.88 mm⁻¹
c = 13.1639 (10) Å	T = 292 K
β = 118.908 (2)°	Block, colourless
V = 2106.3 (3) Å³	0.30 × 0.20 × 0.20 mm
Z = 8

Data collection top

Bruker Kappa APEXII CCD diffractometer	3610 independent reflections
Radiation source: fine-focus sealed tube	2516 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ω and φ scans	θ_max = 31.9°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker 2004)	h = −27→27
T_min = 0.432, T_max = 0.571	k = −14→14
14710 measured reflections	l = −19→13

Refinement top

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0574P)² + 1.9612P] where P = (F_o² + 2F_c²)/3
3610 reflections	(Δ/σ)_max = 0.001
138 parameters	Δρ_max = 1.78 e Å⁻³
0 restraints	Δρ_min = −0.73 e Å⁻³

Crystal data top

C₁₂H₁₁BrO₂	V = 2106.3 (3) Å³
M_r = 267.12	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 18.5025 (14) Å	µ = 3.88 mm⁻¹
b = 9.8785 (7) Å	T = 292 K
c = 13.1639 (10) Å	0.30 × 0.20 × 0.20 mm
β = 118.908 (2)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	3610 independent reflections
Absorption correction: multi-scan (SADABS; Bruker 2004)	2516 reflections with I > 2σ(I)
T_min = 0.432, T_max = 0.571	R_int = 0.026
14710 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.05	Δρ_max = 1.78 e Å⁻³
3610 reflections	Δρ_min = −0.73 e Å⁻³
138 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.36207 (15)	0.1296 (2)	0.0849 (2)	0.0332 (5)
C2	0.39174 (15)	0.1512 (2)	0.2032 (2)	0.0363 (5)
C3	0.40658 (16)	0.2836 (3)	0.24674 (19)	0.0398 (5)
H3	0.4263	0.2974	0.3257	0.048*
C4	0.39291 (16)	0.3930 (3)	0.17644 (19)	0.0366 (5)
H4	0.4033	0.4797	0.2079	0.044*
C5	0.36354 (14)	0.3756 (2)	0.05795 (17)	0.0289 (4)
C6	0.34902 (13)	0.2433 (2)	0.01547 (17)	0.0292 (4)
C7	0.34654 (14)	0.4850 (2)	−0.02371 (18)	0.0303 (4)
C8	0.31617 (15)	0.4562 (2)	−0.13705 (19)	0.0354 (5)
H8	0.3025	0.5272	−0.1896	0.043*
C9	0.30411 (16)	0.3200 (2)	−0.1796 (2)	0.0371 (5)
C10	0.34498 (19)	−0.0090 (2)	0.0328 (3)	0.0460 (6)
H10A	0.3014	−0.0043	−0.0461	0.069*
H10B	0.3287	−0.0674	0.0764	0.069*
H10C	0.3939	−0.0443	0.0346	0.069*
C11	0.4099 (2)	0.0349 (3)	0.2855 (3)	0.0530 (7)
H11A	0.3594	−0.0110	0.2678	0.079*
H11B	0.4350	0.0684	0.3637	0.079*
H11C	0.4469	−0.0271	0.2778	0.079*
C12	0.36044 (16)	0.6286 (2)	0.0163 (2)	0.0383 (5)
H12A	0.3423	0.6421	0.0734	0.046*
H12B	0.3287	0.6883	−0.0489	0.046*
O1	0.32072 (11)	0.21805 (17)	−0.10098 (13)	0.0360 (4)
O2	0.28162 (15)	0.2864 (2)	−0.27881 (15)	0.0554 (5)
Br1	0.478174 (17)	0.67133 (3)	0.08473 (2)	0.04795 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0327 (11)	0.0270 (10)	0.0415 (11)	0.0027 (9)	0.0190 (9)	0.0012 (9)
C2	0.0344 (12)	0.0387 (13)	0.0398 (11)	0.0035 (10)	0.0211 (10)	0.0077 (9)
C3	0.0438 (13)	0.0458 (13)	0.0298 (10)	−0.0008 (11)	0.0178 (9)	−0.0007 (9)
C4	0.0432 (13)	0.0338 (12)	0.0336 (10)	−0.0029 (10)	0.0192 (9)	−0.0068 (9)
C5	0.0311 (11)	0.0248 (9)	0.0302 (9)	0.0002 (8)	0.0143 (8)	−0.0018 (7)
C6	0.0300 (10)	0.0285 (10)	0.0293 (9)	0.0007 (8)	0.0144 (8)	−0.0022 (7)
C7	0.0296 (10)	0.0252 (10)	0.0348 (9)	0.0003 (8)	0.0145 (8)	−0.0006 (8)
C8	0.0386 (12)	0.0317 (11)	0.0333 (9)	−0.0003 (9)	0.0153 (9)	0.0036 (8)
C9	0.0383 (12)	0.0369 (12)	0.0323 (9)	−0.0018 (10)	0.0140 (9)	−0.0019 (9)
C10	0.0564 (16)	0.0264 (11)	0.0576 (14)	0.0007 (11)	0.0295 (13)	−0.0007 (10)
C11	0.0552 (17)	0.0542 (17)	0.0511 (14)	0.0062 (14)	0.0269 (13)	0.0211 (13)
C12	0.0402 (13)	0.0256 (10)	0.0434 (12)	0.0017 (10)	0.0158 (10)	−0.0003 (9)
O1	0.0464 (10)	0.0278 (8)	0.0312 (7)	−0.0013 (7)	0.0169 (7)	−0.0053 (6)
O2	0.0764 (15)	0.0524 (11)	0.0310 (8)	−0.0053 (11)	0.0208 (9)	−0.0057 (8)
Br1	0.04529 (18)	0.04007 (16)	0.04762 (16)	−0.00806 (11)	0.01383 (12)	0.00024 (10)

Geometric parameters (Å, º) top

C1—C6	1.393 (3)	C8—C9	1.433 (3)
C1—C2	1.394 (3)	C8—H8	0.9300
C1—C10	1.495 (3)	C9—O2	1.210 (3)
C2—C3	1.401 (4)	C9—O1	1.368 (3)
C2—C11	1.502 (3)	C10—H10A	0.9600
C3—C4	1.364 (4)	C10—H10B	0.9600
C3—H3	0.9300	C10—H10C	0.9600
C4—C5	1.392 (3)	C11—H11A	0.9600
C4—H4	0.9300	C11—H11B	0.9600
C5—C6	1.396 (3)	C11—H11C	0.9600
C5—C7	1.447 (3)	C12—Br1	1.959 (3)
C6—O1	1.382 (2)	C12—H12A	0.9700
C7—C8	1.346 (3)	C12—H12B	0.9700
C7—C12	1.492 (3)

C6—C1—C2	117.3 (2)	C9—C8—H8	118.9
C6—C1—C10	120.4 (2)	O2—C9—O1	116.7 (2)
C2—C1—C10	122.3 (2)	O2—C9—C8	125.9 (2)
C1—C2—C3	119.6 (2)	O1—C9—C8	117.38 (19)
C1—C2—C11	121.2 (2)	C1—C10—H10A	109.5
C3—C2—C11	119.2 (2)	C1—C10—H10B	109.5
C4—C3—C2	121.7 (2)	H10A—C10—H10B	109.5
C4—C3—H3	119.1	C1—C10—H10C	109.5
C2—C3—H3	119.1	H10A—C10—H10C	109.5
C3—C4—C5	120.4 (2)	H10B—C10—H10C	109.5
C3—C4—H4	119.8	C2—C11—H11A	109.5
C5—C4—H4	119.8	C2—C11—H11B	109.5
C4—C5—C6	117.4 (2)	H11A—C11—H11B	109.5
C4—C5—C7	124.5 (2)	C2—C11—H11C	109.5
C6—C5—C7	118.09 (18)	H11A—C11—H11C	109.5
O1—C6—C1	115.77 (19)	H11B—C11—H11C	109.5
O1—C6—C5	120.65 (19)	C7—C12—Br1	109.33 (17)
C1—C6—C5	123.6 (2)	C7—C12—H12A	109.8
C8—C7—C5	119.4 (2)	Br1—C12—H12A	109.8
C8—C7—C12	120.0 (2)	C7—C12—H12B	109.8
C5—C7—C12	120.64 (19)	Br1—C12—H12B	109.8
C7—C8—C9	122.3 (2)	H12A—C12—H12B	108.3
C7—C8—H8	118.9	C9—O1—C6	122.16 (18)

C6—C1—C2—C3	0.3 (4)	C7—C5—C6—C1	−179.3 (2)
C10—C1—C2—C3	180.0 (2)	C4—C5—C7—C8	−178.3 (2)
C6—C1—C2—C11	−178.3 (2)	C6—C5—C7—C8	1.2 (3)
C10—C1—C2—C11	1.3 (4)	C4—C5—C7—C12	0.3 (4)
C1—C2—C3—C4	−0.1 (4)	C6—C5—C7—C12	179.7 (2)
C11—C2—C3—C4	178.6 (3)	C5—C7—C8—C9	−3.5 (4)
C2—C3—C4—C5	−0.1 (4)	C12—C7—C8—C9	178.0 (2)
C3—C4—C5—C6	0.0 (4)	C7—C8—C9—O2	−175.6 (3)
C3—C4—C5—C7	179.5 (2)	C7—C8—C9—O1	3.3 (4)
C2—C1—C6—O1	179.1 (2)	C8—C7—C12—Br1	−101.7 (2)
C10—C1—C6—O1	−0.5 (3)	C5—C7—C12—Br1	79.8 (2)
C2—C1—C6—C5	−0.4 (4)	O2—C9—O1—C6	178.2 (2)
C10—C1—C6—C5	180.0 (2)	C8—C9—O1—C6	−0.8 (4)
C4—C5—C6—O1	−179.3 (2)	C1—C6—O1—C9	179.1 (2)
C7—C5—C6—O1	1.2 (3)	C5—C6—O1—C9	−1.4 (3)
C4—C5—C6—C1	0.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12B···O2ⁱ	0.97	2.40	3.342 (3)	163

Symmetry code: (i) −x+1/2, y+1/2, −z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₁BrO₂
M_r	267.12
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	292
a, b, c (Å)	18.5025 (14), 9.8785 (7), 13.1639 (10)
β (°)	118.908 (2)
V (Å³)	2106.3 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	3.88
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker 2004)
T_min, T_max	0.432, 0.571
No. of measured, independent and observed [I > 2σ(I)] reflections	14710, 3610, 2516
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.742

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.116, 1.05
No. of reflections	3610
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.78, −0.73

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 PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12B···O2ⁱ	0.97	2.40	3.342 (3)	163

Symmetry code: (i) −x+1/2, y+1/2, −z−1/2.

Footnotes

‡Alternative affiliation: MVJ College of Engineering, Bangalore 560 067, India.

Acknowledgements

RG thanks MVJ College of Engineering, Bangalore (VTU Research center), for providing research facilities. The authors also thank the SAIF IIT Madras, Chennai, for the data collection.

References

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