Methyl 6-bromo-7-meth­oxy-1,3-benzodioxole-5-carboxyl­ate

Fu, X.; Ye, Z.; Mao, L.; Shao, S.

doi:10.1107/S1600536808019399

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1417

doi:10.1107/S1600536808019399

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Methyl 6-bromo-7-methoxy-1,3-benzodioxole-5-carboxylate

Xianshu Fu,^a ^* Zihong Ye,^a Lifei Mao ^a and Sasa Shao ^a

^aCollege of Life Science, China Jiliang University, Hangzhou 310018, People's Republic of China
^*Correspondence e-mail: fuxianshu2003@yahoo.com.cn

(Received 26 May 2008; accepted 25 June 2008; online 5 July 2008)

The non-H atoms of the title compound, C₁₀H₉BrO₅, are essentially coplanar, with the exception of the ester group [the O=C—O—C torsion angle is −143.4 (3)°].

Related literature

For related literature, see: Gerhard et al. (2003 ); Song & Xiao (1982 ).

Experimental

Crystal data

C₁₀H₉BrO₅
M_r = 289.08
Triclinic, $[P \overline 1]$
a = 7.6933 (12) Å
b = 8.0616 (13) Å
c = 9.7039 (15) Å
α = 105.062 (2)°
β = 91.667 (2)°
γ = 113.457 (2)°
V = 527.13 (14) Å³
Z = 2
Mo Kα radiation
μ = 3.90 mm⁻¹
T = 294 (2) K
0.22 × 0.18 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.481, T_max = 0.745
2997 measured reflections
2129 independent reflections
1790 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.096
S = 1.03
2129 reflections
147 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808019399/tk2272sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808019399/tk2272Isup2.hkl

checkCIF report

Comment top

The title compound, (I), is a key intermediate for the preparation of biphenyl derivatives. These may act to moderate liver ailments and, thus, be effective in the treatment of acute and chronic hepatitis (Song & Xiao, 1982). The non-hydrogen atoms in (I), Fig. 1, are essentially co-planar with the exception of the ester group; the O1-C7-C6-C1 torsion angle is -143.4 (3)°.

Related literature top

For related literature, see: Gerhard et al. (2003); Song & Xiao (1982).

Experimental top

The title compound (I) was prepared according to the procedure of Gerhard et al. (2003). The reaction was initiated by the addition of one molar equivalent of methanol to one molar equivalent of 6-bromo-7-methoxybenzo[d][1,3]dioxole-5-carboxylic acid in dichloromethane solution and subsequent stirring at room temperature for 12 h. A white powder resulted (yield 88%) and single crystals suitable for X-ray analysis were obtained by slow evaporation of an acetonitrile solution; m.p. 357 K.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. View of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 35% probability level.

Methyl 6-bromo-7-methoxy-1,3-benzodioxole-5-carboxylate top

Crystal data top

C₁₀H₉BrO₅	Z = 2
M_r = 289.08	F(000) = 288
Triclinic, P1	D_x = 1.821 Mg m⁻³
Hall symbol: -P 1	Melting point: 357 K
a = 7.6933 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.0616 (13) Å	Cell parameters from 1718 reflections
c = 9.7039 (15) Å	θ = 2.9–26.3°
α = 105.062 (2)°	µ = 3.90 mm⁻¹
β = 91.667 (2)°	T = 294 K
γ = 113.457 (2)°	Block, colorless
V = 527.13 (14) Å³	0.22 × 0.18 × 0.08 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2129 independent reflections
Radiation source: fine-focus sealed tube	1790 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ϕ and ω scans	θ_max = 26.4°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −9→9
T_min = 0.481, T_max = 0.745	k = −7→10
2997 measured reflections	l = −11→12

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0596P)² + 0.1433P] where P = (F_o² + 2F_c²)/3
2129 reflections	(Δ/σ)_max = 0.001
147 parameters	Δρ_max = 0.67 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

C₁₀H₉BrO₅	γ = 113.457 (2)°
M_r = 289.08	V = 527.13 (14) Å³
Triclinic, P1	Z = 2
a = 7.6933 (12) Å	Mo Kα radiation
b = 8.0616 (13) Å	µ = 3.90 mm⁻¹
c = 9.7039 (15) Å	T = 294 K
α = 105.062 (2)°	0.22 × 0.18 × 0.08 mm
β = 91.667 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2129 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1790 reflections with I > 2σ(I)
T_min = 0.481, T_max = 0.745	R_int = 0.017
2997 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.03	Δρ_max = 0.67 e Å⁻³
2129 reflections	Δρ_min = −0.42 e Å⁻³
147 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

	x	y	z	U_iso*/U_eq
Br1	0.35252 (5)	1.09757 (4)	0.17325 (3)	0.05585 (16)
O1	0.4065 (4)	0.7325 (4)	0.0679 (3)	0.0741 (8)
O2	0.1696 (3)	0.4868 (3)	0.1074 (2)	0.0508 (5)
O3	0.1494 (4)	0.7239 (3)	0.6385 (2)	0.0559 (6)
O4	0.1874 (4)	1.0334 (3)	0.6889 (2)	0.0591 (6)
O5	0.2912 (4)	1.2488 (3)	0.4655 (2)	0.0627 (7)
C1	0.2920 (4)	0.9669 (4)	0.3141 (3)	0.0379 (6)
C2	0.2692 (4)	1.0680 (4)	0.4491 (3)	0.0411 (6)
C3	0.2222 (4)	0.9728 (4)	0.5508 (3)	0.0393 (6)
C4	0.1986 (4)	0.7872 (4)	0.5206 (3)	0.0394 (6)
C5	0.2151 (4)	0.6849 (4)	0.3893 (3)	0.0399 (6)
H5	0.1945	0.5589	0.3711	0.048*
C6	0.2645 (4)	0.7784 (4)	0.2832 (3)	0.0362 (6)
C7	0.2905 (4)	0.6697 (4)	0.1411 (3)	0.0430 (6)
C8	0.1837 (6)	0.3669 (5)	−0.0273 (4)	0.0601 (9)
H8A	0.1717	0.4182	−0.1041	0.090*
H8B	0.0831	0.2419	−0.0467	0.090*
H8C	0.3057	0.3608	−0.0206	0.090*
C9	0.1525 (6)	0.8809 (5)	0.7482 (3)	0.0559 (8)
H9A	0.2526	0.9183	0.8279	0.067*
H9B	0.0307	0.8472	0.7844	0.067*
C10	0.3163 (6)	1.3726 (5)	0.6061 (4)	0.0565 (8)
H10A	0.1953	1.3405	0.6412	0.085*
H10B	0.3653	1.5008	0.6025	0.085*
H10C	0.4053	1.3601	0.6697	0.085*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0810 (3)	0.0505 (2)	0.0386 (2)	0.02651 (18)	0.01453 (16)	0.01850 (15)
O1	0.0930 (19)	0.0607 (15)	0.0638 (17)	0.0274 (14)	0.0469 (15)	0.0149 (13)
O2	0.0636 (13)	0.0423 (11)	0.0361 (11)	0.0205 (10)	0.0119 (10)	−0.0025 (9)
O3	0.0856 (16)	0.0481 (12)	0.0368 (11)	0.0277 (12)	0.0195 (11)	0.0165 (10)
O4	0.0962 (18)	0.0519 (13)	0.0328 (11)	0.0369 (13)	0.0203 (11)	0.0079 (10)
O5	0.111 (2)	0.0402 (12)	0.0420 (12)	0.0379 (13)	0.0153 (13)	0.0095 (10)
C1	0.0412 (14)	0.0408 (15)	0.0303 (13)	0.0155 (12)	0.0058 (11)	0.0109 (11)
C2	0.0475 (16)	0.0350 (14)	0.0372 (15)	0.0179 (12)	0.0028 (12)	0.0045 (12)
C3	0.0452 (15)	0.0398 (14)	0.0293 (13)	0.0189 (12)	0.0044 (11)	0.0031 (11)
C4	0.0432 (15)	0.0418 (15)	0.0321 (14)	0.0166 (12)	0.0060 (11)	0.0110 (12)
C5	0.0465 (15)	0.0353 (14)	0.0370 (15)	0.0181 (12)	0.0078 (12)	0.0073 (11)
C6	0.0384 (14)	0.0353 (14)	0.0309 (13)	0.0152 (11)	0.0050 (11)	0.0040 (11)
C7	0.0495 (16)	0.0460 (16)	0.0348 (15)	0.0239 (14)	0.0099 (13)	0.0073 (13)
C8	0.076 (2)	0.058 (2)	0.0400 (17)	0.0346 (18)	0.0086 (16)	−0.0053 (15)
C9	0.076 (2)	0.059 (2)	0.0340 (16)	0.0299 (17)	0.0155 (15)	0.0121 (14)
C10	0.080 (2)	0.0455 (17)	0.0461 (18)	0.0349 (17)	0.0083 (16)	0.0027 (14)

Geometric parameters (Å, º) top

Br1—C1	1.895 (3)	C3—C4	1.382 (4)
O1—C7	1.192 (4)	C4—C5	1.366 (4)
O2—C7	1.336 (4)	C5—C6	1.404 (4)
O2—C8	1.446 (4)	C5—H5	0.9300
O3—C4	1.375 (3)	C6—C7	1.496 (4)
O3—C9	1.418 (4)	C8—H8A	0.9600
O4—C3	1.375 (3)	C8—H8B	0.9600
O4—C9	1.424 (4)	C8—H8C	0.9600
O5—C2	1.363 (3)	C9—H9A	0.9700
O5—C10	1.421 (4)	C9—H9B	0.9700
C1—C6	1.396 (4)	C10—H10A	0.9600
C1—C2	1.408 (4)	C10—H10B	0.9600
C2—C3	1.374 (4)	C10—H10C	0.9600

C7—O2—C8	115.8 (3)	O1—C7—O2	123.3 (3)
C4—O3—C9	105.9 (2)	O1—C7—C6	125.9 (3)
C3—O4—C9	105.8 (2)	O2—C7—C6	110.8 (2)
C2—O5—C10	119.7 (2)	O2—C8—H8A	109.5
C6—C1—C2	122.1 (3)	O2—C8—H8B	109.5
C6—C1—Br1	121.5 (2)	H8A—C8—H8B	109.5
C2—C1—Br1	116.4 (2)	O2—C8—H8C	109.5
O5—C2—C3	126.2 (3)	H8A—C8—H8C	109.5
O5—C2—C1	117.2 (3)	H8B—C8—H8C	109.5
C3—C2—C1	116.6 (2)	O3—C9—O4	108.6 (2)
C2—C3—O4	129.3 (3)	O3—C9—H9A	110.0
C2—C3—C4	121.1 (2)	O4—C9—H9A	110.0
O4—C3—C4	109.6 (2)	O3—C9—H9B	110.0
C5—C4—O3	126.8 (3)	O4—C9—H9B	110.0
C5—C4—C3	123.3 (3)	H9A—C9—H9B	108.3
O3—C4—C3	109.8 (2)	O5—C10—H10A	109.5
C4—C5—C6	117.0 (3)	O5—C10—H10B	109.5
C4—C5—H5	121.5	H10A—C10—H10B	109.5
C6—C5—H5	121.5	O5—C10—H10C	109.5
C1—C6—C5	119.8 (2)	H10A—C10—H10C	109.5
C1—C6—C7	122.8 (3)	H10B—C10—H10C	109.5
C5—C6—C7	117.4 (2)

C10—O5—C2—C3	16.9 (5)	O4—C3—C4—O3	−0.4 (3)
C10—O5—C2—C1	−164.8 (3)	O3—C4—C5—C6	179.0 (3)
C6—C1—C2—O5	−177.1 (3)	C3—C4—C5—C6	2.0 (4)
Br1—C1—C2—O5	0.5 (4)	C2—C1—C6—C5	−0.9 (4)
C6—C1—C2—C3	1.3 (4)	Br1—C1—C6—C5	−178.4 (2)
Br1—C1—C2—C3	179.0 (2)	C2—C1—C6—C7	−179.2 (3)
O5—C2—C3—O4	−0.2 (5)	Br1—C1—C6—C7	3.3 (4)
C1—C2—C3—O4	−178.5 (3)	C4—C5—C6—C1	−0.8 (4)
O5—C2—C3—C4	178.2 (3)	C4—C5—C6—C7	177.6 (3)
C1—C2—C3—C4	−0.1 (4)	C8—O2—C7—O1	−1.4 (5)
C9—O4—C3—C2	−177.9 (3)	C8—O2—C7—C6	−179.1 (2)
C9—O4—C3—C4	3.6 (3)	C1—C6—C7—O1	34.9 (5)
C9—O3—C4—C5	179.7 (3)	C5—C6—C7—O1	−143.4 (3)
C9—O3—C4—C3	−3.0 (3)	C1—C6—C7—O2	−147.4 (3)
C2—C3—C4—C5	−1.6 (4)	C5—C6—C7—O2	34.2 (4)
O4—C3—C4—C5	177.0 (3)	C4—O3—C9—O4	5.2 (4)
C2—C3—C4—O3	−179.1 (3)	C3—O4—C9—O3	−5.5 (4)

Experimental details

Crystal data
Chemical formula	C₁₀H₉BrO₅
M_r	289.08
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	7.6933 (12), 8.0616 (13), 9.7039 (15)
α, β, γ (°)	105.062 (2), 91.667 (2), 113.457 (2)
V (Å³)	527.13 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.90
Crystal size (mm)	0.22 × 0.18 × 0.08

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.481, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	2997, 2129, 1790
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.096, 1.03
No. of reflections	2129
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.42

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This research was supported by the foundation of China Jiliang University.

References

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