Methyl 3,5-dibromo-4-methyl-benzoate.

In the title compound, C(9)H(8)Br(2)O(2), the mol-ecule is essentially planar with an r.m.s. deviation of 0.0652 Å from the mean plane through all non-H atoms and a dihedral angle of 7.1 (2)° between the benzene ring plane and the carboxyl-ate substituent. In the crystal structure, weak C-H⋯Br hydrogen bonds and weak inter-molecular O⋯Br contacts [3.095 (2) Å], link adjacent mol-ecules into layers parallel to (102). Additional weak inter-molecular C-H⋯O hydrogen bond inter-actions stack the layers above and below the mol-ecular plane and down the a axis.

Related literature

For use of the title compound in the synthesis of natural products, see: Gray & Whalley (1971 ▶); Saeed & Rama (1994 ▶); Harris & Mantle (2001 ▶); Simpson (1978 ▶). For related structures, see: Moorthy et al. (2002 ▶); Fan et al. (2005 ▶). For inter­molecular O⋯Br contacts, see: Choi et al. (2010a ▶,b ▶); Politzer et al. (2007 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C9H8Br2O2

M = 307.97

Orthorhombic,

a = 3.9716 (2) Å

b = 14.2359 (7) Å

c = 17.2893 (8) Å

V = 977.52 (8) Å3

Z = 4

Mo Kα radiation

μ = 8.26 mm−1

T = 89 K

0.64 × 0.14 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2006 ▶) T min = 0.295, T max = 1.000

17658 measured reflections

3471 independent reflections

2922 reflections with I > 2σ(I)

R int = 0.061

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.065

S = 1.09

3471 reflections

120 parameters

H-atom parameters constrained

Δρmax = 1.15 e Å−3

Δρmin = −1.09 e Å−3

Absolute structure: Flack (1983 ▶), 1659 Friedel pairs

Flack parameter: 0.039 (14)

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: APEX2 and SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and TITAN2000 (Hunter & Simpson, 1999 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004 ▶), PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810011062/jj2027sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810011062/jj2027Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C9H8Br2O2	F(000) = 592
Mr = 307.97	Dx = 2.093 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4848 reflections
a = 3.9716 (2) Å	θ = 2.8–30.4°
b = 14.2359 (7) Å	µ = 8.26 mm−1
c = 17.2893 (8) Å	T = 89 K
V = 977.52 (8) Å3	Rectangular plate, colourless
Z = 4	0.64 × 0.14 × 0.08 mm

Bruker APEXII CCD diffractometer	3471 independent reflections
Radiation source: fine-focus sealed tube	2922 reflections with I > 2σ(I)
graphite	Rint = 0.061
ω scans	θmax = 33.3°, θmin = 3.7°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −6→4
Tmin = 0.295, Tmax = 1.000	k = −21→21
17658 measured reflections	l = −25→25

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)] = 0.033	H-atom parameters constrained
wR(F2) = 0.065	w = 1/[σ2(Fo2) + 0.5972P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max = 0.001
3471 reflections	Δρmax = 1.15 e Å−3
120 parameters	Δρmin = −1.09 e Å−3
0 restraints	Absolute structure: Flack (1983), 1659 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.039 (14)

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 > 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	0.86943 (10)	0.87630 (2)	0.134557 (17)	0.01774 (7)
C1	0.7685 (7)	0.7603 (2)	0.18453 (18)	0.0116 (6)
C2	0.8609 (8)	0.67455 (19)	0.15060 (16)	0.0119 (5)
C21	1.0349 (8)	0.6680 (2)	0.07366 (19)	0.0172 (7)
H21A	1.2073	0.6188	0.0757	0.026*
H21B	1.1411	0.7283	0.0615	0.026*
H21C	0.8697	0.6525	0.0335	0.026*
C3	0.7704 (8)	0.5947 (2)	0.19236 (18)	0.0120 (6)
Br2	0.86513 (9)	0.47350 (2)	0.151431 (17)	0.01548 (7)
C4	0.6050 (9)	0.59686 (19)	0.26311 (17)	0.0128 (5)
H4	0.5508	0.5404	0.2897	0.015*
C5	0.5202 (7)	0.6844 (2)	0.29418 (19)	0.0122 (6)
C6	0.6011 (9)	0.7667 (2)	0.25473 (17)	0.0138 (6)
H6	0.5426	0.8262	0.2756	0.017*
C7	0.3351 (8)	0.69264 (19)	0.36902 (17)	0.0133 (5)
O1	0.2258 (6)	0.76517 (15)	0.39530 (14)	0.0181 (5)
O2	0.3030 (6)	0.60888 (15)	0.40440 (12)	0.0163 (5)
C8	0.1345 (11)	0.6119 (2)	0.47902 (17)	0.0214 (6)
H8A	0.2618	0.6524	0.5144	0.032*
H8B	0.1215	0.5483	0.5005	0.032*
H8C	−0.0933	0.6371	0.4725	0.032*

	U11	U22	U33	U12	U13	U23
Br1	0.02028 (15)	0.01578 (13)	0.01716 (15)	−0.00211 (15)	0.00154 (16)	0.00416 (11)
C1	0.0112 (13)	0.0118 (13)	0.0118 (14)	−0.0026 (10)	−0.0006 (11)	0.0039 (11)
C2	0.0084 (10)	0.0148 (11)	0.0126 (13)	−0.0006 (13)	−0.0016 (14)	0.0007 (10)
C21	0.0153 (14)	0.0231 (16)	0.0131 (16)	0.0021 (13)	0.0022 (12)	0.0006 (12)
C3	0.0122 (14)	0.0129 (13)	0.0109 (14)	−0.0004 (11)	−0.0019 (11)	−0.0009 (10)
Br2	0.01713 (14)	0.01478 (12)	0.01454 (14)	0.00131 (14)	0.00229 (15)	−0.00278 (10)
C4	0.0103 (13)	0.0151 (12)	0.0131 (13)	−0.0003 (13)	−0.0004 (13)	−0.0003 (10)
C5	0.0090 (12)	0.0176 (14)	0.0099 (14)	−0.0004 (11)	−0.0032 (11)	−0.0003 (12)
C6	0.0122 (14)	0.0139 (13)	0.0152 (13)	−0.0009 (13)	−0.0006 (13)	0.0002 (10)
C7	0.0139 (14)	0.0161 (13)	0.0099 (12)	−0.0001 (11)	−0.0028 (12)	−0.0013 (10)
O1	0.0206 (12)	0.0177 (11)	0.0160 (11)	0.0043 (9)	0.0027 (9)	−0.0009 (9)
O2	0.0208 (13)	0.0181 (10)	0.0098 (10)	−0.0014 (9)	0.0048 (9)	0.0003 (8)
C8	0.0235 (16)	0.0295 (16)	0.0113 (14)	−0.0020 (18)	0.0063 (16)	0.0020 (12)

Br1—C1	1.907 (3)	C4—H4	0.9500
C1—C6	1.387 (4)	C5—C6	1.393 (4)
C1—C2	1.403 (4)	C5—C7	1.493 (4)
C2—C3	1.394 (4)	C6—H6	0.9500
C2—C21	1.502 (4)	C7—O1	1.209 (3)
C21—H21A	0.9800	C7—O2	1.346 (3)
C21—H21B	0.9800	O1—Br2i	3.095 (2)
C21—H21C	0.9800	O2—C8	1.454 (4)
C3—C4	1.389 (4)	C8—H8A	0.9800
C3—Br2	1.902 (3)	C8—H8B	0.9800
C4—C5	1.398 (4)	C8—H8C	0.9800
C6—C1—C2	123.3 (3)	C6—C5—C4	120.4 (3)
C6—C1—Br1	116.1 (2)	C6—C5—C7	118.2 (3)
C2—C1—Br1	120.6 (2)	C4—C5—C7	121.4 (3)
C3—C2—C1	115.2 (3)	C1—C6—C5	119.0 (3)
C3—C2—C21	121.8 (3)	C1—C6—H6	120.5
C1—C2—C21	123.0 (3)	C5—C6—H6	120.5
C2—C21—H21A	109.5	O1—C7—O2	123.5 (3)
C2—C21—H21B	109.5	O1—C7—C5	124.7 (3)
H21A—C21—H21B	109.5	O2—C7—C5	111.8 (2)
C2—C21—H21C	109.5	C7—O1—Br2i	139.7 (2)
H21A—C21—H21C	109.5	C7—O2—C8	114.9 (2)
H21B—C21—H21C	109.5	O2—C8—H8A	109.5
C4—C3—C2	124.0 (3)	O2—C8—H8B	109.5
C4—C3—Br2	116.2 (2)	H8A—C8—H8B	109.5
C2—C3—Br2	119.7 (2)	O2—C8—H8C	109.5
C3—C4—C5	118.2 (3)	H8A—C8—H8C	109.5
C3—C4—H4	120.9	H8B—C8—H8C	109.5
C5—C4—H4	120.9
C6—C1—C2—C3	0.4 (4)	C2—C1—C6—C5	0.2 (5)
Br1—C1—C2—C3	−179.4 (2)	Br1—C1—C6—C5	−180.0 (2)
C6—C1—C2—C21	178.5 (3)	C4—C5—C6—C1	−0.4 (4)
Br1—C1—C2—C21	−1.3 (4)	C7—C5—C6—C1	−179.0 (3)
C1—C2—C3—C4	−0.9 (5)	C6—C5—C7—O1	6.2 (5)
C21—C2—C3—C4	−179.0 (3)	C4—C5—C7—O1	−172.5 (3)
C1—C2—C3—Br2	177.7 (2)	C6—C5—C7—O2	−173.9 (3)
C21—C2—C3—Br2	−0.4 (4)	C4—C5—C7—O2	7.5 (4)
C2—C3—C4—C5	0.7 (5)	O2—C7—O1—Br2i	−172.96 (18)
Br2—C3—C4—C5	−177.9 (2)	C5—C7—O1—Br2i	7.0 (5)
C3—C4—C5—C6	−0.1 (4)	O1—C7—O2—C8	−2.0 (4)
C3—C4—C5—C7	178.6 (3)	C5—C7—O2—C8	178.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8C···O2ii	0.98	2.70	3.546 (5)	145
C6—H6···Br2i	0.95	2.93	3.838 (3)	159
C8—H8A···O1iii	0.98	2.69	3.647 (4)	167

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8C⋯O2i	0.98	2.70	3.546 (5)	145
C6—H6⋯Br2ii	0.95	2.93	3.838 (3)	159
C8—H8A⋯O1iii	0.98	2.69	3.647 (4)	167

Symmetry codes: (i) ; (ii) ; (iii) .