Methyl 3,5-dibromo-2-diacetyl-amino-benzoate.

The title methyl benzoate compound, C(12)H(11)Br(2)NO(4), consists of an ortho-substituted diacetyl-amino group and meta-substituted Br atoms. The crystal packing is stabilized by weak inter-molecular C-H⋯O inter-actions.

Related literature

For the use of halogenated benzoates to stimulate the microbial dechlorination of polychlorinated biphenyls, see: Deweerd & Bedard (1999 ▶). For related structures, see: Gowda et al. (2008 ▶); Saeed et al. (2010 ▶); Yathirajan et al. (2007 ▶). For bond lengths, see Allen et al. (1987 ▶).

Experimental

Crystal data

C12H11Br2NO4

M = 393.04

Triclinic,

a = 7.6386 (8) Å

b = 8.8870 (6) Å

c = 10.8691 (8) Å

α = 78.186 (6)°

β = 76.155 (7)°

γ = 82.750 (7)°

V = 698.91 (10) Å3

Z = 2

Mo Kα radiation

μ = 5.81 mm−1

T = 173 K

0.24 × 0.20 × 0.18 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 ▶) T min = 0.336, T max = 0.421

5598 measured reflections

2864 independent reflections

2186 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.070

S = 1.00

2864 reflections

175 parameters

H-atom parameters constrained

Δρmax = 0.43 e Å−3

Δρmin = −0.55 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2010 ▶); 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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811034568/dn2715sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811034568/dn2715Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811034568/dn2715Isup3.cml

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

C12H11Br2NO4	Z = 2
Mr = 393.04	F(000) = 384
Triclinic, P1	Dx = 1.868 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.6386 (8) Å	Cell parameters from 2420 reflections
b = 8.8870 (6) Å	θ = 3.0–32.2°
c = 10.8691 (8) Å	µ = 5.81 mm−1
α = 78.186 (6)°	T = 173 K
β = 76.155 (7)°	Block, colorless
γ = 82.750 (7)°	0.24 × 0.20 × 0.18 mm
V = 698.91 (10) Å3

Oxford Diffraction Xcalibur Eos Gemini diffractometer	2864 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2186 reflections with I > 2σ(I)
graphite	Rint = 0.024
Detector resolution: 16.1500 pixels mm-1	θmax = 26.4°, θmin = 3.0°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	k = −11→11
Tmin = 0.336, Tmax = 0.421	l = −11→13
5598 measured reflections

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.070	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0286P)2 + 0.0926P] where P = (Fo2 + 2Fc2)/3
2864 reflections	(Δ/σ)max < 0.001
175 parameters	Δρmax = 0.43 e Å−3
0 restraints	Δρmin = −0.55 e Å−3

Experimental. The compound was further characterized by 1H nmr and mass spectrum. 1H NMR (CDCl3; 400MHz): - δ 8.165 - 8.17 (d, 1H, J = 2,ArH), 8.038 8.044 (s, 1H, J = 2, ArH,), 3.87 (s, 3H, OCH3), 2.27 (s, 6H , (COCH3)2); 13C NMR ( CDCl3; 100 MHz): - 171.7, 163.39, 139.72, 137.9, 134.0, 131.7, 126.9, 123.3, 53.1, 26.2. Mass data: m/e: - 391 (Molecular ion peak; M+), 393(Isotope peak; M+2), 395 (Isotope peak - M+4).

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	0.13746 (6)	0.87278 (3)	0.09518 (4)	0.05337 (14)
Br2	0.30614 (5)	0.27415 (4)	−0.01150 (3)	0.04699 (13)
O1	0.2257 (4)	0.2652 (3)	0.5162 (2)	0.0654 (8)
O2	0.2736 (3)	0.5047 (2)	0.5174 (2)	0.0455 (6)
O3	0.2313 (3)	−0.0469 (2)	0.3783 (2)	0.0538 (7)
O4	0.6102 (3)	0.2554 (2)	0.2194 (2)	0.0447 (6)
N1	0.3244 (3)	0.1887 (2)	0.2730 (2)	0.0273 (6)
C1	0.2881 (5)	0.4583 (4)	0.6502 (3)	0.0501 (9)
H1A	0.3009	0.5492	0.6844	0.075*
H1B	0.3942	0.3848	0.6553	0.075*
H1C	0.1789	0.4095	0.7009	0.075*
C2	0.2475 (4)	0.3942 (3)	0.4608 (3)	0.0327 (7)
C3	0.2407 (4)	0.4522 (3)	0.3230 (3)	0.0280 (7)
C4	0.2016 (4)	0.6093 (3)	0.2801 (3)	0.0307 (7)
H4A	0.1821	0.6801	0.3377	0.037*
C5	0.1916 (4)	0.6603 (3)	0.1535 (3)	0.0331 (7)
C6	0.2210 (4)	0.5630 (3)	0.0665 (3)	0.0347 (8)
H6A	0.2134	0.6009	−0.0206	0.042*
C7	0.2621 (4)	0.4075 (3)	0.1094 (3)	0.0296 (7)
C8	0.2720 (4)	0.3498 (3)	0.2359 (3)	0.0276 (7)
C9	0.1899 (4)	0.0844 (3)	0.3316 (3)	0.0355 (8)
C10	−0.0001 (5)	0.1457 (4)	0.3313 (4)	0.0465 (9)
H10A	−0.0798	0.0614	0.3641	0.070*
H10B	−0.0102	0.1924	0.2431	0.070*
H10C	−0.0359	0.2239	0.3865	0.070*
C11	0.5116 (5)	0.1516 (3)	0.2524 (3)	0.0344 (8)
C12	0.5843 (5)	−0.0138 (4)	0.2654 (4)	0.0577 (11)
H12A	0.7103	−0.0208	0.2173	0.086*
H12B	0.5118	−0.0714	0.2308	0.086*
H12C	0.5785	−0.0575	0.3565	0.086*

	U11	U22	U33	U12	U13	U23
Br1	0.0831 (3)	0.02434 (17)	0.0510 (2)	0.00970 (17)	−0.0241 (2)	−0.00047 (15)
Br2	0.0767 (3)	0.03558 (18)	0.0315 (2)	−0.00369 (17)	−0.01384 (17)	−0.01074 (14)
O1	0.128 (3)	0.0388 (13)	0.0342 (14)	−0.0195 (15)	−0.0302 (15)	0.0034 (11)
O2	0.0726 (17)	0.0369 (12)	0.0323 (13)	−0.0037 (12)	−0.0202 (12)	−0.0084 (10)
O3	0.0661 (18)	0.0289 (12)	0.0581 (17)	−0.0092 (12)	−0.0070 (13)	0.0061 (11)
O4	0.0358 (14)	0.0382 (12)	0.0600 (17)	−0.0055 (11)	−0.0124 (11)	−0.0050 (11)
N1	0.0329 (15)	0.0171 (11)	0.0305 (14)	−0.0010 (10)	−0.0078 (11)	−0.0009 (10)
C1	0.067 (3)	0.057 (2)	0.034 (2)	−0.0039 (19)	−0.0207 (18)	−0.0143 (17)
C2	0.041 (2)	0.0287 (15)	0.0307 (17)	0.0017 (14)	−0.0128 (14)	−0.0078 (14)
C3	0.0289 (17)	0.0247 (14)	0.0307 (17)	0.0013 (13)	−0.0103 (13)	−0.0035 (12)
C4	0.0350 (18)	0.0253 (14)	0.0332 (17)	0.0015 (13)	−0.0101 (14)	−0.0076 (13)
C5	0.0384 (19)	0.0211 (13)	0.0383 (19)	0.0014 (13)	−0.0115 (14)	−0.0008 (13)
C6	0.041 (2)	0.0314 (15)	0.0301 (18)	−0.0020 (14)	−0.0107 (15)	0.0013 (13)
C7	0.0352 (18)	0.0265 (14)	0.0277 (16)	−0.0022 (13)	−0.0080 (13)	−0.0055 (12)
C8	0.0296 (17)	0.0225 (13)	0.0307 (17)	−0.0007 (12)	−0.0098 (13)	−0.0020 (12)
C9	0.047 (2)	0.0299 (16)	0.0297 (17)	−0.0079 (15)	−0.0066 (15)	−0.0038 (13)
C10	0.040 (2)	0.0471 (19)	0.050 (2)	−0.0118 (17)	−0.0065 (17)	−0.0031 (17)
C11	0.041 (2)	0.0291 (15)	0.0328 (18)	0.0052 (15)	−0.0118 (15)	−0.0065 (13)
C12	0.048 (2)	0.0378 (18)	0.081 (3)	0.0135 (17)	−0.015 (2)	−0.0056 (19)

Br1—C5	1.891 (3)	C3—C8	1.403 (4)
Br2—C7	1.889 (3)	C4—C5	1.376 (4)
O1—C2	1.193 (3)	C4—H4A	0.9500
O2—C2	1.318 (4)	C5—C6	1.370 (4)
O2—C1	1.444 (4)	C6—C7	1.387 (4)
O3—C9	1.209 (3)	C6—H6A	0.9500
O4—C11	1.207 (4)	C7—C8	1.383 (4)
N1—C11	1.400 (4)	C9—C10	1.485 (5)
N1—C9	1.416 (4)	C10—H10A	0.9800
N1—C8	1.439 (3)	C10—H10B	0.9800
C1—H1A	0.9800	C10—H10C	0.9800
C1—H1B	0.9800	C11—C12	1.495 (4)
C1—H1C	0.9800	C12—H12A	0.9800
C2—C3	1.492 (4)	C12—H12B	0.9800
C3—C4	1.397 (4)	C12—H12C	0.9800
C2—O2—C1	115.9 (3)	C8—C7—C6	121.9 (3)
C11—N1—C9	125.7 (2)	C8—C7—Br2	120.3 (2)
C11—N1—C8	114.4 (2)	C6—C7—Br2	117.8 (2)
C9—N1—C8	119.8 (2)	C7—C8—C3	118.9 (2)
O2—C1—H1A	109.5	C7—C8—N1	119.2 (3)
O2—C1—H1B	109.5	C3—C8—N1	121.8 (3)
H1A—C1—H1B	109.5	O3—C9—N1	120.5 (3)
O2—C1—H1C	109.5	O3—C9—C10	123.1 (3)
H1A—C1—H1C	109.5	N1—C9—C10	116.3 (2)
H1B—C1—H1C	109.5	C9—C10—H10A	109.5
O1—C2—O2	123.0 (3)	C9—C10—H10B	109.5
O1—C2—C3	124.9 (3)	H10A—C10—H10B	109.5
O2—C2—C3	112.0 (3)	C9—C10—H10C	109.5
C4—C3—C8	119.5 (3)	H10A—C10—H10C	109.5
C4—C3—C2	119.9 (3)	H10B—C10—H10C	109.5
C8—C3—C2	120.5 (2)	O4—C11—N1	118.5 (3)
C5—C4—C3	119.2 (3)	O4—C11—C12	121.8 (3)
C5—C4—H4A	120.4	N1—C11—C12	119.6 (3)
C3—C4—H4A	120.4	C11—C12—H12A	109.5
C6—C5—C4	122.5 (3)	C11—C12—H12B	109.5
C6—C5—Br1	118.1 (2)	H12A—C12—H12B	109.5
C4—C5—Br1	119.3 (2)	C11—C12—H12C	109.5
C5—C6—C7	117.9 (3)	H12A—C12—H12C	109.5
C5—C6—H6A	121.0	H12B—C12—H12C	109.5
C7—C6—H6A	121.0
C1—O2—C2—O1	4.5 (5)	Br2—C7—C8—N1	2.8 (4)
C1—O2—C2—C3	−178.0 (3)	C4—C3—C8—C7	−0.4 (4)
O1—C2—C3—C4	156.5 (3)	C2—C3—C8—C7	179.1 (3)
O2—C2—C3—C4	−21.0 (4)	C4—C3—C8—N1	175.9 (3)
O1—C2—C3—C8	−23.1 (5)	C2—C3—C8—N1	−4.6 (4)
O2—C2—C3—C8	159.5 (3)	C11—N1—C8—C7	85.5 (4)
C8—C3—C4—C5	1.1 (4)	C9—N1—C8—C7	−97.8 (3)
C2—C3—C4—C5	−178.5 (3)	C11—N1—C8—C3	−90.8 (3)
C3—C4—C5—C6	−0.9 (5)	C9—N1—C8—C3	85.9 (4)
C3—C4—C5—Br1	179.7 (2)	C11—N1—C9—O3	5.9 (5)
C4—C5—C6—C7	0.0 (5)	C8—N1—C9—O3	−170.3 (3)
Br1—C5—C6—C7	179.5 (2)	C11—N1—C9—C10	−173.9 (3)
C5—C6—C7—C8	0.6 (5)	C8—N1—C9—C10	9.9 (4)
C5—C6—C7—Br2	−179.0 (2)	C9—N1—C11—O4	−168.9 (3)
C6—C7—C8—C3	−0.4 (5)	C8—N1—C11—O4	7.5 (4)
Br2—C7—C8—C3	179.2 (2)	C9—N1—C11—C12	14.0 (5)
C6—C7—C8—N1	−176.8 (3)	C8—N1—C11—C12	−169.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O4i	0.98	2.44	3.404 (4)	168.
C6—H6A···O4ii	0.95	2.46	3.237 (4)	140.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O4i	0.98	2.44	3.404 (4)	168
C6—H6A⋯O4ii	0.95	2.46	3.237 (4)	140

Symmetry codes: (i) ; (ii) .