4-[(4-Bromo-phenyl)amino]-2-methyl-idene-4-oxo-butanoic acid.

In the title compound, C11H10BrNO3, two independent mol-ecules (A and B) crystallize in the asymmetric unit. The dihedral angles between the mean planes of the 4-bromo-phenyl ring and amide group are 24.8 (7) in mol-ecule A and 77.1 (6)° in mol-ecule B. The mean plane of the methyl-idene group is further inclined by 75.6 (4) in mol-ecule A and 72.5 (6)° in mol-ecule B from that of the amide group. In the crystal, N-H⋯O hydrogen bonds formed by amide groups and O-H⋯O hydrogen bonds formed by carb-oxy-lic acid groups are observed and supported additionally by weak C-H⋯O inter-actions between the methyl-idene and amide groups. Together, these link the mol-ecules into chains of dimers along [110] and form R 2 (2)(8) graph-set motifs.

Related literature

For the pharmacological activity of amide derivatives, see: Galanakis et al. (2004 ▶); Kumar & Knaus (1993 ▶); Ban et al. (1998 ▶); Ukrainets et al. (2006 ▶), Lesyk & Zimenkovsky (2004 ▶); Gududuru et al. (2004 ▶). For related structures, see: Nayak et al. (2013a ▶,b ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C11H10BrNO3

M = 284.11

Triclinic,

a = 6.2782 (4) Å

b = 8.3251 (5) Å

c = 21.3244 (12) Å

α = 96.462 (5)°

β = 92.026 (5)°

γ = 95.390 (5)°

V = 1101.38 (11) Å3

Z = 4

Cu Kα radiation

μ = 5.04 mm−1

T = 173 K

0.44 × 0.28 × 0.14 mm

Data collection

Agilent Eos Gemini diffractometer

Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ▶) T min = 0.162, T max = 1.000

7163 measured reflections

4131 independent reflections

3490 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.076

wR(F 2) = 0.227

S = 1.03

4131 reflections

291 parameters

H-atom parameters constrained

Δρmax = 2.73 e Å−3

Δρmin = −0.79 e Å−3

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012 ▶); program(s) used to solve structure: SUPERFLIP (Palatinus et al., 2012 ▶); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814012872/bt6983sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814012872/bt6983Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814012872/bt6983Isup3.cml

CCDC reference: 1006395

Additional supporting information: crystallographic information; 3D view; checkCIF report

C11H10BrNO3	V = 1101.38 (11) Å3
Mr = 284.11	Z = 4
Triclinic, P1	F(000) = 568
a = 6.2782 (4) Å	Dx = 1.713 Mg m−3
b = 8.3251 (5) Å	Cu Kα radiation, λ = 1.54184 Å
c = 21.3244 (12) Å	µ = 5.04 mm−1
α = 96.462 (5)°	T = 173 K
β = 92.026 (5)°	Prism, colourless
γ = 95.390 (5)°	0.44 × 0.28 × 0.14 mm

Agilent Eos Gemini diffractometer	3490 reflections with I > 2σ(I)
Detector resolution: 16.0416 pixels mm-1	Rint = 0.033
ω scans	θmax = 71.3°, θmin = 4.2°
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)	h = −7→6
Tmin = 0.162, Tmax = 1.000	k = −8→10
7163 measured reflections	l = −26→25
4131 independent reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.076	H-atom parameters constrained
wR(F2) = 0.227	w = 1/[σ2(Fo2) + (0.1446P)2 + 3.2341P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
4131 reflections	Δρmax = 2.73 e Å−3
291 parameters	Δρmin = −0.79 e Å−3
0 restraints

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.

	x	y	z	Uiso*/Ueq
Br1A	0.19572 (14)	0.90862 (10)	0.46174 (4)	0.0619 (3)
O1A	0.8488 (6)	0.7490 (4)	0.20741 (18)	0.0363 (9)
O2A	0.6832 (6)	0.6335 (5)	0.05368 (18)	0.0338 (8)
O3A	1.0137 (6)	0.7205 (5)	0.02870 (19)	0.0370 (9)
H3A	0.9464	0.7607	0.0005	0.056*
N1A	0.5872 (7)	0.5635 (5)	0.2341 (2)	0.0275 (9)
H1A	0.5246	0.4649	0.2229	0.033*
C1A	0.7571 (7)	0.6114 (6)	0.2006 (2)	0.0240 (9)
C2A	0.8300 (8)	0.4766 (6)	0.1541 (2)	0.0266 (10)
H2AA	0.9036	0.4004	0.1777	0.032*
H2AB	0.7033	0.4152	0.1307	0.032*
C3A	0.9795 (8)	0.5448 (6)	0.1078 (2)	0.0274 (10)
C4A	0.8780 (8)	0.6358 (6)	0.0606 (2)	0.0269 (10)
C5A	1.1839 (9)	0.5217 (7)	0.1064 (3)	0.0354 (11)
H5AA	1.2692	0.5636	0.0749	0.042*
H5AB	1.2461	0.4633	0.1370	0.042*
C6A	0.5009 (8)	0.6552 (6)	0.2849 (2)	0.0279 (10)
C7A	0.6134 (10)	0.7860 (7)	0.3221 (3)	0.0375 (12)
H7A	0.7542	0.8230	0.3118	0.045*
C8A	0.5228 (11)	0.8617 (8)	0.3733 (3)	0.0448 (14)
H8A	0.6006	0.9516	0.3981	0.054*
C9A	0.3196 (10)	0.8086 (7)	0.3892 (3)	0.0400 (13)
C10A	0.2019 (9)	0.6772 (8)	0.3529 (3)	0.0426 (13)
H10A	0.0608	0.6415	0.3634	0.051*
C11A	0.2942 (9)	0.6008 (7)	0.3017 (3)	0.0392 (12)
H11A	0.2172	0.5099	0.2774	0.047*
Br1B	1.30729 (11)	0.53869 (9)	0.55597 (3)	0.0518 (3)
O1B	0.6584 (6)	0.7564 (4)	0.79041 (17)	0.0313 (8)
O2B	0.8098 (5)	0.8720 (5)	0.94320 (18)	0.0333 (8)
O3B	0.4808 (6)	0.7820 (5)	0.96889 (19)	0.0365 (8)
H3B	0.5499	0.7275	0.9919	0.055*
N1B	0.8836 (7)	0.9562 (5)	0.7586 (2)	0.0310 (9)
H1B	0.9272	1.0606	0.7645	0.037*
C1B	0.7305 (7)	0.8992 (6)	0.7954 (2)	0.0237 (9)
C2B	0.6529 (8)	1.0295 (6)	0.8428 (2)	0.0276 (10)
H2BA	0.7784	1.0939	0.8657	0.033*
H2BB	0.5740	1.1040	0.8198	0.033*
C3B	0.5089 (8)	0.9580 (5)	0.8900 (2)	0.0252 (9)
C4B	0.6144 (8)	0.8670 (6)	0.9365 (2)	0.0258 (9)
C5B	0.3032 (8)	0.9786 (7)	0.8930 (2)	0.0331 (11)
H5BA	0.2219	0.9351	0.9250	0.040*
H5BB	0.2367	1.0368	0.8632	0.040*
C6B	0.9792 (8)	0.8566 (6)	0.7107 (2)	0.0297 (10)
C7B	1.1837 (9)	0.8118 (7)	0.7222 (3)	0.0334 (11)
H7B	1.2567	0.8449	0.7620	0.040*
C8B	1.2805 (8)	0.7188 (7)	0.6754 (3)	0.0343 (11)
H8B	1.4207	0.6889	0.6830	0.041*
C9B	1.1733 (9)	0.6699 (7)	0.6181 (2)	0.0336 (11)
C10B	0.9703 (9)	0.7144 (8)	0.6061 (3)	0.0424 (13)
H10B	0.8977	0.6808	0.5663	0.051*
C11B	0.8740 (8)	0.8084 (7)	0.6526 (3)	0.0359 (12)
H11B	0.7350	0.8398	0.6445	0.043*

	U11	U22	U33	U12	U13	U23
Br1A	0.0789 (6)	0.0637 (5)	0.0493 (5)	0.0310 (4)	0.0312 (4)	0.0047 (3)
O1A	0.041 (2)	0.0251 (18)	0.040 (2)	−0.0048 (16)	0.0117 (16)	−0.0027 (14)
O2A	0.0245 (18)	0.039 (2)	0.040 (2)	0.0063 (15)	0.0030 (14)	0.0113 (15)
O3A	0.0278 (18)	0.047 (2)	0.039 (2)	0.0037 (16)	0.0037 (15)	0.0125 (16)
N1A	0.027 (2)	0.0222 (19)	0.032 (2)	−0.0017 (16)	0.0045 (16)	−0.0020 (15)
C1A	0.026 (2)	0.020 (2)	0.026 (2)	0.0045 (18)	0.0000 (17)	0.0010 (17)
C2A	0.029 (2)	0.021 (2)	0.030 (2)	0.0065 (18)	0.0011 (18)	0.0014 (17)
C3A	0.028 (2)	0.021 (2)	0.031 (2)	0.0035 (18)	0.0017 (19)	−0.0039 (18)
C4A	0.026 (2)	0.026 (2)	0.027 (2)	0.0023 (18)	0.0053 (18)	−0.0024 (18)
C5A	0.033 (3)	0.040 (3)	0.034 (3)	0.011 (2)	0.001 (2)	0.003 (2)
C6A	0.030 (2)	0.024 (2)	0.032 (2)	0.0059 (19)	0.0064 (19)	0.0058 (18)
C7A	0.044 (3)	0.030 (3)	0.038 (3)	0.000 (2)	0.007 (2)	0.001 (2)
C8A	0.055 (4)	0.040 (3)	0.038 (3)	0.004 (3)	0.007 (3)	−0.001 (2)
C9A	0.047 (3)	0.039 (3)	0.039 (3)	0.019 (3)	0.021 (2)	0.008 (2)
C10A	0.030 (3)	0.046 (3)	0.054 (4)	0.009 (2)	0.016 (2)	0.008 (3)
C11A	0.030 (3)	0.034 (3)	0.054 (3)	0.003 (2)	0.011 (2)	0.002 (2)
Br1B	0.0503 (5)	0.0635 (5)	0.0428 (4)	0.0220 (3)	0.0143 (3)	−0.0059 (3)
O1B	0.0333 (19)	0.0234 (17)	0.0361 (19)	−0.0004 (14)	0.0089 (14)	−0.0006 (14)
O2B	0.0243 (18)	0.038 (2)	0.039 (2)	0.0041 (15)	0.0041 (14)	0.0113 (15)
O3B	0.0252 (17)	0.047 (2)	0.040 (2)	0.0045 (16)	0.0022 (14)	0.0143 (16)
N1B	0.030 (2)	0.024 (2)	0.037 (2)	0.0008 (17)	0.0092 (17)	−0.0013 (16)
C1B	0.020 (2)	0.024 (2)	0.027 (2)	0.0057 (18)	−0.0015 (17)	0.0004 (17)
C2B	0.030 (2)	0.022 (2)	0.032 (2)	0.0050 (19)	0.0047 (19)	0.0008 (18)
C3B	0.026 (2)	0.020 (2)	0.029 (2)	0.0034 (18)	0.0031 (18)	−0.0034 (17)
C4B	0.024 (2)	0.025 (2)	0.028 (2)	0.0052 (18)	0.0026 (17)	−0.0013 (17)
C5B	0.031 (3)	0.037 (3)	0.031 (3)	0.008 (2)	0.002 (2)	−0.001 (2)
C6B	0.028 (2)	0.026 (2)	0.036 (3)	0.0035 (19)	0.0087 (19)	0.0030 (19)
C7B	0.032 (3)	0.035 (3)	0.033 (3)	0.004 (2)	0.002 (2)	0.002 (2)
C8B	0.030 (3)	0.041 (3)	0.034 (3)	0.013 (2)	0.005 (2)	0.004 (2)
C9B	0.033 (3)	0.036 (3)	0.033 (3)	0.008 (2)	0.009 (2)	0.000 (2)
C10B	0.032 (3)	0.060 (4)	0.034 (3)	0.009 (3)	−0.002 (2)	−0.001 (2)
C11B	0.026 (2)	0.046 (3)	0.038 (3)	0.011 (2)	0.002 (2)	0.006 (2)

Br1A—C9A	1.899 (5)	Br1B—C9B	1.893 (5)
O1A—C1A	1.223 (6)	O1B—C1B	1.224 (6)
O2A—C4A	1.225 (6)	O2B—C4B	1.226 (6)
O3A—H3A	0.8400	O3B—H3B	0.8400
O3A—C4A	1.312 (6)	O3B—C4B	1.311 (6)
N1A—H1A	0.8800	N1B—H1B	0.8800
N1A—C1A	1.359 (6)	N1B—C1B	1.346 (6)
N1A—C6A	1.408 (6)	N1B—C6B	1.428 (6)
C1A—C2A	1.527 (6)	C1B—C2B	1.525 (6)
C2A—H2AA	0.9900	C2B—H2BA	0.9900
C2A—H2AB	0.9900	C2B—H2BB	0.9900
C2A—C3A	1.506 (7)	C2B—C3B	1.511 (7)
C3A—C4A	1.487 (7)	C3B—C4B	1.488 (7)
C3A—C5A	1.316 (7)	C3B—C5B	1.321 (7)
C5A—H5AA	0.9500	C5B—H5BA	0.9500
C5A—H5AB	0.9500	C5B—H5BB	0.9500
C6A—C7A	1.391 (7)	C6B—C7B	1.392 (7)
C6A—C11A	1.406 (7)	C6B—C11B	1.382 (8)
C7A—H7A	0.9500	C7B—H7B	0.9500
C7A—C8A	1.367 (8)	C7B—C8B	1.385 (8)
C8A—H8A	0.9500	C8B—H8B	0.9500
C8A—C9A	1.377 (9)	C8B—C9B	1.375 (8)
C9A—C10A	1.400 (9)	C9B—C10B	1.383 (8)
C10A—H10A	0.9500	C10B—H10B	0.9500
C10A—C11A	1.374 (8)	C10B—C11B	1.384 (8)
C11A—H11A	0.9500	C11B—H11B	0.9500
C4A—O3A—H3A	109.5	C4B—O3B—H3B	109.5
C1A—N1A—H1A	116.6	C1B—N1B—H1B	118.2
C1A—N1A—C6A	126.8 (4)	C1B—N1B—C6B	123.7 (4)
C6A—N1A—H1A	116.6	C6B—N1B—H1B	118.2
O1A—C1A—N1A	123.8 (4)	O1B—C1B—N1B	123.0 (4)
O1A—C1A—C2A	122.0 (4)	O1B—C1B—C2B	123.2 (4)
N1A—C1A—C2A	114.1 (4)	N1B—C1B—C2B	113.8 (4)
C1A—C2A—H2AA	109.4	C1B—C2B—H2BA	109.2
C1A—C2A—H2AB	109.4	C1B—C2B—H2BB	109.2
H2AA—C2A—H2AB	108.0	H2BA—C2B—H2BB	107.9
C3A—C2A—C1A	111.3 (4)	C3B—C2B—C1B	112.3 (4)
C3A—C2A—H2AA	109.4	C3B—C2B—H2BA	109.2
C3A—C2A—H2AB	109.4	C3B—C2B—H2BB	109.2
C4A—C3A—C2A	115.1 (4)	C4B—C3B—C2B	116.0 (4)
C5A—C3A—C2A	123.7 (5)	C5B—C3B—C2B	123.6 (5)
C5A—C3A—C4A	121.1 (5)	C5B—C3B—C4B	120.3 (5)
O2A—C4A—O3A	123.5 (5)	O2B—C4B—O3B	123.7 (4)
O2A—C4A—C3A	121.9 (5)	O2B—C4B—C3B	122.0 (5)
O3A—C4A—C3A	114.5 (4)	O3B—C4B—C3B	114.2 (4)
C3A—C5A—H5AA	120.0	C3B—C5B—H5BA	120.0
C3A—C5A—H5AB	120.0	C3B—C5B—H5BB	120.0
H5AA—C5A—H5AB	120.0	H5BA—C5B—H5BB	120.0
C7A—C6A—N1A	124.1 (5)	C7B—C6B—N1B	119.2 (5)
C7A—C6A—C11A	118.7 (5)	C11B—C6B—N1B	121.0 (5)
C11A—C6A—N1A	117.0 (5)	C11B—C6B—C7B	119.8 (5)
C6A—C7A—H7A	119.7	C6B—C7B—H7B	120.1
C8A—C7A—C6A	120.5 (6)	C8B—C7B—C6B	119.8 (5)
C8A—C7A—H7A	119.7	C8B—C7B—H7B	120.1
C7A—C8A—H8A	119.7	C7B—C8B—H8B	120.1
C7A—C8A—C9A	120.5 (6)	C9B—C8B—C7B	119.8 (5)
C9A—C8A—H8A	119.7	C9B—C8B—H8B	120.1
C8A—C9A—Br1A	120.8 (5)	C8B—C9B—Br1B	118.8 (4)
C8A—C9A—C10A	120.5 (5)	C8B—C9B—C10B	120.8 (5)
C10A—C9A—Br1A	118.6 (4)	C10B—C9B—Br1B	120.4 (4)
C9A—C10A—H10A	120.6	C9B—C10B—H10B	120.3
C11A—C10A—C9A	118.7 (5)	C9B—C10B—C11B	119.4 (5)
C11A—C10A—H10A	120.6	C11B—C10B—H10B	120.3
C6A—C11A—H11A	119.5	C6B—C11B—C10B	120.3 (5)
C10A—C11A—C6A	121.1 (5)	C6B—C11B—H11B	119.8
C10A—C11A—H11A	119.5	C10B—C11B—H11B	119.8
Br1A—C9A—C10A—C11A	−177.6 (5)	Br1B—C9B—C10B—C11B	179.0 (5)
O1A—C1A—C2A—C3A	−15.6 (6)	O1B—C1B—C2B—C3B	10.3 (6)
N1A—C1A—C2A—C3A	166.0 (4)	N1B—C1B—C2B—C3B	−170.7 (4)
N1A—C6A—C7A—C8A	−175.5 (5)	N1B—C6B—C7B—C8B	−178.3 (5)
N1A—C6A—C11A—C10A	176.3 (5)	N1B—C6B—C11B—C10B	178.8 (5)
C1A—N1A—C6A—C7A	−22.1 (8)	C1B—N1B—C6B—C7B	−103.4 (6)
C1A—N1A—C6A—C11A	163.5 (5)	C1B—N1B—C6B—C11B	78.4 (7)
C1A—C2A—C3A—C4A	−70.4 (5)	C1B—C2B—C3B—C4B	69.5 (5)
C1A—C2A—C3A—C5A	112.3 (5)	C1B—C2B—C3B—C5B	−113.4 (5)
C2A—C3A—C4A—O2A	−10.9 (7)	C2B—C3B—C4B—O2B	11.7 (7)
C2A—C3A—C4A—O3A	167.5 (4)	C2B—C3B—C4B—O3B	−168.0 (4)
C5A—C3A—C4A—O2A	166.4 (5)	C5B—C3B—C4B—O2B	−165.5 (5)
C5A—C3A—C4A—O3A	−15.1 (7)	C5B—C3B—C4B—O3B	14.8 (7)
C6A—N1A—C1A—O1A	−6.1 (8)	C6B—N1B—C1B—O1B	−0.6 (8)
C6A—N1A—C1A—C2A	172.3 (4)	C6B—N1B—C1B—C2B	−179.6 (4)
C6A—C7A—C8A—C9A	0.7 (9)	C6B—C7B—C8B—C9B	−0.6 (8)
C7A—C6A—C11A—C10A	1.6 (9)	C7B—C6B—C11B—C10B	0.6 (9)
C7A—C8A—C9A—Br1A	178.0 (5)	C7B—C8B—C9B—Br1B	−178.5 (4)
C7A—C8A—C9A—C10A	−0.6 (10)	C7B—C8B—C9B—C10B	0.9 (9)
C8A—C9A—C10A—C11A	1.0 (9)	C8B—C9B—C10B—C11B	−0.4 (10)
C9A—C10A—C11A—C6A	−1.5 (9)	C9B—C10B—C11B—C6B	−0.3 (9)
C11A—C6A—C7A—C8A	−1.1 (8)	C11B—C6B—C7B—C8B	−0.1 (8)

D—H···A	D—H	H···A	D···A	D—H···A
O3A—H3A···O2Bi	0.84	1.85	2.685 (5)	174
N1A—H1A···O1Bii	0.88	2.06	2.933 (5)	170
O3B—H3B···O2Aiii	0.84	1.82	2.654 (5)	170
N1B—H1B···O1Aiv	0.88	2.04	2.848 (6)	152
C5B—H5BB···O1Av	0.95	2.54	3.464 (7)	164

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3A—H3A⋯O2B i	0.84	1.85	2.685 (5)	174
N1A—H1A⋯O1B ii	0.88	2.06	2.933 (5)	170
O3B—H3B⋯O2A iii	0.84	1.82	2.654 (5)	170
N1B—H1B⋯O1A iv	0.88	2.04	2.848 (6)	152
C5B—H5BB⋯O1A v	0.95	2.54	3.464 (7)	164

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