2-Bromo-N-(4-bromo­phen­yl)acetamide

Abstract

In the title compound, C₈H₇Br₂NO, the conformation of the N—H bond is anti to both the carbonyl and C—Br bonds in the side chain. In the crystal structure, mol­ecules are packed into supra­molecular chains along the c axis by N—H⋯O hydrogen bonds.

Related literature

For the preparation of the title compound, see: Gowda et al. (2003 ▶). For related structures, see: Andreetti et al. (1968 ▶); Gowda et al. (2007a ▶,b ▶,c ▶).

Experimental

Crystal data

• C₈H₇Br₂NO

• M _r = 292.97

• Monoclinic,

• a = 4.4987 (3) Å

• b = 23.152 (1) Å

• c = 9.1098 (5) Å

• β = 99.713 (6)°

• V = 935.22 (9) ų

• Z = 4

• Mo Kα radiation

• μ = 8.62 mm⁻¹

• T = 303 K

• 0.50 × 0.20 × 0.14 mm

Data collection

• Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector

• Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.078, T _max = 0.299

• 3065 measured reflections

• 1661 independent reflections

• 1415 reflections with I > 2σ(I)

• R _int = 0.023

Refinement

• R[F ² > 2σ(F ²)] = 0.049

• wR(F ²) = 0.127

• S = 0.99

• 1661 reflections

• 109 parameters

• H-atom parameters constrained

• Δρ_max = 0.73 e Å⁻³

• Δρ_min = −0.68 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1i	0.86	2.11	2.925 (6)	157

Symmetry code: (i) .

supplementary crystallographic information

Comment

As part of a study of the effect of the ring and the side chain substituents on the structures of N-aromatic amides (Gowda et al., 2007a, b, c), in the present work, the structure of 2-bromo-N-(4-bromophenyl)acetamide (I) has been determined (Fig. 1). The conformation of the N—H bond is anti to both the C=O and the C—Br bonds in the side chain, similar to that observed in 2-chloro-N-(4-chlorophenyl)acetamide (Gowda et al., 2007c), N-(4-bromophenyl)acetamide (Andreetti et al., 1968), and other amides (Gowda et al., 2007a, b).

The crystal packing shows N1—H1N···O1 hydrogen bonds (Table 1) that lead to the formation of molecular chain along the c-axis (Fig. 2).

Experimental

Compound (I) was prepared from 4-bromoaniline and bromoacetylchloride according to the literature method (Gowda et al., 2003). Single crystals were obtained by slow evaporation of an ethanolic solution of (I) held at room temperature.

Refinement

The H atoms were positioned with idealized geometry using a riding model [N—H = 0.86 Å, C—H = 0.93—0.97 Å], and were refined with isotropic displacement parameters (set to 1.2 times of the U_eq of the parent atom).

Figures

Fig. 1.

Molecular structure of (I), showing the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are represented as small spheres of arbitrary radii.

Fig. 2.

Molecular packing of (I) with hydrogen bonds shown as dashed lines.

Crystal data

C8H7Br2NO	F(000) = 560
Mr = 292.97	Dx = 2.081 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2250 reflections
a = 4.4987 (3) Å	θ = 2.9–27.8°
b = 23.152 (1) Å	µ = 8.62 mm−1
c = 9.1098 (5) Å	T = 303 K
β = 99.713 (6)°	Needle, colourless
V = 935.22 (9) Å3	0.50 × 0.20 × 0.14 mm
Z = 4

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	1661 independent reflections
Radiation source: fine-focus sealed tube	1415 reflections with I > 2σ(I)
graphite	Rint = 0.023
Rotation method data acquisition using ω and φ scans	θmax = 25.4°, θmin = 2.9°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −5→4
Tmin = 0.078, Tmax = 0.299	k = −16→27
3065 measured reflections	l = −10→9

Refinement

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127	H-atom parameters constrained
S = 0.99	w = 1/[σ2(Fo2) + (0.0581P)2 + 4.1384P] where P = (Fo2 + 2Fc2)/3
1661 reflections	(Δ/σ)max = 0.001
109 parameters	Δρmax = 0.73 e Å−3
0 restraints	Δρmin = −0.68 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.7460 (14)	0.2109 (3)	0.3871 (6)	0.0489 (15)
H1A	0.6432	0.2287	0.4610	0.059*
H1B	0.9218	0.1909	0.4395	0.059*
C2	0.8475 (13)	0.2577 (3)	0.2905 (6)	0.0400 (13)
C3	1.1568 (13)	0.3474 (2)	0.3295 (6)	0.0388 (12)
C4	1.0573 (14)	0.3743 (3)	0.1927 (6)	0.0445 (14)
H4	0.9070	0.3573	0.1236	0.053*
C5	1.1831 (16)	0.4263 (3)	0.1603 (7)	0.0535 (16)
H5	1.1158	0.4444	0.0697	0.064*
C6	1.4056 (14)	0.4510 (3)	0.2609 (7)	0.0473 (15)
C7	1.5067 (15)	0.4251 (3)	0.3949 (7)	0.0538 (16)
H7	1.6576	0.4424	0.4631	0.065*
C8	1.3832 (14)	0.3731 (3)	0.4283 (7)	0.0476 (14)
H8	1.4542	0.3553	0.5189	0.057*
N1	1.0306 (11)	0.2954 (2)	0.3747 (5)	0.0397 (11)
H1N	1.0770	0.2870	0.4677	0.048*
O1	0.7725 (10)	0.26109 (19)	0.1567 (4)	0.0529 (11)
Br1	0.48101 (16)	0.15590 (3)	0.27451 (8)	0.0576 (3)
Br2	1.5669 (2)	0.52368 (3)	0.21830 (9)	0.0722 (3)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.048 (3)	0.063 (4)	0.033 (3)	−0.015 (3)	0.000 (3)	−0.002 (3)
C2	0.038 (3)	0.044 (3)	0.038 (3)	0.007 (3)	0.007 (2)	−0.001 (3)
C3	0.044 (3)	0.037 (3)	0.037 (3)	0.004 (2)	0.012 (2)	−0.005 (2)
C4	0.053 (4)	0.050 (3)	0.029 (3)	0.004 (3)	0.004 (3)	0.003 (3)
C5	0.072 (4)	0.048 (4)	0.042 (3)	0.007 (3)	0.014 (3)	0.006 (3)
C6	0.058 (4)	0.038 (3)	0.053 (4)	−0.001 (3)	0.027 (3)	−0.003 (3)
C7	0.054 (4)	0.057 (4)	0.052 (4)	−0.012 (3)	0.012 (3)	−0.008 (3)
C8	0.048 (3)	0.052 (4)	0.041 (3)	−0.001 (3)	0.003 (3)	0.001 (3)
N1	0.051 (3)	0.039 (2)	0.028 (2)	−0.001 (2)	0.007 (2)	0.006 (2)
O1	0.072 (3)	0.054 (3)	0.030 (2)	−0.012 (2)	−0.001 (2)	−0.0005 (19)
Br1	0.0632 (5)	0.0541 (4)	0.0528 (4)	−0.0127 (3)	0.0024 (3)	−0.0073 (3)
Br2	0.1010 (7)	0.0456 (4)	0.0785 (6)	−0.0099 (4)	0.0392 (5)	−0.0006 (3)

Geometric parameters (Å, °)

C1—C2	1.513 (8)	C4—H4	0.9300
C1—Br1	1.919 (6)	C5—C6	1.363 (9)
C1—H1A	0.9700	C5—H5	0.9300
C1—H1B	0.9700	C6—C7	1.367 (9)
C2—O1	1.211 (7)	C6—Br2	1.898 (6)
C2—N1	1.349 (7)	C7—C8	1.381 (9)
C3—C8	1.376 (8)	C7—H7	0.9300
C3—C4	1.398 (8)	C8—H8	0.9300
C3—N1	1.421 (7)	N1—H1N	0.8600
C4—C5	1.382 (9)
C2—C1—Br1	112.6 (4)	C6—C5—C4	120.2 (6)
C2—C1—H1A	109.1	C6—C5—H5	119.9
Br1—C1—H1A	109.1	C4—C5—H5	119.9
C2—C1—H1B	109.1	C5—C6—C7	120.8 (6)
Br1—C1—H1B	109.1	C5—C6—Br2	119.8 (5)
H1A—C1—H1B	107.8	C7—C6—Br2	119.3 (5)
O1—C2—N1	124.7 (6)	C6—C7—C8	119.6 (6)
O1—C2—C1	124.9 (5)	C6—C7—H7	120.2
N1—C2—C1	110.4 (5)	C8—C7—H7	120.2
C8—C3—C4	118.8 (6)	C3—C8—C7	120.9 (6)
C8—C3—N1	117.7 (5)	C3—C8—H8	119.6
C4—C3—N1	123.5 (5)	C7—C8—H8	119.6
C5—C4—C3	119.8 (6)	C2—N1—C3	128.3 (5)
C5—C4—H4	120.1	C2—N1—H1N	115.8
C3—C4—H4	120.1	C3—N1—H1N	115.8
Br1—C1—C2—O1	0.2 (8)	Br2—C6—C7—C8	178.0 (5)
Br1—C1—C2—N1	179.5 (4)	C4—C3—C8—C7	1.3 (9)
C8—C3—C4—C5	−1.2 (9)	N1—C3—C8—C7	−176.9 (6)
N1—C3—C4—C5	177.0 (5)	C6—C7—C8—C3	−0.9 (10)
C3—C4—C5—C6	0.6 (9)	O1—C2—N1—C3	4.1 (9)
C4—C5—C6—C7	−0.3 (10)	C1—C2—N1—C3	−175.1 (5)
C4—C5—C6—Br2	−177.8 (5)	C8—C3—N1—C2	−167.5 (6)
C5—C6—C7—C8	0.4 (10)	C4—C3—N1—C2	14.3 (9)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1i	0.86	2.11	2.925 (6)	157

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