2-Bromo-N-(2-chloro­phen­yl)acetamide

Gowda, B.T.; Foro, S.; Suchetan, P.A.; Fuess, H.; Terao, H.

doi:10.1107/S1600536809028918

organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1998

doi:10.1107/S1600536809028918

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2-Bromo-N-(2-chlorophenyl)acetamide

B. Thimme Gowda,^a ^* Sabine Foro,^b P. A. Suchetan,^a Hartmut Fuess ^b and Hiromitsu Terao ^c

^aDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, Mangalore, India, ^bInstitute of Materials Science, Darmstadt University of Technology, Petersenstrasse 23, D-64287 Darmstadt, Germany, and ^cFaculty of Integrated Arts and Sciences, Tokushima University, Minamijosanjima-cho, Tokushima 770-8502, Japan
^*Correspondence e-mail: gowdabt@yahoo.com

(Received 7 July 2009; accepted 21 July 2009; online 25 July 2009)

The conformation of the N—H bond in the structure of the title compound, C₈H₇BrClNO, is syn to the 2-chloro substituent in the aniline ring and anti to both the C=O and C—Br bonds in the side chain, similar to that observed in 2-chloro-N-(2-chlorophenyl)acetamide. In the crystal, molecules are linked into chains along the a axis by N—H⋯O hydrogen bonds. These chains are in turn linked into pairs, in the form of columns, through much weaker C—H⋯Cl and Br⋯Br [4.3027 (3) Å] interactions.

Related literature

For the preparation of the compound, see: Gowda et al. (2003 ). For our studies of the effect of ring and side-chain substituents on the structures of N-aromatic amides, see: Gowda et al. (2007a ,b ,c )

Experimental

Crystal data

C₈H₇BrClNO
M_r = 248.51
Monoclinic, P 2₁ /n
a = 9.9781 (9) Å
b = 4.7161 (5) Å
c = 20.028 (2) Å
β = 102.194 (9)°
V = 921.21 (16) Å³
Z = 4
Cu Kα radiation
μ = 8.36 mm⁻¹
T = 299 K
0.55 × 0.20 × 0.15 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.071, T_max = 0.286
2349 measured reflections
1650 independent reflections
1482 reflections with I > 2σ(I)
R_int = 0.023
3 standard reflections frequency: 120 min intensity decay: 1.0%

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.118
S = 1.11
1650 reflections
113 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.87 e Å⁻³
Δρ_min = −0.88 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.839 (19)	2.05 (2)	2.852 (4)	160 (4)
C8—H8B⋯Cl1ⁱⁱ	0.97	3.09	3.765 (5)	128
Symmetry codes: (i) x, y-1, z; (ii) -x+1, -y, -z+2.

Data collection: CAD-4-PC (Enraf–Nonius, 1996 ); cell refinement: CAD-4-PC; data reduction: REDU4 (Stoe & Cie, 1987 ); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809028918/bg2279sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809028918/bg2279Isup2.hkl

checkCIF report

Comment top

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 we report the structure of 2-bromo-N-(2-chlorophenyl)acetamide (I). The conformation of the N—H bond in the structure is syn to the ortho-Cl substituent in the aniline ring and anti to both the C=O and C—Br bonds in the side chain (Fig. 1), similar to that observed in 2-chloro-N-(2-chlorophenyl)acetamide (Gowda et al., 2007a) and other side chain substituted aromatic amides.

The packing diagram in Fig. 2 shows the formation of molecular chains in the direction of the a axis through the N1—H1N···O1 H-bonds (Table 1). These chains are in turn linked into pairs, in the form of strips, through much weaker C—H···Cl and Br···Br interactions.

Related literature top

For preparation of the compound, see: Gowda et al. (2003). For our study of the effect of ring and side-chain substituents on the structures of N-aromatic amides, see: Gowda et al. (2007a,b,c)

Experimental top

The title compound was prepared from 2-chloroaniline and bromoacetylchloride according to the literature method (Gowda et al., 2003). The purity of the compound was checked by determining its melting point, and further characterized by recording its infrared spectra (Gowda et al., 2003). Single crystals of the title compound used for X-ray diffraction studies were obtained by slow evaporation of an ethanolic solution at room temperature.

Computing details top

Data collection: CAD-4-PC (Enraf–Nonius, 1996); cell refinement: CAD-4-PC (Enraf–Nonius, 1996); data reduction: REDU4 (Stoe & Cie, 1987); 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 (Sheldrick, 2008).

Figures top

	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) showing chains, with hydrogen bonds shown as dashed lines. The unit cell is shown as "broken" along the c direction, for completeness.

2-Bromo-N-(2-chlorophenyl)acetamide top

Crystal data top

C₈H₇BrClNO	F(000) = 488
M_r = 248.51	D_x = 1.792 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 9.9781 (9) Å	θ = 7.3–22.5°
b = 4.7161 (5) Å	µ = 8.36 mm⁻¹
c = 20.028 (2) Å	T = 299 K
β = 102.194 (9)°	Rod, colourless
V = 921.21 (16) Å³	0.55 × 0.20 × 0.15 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1482 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.023
Graphite monochromator	θ_max = 67.0°, θ_min = 4.5°
ω/2θ scans	h = −11→3
Absorption correction: ψ scan (North et al., 1968)	k = −5→0
T_min = 0.071, T_max = 0.286	l = −23→23
2349 measured reflections	3 standard reflections every 120 min
1650 independent reflections	intensity decay: 1.0%

Refinement top

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)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.118	w = 1/[σ²(F_o²) + (0.0557P)² + 1.2453P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max = 0.002
1650 reflections	Δρ_max = 0.87 e Å⁻³
113 parameters	Δρ_min = −0.88 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0137 (8)

Crystal data top

C₈H₇BrClNO	V = 921.21 (16) Å³
M_r = 248.51	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 9.9781 (9) Å	µ = 8.36 mm⁻¹
b = 4.7161 (5) Å	T = 299 K
c = 20.028 (2) Å	0.55 × 0.20 × 0.15 mm
β = 102.194 (9)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1482 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.023
T_min = 0.071, T_max = 0.286	3 standard reflections every 120 min
2349 measured reflections	intensity decay: 1.0%
1650 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	1 restraint
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.87 e Å⁻³
1650 reflections	Δρ_min = −0.88 e Å⁻³
113 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
C1	0.2297 (3)	0.0215 (7)	1.03419 (17)	0.0397 (7)
C2	0.3291 (3)	−0.0895 (7)	1.08624 (18)	0.0425 (8)
C3	0.3353 (4)	−0.0151 (10)	1.15353 (19)	0.0551 (9)
H3	0.4019	−0.0941	1.1881	0.066*
C4	0.2433 (5)	0.1749 (10)	1.1691 (2)	0.0629 (11)
H4	0.2482	0.2279	1.2143	0.075*
C5	0.1426 (5)	0.2888 (9)	1.1178 (2)	0.0591 (10)
H5	0.0795	0.4170	1.1285	0.071*
C6	0.1361 (4)	0.2117 (9)	1.0508 (2)	0.0501 (9)
H6	0.0683	0.2881	1.0165	0.060*
C7	0.2077 (4)	0.1136 (7)	0.91258 (19)	0.0446 (8)
C8	0.2212 (5)	−0.0244 (9)	0.84652 (19)	0.0564 (10)
H8A	0.2136	−0.2284	0.8507	0.068*
H8B	0.3111	0.0170	0.8378	0.068*
N1	0.2235 (3)	−0.0623 (6)	0.96571 (15)	0.0421 (6)
H1N	0.234 (4)	−0.233 (5)	0.957 (2)	0.050*
O1	0.1903 (4)	0.3694 (5)	0.91641 (16)	0.0658 (8)
Cl1	0.44859 (10)	−0.3266 (2)	1.06732 (5)	0.0583 (3)
Br1	0.08344 (5)	0.10591 (13)	0.77113 (2)	0.0742 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0435 (16)	0.0345 (16)	0.0401 (17)	−0.0053 (14)	0.0065 (13)	−0.0034 (14)
C2	0.0444 (17)	0.0402 (17)	0.0426 (18)	−0.0046 (14)	0.0083 (14)	−0.0022 (14)
C3	0.067 (2)	0.057 (2)	0.0396 (19)	−0.0064 (19)	0.0055 (17)	−0.0013 (18)
C4	0.080 (3)	0.067 (3)	0.047 (2)	−0.010 (2)	0.025 (2)	−0.013 (2)
C5	0.065 (2)	0.055 (2)	0.064 (2)	0.002 (2)	0.029 (2)	−0.013 (2)
C6	0.0485 (19)	0.048 (2)	0.054 (2)	0.0036 (16)	0.0099 (16)	−0.0042 (18)
C7	0.0530 (19)	0.0367 (18)	0.0393 (18)	0.0005 (14)	−0.0010 (14)	−0.0023 (14)
C8	0.076 (3)	0.051 (2)	0.0387 (19)	0.009 (2)	0.0048 (17)	−0.0008 (18)
N1	0.0542 (16)	0.0332 (14)	0.0353 (15)	0.0038 (13)	0.0016 (12)	−0.0039 (12)
O1	0.108 (2)	0.0331 (14)	0.0523 (17)	0.0082 (14)	0.0087 (16)	−0.0002 (11)
Cl1	0.0509 (5)	0.0628 (6)	0.0573 (6)	0.0146 (4)	0.0025 (4)	−0.0032 (5)
Br1	0.0792 (4)	0.0936 (5)	0.0427 (3)	−0.0058 (3)	−0.0035 (2)	0.0111 (2)

Geometric parameters (Å, º) top

C1—C2	1.381 (5)	C5—H5	0.9300
C1—C6	1.385 (5)	C6—H6	0.9300
C1—N1	1.416 (4)	C7—O1	1.223 (4)
C2—C3	1.381 (5)	C7—N1	1.332 (5)
C2—Cl1	1.734 (4)	C7—C8	1.506 (5)
C3—C4	1.365 (6)	C8—Br1	1.916 (4)
C3—H3	0.9300	C8—H8A	0.9700
C4—C5	1.385 (7)	C8—H8B	0.9700
C4—H4	0.9300	N1—H1N	0.839 (19)
C5—C6	1.377 (6)

C2—C1—C6	118.5 (3)	C5—C6—C1	120.6 (4)
C2—C1—N1	120.2 (3)	C5—C6—H6	119.7
C6—C1—N1	121.3 (3)	C1—C6—H6	119.7
C1—C2—C3	121.2 (3)	O1—C7—N1	124.0 (4)
C1—C2—Cl1	119.8 (3)	O1—C7—C8	121.4 (4)
C3—C2—Cl1	119.1 (3)	N1—C7—C8	114.5 (3)
C4—C3—C2	119.7 (4)	C7—C8—Br1	111.8 (3)
C4—C3—H3	120.1	C7—C8—H8A	109.3
C2—C3—H3	120.1	Br1—C8—H8A	109.3
C3—C4—C5	120.1 (4)	C7—C8—H8B	109.3
C3—C4—H4	119.9	Br1—C8—H8B	109.3
C5—C4—H4	119.9	H8A—C8—H8B	107.9
C6—C5—C4	119.8 (4)	C7—N1—C1	125.0 (3)
C6—C5—H5	120.1	C7—N1—H1N	115 (3)
C4—C5—H5	120.1	C1—N1—H1N	120 (3)

C6—C1—C2—C3	0.4 (5)	C2—C1—C6—C5	0.3 (6)
N1—C1—C2—C3	−178.7 (3)	N1—C1—C6—C5	179.3 (4)
C6—C1—C2—Cl1	−179.6 (3)	O1—C7—C8—Br1	−46.2 (5)
N1—C1—C2—Cl1	1.3 (4)	N1—C7—C8—Br1	137.2 (3)
C1—C2—C3—C4	−1.1 (6)	O1—C7—N1—C1	−3.4 (6)
Cl1—C2—C3—C4	178.9 (3)	C8—C7—N1—C1	173.1 (3)
C2—C3—C4—C5	1.1 (7)	C2—C1—N1—C7	−134.5 (4)
C3—C4—C5—C6	−0.5 (7)	C6—C1—N1—C7	46.5 (5)
C4—C5—C6—C1	−0.2 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.84 (2)	2.05 (2)	2.852 (4)	160 (4)
C8—H8B···Cl1ⁱⁱ	0.97	3.09	3.765 (5)	128

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

Experimental details

Crystal data
Chemical formula	C₈H₇BrClNO
M_r	248.51
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	299
a, b, c (Å)	9.9781 (9), 4.7161 (5), 20.028 (2)
β (°)	102.194 (9)
V (Å³)	921.21 (16)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	8.36
Crystal size (mm)	0.55 × 0.20 × 0.15

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.071, 0.286
No. of measured, independent and observed [I > 2σ(I)] reflections	2349, 1650, 1482
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.118, 1.11
No. of reflections	1650
No. of parameters	113
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.87, −0.88

Computer programs: CAD-4-PC (Enraf–Nonius, 1996), REDU4 (Stoe & Cie, 1987), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.839 (19)	2.05 (2)	2.852 (4)	160 (4)
C8—H8B···Cl1ⁱⁱ	0.97	3.09	3.765 (5)	127.6

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

Acknowledgements

BTG thanks the Alexander von Humboldt Foundation, Bonn, Germany, for extensions of his research fellowship.

References

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