2,2,2-Tribromo-N-(3-chloro­phen­yl)acetamide

Abstract

In the title compound, C₈H₅Br₃ClNO, the conformation of the N—H bond is anti to the 3-chloro substituent in the benzene ring. An intra­molecular N—H⋯Br hydrogen bond occurs. In the crystal, mol­ecules are packed into infinite chains in the a-axis direction by N—H⋯O hydrogen bonds.

Related literature

For the preparation of the title compound, see: Gowda et al. (2003 ▶). For background and related structures, see: Brown (1966 ▶); Gowda et al. (2008 ▶, 2009 ▶, 2010 ▶).

Experimental

Crystal data

• C₈H₅Br₃ClNO

• M _r = 406.31

• Orthorhombic,

• a = 12.803 (1) Å

• b = 9.146 (1) Å

• c = 20.221 (3) Å

• V = 2367.8 (5) ų

• Z = 8

• Cu Kα radiation

• μ = 14.47 mm⁻¹

• T = 299 K

• 0.53 × 0.33 × 0.25 mm

Data collection

• Enraf–Nonius CAD-4 diffractometer

• Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.049, T _max = 0.123

• 3870 measured reflections

• 2114 independent reflections

• 1646 reflections with I > 2σ(I)

• R _int = 0.110

• 3 standard reflections every 120 min intensity decay: 1.5%

Refinement

• R[F ² > 2σ(F ²)] = 0.086

• wR(F ²) = 0.387

• S = 1.59

• 2114 reflections

• 127 parameters

• H-atom parameters constrained

• Δρ_max = 2.07 e Å⁻³

• Δρ_min = −1.56 e Å⁻³

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.

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	2.20	3.032 (13)	162
N1—H1N⋯Br3	0.86	2.84	3.177 (9)	105

Symmetry code: (i) .

supplementary crystallographic information

Comment

The structure of (I), was determined as a part of our ongoing study of the effect of ring and side chain substituents on the crystal structures of N-aromatic amides (Gowda et al., 2008, 2009, 2010). In (I) the conformation of the N—H bond is anti to the 3-chloro substituent in the benzene ring (Fig.1), similar to that observed in N-(3-chlorophenyl)acetamide (II)(Gowda et al., 2008), and that between the N—H bond and the 3-methyl group in N-(3-methylphenyl)2,2,2-tribromoacetamide (III)(Gowda et al., 2009), but contrary to the syn conformation observed between the N—H bond and the 2-Chloro group in N-(2-chlorophenyl)2,2,2-tribromoacetamide (IV) (Gowda et al., 2010).

Further, the conformation of the N—H bond in (I) is anti to the C=O bond in the side chain, similar to that observed in N-(phenyl)2,2,2-tribromoacetamide, (II), (III) and (IV) (Gowda et al., 2008, 2009, 2010) and other amides (Brown, 1966).

The structure of (I) shows both intramolecular N—H···Br and intermolecular N—H···O H-bonding. A packing diagram (Fig. 2) illustrates the N1—H1N···O1 hydrogen bonds (Table 1) involved in the formation of molecular chains along the a-axis of the unit cell.

Experimental

The title compound was prepared from 3-chloroaniline, tribromoacetic acid and phosphorylchloride according to the literature method (Gowda et al., 2003). The purity of the compound was checked by determining its melting point. It was further characterized by recording its infrared spectra. Rod like colourless single crystals of the title compound used for X-ray diffraction studies were obtained by a slow evaporation of its ethanolic solution 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 Å] and were refined with a riding model conith isotropic displacement parameters (set to 1.2 times of the U_eq of the parent atom).

The residual electron-density features are located in the region of Br1 and Br2. The highest peak is 0.98 Å from Br1 and the deepest hole is 1.39 Å from Br2.

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

C8H5Br3ClNO	F(000) = 1520
Mr = 406.31	Dx = 2.280 Mg m−3
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 12.803 (1) Å	θ = 4.4–20.5°
b = 9.146 (1) Å	µ = 14.47 mm−1
c = 20.221 (3) Å	T = 299 K
V = 2367.8 (5) Å3	Rod, colourless
Z = 8	0.53 × 0.33 × 0.25 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	1646 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.110
graphite	θmax = 67.0°, θmin = 4.4°
ω/2θ scans	h = −15→11
Absorption correction: ψ scan (North et al., 1968)	k = −10→0
Tmin = 0.049, Tmax = 0.123	l = −24→0
3870 measured reflections	3 standard reflections every 120 min
2114 independent reflections	intensity decay: 1.5%

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)] = 0.086	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.387	H-atom parameters constrained
S = 1.59	w = 1/[σ2(Fo2) + (0.2P)2] where P = (Fo2 + 2Fc2)/3
2114 reflections	(Δ/σ)max = 0.006
127 parameters	Δρmax = 2.07 e Å−3
0 restraints	Δρmin = −1.56 e Å−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.8142 (8)	0.2739 (12)	0.3141 (5)	0.042 (2)
C2	0.7763 (8)	0.3768 (12)	0.2709 (6)	0.043 (2)
H2	0.7101	0.4167	0.2769	0.051*
C3	0.8383 (13)	0.4204 (15)	0.2184 (6)	0.057 (3)
C4	0.9361 (13)	0.3617 (16)	0.2099 (8)	0.071 (4)
H4	0.9773	0.3902	0.1743	0.085*
C5	0.9715 (11)	0.2635 (18)	0.2533 (9)	0.077 (5)
H5	1.0374	0.2231	0.2467	0.092*
C6	0.9141 (11)	0.2199 (13)	0.3074 (8)	0.059 (3)
H6	0.9419	0.1559	0.3385	0.071*
C7	0.6833 (9)	0.2898 (11)	0.4008 (5)	0.042 (2)
C8	0.6221 (8)	0.2020 (11)	0.4511 (6)	0.043 (2)
Br1	0.55384 (15)	0.04007 (19)	0.40907 (9)	0.0787 (8)
Br2	0.52069 (17)	0.31822 (18)	0.49631 (11)	0.0893 (9)
Br3	0.71709 (15)	0.1263 (3)	0.51772 (8)	0.0856 (8)
Cl1	0.7921 (4)	0.5505 (5)	0.16439 (19)	0.0817 (13)
N1	0.7560 (8)	0.2201 (11)	0.3684 (5)	0.050 (2)
H1N	0.7701	0.1327	0.3814	0.060*
O1	0.6555 (7)	0.4164 (8)	0.3902 (4)	0.0494 (19)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.032 (5)	0.046 (5)	0.047 (6)	−0.008 (4)	0.008 (4)	−0.005 (5)
C2	0.036 (5)	0.045 (5)	0.048 (6)	−0.006 (4)	0.000 (4)	0.005 (4)
C3	0.069 (8)	0.065 (7)	0.039 (5)	−0.018 (6)	0.006 (5)	0.001 (5)
C4	0.082 (10)	0.051 (7)	0.079 (10)	−0.009 (7)	0.041 (8)	−0.003 (7)
C5	0.045 (8)	0.070 (9)	0.116 (12)	−0.003 (7)	0.040 (8)	0.004 (10)
C6	0.060 (7)	0.040 (5)	0.076 (8)	0.003 (5)	0.017 (6)	0.004 (6)
C7	0.044 (6)	0.037 (5)	0.044 (5)	−0.002 (4)	−0.001 (4)	0.000 (4)
C8	0.032 (5)	0.037 (5)	0.061 (6)	0.006 (4)	0.004 (5)	−0.005 (4)
Br1	0.0826 (13)	0.0758 (12)	0.0776 (12)	−0.0431 (9)	0.0248 (8)	−0.0149 (8)
Br2	0.0953 (15)	0.0610 (12)	0.1114 (16)	0.0226 (9)	0.0628 (12)	0.0087 (9)
Br3	0.0700 (12)	0.1248 (18)	0.0619 (12)	0.0134 (10)	−0.0027 (7)	0.0327 (10)
Cl1	0.117 (3)	0.079 (2)	0.0498 (19)	−0.006 (2)	0.0019 (18)	0.0161 (16)
N1	0.056 (6)	0.041 (4)	0.052 (5)	0.000 (4)	0.016 (5)	0.015 (4)
O1	0.042 (4)	0.037 (3)	0.069 (5)	0.000 (3)	0.008 (4)	0.009 (3)

Geometric parameters (Å, °)

C1—C2	1.372 (16)	C5—H5	0.9300
C1—C6	1.378 (17)	C6—H6	0.9300
C1—N1	1.416 (13)	C7—O1	1.229 (14)
C2—C3	1.385 (16)	C7—N1	1.305 (16)
C2—H2	0.9300	C7—C8	1.515 (15)
C3—C4	1.37 (2)	C8—Br2	1.911 (10)
C3—Cl1	1.720 (15)	C8—Br1	1.918 (11)
C4—C5	1.33 (2)	C8—Br3	1.943 (11)
C4—H4	0.9300	N1—H1N	0.8600
C5—C6	1.377 (18)
C2—C1—C6	120.8 (10)	C5—C6—C1	118.0 (14)
C2—C1—N1	123.1 (10)	C5—C6—H6	121.0
C6—C1—N1	116.1 (11)	C1—C6—H6	121.0
C1—C2—C3	118.8 (11)	O1—C7—N1	125.4 (10)
C1—C2—H2	120.6	O1—C7—C8	117.8 (10)
C3—C2—H2	120.6	N1—C7—C8	116.5 (9)
C4—C3—C2	120.4 (13)	C7—C8—Br2	112.2 (7)
C4—C3—Cl1	120.3 (10)	C7—C8—Br1	110.4 (8)
C2—C3—Cl1	119.3 (12)	Br2—C8—Br1	109.4 (5)
C5—C4—C3	119.4 (12)	C7—C8—Br3	109.3 (7)
C5—C4—H4	120.3	Br2—C8—Br3	107.0 (6)
C3—C4—H4	120.3	Br1—C8—Br3	108.5 (5)
C4—C5—C6	122.4 (14)	C7—N1—C1	126.5 (10)
C4—C5—H5	118.8	C7—N1—H1N	116.8
C6—C5—H5	118.8	C1—N1—H1N	116.8
C6—C1—C2—C3	3.2 (17)	O1—C7—C8—Br2	−6.9 (13)
N1—C1—C2—C3	−178.6 (11)	N1—C7—C8—Br2	178.6 (9)
C1—C2—C3—C4	−0.3 (19)	O1—C7—C8—Br1	115.4 (10)
C1—C2—C3—Cl1	−179.4 (9)	N1—C7—C8—Br1	−59.1 (12)
C2—C3—C4—C5	−1(2)	O1—C7—C8—Br3	−125.4 (9)
Cl1—C3—C4—C5	178.3 (13)	N1—C7—C8—Br3	60.1 (12)
C3—C4—C5—C6	−1(3)	O1—C7—N1—C1	−2(2)
C4—C5—C6—C1	4(2)	C8—C7—N1—C1	171.9 (11)
C2—C1—C6—C5	−5(2)	C2—C1—N1—C7	−28.2 (19)
N1—C1—C6—C5	176.7 (13)	C6—C1—N1—C7	150.0 (13)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1i	0.86	2.20	3.032 (13)	162
N1—H1N···Br3	0.86	2.84	3.177 (9)	105

Symmetry codes: (i) −x+3/2, y−1/2, z.