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

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

doi:10.1107/S160053681001411X

organic compounds

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ISSN: 2056-9890

Volume 66| Part 5| May 2010| Page o1140

https://doi.org/10.1107/S160053681001411X

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

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

^aDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, Mangalore, India, and ^bInstitute of Materials Science, Darmstadt University of Technology, Petersenstrasse 23, D-64287 Darmstadt, Germany
^*Correspondence e-mail: gowdabt@yahoo.com

(Received 3 April 2010; accepted 16 April 2010; online 24 April 2010)

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, P b c a
a = 12.803 (1) Å
b = 9.146 (1) Å
c = 20.221 (3) Å
V = 2367.8 (5) Å³
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[F² > 2σ(F²)] = 0.086
wR(F²) = 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

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) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ .

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: https://doi.org/10.1107/S160053681001411X/fl2301sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681001411X/fl2301Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Structure description top

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).

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) with hydrogen bonds shown as dashed lines.

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

Crystal data top

C₈H₅Br₃ClNO	F(000) = 1520
M_r = 406.31	D_x = 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 top

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

Refinement top

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(F_o²) + (0.2P)²] where P = (F_o² + 2F_c²)/3
2114 reflections	(Δ/σ)_max = 0.006
127 parameters	Δρ_max = 2.07 e Å⁻³
0 restraints	Δρ_min = −1.56 e Å⁻³

Crystal data top

C₈H₅Br₃ClNO	V = 2367.8 (5) Å³
M_r = 406.31	Z = 8
Orthorhombic, Pbca	Cu Kα radiation
a = 12.803 (1) Å	µ = 14.47 mm⁻¹
b = 9.146 (1) Å	T = 299 K
c = 20.221 (3) Å	0.53 × 0.33 × 0.25 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1646 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.110
T_min = 0.049, T_max = 0.123	3 standard reflections every 120 min
3870 measured reflections	intensity decay: 1.5%
2114 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.086	0 restraints
wR(F²) = 0.387	H-atom parameters constrained
S = 1.59	Δρ_max = 2.07 e Å⁻³
2114 reflections	Δρ_min = −1.56 e Å⁻³
127 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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) −x+3/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₈H₅Br₃ClNO
M_r	406.31
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	299
a, b, c (Å)	12.803 (1), 9.146 (1), 20.221 (3)
V (Å³)	2367.8 (5)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	14.47
Crystal size (mm)	0.53 × 0.33 × 0.25

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.049, 0.123
No. of measured, independent and observed [I > 2σ(I)] reflections	3870, 2114, 1646
R_int	0.110
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.086, 0.387, 1.59
No. of reflections	2114
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.07, −1.56

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	0.86	2.20	3.032 (13)	161.7
N1—H1N···Br3	0.86	2.84	3.177 (9)	105.4

Symmetry code: (i) −x+3/2, y−1/2, z.

Acknowledgements

P.A.S. thanks the Council of Scientific and Industrial Research (CSIR), Government of India, New Delhi, for the award of a research fellowship.

References

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