2,2,2-Tribromo-N-phenyl­acetamide

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

doi:10.1107/S160053680903298X

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2226

doi:10.1107/S160053680903298X

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2,2,2-Tribromo-N-phenylacetamide

B. Thimme Gowda,^a ^* Sabine Foro,^b P. A. Suchetan ^a 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 7 August 2009; accepted 19 August 2009; online 22 August 2009)

In the title compound, C₈H₆Br₃NO, the N—H bond is anti to the carbonyl bond in the side chain. The N—H hydrogen atom is involved in a two-centered bond as it shows simultaneous N—H⋯Br intra- and N—H⋯O intermolecular interactions in the structure. In the crystal, molecules are packed into column-like chains along the b axis through the N—H⋯O hydrogen bonds.

Related literature

For the preparation of the compound, see: Gowda et al. (2003 ). For related structures, see: Brown et al. (1966 ); Dou et al. (1994 ); Gowda et al. (2007 , 2009 ).

Experimental

Crystal data

C₈H₆Br₃NO
M_r = 371.87
Orthorhombic, P c a 2₁
a = 10.1863 (8) Å
b = 9.1483 (7) Å
c = 11.8856 (9) Å
V = 1107.59 (15) Å³
Z = 4
Cu Kα radiation
μ = 13.22 mm⁻¹
T = 299 K
0.50 × 0.18 × 0.13 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.037, T_max = 0.178
2653 measured reflections
1311 independent reflections
1237 reflections with I > 2σ(I)
R_int = 0.052
3 standard reflections frequency: 120 min intensity decay: 1.5%

Refinement

R[F² > 2σ(F²)] = 0.079
wR(F²) = 0.237
S = 1.05
1311 reflections
119 parameters
25 restraints
H-atom parameters constrained
Δρ_max = 1.86 e Å⁻³
Δρ_min = −1.18 e Å⁻³
Absolute structure: Flack (1983 ), 276 Friedel pairs
Flack parameter: 0.00 (13)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.86	2.19	2.967 (13)	150
N1—H1N⋯Br1	0.86	2.68	3.123 (13)	114
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+1, z]$ .

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: 10.1107/S160053680903298X/fl2260sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680903298X/fl2260Isup2.hkl

checkCIF report

Comment top

The structure of (I) has been determined (Fig. 1) as part of a study on the effect of ring and side chain substituents on the structures of N-aromatic amides (Dou et al., 1994; Gowda et al., 2007, 2009). The N—H bond in (I) is anti to the C=O bond in the side chain, similar to that observed in N-(phenyl)acetamide (Brown, 1966), 2,2,2-trichloro-N-(phenyl)acetamide (Dou et al., 1994), 2,2,2-trimethyl-N-(phenyl)acetamide (Gowda et al., 2007) and other amides (Gowda et al., 2009). The N—H hydrogen atom is involved as the donor in a two-centered bond; an intramolecular N—H···Br bond and an intermolecular N—H···O bond (Table 1). The N1—H1N···O1 bonds involved in the formation of molecular chains in the direction of the b-axis are shown Fig. 2.

Related literature top

For the preparation of the compound, see: Gowda et al. (2003). For related structures, see: Brown et al. (1966); Dou et al. (1994); Gowda et al. (2007, 2009).

Experimental top

The title compound was prepared from aniline, 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. Single crystals of the title compound used for X-ray diffraction studies were obtained by a slow evaporation from petroleum ether 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) with hydrogen bonds shown as dashed lines.

2,2,2-Tribromo-N-phenylacetamide top

Crystal data top

C₈H₆Br₃NO	F(000) = 696
M_r = 371.87	D_x = 2.230 Mg m⁻³
Orthorhombic, Pca2₁	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: P 2c -2ac	Cell parameters from 25 reflections
a = 10.1863 (8) Å	θ = 4.8–20.7°
b = 9.1483 (7) Å	µ = 13.22 mm⁻¹
c = 11.8856 (9) Å	T = 299 K
V = 1107.59 (15) Å³	Needle, colourless
Z = 4	0.50 × 0.18 × 0.13 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1237 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.052
Graphite monochromator	θ_max = 67.0°, θ_min = 4.8°
ω/2θ scans	h = −12→0
Absorption correction: ψ scan (North et al., 1968)	k = −10→10
T_min = 0.037, T_max = 0.178	l = −11→14
2653 measured reflections	3 standard reflections every 120 min
1311 independent reflections	intensity decay: 1.5%

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.079	w = 1/[σ²(F_o²) + (0.1659P)² + 2.9656P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.237	(Δ/σ)_max = 0.002
S = 1.05	Δρ_max = 1.86 e Å⁻³
1311 reflections	Δρ_min = −1.18 e Å⁻³
119 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
25 restraints	Extinction coefficient: 0.0035 (8)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 276 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.00 (13)

Crystal data top

C₈H₆Br₃NO	V = 1107.59 (15) Å³
M_r = 371.87	Z = 4
Orthorhombic, Pca2₁	Cu Kα radiation
a = 10.1863 (8) Å	µ = 13.22 mm⁻¹
b = 9.1483 (7) Å	T = 299 K
c = 11.8856 (9) Å	0.50 × 0.18 × 0.13 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1237 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.052
T_min = 0.037, T_max = 0.178	3 standard reflections every 120 min
2653 measured reflections	intensity decay: 1.5%
1311 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.079	H-atom parameters constrained
wR(F²) = 0.237	Δρ_max = 1.86 e Å⁻³
S = 1.05	Δρ_min = −1.18 e Å⁻³
1311 reflections	Absolute structure: Flack (1983), 276 Friedel pairs
119 parameters	Absolute structure parameter: 0.00 (13)
25 restraints

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	0.2439 (16)	0.3139 (13)	0.6091 (14)	0.057 (3)
C2	0.1483 (19)	0.2891 (18)	0.6869 (19)	0.078 (4)
H2	0.0753	0.3500	0.6914	0.094*
C3	0.162 (3)	0.169 (3)	0.761 (3)	0.110 (7)
H3	0.1010	0.1557	0.8185	0.132*
C4	0.256 (3)	0.077 (2)	0.751 (2)	0.095 (5)
H4	0.2575	−0.0070	0.7947	0.114*
C5	0.3521 (19)	0.1043 (17)	0.6774 (19)	0.079 (4)
H5	0.4247	0.0427	0.6773	0.095*
C6	0.3495 (16)	0.2176 (13)	0.6019 (17)	0.065 (4)
H6	0.4153	0.2297	0.5484	0.078*
C7	0.3328 (12)	0.5181 (14)	0.5056 (12)	0.053 (3)
C8	0.3002 (15)	0.6556 (17)	0.4339 (16)	0.069 (4)
N1	0.2341 (10)	0.4331 (11)	0.5359 (12)	0.058 (2)
H1N	0.1579	0.4526	0.5085	0.069*
O1	0.4489 (8)	0.5008 (11)	0.5332 (12)	0.076 (4)
Br1	0.1668 (3)	0.6121 (3)	0.3197 (2)	0.0988 (9)
Br2	0.2294 (3)	0.80125 (17)	0.5320 (2)	0.1007 (10)
Br3	0.4497 (2)	0.7263 (3)	0.3550 (3)	0.1230 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.049 (6)	0.064 (7)	0.059 (8)	−0.012 (6)	−0.003 (6)	0.003 (6)
C2	0.075 (8)	0.080 (7)	0.079 (8)	−0.011 (6)	0.014 (7)	0.021 (6)
C3	0.112 (11)	0.110 (9)	0.108 (11)	−0.016 (8)	0.014 (9)	0.020 (8)
C4	0.106 (9)	0.085 (7)	0.095 (10)	−0.013 (8)	−0.013 (8)	0.014 (7)
C5	0.082 (8)	0.069 (6)	0.087 (9)	−0.002 (6)	−0.016 (7)	0.004 (6)
C6	0.060 (8)	0.052 (6)	0.083 (10)	0.004 (5)	−0.022 (7)	0.001 (6)
C7	0.038 (5)	0.066 (6)	0.054 (7)	0.001 (4)	0.005 (5)	0.017 (6)
C8	0.057 (8)	0.068 (7)	0.081 (11)	0.014 (6)	0.006 (7)	0.020 (7)
N1	0.037 (5)	0.068 (5)	0.068 (7)	0.005 (4)	−0.007 (5)	0.008 (6)
O1	0.035 (4)	0.085 (6)	0.109 (10)	−0.008 (4)	−0.007 (5)	0.042 (7)
Br1	0.1101 (17)	0.1157 (14)	0.0705 (12)	−0.0051 (11)	−0.0328 (12)	0.0179 (10)
Br2	0.164 (2)	0.0664 (9)	0.0719 (12)	0.0155 (10)	0.0171 (14)	0.0000 (8)
Br3	0.0680 (11)	0.1321 (19)	0.169 (3)	0.0095 (10)	0.0356 (14)	0.091 (2)

Geometric parameters (Å, º) top

C1—C2	1.36 (3)	C5—H5	0.9300
C1—C6	1.39 (2)	C6—H6	0.9300
C1—N1	1.399 (19)	C7—O1	1.237 (16)
C2—C3	1.42 (3)	C7—N1	1.321 (16)
C2—H2	0.9300	C7—C8	1.555 (18)
C3—C4	1.27 (4)	C8—Br3	1.902 (16)
C3—H3	0.9300	C8—Br2	1.913 (17)
C4—C5	1.34 (4)	C8—Br1	1.960 (19)
C4—H4	0.9300	N1—H1N	0.8600
C5—C6	1.37 (2)

C2—C1—C6	119.3 (15)	C5—C6—C1	116.9 (18)
C2—C1—N1	120.1 (15)	C5—C6—H6	121.6
C6—C1—N1	120.6 (15)	C1—C6—H6	121.6
C1—C2—C3	118.7 (19)	O1—C7—N1	125.5 (11)
C1—C2—H2	120.6	O1—C7—C8	117.0 (11)
C3—C2—H2	120.6	N1—C7—C8	117.5 (11)
C4—C3—C2	122 (3)	C7—C8—Br3	111.9 (9)
C4—C3—H3	119.2	C7—C8—Br2	108.1 (11)
C2—C3—H3	119.2	Br3—C8—Br2	111.4 (9)
C3—C4—C5	119 (2)	C7—C8—Br1	111.3 (11)
C3—C4—H4	120.3	Br3—C8—Br1	106.4 (9)
C5—C4—H4	120.3	Br2—C8—Br1	107.6 (7)
C4—C5—C6	123.6 (18)	C7—N1—C1	125.0 (11)
C4—C5—H5	118.2	C7—N1—H1N	117.5
C6—C5—H5	118.2	C1—N1—H1N	117.5

C6—C1—C2—C3	2 (3)	N1—C7—C8—Br3	−159.7 (12)
N1—C1—C2—C3	−179.1 (19)	O1—C7—C8—Br2	−100.0 (14)
C1—C2—C3—C4	−5 (4)	N1—C7—C8—Br2	77.2 (16)
C2—C3—C4—C5	8 (4)	O1—C7—C8—Br1	142.1 (13)
C3—C4—C5—C6	−7 (4)	N1—C7—C8—Br1	−40.7 (17)
C4—C5—C6—C1	4 (3)	O1—C7—N1—C1	4 (3)
C2—C1—C6—C5	−2 (2)	C8—C7—N1—C1	−173.4 (14)
N1—C1—C6—C5	179.6 (15)	C2—C1—N1—C7	139.6 (18)
O1—C7—C8—Br3	23.1 (19)	C6—C1—N1—C7	−42 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.86	2.19	2.967 (13)	150
N1—H1N···Br1	0.86	2.68	3.123 (13)	114

Symmetry code: (i) x−1/2, −y+1, z.

Experimental details

Crystal data
Chemical formula	C₈H₆Br₃NO
M_r	371.87
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	299
a, b, c (Å)	10.1863 (8), 9.1483 (7), 11.8856 (9)
V (Å³)	1107.59 (15)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	13.22
Crystal size (mm)	0.50 × 0.18 × 0.13

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.037, 0.178
No. of measured, independent and observed [I > 2σ(I)] reflections	2653, 1311, 1237
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.079, 0.237, 1.05
No. of reflections	1311
No. of parameters	119
No. of restraints	25
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.86, −1.18
Absolute structure	Flack (1983), 276 Friedel pairs
Absolute structure parameter	0.00 (13)

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	2.19	2.967 (13)	150.0
N1—H1N···Br1	0.86	2.68	3.123 (13)	113.6

Symmetry code: (i) x−1/2, −y+1, z.

Acknowledgements

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

References

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