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

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

doi:10.1107/S1600536810001467

organic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page o386

https://doi.org/10.1107/S1600536810001467

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

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 10 January 2010; accepted 12 January 2010; online 16 January 2010)

In the title compound, C₈H₅Br₃ClNO, the conformation of the N—H bond is syn to the 2-chloro substituent in the benzene ring. There are no classical intermolecular hydrogen bonds, but intramolecular N—H⋯Br and N—H⋯Cl contacts occur.

Related literature

For preparation of the title compound, see: Gowda et al. (2003 ). For background to our studies on the effect of the ring and the side-chain substituents on the crystal structures of N-aromatic amides, see: Gowda et al. (2007 , 2009 ). For the conformations of other amides, see: Brown (1966 ).

Experimental

Crystal data

C₈H₅Br₃ClNO
M_r = 406.31
Orthorhombic, P n a 2₁
a = 9.1947 (6) Å
b = 12.9645 (7) Å
c = 9.5213 (6) Å
V = 1134.98 (12) Å³
Z = 4
Mo Kα radiation
μ = 10.86 mm⁻¹
T = 299 K
0.40 × 0.40 × 0.34 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.098, T_max = 0.120
4524 measured reflections
1645 independent reflections
1491 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.066
S = 1.07
1645 reflections
131 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.77 e Å⁻³
Δρ_min = −0.56 e Å⁻³
Absolute structure: Flack (1983 ), 416 Friedel pairs
Flack parameter: 0.049 (18)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯Br1	0.85 (3)	2.78 (8)	3.155 (6)	109 (6)
N1—H1N⋯Cl1	0.85 (3)	2.59 (7)	2.961 (5)	107 (5)

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810001467/bt5167sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810001467/bt5167Isup2.hkl

checkCIF report

Comment top

As a part of studying the effect of the ring and the side chain substituents on the crystal structures of N-aromatic amides (Gowda et al., 2007, 2009), in the present work, the structure of N-(2-chlorophenyl)2,2,2-tribromoacetamide (I) has been determined (Fig.1). The conformation of the N—H bond is syn to the 2-chloro substituent in the benzene ring, similar to that observed in N-(2-chlorophenyl)acetamide and N-(2-chlorophenyl)2,2,2-trichloroacetamide (Gowda et al., 2007), but contrary to the anti conformation observed between the N—H bond and the 3-methyl group in N-(3-methylphenyl)2,2,2-tribromoacetamide (Gowda et al., 2009). Further, the conformation of the N—H bond in the structure is anti to the C=O bond in the side chain, similar to that observed in N-(phenyl)2,2,2-tribromoacetamide (Gowda et al., 2009) and other amides (Brown, 1966; Gowda et al., 2007, 2009). The structure shows simultaneous N—H···Br and N—H···Cl intramolecular H-bonding. The packing diagram of the molecules is shown in Fig. 2.

Related literature top

For preparation of the title compound, see: Gowda et al. (2003). For background to our studies on the effect of the ring and the side-chain substituents on the crystal structures of N-aromatic amides, see: Gowda et al. (2007, 2009). For the conformations of other amides, see: Brown (1966).

Experimental top

The title compound was prepared from 2-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. 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 preparation of the title compound, see: Gowda et al. (2003). For background to our studies on the effect of the ring and the side-chain substituents on the crystal structures of N-aromatic amides, see: Gowda et al. (2007, 2009). For the conformations of other amides, see: Brown (1966).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); 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 the title compound, showing the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and the H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Molecular packing of the title compound with hydrogen bonds shown as dashed lines.

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

Crystal data top

C₈H₅Br₃ClNO	F(000) = 760
M_r = 406.31	D_x = 2.378 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 3507 reflections
a = 9.1947 (6) Å	θ = 2.7–27.8°
b = 12.9645 (7) Å	µ = 10.86 mm⁻¹
c = 9.5213 (6) Å	T = 299 K
V = 1134.98 (12) Å³	Rod, colourless
Z = 4	0.40 × 0.40 × 0.34 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	1645 independent reflections
Radiation source: fine-focus sealed tube	1491 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Rotation method data acquisition using ω and φ scans.	θ_max = 26.4°, θ_min = 2.7°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	h = −11→11
T_min = 0.098, T_max = 0.120	k = −16→15
4524 measured reflections	l = −11→6

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.027	w = 1/[σ²(F_o²) + (0.0357P)² + 1.2795P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.066	(Δ/σ)_max = 0.004
S = 1.07	Δρ_max = 0.77 e Å⁻³
1645 reflections	Δρ_min = −0.56 e Å⁻³
131 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.0072 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 416 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.049 (18)

Crystal data top

C₈H₅Br₃ClNO	V = 1134.98 (12) Å³
M_r = 406.31	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 9.1947 (6) Å	µ = 10.86 mm⁻¹
b = 12.9645 (7) Å	T = 299 K
c = 9.5213 (6) Å	0.40 × 0.40 × 0.34 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	1645 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	1491 reflections with I > 2σ(I)
T_min = 0.098, T_max = 0.120	R_int = 0.022
4524 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.066	Δρ_max = 0.77 e Å⁻³
S = 1.07	Δρ_min = −0.56 e Å⁻³
1645 reflections	Absolute structure: Flack (1983), 416 Friedel pairs
131 parameters	Absolute structure parameter: 0.049 (18)
2 restraints

Special details top

Experimental. CrysAlis RED (Oxford Diffraction, 2009) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
Br1	0.56049 (8)	0.28366 (5)	1.15778 (8)	0.0510 (2)
Br2	0.43394 (7)	0.06152 (5)	1.19542 (7)	0.0483 (2)
Br3	0.70743 (6)	0.09279 (5)	1.00260 (9)	0.0474 (2)
Cl1	0.5017 (2)	0.46215 (12)	0.7770 (2)	0.0536 (5)
O1	0.3140 (5)	0.1287 (4)	0.9233 (5)	0.0521 (13)
N1	0.4832 (5)	0.2390 (4)	0.8407 (6)	0.0366 (12)
H1N	0.554 (5)	0.277 (4)	0.866 (9)	0.044*
C1	0.4101 (6)	0.2689 (4)	0.7164 (7)	0.0311 (12)
C2	0.4114 (6)	0.3709 (4)	0.6763 (7)	0.0360 (14)
C3	0.3435 (8)	0.4026 (5)	0.5526 (7)	0.0475 (17)
H3	0.3476	0.4712	0.5244	0.057*
C4	0.2701 (8)	0.3305 (6)	0.4724 (8)	0.0573 (19)
H4	0.2235	0.3506	0.3901	0.069*
C5	0.2660 (9)	0.2308 (6)	0.5136 (9)	0.063 (2)
H5	0.2152	0.1829	0.4598	0.076*
C6	0.3362 (8)	0.1987 (5)	0.6347 (7)	0.0471 (17)
H6	0.3335	0.1296	0.6607	0.057*
C7	0.4282 (6)	0.1716 (4)	0.9346 (6)	0.0278 (12)
C8	0.5253 (6)	0.1542 (4)	1.0638 (7)	0.0288 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0744 (5)	0.0373 (3)	0.0411 (4)	−0.0059 (3)	−0.0169 (4)	−0.0036 (3)
Br2	0.0476 (4)	0.0509 (4)	0.0464 (4)	−0.0058 (3)	0.0000 (3)	0.0248 (3)
Br3	0.0328 (3)	0.0471 (4)	0.0623 (5)	0.0097 (3)	0.0018 (3)	0.0139 (4)
Cl1	0.0620 (10)	0.0384 (8)	0.0604 (12)	−0.0142 (8)	−0.0155 (9)	0.0153 (8)
O1	0.047 (3)	0.067 (3)	0.043 (3)	−0.025 (2)	−0.009 (2)	0.011 (3)
N1	0.040 (3)	0.035 (3)	0.035 (3)	−0.007 (2)	−0.008 (2)	0.013 (3)
C1	0.035 (3)	0.032 (3)	0.026 (3)	0.008 (2)	0.000 (2)	0.004 (2)
C2	0.032 (3)	0.036 (3)	0.040 (4)	0.004 (2)	0.004 (3)	0.004 (3)
C3	0.057 (4)	0.052 (4)	0.033 (4)	0.018 (3)	0.004 (3)	0.018 (3)
C4	0.074 (5)	0.070 (5)	0.028 (4)	0.010 (4)	−0.017 (4)	0.012 (4)
C5	0.092 (5)	0.065 (5)	0.033 (4)	0.011 (4)	−0.020 (4)	−0.016 (4)
C6	0.068 (4)	0.039 (3)	0.034 (4)	0.011 (3)	−0.005 (4)	−0.002 (3)
C7	0.028 (3)	0.027 (3)	0.029 (3)	0.002 (2)	0.000 (2)	0.000 (2)
C8	0.032 (3)	0.027 (3)	0.027 (3)	0.001 (2)	−0.001 (2)	0.008 (2)

Geometric parameters (Å, º) top

Br1—C8	1.929 (6)	C2—C3	1.395 (9)
Br2—C8	1.929 (6)	C3—C4	1.383 (10)
Br3—C8	1.944 (6)	C3—H3	0.9300
Cl1—C2	1.735 (7)	C4—C5	1.351 (11)
O1—C7	1.193 (6)	C4—H4	0.9300
N1—C7	1.349 (7)	C5—C6	1.385 (10)
N1—C1	1.415 (8)	C5—H5	0.9300
N1—H1N	0.85 (3)	C6—H6	0.9300
C1—C6	1.377 (9)	C7—C8	1.537 (8)
C1—C2	1.376 (8)

C7—N1—C1	123.6 (5)	C4—C5—C6	121.1 (7)
C7—N1—H1N	118 (6)	C4—C5—H5	119.5
C1—N1—H1N	116 (5)	C6—C5—H5	119.5
C6—C1—C2	118.8 (6)	C1—C6—C5	120.1 (6)
C6—C1—N1	121.7 (5)	C1—C6—H6	119.9
C2—C1—N1	119.4 (6)	C5—C6—H6	119.9
C1—C2—C3	120.9 (6)	O1—C7—N1	124.9 (6)
C1—C2—Cl1	120.4 (5)	O1—C7—C8	121.0 (5)
C3—C2—Cl1	118.7 (5)	N1—C7—C8	114.1 (4)
C4—C3—C2	119.0 (6)	C7—C8—Br1	110.0 (4)
C4—C3—H3	120.5	C7—C8—Br2	111.0 (4)
C2—C3—H3	120.5	Br1—C8—Br2	108.3 (3)
C5—C4—C3	120.0 (6)	C7—C8—Br3	108.7 (4)
C5—C4—H4	120.0	Br1—C8—Br3	110.5 (3)
C3—C4—H4	120.0	Br2—C8—Br3	108.3 (3)

C7—N1—C1—C6	−41.6 (9)	N1—C1—C6—C5	−179.9 (6)
C7—N1—C1—C2	137.9 (6)	C4—C5—C6—C1	0.9 (12)
C6—C1—C2—C3	−2.1 (9)	C1—N1—C7—O1	1.1 (9)
N1—C1—C2—C3	178.4 (6)	C1—N1—C7—C8	−177.9 (5)
C6—C1—C2—Cl1	179.4 (5)	O1—C7—C8—Br1	−121.3 (5)
N1—C1—C2—Cl1	−0.1 (8)	N1—C7—C8—Br1	57.7 (6)
C1—C2—C3—C4	2.2 (10)	O1—C7—C8—Br2	−1.5 (7)
Cl1—C2—C3—C4	−179.4 (5)	N1—C7—C8—Br2	177.5 (4)
C2—C3—C4—C5	−0.7 (11)	O1—C7—C8—Br3	117.5 (5)
C3—C4—C5—C6	−0.9 (12)	N1—C7—C8—Br3	−63.4 (5)
C2—C1—C6—C5	0.6 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···Br1	0.85 (3)	2.78 (8)	3.155 (6)	109 (6)
N1—H1N···Cl1	0.85 (3)	2.59 (7)	2.961 (5)	107 (5)

Experimental details

Crystal data
Chemical formula	C₈H₅Br₃ClNO
M_r	406.31
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	299
a, b, c (Å)	9.1947 (6), 12.9645 (7), 9.5213 (6)
V (Å³)	1134.98 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	10.86
Crystal size (mm)	0.40 × 0.40 × 0.34

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009)
T_min, T_max	0.098, 0.120
No. of measured, independent and observed [I > 2σ(I)] reflections	4524, 1645, 1491
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.066, 1.07
No. of reflections	1645
No. of parameters	131
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.77, −0.56
Absolute structure	Flack (1983), 416 Friedel pairs
Absolute structure parameter	0.049 (18)

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), 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···Br1	0.85 (3)	2.78 (8)	3.155 (6)	109 (6)
N1—H1N···Cl1	0.85 (3)	2.59 (7)	2.961 (5)	107 (5)

Acknowledgements

PAS 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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