2,2,2-Tribromo-N-(4-chloro­phen­yl)acetamide

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

doi:10.1107/S1600536809032139

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2172

doi:10.1107/S1600536809032139

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2,2,2-Tribromo-N-(4-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 11 August 2009; accepted 13 August 2009; online 15 August 2009)

The crystal structure of the title compound, C₈H₅Br₃ClNO, shows both intramolecular N—H⋯Br and intermolecular N—H⋯O hydrogen bonding. In the crystal, the molecules are packed into column-like chains in the c-axis direction via the N—H⋯O hydrogen bonds.

Related literature

For the preparation of the compound, see: Gowda et al. (2003 ). For our study of the effect of ring and side-chain substituents on the solid state structures of N-aromatic amides, see: Gowda et al. (2000 , 2007 , 2009 ).

Experimental

Crystal data

C₈H₅Br₃ClNO
M_r = 406.31
Orthorhombic, P b c a
a = 9.7332 (8) Å
b = 10.2462 (9) Å
c = 23.898 (2) Å
V = 2383.3 (3) Å³
Z = 8
Mo Kα radiation
μ = 10.35 mm⁻¹
T = 299 K
0.40 × 0.16 × 0.10 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 = 0.104, T_max = 0.355
5692 measured reflections
2353 independent reflections
1643 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.080
wR(F²) = 0.205
S = 1.04
2353 reflections
130 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 2.04 e Å⁻³
Δρ_min = −0.95 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯Br1	0.84 (5)	2.87 (10)	3.197 (8)	105 (8)
N1—H1N⋯O1ⁱ	0.84 (5)	2.21 (5)	3.038 (9)	168 (10)
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

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: 10.1107/S1600536809032139/pk2183sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809032139/pk2183Isup2.hkl

checkCIF report

Comment top

As part of a study of the effect of the ring and side chain substituents on the solid state structures of N-aromatic amides (Gowda et al., 2000, 2007, 2009), the structure of 2,2,2-tribromo-N-(4-chlorophenyl)acetamide has been determined (Fig.1). The conformation of the N—H bond is anti to the C=O bond in the side chain, similar to that observed in N-(4-chlorophenyl)acetamide (Gowda et al., 2007), 2,2,2-trichloro-N-(4-chlorophenyl)acetamide (Gowda et al., 2003), and other amides (Gowda et al., 2009). The structure shows both intramolecular N—H···Br and intermolecular N—H···O H-bonding. The packing diagram of molecules showing the hydrogen bonds N1—H1N···O1 (Table 1) involved in the formation of molecular chains in the direction of the c-axis is given in Fig. 2.

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 solid state structures of N-aromatic amides, see: Gowda et al. (2000, 2007, 2009).

Experimental top

The title compound was prepared from 4-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 solution in petroleum ether at room temperature.

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 (I), showing the atom labelling scheme and displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Molecular packing of (I) with hydrogen bonding shown as dashed lines.

2,2,2-Tribromo-N-(4-chlorophenyl)acetamide top

Crystal data top

C₈H₅Br₃ClNO	F(000) = 1520
M_r = 406.31	D_x = 2.265 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2849 reflections
a = 9.7332 (8) Å	θ = 2.6–27.8°
b = 10.2462 (9) Å	µ = 10.35 mm⁻¹
c = 23.898 (2) Å	T = 299 K
V = 2383.3 (3) Å³	Long needle, colourless
Z = 8	0.40 × 0.16 × 0.10 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	2353 independent reflections
Radiation source: fine-focus sealed tube	1643 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
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 = −12→8
T_min = 0.104, T_max = 0.355	k = −12→9
5692 measured reflections	l = −29→21

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)] = 0.080	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.205	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0891P)² + 22.8289P] where P = (F_o² + 2F_c²)/3
2353 reflections	(Δ/σ)_max = 0.005
130 parameters	Δρ_max = 2.04 e Å⁻³
1 restraint	Δρ_min = −0.95 e Å⁻³

Crystal data top

C₈H₅Br₃ClNO	V = 2383.3 (3) Å³
M_r = 406.31	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 9.7332 (8) Å	µ = 10.35 mm⁻¹
b = 10.2462 (9) Å	T = 299 K
c = 23.898 (2) Å	0.40 × 0.16 × 0.10 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector	2353 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	1643 reflections with I > 2σ(I)
T_min = 0.104, T_max = 0.355	R_int = 0.033
5692 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.080	1 restraint
wR(F²) = 0.205	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0891P)² + 22.8289P] where P = (F_o² + 2F_c²)/3
2353 reflections	Δρ_max = 2.04 e Å⁻³
130 parameters	Δρ_min = −0.95 e Å⁻³

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
C1	0.4391 (10)	0.4634 (8)	0.1037 (4)	0.038 (2)
C2	0.4633 (11)	0.3604 (9)	0.0673 (5)	0.048 (2)
H2	0.3990	0.2939	0.0633	0.058*
C3	0.5841 (10)	0.3580 (10)	0.0369 (5)	0.051 (3)
H3	0.6017	0.2885	0.0129	0.062*
C4	0.6786 (10)	0.4569 (10)	0.0418 (4)	0.051 (3)
C5	0.6549 (10)	0.5578 (10)	0.0790 (5)	0.053 (3)
H5	0.7196	0.6240	0.0829	0.064*
C6	0.5357 (11)	0.5609 (9)	0.1103 (4)	0.048 (2)
H6	0.5206	0.6282	0.1357	0.058*
C7	0.2449 (10)	0.5644 (8)	0.1518 (4)	0.039 (2)
C8	0.1178 (10)	0.5312 (8)	0.1876 (4)	0.043 (2)
N1	0.3172 (8)	0.4601 (6)	0.1361 (3)	0.0425 (19)
H1N	0.283 (10)	0.386 (6)	0.140 (4)	0.051*
O1	0.2715 (7)	0.6760 (5)	0.1408 (3)	0.0521 (18)
Cl1	0.8276 (3)	0.4561 (4)	0.00254 (14)	0.0775 (10)
Br1	−0.00883 (11)	0.42751 (13)	0.14426 (6)	0.0737 (5)
Br2	0.02425 (15)	0.68618 (11)	0.21207 (7)	0.0817 (5)
Br3	0.17735 (16)	0.43813 (13)	0.25385 (5)	0.0792 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.053 (5)	0.028 (4)	0.033 (5)	0.007 (4)	0.005 (4)	0.006 (4)
C2	0.054 (6)	0.036 (5)	0.054 (6)	0.003 (4)	0.005 (5)	−0.001 (5)
C3	0.047 (6)	0.053 (6)	0.054 (6)	0.017 (5)	0.009 (5)	−0.006 (5)
C4	0.040 (5)	0.073 (7)	0.040 (5)	0.011 (5)	0.004 (4)	0.004 (5)
C5	0.040 (5)	0.050 (6)	0.070 (7)	−0.004 (4)	0.008 (5)	−0.006 (5)
C6	0.055 (6)	0.042 (5)	0.046 (6)	0.001 (5)	0.000 (5)	−0.014 (5)
C7	0.042 (4)	0.035 (5)	0.040 (5)	−0.001 (4)	0.009 (4)	0.007 (4)
C8	0.053 (5)	0.023 (4)	0.052 (6)	0.002 (4)	0.011 (5)	−0.005 (4)
N1	0.051 (5)	0.025 (4)	0.052 (5)	0.002 (3)	0.013 (4)	0.007 (3)
O1	0.056 (4)	0.024 (3)	0.077 (5)	0.003 (3)	0.022 (4)	0.003 (3)
Cl1	0.0468 (15)	0.117 (3)	0.069 (2)	0.0073 (16)	0.0172 (14)	−0.0168 (19)
Br1	0.0450 (6)	0.0856 (9)	0.0904 (10)	−0.0022 (6)	−0.0020 (6)	−0.0336 (8)
Br2	0.0900 (9)	0.0439 (6)	0.1112 (12)	0.0043 (6)	0.0532 (8)	−0.0141 (7)
Br3	0.0860 (9)	0.0990 (10)	0.0527 (7)	−0.0108 (7)	0.0088 (7)	0.0255 (7)

Geometric parameters (Å, º) top

C1—C6	1.380 (13)	C5—H5	0.9300
C1—C2	1.389 (13)	C6—H6	0.9300
C1—N1	1.416 (12)	C7—O1	1.202 (10)
C2—C3	1.382 (14)	C7—N1	1.334 (11)
C2—H2	0.9300	C7—C8	1.542 (13)
C3—C4	1.374 (14)	C8—Br2	1.921 (8)
C3—H3	0.9300	C8—Br1	1.929 (10)
C4—C5	1.383 (14)	C8—Br3	1.937 (10)
C4—Cl1	1.727 (10)	N1—H1N	0.84 (5)
C5—C6	1.382 (14)

C6—C1—C2	120.4 (9)	C1—C6—C5	119.5 (9)
C6—C1—N1	121.7 (8)	C1—C6—H6	120.2
C2—C1—N1	117.8 (8)	C5—C6—H6	120.2
C3—C2—C1	119.2 (9)	O1—C7—N1	126.0 (8)
C3—C2—H2	120.4	O1—C7—C8	120.2 (8)
C1—C2—H2	120.4	N1—C7—C8	113.8 (7)
C4—C3—C2	120.8 (9)	C7—C8—Br2	111.5 (6)
C4—C3—H3	119.6	C7—C8—Br1	109.6 (6)
C2—C3—H3	119.6	Br2—C8—Br1	108.4 (5)
C3—C4—C5	119.6 (9)	C7—C8—Br3	108.8 (7)
C3—C4—Cl1	120.8 (8)	Br2—C8—Br3	107.4 (5)
C5—C4—Cl1	119.5 (8)	Br1—C8—Br3	111.0 (4)
C6—C5—C4	120.4 (9)	C7—N1—C1	125.2 (7)
C6—C5—H5	119.8	C7—N1—H1N	119 (7)
C4—C5—H5	119.8	C1—N1—H1N	115 (7)

C6—C1—C2—C3	−1.2 (15)	O1—C7—C8—Br2	−2.7 (12)
N1—C1—C2—C3	−177.3 (9)	N1—C7—C8—Br2	176.9 (7)
C1—C2—C3—C4	−1.1 (15)	O1—C7—C8—Br1	117.4 (9)
C2—C3—C4—C5	2.3 (16)	N1—C7—C8—Br1	−63.0 (10)
C2—C3—C4—Cl1	−178.3 (8)	O1—C7—C8—Br3	−121.0 (9)
C3—C4—C5—C6	−1.3 (16)	N1—C7—C8—Br3	58.6 (9)
Cl1—C4—C5—C6	179.3 (8)	O1—C7—N1—C1	0.5 (16)
C2—C1—C6—C5	2.2 (15)	C8—C7—N1—C1	−179.1 (9)
N1—C1—C6—C5	178.1 (9)	C6—C1—N1—C7	36.9 (14)
C4—C5—C6—C1	−1.0 (16)	C2—C1—N1—C7	−147.1 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···Br1	0.84 (5)	2.87 (10)	3.197 (8)	105 (8)
N1—H1N···O1ⁱ	0.84 (5)	2.21 (5)	3.038 (9)	168 (10)

Symmetry code: (i) −x+1/2, 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)	9.7332 (8), 10.2462 (9), 23.898 (2)
V (Å³)	2383.3 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	10.35
Crystal size (mm)	0.40 × 0.16 × 0.10

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	0.104, 0.355
No. of measured, independent and observed [I > 2σ(I)] reflections	5692, 2353, 1643
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.080, 0.205, 1.04
No. of reflections	2353
No. of parameters	130
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
	w = 1/[σ²(F_o²) + (0.0891P)² + 22.8289P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	2.04, −0.95

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	0.84 (5)	2.87 (10)	3.197 (8)	105 (8)
N1—H1N···O1ⁱ	0.84 (5)	2.21 (5)	3.038 (9)	168 (10)

Symmetry code: (i) −x+1/2, y−1/2, z.

Acknowledgements

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

References

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