Acta Cryst. (2010). E66, o386 [ doi:10.1107/S1600536810001467 ]
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-HCl contacts occur.
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.
The H atom of the NH group was located in a difference map and later restrained to the distance N—H = 0.86 (3) Å. The other H atoms were positioned with idealized geometry using a riding model [C—H = 0.93 Å]. All H atoms were refined with isotropic displacement parameters set to 1.2 times of the Ueq of the parent atom.
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).
![[Figure 1]](./bt5167fig1thm.gif)
| 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. |
![[Figure 2]](./bt5167fig2thm.gif)
| Fig. 2. Molecular packing of the title compound with hydrogen bonds shown as dashed lines. |
| C8H5Br3ClNO | F(000) = 760 |
| Mr = 406.31 | Dx = 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 |
| 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 | Rint = 0.022 |
| Rotation method data acquisition using ω and φ scans. | θmax = 26.4°, θmin = 2.7° |
| Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009) | h = −11→11 |
| Tmin = 0.098, Tmax = 0.120 | k = −16→15 |
| 4524 measured reflections | l = −11→6 |
| 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(Fo2) + (0.0357P)2 + 1.2795P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.066 | (Δ/σ)max = 0.004 |
| S = 1.07 | Δρmax = 0.77 e Å−3 |
| 1645 reflections | Δρmin = −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 | Flack parameter: 0.049 (18) |
| C8H5Br3ClNO | V = 1134.98 (12) Å3 |
| Mr = 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 |
| 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) |
| Tmin = 0.098, Tmax = 0.120 | Rint = 0.022 |
| 4524 measured reflections | θmax = 26.4° |
| R[F2 > 2σ(F2)] = 0.027 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.066 | Δρmax = 0.77 e Å−3 |
| S = 1.07 | Δρmin = −0.56 e Å−3 |
| 1645 reflections | Absolute structure: Flack (1983), 416 Friedel pairs |
| 131 parameters | Flack parameter: 0.049 (18) |
| 2 restraints |
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. |
| x | y | z | Uiso*/Ueq | ||
| 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) |
| 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) |
| 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) |
| 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) |
| 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) |
PAS thanks the Council of Scientific and Industrial Research (CSIR), Government of India, New Delhi, for the award of a research fellowship.
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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.