Acta Cryst. (2009). E65, o2172 [ doi:10.1107/S1600536809032139 ]
The crystal structure of the title compound, C8H5Br3ClNO, shows both intramolecular N-H
Br and intermolecular N-HO hydrogen bonding. In the crystal, the molecules are packed into column-like chains in the c-axis direction via the N-HO hydrogen bonds.
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.
The H atom of the NH group was located in a difference map and later restrained to the distance N—H = 0.86 (5) 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).
The largest residual electron-density features are located in the region of Br3 and Br2. The highest peak is 0.98 Å from Br3 and the deepest hole is 0.50 Å from Br2.
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]](./pk2183fig1thm.gif)
| Fig. 1. Molecular structure of (I), showing the atom labelling scheme and displacement ellipsoids are drawn at the 50% probability level. |
![[Figure 2]](./pk2183fig2thm.gif)
| Fig. 2. Molecular packing of (I) with hydrogen bonding shown as dashed lines. |
| C8H5Br3ClNO | F(000) = 1520 |
| Mr = 406.31 | Dx = 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 |
| 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 | Rint = 0.033 |
| 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 = −12→8 |
| Tmin = 0.104, Tmax = 0.355 | k = −12→9 |
| 5692 measured reflections | l = −29→21 |
| 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(Fo2) + (0.0891P)2 + 22.8289P] where P = (Fo2 + 2Fc2)/3 |
| 2353 reflections | (Δ/σ)max = 0.005 |
| 130 parameters | Δρmax = 2.04 e Å−3 |
| 1 restraint | Δρmin = −0.95 e Å−3 |
| C8H5Br3ClNO | V = 2383.3 (3) Å3 |
| Mr = 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 |
| 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) |
| Tmin = 0.104, Tmax = 0.355 | Rint = 0.033 |
| 5692 measured reflections | θmax = 26.4° |
| R[F2 > 2σ(F2)] = 0.080 | w = 1/[σ2(Fo2) + (0.0891P)2 + 22.8289P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.205 | Δρmax = 2.04 e Å−3 |
| S = 1.04 | Δρmin = −0.95 e Å−3 |
| 2353 reflections | Absolute structure: ? |
| 130 parameters | Flack parameter: ? |
| 1 restraint | Rogers parameter: ? |
| H atoms treated by a mixture of independent and constrained refinement |
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 | ||
| 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) |
| 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) |
| 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) |
| 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 codes: (i) −x+1/2, y−1/2, z. |
| 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 codes: (i) −x+1/2, y−1/2, z. |
BTG thanks the Alexander von Humboldt Foundation, Bonn, Germany, for an extension of his research fellowship.
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Gowda, B. T., Foro, S. & Fuess, H. (2007). Acta Cryst. E63, o3392.
Gowda, B. T., Usha, K. M. & Jayalakshmi, K. L. (2003). Z. Naturforsch. Teil A, 58, 801–806.
Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
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.