Acta Cryst. (2009). E65, o1333 [ doi:10.1107/S1600536809018273 ]
The title compound, C7H6BrNS, crystallizes with two molecules in the asymmetric unit. The dihedral angles between the aromatic ring and the thioamide fragment are 23.6 (4) and 20.5 (3)° in the two molecules. In the crystal, there are intermolecular N-H
S hydrogen-bonding interactions between the amine group and the S atoms.
The slurry of 70% sodium hydrogen sulfide hydrate (21.98 mmol) and magnesium chloride hexahydrate (10.99 mmol) was prepared in DMF (40 mL). 4-Bromobenzonitrile (11.0 mmol) was added to the slurry and the mixture stirred at room temperature for 2 h. The resulting mixture was poured into water (100 mL) and the precipitated solid collected by filtration. The product obtained was resuspended in 1 N HCl (50 ml), stirred for another 30 min, filtered and washed with excess water. The recrystallization of the product from chloroform afforded the crystals of 4-bromobenzothioamide suitable for X-ray analysis.
The hydrogen atoms were placed in geometrically idealized positions of 0.93Å (aromatic C—H) and 0.86Å (amide N—H) and constrained to ride on the parent atom with Uiso(H) = 1.2 UEq(c) for aromatic and amide protons.
Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./bt2956fig1thm.gif)
| Fig. 1. Molecular structure of 4-bromobenzothioamide showing displacement ellipsoids at the 50% probability level (for non-H atoms). |
![[Figure 2]](./bt2956fig2thm.gif)
| Fig. 2. Packing diagram of 4-bromobenzothioamide. Displacement ellipsoids are shown at the 50% probability level (for non-H atoms). |
| C7H6BrNS | F000 = 848 |
| Mr = 216.10 | Dx = 1.775 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 3900 reflections |
| a = 19.6325 (11) Å | θ = 2.2–26.9º |
| b = 10.6101 (6) Å | µ = 5.26 mm−1 |
| c = 7.8859 (5) Å | T = 296 K |
| β = 100.0780 (10)º | Block, yellow |
| V = 1617.31 (16) Å3 | 0.21 × 0.17 × 0.09 mm |
| Z = 8 |
| Bruker APEXII CCD diffractometer | 3911 independent reflections |
| Radiation source: fine-focus sealed tube | 2706 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.025 |
| T = 296 K | θmax = 28.3º |
| φ and ω scans | θmin = 2.1º |
| Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −25→25 |
| Tmin = 0.384, Tmax = 0.620 | k = −13→14 |
| 12968 measured reflections | l = −10→10 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
| wR(F2) = 0.087 | w = 1/[σ2(Fo2) + (0.0372P)2 + 0.7786P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.03 | (Δ/σ)max = 0.001 |
| 3911 reflections | Δρmax = 0.82 e Å−3 |
| 181 parameters | Δρmin = −0.77 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C7H6BrNS | V = 1617.31 (16) Å3 |
| Mr = 216.10 | Z = 8 |
| Monoclinic, P21/c | Mo Kα |
| a = 19.6325 (11) Å | µ = 5.26 mm−1 |
| b = 10.6101 (6) Å | T = 296 K |
| c = 7.8859 (5) Å | 0.21 × 0.17 × 0.09 mm |
| β = 100.0780 (10)º |
| Bruker APEXII CCD diffractometer | 3911 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2008) | 2706 reflections with I > 2σ(I) |
| Tmin = 0.384, Tmax = 0.620 | Rint = 0.025 |
| 12968 measured reflections |
| R[F2 > 2σ(F2)] = 0.035 | 181 parameters |
| wR(F2) = 0.087 | H-atom parameters constrained |
| S = 1.03 | Δρmax = 0.82 e Å−3 |
| 3911 reflections | Δρmin = −0.77 e Å−3 |
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 | ||
| Br2 | 0.315314 (16) | 0.36346 (4) | 0.36641 (5) | 0.07035 (13) | |
| Br1 | 0.538072 (18) | 0.69050 (5) | 1.27120 (5) | 0.08477 (16) | |
| S2 | −0.04123 (4) | 0.26135 (7) | 0.39188 (10) | 0.05003 (18) | |
| S1 | 0.21328 (4) | 0.52885 (7) | 0.75427 (10) | 0.05230 (19) | |
| N2 | −0.03383 (11) | 0.4881 (2) | 0.2688 (3) | 0.0473 (6) | |
| H2A | −0.0119 | 0.5515 | 0.2367 | 0.057* | |
| H2B | −0.0780 | 0.4916 | 0.2623 | 0.057* | |
| C1 | 0.23831 (13) | 0.6495 (2) | 0.8875 (3) | 0.0412 (6) | |
| C9 | 0.07643 (12) | 0.3842 (2) | 0.3369 (3) | 0.0342 (5) | |
| C12 | 0.21855 (13) | 0.3743 (3) | 0.3549 (3) | 0.0429 (6) | |
| C10 | 0.10919 (14) | 0.4633 (2) | 0.2364 (4) | 0.0459 (6) | |
| H10A | 0.0831 | 0.5200 | 0.1618 | 0.055* | |
| C14 | 0.11668 (14) | 0.3004 (3) | 0.4448 (3) | 0.0474 (7) | |
| H14A | 0.0956 | 0.2466 | 0.5131 | 0.057* | |
| C5 | 0.44606 (15) | 0.6804 (3) | 1.1491 (4) | 0.0558 (8) | |
| C8 | 0.00020 (13) | 0.3859 (2) | 0.3280 (3) | 0.0370 (5) | |
| C13 | 0.18748 (14) | 0.2945 (3) | 0.4535 (4) | 0.0515 (7) | |
| H13A | 0.2137 | 0.2366 | 0.5260 | 0.062* | |
| C11 | 0.18020 (15) | 0.4589 (3) | 0.2457 (4) | 0.0498 (7) | |
| H11A | 0.2018 | 0.5127 | 0.1785 | 0.060* | |
| N1 | 0.19425 (12) | 0.7375 (2) | 0.9174 (3) | 0.0554 (6) | |
| H1A | 0.2082 | 0.7985 | 0.9867 | 0.067* | |
| H1B | 0.1517 | 0.7338 | 0.8675 | 0.067* | |
| C2 | 0.31088 (13) | 0.6623 (2) | 0.9781 (3) | 0.0408 (6) | |
| C6 | 0.40650 (16) | 0.7873 (3) | 1.1197 (4) | 0.0622 (8) | |
| H6A | 0.4250 | 0.8654 | 1.1563 | 0.075* | |
| C3 | 0.35274 (15) | 0.5562 (3) | 1.0060 (4) | 0.0549 (7) | |
| H3A | 0.3351 | 0.4783 | 0.9659 | 0.066* | |
| C7 | 0.33903 (15) | 0.7780 (3) | 1.0352 (4) | 0.0540 (7) | |
| H7A | 0.3119 | 0.8502 | 1.0162 | 0.065* | |
| C4 | 0.42000 (16) | 0.5644 (3) | 1.0919 (4) | 0.0639 (9) | |
| H4A | 0.4475 | 0.4926 | 1.1110 | 0.077* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br2 | 0.03962 (17) | 0.0895 (3) | 0.0834 (3) | 0.00005 (15) | 0.01476 (15) | 0.00159 (19) |
| Br1 | 0.04511 (19) | 0.1196 (4) | 0.0842 (3) | −0.00878 (19) | −0.00386 (16) | −0.0108 (2) |
| S2 | 0.0434 (4) | 0.0390 (4) | 0.0685 (5) | −0.0063 (3) | 0.0120 (3) | 0.0056 (3) |
| S1 | 0.0465 (4) | 0.0459 (4) | 0.0626 (5) | −0.0022 (3) | 0.0043 (3) | −0.0081 (3) |
| N2 | 0.0398 (12) | 0.0358 (12) | 0.0667 (15) | 0.0016 (9) | 0.0101 (11) | 0.0030 (11) |
| C1 | 0.0427 (14) | 0.0402 (14) | 0.0415 (14) | 0.0002 (11) | 0.0096 (11) | 0.0055 (11) |
| C9 | 0.0400 (13) | 0.0271 (12) | 0.0358 (13) | −0.0022 (10) | 0.0076 (10) | −0.0035 (10) |
| C12 | 0.0405 (14) | 0.0435 (15) | 0.0448 (15) | −0.0022 (12) | 0.0078 (11) | −0.0071 (12) |
| C10 | 0.0485 (15) | 0.0347 (14) | 0.0566 (17) | 0.0078 (12) | 0.0150 (12) | 0.0086 (12) |
| C14 | 0.0444 (15) | 0.0515 (17) | 0.0459 (15) | −0.0021 (12) | 0.0067 (12) | 0.0152 (13) |
| C5 | 0.0392 (15) | 0.078 (2) | 0.0497 (17) | −0.0057 (15) | 0.0057 (12) | −0.0030 (15) |
| C8 | 0.0428 (13) | 0.0305 (13) | 0.0375 (13) | −0.0018 (10) | 0.0065 (10) | −0.0057 (10) |
| C13 | 0.0420 (15) | 0.0607 (18) | 0.0499 (16) | 0.0040 (13) | 0.0023 (12) | 0.0138 (14) |
| C11 | 0.0552 (17) | 0.0372 (15) | 0.0628 (18) | −0.0003 (13) | 0.0261 (14) | 0.0071 (13) |
| N1 | 0.0442 (13) | 0.0528 (15) | 0.0659 (16) | 0.0090 (11) | 0.0004 (11) | −0.0115 (12) |
| C2 | 0.0395 (13) | 0.0418 (15) | 0.0420 (14) | 0.0003 (11) | 0.0099 (11) | 0.0036 (11) |
| C6 | 0.0509 (18) | 0.063 (2) | 0.072 (2) | −0.0100 (15) | 0.0088 (15) | −0.0202 (17) |
| C3 | 0.0483 (16) | 0.0439 (16) | 0.069 (2) | −0.0015 (13) | 0.0022 (14) | 0.0035 (14) |
| C7 | 0.0518 (17) | 0.0471 (17) | 0.0633 (19) | −0.0007 (13) | 0.0108 (14) | −0.0083 (14) |
| C4 | 0.0477 (17) | 0.058 (2) | 0.082 (2) | 0.0054 (15) | 0.0008 (15) | 0.0080 (17) |
| Br2—C12 | 1.890 (3) | C14—C13 | 1.381 (4) |
| Br1—C5 | 1.896 (3) | C14—H14A | 0.9300 |
| S2—C8 | 1.675 (3) | C5—C6 | 1.371 (5) |
| S1—C1 | 1.674 (3) | C5—C4 | 1.379 (5) |
| N2—C8 | 1.316 (3) | C13—H13A | 0.9300 |
| N2—H2A | 0.8600 | C11—H11A | 0.9300 |
| N2—H2B | 0.8600 | N1—H1A | 0.8600 |
| C1—N1 | 1.322 (3) | N1—H1B | 0.8600 |
| C1—C2 | 1.484 (4) | C2—C3 | 1.388 (4) |
| C9—C14 | 1.380 (3) | C2—C7 | 1.389 (4) |
| C9—C10 | 1.388 (3) | C6—C7 | 1.378 (4) |
| C9—C8 | 1.486 (3) | C6—H6A | 0.9300 |
| C12—C13 | 1.364 (4) | C3—C4 | 1.377 (4) |
| C12—C11 | 1.373 (4) | C3—H3A | 0.9300 |
| C10—C11 | 1.384 (4) | C7—H7A | 0.9300 |
| C10—H10A | 0.9300 | C4—H4A | 0.9300 |
| C8—N2—H2A | 120.0 | C12—C13—C14 | 119.3 (3) |
| C8—N2—H2B | 120.0 | C12—C13—H13A | 120.3 |
| H2A—N2—H2B | 120.0 | C14—C13—H13A | 120.3 |
| N1—C1—C2 | 116.9 (2) | C12—C11—C10 | 119.5 (3) |
| N1—C1—S1 | 121.5 (2) | C12—C11—H11A | 120.3 |
| C2—C1—S1 | 121.58 (19) | C10—C11—H11A | 120.3 |
| C14—C9—C10 | 118.0 (2) | C1—N1—H1A | 120.0 |
| C14—C9—C8 | 120.0 (2) | C1—N1—H1B | 120.0 |
| C10—C9—C8 | 122.0 (2) | H1A—N1—H1B | 120.0 |
| C13—C12—C11 | 120.8 (3) | C3—C2—C7 | 118.3 (3) |
| C13—C12—Br2 | 118.7 (2) | C3—C2—C1 | 119.6 (2) |
| C11—C12—Br2 | 120.4 (2) | C7—C2—C1 | 122.1 (2) |
| C11—C10—C9 | 120.8 (2) | C5—C6—C7 | 119.3 (3) |
| C11—C10—H10A | 119.6 | C5—C6—H6A | 120.3 |
| C9—C10—H10A | 119.6 | C7—C6—H6A | 120.3 |
| C9—C14—C13 | 121.5 (2) | C4—C3—C2 | 121.1 (3) |
| C9—C14—H14A | 119.2 | C4—C3—H3A | 119.4 |
| C13—C14—H14A | 119.2 | C2—C3—H3A | 119.4 |
| C6—C5—C4 | 121.1 (3) | C6—C7—C2 | 121.0 (3) |
| C6—C5—Br1 | 120.0 (2) | C6—C7—H7A | 119.5 |
| C4—C5—Br1 | 118.9 (2) | C2—C7—H7A | 119.5 |
| N2—C8—C9 | 118.1 (2) | C3—C4—C5 | 119.1 (3) |
| N2—C8—S2 | 120.9 (2) | C3—C4—H4A | 120.5 |
| C9—C8—S2 | 120.96 (18) | C5—C4—H4A | 120.5 |
| C3—C1—C2—S1 | 23.6 (3) | C14—C8—C9—S2 | 20.5 (3) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···S2i | 0.86 | 2.73 | 3.583 (2) | 172 |
| N2—H2B···S1ii | 0.86 | 2.65 | 3.500 (2) | 173 |
| N1—H1A···S1iii | 0.86 | 2.78 | 3.605 (3) | 160 |
| N1—H1B···S2ii | 0.86 | 2.71 | 3.523 (2) | 158 |
| Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x, −y+1, −z+1; (iii) x, −y+3/2, z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···S2i | 0.86 | 2.73 | 3.583 (2) | 172 |
| N2—H2B···S1ii | 0.86 | 2.65 | 3.500 (2) | 173 |
| N1—H1A···S1iii | 0.86 | 2.78 | 3.605 (3) | 160 |
| N1—H1B···S2ii | 0.86 | 2.71 | 3.523 (2) | 158 |
| Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x, −y+1, −z+1; (iii) x, −y+3/2, z+1/2. |
The authours thank the HEC, Pakistan, for a Ph.D. fellowship awarded to MuHK under the indiginous Ph.D. Program. JDM thanks Saint Mary's University for funding.
Akhtar, T., Hameed, S., Al-Masoudi, N. A. & Khan, K. M. (2007). Heteroat. Chem. 18, 316–322.
Akhtar, T., Hameed, S., Al-Masoudi, N. A., Loddo, R. & La Colla, P. (2008). Acta Pharm. 58, 135–149.
Akhtar, T., Hameed, S., Lu, X., Yasin, K. A. & Khan, M. H. (2006). X-ray Struct. Anal. Online, 22, x307–x308.
Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Cava, M. P. & Levinson, M. I. (1985). Tetrahedron, 41, 5061–5087.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Jagodzinski, T. S. (2003). Chem. Rev. 103, 197–227.
Jian, F. F., Zhao, P., Zhang, L. & Zheng, J. (2006). J. Fluorine Chem. 127, 63–67.
Kaboudin, B. & Elhamifar, D. (2006). Synthesis Stuttgart, pp. 224–226.
Khan, M.-H., Hameed, S., Akhtar, T. & Masuda, J. D. (2009). Acta Cryst. E65, o1128.
Klimesova, V., Svoboda, M., Waisser, K. K., Kaustova, J., Buchta, V. & Kra'lova, K. (1999). Eur. J. Med. Chem. 34, 433–440.
Manaka, A. & Sato, M. (2005). Synth. Commun. 35, 761–764.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Wei, Q.-L., Zhang, S.-S., Gao, J., Li, W.-H., Xu, L.-Z. & Yu, Z.-G. (2006). Bioorg. Med. Chem. 14, 7146–7153.
Thioamides are biologically active compounds, possessing a wide spectrum of activities (Klimesova et al., 1999; Wei et al., 2006). They have enormous practical and synthetic applicability and their importance and impact as synthetic intermediates is continuously growing (Jagodzinski et al., 2003). Thioamides are generally synthesized using Lawesson's reagent (Cava et al., 1985) or phosphorus penta sulfide (Kaboudin et al., 2006). In this article, we wish to report the crystal structure of 4-bromobenzothioamide, which was synthesized by treating 4-bromobenzonitrile with 70% sodium hydrogen sulfide hydrate and magnesium chloride hexahydrate (Manaka & Sato, 2005) in continuation of our previous work on the synthesis and biological screenings of five membered heterocycles (Akhtar et al., 2006, 2007, 2008).
The hydrogen bonding interactions between the nitrogen and sulfur atoms (3.500 (2)Å to 3.605 (3) Å) are in the range of those seen in p-trifluoromethylbenzothioamide where the corresponding interactions are between 3.3735Å and 3.5133Å (Jian et al., 2006) and in the analogus chloride compound where the N···S distances are 3.3769 (15)Å and 3.4527 (15)Å (Khan et al., 2009).