Acta Cryst. (2008). E64, o1884 [ doi:10.1107/S1600536808027827 ]
In the title compound, C8H6BrN3S, the thiadiazole ring is oriented at a dihedral angle of 48.35 (3)° with respect to the bromophenyl ring. In the crystal structure, intermolecular N-H
N hydrogen bonds link the molecules.
For the preparation of the title compound, 2-bromobenzoic acid (5 mmol) and thiosemicarbazide (5 mmol) were added in toluene (50 ml), which is heated under reflux for 4 h. The reaction mixture was left to cool to room temperature, poured into ice water, filtered, and the filter cake was crystallized from acetone to give title compound (m.p. 486–487 K). Crystals suitable for X-ray analysis were obtained by slow evaporation of an acetone solution.
H atoms were positioned geometrically, with N—H = 0.86 Å (for NH2) and C—H = 0.93 Å for aromatic H, respectively, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C,N).
Data collection: CAD4 Software (Enraf–Nonius, 1989); cell refinement: CAD4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./hk2522fig1thm.gif)
| Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. |
![[Figure 2]](./hk2522fig2thm.gif)
| Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines. |
| C8H6BrN3S | F(000) = 504 |
| Mr = 256.13 | Dx = 1.809 Mg m−3 |
| Monoclinic, P21/c | Melting point = 486–487 K |
| Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
| a = 14.869 (3) Å | Cell parameters from 25 reflections |
| b = 8.0250 (16) Å | θ = 10–14° |
| c = 7.9480 (16) Å | µ = 4.55 mm−1 |
| β = 97.43 (3)° | T = 298 K |
| V = 940.4 (3) Å3 | Block, colorless |
| Z = 4 | 0.30 × 0.10 × 0.10 mm |
| Enraf–Nonius CAD-4 diffractometer | 972 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.034 |
| graphite | θmax = 25.2°, θmin = 1.4° |
| ω/2θ scans | h = −17→17 |
| Absorption correction: ψ scan (North et al., 1968) | k = 0→9 |
| Tmin = 0.343, Tmax = 0.659 | l = 0→9 |
| 1832 measured reflections | 3 standard reflections every 120 min |
| 1694 independent reflections | intensity decay: none |
| 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)] = 0.060 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.153 | H-atom parameters constrained |
| S = 0.97 | w = 1/[σ2(Fo2) + (0.0838P)2] where P = (Fo2 + 2Fc2)/3 |
| 1694 reflections | (Δ/σ)max < 0.001 |
| 118 parameters | Δρmax = 0.41 e Å−3 |
| 0 restraints | Δρmin = −0.57 e Å−3 |
| C8H6BrN3S | V = 940.4 (3) Å3 |
| Mr = 256.13 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 14.869 (3) Å | µ = 4.55 mm−1 |
| b = 8.0250 (16) Å | T = 298 K |
| c = 7.9480 (16) Å | 0.30 × 0.10 × 0.10 mm |
| β = 97.43 (3)° |
| Enraf–Nonius CAD-4 diffractometer | 972 reflections with I > 2σ(I) |
| Absorption correction: ψ scan (North et al., 1968) | Rint = 0.034 |
| Tmin = 0.343, Tmax = 0.659 | θmax = 25.2° |
| 1832 measured reflections | 3 standard reflections every 120 min |
| 1694 independent reflections | intensity decay: none |
| R[F2 > 2σ(F2)] = 0.060 | H-atom parameters constrained |
| wR(F2) = 0.153 | Δρmax = 0.41 e Å−3 |
| S = 0.97 | Δρmin = −0.57 e Å−3 |
| 1694 reflections | Absolute structure: ? |
| 118 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | ||
| Br | 0.88329 (5) | 1.09232 (10) | 1.09121 (14) | 0.0845 (5) | |
| S | 0.65602 (11) | 1.1146 (2) | 1.0932 (2) | 0.0458 (5) | |
| N1 | 0.6259 (3) | 0.9573 (7) | 0.8134 (6) | 0.0424 (13) | |
| N2 | 0.5587 (3) | 1.0773 (6) | 0.8048 (6) | 0.0430 (13) | |
| N3 | 0.5081 (3) | 1.2909 (6) | 0.9666 (6) | 0.0480 (14) | |
| H3A | 0.4635 | 1.3143 | 0.8901 | 0.058* | |
| H3B | 0.5158 | 1.3467 | 1.0597 | 0.058* | |
| C1 | 0.7308 (5) | 0.6693 (8) | 0.9656 (9) | 0.0512 (18) | |
| H1 | 0.6722 | 0.6431 | 0.9176 | 0.061* | |
| C2 | 0.7921 (5) | 0.5423 (8) | 1.0064 (10) | 0.0591 (19) | |
| H2 | 0.7750 | 0.4319 | 0.9866 | 0.071* | |
| C3 | 0.8787 (5) | 0.5816 (10) | 1.0769 (10) | 0.068 (2) | |
| H3 | 0.9204 | 0.4968 | 1.1067 | 0.081* | |
| C4 | 0.9041 (4) | 0.7438 (10) | 1.1036 (9) | 0.059 (2) | |
| H4 | 0.9630 | 0.7698 | 1.1506 | 0.071* | |
| C5 | 0.8416 (4) | 0.8692 (8) | 1.0602 (9) | 0.0493 (17) | |
| C6 | 0.7542 (4) | 0.8348 (7) | 0.9941 (8) | 0.0378 (14) | |
| C7 | 0.6811 (4) | 0.9618 (8) | 0.9507 (7) | 0.0363 (14) | |
| C8 | 0.5647 (4) | 1.1688 (7) | 0.9412 (7) | 0.0332 (14) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br | 0.0417 (5) | 0.0576 (5) | 0.1483 (10) | −0.0105 (4) | −0.0096 (5) | −0.0066 (6) |
| S | 0.0396 (9) | 0.0538 (10) | 0.0394 (9) | 0.0102 (8) | −0.0131 (7) | −0.0097 (8) |
| N1 | 0.042 (3) | 0.046 (3) | 0.037 (3) | 0.000 (3) | −0.001 (3) | −0.003 (3) |
| N2 | 0.045 (3) | 0.043 (3) | 0.037 (3) | 0.008 (3) | −0.008 (2) | −0.005 (3) |
| N3 | 0.049 (3) | 0.056 (4) | 0.036 (3) | 0.015 (3) | −0.008 (2) | −0.007 (3) |
| C1 | 0.046 (4) | 0.049 (4) | 0.057 (5) | −0.003 (3) | 0.005 (3) | 0.001 (4) |
| C2 | 0.057 (4) | 0.035 (4) | 0.086 (5) | 0.004 (3) | 0.013 (4) | 0.004 (4) |
| C3 | 0.050 (4) | 0.068 (6) | 0.083 (6) | 0.021 (4) | 0.005 (4) | 0.012 (5) |
| C4 | 0.037 (4) | 0.064 (5) | 0.073 (5) | 0.009 (4) | −0.003 (4) | 0.009 (4) |
| C5 | 0.031 (3) | 0.049 (4) | 0.065 (4) | −0.004 (3) | −0.004 (3) | 0.006 (3) |
| C6 | 0.038 (3) | 0.040 (3) | 0.036 (3) | −0.002 (3) | 0.006 (3) | −0.004 (3) |
| C7 | 0.029 (3) | 0.042 (3) | 0.037 (3) | −0.006 (3) | 0.001 (3) | 0.001 (3) |
| C8 | 0.029 (3) | 0.035 (3) | 0.034 (4) | 0.000 (3) | −0.003 (3) | 0.004 (3) |
| Br—C5 | 1.901 (7) | C3—H3 | 0.9300 |
| N1—N2 | 1.383 (7) | C4—C5 | 1.383 (9) |
| N3—H3A | 0.8600 | C4—H4 | 0.9300 |
| N3—H3B | 0.8600 | C5—C6 | 1.365 (8) |
| C1—C2 | 1.377 (9) | C6—C7 | 1.498 (8) |
| C1—C6 | 1.384 (8) | C7—N1 | 1.278 (7) |
| C1—H1 | 0.9300 | C7—S | 1.742 (6) |
| C2—C3 | 1.373 (10) | C8—N2 | 1.302 (7) |
| C2—H2 | 0.9300 | C8—N3 | 1.325 (7) |
| C3—C4 | 1.365 (11) | C8—S | 1.752 (6) |
| C2—C1—C6 | 121.8 (7) | C5—C6—C1 | 117.6 (6) |
| C2—C1—H1 | 119.1 | C5—C6—C7 | 125.3 (6) |
| C6—C1—H1 | 119.1 | C1—C6—C7 | 117.1 (6) |
| C3—C2—C1 | 118.9 (7) | N1—C7—C6 | 123.0 (6) |
| C3—C2—H2 | 120.5 | N1—C7—S | 114.0 (5) |
| C1—C2—H2 | 120.5 | C6—C7—S | 122.6 (4) |
| C4—C3—C2 | 120.6 (7) | N2—C8—N3 | 124.6 (5) |
| C4—C3—H3 | 119.7 | N2—C8—S | 113.4 (4) |
| C2—C3—H3 | 119.7 | N3—C8—S | 122.0 (5) |
| C3—C4—C5 | 119.4 (6) | C7—N1—N2 | 113.7 (5) |
| C3—C4—H4 | 120.3 | C8—N2—N1 | 112.4 (5) |
| C5—C4—H4 | 120.3 | C8—N3—H3A | 120.0 |
| C6—C5—C4 | 121.6 (6) | C8—N3—H3B | 120.0 |
| C6—C5—Br | 121.2 (5) | H3A—N3—H3B | 120.0 |
| C4—C5—Br | 117.1 (5) | C7—S—C8 | 86.4 (3) |
| C6—C1—C2—C3 | −0.2 (11) | C1—C6—C7—N1 | −44.3 (9) |
| C1—C2—C3—C4 | −1.0 (12) | C5—C6—C7—S | −51.2 (8) |
| C2—C3—C4—C5 | 0.5 (12) | C1—C6—C7—S | 128.4 (6) |
| C3—C4—C5—C6 | 1.3 (11) | C6—C7—N1—N2 | 174.6 (5) |
| C3—C4—C5—Br | −177.2 (6) | S—C7—N1—N2 | 1.3 (7) |
| C4—C5—C6—C1 | −2.5 (11) | N3—C8—N2—N1 | −179.0 (6) |
| Br—C5—C6—C1 | 176.0 (5) | S—C8—N2—N1 | 0.6 (6) |
| C4—C5—C6—C7 | 177.2 (6) | C7—N1—N2—C8 | −1.2 (7) |
| Br—C5—C6—C7 | −4.4 (9) | N1—C7—S—C8 | −0.8 (5) |
| C2—C1—C6—C5 | 1.9 (11) | C6—C7—S—C8 | −174.1 (5) |
| C2—C1—C6—C7 | −177.8 (6) | N2—C8—S—C7 | 0.1 (5) |
| C5—C6—C7—N1 | 136.1 (7) | N3—C8—S—C7 | 179.6 (5) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H3A···N1i | 0.86 | 2.27 | 3.092 (7) | 160. |
| N3—H3A···N2i | 0.86 | 2.61 | 3.221 (7) | 129. |
| N3—H3B···N2ii | 0.86 | 2.06 | 2.896 (7) | 163. |
| Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, −y+5/2, z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H3A···N1i | 0.86 | 2.27 | 3.092 (7) | 160. |
| N3—H3A···N2i | 0.86 | 2.61 | 3.221 (7) | 129. |
| N3—H3B···N2ii | 0.86 | 2.06 | 2.896 (7) | 163. |
| Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, −y+5/2, z+1/2. |
The authors gratefully acknowledge Professor Hua-Qin Wang of the Analysis Center, Nanjing University, for providing the Enraf?Nonius CAD4 diffractometer for this research project.
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1,3,4-Thiadiazole derivatives represent an interesting class of compounds possessing broad spectrum biological activities (Nakagawa et al., 1996). These compounds are known to exhibit diverse biological effects, such as insecticidal and fungicidal activities (Wang et al., 1999). It can also be widely used in the field of medicine, such as anti-cancer drugs (Omar et al., 1986).
In the molecule of the title compound, (Fig. 1), the bond lengths (Allen et al., 1987) and angles are generally within normal ranges. Rings A (C1–C6) and B (S/N1/N2/C7/C8) are, of course, planar, and they are oriented at a dihedral angle of 48.35 (3)°.
In the crystal structure, intermolecular N—H···N hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure.