Acta Cryst. (2009). E65, o1250 [ doi:10.1107/S1600536809016614 ]
The title compound, C8H5FN4O2S, was synthesized by the reaction of 2-fluoro-4-nitrobenzoic acid and thiosemicarbazide. The dihedral angle between the thiadiazole and benzene rings is 27.1 (2)°. In the crystal, intermolecular N-H
N and C-HO hydrogen bonds link the molecules.
2-Fluoro-4-nitrobenzoic acid (2 mmol) and thiosemicarbazide (5 mmol) were mixed in a 25 ml flask, and kept in the oil bath at 363 K for 6 h. After cooling, the crude product (I) precipitated and was filted. Pure compound (I) was obtained by crystallization from ethanol (20 ml). Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of an acetone solution.
H atoms were placed geometrically with C—H = 0.93 Å and N—H = 0.86 Å, and included in the refinement in riding motion approximation with Uiso(H) = 1.2 or 1.5Ueq of the carrier atom.
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 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: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./at2775fig1thm.gif)
| Fig. 1. A view of the molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level. |
![[Figure 2]](./at2775fig2thm.gif)
| Fig. 2. Partial packing view showing the hydrogen-bonded network. Dashed lines indicate intermolecular N—H···N and C—H···O hydrogen bonds. |
| C8H5FN4O2S | F000 = 488 |
| Mr = 240.22 | Dx = 1.665 Mg m−3 |
| Monoclinic, P21/c | Melting point: 476 K |
| Hall symbol: -P 2ybc | Mo Kα radiation λ = 0.71073 Å |
| a = 9.1780 (18) Å | Cell parameters from 25 reflections |
| b = 9.3720 (19) Å | θ = 9–12º |
| c = 11.413 (2) Å | µ = 0.34 mm−1 |
| β = 102.55 (3)º | T = 293 K |
| V = 958.2 (3) Å3 | Block, colourless |
| Z = 4 | 0.20 × 0.10 × 0.10 mm |
| Enraf–Nonius CAD-4 diffractometer | Rint = 0.047 |
| Radiation source: fine-focus sealed tube | θmax = 25.2º |
| Monochromator: graphite | θmin = 2.3º |
| T = 293 K | h = 0→11 |
| ω/2θ scans | k = 0→11 |
| Absorption correction: ψ scan (North et al., 1968) | l = −13→13 |
| Tmin = 0.935, Tmax = 0.967 | 3 standard reflections |
| 1832 measured reflections | every 200 reflections |
| 1720 independent reflections | intensity decay: 1% |
| 1301 reflections with I > 2σ(I) |
| 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)] = 0.056 | H-atom parameters constrained |
| wR(F2) = 0.194 | w = 1/[σ2(Fo2) + (0.1P)2 + 2.P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.01 | (Δ/σ)max < 0.001 |
| 1720 reflections | Δρmax = 0.43 e Å−3 |
| 145 parameters | Δρmin = −0.47 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C8H5FN4O2S | V = 958.2 (3) Å3 |
| Mr = 240.22 | Z = 4 |
| Monoclinic, P21/c | Mo Kα |
| a = 9.1780 (18) Å | µ = 0.34 mm−1 |
| b = 9.3720 (19) Å | T = 293 K |
| c = 11.413 (2) Å | 0.20 × 0.10 × 0.10 mm |
| β = 102.55 (3)º |
| Enraf–Nonius CAD-4 diffractometer | 1301 reflections with I > 2σ(I) |
| Absorption correction: ψ scan (North et al., 1968) | Rint = 0.047 |
| Tmin = 0.935, Tmax = 0.967 | 3 standard reflections |
| 1832 measured reflections | every 200 reflections |
| 1720 independent reflections | intensity decay: 1% |
| R[F2 > 2σ(F2)] = 0.056 | 145 parameters |
| wR(F2) = 0.194 | H-atom parameters constrained |
| S = 1.01 | Δρmax = 0.43 e Å−3 |
| 1720 reflections | Δρmin = −0.47 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 | ||
| S | 0.65883 (14) | 0.15613 (12) | 0.66472 (10) | 0.0442 (4) | |
| F | 0.6863 (3) | −0.1515 (3) | 0.6466 (2) | 0.0539 (8) | |
| N1 | 0.9259 (5) | −0.4021 (5) | 0.3718 (4) | 0.0537 (11) | |
| C1 | 0.8706 (5) | −0.2697 (4) | 0.4162 (4) | 0.0404 (10) | |
| O1 | 1.0171 (6) | −0.3935 (5) | 0.3093 (4) | 0.0892 (15) | |
| O2 | 0.8765 (4) | −0.5153 (4) | 0.4009 (4) | 0.0656 (11) | |
| N2 | 0.6452 (5) | 0.2128 (4) | 0.4420 (3) | 0.0449 (9) | |
| C2 | 0.8888 (5) | −0.1427 (5) | 0.3565 (4) | 0.0448 (11) | |
| H2B | 0.9387 | −0.1415 | 0.2938 | 0.054* | |
| N3 | 0.5854 (5) | 0.3311 (4) | 0.4867 (3) | 0.0475 (10) | |
| C3 | 0.8298 (5) | −0.0180 (5) | 0.3938 (4) | 0.0412 (10) | |
| H3B | 0.8386 | 0.0674 | 0.3544 | 0.049* | |
| N4 | 0.5320 (5) | 0.4162 (4) | 0.6663 (3) | 0.0535 (11) | |
| H4A | 0.4951 | 0.4943 | 0.6329 | 0.064* | |
| H4B | 0.5347 | 0.4016 | 0.7412 | 0.064* | |
| C4 | 0.7568 (5) | −0.0197 (4) | 0.4903 (4) | 0.0358 (10) | |
| C5 | 0.7505 (5) | −0.1484 (5) | 0.5495 (4) | 0.0388 (10) | |
| C6 | 0.8026 (5) | −0.2754 (5) | 0.5131 (4) | 0.0421 (10) | |
| H6A | 0.7925 | −0.3609 | 0.5519 | 0.050* | |
| C7 | 0.6885 (5) | 0.1134 (4) | 0.5224 (4) | 0.0367 (10) | |
| C8 | 0.5851 (5) | 0.3175 (4) | 0.6019 (4) | 0.0378 (10) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S | 0.0663 (8) | 0.0343 (6) | 0.0343 (6) | 0.0124 (5) | 0.0166 (5) | 0.0053 (4) |
| F | 0.0753 (19) | 0.0440 (16) | 0.0517 (16) | 0.0078 (13) | 0.0340 (14) | 0.0074 (12) |
| N1 | 0.069 (3) | 0.038 (2) | 0.054 (2) | 0.013 (2) | 0.012 (2) | −0.0076 (19) |
| C1 | 0.047 (2) | 0.031 (2) | 0.042 (2) | 0.0064 (19) | 0.0066 (19) | −0.0057 (19) |
| O1 | 0.125 (4) | 0.067 (3) | 0.096 (3) | 0.032 (3) | 0.068 (3) | −0.003 (2) |
| O2 | 0.075 (3) | 0.041 (2) | 0.075 (3) | 0.0038 (18) | 0.003 (2) | −0.0161 (19) |
| N2 | 0.068 (3) | 0.0328 (19) | 0.0379 (19) | 0.0120 (18) | 0.0200 (18) | 0.0030 (16) |
| C2 | 0.053 (3) | 0.040 (3) | 0.045 (2) | 0.006 (2) | 0.019 (2) | −0.005 (2) |
| N3 | 0.073 (3) | 0.0292 (19) | 0.045 (2) | 0.0150 (18) | 0.0237 (19) | 0.0044 (16) |
| C3 | 0.055 (3) | 0.032 (2) | 0.038 (2) | 0.0018 (19) | 0.014 (2) | 0.0020 (18) |
| N4 | 0.084 (3) | 0.040 (2) | 0.039 (2) | 0.020 (2) | 0.018 (2) | 0.0030 (17) |
| C4 | 0.040 (2) | 0.032 (2) | 0.034 (2) | 0.0034 (18) | 0.0068 (18) | −0.0020 (17) |
| C5 | 0.043 (2) | 0.037 (2) | 0.038 (2) | 0.0015 (19) | 0.0131 (18) | −0.0014 (18) |
| C6 | 0.056 (3) | 0.030 (2) | 0.041 (2) | 0.003 (2) | 0.012 (2) | 0.0016 (18) |
| C7 | 0.042 (2) | 0.031 (2) | 0.038 (2) | 0.0026 (18) | 0.0120 (19) | 0.0016 (18) |
| C8 | 0.048 (2) | 0.032 (2) | 0.035 (2) | 0.0058 (18) | 0.0101 (19) | 0.0053 (17) |
| S—C8 | 1.746 (4) | C2—H2B | 0.9300 |
| S—C7 | 1.750 (4) | N3—C8 | 1.321 (6) |
| F—C5 | 1.363 (5) | C3—C4 | 1.409 (6) |
| N1—O1 | 1.214 (6) | C3—H3B | 0.9300 |
| N1—O2 | 1.227 (5) | N4—C8 | 1.338 (6) |
| N1—C1 | 1.472 (6) | N4—H4A | 0.8600 |
| C1—C6 | 1.384 (6) | N4—H4B | 0.8600 |
| C1—C2 | 1.400 (6) | C4—C5 | 1.389 (6) |
| N2—C7 | 1.308 (5) | C4—C7 | 1.478 (6) |
| N2—N3 | 1.382 (5) | C5—C6 | 1.381 (6) |
| C2—C3 | 1.392 (6) | C6—H6A | 0.9300 |
| C8—S—C7 | 86.65 (19) | H4A—N4—H4B | 120.0 |
| O1—N1—O2 | 124.0 (4) | C5—C4—C3 | 117.9 (4) |
| O1—N1—C1 | 118.6 (4) | C5—C4—C7 | 123.2 (4) |
| O2—N1—C1 | 117.4 (4) | C3—C4—C7 | 118.9 (4) |
| C6—C1—C2 | 123.0 (4) | F—C5—C6 | 117.7 (4) |
| C6—C1—N1 | 119.4 (4) | F—C5—C4 | 119.0 (4) |
| C2—C1—N1 | 117.6 (4) | C6—C5—C4 | 123.3 (4) |
| C7—N2—N3 | 113.4 (3) | C5—C6—C1 | 116.9 (4) |
| C3—C2—C1 | 118.0 (4) | C5—C6—H6A | 121.5 |
| C3—C2—H2B | 121.0 | C1—C6—H6A | 121.5 |
| C1—C2—H2B | 121.0 | N2—C7—C4 | 120.6 (4) |
| C8—N3—N2 | 112.1 (3) | N2—C7—S | 113.8 (3) |
| C2—C3—C4 | 120.8 (4) | C4—C7—S | 125.7 (3) |
| C2—C3—H3B | 119.6 | N3—C8—N4 | 124.0 (4) |
| C4—C3—H3B | 119.6 | N3—C8—S | 114.1 (3) |
| C8—N4—H4A | 120.0 | N4—C8—S | 121.9 (3) |
| C8—N4—H4B | 120.0 | ||
| O1—N1—C1—C6 | −161.4 (5) | C4—C5—C6—C1 | 3.3 (7) |
| O2—N1—C1—C6 | 18.5 (6) | C2—C1—C6—C5 | 0.5 (7) |
| O1—N1—C1—C2 | 19.2 (7) | N1—C1—C6—C5 | −178.9 (4) |
| O2—N1—C1—C2 | −161.0 (5) | N3—N2—C7—C4 | −179.2 (4) |
| C6—C1—C2—C3 | −2.8 (7) | N3—N2—C7—S | 0.2 (5) |
| N1—C1—C2—C3 | 176.7 (4) | C5—C4—C7—N2 | −153.1 (4) |
| C7—N2—N3—C8 | 0.0 (6) | C3—C4—C7—N2 | 25.6 (6) |
| C1—C2—C3—C4 | 1.3 (7) | C5—C4—C7—S | 27.5 (6) |
| C2—C3—C4—C5 | 2.2 (7) | C3—C4—C7—S | −153.7 (4) |
| C2—C3—C4—C7 | −176.6 (4) | C8—S—C7—N2 | −0.2 (4) |
| C3—C4—C5—F | 177.2 (4) | C8—S—C7—C4 | 179.2 (4) |
| C7—C4—C5—F | −4.0 (7) | N2—N3—C8—N4 | −179.3 (4) |
| C3—C4—C5—C6 | −4.7 (7) | N2—N3—C8—S | −0.2 (5) |
| C7—C4—C5—C6 | 174.1 (4) | C7—S—C8—N3 | 0.2 (4) |
| F—C5—C6—C1 | −178.5 (4) | C7—S—C8—N4 | 179.4 (4) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N4—H4A···N3i | 0.86 | 2.16 | 3.000 (5) | 167 |
| C3—H3B···O1ii | 0.93 | 2.54 | 3.182 (7) | 126 |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, y+1/2, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N4—H4A···N3i | 0.86 | 2.16 | 3.000 (5) | 167 |
| C3—H3B···O1ii | 0.93 | 2.54 | 3.182 (7) | 126 |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, y+1/2, −z+1/2. |
The authors thank Professor Hua-qin Wang of the Analysis Centre, Nanjing University, for providing the Enraf–Nonius CAD-4 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, fungicidal activities (Wang et al., 1999).
The structure of the title compound, (I), is shown in Fig. 1, in which the bond lengths and angles are generally within normal ranges (Allen et al., 1987). The dihedral angle between the thiadiazole and benzene ring is 27.1 (2)°. There are intermolecular N—H···N and C—H···O hydrogen bonds, linking the molecules, forming chains along the b axis (Fig. 2),.