Acta Cryst. (2008). E64, o416 [ doi:10.1107/S160053680800024X ]
In the title compound, C6H6F5NS, the environment of the S atom is roughly octahedral. The axial F-S bond appears slightly elongated with respect to the four equatorial F-S bonds. Equatorial F atoms are staggered with respect to the benzene ring. The N atom is displaced from the benzene plane by 0.154 (4) Å. The F-S-C-C torsion angles differ greatly from the values observed in the related structure of 4-acetamidophenylsulfur pentafluoride. The packing is stabilized by weak N-H
F contacts.
Sample of 4-aminohenylsulfur pentafluoride was prepared in three steps according to original procedure (Sheppard, 1962). Bis-(4-nitrophenyl)-disulfide was fluorinated with silver difluoride in CFC113 solvent and the product 4-nitrophenylsulfur-pentafluoride was obtained in 10.0% yield and was consequently purified by preparative HPLC. 95% pure 4-nitrophenylsulfur pentafluoride was hydrogenated with hydrogen gas in acidic (HCL) ethanol solution, PtO2 was used as a catalyst. The 4-aminophenylsulfur pentafluoride hydrochloride obtained was reacted with sodium bicarbonate water solution and the product 4-aminophenylsulfur pentafluoride was extracted with diethyl ether and recrystallized from pentane. 4-Aminophenylsulfur pentafluoride crystallizes as white needles.
All H atoms attached to C atoms were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic) with Uiso(H) = 1.2Ueq(C). H atoms of amino group were located in difference Fourier maps and included in the subsequent refinement using restraints (N—H= 0.89 (1)Å and H···H= 1.57 (2) Å) with Uiso(H) = 1.2Ueq(N). In the last stage of refinement, they were treated as riding on their parent N atom.
Data collection: CrystalClear (Rigaku, 1999); cell refinement: CrystalClear (Rigaku, 1999); data reduction: CrystalClear (Rigaku, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and enCIFer (Allen et al., 2004).
![[Figure 1]](./dn2303fig1thm.gif)
| Fig. 1. Molecular view of I with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small sphers of arbitrary radii. |
| C6H6F5NS | F000 = 880 |
| Mr = 219.18 | Dx = 1.801 Mg m−3 |
| Orthorhombic, Pbca | Mo Kα radiation λ = 0.71069 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 71 reflections |
| a = 16.0369 (13) Å | θ = 1.2–29.1º |
| b = 5.7514 (5) Å | µ = 0.44 mm−1 |
| c = 17.5305 (15) Å | T = 200 K |
| V = 1616.9 (2) Å3 | Chunk, colourless |
| Z = 8 | 0.1 × 0.08 × 0.05 mm |
| Mercury CCD (2x2 bin mode) diffractometer | Rint = 0.051 |
| dtprofit.ref scans | θmax = 26.4º |
| Absorption correction: multi-scan (Blessing, 1995) | θmin = 2.3º |
| Tmin = 0.959, Tmax = 0.981 | h = 0→20 |
| 6533 measured reflections | k = 0→7 |
| 1650 independent reflections | l = 0→21 |
| 633 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)] = 0.031 | H-atom parameters constrained |
| wR(F2) = 0.065 | w = 1/[σ2(Fo2)] |
| S = 0.58 | (Δ/σ)max = 0.001 |
| 1650 reflections | Δρmax = 0.26 e Å−3 |
| 118 parameters | Δρmin = −0.22 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C6H6F5NS | V = 1616.9 (2) Å3 |
| Mr = 219.18 | Z = 8 |
| Orthorhombic, Pbca | Mo Kα |
| a = 16.0369 (13) Å | µ = 0.44 mm−1 |
| b = 5.7514 (5) Å | T = 200 K |
| c = 17.5305 (15) Å | 0.1 × 0.08 × 0.05 mm |
| Mercury CCD (2x2 bin mode) diffractometer | 1650 independent reflections |
| Absorption correction: multi-scan (Blessing, 1995) | 633 reflections with I > 2σ(I) |
| Tmin = 0.959, Tmax = 0.981 | Rint = 0.051 |
| 6533 measured reflections |
| R[F2 > 2σ(F2)] = 0.031 | 118 parameters |
| wR(F2) = 0.065 | H-atom parameters constrained |
| S = 0.58 | Δρmax = 0.26 e Å−3 |
| 1650 reflections | Δρmin = −0.22 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. |
| x | y | z | Uiso*/Ueq | ||
| S1 | 0.89753 (5) | 0.08028 (15) | 0.09772 (6) | 0.0401 (2) | |
| F1 | 0.87251 (10) | 0.3449 (3) | 0.10747 (12) | 0.0606 (6) | |
| F2 | 0.80397 (8) | 0.0204 (3) | 0.07597 (11) | 0.0597 (6) | |
| F3 | 0.92307 (9) | −0.1787 (3) | 0.07811 (11) | 0.0529 (6) | |
| F4 | 0.99217 (9) | 0.1448 (3) | 0.10997 (12) | 0.0566 (6) | |
| F5 | 0.91119 (10) | 0.1370 (3) | 0.00922 (11) | 0.0608 (6) | |
| C1 | 0.84866 (18) | −0.0742 (6) | 0.3495 (2) | 0.0417 (9) | |
| C2 | 0.89380 (16) | 0.1215 (6) | 0.3276 (2) | 0.0424 (9) | |
| H2 | 0.9136 | 0.2228 | 0.3648 | 0.051* | |
| C3 | 0.90968 (17) | 0.1681 (5) | 0.2514 (2) | 0.0391 (9) | |
| H3 | 0.9394 | 0.3005 | 0.2377 | 0.047* | |
| C4 | 0.88150 (16) | 0.0181 (5) | 0.19639 (18) | 0.0303 (8) | |
| C5 | 0.83895 (16) | −0.1814 (5) | 0.2167 (2) | 0.0364 (8) | |
| H5 | 0.8205 | −0.2842 | 0.1794 | 0.044* | |
| C6 | 0.82413 (17) | −0.2267 (5) | 0.2925 (2) | 0.0415 (9) | |
| H6 | 0.7969 | −0.3635 | 0.3059 | 0.050* | |
| N1 | 0.82569 (15) | −0.1078 (5) | 0.42463 (17) | 0.0618 (9) | |
| H11 | 0.8081 | −0.2512 | 0.4320 | 0.074* | |
| H12 | 0.8522 | −0.0289 | 0.4603 | 0.074* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0450 (5) | 0.0386 (5) | 0.0367 (6) | 0.0025 (4) | 0.0026 (5) | −0.0008 (5) |
| F1 | 0.0980 (14) | 0.0353 (11) | 0.0486 (15) | 0.0151 (10) | 0.0129 (12) | 0.0070 (11) |
| F2 | 0.0412 (10) | 0.0926 (15) | 0.0453 (15) | −0.0039 (9) | −0.0090 (10) | −0.0005 (12) |
| F3 | 0.0731 (12) | 0.0369 (11) | 0.0487 (15) | 0.0077 (9) | 0.0085 (11) | −0.0127 (10) |
| F4 | 0.0432 (10) | 0.0714 (13) | 0.0552 (16) | −0.0147 (9) | 0.0108 (10) | −0.0010 (12) |
| F5 | 0.0819 (13) | 0.0706 (14) | 0.0300 (13) | 0.0071 (10) | 0.0147 (11) | 0.0067 (11) |
| C1 | 0.040 (2) | 0.053 (2) | 0.032 (2) | 0.0120 (17) | 0.0036 (18) | 0.009 (2) |
| C2 | 0.0417 (19) | 0.047 (2) | 0.038 (2) | −0.0027 (17) | −0.0073 (18) | −0.0070 (19) |
| C3 | 0.0419 (19) | 0.037 (2) | 0.038 (2) | −0.0076 (15) | 0.0024 (18) | −0.0009 (19) |
| C4 | 0.0336 (17) | 0.0276 (18) | 0.030 (2) | 0.0041 (14) | 0.0002 (15) | −0.0005 (16) |
| C5 | 0.0362 (18) | 0.0312 (19) | 0.042 (2) | −0.0041 (15) | 0.0018 (17) | −0.0071 (19) |
| C6 | 0.0424 (19) | 0.033 (2) | 0.049 (3) | −0.0003 (16) | 0.0081 (19) | 0.004 (2) |
| N1 | 0.0770 (19) | 0.068 (2) | 0.040 (2) | −0.0009 (16) | 0.0052 (17) | 0.0081 (19) |
| S1—F4 | 1.5771 (16) | C2—H2 | 0.9300 |
| S1—F3 | 1.5826 (17) | C3—C4 | 1.370 (4) |
| S1—F1 | 1.5832 (17) | C3—H3 | 0.9300 |
| S1—F2 | 1.5860 (16) | C4—C5 | 1.382 (4) |
| S1—F5 | 1.600 (2) | C5—C6 | 1.375 (4) |
| S1—C4 | 1.785 (3) | C5—H5 | 0.9300 |
| C1—N1 | 1.381 (4) | C6—H6 | 0.9300 |
| C1—C6 | 1.386 (4) | N1—H11 | 0.8813 |
| C1—C2 | 1.392 (4) | N1—H12 | 0.8823 |
| C2—C3 | 1.386 (4) | ||
| F4—S1—F3 | 90.11 (9) | C3—C2—C1 | 121.2 (3) |
| F4—S1—F1 | 90.18 (10) | C3—C2—H2 | 119.4 |
| F3—S1—F1 | 173.62 (13) | C1—C2—H2 | 119.4 |
| F4—S1—F2 | 173.86 (13) | C4—C3—C2 | 119.7 (3) |
| F3—S1—F2 | 89.33 (10) | C4—C3—H3 | 120.1 |
| F1—S1—F2 | 89.70 (10) | C2—C3—H3 | 120.1 |
| F4—S1—F5 | 87.26 (10) | C3—C4—C5 | 120.2 (3) |
| F3—S1—F5 | 86.90 (11) | C3—C4—S1 | 120.6 (2) |
| F1—S1—F5 | 86.75 (11) | C5—C4—S1 | 119.2 (3) |
| F2—S1—F5 | 86.60 (11) | C6—C5—C4 | 119.5 (3) |
| F4—S1—C4 | 93.09 (12) | C6—C5—H5 | 120.2 |
| F3—S1—C4 | 93.40 (12) | C4—C5—H5 | 120.2 |
| F1—S1—C4 | 92.95 (13) | C5—C6—C1 | 121.8 (3) |
| F2—S1—C4 | 93.05 (12) | C5—C6—H6 | 119.1 |
| F5—S1—C4 | 179.54 (13) | C1—C6—H6 | 119.1 |
| N1—C1—C6 | 121.5 (3) | C1—N1—H11 | 110.9 |
| N1—C1—C2 | 121.0 (4) | C1—N1—H12 | 118.5 |
| C6—C1—C2 | 117.4 (3) | H11—N1—H12 | 122.1 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H12···F5i | 0.89 | 2.59 | 3.38 | 148 |
| Symmetry codes: (i) x, −y+1/2, z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H12···F5i | 0.89 | 2.59 | 3.38 | 148 |
| Symmetry codes: (i) x, −y+1/2, z+1/2. |
The authors gratefully acknowledge the Ministry of Science and Education of Slovenia and the European Scientific Foundation (COST 527 project).
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Phenylsulfur pentafluorides were first synthesized (Sheppard, 1960) by the fluorination of aromatic disulfides with silver difluoride. Some SF5-benzene derivatives were patented as plant regulants, herbicides and bactericides (Raasch, 1963).
In the title compound, the environment of sulfur atom appears to be approximately octahedral (Fig. 1) with the C – S bond being 1.786 (3) Å, four equatorial S - F bonds of 1.577 (2) – 1.586 (2) Å and noticeably elongated to 1.600 (2) Å axial S – F bond. Equatorial F atoms are declined slightly away from the benzene ring resulting in the medium value of Feq – S – Fax angle of 86.9 °. Similar staggered conformation was observed earlier in the structure of 4-acetamidophenylsulfur pentafluoride (Bowden et al., 2000). The F – S – C – C dihedral angles values of 43 and 47 ° differ from observed in above mentioned structure of 4-acetamidophenylsulfur pentafluoride 30 and 60 ° respectively. The packing is stabilized by weak N—H···F contacts.