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Acta Crystallogr Sect E Struct Rep Online. 2008 February 1; 64(Pt 2): o416.
Published online 2008 January 9. doi:  10.1107/S160053680800024X
PMCID: PMC2960437

4-Amino­phenyl­sulfur penta­fluoride

Abstract

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.

Related literature

For related literature, see: Raasch (1963 [triangle]); Bowden et al. (2000 [triangle]); Sheppard (1960 [triangle], 1962 [triangle]).

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Object name is e-64-0o416-scheme1.jpg

Experimental

Crystal data

  • C6H6F5NS
  • M r = 219.18
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o416-efi1.jpg
  • a = 16.0369 (13) Å
  • b = 5.7514 (5) Å
  • c = 17.5305 (15) Å
  • V = 1616.9 (2) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.44 mm−1
  • T = 200 K
  • 0.1 × 0.08 × 0.05 mm

Data collection

  • Rigaku Mercury CCDdiffractometer
  • Absorption correction: multi-scan (Blessing, 1995 [triangle]) T min = 0.959, T max = 0.981
  • 6533 measured reflections
  • 1650 independent reflections
  • 633 reflections with I > 2σ(I)
  • R int = 0.051

Refinement

  • R[F 2 > 2σ(F 2)] = 0.031
  • wR(F 2) = 0.065
  • S = 0.58
  • 1650 reflections
  • 118 parameters
  • H-atom parameters constrained
  • Δρmax = 0.26 e Å−3
  • Δρmin = −0.22 e Å−3

Data collection: CrystalClear (Rigaku, 1999 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR92 (Altomare et al., 1993 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 [triangle]) and ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and enCIFer (Allen et al., 2004 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680800024X/dn2303sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680800024X/dn2303Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors gratefully acknowledge the Ministry of Science and Education of Slovenia and the European Scientific Foundation (COST 527 project).

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

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.

Figures

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.

Crystal data

C6H6F5NSF000 = 880
Mr = 219.18Dx = 1.801 Mg m3
Orthorhombic, PbcaMo Kα radiation λ = 0.71069 Å
Hall symbol: -P 2ac 2abCell parameters from 71 reflections
a = 16.0369 (13) Åθ = 1.2–29.1º
b = 5.7514 (5) ŵ = 0.44 mm1
c = 17.5305 (15) ÅT = 200 K
V = 1616.9 (2) Å3Chunk, colourless
Z = 80.1 × 0.08 × 0.05 mm

Data collection

Mercury CCD (2x2 bin mode) diffractometerRint = 0.051
dtprofit.ref scansθmax = 26.4º
Absorption correction: multi-scan(Blessing, 1995)θmin = 2.3º
Tmin = 0.959, Tmax = 0.981h = 0→20
6533 measured reflectionsk = 0→7
1650 independent reflectionsl = 0→21
633 reflections with I > 2σ(I)

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.065  w = 1/[σ2(Fo2)]
S = 0.58(Δ/σ)max = 0.001
1650 reflectionsΔρmax = 0.26 e Å3
118 parametersΔρmin = −0.22 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
S10.89753 (5)0.08028 (15)0.09772 (6)0.0401 (2)
F10.87251 (10)0.3449 (3)0.10747 (12)0.0606 (6)
F20.80397 (8)0.0204 (3)0.07597 (11)0.0597 (6)
F30.92307 (9)−0.1787 (3)0.07811 (11)0.0529 (6)
F40.99217 (9)0.1448 (3)0.10997 (12)0.0566 (6)
F50.91119 (10)0.1370 (3)0.00922 (11)0.0608 (6)
C10.84866 (18)−0.0742 (6)0.3495 (2)0.0417 (9)
C20.89380 (16)0.1215 (6)0.3276 (2)0.0424 (9)
H20.91360.22280.36480.051*
C30.90968 (17)0.1681 (5)0.2514 (2)0.0391 (9)
H30.93940.30050.23770.047*
C40.88150 (16)0.0181 (5)0.19639 (18)0.0303 (8)
C50.83895 (16)−0.1814 (5)0.2167 (2)0.0364 (8)
H50.8205−0.28420.17940.044*
C60.82413 (17)−0.2267 (5)0.2925 (2)0.0415 (9)
H60.7969−0.36350.30590.050*
N10.82569 (15)−0.1078 (5)0.42463 (17)0.0618 (9)
H110.8081−0.25120.43200.074*
H120.8522−0.02890.46030.074*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0450 (5)0.0386 (5)0.0367 (6)0.0025 (4)0.0026 (5)−0.0008 (5)
F10.0980 (14)0.0353 (11)0.0486 (15)0.0151 (10)0.0129 (12)0.0070 (11)
F20.0412 (10)0.0926 (15)0.0453 (15)−0.0039 (9)−0.0090 (10)−0.0005 (12)
F30.0731 (12)0.0369 (11)0.0487 (15)0.0077 (9)0.0085 (11)−0.0127 (10)
F40.0432 (10)0.0714 (13)0.0552 (16)−0.0147 (9)0.0108 (10)−0.0010 (12)
F50.0819 (13)0.0706 (14)0.0300 (13)0.0071 (10)0.0147 (11)0.0067 (11)
C10.040 (2)0.053 (2)0.032 (2)0.0120 (17)0.0036 (18)0.009 (2)
C20.0417 (19)0.047 (2)0.038 (2)−0.0027 (17)−0.0073 (18)−0.0070 (19)
C30.0419 (19)0.037 (2)0.038 (2)−0.0076 (15)0.0024 (18)−0.0009 (19)
C40.0336 (17)0.0276 (18)0.030 (2)0.0041 (14)0.0002 (15)−0.0005 (16)
C50.0362 (18)0.0312 (19)0.042 (2)−0.0041 (15)0.0018 (17)−0.0071 (19)
C60.0424 (19)0.033 (2)0.049 (3)−0.0003 (16)0.0081 (19)0.004 (2)
N10.0770 (19)0.068 (2)0.040 (2)−0.0009 (16)0.0052 (17)0.0081 (19)

Geometric parameters (Å, °)

S1—F41.5771 (16)C2—H20.9300
S1—F31.5826 (17)C3—C41.370 (4)
S1—F11.5832 (17)C3—H30.9300
S1—F21.5860 (16)C4—C51.382 (4)
S1—F51.600 (2)C5—C61.375 (4)
S1—C41.785 (3)C5—H50.9300
C1—N11.381 (4)C6—H60.9300
C1—C61.386 (4)N1—H110.8813
C1—C21.392 (4)N1—H120.8823
C2—C31.386 (4)
F4—S1—F390.11 (9)C3—C2—C1121.2 (3)
F4—S1—F190.18 (10)C3—C2—H2119.4
F3—S1—F1173.62 (13)C1—C2—H2119.4
F4—S1—F2173.86 (13)C4—C3—C2119.7 (3)
F3—S1—F289.33 (10)C4—C3—H3120.1
F1—S1—F289.70 (10)C2—C3—H3120.1
F4—S1—F587.26 (10)C3—C4—C5120.2 (3)
F3—S1—F586.90 (11)C3—C4—S1120.6 (2)
F1—S1—F586.75 (11)C5—C4—S1119.2 (3)
F2—S1—F586.60 (11)C6—C5—C4119.5 (3)
F4—S1—C493.09 (12)C6—C5—H5120.2
F3—S1—C493.40 (12)C4—C5—H5120.2
F1—S1—C492.95 (13)C5—C6—C1121.8 (3)
F2—S1—C493.05 (12)C5—C6—H6119.1
F5—S1—C4179.54 (13)C1—C6—H6119.1
N1—C1—C6121.5 (3)C1—N1—H11110.9
N1—C1—C2121.0 (4)C1—N1—H12118.5
C6—C1—C2117.4 (3)H11—N1—H12122.1

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H12···F5i0.892.593.38148

Symmetry codes: (i) x, −y+1/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: DN2303).

References

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  • Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.
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  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
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