4-Amino­phenyl­sulfur penta­fluoride

Eva Lina Nava; Adolf Jesih; Evgeny Goreshnik

doi:10.1107/S160053680800024X

. 2008 Jan 9;64(Pt 2):o416. doi: 10.1107/S160053680800024X

4-Aminophenylsulfur pentafluoride

Eva Lina Nava ^a, Adolf Jesih ^a, Evgeny Goreshnik ^a,^*

PMCID: PMC2960437 PMID: 21201443

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 ▶); Bowden et al. (2000 ▶); Sheppard (1960 ▶, 1962 ▶).

Experimental

Crystal data

C₆H₆F₅NS
M _r = 219.18
Orthorhombic,
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 ▶) 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
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: CrystalClear (Rigaku, 1999 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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 ▶).

Supplementary Material

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

e-64-0o416-sup1.cif^{(12.5KB, cif)}

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

e-64-0o416-Isup2.hkl^{(94.9KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H12⋯F5ⁱ	0.89	2.59	3.38	148

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Symmetry code: (i) Inline graphic .

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.