2-Iodo-N-(2-nitro­phenyl­sulfan­yl)aniline

Iván Brito; Alejandro Cárdenas; Aldo Mundaca; Matías López-Rodríguez; Andrea Reyes

doi:10.1107/S1600536808019491

. 2008 Jul 5;64(Pt 8):o1387. doi: 10.1107/S1600536808019491

2-Iodo-N-(2-nitrophenylsulfanyl)aniline

Iván Brito ^a,^*, Alejandro Cárdenas ^b, Aldo Mundaca ^a, Matías López-Rodríguez ^c, Andrea Reyes ^a

PMCID: PMC2962020 PMID: 21203107

Abstract

In title compound, C₁₂H₉IN₂O₂S, the nitro group is rotated slightly, by 8.91 (3)°, out of the plane of the aromatic ring to which it is bonded. Between the two aromatic rings the CSN plane is at a dihedral angle of 84.0 (7)° to the HNC plane. Molecules are linked by C—H⋯O interactions into a double helical supramolecular architecture. There are no iodo–nitro, π–π or C—H⋯π(arene) interactions.

Related literature

For related literature, see: Bernstein et al. (1995 ▶); Brito et al. (2004 ▶, 2005 ▶, 2006 ▶); Glidewell et al. (2003 ▶); Kuhle (1973 ▶); Pauling (1960 ▶).

Experimental

Crystal data

C₁₂H₉IN₂O₂S
M _r = 372.17
Trigonal,
a = 28.6221 (12) Å
c = 8.4062 (17) Å
V = 5963.9 (13) Å³
Z = 18
Mo Kα radiation
μ = 2.57 mm⁻¹
T = 298 (2) K
0.47 × 0.32 × 0.20 mm

Data collection

Nonius KappaCCD area-detector diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ▶) T _min = 0.380, T _max = 0.600
11358 measured reflections
3251 independent reflections
2801 reflections with I > 2σ(I)
R _int = 0.059

Refinement

R[F ² > 2σ(F ²)] = 0.072
wR(F ²) = 0.205
S = 1.21
3251 reflections
166 parameters
H-atom parameters constrained
Δρ_max = 1.04 e Å⁻³
Δρ_min = −1.05 e Å⁻³

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ▶); data reduction: DENZO-SMN; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2003 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808019491/fl2204sup1.cif

e-64-o1387-sup1.cif^{(16.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808019491/fl2204Isup2.hkl

e-64-o1387-Isup2.hkl^{(156.6KB, 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
C10—H10⋯O1ⁱ	0.93	2.55	3.445 (10)	161

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by a grant from the Universidad de Antofagasta (DI-1324–06). We thank the Spanish Research Council (CSIC) for providing us with a free-of-charge licence for the CSD system. AM and AR thank the Universidad de Antofagasta for PhD fellowships.

supplementary crystallographic information

Comment

Sulfenamides are important compounds with versatile industrial applications (Kuhle, 1973). Bond polarization in sulfenamide derivatives, resulting from the difference in electronegativity between sulfur and nitrogen, activates the S—N bond for attack by both nucleophiles and electrophiles, and appears to be the factor primarily responsible for the chemistry of these compounds. The title compound, (I), is a positional isomer of 4-Iodo -N-(2-nitrophenylsulfanyl)-aniline (Glidewell et al.,2003) and shows excellent agreement with its bonding geometries. The title compound is the result of the condensation reaction of 2-nitrophenylsulfenyl choride and 1-iodoaniline. Its structure is described here as part of our work involving the study of the synthesis and structural characterization of divalent-sulfur compounds (Brito et al., 2004, 2005, 2006). A view of the molecular structure of (I) is given in Fig.1. In (I) the 1-Iodo-benzene fragment is connected by an –NH—S– linker unit to the 2-nitrophenyl fragment. It contains an N atom as a chiral center, though the material is a racemic mixture. The nitro group is rotated by 8.91 (3)°. The S—N distance of 1.696 (6)Å is shorter than a normal S—N single-bond length (1.74 Å, Pauling, 1960), but is normal for this type of structure, many of which have S—N single bonds in the range 1.63–1.68 Å as a result of the π character of the S—N bond. The C7/S1/N1 plane makes a dihedral angle of 84.0 (7) ° with the H1/N1/C2 plane, in good agreement with the values of ~90.0 ° for the torsional ground state of this type species. The molecules are linked into a double helical supramolecular architecture with only hydrogen bonding contributing to the double helical arrangement (Bernstein et al., 1995). Atom C10 and nitro atom O1 in the molecule at (x, y, z) act as hydrogen-bond donor and acceptor respectively, Fig.2, Table 1. There are no iodo-nitro, π-π and C—H··· π (arene) interactions.

Experimental

A sample of compound (I) was prepared by reaction of equimolar quantities of 2-nitrophenylsulfenyl chloride (0.01 mol,1.895 g) and 4-iodoaniline (0.01 mol, 2.190 g) in dichloromethane solution, in the presence of an excess of triethylamine. Purification was by thin-layer chromatography and crystals of (I) suitable for single-crystal X-ray diffraction were grown by slow evaporation of a solution in ethanol [m.p. 472 K]. FT—IR (KBr pellet, cm^-1): ν (w, N—H amine) 3091, ν (w, S—N) 1039, ν (w, C—S) 731, ν (s, C—H disubstitution) 855, ν (versus, NO₂) 1567.