N-(3-Methoxy­phen­yl)-tert-butane­sulfinamide

Mrityunjoy Datta; Alan J Buglass; Mark R J Elsegood

doi:10.1107/S1600536809052507

. 2009 Dec 12;66(Pt 1):o109. doi: 10.1107/S1600536809052507

N-(3-Methoxyphenyl)-tert-butanesulfinamide

Mrityunjoy Datta ^a, Alan J Buglass ^a,^*, Mark R J Elsegood ^b

PMCID: PMC2980236 PMID: 21579998

Abstract

In the title compound, C₁₁H₁₇NO₂S, the molecules interact in a head-to-tail fashion through pairs of N—H⋯O hydrogen bonds, giving discrete centrosymmetric dimers. The N(H)S(O)^tBu fragment is disordered over two sets of positions, with the major component comprising 90.0 (2)%.

Related literature

For N-arylalkanesulfinamides, see: Datta et al. (2008 ▶, 2009 ▶). For N-alkylalkanesulfinamides, see: Sato et al. (1975 ▶); Ferreira et al. (2005 ▶); Schuckmann et al. (1978 ▶). For the synthesis, see: Stretter et al. (1969 ▶).

Experimental

Crystal data

C₁₁H₁₇NO₂S
M _r = 227.32
Monoclinic,
a = 12.4068 (13) Å
b = 7.3076 (8) Å
c = 12.9230 (13) Å
β = 93.2992 (15)°
V = 1169.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 150 K
0.37 × 0.22 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T _min = 0.911, T _max = 0.950
10627 measured reflections
2633 independent reflections
2237 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.117
S = 1.07
2633 reflections
166 parameters
149 restraints
H-atom parameters constrained
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; 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: SHELXTL and local programs.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809052507/ng2698sup1.cif

e-66-0o109-sup1.cif^{(19.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809052507/ng2698Isup2.hkl

e-66-0o109-Isup2.hkl^{(129.3KB, 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—H1⋯O1ⁱ	0.88	2.24	2.884 (2)	130
N1X—H1X⋯O1Xⁱⁱ	0.88	2.21	2.94 (2)	141

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

MD and AJB thank KAIST for financial assistance.

supplementary crystallographic information

Comment

The molecular structure of the title compound (I) exhibits disorder of the N(H)S(O)^tBu fragment over two sets of positions. The major component comprises 90.0 (2)% (Fig. 1), in which the N—C_arylbond length is 1.418 (2) Å, similar to that [1.4225 (14) Å] in N-(4-methoxyphenyl)-tert-butanesulfinamide (Datta et al., 2009). The corresponding bond length [1.457 (16) Å] in the minor component is longer, though far less precisely determined. This perhaps suggests weaker delocalization of electrons over N and the aromatic ring, which would correlate with the greater non-coplanarity of the aromatic ring and sulfinyl moiety in this component. In either case, however, the N—C_arylbond is shorter than the N—C_alkyl bonds [1.470–1.530 Å] observed in structures of N-alkylalkanesulfinamides (Sato et al., 1975; Schuckmann et al., 1978; Ferreira et al., 2005). The crystal packing of (I) shows head-to-tail interaction through NH···OS hydrogen bonds, forming discrete centrosymmetric dimers, as illustrated for the major component in Fig. 2. The hydrogen bonding data for both components are listed in Table 1. There is no evidence of hydrogen bonding involving the methoxy group, nor of weak CH···.OS hydrogen bonding, as observed in the packing of N-phenyladamantane-1-sulfinamide (Datta et al., 2008).

Experimental

Compound (I) was prepared by the method of Stretter et al. (1969), using tert-butanesulfinyl chloride (281 mg, 2 mmol) and 3-methoxyaniline (492 mg, 4 mmol) in dry ether (20 ml). After 5 h (with TLC monitoring) the colourless solid amine salt was fitered off and the solvent was removed under reduced pressure. Column chromatography (silica gel, 1% methanol-dichloromethane) provided (I) as colourless crystals (430 mg, 95%), m.p. 367 K. Single crystals suitable for X-ray analysis were obtained by evaporation of a solution of (I) in dichloromethane:hexane (1:1) at room temperature. Spectroscopic analysis: FTIR (KBr) (cm^-1) 3024, 1603, 1496, 1473, 1368, 1278, 1227, 1214, 1156, 1069, 953, 834. ¹H NMR (400 MHz, CDCl₃ p.p.m. with respect to TMS) δ 7.13 (dd, J = 8.0, 8.5 Hz, 1H), 6.58–6.53 (m, 3H), 5.41 (bs, 1H), 3.75 (d, J = 0.6 Hz, 3H), 1.30 (s, 9H). ¹³C (100 MHz, CDCl₃ p.p.m. with respect to TMS) δ 160.6, 143.3, 130.2, 110.6, 108.4, 104.2, 56.4. 55.2. 22.4. EIMS m/z (%) 228 (MH⁺, 85), 227 (M⁺, 25), 213 (17), 171 (MH⁺- tBu, 100), 123 (MH⁺ - ^tBuSO, 6), 108 (MH⁺ - ^tBuSONH, 12), 95 (53). To our knowledge, these are the first reported analytical data for (I).