N-Phenyl-tert-butane­sulfinamide

Abstract

In the racemic title compound, C₁₀H₁₅NOS, the packing exhibits centrosymmetric pairs of mol­ecules linked by N—H⋯O=S hydrogen bonds in a head-to-tail fashion. The N—C_ar­yl bond [1.4083 (12) Å] is considerably shorter than the N—C_alk­yl bonds typically found in N-alkyl­alkanesulfinamides (1.470–1.530 Å).

Related literature

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

Experimental

Crystal data

• C₁₀H₁₅NOS

• M _r = 197.29

• Monoclinic,

• a = 7.4822 (3) Å

• b = 15.7881 (6) Å

• c = 8.8333 (4) Å

• β = 99.3865 (6)°

• V = 1029.50 (7) ų

• Z = 4

• Mo Kα radiation

• μ = 0.28 mm⁻¹

• T = 150 K

• 0.54 × 0.49 × 0.39 mm

Data collection

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T _min = 0.866, T _max = 0.900

• 12022 measured reflections

• 3150 independent reflections

• 2861 reflections with I > 2σ(I)

• R _int = 0.020

Refinement

• R[F ² > 2σ(F ²)] = 0.034

• wR(F ²) = 0.092

• S = 1.05

• 3150 reflections

• 125 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.38 e Å⁻³

• Δρ_min = −0.36 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

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	0.808 (12)	2.085 (12)	2.8882 (11)	173.1 (14)

Symmetry code: (i) .

supplementary crystallographic information

Comment

The molecular structure of (I) (Fig. 1) exhibits a short N—(aryl)C Bond (1.4083 (12) Å), like that in N-phenyladamantane-1-sulfinamide (1.409 (2) Å) (Datta et al., 2008), and in contrast with N—(alkyl)C bonds in N-alkylalkanesulfinamides (1.470–1.530 Å) (Sato et al., 1975; Schuckmann et al., 1978; Ferreira et al., 2005). Otherwise, molecular geometry is similar to other sulfinamides. The molecules of (I) in the crystal lattice are linked by pairs of N—H···O=S hydrogen bonds (Fig. 2 and Table 1). There is no evidence of weak intermolecular C—H···O=S hydrogen bonds, as in the packing of N-phenyladamantane-1-sulfinamide (Datta et al., 2008). The crystal system and space group for (I) and N-phenyladamantane-1-sulfinamide are the same (namely monoclinic and P2₁/c, respectively).

Experimental

Compound (I) was prepared by the method of Stretter et al. (1969), using tert-butanesulfinyl chloride (702.5 mg, 5 mmol) and aniline (930 mg, 10 mmol) in dry chloroform (30 ml). After 6 h (with TLC monitoring) the white solid amine salt was filtered off and the solvent was removed under reduced pressure. Column chromatography (silica gel, dichloromethane) provided (I) as white crystals (950 mg, 96%), m.p. 376–377 K. Single crystals suitable for X-ray analysis were obtained by evaporation of a solution of (I) in dichloromethane at room temperature. Spectroscopic analysis: FTIR (KBr) (cm^-1) 3015, 2599, 2330, 1496, 1469, 1420, 1370, 1274, 1068,1026, 888, 859. ¹H NMR (400 MHz, CDCl₃ p.p.m. with respect to TMS) δ 7.26–7.22 (m, 2H), 7.00–6.98 (m, 3H), 5.48 (bs, 1H), 1.30 (s, 9H). ¹³C NMR (100 MHz, CDCl₃ p.p.m. with respect to TMS) δ 142.0, 129.4, 123.0, 118.4, 56.5, 22.4. EIMS m/z (%) 197 (M⁺, 18) 141 (100), 140 (M⁺-^tBu, 28), 105 (M⁺—PhNH, 86), 92 (M⁺-^tBuSO, 72), 78 (77), 57 (93).

Refinement

H atoms were located in a difference Fourier map and refined geometrically using a riding model except for NHfor which the coordinates were freely refined. Bond lengths and displacement parameters were constrained as follows: C—H = 0.95–0.98 Å and U_iso(H) = 1.2 (1.5 for CH₃) times U_eq(C, N).

Figures

Fig. 1.

Molecular structure of (I), with atom labels and 50% probablility displacement ellipsoids for non-H atoms.

Fig. 2.

Intermolecular hydrogen bonding between a pair of opposite enantiomers of (I) in the crystal packing. Symmetry code i = -x, -y + 1, -z + 1.

Crystal data

C10H15NOS	F(000) = 424
Mr = 197.29	Dx = 1.273 Mg m−3
Monoclinic, P21/c	Melting point = 376–377 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.4822 (3) Å	Cell parameters from 6597 reflections
b = 15.7881 (6) Å	θ = 2.3–30.5°
c = 8.8333 (4) Å	µ = 0.28 mm−1
β = 99.3865 (6)°	T = 150 K
V = 1029.50 (7) Å3	Block, colourless
Z = 4	0.54 × 0.49 × 0.39 mm

Data collection

Bruker APEXII CCD diffractometer	3150 independent reflections
Radiation source: fine-focus sealed tube	2861 reflections with I > 2σ(I)
graphite	Rint = 0.020
ω rotation with narrow frames scans	θmax = 30.6°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	h = −10→10
Tmin = 0.866, Tmax = 0.900	k = −22→22
12022 measured reflections	l = −12→12

Refinement

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)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.092	w = 1/[σ2(Fo2) + (0.0516P)2 + 0.2529P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.002
3150 reflections	Δρmax = 0.38 e Å−3
125 parameters	Δρmin = −0.36 e Å−3
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.020 (3)

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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
O1	−0.06049 (10)	0.60738 (4)	0.41648 (9)	0.02295 (16)
S1	0.10835 (3)	0.601595 (13)	0.34614 (3)	0.01896 (9)
N1	0.17155 (13)	0.50050 (5)	0.35165 (10)	0.02446 (18)
H1	0.1463 (19)	0.4727 (9)	0.4219 (15)	0.029*
C1	0.19492 (12)	0.45439 (6)	0.21979 (11)	0.01998 (18)
C2	0.24483 (16)	0.49296 (7)	0.09080 (12)	0.0281 (2)
H2	0.2589	0.5527	0.0877	0.034*
C3	0.27381 (17)	0.44344 (7)	−0.03327 (13)	0.0318 (2)
H3	0.3053	0.4700	−0.1218	0.038*
C4	0.25757 (15)	0.35617 (7)	−0.02991 (13)	0.0295 (2)
H4	0.2790	0.3230	−0.1148	0.035*
C5	0.20955 (14)	0.31769 (6)	0.09922 (12)	0.0257 (2)
H5	0.1990	0.2578	0.1029	0.031*
C6	0.17690 (13)	0.36629 (6)	0.22303 (11)	0.02134 (18)
H6	0.1422	0.3396	0.3101	0.026*
C7	0.29072 (13)	0.64579 (6)	0.48984 (11)	0.02172 (18)
C8	0.24368 (16)	0.73950 (7)	0.50283 (14)	0.0316 (2)
H8A	0.3444	0.7687	0.5668	0.047*
H8B	0.1342	0.7448	0.5497	0.047*
H8C	0.2223	0.7650	0.4003	0.047*
C9	0.46486 (15)	0.63537 (8)	0.42278 (14)	0.0312 (2)
H9A	0.5658	0.6613	0.4919	0.047*
H9B	0.4512	0.6632	0.3224	0.047*
H9C	0.4894	0.5750	0.4110	0.047*
C10	0.30068 (15)	0.60073 (6)	0.64357 (12)	0.0265 (2)
H10A	0.3290	0.5408	0.6314	0.040*
H10B	0.1839	0.6057	0.6794	0.040*
H10C	0.3956	0.6267	0.7188	0.040*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0218 (3)	0.0215 (3)	0.0264 (4)	0.0011 (2)	0.0067 (3)	0.0021 (2)
S1	0.02263 (13)	0.01561 (12)	0.01895 (13)	0.00052 (7)	0.00429 (8)	0.00155 (7)
N1	0.0397 (5)	0.0153 (3)	0.0206 (4)	0.0013 (3)	0.0114 (3)	0.0012 (3)
C1	0.0214 (4)	0.0187 (4)	0.0202 (4)	0.0003 (3)	0.0045 (3)	−0.0011 (3)
C2	0.0397 (6)	0.0210 (4)	0.0254 (5)	−0.0014 (4)	0.0112 (4)	0.0010 (4)
C3	0.0422 (6)	0.0327 (6)	0.0224 (5)	0.0011 (4)	0.0111 (4)	0.0006 (4)
C4	0.0324 (5)	0.0316 (5)	0.0251 (5)	0.0014 (4)	0.0063 (4)	−0.0080 (4)
C5	0.0247 (5)	0.0218 (4)	0.0304 (5)	−0.0010 (3)	0.0043 (4)	−0.0060 (4)
C6	0.0207 (4)	0.0186 (4)	0.0252 (4)	−0.0012 (3)	0.0053 (3)	−0.0006 (3)
C7	0.0218 (4)	0.0186 (4)	0.0242 (4)	0.0006 (3)	0.0022 (3)	−0.0001 (3)
C8	0.0352 (5)	0.0183 (4)	0.0387 (6)	−0.0002 (4)	−0.0013 (4)	−0.0037 (4)
C9	0.0230 (5)	0.0366 (6)	0.0346 (6)	0.0004 (4)	0.0065 (4)	0.0042 (4)
C10	0.0290 (5)	0.0278 (5)	0.0220 (5)	0.0026 (4)	0.0020 (4)	0.0006 (3)

Geometric parameters (Å, °)

O1—S1	1.4988 (7)	C5—H5	0.9500
S1—N1	1.6632 (9)	C6—H6	0.9500
S1—C7	1.8426 (10)	C7—C10	1.5241 (14)
N1—C1	1.4083 (12)	C7—C9	1.5255 (14)
N1—H1	0.808 (12)	C7—C8	1.5294 (14)
C1—C2	1.3954 (13)	C8—H8A	0.9800
C1—C6	1.3982 (12)	C8—H8B	0.9800
C2—C3	1.3918 (15)	C8—H8C	0.9800
C2—H2	0.9500	C9—H9A	0.9800
C3—C4	1.3838 (17)	C9—H9B	0.9800
C3—H3	0.9500	C9—H9C	0.9800
C4—C5	1.3903 (15)	C10—H10A	0.9800
C4—H4	0.9500	C10—H10B	0.9800
C5—C6	1.3898 (13)	C10—H10C	0.9800
O1—S1—N1	107.53 (4)	C10—C7—C9	112.02 (8)
O1—S1—C7	105.72 (4)	C10—C7—C8	111.29 (9)
N1—S1—C7	99.69 (5)	C9—C7—C8	110.80 (9)
C1—N1—S1	123.02 (7)	C10—C7—S1	111.11 (7)
C1—N1—H1	115.5 (10)	C9—C7—S1	105.97 (7)
S1—N1—H1	116.3 (10)	C8—C7—S1	105.33 (7)
C2—C1—C6	119.36 (9)	C7—C8—H8A	109.5
C2—C1—N1	122.39 (8)	C7—C8—H8B	109.5
C6—C1—N1	118.16 (8)	H8A—C8—H8B	109.5
C3—C2—C1	119.65 (10)	C7—C8—H8C	109.5
C3—C2—H2	120.2	H8A—C8—H8C	109.5
C1—C2—H2	120.2	H8B—C8—H8C	109.5
C4—C3—C2	121.12 (10)	C7—C9—H9A	109.5
C4—C3—H3	119.4	C7—C9—H9B	109.5
C2—C3—H3	119.4	H9A—C9—H9B	109.5
C3—C4—C5	119.21 (9)	C7—C9—H9C	109.5
C3—C4—H4	120.4	H9A—C9—H9C	109.5
C5—C4—H4	120.4	H9B—C9—H9C	109.5
C6—C5—C4	120.43 (9)	C7—C10—H10A	109.5
C6—C5—H5	119.8	C7—C10—H10B	109.5
C4—C5—H5	119.8	H10A—C10—H10B	109.5
C5—C6—C1	120.21 (9)	C7—C10—H10C	109.5
C5—C6—H6	119.9	H10A—C10—H10C	109.5
C1—C6—H6	119.9	H10B—C10—H10C	109.5
O1—S1—N1—C1	123.13 (8)	C4—C5—C6—C1	−1.02 (15)
C7—S1—N1—C1	−126.86 (8)	C2—C1—C6—C5	0.40 (14)
S1—N1—C1—C2	28.58 (14)	N1—C1—C6—C5	−176.09 (9)
S1—N1—C1—C6	−155.05 (8)	O1—S1—C7—C10	54.89 (8)
C6—C1—C2—C3	0.76 (16)	N1—S1—C7—C10	−56.55 (8)
N1—C1—C2—C3	177.09 (10)	O1—S1—C7—C9	176.79 (7)
C1—C2—C3—C4	−1.32 (18)	N1—S1—C7—C9	65.35 (7)
C2—C3—C4—C5	0.70 (17)	O1—S1—C7—C8	−65.73 (8)
C3—C4—C5—C6	0.48 (16)	N1—S1—C7—C8	−177.17 (7)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1i	0.81 (1)	2.09 (1)	2.8882 (11)	173 (1)

Symmetry codes: (i) −x, −y+1, −z+1.