N-(tert-Butyl)-S-(4-methyl­phenyl)­thiohydroxy­lamine

The title compound, (CH₃)₃CN(H)–SC₆H₄CH₃-4, is the first example of a simple alkyl­aryl­sulfen­amide to be structurally characterized. Crystal packing consists of ribbons formed by N—H...S hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.044
• wR factor = 0.114
• Data-to-parameter ratio = 16.2

checkCIF results

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ADDSYM reports no extra symmetry

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S1. Comment

Sulfenamides, RN(H)–SR' (R, R' = alkyl or aryl), are compounds with simple structure yet remarkably rich chemistry. Their photolysis or chemical oxidation results in the formation of free radicals, some of them are presistent for long periods of time and others decay through complicated pathways (Miura, 1997). Deprotonation yields anions that act as ambidentate ligands towards transition (Hankin et al., 1995, 1996a,b; Danopoulos et al., 2000) and main-group metal ions (Mahmoudkhani et al., 2003). There are only two compounds structurally characterized, bearing the sulfenamide functional group as a part of a more complex molecule (Lee, et al., 1995; Gotthardt et al., 1987). However the structure of the most simple members of the family was not examined until now, partly because of their low melting points. Highly pure (p-tolyl)(tert-butyl)sulfenamide, (I), solidifies just below room temperature, which allowed this study. The compound crystallizes in monoclinic system with space group C2/c (No. 15). The molecular structure is shown in Fig. 1. It contains an N atom as a chiral center, though the material is a racemic mixture. The C–N–S–C center adopts a gauche conformation with a torsion angle of −113.8 (2)°. The (N—)H atoms are engaged in intermolecular hydrogen bonds with the S atoms, forming a ribbon, self-assembled along the b axis (see Fig. 2).

S2. Experimental

The synthesis of (I) was described previously (Mahmoudkhani et al., 2003). Crystals were grown from the melt upon standing at room temperature overnight.

S3. Refinement

The (N—)H atom was located from a difference Fourier map, whereas the (C—)H atoms were constrained to idealized geometries using the appropriate riding model and refined isotropically.

Computing details

Data collection: SMART (Bruker. 1997); cell refinement: SMART and SAINT (Bruker. 1997); data reduction: SAINT and SADABS; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are shown at the 50% probability level.
	Fig. 2. Representation of the ribbon structure of (I). The (C—)H atoms have been omitted for clarity.

N-(tert-Butyl)-S-(4-Methylphenyl)thiohydroxylamine

Crystal data

C11H17NS	F(000) = 848
Mr = 195.32	Dx = 1.128 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 833 reflections
a = 24.604 (15) Å	θ = 1–24°
b = 6.267 (4) Å	µ = 0.24 mm^−1
c = 16.533 (10) Å	T = 173 K
β = 115.533 (9)°	Needle, colorless
V = 2300 (2) Å^3	0.40 × 0.12 × 0.02 mm
Z = 8

Data collection

Bruker P4 CCD diffractometer	2108 independent reflections
Radiation source: rotating anode	1359 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.066
ω scans	θmax = 25.4°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −27→29
Tmin = 0.910, Tmax = 0.996	k = −7→7
8741 measured reflections	l = −19→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0538P)^2 + 0.5048P] where P = (Fo^2 + 2Fc^2)/3
2108 reflections	(Δ/σ)max = 0.008
130 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−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
S1	0.19646 (3)	0.22861 (9)	0.24637 (4)	0.0330 (2)
N1	0.17883 (10)	−0.0219 (3)	0.26544 (15)	0.0296 (5)
C1	0.14122 (11)	0.2862 (4)	0.13632 (16)	0.0280 (6)
C2	0.09857 (11)	0.1387 (4)	0.08236 (17)	0.0313 (6)
H2	0.0982	−0.0019	0.1036	0.038 (7)*
C3	0.05673 (12)	0.1983 (4)	−0.00225 (17)	0.0332 (6)
H3	0.0280	0.0964	−0.0385	0.028 (6)*
C4	0.05537 (11)	0.4034 (4)	−0.03618 (17)	0.0308 (6)
C5	0.09886 (11)	0.5476 (4)	0.01906 (18)	0.0327 (6)
H5	0.0995	0.6881	−0.0021	0.032 (7)*
C6	0.14082 (11)	0.4906 (4)	0.10353 (17)	0.0320 (6)
H6	0.1698	0.5921	0.1397	0.043 (8)*
C7	0.15740 (11)	−0.0537 (3)	0.33597 (17)	0.0290 (6)
C8	0.09554 (12)	0.0507 (4)	0.30440 (19)	0.0403 (7)
H8A	0.0991	0.2042	0.2963	0.060*
H8B	0.0801	0.0278	0.3493	0.060*
H8C	0.0678	−0.0128	0.2473	0.060*
C9	0.15287 (13)	−0.2951 (4)	0.34376 (19)	0.0421 (7)
H9A	0.1260	−0.3541	0.2852	0.063*
H9B	0.1368	−0.3274	0.3873	0.063*
H9C	0.1930	−0.3589	0.3638	0.063*
C10	0.20082 (14)	0.0396 (4)	0.42626 (18)	0.0489 (8)
H10A	0.2408	−0.0234	0.4445	0.073*
H10B	0.1861	0.0074	0.4714	0.073*
H10C	0.2033	0.1946	0.4207	0.073*
C11	0.00922 (12)	0.4666 (4)	−0.12766 (17)	0.0416 (7)
H11A	−0.0034	0.3404	−0.1663	0.062*
H11B	0.0267	0.5718	−0.1535	0.062*
H11C	−0.0258	0.5291	−0.1229	0.062*
H1	0.2060 (10)	−0.104 (3)	0.2716 (15)	0.021 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0284 (4)	0.0334 (3)	0.0326 (4)	−0.0050 (3)	0.0087 (3)	0.0021 (3)
N1	0.0301 (13)	0.0258 (10)	0.0370 (14)	0.0053 (10)	0.0184 (11)	0.0012 (10)
C1	0.0234 (14)	0.0325 (12)	0.0286 (14)	−0.0003 (10)	0.0118 (12)	−0.0015 (11)
C2	0.0351 (17)	0.0292 (12)	0.0306 (15)	−0.0045 (11)	0.0151 (14)	−0.0014 (11)
C3	0.0323 (16)	0.0389 (14)	0.0290 (15)	−0.0112 (12)	0.0138 (13)	−0.0092 (13)
C4	0.0277 (16)	0.0417 (14)	0.0260 (15)	0.0007 (11)	0.0145 (13)	−0.0008 (12)
C5	0.0371 (17)	0.0301 (13)	0.0323 (16)	0.0000 (12)	0.0164 (14)	0.0009 (12)
C6	0.0322 (16)	0.0284 (13)	0.0354 (16)	−0.0063 (11)	0.0144 (14)	−0.0049 (12)
C7	0.0321 (16)	0.0294 (12)	0.0268 (14)	0.0006 (11)	0.0140 (13)	0.0011 (11)
C8	0.0377 (18)	0.0461 (15)	0.0427 (18)	0.0030 (13)	0.0226 (15)	0.0006 (13)
C9	0.051 (2)	0.0365 (14)	0.0438 (17)	−0.0010 (13)	0.0249 (16)	0.0051 (13)
C10	0.056 (2)	0.0528 (16)	0.0334 (18)	−0.0077 (15)	0.0156 (16)	−0.0036 (14)
C11	0.0391 (18)	0.0540 (16)	0.0296 (16)	0.0025 (13)	0.0128 (15)	0.0030 (13)

Geometric parameters (Å, º)

S1—N1	1.694 (2)	C7—C9	1.527 (3)
S1—C1	1.776 (3)	C7—C10	1.529 (4)
N1—C7	1.486 (3)	C7—C8	1.527 (4)
N1—H1	0.82 (2)	C8—H8A	0.98
C1—C6	1.390 (3)	C8—H8B	0.98
C1—C2	1.394 (3)	C8—H8C	0.98
C2—C3	1.384 (3)	C9—H9A	0.98
C2—H2	0.95	C9—H9B	0.98
C3—C4	1.397 (3)	C9—H9C	0.98
C3—H3	0.95	C10—H10A	0.98
C4—C5	1.398 (3)	C10—H10B	0.98
C4—C11	1.501 (4)	C10—H10C	0.98
C5—C6	1.379 (4)	C11—H11A	0.98
C5—H5	0.95	C11—H11B	0.98
C6—H6	0.95	C11—H11C	0.98
N1—S1—C1	103.57 (11)	C9—C7—C8	110.8 (2)
C7—N1—S1	118.43 (16)	C10—C7—C8	110.1 (2)
C7—N1—H1	111.4 (16)	C7—C8—H8A	109.5
S1—N1—H1	110.4 (16)	C7—C8—H8B	109.5
C6—C1—C2	119.0 (2)	H8A—C8—H8B	109.5
C6—C1—S1	117.4 (2)	C7—C8—H8C	109.5
C2—C1—S1	123.6 (2)	H8A—C8—H8C	109.5
C3—C2—C1	119.7 (2)	H8B—C8—H8C	109.5
C3—C2—H2	120.2	C7—C9—H9A	109.5
C1—C2—H2	120.2	C7—C9—H9B	109.5
C2—C3—C4	122.2 (2)	H9A—C9—H9B	109.5
C2—C3—H3	118.9	C7—C9—H9C	109.5
C4—C3—H3	118.9	H9A—C9—H9C	109.5
C3—C4—C5	117.0 (2)	H9B—C9—H9C	109.5
C3—C4—C11	121.6 (2)	C7—C10—H10A	109.5
C5—C4—C11	121.4 (2)	C7—C10—H10B	109.5
C6—C5—C4	121.5 (2)	H10A—C10—H10B	109.5
C6—C5—H5	119.3	C7—C10—H10C	109.5
C4—C5—H5	119.3	H10A—C10—H10C	109.5
C5—C6—C1	120.7 (2)	H10B—C10—H10C	109.5
C5—C6—H6	119.7	C4—C11—H11A	109.5
C1—C6—H6	119.6	C4—C11—H11B	109.5
N1—C7—C9	105.2 (2)	H11A—C11—H11B	109.5
N1—C7—C10	112.3 (2)	C4—C11—H11C	109.5
C9—C7—C10	110.0 (2)	H11A—C11—H11C	109.5
N1—C7—C8	108.2 (2)	H11B—C11—H11C	109.5
C1—S1—N1—C7	−113.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1^i	0.82 (2)	2.75 (2)	3.523 (3)	159 (2)

Symmetry code: (i) −x+1/2, y−1/2, −z+1/2.