2-[(4-Methyl­phen­yl)sulfan­yl]aniline

Betz, R.; Gerber, T.; Schalekamp, H.

doi:10.1107/S1600536811002820

organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o489

doi:10.1107/S1600536811002820

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2-[(4-Methylphenyl)sulfanyl]aniline

Richard Betz,^a ^* Thomas Gerber ^a and Henk Schalekamp ^a

^aNelson Mandela Metropolitan University, Summerstrand Campus, Department of Chemistry, University Way, Summerstrand, PO Box 77000, Port Elizabeth 6031, South Africa
^*Correspondence e-mail: richard.betz@webmail.co.za

(Received 19 January 2011; accepted 20 January 2011; online 26 January 2011)

The least-squares planes defined by the aromatic moieties in the title aniline derivative, C₁₃H₁₃NS, are nearly perpendicular to each other, forming a dihedral angle of 87.80 (7)°. Apart from a weak intramolecular N—H⋯S hydrogen bond, a co-operative set of N—H⋯N hydrogen bonds present in the crystal structure leads to the formation of tetrameric units.

Related literature

For structures of aniline derivatives bearing an S atom in the ortho position to their respective amino group(s), see: Yuan et al. (2008 ); Sellmann et al. (1999 ); Heinisch et al. (1999 ). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ); Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₃H₁₃NS
M_r = 215.30
Tetragonal, P 4₂ /n
a = 17.8881 (7) Å
c = 7.2129 (3) Å
V = 2308.0 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 200 K
0.55 × 0.39 × 0.26 mm

Data collection

Bruker APEXII CCD diffractometer
10035 measured reflections
2748 independent reflections
2216 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.075
wR(F²) = 0.147
S = 1.20
2748 reflections
142 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H71⋯N1ⁱ	0.90 (3)	2.19 (4)	3.083 (3)	170 (3)
N1—H72⋯S1	0.81 (3)	2.60 (3)	3.032 (3)	115 (3)
Symmetry code: (i) $[-y+{\script{1\over 2}}, x, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2010 ); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811002820/tk2711sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811002820/tk2711Isup2.hkl

checkCIF report

Comment top

2-(p-Tolylthio)benzenamine is a derivative of aniline bearing a para-methylbenzene sulfide moiety in a position ortho to its amino group. Given its N,S set of donor atoms, it can act as a monodentate via either donor or as a bidentate ligand forming a five-membered chelate ring. The possibility to coordinate it as a purely neutral or, upon deprotonation, as an anionic ligand adds to its versatility. In our continued efforts to elucidate the coordination behaviour of nitrogen- and sulfur-containing ligands, it seemed of interest to determine the structure of the free ligand to enable comparative studies with related structures (Yuan et al., 2008; Sellmann et al., 1999; Heinisch et al., 1999).

The least-squares planes defined by the two aromatic moieties in the molecule are orientated nearly perpendicular to each other; they enclose an angle of 87.80 (7)°. The C2–S1–C7 angle is 103.21 (12) ° (Fig. 1).

In the crystal structure, two different sets of hydrogen bonds can be observed, Table 1. While one of the hydrogen atoms of the amino group forms an intramolecular hydrogen bond to the sulfur atom, the remaining hydrogen atom of the NH₂ group participates in a cooperative system of hydrogen bonds. The latter give rise to the formation of tetrameric units. In terms of graph-set analysis (Etter et al., 1990; Bernstein et al., 1995), the descriptor for the intramolecular interaction is S(5) while the cooperative system of hydrogen bonds necessitates a C¹₁(2) descriptor. The tetramer has a hydrophilic core which is shielded by the lipophilic parts of the molecules (Fig. 2). The closest distance between two aromatic systems is 4.0711 (16) Å. The molecular packing of the compound is shown in Fig. 3.

Related literature top

For structures of aniline derivatives bearing an S atom in the ortho position to their respective amino group(s), see: Yuan et al. (2008); Sellmann et al. (1999); Heinisch et al. (1999). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990); Bernstein et al. (1995).

Experimental top

The structural analysis was performed on a sample taken from a commercially obtained (Sigma Aldrich) batch of the title compound.

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and anisotropic displacement ellipsoids drawn at 50% probability level.
	Fig. 2. Hydrogen bonds in the title compound, viewed along [0 0 1]. The N–H···N contacts are illustrated in green, N–H···S contacts are illustrated in red. Symmetry operators: i y, -x + 1/2, -z + 1/2; ii -y + 1/2, x, -z + 1/2.
	Fig. 3. Molecular packing of the title compound, viewed along [-1 0 0] (anisotropic displacement ellipsoids drawn at 50% probability level).

2-[(4-Methylphenyl)sulfanyl]aniline top

Crystal data top

C₁₃H₁₃NS	D_x = 1.239 Mg m⁻³
M_r = 215.30	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4₂/n	Cell parameters from 5143 reflections
Hall symbol: -P 4bc	θ = 3.1–28.2°
a = 17.8881 (7) Å	µ = 0.25 mm⁻¹
c = 7.2129 (3) Å	T = 200 K
V = 2308.0 (2) Å³	Block, colourless
Z = 8	0.55 × 0.39 × 0.26 mm
F(000) = 912

Data collection top

Bruker APEXII CCD diffractometer	2216 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.055
Graphite monochromator	θ_max = 28.0°, θ_min = 3.1°
ϕ and ω scans	h = −20→23
10035 measured reflections	k = −18→23
2748 independent reflections	l = −7→9

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.075	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.147	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	w = 1/[σ²(F_o²) + (0.031P)² + 3.0953P] where P = (F_o² + 2F_c²)/3
2748 reflections	(Δ/σ)_max < 0.001
142 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₁₃H₁₃NS	Z = 8
M_r = 215.30	Mo Kα radiation
Tetragonal, P4₂/n	µ = 0.25 mm⁻¹
a = 17.8881 (7) Å	T = 200 K
c = 7.2129 (3) Å	0.55 × 0.39 × 0.26 mm
V = 2308.0 (2) Å³

Data collection top

Bruker APEXII CCD diffractometer	2216 reflections with I > 2σ(I)
10035 measured reflections	R_int = 0.055
2748 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.075	0 restraints
wR(F²) = 0.147	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	Δρ_max = 0.32 e Å⁻³
2748 reflections	Δρ_min = −0.35 e Å⁻³
142 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.01389 (4)	0.40662 (4)	0.20839 (10)	0.0345 (2)
N1	0.13486 (13)	0.28819 (14)	0.2293 (3)	0.0299 (5)
H71	0.1533 (19)	0.2420 (19)	0.252 (4)	0.045*
H72	0.1093 (19)	0.3055 (19)	0.312 (5)	0.045*
C1	0.10172 (14)	0.29629 (14)	0.0560 (3)	0.0227 (5)
C2	0.04739 (14)	0.35093 (14)	0.0231 (3)	0.0258 (5)
C3	0.01567 (16)	0.35781 (16)	−0.1524 (4)	0.0342 (6)
H3	−0.0216	0.3947	−0.1737	0.041*
C4	0.03771 (17)	0.31167 (17)	−0.2956 (4)	0.0379 (7)
H4	0.0154	0.3163	−0.4146	0.045*
C5	0.09245 (17)	0.25864 (16)	−0.2644 (4)	0.0338 (6)
H5	0.1079	0.2268	−0.3627	0.041*
C6	0.12488 (15)	0.25144 (14)	−0.0917 (4)	0.0282 (6)
H6	0.1634	0.2156	−0.0731	0.034*
C7	0.08960 (15)	0.46865 (15)	0.2526 (4)	0.0301 (6)
C8	0.10088 (18)	0.49272 (16)	0.4335 (4)	0.0373 (7)
H8	0.0718	0.4723	0.5315	0.045*
C9	0.15445 (19)	0.54640 (18)	0.4708 (5)	0.0461 (8)
H9	0.1613	0.5628	0.5949	0.055*
C10	0.19821 (19)	0.57669 (17)	0.3324 (5)	0.0485 (9)
C11	0.18758 (19)	0.55109 (18)	0.1530 (5)	0.0489 (8)
H11	0.2179	0.5703	0.0560	0.059*
C12	0.13358 (17)	0.49803 (17)	0.1122 (4)	0.0395 (7)
H12	0.1267	0.4818	−0.0120	0.047*
C13	0.2567 (2)	0.6356 (2)	0.3744 (7)	0.0757 (13)
H13A	0.2811	0.6510	0.2590	0.114*
H13B	0.2941	0.6149	0.4593	0.114*
H13C	0.2327	0.6790	0.4322	0.114*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0299 (4)	0.0405 (4)	0.0331 (3)	0.0092 (3)	0.0032 (3)	−0.0088 (3)
N1	0.0299 (12)	0.0312 (13)	0.0286 (11)	0.0066 (10)	−0.0038 (10)	−0.0012 (10)
C1	0.0211 (12)	0.0207 (12)	0.0263 (11)	−0.0032 (10)	0.0006 (10)	0.0011 (10)
C2	0.0253 (13)	0.0272 (13)	0.0250 (11)	0.0017 (11)	0.0019 (10)	−0.0025 (10)
C3	0.0386 (16)	0.0352 (16)	0.0287 (12)	0.0081 (13)	−0.0034 (12)	0.0034 (12)
C4	0.0466 (18)	0.0436 (17)	0.0234 (12)	−0.0021 (14)	−0.0029 (13)	−0.0006 (12)
C5	0.0409 (16)	0.0325 (15)	0.0281 (12)	−0.0056 (13)	0.0065 (12)	−0.0050 (11)
C6	0.0270 (14)	0.0227 (13)	0.0349 (13)	0.0008 (11)	0.0062 (11)	−0.0016 (11)
C7	0.0281 (14)	0.0263 (13)	0.0361 (14)	0.0114 (11)	−0.0007 (11)	−0.0040 (11)
C8	0.0436 (18)	0.0323 (16)	0.0360 (14)	0.0102 (13)	−0.0030 (13)	−0.0023 (12)
C9	0.054 (2)	0.0353 (17)	0.0494 (18)	0.0076 (16)	−0.0109 (16)	−0.0085 (15)
C10	0.0423 (18)	0.0264 (16)	0.077 (2)	0.0051 (14)	−0.0024 (18)	−0.0061 (16)
C11	0.047 (2)	0.0338 (17)	0.066 (2)	0.0060 (15)	0.0165 (17)	0.0000 (16)
C12	0.0415 (17)	0.0362 (16)	0.0408 (15)	0.0134 (14)	0.0094 (13)	−0.0021 (13)
C13	0.068 (3)	0.042 (2)	0.117 (4)	−0.0092 (19)	−0.005 (3)	−0.008 (2)

Geometric parameters (Å, º) top

S1—C2	1.771 (3)	C7—C12	1.386 (4)
S1—C7	1.780 (3)	C7—C8	1.389 (4)
N1—C1	1.391 (3)	C8—C9	1.383 (4)
N1—H71	0.90 (3)	C8—H8	0.9500
N1—H72	0.81 (3)	C9—C10	1.379 (5)
C1—C6	1.396 (3)	C9—H9	0.9500
C1—C2	1.399 (4)	C10—C11	1.386 (5)
C2—C3	1.392 (3)	C10—C13	1.516 (5)
C3—C4	1.380 (4)	C11—C12	1.386 (5)
C3—H3	0.9500	C11—H11	0.9500
C4—C5	1.382 (4)	C12—H12	0.9500
C4—H4	0.9500	C13—H13A	0.9800
C5—C6	1.380 (4)	C13—H13B	0.9800
C5—H5	0.9500	C13—H13C	0.9800
C6—H6	0.9500

C2—S1—C7	103.21 (12)	C12—C7—S1	122.5 (2)
C1—N1—H71	114 (2)	C8—C7—S1	118.2 (2)
C1—N1—H72	112 (2)	C9—C8—C7	119.9 (3)
H71—N1—H72	115 (3)	C9—C8—H8	120.1
N1—C1—C6	120.0 (2)	C7—C8—H8	120.1
N1—C1—C2	121.4 (2)	C10—C9—C8	121.7 (3)
C6—C1—C2	118.6 (2)	C10—C9—H9	119.2
C3—C2—C1	119.9 (2)	C8—C9—H9	119.2
C3—C2—S1	119.9 (2)	C9—C10—C11	117.9 (3)
C1—C2—S1	120.00 (19)	C9—C10—C13	121.3 (4)
C4—C3—C2	120.7 (3)	C11—C10—C13	120.8 (4)
C4—C3—H3	119.6	C10—C11—C12	121.3 (3)
C2—C3—H3	119.6	C10—C11—H11	119.3
C3—C4—C5	119.4 (3)	C12—C11—H11	119.3
C3—C4—H4	120.3	C7—C12—C11	120.0 (3)
C5—C4—H4	120.3	C7—C12—H12	120.0
C6—C5—C4	120.6 (2)	C11—C12—H12	120.0
C6—C5—H5	119.7	C10—C13—H13A	109.5
C4—C5—H5	119.7	C10—C13—H13B	109.5
C5—C6—C1	120.7 (2)	H13A—C13—H13B	109.5
C5—C6—H6	119.7	C10—C13—H13C	109.5
C1—C6—H6	119.7	H13A—C13—H13C	109.5
C12—C7—C8	119.1 (3)	H13B—C13—H13C	109.5

N1—C1—C2—C3	179.6 (2)	C2—S1—C7—C12	37.3 (3)
C6—C1—C2—C3	2.3 (4)	C2—S1—C7—C8	−147.8 (2)
N1—C1—C2—S1	−5.1 (3)	C12—C7—C8—C9	1.3 (4)
C6—C1—C2—S1	177.62 (19)	S1—C7—C8—C9	−173.8 (2)
C7—S1—C2—C3	−111.1 (2)	C7—C8—C9—C10	−0.7 (5)
C7—S1—C2—C1	73.6 (2)	C8—C9—C10—C11	−0.7 (5)
C1—C2—C3—C4	−0.6 (4)	C8—C9—C10—C13	179.9 (3)
S1—C2—C3—C4	−175.9 (2)	C9—C10—C11—C12	1.5 (5)
C2—C3—C4—C5	−0.7 (4)	C13—C10—C11—C12	−179.1 (3)
C3—C4—C5—C6	0.2 (4)	C8—C7—C12—C11	−0.5 (4)
C4—C5—C6—C1	1.6 (4)	S1—C7—C12—C11	174.4 (2)
N1—C1—C6—C5	179.8 (2)	C10—C11—C12—C7	−0.9 (5)
C2—C1—C6—C5	−2.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H71···N1ⁱ	0.90 (3)	2.19 (4)	3.083 (3)	170 (3)
N1—H72···S1	0.81 (3)	2.60 (3)	3.032 (3)	115 (3)

Symmetry code: (i) −y+1/2, x, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₃NS
M_r	215.30
Crystal system, space group	Tetragonal, P4₂/n
Temperature (K)	200
a, c (Å)	17.8881 (7), 7.2129 (3)
V (Å³)	2308.0 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.55 × 0.39 × 0.26

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	10035, 2748, 2216
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.075, 0.147, 1.20
No. of reflections	2748
No. of parameters	142
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.35

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H71···N1ⁱ	0.90 (3)	2.19 (4)	3.083 (3)	170 (3)
N1—H72···S1	0.81 (3)	2.60 (3)	3.032 (3)	115 (3)

Symmetry code: (i) −y+1/2, x, −z+1/2.

Acknowledgements

The authors thank Mrs Rose van der Vywer for helpful discussions.

References

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