organic compounds
2-(Phenylsulfanyl)aniline
aDepartment of Chemistry and Biochemistry, University of Massachusetts Dartmouth, 285 Old Westport Road, North Dartmouth, MA 02747, USA
*Correspondence e-mail: dmanke@umassd.edu
In the title compound, C12H11NS, the aniline and phenyl rings have a skewed conformation with a dihedral angle of 81.31 (7)°. There is a short intramolecular N–H⋯S contact enclosing an S(5) ring motif. In the crystal, molecules are linked via N–H⋯S hydrogen bonds, forming chains along [10-3]. The chains are linked via N—H⋯π and C—H⋯π interactions, forming layers parallel to plane (010). No π–π interactions are noted between the layers.
Keywords: crystal structure; anilines; 2-arylthioanilines; hydrogen bonding.
CCDC reference: 1444623
Structure description
2-(Arylsulfanyl)anilines have potential as pharmaceuticals, and herein we report the , the aniline and phenyl rings have a skewed conformation with a dihedral angle of 81.31 (7)° and the C2—S1—C7 angle is 105.42 (10)°. This varies slightly from the values for 2-(p-tolylsulfanyl)aniline, where the corresponding dihedral angle is 87.80 (7)° and the C—S—C angle is 103.21 (12)° (Betz et al., 2011). There is a short intramolecular N1—H1B⋯S1 contact forming an S(5) ring motif (Table 1).
of the parent 2-(phenylsulfanyl)aniline. In the title compound, Fig. 1In the crystal, molecules are linked via N1—H1A⋯S1 hydrogen bonds, forming chains along [10]. The chains are linked by N—H⋯π and C—H⋯π interactions, forming layers that lie parallel to plane (010); Table 1 and Fig. 2. No π–π interactions are noted between the layers.
Though other 2-arylsulfanylanilines demonstrate intramolecular N—H⋯S hydrogen bonding, the observed intermolecular interactions are N—H⋯N hydrogen bonds (Yao et al., 2012; Beppu et al., 2014; Sellmann et al., 1999; Yuan et al., 2008). The structure of 2-[(4-methylphenyl)sulfanyl]aniline has been reported (Betz et al., 2011), as has that of another 2-arylthioaniline, 2-[(4-bromophenyl)sulfanyl]-4-nitroaniline (Yao et al., 2012).
Synthesis and crystallization
A commercial sample (Tokyo Chemical Industries) of the title compound was used for crystallization. Single crystals suitable for X-ray diffraction studies were grown by slow evaporation of a hexanes solution.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2
|
Structural data
CCDC reference: 1444623
10.1107/S241431461502489X/su4007sup1.cif
contains datablocks Global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S241431461502489X/su4007Isup2.hkl
A commercial sample (Tokyo Chemical Industries) of the title compound was used for crystallization. Single crystals suitable for X-ray diffraction studies were grown by slow evaporation of a hexanes solution.
Crystal data, data collection and structure
details are summarized in Table 2. The NH2 H atoms, H1A and H2A, were found from a difference Fourier map and refined with a distance restraint: N—H = 0.860 (5) Å with Uiso(H) = 1.20Ueq(N). The remaining H atoms were placed in calculated positions and refined as riding: C—H = 0.95 Å with Uiso(H) = 1.20Ueq(C).2-(Arylsulfanyl)anilines have potential as pharmaceuticals, and herein we report the
of the parent 2-(phenylsulfanyl)aniline. In the title compound, Fig. 1, the aniline and phenyl rings have a skewed conformation with a dihedral angle of 81.31 (7)° and the C2—S1—C7 angle is 105.42 (10)°. This varies slightly from the values for 2-(p-tolylsulfanyl)aniline, where the corresponding dihedral angle is 87.80 (7)° and the C–S–C angle is 103.21 (12)° (Betz et al., 2011). There is a short intramolecular N1—H1B···S1 contact forming an S(5) ring motif (Table 1).In the crystal, molecules are linked via N1—H1A···S1 hydrogen bonds, forming chains along [103]. The chains are linked by N—H···π and C—H···π interactions, forming layers that lie parallel to plane (010); Table 1 and Fig. 2. No π–π interactions are noted between the layers.
Though other 2-arylsulfanylanilines demonstrate intramolecular N—H···S hydrogen bonding, the observed intermolecular interactions are N—H···N hydrogen bonds (Yao et al., 2012; Beppu et al., 2014; Sellmann et al., 1999; Yuan et al., 2008). The structure of 2-[(4-methylphenyl)sulfanyl]aniline has been reported (Betz et al., 2011), as has that of another 2-arylsulfanylaniline, 2-[(4-bromophenyl)sulfanyl]-4-nitroaniline (Yao et al., 2012).
Data collection: APEX2 (Bruker, 2014); cell
SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).Fig. 1. Molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. The short intramolecular N—H···S contact is shown as a dashed line (see Table 1). | |
Fig. 2. A view along the c axis of the crystal packing of the title compound, with hydrogen bonds shown as dashed lines (see Table 1). |
C12H11NS | F(000) = 1696 |
Mr = 201.28 | Dx = 1.315 Mg m−3 |
Orthorhombic, Fdd2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: F 2 -2d | Cell parameters from 7209 reflections |
a = 17.7430 (7) Å | θ = 3.2–25.3° |
b = 37.3075 (19) Å | µ = 0.27 mm−1 |
c = 6.1420 (2) Å | T = 120 K |
V = 4065.7 (3) Å3 | Block, colourless |
Z = 16 | 0.4 × 0.2 × 0.2 mm |
Bruker D8 Venture CMOS diffractometer | 1862 independent reflections |
Radiation source: fine-focus sealed tube | 1776 reflections with I > 2σ(I) |
TRIUMPH monochromator | Rint = 0.043 |
φ and ω scans | θmax = 25.4°, θmin = 3.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | h = −21→21 |
Tmin = 0.717, Tmax = 0.745 | k = −44→44 |
14523 measured reflections | l = −7→7 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.023 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.055 | w = 1/[σ2(Fo2) + (0.0293P)2 + 1.8762P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max = 0.001 |
1862 reflections | Δρmax = 0.15 e Å−3 |
134 parameters | Δρmin = −0.16 e Å−3 |
3 restraints | Absolute structure: Flack x determined using 779 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.04 (3) |
C12H11NS | V = 4065.7 (3) Å3 |
Mr = 201.28 | Z = 16 |
Orthorhombic, Fdd2 | Mo Kα radiation |
a = 17.7430 (7) Å | µ = 0.27 mm−1 |
b = 37.3075 (19) Å | T = 120 K |
c = 6.1420 (2) Å | 0.4 × 0.2 × 0.2 mm |
Bruker D8 Venture CMOS diffractometer | 1862 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | 1776 reflections with I > 2σ(I) |
Tmin = 0.717, Tmax = 0.745 | Rint = 0.043 |
14523 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.055 | Δρmax = 0.15 e Å−3 |
S = 1.10 | Δρmin = −0.16 e Å−3 |
1862 reflections | Absolute structure: Flack x determined using 779 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
134 parameters | Absolute structure parameter: 0.04 (3) |
3 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.24353 (3) | 0.61620 (2) | 0.24971 (10) | 0.01900 (14) | |
N1 | 0.15876 (11) | 0.61631 (5) | 0.6825 (3) | 0.0238 (4) | |
C1 | 0.20904 (11) | 0.64429 (6) | 0.6541 (4) | 0.0175 (5) | |
C2 | 0.25623 (10) | 0.64606 (5) | 0.4712 (3) | 0.0169 (5) | |
C3 | 0.30828 (12) | 0.67388 (5) | 0.4495 (4) | 0.0206 (5) | |
H3 | 0.3399 | 0.6748 | 0.3249 | 0.025* | |
C4 | 0.31437 (13) | 0.70019 (6) | 0.6072 (4) | 0.0256 (5) | |
H4 | 0.3500 | 0.7191 | 0.5920 | 0.031* | |
C5 | 0.26753 (13) | 0.69856 (6) | 0.7883 (4) | 0.0245 (5) | |
H5 | 0.2711 | 0.7165 | 0.8973 | 0.029* | |
C6 | 0.21570 (12) | 0.67112 (6) | 0.8121 (4) | 0.0209 (5) | |
H6 | 0.1843 | 0.6705 | 0.9373 | 0.025* | |
C7 | 0.28473 (12) | 0.57490 (6) | 0.3348 (4) | 0.0171 (5) | |
C8 | 0.32540 (11) | 0.57064 (5) | 0.5250 (4) | 0.0194 (5) | |
H8 | 0.3286 | 0.5897 | 0.6272 | 0.023* | |
C9 | 0.36152 (12) | 0.53829 (6) | 0.5658 (4) | 0.0239 (5) | |
H9 | 0.3902 | 0.5354 | 0.6953 | 0.029* | |
C10 | 0.35599 (13) | 0.51019 (6) | 0.4184 (4) | 0.0267 (5) | |
H10 | 0.3815 | 0.4883 | 0.4457 | 0.032* | |
C11 | 0.31329 (12) | 0.51427 (6) | 0.2318 (4) | 0.0271 (5) | |
H11 | 0.3082 | 0.4948 | 0.1331 | 0.033* | |
C12 | 0.27773 (13) | 0.54671 (6) | 0.1877 (4) | 0.0230 (5) | |
H12 | 0.2489 | 0.5496 | 0.0585 | 0.028* | |
H1A | 0.1217 (10) | 0.6211 (6) | 0.767 (4) | 0.028* | |
H1B | 0.1497 (15) | 0.6036 (6) | 0.568 (3) | 0.037 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0204 (2) | 0.0204 (2) | 0.0162 (2) | 0.0016 (2) | −0.0004 (2) | 0.0009 (2) |
N1 | 0.0230 (10) | 0.0262 (10) | 0.0222 (11) | −0.0040 (8) | 0.0085 (8) | −0.0004 (9) |
C1 | 0.0157 (10) | 0.0181 (10) | 0.0186 (11) | 0.0045 (8) | −0.0003 (9) | 0.0051 (9) |
C2 | 0.0149 (9) | 0.0161 (10) | 0.0198 (12) | 0.0032 (7) | −0.0016 (9) | 0.0007 (9) |
C3 | 0.0181 (10) | 0.0205 (10) | 0.0233 (12) | 0.0007 (8) | 0.0027 (9) | 0.0052 (10) |
C4 | 0.0252 (12) | 0.0176 (11) | 0.0339 (14) | −0.0032 (9) | −0.0025 (11) | 0.0027 (10) |
C5 | 0.0324 (12) | 0.0167 (10) | 0.0245 (15) | 0.0062 (9) | −0.0057 (10) | −0.0030 (10) |
C6 | 0.0196 (10) | 0.0245 (12) | 0.0187 (11) | 0.0084 (9) | 0.0006 (9) | 0.0023 (9) |
C7 | 0.0144 (10) | 0.0158 (11) | 0.0212 (11) | −0.0020 (8) | 0.0037 (9) | −0.0009 (9) |
C8 | 0.0213 (10) | 0.0172 (10) | 0.0197 (11) | −0.0036 (8) | 0.0006 (10) | −0.0005 (9) |
C9 | 0.0244 (11) | 0.0241 (11) | 0.0233 (12) | −0.0007 (9) | −0.0001 (10) | 0.0034 (10) |
C10 | 0.0285 (12) | 0.0176 (11) | 0.0339 (14) | 0.0021 (9) | 0.0063 (11) | 0.0032 (10) |
C11 | 0.0300 (11) | 0.0196 (11) | 0.0318 (14) | −0.0033 (9) | 0.0069 (11) | −0.0088 (11) |
C12 | 0.0215 (11) | 0.0275 (12) | 0.0202 (12) | −0.0029 (9) | 0.0005 (9) | −0.0031 (9) |
S1—C2 | 1.772 (2) | C5—C6 | 1.384 (3) |
S1—C7 | 1.784 (2) | C6—H6 | 0.9500 |
N1—C1 | 1.384 (3) | C7—C8 | 1.383 (3) |
N1—H1A | 0.857 (7) | C7—C12 | 1.392 (3) |
N1—H1B | 0.862 (7) | C8—H8 | 0.9500 |
C1—C2 | 1.403 (3) | C8—C9 | 1.389 (3) |
C1—C6 | 1.400 (3) | C9—H9 | 0.9500 |
C2—C3 | 1.396 (3) | C9—C10 | 1.388 (3) |
C3—H3 | 0.9500 | C10—H10 | 0.9500 |
C3—C4 | 1.383 (3) | C10—C11 | 1.382 (4) |
C4—H4 | 0.9500 | C11—H11 | 0.9500 |
C4—C5 | 1.390 (3) | C11—C12 | 1.391 (3) |
C5—H5 | 0.9500 | C12—H12 | 0.9500 |
C2—S1—C7 | 105.42 (10) | C5—C6—C1 | 120.8 (2) |
C1—N1—H1A | 114.4 (16) | C5—C6—H6 | 119.6 |
C1—N1—H1B | 115.7 (19) | C8—C7—S1 | 124.12 (17) |
H1A—N1—H1B | 118 (3) | C8—C7—C12 | 120.5 (2) |
N1—C1—C2 | 121.4 (2) | C12—C7—S1 | 115.22 (17) |
N1—C1—C6 | 120.4 (2) | C7—C8—H8 | 120.2 |
C6—C1—C2 | 118.13 (19) | C7—C8—C9 | 119.5 (2) |
C1—C2—S1 | 120.60 (16) | C9—C8—H8 | 120.2 |
C3—C2—S1 | 118.58 (16) | C8—C9—H9 | 119.8 |
C3—C2—C1 | 120.4 (2) | C10—C9—C8 | 120.4 (2) |
C2—C3—H3 | 119.6 | C10—C9—H9 | 119.8 |
C4—C3—C2 | 120.8 (2) | C9—C10—H10 | 120.1 |
C4—C3—H3 | 119.6 | C11—C10—C9 | 119.7 (2) |
C3—C4—H4 | 120.6 | C11—C10—H10 | 120.1 |
C3—C4—C5 | 118.9 (2) | C10—C11—H11 | 119.8 |
C5—C4—H4 | 120.6 | C10—C11—C12 | 120.4 (2) |
C4—C5—H5 | 119.5 | C12—C11—H11 | 119.8 |
C6—C5—C4 | 121.0 (2) | C7—C12—H12 | 120.3 |
C6—C5—H5 | 119.5 | C11—C12—C7 | 119.4 (2) |
C1—C6—H6 | 119.6 | C11—C12—H12 | 120.3 |
S1—C2—C3—C4 | 172.78 (17) | C4—C5—C6—C1 | −0.1 (3) |
S1—C7—C8—C9 | −173.59 (16) | C6—C1—C2—S1 | −172.52 (16) |
S1—C7—C12—C11 | 174.84 (17) | C6—C1—C2—C3 | 0.1 (3) |
N1—C1—C2—S1 | 9.5 (3) | C7—S1—C2—C1 | −78.46 (18) |
N1—C1—C2—C3 | −177.8 (2) | C7—S1—C2—C3 | 108.74 (16) |
N1—C1—C6—C5 | 177.9 (2) | C7—C8—C9—C10 | −1.0 (3) |
C1—C2—C3—C4 | 0.0 (3) | C8—C7—C12—C11 | −1.2 (3) |
C2—S1—C7—C8 | −7.2 (2) | C8—C9—C10—C11 | −1.1 (3) |
C2—S1—C7—C12 | 176.93 (16) | C9—C10—C11—C12 | 1.9 (3) |
C2—C1—C6—C5 | −0.1 (3) | C10—C11—C12—C7 | −0.8 (3) |
C2—C3—C4—C5 | −0.1 (3) | C12—C7—C8—C9 | 2.1 (3) |
C3—C4—C5—C6 | 0.2 (3) |
Cg1 and Cg2 are the centroids of the C1–C6 and C7–C12 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···S1 | 0.86 (1) | 2.61 (3) | 3.054 (2) | 113 (2) |
N1—H1A···S1i | 0.86 (1) | 2.73 (1) | 3.580 (2) | 174 (2) |
N1—H1B···Cg1ii | 0.86 (1) | 2.87 (3) | 3.510 (2) | 132 (2) |
C6—H6···Cg2i | 0.95 | 2.72 | 3.506 (2) | 141 |
C9—H9···Cg1iii | 0.95 | 2.90 | 3.606 (2) | 132 |
Symmetry codes: (i) x−1/4, −y+5/4, z+3/4; (ii) x−1/4, −y+5/4, z−1/4; (iii) x+1/4, −y+5/4, z+1/4. |
Cg1 and Cg2 are the centroids of the C1–C6 and C7–C12 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···S1 | 0.86 (1) | 2.61 (3) | 3.054 (2) | 113 (2) |
N1—H1A···S1i | 0.86 (1) | 2.727 (8) | 3.580 (2) | 174 (2) |
N1—H1B···Cg1ii | 0.862 (7) | 2.87 (3) | 3.510 (2) | 132 (2) |
C6—H6···Cg2i | 0.95 | 2.72 | 3.506 (2) | 141 |
C9—H9···Cg1iii | 0.95 | 2.90 | 3.606 (2) | 132 |
Symmetry codes: (i) x−1/4, −y+5/4, z+3/4; (ii) x−1/4, −y+5/4, z−1/4; (iii) x+1/4, −y+5/4, z+1/4. |
Experimental details
Crystal data | |
Chemical formula | C12H11NS |
Mr | 201.28 |
Crystal system, space group | Orthorhombic, Fdd2 |
Temperature (K) | 120 |
a, b, c (Å) | 17.7430 (7), 37.3075 (19), 6.1420 (2) |
V (Å3) | 4065.7 (3) |
Z | 16 |
Radiation type | Mo Kα |
µ (mm−1) | 0.27 |
Crystal size (mm) | 0.4 × 0.2 × 0.2 |
Data collection | |
Diffractometer | Bruker D8 Venture CMOS |
Absorption correction | Multi-scan (SADABS; Bruker, 2014) |
Tmin, Tmax | 0.717, 0.745 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14523, 1862, 1776 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.603 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.055, 1.10 |
No. of reflections | 1862 |
No. of parameters | 134 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.15, −0.16 |
Absolute structure | Flack x determined using 779 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Absolute structure parameter | 0.04 (3) |
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), OLEX2 (Dolomanov et al., 2009), OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).
Acknowledgements
Support from the National Science Foundation (CHE-1429086) is gratefully acknowledge.
References
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