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ISSN: 2056-9890

1-Methyl-3-phenyl­thio­urea

aLvliang University, Lvliang, Shanxi 033001, People's Republic of China
*Correspondence e-mail: li.xy2003@163.com

(Received 18 March 2014; accepted 3 April 2014; online 9 April 2014)

The title compound, C8H10N2S, was prepared by reaction of methyl­amine solution, KOH and phenyl-iso­thio­cyanate in ethanol. It adopts a syn-Me and anti-Ph conformation relative to the C=S double bond. The dihedral angle between the N—C(=S)—N thio­urea and phenyl planes is 67.83 (6)°. In the crystal, the mol­ecules centrosymmetrical dimers by pairs of N(Ph)—H⋯S hydrogen bonds. The dimers are linked by N(Me)—H⋯S hydrogen bonds into layers parallel to (100).

Related literature

For applications of thio­urea derivatives, see: Madan & Taneja (1991[Madan, V. K. & Taneja, A. D. (1991). J. Indian Chem. Soc. 68, 162-163.]); Xu et al. (2004[Xu, L., Jian, F., Qin, Y., Yu, G. & Jiao, K. (2004). Chem. Res. Chin. Univ. 20, 305-307.]); Borisova et al. (2007[Borisova, N. E., Reshetova, M. D. & Ustynyuk, Y. A. (2007). Chem. Rev. 107, 46-79.]). For the crystal structures of related compounds, see: Ji et al. (2002[Ji, B. M., Du, C. X., Zhu, Y. & Wang, Y. (2002). Chin. J. Struct. Chem. 21, 252-255.]); Wenzel et al. (2011[Wenzel, M., Light, M. E., Davis, A. P. & Gale, P. A. (2011). Chem. Commun. 47, 7641-7643.]).

[Scheme 1]

Experimental

Crystal data
  • C8H10N2S

  • Mr = 166.24

  • Monoclinic, C 2/c

  • a = 17.348 (3) Å

  • b = 8.6023 (13) Å

  • c = 12.1672 (18) Å

  • β = 99.637 (3)°

  • V = 1790.1 (5) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 0.30 mm−1

  • T = 296 K

  • 0.25 × 0.23 × 0.20 mm

Data collection
  • Bruker SMART CCD area-detector diffractometer

  • 5444 measured reflections

  • 2026 independent reflections

  • 1424 reflections with I > 2σ(I)

  • Rint = 0.033

Refinement
  • R[F2 > 2σ(F2)] = 0.041

  • wR(F2) = 0.114

  • S = 1.03

  • 2026 reflections

  • 109 parameters

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

  • Δρmax = 0.24 e Å−3

  • Δρmin = −0.24 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯S1i 0.81 (2) 2.55 (2) 3.351 (2) 169 (2)
N2—H2⋯S1ii 0.77 (2) 2.78 (2) 3.4229 (19) 142 (2)
Symmetry codes: (i) [-x+{\script{1\over 2}}, -y+{\script{5\over 2}}, -z+1]; (ii) [-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}].

Data collection: SMART (Bruker 1997[Bruker (1997). SMART and SAINT. Bruker AXS, Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker 1997[Bruker (1997). SMART and SAINT. Bruker AXS, Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

Thioureas have been studied for many years because of their broad antibiosis and sterilibzation properties. Recent years study shows that thioureas not only can be used to kill insects and adjust plant growth but also have anti-viral activities (Madan & Taneja, 1991; Borisova et al., 2007). From our early quantum study on these compounds we find that they have several active centers and cart form polyligand complexes with metals easily (Xu et al., 2004). These complexes are widely used as anti-medicines. Therefore study on thioureas has important impact on the future. In order to search for new compounds with higher bioactivity, the title compound was synthesized.

In the title compound, C8H10N2S (I), the bond lengths and angles are in a good agreement with those found in the related compounds (Ji et al., 2002; Wenzel et al. 2011). Compound I adopts a cis-Me and trans-Ph conformation relative to the CS double bond (Figure 1). The dihedral angle between the N1—C7(S1)—N1 thiourea and phenyl planes is 67.83 (6)°.

In the crystal, the molecules of I form centrosymmetrical dimers by the two intermolecular N1—H1···S1i hydrogen bonds (Table 1, Figure 2). The dimers are further bound to each other by the intermolecular N2—H2···S1ii hydrogen bonds (Table 1) into layers parallel to (100) (Figure 2). Symmetry codes: (i) –x + 1/2, –y + 5/2, –z + 1; (ii) –x + 1/2, y–1/2, –z + 1/2.

Related literature top

For applications of thiourea derivatives, see: Madan & Taneja (1991); Xu et al. (2004); Borisova et al. (2007). For the crystal structures of related compounds, see: Ji et al. (2002); Wenzel et al. (2011).

Experimental top

The title compound was prepared by reaction of methylamine solution (40%, 0.05 mol, 5.5 ml), KOH (0.15 mol, 8.4 g) and phenyl-isothiocyanate(0.05 mol, 4.65 g) in the ethanol solution (40 ml) at room temperature. Single-crystals of the title compound suitable for X-ray measurements was obtained by recrystallization from ethanol/acetone (v/v=1:1) at room temperature.

Refinement top

The hydrogen atoms of the amino groups were localized in the difference Fourier map and refined isotropically. The other hydrogen atoms were placed in the calculated positions with C—H = 0.93 Å (aryl–H) and 0.96 Å (methyl–H) and refined in the riding model with fixed isotropic displacement parameters: Uiso(H) = 1.5Ueq(C) for the CH3 group and 1.2Ueq(C) for the other CH groups.

Computing details top

Data collection: SMART (Bruker 1997); cell refinement: SAINT (Bruker 1997); data reduction: SAINT (Bruker 1997); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of I. Displacement ellipsoids are presented at the 40% probability level. H atoms are depicted as small spheres of arbitrary radius.
[Figure 2] Fig. 2. A portion of the crystal structure of I demonstrating the H–bonded dimers and layers parallel to (100). The hydrogen atoms participating in the formation of hydrogen bonds are shown only. The intermolecular N—H···S hydrogen bonds are depicted by dashed lines.
1-Methyl-3-phenylthiourea top
Crystal data top
C8H10N2SF(000) = 704
Mr = 166.24Dx = 1.234 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 17.348 (3) ÅCell parameters from 1286 reflections
b = 8.6023 (13) Åθ = 2.4–24.8°
c = 12.1672 (18) ŵ = 0.30 mm1
β = 99.637 (3)°T = 296 K
V = 1790.1 (5) Å3Bar, colorless
Z = 80.25 × 0.23 × 0.20 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
Rint = 0.033
Radiation source: sealed tubeθmax = 27.5°, θmin = 2.4°
phi and ω scansh = 2221
5444 measured reflectionsk = 811
2026 independent reflectionsl = 1515
1424 reflections with I > 2σ(I)
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: difference Fourier map
wR(F2) = 0.114H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0587P)2 + 0.1272P]
where P = (Fo2 + 2Fc2)/3
2026 reflections(Δ/σ)max < 0.001
109 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C8H10N2SV = 1790.1 (5) Å3
Mr = 166.24Z = 8
Monoclinic, C2/cMo Kα radiation
a = 17.348 (3) ŵ = 0.30 mm1
b = 8.6023 (13) ÅT = 296 K
c = 12.1672 (18) Å0.25 × 0.23 × 0.20 mm
β = 99.637 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1424 reflections with I > 2σ(I)
5444 measured reflectionsRint = 0.033
2026 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.114H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.24 e Å3
2026 reflectionsΔρmin = 0.24 e Å3
109 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.16423 (3)1.19173 (6)0.35515 (4)0.04468 (19)
N10.29456 (9)1.0463 (2)0.43958 (15)0.0467 (5)
N20.23002 (10)0.9493 (2)0.27416 (15)0.0485 (5)
C10.35645 (10)0.9351 (2)0.45446 (17)0.0401 (5)
C20.36233 (13)0.8311 (3)0.5403 (2)0.0648 (7)
H2A0.32510.83030.58710.078*
C30.42442 (15)0.7264 (3)0.5572 (3)0.0814 (9)
H30.42870.65550.61560.098*
C40.47899 (13)0.7275 (3)0.4884 (3)0.0683 (7)
H40.52020.65690.49970.082*
C50.47334 (12)0.8309 (3)0.4037 (2)0.0646 (7)
H50.51090.83170.35730.077*
C60.41193 (11)0.9357 (3)0.38576 (18)0.0510 (5)
H60.40821.00640.32730.061*
C70.23382 (9)1.0531 (2)0.35543 (15)0.0353 (4)
C80.16755 (12)0.9440 (3)0.1781 (2)0.0685 (7)
H8A0.17401.02780.12840.103*
H8B0.11800.95400.20260.103*
H8C0.16950.84670.14010.103*
H10.2993 (12)1.117 (3)0.4843 (19)0.054 (7)*
H20.2646 (12)0.893 (3)0.2769 (18)0.052 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0346 (3)0.0467 (3)0.0524 (3)0.0114 (2)0.0062 (2)0.0000 (2)
N10.0401 (9)0.0497 (11)0.0462 (11)0.0157 (8)0.0043 (8)0.0147 (9)
N20.0365 (9)0.0573 (12)0.0482 (11)0.0134 (8)0.0034 (8)0.0132 (9)
C10.0293 (8)0.0418 (11)0.0457 (11)0.0061 (8)0.0044 (8)0.0085 (9)
C20.0512 (13)0.0680 (17)0.0758 (17)0.0096 (11)0.0123 (12)0.0206 (13)
C30.0690 (17)0.0612 (18)0.109 (2)0.0133 (14)0.0015 (16)0.0307 (16)
C40.0427 (12)0.0587 (16)0.097 (2)0.0177 (11)0.0081 (13)0.0096 (15)
C50.0364 (10)0.090 (2)0.0637 (16)0.0163 (11)0.0007 (10)0.0205 (14)
C60.0397 (10)0.0647 (15)0.0465 (12)0.0101 (10)0.0009 (9)0.0033 (11)
C70.0298 (9)0.0394 (11)0.0373 (10)0.0024 (7)0.0075 (8)0.0004 (9)
C80.0504 (12)0.093 (2)0.0555 (14)0.0138 (12)0.0108 (11)0.0244 (14)
Geometric parameters (Å, º) top
S1—C71.6964 (17)C3—C41.365 (4)
N1—C71.342 (2)C3—H30.9300
N1—C11.427 (2)C4—C51.353 (4)
N1—H10.81 (2)C4—H40.9300
N2—C71.326 (2)C5—C61.384 (3)
N2—C81.455 (3)C5—H50.9300
N2—H20.77 (2)C6—H60.9300
C1—C21.366 (3)C8—H8A0.9600
C1—C61.376 (3)C8—H8B0.9600
C2—C31.393 (3)C8—H8C0.9600
C2—H2A0.9300
C7—N1—C1127.17 (17)C3—C4—H4119.9
C7—N1—H1117.4 (16)C4—C5—C6120.2 (2)
C1—N1—H1115.2 (16)C4—C5—H5119.9
C7—N2—C8123.87 (18)C6—C5—H5119.9
C7—N2—H2117.0 (17)C1—C6—C5120.0 (2)
C8—N2—H2119.0 (17)C1—C6—H6120.0
C2—C1—C6119.74 (18)C5—C6—H6120.0
C2—C1—N1119.64 (18)N2—C7—N1118.32 (17)
C6—C1—N1120.57 (18)N2—C7—S1121.70 (15)
C1—C2—C3119.6 (2)N1—C7—S1119.98 (14)
C1—C2—H2A120.2N2—C8—H8A109.5
C3—C2—H2A120.2N2—C8—H8B109.5
C4—C3—C2120.2 (3)H8A—C8—H8B109.5
C4—C3—H3119.9N2—C8—H8C109.5
C2—C3—H3119.9H8A—C8—H8C109.5
C5—C4—C3120.2 (2)H8B—C8—H8C109.5
C5—C4—H4119.9
C7—N1—C1—C2112.2 (2)C2—C1—C6—C50.1 (3)
C7—N1—C1—C670.3 (3)N1—C1—C6—C5177.57 (19)
C6—C1—C2—C30.1 (3)C4—C5—C6—C10.2 (3)
N1—C1—C2—C3177.7 (2)C8—N2—C7—N1179.8 (2)
C1—C2—C3—C40.1 (4)C8—N2—C7—S10.4 (3)
C2—C3—C4—C50.4 (4)C1—N1—C7—N21.9 (3)
C3—C4—C5—C60.4 (4)C1—N1—C7—S1177.91 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S1i0.81 (2)2.55 (2)3.351 (2)169 (2)
N2—H2···S1ii0.77 (2)2.78 (2)3.4229 (19)142 (2)
Symmetry codes: (i) x+1/2, y+5/2, z+1; (ii) x+1/2, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S1i0.81 (2)2.55 (2)3.351 (2)169 (2)
N2—H2···S1ii0.77 (2)2.78 (2)3.4229 (19)142 (2)
Symmetry codes: (i) x+1/2, y+5/2, z+1; (ii) x+1/2, y1/2, z+1/2.
 

Acknowledgements

The diffraction data collection was carried by Hai-lian Xiao in the New Materials & Function Coordination Chemistry Laboratory, Qingdao University of Science & Technology.

References

First citationBorisova, N. E., Reshetova, M. D. & Ustynyuk, Y. A. (2007). Chem. Rev. 107, 46–79.  Web of Science CrossRef PubMed CAS
First citationBruker (1997). SMART and SAINT. Bruker AXS, Inc., Madison, Wisconsin, USA.
First citationJi, B. M., Du, C. X., Zhu, Y. & Wang, Y. (2002). Chin. J. Struct. Chem. 21, 252–255.  CAS
First citationMadan, V. K. & Taneja, A. D. (1991). J. Indian Chem. Soc. 68, 162–163.  CAS
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationWenzel, M., Light, M. E., Davis, A. P. & Gale, P. A. (2011). Chem. Commun. 47, 7641–7643.  Web of Science CSD CrossRef CAS
First citationXu, L., Jian, F., Qin, Y., Yu, G. & Jiao, K. (2004). Chem. Res. Chin. Univ. 20, 305–307.  CAS

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ISSN: 2056-9890
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