1-Methyl-3-phenyl­thio­urea

Su, H.

doi:10.1107/S1600536814007442

organic compounds

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Volume 70| Part 5| May 2014| Page o528

doi:10.1107/S1600536814007442

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1-Methyl-3-phenylthiourea

Hou-xiang Su ^a ^*

^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).

CCDC reference: 995308

Related literature

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

Crystal data

C₈H₁₀N₂S
M_r = 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)
R_int = 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
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: SAINT (Bruker 1997); data reduction: SAINT; 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.

Supporting information

CCDC reference: 995308

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814007442/kq2012sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814007442/kq2012Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814007442/kq2012Isup3.cml

checkCIF report

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 C═S 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.

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

	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.
	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

C₈H₁₀N₂S	F(000) = 704
M_r = 166.24	D_x = 1.234 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.348 (3) Å	Cell parameters from 1286 reflections
b = 8.6023 (13) Å	θ = 2.4–24.8°
c = 12.1672 (18) Å	µ = 0.30 mm⁻¹
β = 99.637 (3)°	T = 296 K
V = 1790.1 (5) Å³	Bar, colorless
Z = 8	0.25 × 0.23 × 0.20 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	R_int = 0.033
Radiation source: sealed tube	θ_max = 27.5°, θ_min = 2.4°
phi and ω scans	h = −22→21
5444 measured reflections	k = −8→11
2026 independent reflections	l = −15→15
1424 reflections with I > 2σ(I)

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)] = 0.041	Hydrogen site location: difference Fourier map
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0587P)² + 0.1272P] where P = (F_o² + 2F_c²)/3
2026 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₈H₁₀N₂S	V = 1790.1 (5) Å³
M_r = 166.24	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 17.348 (3) Å	µ = 0.30 mm⁻¹
b = 8.6023 (13) Å	T = 296 K
c = 12.1672 (18) Å	0.25 × 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 reflections	R_int = 0.033
2026 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.24 e Å⁻³
2026 reflections	Δρ_min = −0.24 e Å⁻³
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

	x	y	z	U_iso*/U_eq
S1	0.16423 (3)	1.19173 (6)	0.35515 (4)	0.04468 (19)
N1	0.29456 (9)	1.0463 (2)	0.43958 (15)	0.0467 (5)
N2	0.23002 (10)	0.9493 (2)	0.27416 (15)	0.0485 (5)
C1	0.35645 (10)	0.9351 (2)	0.45446 (17)	0.0401 (5)
C2	0.36233 (13)	0.8311 (3)	0.5403 (2)	0.0648 (7)
H2A	0.3251	0.8303	0.5871	0.078*
C3	0.42442 (15)	0.7264 (3)	0.5572 (3)	0.0814 (9)
H3	0.4287	0.6555	0.6156	0.098*
C4	0.47899 (13)	0.7275 (3)	0.4884 (3)	0.0683 (7)
H4	0.5202	0.6569	0.4997	0.082*
C5	0.47334 (12)	0.8309 (3)	0.4037 (2)	0.0646 (7)
H5	0.5109	0.8317	0.3573	0.077*
C6	0.41193 (11)	0.9357 (3)	0.38576 (18)	0.0510 (5)
H6	0.4082	1.0064	0.3273	0.061*
C7	0.23382 (9)	1.0531 (2)	0.35543 (15)	0.0353 (4)
C8	0.16755 (12)	0.9440 (3)	0.1781 (2)	0.0685 (7)
H8A	0.1740	1.0278	0.1284	0.103*
H8B	0.1180	0.9540	0.2026	0.103*
H8C	0.1695	0.8467	0.1401	0.103*
H1	0.2993 (12)	1.117 (3)	0.4843 (19)	0.054 (7)*
H2	0.2646 (12)	0.893 (3)	0.2769 (18)	0.052 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0346 (3)	0.0467 (3)	0.0524 (3)	0.0114 (2)	0.0062 (2)	0.0000 (2)
N1	0.0401 (9)	0.0497 (11)	0.0462 (11)	0.0157 (8)	−0.0043 (8)	−0.0147 (9)
N2	0.0365 (9)	0.0573 (12)	0.0482 (11)	0.0134 (8)	−0.0034 (8)	−0.0132 (9)
C1	0.0293 (8)	0.0418 (11)	0.0457 (11)	0.0061 (8)	−0.0044 (8)	−0.0085 (9)
C2	0.0512 (13)	0.0680 (17)	0.0758 (17)	0.0096 (11)	0.0123 (12)	0.0206 (13)
C3	0.0690 (17)	0.0612 (18)	0.109 (2)	0.0133 (14)	0.0015 (16)	0.0307 (16)
C4	0.0427 (12)	0.0587 (16)	0.097 (2)	0.0177 (11)	−0.0081 (13)	−0.0096 (15)
C5	0.0364 (10)	0.090 (2)	0.0637 (16)	0.0163 (11)	−0.0007 (10)	−0.0205 (14)
C6	0.0397 (10)	0.0647 (15)	0.0465 (12)	0.0101 (10)	0.0009 (9)	−0.0033 (11)
C7	0.0298 (9)	0.0394 (11)	0.0373 (10)	0.0024 (7)	0.0075 (8)	0.0004 (9)
C8	0.0504 (12)	0.093 (2)	0.0555 (14)	0.0138 (12)	−0.0108 (11)	−0.0244 (14)

Geometric parameters (Å, º) top

S1—C7	1.6964 (17)	C3—C4	1.365 (4)
N1—C7	1.342 (2)	C3—H3	0.9300
N1—C1	1.427 (2)	C4—C5	1.353 (4)
N1—H1	0.81 (2)	C4—H4	0.9300
N2—C7	1.326 (2)	C5—C6	1.384 (3)
N2—C8	1.455 (3)	C5—H5	0.9300
N2—H2	0.77 (2)	C6—H6	0.9300
C1—C2	1.366 (3)	C8—H8A	0.9600
C1—C6	1.376 (3)	C8—H8B	0.9600
C2—C3	1.393 (3)	C8—H8C	0.9600
C2—H2A	0.9300

C7—N1—C1	127.17 (17)	C3—C4—H4	119.9
C7—N1—H1	117.4 (16)	C4—C5—C6	120.2 (2)
C1—N1—H1	115.2 (16)	C4—C5—H5	119.9
C7—N2—C8	123.87 (18)	C6—C5—H5	119.9
C7—N2—H2	117.0 (17)	C1—C6—C5	120.0 (2)
C8—N2—H2	119.0 (17)	C1—C6—H6	120.0
C2—C1—C6	119.74 (18)	C5—C6—H6	120.0
C2—C1—N1	119.64 (18)	N2—C7—N1	118.32 (17)
C6—C1—N1	120.57 (18)	N2—C7—S1	121.70 (15)
C1—C2—C3	119.6 (2)	N1—C7—S1	119.98 (14)
C1—C2—H2A	120.2	N2—C8—H8A	109.5
C3—C2—H2A	120.2	N2—C8—H8B	109.5
C4—C3—C2	120.2 (3)	H8A—C8—H8B	109.5
C4—C3—H3	119.9	N2—C8—H8C	109.5
C2—C3—H3	119.9	H8A—C8—H8C	109.5
C5—C4—C3	120.2 (2)	H8B—C8—H8C	109.5
C5—C4—H4	119.9

C7—N1—C1—C2	−112.2 (2)	C2—C1—C6—C5	0.1 (3)
C7—N1—C1—C6	70.3 (3)	N1—C1—C6—C5	177.57 (19)
C6—C1—C2—C3	−0.1 (3)	C4—C5—C6—C1	0.2 (3)
N1—C1—C2—C3	−177.7 (2)	C8—N2—C7—N1	−179.8 (2)
C1—C2—C3—C4	−0.1 (4)	C8—N2—C7—S1	0.4 (3)
C2—C3—C4—C5	0.4 (4)	C1—N1—C7—N2	−1.9 (3)
C3—C4—C5—C6	−0.4 (4)	C1—N1—C7—S1	177.91 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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+1/2, −y+5/2, −z+1; (ii) −x+1/2, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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+1/2, −y+5/2, −z+1; (ii) −x+1/2, y−1/2, −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

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