1-(o-Tol­yl)thio­urea

Corrêa, R.S.; Ribeiro, L.; Ellena, J.; Estévez-Hernández, O.; Duque, J.

doi:10.1107/S1600536808024161

organic compounds

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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Pages o1670-o1671

doi:10.1107/S1600536808024161

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1-(o-Tolyl)thiourea

Rodrigo S. Corrêa,^a Leandro Ribeiro,^a Javier Ellena,^a Osvaldo Estévez-Hernández ^b and Julio Duque ^b ^*

^aGrupo de Cristalografía, Instituto de Física de São Carlos, Universidade de São Paulo, São Carlos, Brazil, and ^bDepartment of Structure Analysis, Institute of Materials, Zapata & G, University of Havana, Cuba
^*Correspondence e-mail: duque@imre.co.uh.cu

(Received 10 July 2008; accepted 29 July 2008; online 6 August 2008)

In the title compound, C₈H₁₀N₂S, the o-tolyl group and the thiourea core are planar. The mean planes of the two groups are almost perpendicular [82.19 (8)°]. The thiourea group is in the thioamide form, in which resonance is present. In the crystal structure, molecules are linked by intermolecular N—H⋯S hydrogen bonds, forming two infinite chains parallel to the (110) and (1 $[\overline{1}]$ 0) planes.

Related literature

For general background, see: Koketsu & Ishihara (2006 ); Struga et al. (2007 ). For related structures, see: Corrêa et al. (2006 ); Corrêa et al. (2008 ); Estévez-Hernández et al. (2008 ); Duque et al. (2008 ). For the synthesis, see: Otazo-Sánches et al. (2001 ). For related literature, see: Otazo et al. (2001 ); Ramadas et al. (1998 ).

Experimental

Crystal data

C₈H₁₀N₂S
M_r = 166.25
Monoclinic, C 2/c
a = 15.1323 (3) Å
b = 7.7965 (2) Å
c = 15.3222 (4) Å
β = 90.828 (2)°
V = 1807.61 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 294 K
0.31 × 0.22 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: gaussian (Coppens et al., 1965 ) T_min = 0.973, T_max = 0.991
6748 measured reflections
1914 independent reflections
1438 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.140
S = 1.03
1914 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

C1—N2	1.321 (2)
C1—N1	1.329 (2)
C1—S1	1.6868 (18)
C2—N1	1.435 (2)

N2—C1—N1	117.34 (16)
N2—C1—S1	121.63 (14)
N1—C1—S1	121.03 (13)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S1ⁱ	0.86	2.53	3.368 (2)	165
N2—H2B⋯S1ⁱⁱ	0.86	2.52	3.362 (2)	166
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ ; (ii) -x, -y+2, -z.

Data collection: COLLECT (Nonius, 2000 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808024161/fb2105sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808024161/fb2105Isup2.hkl

checkCIF report

Comment top

Thiourea itself as well as its derivatives are known to be biologically active (Koketsu & Ishihara, 2006). Their antimicrobial, cytotoxic and anti-HIV activities have been recently tested (Struga et al., 2007). Also, ortho-substituted aromatic thiourea derivatives have received special attention because of their fungicidal activity (Ramadas et al., 1998). The reaction of the furoyl isothiocyanate with o-toluidine in dry acetone yielded the title compound, N-(o-tolyl) thiourea, as a secondary product (Fig. 1).

The title molecule is present in the thioamide form and it is a typical N-monosubstituted thiourea derivative with usual geometric parameters. The C—S bond [1.687 (2) Å] shows the expected double-bond character. The short bond-lengths of the C1—N1 [1.329 (2) Å] and C1—N2 [1.321 (2) Å] indicate partial double bond character, similarly to other thiourea derivatives where electron delocalization in the N—C—S moiety is present (Corrêa et al., 2008; Estévez-Hernández et al., 2008, Duque et al., 2008). In addition, the values of the bond angles that are close to 120° also suggest the resonance effect.

As might be expected both the central thiourea fragment as well as the o-tolyl group are planar. The largest deviation from the least square plane through the seven atoms of the o-tolyl group occurs for the atom C2 [displacement = 0.0038 (15) Å], with a r.m.s. deviation of 0.0022 Å for all the carbons in the o-tolyl group. In the thiourea fragment, the largest displacement is for the atom C1 [0.001 (1) Å], with a r.m.s. deviation of 0.003 Å. The o-tolyl group is almost perpendicular to the plane formed by the thiourea molecule (82.19 (8)°).

Fig. 2 shows the arrangement of the molecules in the unit cell. In the crystal structure, the molecules are linked by N—H···S hydrogen bonds that stabilize the packing (Table 1). In the previous studies (Corrêa et al., 2006; Corrêa et al., 2008) have been reported the N—H···S interactions with the formation of the centrosymmetric dimers. In contrast to these structures, in the present structure these intermolecular interactions form two independent chains parallel to the (110) and (1–10) planes (Figure 3).

Related literature top

For general background, see: Koketsu & Ishihara (2006); Struga et al. (2007). For related structures, see: Corrêa et al. (2006); Corrêa et al. (2008); Estévez-Hernández et al. (2008); Duque et al. (2008). For the synthesis, see: Otazo-Sánches et al. (2001).

For related literature, see: Otazo et al. (2001); Ramadas et al. (1998).

Experimental top

The title compound was obtained as a secondary product during the synthesis of 1-(2-furoyl)-3-(o-tolyl) thiourea according to procedure described by Otazo-Sánchez et al. (2001) by converting furoyl chloride into furoyl isothiocyanate and then condensing with the appropriate 0-toluidine. The colourless prism-shaped single crystals were formed by slow evaporation from a methanol/acetonitrile (1:1) solution.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The title molecule with the atom-numbering scheme. The displacement ellipsoids are drawn at the 50% probability level and the H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Representation of the chains linked by N—H···S hydrogen bonds.
	Fig. 3. Crystal packing view along c axis showing the two independent chains.

1-(o-Tolyl)thiourea top

Crystal data top

C₈H₁₀N₂S	F(000) = 704
M_r = 166.25	D_x = 1.222 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 15611 reflections
a = 15.1323 (3) Å	θ = 2.9–26.7°
b = 7.7965 (2) Å	µ = 0.30 mm⁻¹
c = 15.3222 (4) Å	T = 294 K
β = 90.828 (2)°	Prism, colourless
V = 1807.61 (8) Å³	0.31 × 0.22 × 0.10 mm
Z = 8

Data collection top

Nonius KappaCCD diffractometer	1914 independent reflections
Radiation source: fine-focus sealed tube Enraf Nonius FR590	1438 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	R_int = 0.031
ϕ scans and ω scans winth κ offsets	θ_max = 26.8°, θ_min = 3.8°
Absorption correction: gaussian (Coppens et al., 1965)	h = −19→18
T_min = 0.973, T_max = 0.991	k = −9→9
6748 measured reflections	l = −19→19

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)] = 0.046	Hydrogen site location: difference Fourier map
wR(F²) = 0.140	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0896P)² + 0.2205P] where P = (F_o² + 2F_c²)/3
1914 reflections	(Δ/σ)_max < 0.001
101 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³
40 constraints

Crystal data top

C₈H₁₀N₂S	V = 1807.61 (8) Å³
M_r = 166.25	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 15.1323 (3) Å	µ = 0.30 mm⁻¹
b = 7.7965 (2) Å	T = 294 K
c = 15.3222 (4) Å	0.31 × 0.22 × 0.10 mm
β = 90.828 (2)°

Data collection top

Nonius KappaCCD diffractometer	1914 independent reflections
Absorption correction: gaussian (Coppens et al., 1965)	1438 reflections with I > 2σ(I)
T_min = 0.973, T_max = 0.991	R_int = 0.031
6748 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.140	H-atom parameters constrained
S = 1.03	Δρ_max = 0.19 e Å⁻³
1914 reflections	Δρ_min = −0.21 e Å⁻³
101 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
C1	0.11314 (11)	0.8287 (2)	0.06714 (12)	0.0577 (5)
C2	0.15409 (11)	0.6359 (3)	0.18736 (12)	0.0611 (5)
C3	0.12742 (14)	0.4692 (3)	0.18788 (14)	0.0740 (6)
C4	0.11722 (18)	0.3923 (3)	0.27051 (17)	0.0886 (7)
H4	0.0995	0.2783	0.2737	0.106*
C5	0.13277 (17)	0.4810 (4)	0.34545 (15)	0.0887 (7)
H5	0.1256	0.4269	0.399	0.106*
C6	0.15879 (16)	0.6486 (4)	0.34321 (15)	0.0884 (7)
H6	0.1691	0.7089	0.3947	0.106*
C7	0.16938 (15)	0.7262 (3)	0.26419 (14)	0.0769 (6)
H7	0.187	0.8404	0.2618	0.092*
C8	0.1108 (2)	0.3713 (4)	0.10584 (18)	0.1082 (9)
H8A	0.0882	0.2598	0.1197	0.162*
H8B	0.1651	0.3594	0.0748	0.162*
H8C	0.0685	0.4317	0.0701	0.162*
N1	0.16917 (10)	0.7203 (2)	0.10564 (10)	0.0665 (5)
H1	0.218	0.6992	0.0797	0.08*
N2	0.03568 (11)	0.8514 (3)	0.10408 (12)	0.0897 (7)
H2A	0.0232	0.797	0.1512	0.108*
H2B	−0.0023	0.9205	0.081	0.108*
S1	0.14045 (3)	0.93276 (6)	−0.02514 (3)	0.0663 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0496 (9)	0.0631 (10)	0.0607 (10)	0.0091 (8)	0.0069 (8)	0.0058 (8)
C2	0.0486 (9)	0.0738 (12)	0.0610 (11)	0.0136 (8)	0.0074 (8)	0.0143 (9)
C3	0.0718 (13)	0.0793 (14)	0.0711 (13)	0.0099 (11)	0.0082 (10)	0.0043 (10)
C4	0.0938 (16)	0.0817 (14)	0.0906 (17)	0.0062 (12)	0.0181 (14)	0.0225 (13)
C5	0.0963 (16)	0.1078 (18)	0.0624 (13)	0.0242 (15)	0.0148 (11)	0.0210 (13)
C6	0.0920 (16)	0.1113 (19)	0.0619 (13)	0.0199 (14)	0.0023 (11)	0.0010 (13)
C7	0.0741 (13)	0.0871 (14)	0.0696 (13)	0.0052 (11)	0.0053 (10)	0.0012 (11)
C8	0.130 (2)	0.1022 (18)	0.0930 (18)	−0.0140 (18)	0.0182 (17)	−0.0160 (16)
N1	0.0539 (8)	0.0834 (11)	0.0626 (9)	0.0202 (7)	0.0146 (7)	0.0205 (8)
N2	0.0616 (10)	0.1243 (16)	0.0838 (12)	0.0374 (10)	0.0250 (9)	0.0451 (12)
S1	0.0622 (4)	0.0697 (4)	0.0673 (4)	0.0189 (2)	0.0158 (2)	0.0183 (2)

Geometric parameters (Å, º) top

C1—N2	1.321 (2)	C5—H5	0.93
C1—N1	1.329 (2)	C6—C7	1.365 (3)
C1—S1	1.6868 (18)	C6—H6	0.93
C2—C3	1.361 (3)	C7—H7	0.93
C2—C7	1.388 (3)	C8—H8A	0.96
C2—N1	1.435 (2)	C8—H8B	0.96
C3—C4	1.411 (3)	C8—H8C	0.96
C3—C8	1.489 (3)	N1—H1	0.86
C4—C5	1.358 (4)	N2—H2A	0.86
C4—H4	0.93	N2—H2B	0.86
C5—C6	1.365 (4)

N2—C1—N1	117.34 (16)	C5—C6—H6	120.5
N2—C1—S1	121.63 (14)	C6—C7—C2	120.5 (2)
N1—C1—S1	121.03 (13)	C6—C7—H7	119.8
C3—C2—C7	121.68 (19)	C2—C7—H7	119.8
C3—C2—N1	119.57 (19)	C3—C8—H8A	109.5
C7—C2—N1	118.73 (19)	C3—C8—H8B	109.5
C2—C3—C4	116.6 (2)	H8A—C8—H8B	109.5
C2—C3—C8	122.1 (2)	C3—C8—H8C	109.5
C4—C3—C8	121.4 (2)	H8A—C8—H8C	109.5
C5—C4—C3	121.5 (2)	H8B—C8—H8C	109.5
C5—C4—H4	119.3	C1—N1—C2	124.75 (15)
C3—C4—H4	119.3	C1—N1—H1	117.6
C4—C5—C6	120.9 (2)	C2—N1—H1	117.6
C4—C5—H5	119.6	C1—N2—H2A	120
C6—C5—H5	119.6	C1—N2—H2B	120
C7—C6—C5	119.0 (2)	H2A—N2—H2B	120
C7—C6—H6	120.5

C7—C2—C3—C4	−0.8 (3)	C5—C6—C7—C2	−0.1 (3)
N1—C2—C3—C4	177.56 (18)	C3—C2—C7—C6	0.7 (3)
C7—C2—C3—C8	180.0 (2)	N1—C2—C7—C6	−177.68 (18)
N1—C2—C3—C8	−1.7 (3)	N2—C1—N1—C2	−4.6 (3)
C2—C3—C4—C5	0.4 (3)	S1—C1—N1—C2	175.28 (16)
C8—C3—C4—C5	179.6 (3)	C3—C2—N1—C1	101.4 (2)
C3—C4—C5—C6	0.1 (4)	C7—C2—N1—C1	−80.2 (3)
C4—C5—C6—C7	−0.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1ⁱ	0.86	2.53	3.368 (2)	165
N2—H2B···S1ⁱⁱ	0.86	2.52	3.362 (2)	166

Symmetry codes: (i) −x+1/2, −y+3/2, −z; (ii) −x, −y+2, −z.

Experimental details

Crystal data
Chemical formula	C₈H₁₀N₂S
M_r	166.25
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	294
a, b, c (Å)	15.1323 (3), 7.7965 (2), 15.3222 (4)
β (°)	90.828 (2)
V (Å³)	1807.61 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.31 × 0.22 × 0.10

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Gaussian (Coppens et al., 1965)
T_min, T_max	0.973, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	6748, 1914, 1438
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.634

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.140, 1.03
No. of reflections	1914
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.21

Computer programs: COLLECT (Nonius, 2000), SCALEPACK (Otwinowski & Minor, 1997), DENZO (Otwinowski & Minor, 1997) and SCALEPACK, SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

C1—N2	1.321 (2)	C1—S1	1.6868 (18)
C1—N1	1.329 (2)	C2—N1	1.435 (2)

N2—C1—N1	117.34 (16)	N1—C1—S1	121.03 (13)
N2—C1—S1	121.63 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1ⁱ	0.86	2.53	3.368 (2)	165
N2—H2B···S1ⁱⁱ	0.86	2.52	3.362 (2)	166

Symmetry codes: (i) −x+1/2, −y+3/2, −z; (ii) −x, −y+2, −z.

Acknowledgements

The authors are grateful for financial support from the Brazilian agencies CNPq, FAPESP and CAPES. RSC acknowledges the CNPq for a fellowship (Project 134576/2007–1).

References

Coppens, P., Leiserowitz, L. & Rabinovich, D. (1965). Acta Cryst. 18, 1035–1038. CrossRef CAS IUCr Journals Web of Science Google Scholar
Corrêa, R. S., Estévez-Hernández, O., Ellena, J. & Duque, J. (2008). Acta Cryst. E64, o1414. Web of Science CSD CrossRef IUCr Journals Google Scholar
Corrêa, R. S., Santana, S. A., Salloum, R., Silva, R. M. & Doriguetto, A. C. (2006). Acta Cryst. C62, o115–o117. Web of Science CSD CrossRef IUCr Journals Google Scholar
Duque, J., Estevez-Hernandez, O., Reguera, E., Corrêa, R. S. & Gutierrez Maria, P. Acta Cryst. E64, o1068. Google Scholar
Estévez-Hernández, O., Duque, J., Ellena, J. & Corrêa, R. S. (2008). Acta Cryst. E64, o1157. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Koketsu, M. & Ishihara, H. (2006). Curr. Org. Synth. 3, 439–455. Web of Science CrossRef CAS Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
Nonius (2000). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otazo, E., Pérez, L., Estévez, O., Rojas, S. & Alonso, J. (2001). J. Chem. Soc. Perkin Trans. 2, pp. 2211–2218. Google Scholar
Otazo-Sánchez, E., Pérez-Marín, L., Estévez-Hernández, O., Rojas-Lima, S. & Alonso-Chamorro, J. (2001). J. Chem. Soc. Perkin Trans. 2, pp. 2211–2218. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Ramadas, K., Suresh, G., Janarthanan, N. & Masilamani, S. (1998). Pestic. Sci. 52, 145–151. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Struga, M., Kossakowski, J., Kedzierska, E., Fidecka, S. & Stefanska, J. (2007). Chem. Pharm. Bull. 55, 796–799. Web of Science CrossRef PubMed CAS Google Scholar