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Acta Cryst. (2008). E64, o1670-o1671    [ doi:10.1107/S1600536808024161 ]

1-(o-Tolyl)thiourea

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

Abstract top

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.

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.

Refinement top

All the hydrogen atoms were located in the difference Fourier maps. Nevertheless, they were situated in the idealized positions and refined using the riding-hydrogen model. N—H = 0.86 Å, Caryl—H = 0.93 Å, Cmethyl= 0.96 Å. Uiso(H) = 1.2Ueq(N,Caryl) or Uiso(H) = 1.5Ueq(Cmethyl).

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
[Figure 1] 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.
[Figure 2] Fig. 2. Representation of the chains linked by N—H···S hydrogen bonds.
[Figure 3] Fig. 3. Crystal packing view along c axis showing the two independent chains.
1-(o-Tolyl)thiourea top
Crystal data top
C8H10N2SF000 = 704
Mr = 166.25Dx = 1.222 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 15611 reflections
a = 15.1323 (3) Åθ = 2.9–26.7º
b = 7.7965 (2) ŵ = 0.30 mm−1
c = 15.3222 (4) ÅT = 294 K
β = 90.828 (2)ºPrism, colourless
V = 1807.61 (8) Å30.31 × 0.22 × 0.10 mm
Z = 8
Data collection top
Nonius KappaCCD
diffractometer		1438 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube Enraf Nonius FR590Rint = 0.031
Monochromator: horizontally mounted graphite crystalθmax = 26.8º
φ scans and ω scans winth κ offsetsθmin = 3.8º
Absorption correction: gaussian
(Coppens et al., 1965)		h = −19→18
Tmin = 0.973, Tmax = 0.991k = −9→9
6748 measured reflectionsl = −19→19
1914 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.140  w = 1/[σ2(Fo2) + (0.0896P)2 + 0.2205P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
1914 reflectionsΔρmax = 0.19 e Å−3
101 parametersΔρmin = −0.21 e Å−3
40 constraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
C8H10N2SV = 1807.61 (8) Å3
Mr = 166.25Z = 8
Monoclinic, C2/cMo Kα
a = 15.1323 (3) ŵ = 0.30 mm−1
b = 7.7965 (2) ÅT = 294 K
c = 15.3222 (4) Å0.31 × 0.22 × 0.10 mm
β = 90.828 (2)º
Data collection top
Nonius KappaCCD
diffractometer		1914 independent reflections
Absorption correction: gaussian
(Coppens et al., 1965)		1438 reflections with I > 2σ(I)
Tmin = 0.973, Tmax = 0.991Rint = 0.031
6748 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.046101 parameters
wR(F2) = 0.140H-atom parameters constrained
S = 1.03Δρmax = 0.19 e Å−3
1914 reflectionsΔρmin = −0.21 e Å−3
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
C10.11314 (11)0.8287 (2)0.06714 (12)0.0577 (5)
C20.15409 (11)0.6359 (3)0.18736 (12)0.0611 (5)
C30.12742 (14)0.4692 (3)0.18788 (14)0.0740 (6)
C40.11722 (18)0.3923 (3)0.27051 (17)0.0886 (7)
H40.09950.27830.27370.106*
C50.13277 (17)0.4810 (4)0.34545 (15)0.0887 (7)
H50.12560.42690.3990.106*
C60.15879 (16)0.6486 (4)0.34321 (15)0.0884 (7)
H60.16910.70890.39470.106*
C70.16938 (15)0.7262 (3)0.26419 (14)0.0769 (6)
H70.1870.84040.26180.092*
C80.1108 (2)0.3713 (4)0.10584 (18)0.1082 (9)
H8A0.08820.25980.11970.162*
H8B0.16510.35940.07480.162*
H8C0.06850.43170.07010.162*
N10.16917 (10)0.7203 (2)0.10564 (10)0.0665 (5)
H10.2180.69920.07970.08*
N20.03568 (11)0.8514 (3)0.10408 (12)0.0897 (7)
H2A0.02320.7970.15120.108*
H2B−0.00230.92050.0810.108*
S10.14045 (3)0.93276 (6)−0.02514 (3)0.0663 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0496 (9)0.0631 (10)0.0607 (10)0.0091 (8)0.0069 (8)0.0058 (8)
C20.0486 (9)0.0738 (12)0.0610 (11)0.0136 (8)0.0074 (8)0.0143 (9)
C30.0718 (13)0.0793 (14)0.0711 (13)0.0099 (11)0.0082 (10)0.0043 (10)
C40.0938 (16)0.0817 (14)0.0906 (17)0.0062 (12)0.0181 (14)0.0225 (13)
C50.0963 (16)0.1078 (18)0.0624 (13)0.0242 (15)0.0148 (11)0.0210 (13)
C60.0920 (16)0.1113 (19)0.0619 (13)0.0199 (14)0.0023 (11)0.0010 (13)
C70.0741 (13)0.0871 (14)0.0696 (13)0.0052 (11)0.0053 (10)0.0012 (11)
C80.130 (2)0.1022 (18)0.0930 (18)−0.0140 (18)0.0182 (17)−0.0160 (16)
N10.0539 (8)0.0834 (11)0.0626 (9)0.0202 (7)0.0146 (7)0.0205 (8)
N20.0616 (10)0.1243 (16)0.0838 (12)0.0374 (10)0.0250 (9)0.0451 (12)
S10.0622 (4)0.0697 (4)0.0673 (4)0.0189 (2)0.0158 (2)0.0183 (2)
Geometric parameters (Å, °) top
C1—N21.321 (2)C5—H50.93
C1—N11.329 (2)C6—C71.365 (3)
C1—S11.6868 (18)C6—H60.93
C2—C31.361 (3)C7—H70.93
C2—C71.388 (3)C8—H8A0.96
C2—N11.435 (2)C8—H8B0.96
C3—C41.411 (3)C8—H8C0.96
C3—C81.489 (3)N1—H10.86
C4—C51.358 (4)N2—H2A0.86
C4—H40.93N2—H2B0.86
C5—C61.365 (4)
N2—C1—N1117.34 (16)C5—C6—H6120.5
N2—C1—S1121.63 (14)C6—C7—C2120.5 (2)
N1—C1—S1121.03 (13)C6—C7—H7119.8
C3—C2—C7121.68 (19)C2—C7—H7119.8
C3—C2—N1119.57 (19)C3—C8—H8A109.5
C7—C2—N1118.73 (19)C3—C8—H8B109.5
C2—C3—C4116.6 (2)H8A—C8—H8B109.5
C2—C3—C8122.1 (2)C3—C8—H8C109.5
C4—C3—C8121.4 (2)H8A—C8—H8C109.5
C5—C4—C3121.5 (2)H8B—C8—H8C109.5
C5—C4—H4119.3C1—N1—C2124.75 (15)
C3—C4—H4119.3C1—N1—H1117.6
C4—C5—C6120.9 (2)C2—N1—H1117.6
C4—C5—H5119.6C1—N2—H2A120
C6—C5—H5119.6C1—N2—H2B120
C7—C6—C5119.0 (2)H2A—N2—H2B120
C7—C6—H6120.5
C7—C2—C3—C4−0.8 (3)C5—C6—C7—C2−0.1 (3)
N1—C2—C3—C4177.56 (18)C3—C2—C7—C60.7 (3)
C7—C2—C3—C8180.0 (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—C50.4 (3)S1—C1—N1—C2175.28 (16)
C8—C3—C4—C5179.6 (3)C3—C2—N1—C1101.4 (2)
C3—C4—C5—C60.1 (4)C7—C2—N1—C1−80.2 (3)
C4—C5—C6—C7−0.2 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S1i0.862.533.368 (2)165
N2—H2B···S1ii0.862.523.362 (2)166
Symmetry codes: (i) −x+1/2, −y+3/2, −z; (ii) −x, −y+2, −z.
Table 1
Selected geometric parameters (Å, °) top
C1—N21.321 (2)C1—S11.6868 (18)
C1—N11.329 (2)C2—N11.435 (2)
N2—C1—N1117.34 (16)N1—C1—S1121.03 (13)
N2—C1—S1121.63 (14)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S1i0.862.533.368 (2)165
N2—H2B···S1ii0.862.523.362 (2)166
Symmetry codes: (i) −x+1/2, −y+3/2, −z; (ii) −x, −y+2, −z.
Acknowledgements top

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
References top

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