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Acta Cryst. (2009). E65, o961    [ doi:10.1107/S1600536809011234 ]

5-(2-Methylphenyl)-1,3,4-thiadiazol-2-amine

Y. Wang, X.-J. Kong, R. Wan, F. Han and P. Wang

Abstract top

The asymmetric unit of the title compound, C9H9N3S, contains two crystallographically independent molecules, in which the thiadiazole and tolyl rings are oriented at dihedral angles of 32.25 (3) and 74.50 (3)°. An intramolecular C-H...S interaction results in the formation of a five-membered ring. In the crystal structure, intermolecular N-H...N hydrogen bonds link the molecules into chains along the a axis. A [pi]-[pi] contact between the thiadiazole rings [centroid-centroid distance = 3.910 (3) Å] may further stabilize the structure. There is also a weak C-H...[pi] interaction.

Comment top

1,3,4-Thiadiazole derivatives represent an interesting class of compounds possessing broad spectrum biological activities (Nakagawa et al., 1996; Wang et al., 1999). These compounds are known to exhibit diverse biological effects, such as insecticidal and fungicidal activities (Wang et al., 1999). We are focused our synthetic and structural studies on 1,3,4 -thiadiazole derivatives and we have published the structure of 5-m -tolyl-1,3,4-thiadiazol-2-ylamine (Han et al., 2007). We report herein the crystal structure of the title compound.

The asymmetric unit of the title compound contains two crystallographically independent molecules (Fig. 1), in which the bond lengths (Allen et al., 1987) and angles are generally within normal ranges. Rings A (C2A-C7A), B (S1A/N1A/N2A/C8A/C9A) and C (C2B-C7B), D (S1B/N1B/N2B/C8B/C9B) are, of course, planar, and they are oriented at dihedral angles of A/B = 32.25 (3) and C/D = 74.50 (3) °. The intramolecular C-H···S interaction (Table 1) results in the formation of a five-membered ring E (S1A/C6A-C8A/H6A) adopting envelope conformation with S1A atom displaced by 0.813 (3) Å from the plane of the other ring atoms.

In the crystal structure, intra- and intermolecular N-H···N hydrogen bonds (Table 1) link the molecules into chains along the a axis (Fig. 2), in which they may be effective in the stabilization of the structure. The π-π contact between the thiadiazole rings, Cg1—Cg2i [symmetry code: (i) x, 1 + y, -1 + z, where Cg1 and Cg2 are centroids of the rings B (S1A/N1A/N2A/C8A/C9A) and D (S1B/N1B/N2B/C8B/C9B), respectively] may further stabilize the structure, with centroid-centroid distance of 3.910 (3) Å. There also exists a weak C—H···π interaction (Table 1).

Related literature top

For general background, see: Nakagawa et al. (1996); Wang et al. (1999). For a related structure, see: Han et al. (2007). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, 3-methyl-benzoic acid (5 mmol) and thiosemicarbazide (5 mmol) were added in toluene (50 ml), and kept in the oil bath at 363 K for 6 h. After cooling, the crude product precipitated and was filted. Crystals suitable for X-ray analysis were obtained by slow evaporation of an acetone solution.

Refinement top

H atoms were positioned geometrically, with N-H = 0.86 Å (for NH2) and C-H = 0.93 and 0.96 Å for aromatic and methyl H, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,N), where x = 1.5 for methyl H and x = 1.2 for all other H atoms.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines.
[Figure 2] Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.
5-(2-Methylphenyl)-1,3,4-thiadiazol-2-amine top
Crystal data top
C9H9N3SF(000) = 400
Mr = 191.26Dx = 1.363 Mg m−3
Monoclinic, P21Melting point: 541 K
Hall symbol: P 2ybMo Kα radiation, λ = 0.71073 Å
a = 10.792 (2) ÅCell parameters from 25 reflections
b = 7.3400 (15) Åθ = 10–13°
c = 11.831 (2) ŵ = 0.30 mm−1
β = 96.15 (3)°T = 294 K
V = 931.8 (3) Å3Block, colorless
Z = 40.20 × 0.10 × 0.10 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		1620 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.0000
graphiteθmax = 27.0°, θmin = 1.7°
ω/2θ scansh = −13→13
Absorption correction: ψ scan
(North et al., 1968)		k = 0→9
Tmin = 0.942, Tmax = 0.971l = 0→15
2190 measured reflections3 standard reflections every 120 min
2190 independent reflections intensity decay: 1%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.162 w = 1/[σ2(Fo2) + (0.1P)2 + 0.06P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
2190 reflectionsΔρmax = 0.29 e Å−3
237 parametersΔρmin = −0.27 e Å−3
1 restraintAbsolute structure: Flack (1983), 113 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.04 (18)
Crystal data top
C9H9N3SV = 931.8 (3) Å3
Mr = 191.26Z = 4
Monoclinic, P21Mo Kα radiation
a = 10.792 (2) ŵ = 0.30 mm−1
b = 7.3400 (15) ÅT = 294 K
c = 11.831 (2) Å0.20 × 0.10 × 0.10 mm
β = 96.15 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		1620 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.0000
Tmin = 0.942, Tmax = 0.971θmax = 27.0°
2190 measured reflections3 standard reflections every 120 min
2190 independent reflections intensity decay: 1%
Refinement top
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.162Δρmax = 0.29 e Å−3
S = 1.00Δρmin = −0.27 e Å−3
2190 reflectionsAbsolute structure: Flack (1983), 113 Friedel pairs
237 parametersFlack parameter: 0.04 (18)
1 restraint
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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S1A0.87687 (12)0.61482 (19)0.83012 (11)0.0525 (4)
N1A0.6530 (4)0.6359 (8)0.8777 (4)0.0504 (12)
N2A0.7123 (4)0.7860 (7)0.9302 (4)0.0506 (12)
N3A0.9083 (4)0.9167 (8)0.9573 (4)0.0572 (13)
H3A0.88271.00190.99900.069*
H3B0.98500.91350.94390.069*
C1A0.4713 (6)0.4830 (15)0.6920 (7)0.102 (3)
H1B0.40320.44670.63780.153*
H1C0.50460.59670.66880.153*
H1D0.44220.49700.76540.153*
C2A0.5735 (6)0.3366 (11)0.6984 (5)0.0719 (19)
C3A0.5524 (9)0.1754 (12)0.6397 (6)0.089 (3)
H3C0.47480.15410.59970.107*
C4A0.6461 (11)0.0427 (13)0.6393 (7)0.101 (3)
H4A0.6297−0.06650.60080.121*
C5A0.7622 (10)0.0745 (13)0.6961 (6)0.099 (3)
H5A0.8256−0.01090.69430.118*
C6A0.7826 (8)0.2317 (11)0.7545 (5)0.078 (2)
H6A0.86050.25060.79430.094*
C7A0.6914 (6)0.3683 (10)0.7579 (4)0.0584 (15)
C8A0.7246 (5)0.5356 (9)0.8216 (4)0.0498 (14)
C9A0.8294 (5)0.7902 (9)0.9137 (4)0.0480 (13)
S1B0.37988 (11)0.8934 (2)0.83030 (11)0.0573 (5)
N1B0.1506 (4)0.8716 (9)0.8594 (4)0.0568 (13)
N2B0.2089 (4)0.7424 (9)0.9293 (4)0.0584 (13)
N3B0.4089 (4)0.6193 (10)0.9831 (4)0.0746 (18)
H6B0.38160.54271.02950.090*
H6C0.48700.62260.97450.090*
C1B0.2175 (8)0.8875 (11)0.5560 (5)0.082 (2)
H10A0.20770.88890.47440.124*
H10B0.16310.79730.58270.124*
H10C0.30230.85860.58290.124*
C2B0.1846 (5)1.0742 (9)0.6006 (4)0.0532 (13)
C3B0.1501 (6)1.2157 (11)0.5268 (5)0.0688 (17)
H12A0.14771.19660.44890.083*
C4B0.1192 (5)1.3853 (10)0.5666 (5)0.0660 (16)
H13A0.09601.47830.51520.079*
C5B0.1226 (6)1.4175 (13)0.6825 (6)0.076 (2)
H14A0.10141.53120.70930.092*
C6B0.1574 (6)1.2795 (9)0.7564 (5)0.0616 (16)
H15A0.16161.30120.83420.074*
C7B0.1866 (4)1.1078 (9)0.7184 (4)0.0466 (12)
C8B0.2252 (5)0.9641 (9)0.8013 (4)0.0469 (13)
C9B0.3289 (5)0.7347 (9)0.9235 (4)0.0496 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S1A0.0373 (7)0.0732 (9)0.0484 (7)0.0080 (7)0.0115 (5)−0.0080 (7)
N1A0.040 (2)0.066 (3)0.048 (2)−0.007 (2)0.0155 (18)−0.010 (2)
N2A0.038 (2)0.065 (3)0.051 (3)−0.005 (2)0.012 (2)−0.018 (2)
N3A0.039 (2)0.075 (3)0.060 (3)0.002 (3)0.014 (2)−0.021 (3)
C1A0.057 (4)0.148 (8)0.098 (5)−0.003 (5)−0.004 (4)−0.041 (6)
C2A0.063 (4)0.097 (5)0.060 (3)−0.016 (4)0.022 (3)−0.019 (4)
C3A0.106 (6)0.094 (6)0.072 (5)−0.041 (5)0.031 (4)−0.025 (4)
C4A0.165 (9)0.081 (5)0.062 (4)−0.044 (6)0.042 (6)−0.003 (4)
C5A0.159 (9)0.086 (5)0.051 (4)0.022 (6)0.016 (5)0.003 (4)
C6A0.104 (5)0.083 (5)0.048 (3)0.013 (4)0.008 (3)0.007 (4)
C7A0.061 (3)0.076 (4)0.039 (3)−0.005 (3)0.015 (2)0.006 (3)
C8A0.039 (3)0.078 (4)0.032 (2)−0.006 (3)0.002 (2)0.001 (3)
C9A0.039 (3)0.069 (3)0.036 (2)0.003 (3)0.007 (2)−0.001 (3)
S1B0.0337 (7)0.0842 (11)0.0549 (8)−0.0021 (8)0.0086 (6)0.0203 (9)
N1B0.038 (2)0.086 (4)0.048 (2)0.002 (3)0.0128 (18)0.018 (3)
N2B0.036 (2)0.089 (4)0.053 (3)0.000 (3)0.017 (2)0.013 (3)
N3B0.035 (2)0.115 (5)0.075 (3)0.013 (3)0.012 (2)0.047 (4)
C1B0.114 (6)0.085 (5)0.047 (3)−0.002 (5)0.004 (3)−0.023 (4)
C2B0.053 (3)0.066 (3)0.040 (2)−0.011 (3)0.002 (2)−0.005 (3)
C3B0.073 (4)0.092 (5)0.041 (3)−0.014 (4)0.002 (3)0.005 (3)
C4B0.053 (3)0.081 (4)0.065 (4)0.005 (3)0.009 (3)0.021 (4)
C5B0.071 (4)0.091 (5)0.071 (4)0.005 (4)0.029 (3)0.000 (4)
C6B0.064 (4)0.072 (4)0.052 (3)0.014 (3)0.023 (3)0.000 (3)
C7B0.037 (2)0.062 (3)0.041 (3)−0.008 (3)0.006 (2)0.005 (3)
C8B0.037 (3)0.066 (3)0.039 (3)−0.006 (3)0.010 (2)−0.001 (3)
C9B0.037 (3)0.073 (4)0.040 (3)−0.002 (3)0.012 (2)0.010 (3)
Geometric parameters (Å, °) top
S1A—C9A1.734 (6)S1B—C9B1.733 (6)
S1A—C8A1.736 (5)S1B—C8B1.747 (5)
N1A—C8A1.300 (7)N1B—C8B1.304 (7)
N1A—N2A1.387 (7)N1B—N2B1.366 (8)
N2A—C9A1.299 (6)N2B—C9B1.306 (6)
N3A—C9A1.326 (7)N3B—C9B1.352 (8)
N3A—H3A0.8600N3B—H6B0.8600
N3A—H3B0.8600N3B—H6C0.8600
C1A—C2A1.536 (11)C1B—C2B1.524 (9)
C1A—H1B0.9600C1B—H10A0.9600
C1A—H1C0.9600C1B—H10B0.9600
C1A—H1D0.9600C1B—H10C0.9600
C2A—C3A1.379 (10)C2B—C3B1.382 (9)
C2A—C7A1.406 (9)C2B—C7B1.413 (7)
C3A—C4A1.404 (13)C3B—C4B1.384 (10)
C3A—H3C0.9300C3B—H12A0.9300
C4A—C5A1.377 (12)C4B—C5B1.388 (9)
C4A—H4A0.9300C4B—H13A0.9300
C5A—C6A1.351 (12)C5B—C6B1.365 (10)
C5A—H5A0.9300C5B—H14A0.9300
C6A—C7A1.408 (10)C6B—C7B1.386 (8)
C6A—H6A0.9300C6B—H15A0.9300
C7A—C8A1.465 (9)C7B—C8B1.470 (8)
C9A—S1A—C8A86.9 (3)C9B—S1B—C8B87.9 (3)
C8A—N1A—N2A114.1 (4)C8B—N1B—N2B114.2 (4)
C9A—N2A—N1A111.2 (5)C9B—N2B—N1B113.2 (5)
C9A—N3A—H3A120.0C9B—N3B—H6B120.0
C9A—N3A—H3B120.0C9B—N3B—H6C120.0
H3A—N3A—H3B120.0H6B—N3B—H6C120.0
C2A—C1A—H1B109.5C2B—C1B—H10A109.5
C2A—C1A—H1C109.5C2B—C1B—H10B109.5
H1B—C1A—H1C109.5H10A—C1B—H10B109.5
C2A—C1A—H1D109.5C2B—C1B—H10C109.5
H1B—C1A—H1D109.5H10A—C1B—H10C109.5
H1C—C1A—H1D109.5H10B—C1B—H10C109.5
C3A—C2A—C7A119.1 (8)C3B—C2B—C7B117.8 (6)
C3A—C2A—C1A119.8 (7)C3B—C2B—C1B121.0 (5)
C7A—C2A—C1A121.0 (6)C7B—C2B—C1B121.2 (5)
C2A—C3A—C4A121.1 (8)C2B—C3B—C4B121.3 (6)
C2A—C3A—H3C119.5C2B—C3B—H12A119.3
C4A—C3A—H3C119.5C4B—C3B—H12A119.3
C5A—C4A—C3A119.9 (8)C3B—C4B—C5B120.5 (7)
C5A—C4A—H4A120.0C3B—C4B—H13A119.8
C3A—C4A—H4A120.0C5B—C4B—H13A119.8
C6A—C5A—C4A119.0 (9)C6B—C5B—C4B118.9 (7)
C6A—C5A—H5A120.5C6B—C5B—H14A120.5
C4A—C5A—H5A120.5C4B—C5B—H14A120.5
C5A—C6A—C7A123.2 (8)C5B—C6B—C7B121.5 (5)
C5A—C6A—H6A118.4C5B—C6B—H15A119.2
C7A—C6A—H6A118.4C7B—C6B—H15A119.2
C2A—C7A—C6A117.7 (7)C6B—C7B—C2B119.9 (5)
C2A—C7A—C8A123.6 (6)C6B—C7B—C8B119.6 (5)
C6A—C7A—C8A118.6 (6)C2B—C7B—C8B120.4 (6)
N1A—C8A—C7A127.7 (5)N1B—C8B—C7B125.4 (5)
N1A—C8A—S1A113.0 (5)N1B—C8B—S1B111.9 (4)
C7A—C8A—S1A119.2 (4)C7B—C8B—S1B122.7 (4)
N2A—C9A—N3A123.5 (5)N2B—C9B—N3B125.5 (5)
N2A—C9A—S1A114.8 (5)N2B—C9B—S1B112.9 (4)
N3A—C9A—S1A121.7 (4)N3B—C9B—S1B121.6 (4)
C8A—N1A—N2A—C9A−1.8 (7)C8B—N1B—N2B—C9B−0.8 (8)
C7A—C2A—C3A—C4A0.4 (10)C7B—C2B—C3B—C4B0.3 (9)
C1A—C2A—C3A—C4A176.9 (7)C1B—C2B—C3B—C4B179.5 (6)
C2A—C3A—C4A—C5A−1.5 (11)C2B—C3B—C4B—C5B0.3 (10)
C3A—C4A—C5A—C6A2.1 (11)C3B—C4B—C5B—C6B0.3 (10)
C4A—C5A—C6A—C7A−1.8 (11)C4B—C5B—C6B—C7B−1.4 (10)
C3A—C2A—C7A—C6A−0.1 (9)C5B—C6B—C7B—C2B2.0 (9)
C1A—C2A—C7A—C6A−176.4 (6)C5B—C6B—C7B—C8B179.2 (5)
C3A—C2A—C7A—C8A179.1 (6)C3B—C2B—C7B—C6B−1.5 (8)
C1A—C2A—C7A—C8A2.7 (9)C1B—C2B—C7B—C6B179.4 (6)
C5A—C6A—C7A—C2A0.8 (10)C3B—C2B—C7B—C8B−178.6 (5)
C5A—C6A—C7A—C8A−178.4 (6)C1B—C2B—C7B—C8B2.2 (8)
N2A—N1A—C8A—C7A179.5 (5)N2B—N1B—C8B—C7B178.6 (6)
N2A—N1A—C8A—S1A1.3 (6)N2B—N1B—C8B—S1B0.3 (7)
C2A—C7A—C8A—N1A34.2 (9)C6B—C7B—C8B—N1B77.1 (8)
C6A—C7A—C8A—N1A−146.6 (6)C2B—C7B—C8B—N1B−105.7 (7)
C2A—C7A—C8A—S1A−147.7 (5)C6B—C7B—C8B—S1B−104.7 (6)
C6A—C7A—C8A—S1A31.4 (7)C2B—C7B—C8B—S1B72.5 (7)
C9A—S1A—C8A—N1A−0.4 (5)C9B—S1B—C8B—N1B0.2 (5)
C9A—S1A—C8A—C7A−178.7 (5)C9B—S1B—C8B—C7B−178.2 (5)
N1A—N2A—C9A—N3A−178.1 (5)N1B—N2B—C9B—N3B−179.8 (6)
N1A—N2A—C9A—S1A1.4 (6)N1B—N2B—C9B—S1B1.0 (7)
C8A—S1A—C9A—N2A−0.6 (5)C8B—S1B—C9B—N2B−0.7 (5)
C8A—S1A—C9A—N3A178.9 (5)C8B—S1B—C9B—N3B−179.9 (6)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3A—H3A···N2Bi0.862.233.079 (8)167
N3A—H3B···N1Bii0.862.162.990 (6)162
N3B—H6B···N2Aiii0.862.223.006 (8)153
N3B—H6C···N1A0.862.233.035 (6)156
C6A—H6A···S1A0.932.713.090 (8)105
C1B—H10A···Cg3iv0.962.893.623 (3)134
Symmetry codes: (i) −x+1, y+1/2, −z+2; (ii) x+1, y, z; (iii) −x+1, y−1/2, −z+2; (iv) x, y−1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3A—H3A···N2Bi0.862.233.079 (8)167
N3A—H3B···N1Bii0.862.162.990 (6)162
N3B—H6B···N2Aiii0.862.223.006 (8)153
N3B—H6C···N1A0.862.233.035 (6)156
C6A—H6A···S1A0.932.713.090 (8)105
C1B—H10A···Cg3iv0.962.893.623 (3)134
Symmetry codes: (i) −x+1, y+1/2, −z+2; (ii) x+1, y, z; (iii) −x+1, y−1/2, −z+2; (iv) x, y−1, z.
Acknowledgements top

The authors thank Professor Hua-qin Wang of the Analysis Centre, Nanjing University, for carrying out the X-ray crystallographic analysis.

references
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