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Acta Cryst. (2009). E65, o2401    [ doi:10.1107/S1600536809035569 ]

N-(3,4-Dichlorophenyl)thiourea

H.-B. Shi, W.-X. Hu and Y.-F. Lin

Abstract top

In the title compound, C7H6Cl2N2S, the benzene ring and the mean plane of the thiourea fragment [-N-C(=S)-N] make a dihedral angle of 66.77 (3)°. Intermolecular N-H...S and N-H...Cl hydrogen bonds link the molecules into a three-dimensional network.

Comment top

Thiazoles and their derivatives are found to be associated with various biological activities such as antibacterial, antifungal, anti-inflammatory activities(Holla et al., 2003).The title compound, N-(3,4-dichlorophenyl)thiourea(I),is an important intermediate in the synthesis of thiazole and their derivatives. In our work, we present its crystal structure. In Fig.1, the benzene ring of (I) is twisted out ofthe mean plane through the –N7—C8(=S9)—N10 group by a diherdral angle of 66.77 (3)°. Weak intermolecular N—H···S and N—H···Cl hydrogen bonds (Table 1) link the molecules into a three-dimensional network.

Related literature top

For the synthesis of the title compound, see: Liu et al. (1994). For details of the biological activities of thiazole and its derivatives, see: Holla et al. (2003).

Experimental top

The title compound was obtained by refluxing 3,4-dichloroaniline(48.6 g, 0.3 mol), 36% aqueous HCl(30.4 g,0.3 mol) and ammonium thiocyanate(22.8 g, 0.3 mol) in water for 7 hr, then a white precipitate was observed and filtered. The solid was recrystallized from alcohol to give the pure product. This was dissolved in THF, and the solution evaporated gradually at room temperature to afford single crystals of (I).(m.p. 489–490 K). MS(m/z,%): 220 (M+, 90), 187 (15), 178 (16), 161 (98), 126 (7), 99 (10), 74 (8), 60 (55).

Refinement top

Atoms H7X, H10X and H10Y were located in difference Fourier maps and refined isotropically with the N—H bond restraint of 0.87 (2) Å. Other H atoms were placed in calculated positions with C—H = 0.93 Å, and refined in riding mode, with Uiso(H) = 1.2 Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of (I), shown with 30% probability displacement ellipsoids.
[Figure 2] Fig. 2. N—H···S and N—H···Cl interactions (dotted line) in the title compound.
N-(3,4-Dichlorophenyl)thiourea top
Crystal data top
C7H6Cl2N2SZ = 2
Mr = 221.10F(000) = 224
Triclinic, P1Dx = 1.607 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.8168 (19) ÅCell parameters from 843 reflections
b = 8.489 (3) Åθ = 2.5–27.0°
c = 9.771 (3) ŵ = 0.88 mm−1
α = 107.042 (4)°T = 291 K
β = 94.468 (4)°Prism, orange
γ = 94.778 (4)°0.15 × 0.10 × 0.08 mm
V = 457.0 (3) Å3
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		1562 independent reflections
Radiation source: fine-focus sealed tube1410 reflections with I > 2σ(I)
graphiteRint = 0.062
φ and ω scansθmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −6→3
Tmin = 0.879, Tmax = 0.933k = −9→10
1882 measured reflectionsl = −11→11
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)] = 0.084H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.236 w = 1/[σ2(Fo2) + (0.1955P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max < 0.001
1562 reflectionsΔρmax = 0.75 e Å−3
122 parametersΔρmin = −0.76 e Å−3
3 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.13 (4)
Crystal data top
C7H6Cl2N2Sγ = 94.778 (4)°
Mr = 221.10V = 457.0 (3) Å3
Triclinic, P1Z = 2
a = 5.8168 (19) ÅMo Kα radiation
b = 8.489 (3) ŵ = 0.88 mm−1
c = 9.771 (3) ÅT = 291 K
α = 107.042 (4)°0.15 × 0.10 × 0.08 mm
β = 94.468 (4)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		1562 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1410 reflections with I > 2σ(I)
Tmin = 0.879, Tmax = 0.933Rint = 0.062
1882 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.084H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.236Δρmax = 0.75 e Å−3
S = 1.10Δρmin = −0.76 e Å−3
1562 reflectionsAbsolute structure: ?
122 parametersFlack parameter: ?
3 restraintsRogers parameter: ?
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
Cl10.19736 (17)0.43998 (14)0.66939 (11)0.0560 (6)
Cl2−0.27770 (17)0.21189 (14)0.62155 (11)0.0565 (6)
C10.1662 (6)0.1685 (4)0.2584 (4)0.0365 (9)
C20.2383 (6)0.2836 (4)0.3921 (4)0.0398 (9)
H20.37770.35120.40620.048*
C30.1023 (6)0.2971 (4)0.5034 (4)0.0374 (9)
C4−0.1046 (6)0.1948 (4)0.4830 (4)0.0388 (9)
C5−0.1748 (6)0.0795 (5)0.3507 (4)0.0480 (11)
H5−0.31270.01030.33720.058*
C6−0.0398 (7)0.0669 (4)0.2380 (4)0.0446 (9)
H6−0.0879−0.01010.14850.054*
N70.3073 (6)0.1521 (3)0.1444 (3)0.0424 (9)
H7X0.371 (7)0.061 (4)0.113 (5)0.071 (15)*
C80.3732 (6)0.2709 (4)0.0853 (4)0.0353 (8)
S90.58001 (18)0.24215 (10)−0.03037 (11)0.0493 (6)
N100.2718 (6)0.4075 (4)0.1191 (4)0.0508 (10)
H10X0.308 (7)0.486 (5)0.083 (5)0.055 (12)*
H10Y0.159 (5)0.422 (6)0.173 (4)0.054 (12)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0546 (8)0.0620 (8)0.0427 (7)0.0057 (5)0.0146 (5)0.0001 (5)
Cl20.0577 (8)0.0636 (9)0.0549 (8)0.0087 (5)0.0328 (5)0.0209 (6)
C10.0534 (19)0.0253 (16)0.0377 (19)0.0123 (14)0.0214 (15)0.0137 (14)
C20.0404 (18)0.0334 (18)0.050 (2)0.0026 (14)0.0167 (15)0.0160 (16)
C30.0453 (19)0.0341 (18)0.0375 (19)0.0122 (14)0.0132 (14)0.0139 (15)
C40.0433 (19)0.0396 (19)0.042 (2)0.0106 (15)0.0200 (15)0.0195 (16)
C50.048 (2)0.043 (2)0.051 (2)−0.0046 (16)0.0107 (18)0.0127 (18)
C60.060 (2)0.0344 (19)0.039 (2)0.0023 (15)0.0123 (16)0.0087 (15)
N70.064 (2)0.0251 (15)0.0460 (18)0.0146 (13)0.0319 (14)0.0136 (13)
C80.0489 (19)0.0257 (16)0.0338 (18)0.0059 (13)0.0167 (14)0.0091 (13)
S90.0722 (9)0.0288 (7)0.0572 (8)0.0151 (5)0.0417 (6)0.0175 (5)
N100.072 (2)0.0312 (17)0.064 (2)0.0175 (15)0.0434 (17)0.0239 (15)
Geometric parameters (Å, °) top
Cl1—C31.733 (4)C5—C61.386 (5)
Cl2—C41.729 (4)C5—H50.9300
C1—C61.382 (5)C6—H60.9300
C1—C21.391 (5)N7—C81.345 (4)
C1—N71.416 (5)N7—H7X0.87 (2)
C2—C31.378 (6)C8—N101.312 (5)
C2—H20.9300C8—S91.698 (4)
C3—C41.389 (5)N10—H10X0.86 (3)
C4—C51.380 (6)N10—H10Y0.87 (3)
C6—C1—C2120.1 (3)C6—C5—H5120.0
C6—C1—N7120.0 (3)C1—C6—C5120.0 (3)
C2—C1—N7120.0 (3)C1—C6—H6120.0
C3—C2—C1119.7 (3)C5—C6—H6120.0
C3—C2—H2120.1C8—N7—C1126.3 (3)
C1—C2—H2120.1C8—N7—H7X114 (3)
C2—C3—C4120.2 (3)C1—N7—H7X119 (3)
C2—C3—Cl1118.9 (3)N10—C8—N7118.0 (3)
C4—C3—Cl1120.9 (3)N10—C8—S9121.7 (3)
C5—C4—C3119.9 (3)N7—C8—S9120.4 (3)
C5—C4—Cl2119.5 (3)C8—N10—H10X121 (3)
C3—C4—Cl2120.6 (3)C8—N10—H10Y123 (3)
C4—C5—C6120.0 (3)H10X—N10—H10Y116 (4)
C4—C5—H5120.0
C6—C1—C2—C3−0.7 (5)Cl2—C4—C5—C6178.7 (3)
N7—C1—C2—C3−178.9 (3)C2—C1—C6—C50.0 (5)
C1—C2—C3—C40.9 (5)N7—C1—C6—C5178.1 (3)
C1—C2—C3—Cl1179.3 (3)C4—C5—C6—C10.6 (5)
C2—C3—C4—C5−0.2 (5)C6—C1—N7—C8121.2 (4)
Cl1—C3—C4—C5−178.7 (3)C2—C1—N7—C8−60.7 (5)
C2—C3—C4—Cl2−179.5 (2)C1—N7—C8—N10−11.2 (5)
Cl1—C3—C4—Cl22.1 (4)C1—N7—C8—S9169.3 (3)
C3—C4—C5—C6−0.5 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N7—H7X···S9i0.86 (3)2.51 (2)3.342 (3)161 (4)
N10—H10Y···Cl1ii0.87 (3)2.80 (2)3.646 (3)163 (4)
Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N7—H7X···S9i0.86 (3)2.51 (2)3.342 (3)161 (4)
N10—H10Y···Cl1ii0.87 (3)2.80 (2)3.646 (3)163 (4)
Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y+1, −z+1.
Acknowledgements top

The authors are very grateful to the Natural Science Foundation of Ningbo City for financial support (grant No. 2009 A610185).

references
References top

Bruker (2005). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Holla, B. S., Maline, K. V., Rao, B. S., Sarojini, B. K. & Kumari, N. S. (2003). Eur. J. Med. Chem. 38, 313–318.

Liu, B., Gao, H. Q. & Zhou, X. J. (1994). Hua Xue Tong Bao, 5, 42-43.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.