N-(3,4-Dichloro­phen­yl)thio­urea

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

doi:10.1107/S1600536809035569

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2401

doi:10.1107/S1600536809035569

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N-(3,4-Dichlorophenyl)thiourea

Hai-Bo Shi,^a,^b Wei-Xiao Hu ^a ^* and Yan-Fang Lin ^a

^aCollege of Pharmaceutical Science, Zhejiang University of Technology, Hangzhou 310032, People's Republic of China, and ^bZhejiang Pharmaceutical College, Ningbo 315100, People's Republic of China
^*Correspondence e-mail: huyang@mail.hz.zj.cn

(Received 26 August 2009; accepted 3 September 2009; online 9 September 2009)

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.

Related literature

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

Experimental

Crystal data

C₇H₆Cl₂N₂S
M_r = 221.10
Triclinic, $[P \overline 1]$
a = 5.8168 (19) Å
b = 8.489 (3) Å
c = 9.771 (3) Å
α = 107.042 (4)°
β = 94.468 (4)°
γ = 94.778 (4)°
V = 457.0 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.88 mm⁻¹
T = 291 K
0.15 × 0.10 × 0.08 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.879, T_max = 0.933
1882 measured reflections
1562 independent reflections
1410 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.084
wR(F²) = 0.236
S = 1.10
1562 reflections
122 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.75 e Å⁻³
Δρ_min = −0.76 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N7—H7X⋯S9ⁱ	0.86 (3)	2.51 (2)	3.342 (3)	161 (4)
N10—H10Y⋯Cl1ⁱⁱ	0.87 (3)	2.80 (2)	3.646 (3)	163 (4)
Symmetry codes: (i) -x+1, -y, -z; (ii) -x, -y+1, -z+1.

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809035569/bg2297sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809035569/bg2297Isup2.hkl

checkCIF report

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).

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

	Fig. 1. The structure of (I), shown with 30% probability displacement ellipsoids.
	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

C₇H₆Cl₂N₂S	Z = 2
M_r = 221.10	F(000) = 224
Triclinic, P1	D_x = 1.607 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.8168 (19) Å	Cell parameters from 843 reflections
b = 8.489 (3) Å	θ = 2.5–27.0°
c = 9.771 (3) Å	µ = 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 tube	1410 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→3
T_min = 0.879, T_max = 0.933	k = −9→10
1882 measured reflections	l = −11→11

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.084	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.236	w = 1/[σ²(F_o²) + (0.1955P)²] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
1562 reflections	Δρ_max = 0.75 e Å⁻³
122 parameters	Δρ_min = −0.76 e Å⁻³
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.13 (4)

Crystal data top

C₇H₆Cl₂N₂S	γ = 94.778 (4)°
M_r = 221.10	V = 457.0 (3) Å³
Triclinic, P1	Z = 2
a = 5.8168 (19) Å	Mo Kα radiation
b = 8.489 (3) Å	µ = 0.88 mm⁻¹
c = 9.771 (3) Å	T = 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)
T_min = 0.879, T_max = 0.933	R_int = 0.062
1882 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.084	3 restraints
wR(F²) = 0.236	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.75 e Å⁻³
1562 reflections	Δρ_min = −0.76 e Å⁻³
122 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.

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

	x	y	z	U_iso*/U_eq
Cl1	0.19736 (17)	0.43998 (14)	0.66939 (11)	0.0560 (6)
Cl2	−0.27770 (17)	0.21189 (14)	0.62155 (11)	0.0565 (6)
C1	0.1662 (6)	0.1685 (4)	0.2584 (4)	0.0365 (9)
C2	0.2383 (6)	0.2836 (4)	0.3921 (4)	0.0398 (9)
H2	0.3777	0.3512	0.4062	0.048*
C3	0.1023 (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	−0.3127	0.0103	0.3372	0.058*
C6	−0.0398 (7)	0.0669 (4)	0.2380 (4)	0.0446 (9)
H6	−0.0879	−0.0101	0.1485	0.054*
N7	0.3073 (6)	0.1521 (3)	0.1444 (3)	0.0424 (9)
H7X	0.371 (7)	0.061 (4)	0.113 (5)	0.071 (15)*
C8	0.3732 (6)	0.2709 (4)	0.0853 (4)	0.0353 (8)
S9	0.58001 (18)	0.24215 (10)	−0.03037 (11)	0.0493 (6)
N10	0.2718 (6)	0.4075 (4)	0.1191 (4)	0.0508 (10)
H10X	0.308 (7)	0.486 (5)	0.083 (5)	0.055 (12)*
H10Y	0.159 (5)	0.422 (6)	0.173 (4)	0.054 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0546 (8)	0.0620 (8)	0.0427 (7)	0.0057 (5)	0.0146 (5)	0.0001 (5)
Cl2	0.0577 (8)	0.0636 (9)	0.0549 (8)	0.0087 (5)	0.0328 (5)	0.0209 (6)
C1	0.0534 (19)	0.0253 (16)	0.0377 (19)	0.0123 (14)	0.0214 (15)	0.0137 (14)
C2	0.0404 (18)	0.0334 (18)	0.050 (2)	0.0026 (14)	0.0167 (15)	0.0160 (16)
C3	0.0453 (19)	0.0341 (18)	0.0375 (19)	0.0122 (14)	0.0132 (14)	0.0139 (15)
C4	0.0433 (19)	0.0396 (19)	0.042 (2)	0.0106 (15)	0.0200 (15)	0.0195 (16)
C5	0.048 (2)	0.043 (2)	0.051 (2)	−0.0046 (16)	0.0107 (18)	0.0127 (18)
C6	0.060 (2)	0.0344 (19)	0.039 (2)	0.0023 (15)	0.0123 (16)	0.0087 (15)
N7	0.064 (2)	0.0251 (15)	0.0460 (18)	0.0146 (13)	0.0319 (14)	0.0136 (13)
C8	0.0489 (19)	0.0257 (16)	0.0338 (18)	0.0059 (13)	0.0167 (14)	0.0091 (13)
S9	0.0722 (9)	0.0288 (7)	0.0572 (8)	0.0151 (5)	0.0417 (6)	0.0175 (5)
N10	0.072 (2)	0.0312 (17)	0.064 (2)	0.0175 (15)	0.0434 (17)	0.0239 (15)

Geometric parameters (Å, º) top

Cl1—C3	1.733 (4)	C5—C6	1.386 (5)
Cl2—C4	1.729 (4)	C5—H5	0.9300
C1—C6	1.382 (5)	C6—H6	0.9300
C1—C2	1.391 (5)	N7—C8	1.345 (4)
C1—N7	1.416 (5)	N7—H7X	0.87 (2)
C2—C3	1.378 (6)	C8—N10	1.312 (5)
C2—H2	0.9300	C8—S9	1.698 (4)
C3—C4	1.389 (5)	N10—H10X	0.86 (3)
C4—C5	1.380 (6)	N10—H10Y	0.87 (3)

C6—C1—C2	120.1 (3)	C6—C5—H5	120.0
C6—C1—N7	120.0 (3)	C1—C6—C5	120.0 (3)
C2—C1—N7	120.0 (3)	C1—C6—H6	120.0
C3—C2—C1	119.7 (3)	C5—C6—H6	120.0
C3—C2—H2	120.1	C8—N7—C1	126.3 (3)
C1—C2—H2	120.1	C8—N7—H7X	114 (3)
C2—C3—C4	120.2 (3)	C1—N7—H7X	119 (3)
C2—C3—Cl1	118.9 (3)	N10—C8—N7	118.0 (3)
C4—C3—Cl1	120.9 (3)	N10—C8—S9	121.7 (3)
C5—C4—C3	119.9 (3)	N7—C8—S9	120.4 (3)
C5—C4—Cl2	119.5 (3)	C8—N10—H10X	121 (3)
C3—C4—Cl2	120.6 (3)	C8—N10—H10Y	123 (3)
C4—C5—C6	120.0 (3)	H10X—N10—H10Y	116 (4)
C4—C5—H5	120.0

C6—C1—C2—C3	−0.7 (5)	Cl2—C4—C5—C6	178.7 (3)
N7—C1—C2—C3	−178.9 (3)	C2—C1—C6—C5	0.0 (5)
C1—C2—C3—C4	0.9 (5)	N7—C1—C6—C5	178.1 (3)
C1—C2—C3—Cl1	179.3 (3)	C4—C5—C6—C1	0.6 (5)
C2—C3—C4—C5	−0.2 (5)	C6—C1—N7—C8	121.2 (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—Cl2	2.1 (4)	C1—N7—C8—S9	169.3 (3)
C3—C4—C5—C6	−0.5 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7X···S9ⁱ	0.86 (3)	2.51 (2)	3.342 (3)	161 (4)
N10—H10Y···Cl1ⁱⁱ	0.87 (3)	2.80 (2)	3.646 (3)	163 (4)

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

Experimental details

Crystal data
Chemical formula	C₇H₆Cl₂N₂S
M_r	221.10
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	5.8168 (19), 8.489 (3), 9.771 (3)
α, β, γ (°)	107.042 (4), 94.468 (4), 94.778 (4)
V (Å³)	457.0 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.88
Crystal size (mm)	0.15 × 0.10 × 0.08

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.879, 0.933
No. of measured, independent and observed [I > 2σ(I)] reflections	1882, 1562, 1410
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.084, 0.236, 1.10
No. of reflections	1562
No. of parameters	122
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.75, −0.76

Computer programs: SMART (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7X···S9ⁱ	0.86 (3)	2.51 (2)	3.342 (3)	161 (4)
N10—H10Y···Cl1ⁱⁱ	0.87 (3)	2.80 (2)	3.646 (3)	163 (4)

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

Acknowledgements

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

References

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