1-(3-Chloro­phen­yl)thio­urea

Abstract

In the title compound, C₇H₇ClN₂S, the thio­urea N—C(=S)—N plane forms a dihedral angle of 64.80 (6)° with the benzene ring. In the crystal, mol­ecules are linked via inter­molecular N—H⋯S and N—H⋯Cl hydrogen bonds into a sheet extending parallel to the (101) plane.

Related literature  

For related structures, see: Saleem & Yamin (2010 ▶); Sarojini et al. (2007 ▶). For standard bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental  

Crystal data  

• C₇H₇ClN₂S

• M _r = 186.66

• Triclinic,

• a = 5.4406 (3) Å

• b = 8.5715 (4) Å

• c = 9.2392 (4) Å

• α = 104.221 (2)°

• β = 91.776 (2)°

• γ = 96.362 (2)°

• V = 414.33 (3) ų

• Z = 2

• Mo Kα radiation

• μ = 0.64 mm⁻¹

• T = 100 K

• 0.38 × 0.30 × 0.07 mm

Data collection  

• Bruker SMART APEXII DUO CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.791, T _max = 0.956

• 8525 measured reflections

• 2414 independent reflections

• 2194 reflections with I > 2σ(I)

• R _int = 0.033

Refinement  

• R[F ² > 2σ(F ²)] = 0.031

• wR(F ²) = 0.085

• S = 1.08

• 2414 reflections

• 112 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.68 e Å⁻³

• Δρ_min = −0.37 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S160053681203084X/is5164Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N2⋯Cl1i	0.80 (2)	2.64 (2)	3.3583 (12)	150 (2)
N2—H1N2⋯S1ii	0.83 (3)	2.54 (3)	3.3619 (13)	167.5 (19)
N1—H1N1⋯S1iii	0.84 (2)	2.49 (3)	3.3149 (12)	167 (2)

Symmetry codes: (i) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

In view of importance of thiourea derivatives (Saleem & Yamin, 2010; Sarojini et al., 2007), the title compound (I) is prepared and its crystal structure is reported.

In the title molecule (Fig. 1), the thiourea moiety (S1/N1/N2/C7) is planar (r.m.s. deviation = < 0.001) and it forms a dihedral angle of 64.80 (6)° with the benzene ring (C1–C6). Bond lengths (Allen et al., 1987) and angles are within normal ranges. In the crystal structure (Fig. 2), molecules are linked via intermolecular N2—H2N2···S1, N2—H1N2···Cl1 and N1—H11···S1 hydrogen bonds (Table 1) into two-dimensional sheets parallel to the (101) plane.

Experimental

3-Chloroaniline (0.65 ml, 0.0081 mol) was refluxed with potassium thiocyanate (1.4 g, 0.0142 mol) in 20 ml of water and 1.6 ml of conc. HCl for 3 h. The reaction mixture was then cooled to room temperature and stirred overnight. The precipitated product was then filetred, washed with water, dried and single crystals were grown from toluene and acetone (1:1) mixture by the slow evaporation method (m.p. 402 K).

Refinement

N-bound hydrogen atoms were located in a difference Fourier map and refined freely [N—H = 0.80 (2)–0.84 (2) Å]. The remaining H atoms were positioned geometrically and refined using a riding model with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

The molecular structure of the title compound showing 50% probability displacement ellipsoids for non-H atoms.

Fig. 2.

The crystal structure of the title compound, viewed along the b axis. H atoms not involved in hydrogen bonds (dashed lines) have been omitted for clarity.

Crystal data

C7H7ClN2S	Z = 2
Mr = 186.66	F(000) = 192
Triclinic, P1	Dx = 1.496 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.4406 (3) Å	Cell parameters from 5475 reflections
b = 8.5715 (4) Å	θ = 2.9–30.0°
c = 9.2392 (4) Å	µ = 0.64 mm−1
α = 104.221 (2)°	T = 100 K
β = 91.776 (2)°	Plate, colourless
γ = 96.362 (2)°	0.38 × 0.30 × 0.07 mm
V = 414.33 (3) Å3

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer	2414 independent reflections
Radiation source: fine-focus sealed tube	2194 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
φ and ω scans	θmax = 30.1°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −7→7
Tmin = 0.791, Tmax = 0.956	k = −12→12
8525 measured reflections	l = −13→13

Refinement

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0374P)2 + 0.222P] where P = (Fo2 + 2Fc2)/3
2414 reflections	(Δ/σ)max = 0.001
112 parameters	Δρmax = 0.68 e Å−3
0 restraints	Δρmin = −0.37 e Å−3

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.18973 (6)	0.42500 (4)	1.19169 (4)	0.02562 (10)
S1	0.60726 (6)	0.24290 (3)	0.46595 (4)	0.01698 (10)
N1	0.2888 (2)	0.14096 (13)	0.64519 (13)	0.0164 (2)
N2	0.2660 (2)	0.39857 (14)	0.61960 (14)	0.0190 (2)
C1	−0.0855 (2)	0.05999 (16)	0.76120 (15)	0.0181 (2)
H1	−0.1397	−0.0171	0.6730	0.022*
C2	−0.2277 (2)	0.07757 (17)	0.88598 (16)	0.0214 (3)
H2	−0.3772	0.0116	0.8802	0.026*
C3	−0.1494 (2)	0.19203 (17)	1.01876 (15)	0.0201 (3)
H3	−0.2460	0.2046	1.1012	0.024*
C4	0.0770 (2)	0.28730 (15)	1.02523 (14)	0.0172 (2)
C5	0.2222 (2)	0.27251 (15)	0.90312 (15)	0.0167 (2)
H4	0.3731	0.3372	0.9097	0.020*
C6	0.1378 (2)	0.15877 (14)	0.76997 (14)	0.0150 (2)
C7	0.3726 (2)	0.26353 (14)	0.58419 (14)	0.0150 (2)
H2N2	0.147 (4)	0.404 (3)	0.669 (2)	0.033 (5)*
H1N2	0.310 (4)	0.479 (3)	0.587 (2)	0.028 (5)*
H1N1	0.335 (4)	0.050 (3)	0.610 (2)	0.029 (5)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.02138 (16)	0.03212 (19)	0.01919 (17)	0.00492 (13)	−0.00105 (12)	−0.00194 (13)
S1	0.01841 (15)	0.01114 (14)	0.02287 (17)	0.00166 (10)	0.00657 (11)	0.00646 (11)
N1	0.0210 (5)	0.0096 (4)	0.0193 (5)	0.0014 (4)	0.0059 (4)	0.0046 (4)
N2	0.0195 (5)	0.0133 (5)	0.0271 (6)	0.0038 (4)	0.0083 (4)	0.0091 (4)
C1	0.0178 (5)	0.0168 (5)	0.0196 (6)	−0.0018 (4)	−0.0009 (4)	0.0065 (4)
C2	0.0164 (5)	0.0246 (6)	0.0246 (6)	−0.0027 (5)	0.0011 (5)	0.0107 (5)
C3	0.0167 (5)	0.0255 (6)	0.0206 (6)	0.0031 (5)	0.0034 (5)	0.0099 (5)
C4	0.0170 (5)	0.0184 (5)	0.0166 (6)	0.0042 (4)	−0.0006 (4)	0.0041 (4)
C5	0.0142 (5)	0.0148 (5)	0.0208 (6)	0.0006 (4)	0.0008 (4)	0.0049 (4)
C6	0.0160 (5)	0.0128 (5)	0.0176 (6)	0.0016 (4)	0.0021 (4)	0.0065 (4)
C7	0.0153 (5)	0.0122 (5)	0.0176 (5)	−0.0005 (4)	0.0006 (4)	0.0047 (4)

Geometric parameters (Å, º)

Cl1—C4	1.7389 (13)	C1—C2	1.3948 (19)
S1—C7	1.7021 (13)	C1—H1	0.9300
N1—C7	1.3527 (15)	C2—C3	1.390 (2)
N1—C6	1.4239 (16)	C2—H2	0.9300
N1—H1N1	0.83 (2)	C3—C4	1.3918 (17)
N2—C7	1.3257 (17)	C3—H3	0.9300
N2—H2N2	0.80 (2)	C4—C5	1.3855 (18)
N2—H1N2	0.84 (2)	C5—C6	1.3968 (17)
C1—C6	1.3901 (16)	C5—H4	0.9300
C7—N1—C6	124.20 (11)	C4—C3—H3	120.8
C7—N1—H1N1	117.8 (14)	C5—C4—C3	121.85 (12)
C6—N1—H1N1	117.9 (14)	C5—C4—Cl1	118.15 (10)
C7—N2—H2N2	121.1 (16)	C3—C4—Cl1	119.97 (10)
C7—N2—H1N2	122.5 (14)	C4—C5—C6	118.84 (11)
H2N2—N2—H1N2	116 (2)	C4—C5—H4	120.6
C6—C1—C2	119.36 (12)	C6—C5—H4	120.6
C6—C1—H1	120.3	C1—C6—C5	120.51 (12)
C2—C1—H1	120.3	C1—C6—N1	120.46 (11)
C3—C2—C1	121.08 (12)	C5—C6—N1	118.98 (11)
C3—C2—H2	119.5	N2—C7—N1	117.85 (12)
C1—C2—H2	119.5	N2—C7—S1	121.69 (10)
C2—C3—C4	118.34 (12)	N1—C7—S1	120.45 (10)
C2—C3—H3	120.8
C6—C1—C2—C3	−0.1 (2)	C2—C1—C6—N1	178.69 (12)
C1—C2—C3—C4	−1.1 (2)	C4—C5—C6—C1	−1.26 (19)
C2—C3—C4—C5	1.1 (2)	C4—C5—C6—N1	−178.74 (11)
C2—C3—C4—Cl1	−176.81 (10)	C7—N1—C6—C1	126.31 (14)
C3—C4—C5—C6	0.1 (2)	C7—N1—C6—C5	−56.21 (18)
Cl1—C4—C5—C6	177.99 (10)	C6—N1—C7—N2	−15.51 (19)
C2—C1—C6—C5	1.24 (19)	C6—N1—C7—S1	164.53 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N2···Cl1i	0.80 (2)	2.64 (2)	3.3583 (12)	150 (2)
N2—H1N2···S1ii	0.83 (3)	2.54 (3)	3.3619 (13)	167.5 (19)
N1—H1N1···S1iii	0.84 (2)	2.49 (3)	3.3149 (12)	167 (2)

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