1-(3-Chloro­phen­yl)thio­urea

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.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.031
• wR factor = 0.085
• Data-to-parameter ratio = 21.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         12

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal ..........    0.00200 Deg.
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          3
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          8

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. 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.

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).

S2. 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).

S3. 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).

Computing details

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

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.

1-(3-Chlorophenyl)thiourea

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) Å^3

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 F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0374P)^2 + 0.222P] where P = (Fo^2 + 2Fc^2)/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)

	U^11	U^22	U^33	U^12	U^13	U^23
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···Cl1^i	0.80 (2)	2.64 (2)	3.3583 (12)	150 (2)
N2—H1N2···S1^ii	0.83 (3)	2.54 (3)	3.3619 (13)	167.5 (19)
N1—H1N1···S1^iii	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.