Redetermination of N,N′-bis­(4-chloro­phenyl)­thio­urea at 173 K

The structure of the title compound, C₁₃H₁₀Cl₂N₂S, has already been determined at room temperature [Soriano-García, Chávez, Cedillo, Pérez & Hernández (2001). Anal. Sci. 17, 799–800]. However, the positions of the H atoms were not provided. Thus, we present here the complete structure determined from data at low temperature (173 K). The mol­ecules are connected via bifurcated N—H...S hydrogen bonds to form zigzag chains running along the b axis. The title compound is isomorphous with 1,3-bis­(4-bromo­phen­yl)thio­urea.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.032
• wR factor = 0.083
• Data-to-parameter ratio = 18.1

checkCIF/PLATON results

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Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     -   C7      ..       5.28 su

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
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S1. Comment

The structure of the title compound, C₁₃H₁₀Cl₂N₂S, has already been determined at room temperature [Soriano-García, Chávez, Cedillo, Pérez & Hernández (2001). Anal. Sci. 17, 799–800]. However, the postitions of the H atoms have not been provided. Thus, we present here the complete structure determined from data at low temperature.

The molecules are connected via bifurcated N—H···S hydrogen bonds to form zigzag chains running along the b axis. The title compound is isomorphous with 1,3-bis(4-bromophenyl)thiourea (Muhammed et al., 2007).

Related literature

For related literature, see: Muhammed et al. (2007).

S2. Experimental

4-Chloroaniline (2.07 g, 0.0081 mol) was refluxed with potassium thiocyanate (1.4 g, 0.0142 mol) in 30 ml water and 1.6 ml conc. HCl for 3 h. The reaction mixture was then cooled to room temperature and stirred overnight. The precipitated product was then filtered, washed with water, dried and recrystallized from (9:1) acetone and toluene mixture (m.p.: 417–419 K). Analysis for C₁₃H₁₀Cl₂N₂S: Found (Calculated): C 52.45 (52.54), H 3.32 (3.39), N 9.36 (9.43), S 10.70% (10.79%).

S3. Refinement

H atoms were found in a difference map, but those bonded to C were refined using a riding model with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C). The H atoms bonded to N were freely refined.

Computing details

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA [Or X-RED?]; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. Perspective view of the title compound with the atom numbering; displacement ellipsoids are at the 50% probability level.

N,N'-bis(4-chlorophenyl)thiourea

Crystal data

C13H10Cl2N2S	F(000) = 608
Mr = 297.19	Dx = 1.446 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 17612 reflections
a = 13.8552 (11) Å	θ = 3.6–27.7°
b = 7.1640 (4) Å	µ = 0.61 mm^−1
c = 14.1324 (11) Å	T = 173 K
β = 103.290 (6)°	Block, colourless
V = 1365.20 (17) Å^3	0.37 × 0.34 × 0.32 mm
Z = 4

Data collection

Stoe IPDS II two-circle diffractometer	3118 independent reflections
Radiation source: fine-focus sealed tube	2828 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
ω scans	θmax = 27.6°, θmin = 3.6°
Absorption correction: multi-scan [MULABS (Spek, 2003; Blessing, 1995)]	h = −17→17
Tmin = 0.806, Tmax = 0.829	k = −9→9
18732 measured reflections	l = −18→17

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.083	w = 1/[σ^2(Fo^2) + (0.0416P)^2 + 0.5812P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
3118 reflections	Δρmax = 0.43 e Å^−3
172 parameters	Δρmin = −0.48 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0115 (13)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.86710 (4)	0.20429 (9)	0.48109 (4)	0.05742 (17)
Cl2	0.02930 (3)	0.21344 (9)	0.83408 (4)	0.05364 (16)
S1	0.41410 (2)	0.15822 (5)	0.60687 (2)	0.02176 (10)
N1	0.55058 (9)	0.41911 (17)	0.68187 (9)	0.0243 (2)
H1	0.5712 (13)	0.492 (3)	0.7280 (14)	0.034 (5)*
N2	0.40903 (9)	0.43015 (17)	0.73673 (9)	0.0248 (3)
H2	0.4436 (15)	0.501 (3)	0.7800 (16)	0.045 (6)*
C1	0.77329 (12)	0.2673 (2)	0.53935 (13)	0.0333 (3)
C2	0.79706 (11)	0.3009 (2)	0.63856 (13)	0.0349 (4)
H2A	0.8638	0.2923	0.6746	0.042*
C3	0.72165 (11)	0.3476 (2)	0.68460 (11)	0.0290 (3)
H3	0.7370	0.3706	0.7526	0.035*
C4	0.62372 (10)	0.36086 (18)	0.63133 (10)	0.0223 (3)
C5	0.60103 (11)	0.3290 (2)	0.53124 (10)	0.0253 (3)
H5	0.5345	0.3395	0.4947	0.030*
C6	0.67648 (12)	0.2815 (2)	0.48504 (11)	0.0300 (3)
H6	0.6617	0.2590	0.4170	0.036*
C7	0.45935 (9)	0.34474 (18)	0.67691 (9)	0.0197 (3)
C8	0.31635 (10)	0.37305 (19)	0.75578 (10)	0.0222 (3)
C9	0.23088 (11)	0.3522 (2)	0.68238 (10)	0.0301 (3)
H9	0.2331	0.3717	0.6164	0.036*
C10	0.14188 (11)	0.3024 (3)	0.70598 (12)	0.0345 (4)
H10	0.0835	0.2849	0.6562	0.041*
C11	0.13964 (11)	0.2786 (2)	0.80308 (12)	0.0318 (3)
C12	0.22385 (11)	0.3042 (2)	0.87692 (11)	0.0299 (3)
H12	0.2209	0.2901	0.9430	0.036*
C13	0.31273 (10)	0.3509 (2)	0.85273 (10)	0.0255 (3)
H13	0.3711	0.3677	0.9026	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0447 (3)	0.0746 (4)	0.0649 (3)	0.0117 (2)	0.0372 (2)	0.0028 (3)
Cl2	0.0270 (2)	0.0809 (4)	0.0574 (3)	−0.0063 (2)	0.01892 (19)	0.0048 (3)
S1	0.02455 (17)	0.02253 (17)	0.01732 (16)	−0.00173 (12)	0.00302 (12)	−0.00205 (12)
N1	0.0254 (6)	0.0260 (6)	0.0227 (6)	−0.0047 (5)	0.0080 (5)	−0.0075 (5)
N2	0.0244 (6)	0.0275 (6)	0.0236 (6)	−0.0036 (5)	0.0080 (5)	−0.0071 (5)
C1	0.0322 (8)	0.0322 (8)	0.0419 (9)	0.0024 (6)	0.0220 (7)	0.0038 (7)
C2	0.0229 (7)	0.0401 (9)	0.0424 (9)	−0.0011 (6)	0.0093 (6)	0.0038 (7)
C3	0.0256 (7)	0.0331 (7)	0.0279 (7)	−0.0044 (6)	0.0054 (6)	−0.0003 (6)
C4	0.0237 (6)	0.0197 (6)	0.0251 (6)	−0.0020 (5)	0.0092 (5)	0.0003 (5)
C5	0.0269 (7)	0.0247 (7)	0.0251 (7)	0.0009 (5)	0.0076 (5)	0.0024 (5)
C6	0.0379 (8)	0.0291 (7)	0.0272 (7)	0.0007 (6)	0.0160 (6)	0.0012 (6)
C7	0.0229 (6)	0.0207 (6)	0.0149 (5)	0.0008 (5)	0.0033 (5)	0.0029 (5)
C8	0.0223 (6)	0.0225 (6)	0.0225 (6)	0.0013 (5)	0.0070 (5)	−0.0019 (5)
C9	0.0263 (7)	0.0426 (8)	0.0206 (6)	0.0033 (6)	0.0040 (5)	0.0002 (6)
C10	0.0216 (7)	0.0493 (10)	0.0310 (8)	0.0022 (6)	0.0023 (6)	−0.0026 (7)
C11	0.0219 (7)	0.0387 (8)	0.0367 (8)	0.0014 (6)	0.0109 (6)	0.0001 (7)
C12	0.0305 (7)	0.0365 (8)	0.0247 (7)	0.0014 (6)	0.0105 (6)	0.0020 (6)
C13	0.0249 (6)	0.0301 (7)	0.0213 (6)	0.0012 (5)	0.0047 (5)	−0.0019 (5)

Geometric parameters (Å, º)

Cl1—C1	1.7502 (15)	C4—C5	1.3955 (19)
Cl2—C11	1.7480 (15)	C5—C6	1.396 (2)
S1—C7	1.6950 (14)	C5—H5	0.9500
N1—C7	1.3586 (17)	C6—H6	0.9500
N1—C4	1.4297 (17)	C8—C9	1.391 (2)
N1—H1	0.83 (2)	C8—C13	1.3916 (19)
N2—C7	1.3588 (17)	C9—C10	1.396 (2)
N2—C8	1.4309 (17)	C9—H9	0.9500
N2—H2	0.85 (2)	C10—C11	1.390 (2)
C1—C2	1.386 (2)	C10—H10	0.9500
C1—C6	1.388 (2)	C11—C12	1.387 (2)
C2—C3	1.393 (2)	C12—C13	1.393 (2)
C2—H2A	0.9500	C12—H12	0.9500
C3—C4	1.3954 (19)	C13—H13	0.9500
C3—H3	0.9500
C7—N1—C4	128.14 (12)	C5—C6—H6	120.3
C7—N1—H1	115.7 (12)	N1—C7—N2	113.31 (12)
C4—N1—H1	114.8 (12)	N1—C7—S1	123.65 (10)
C7—N2—C8	126.82 (12)	N2—C7—S1	122.99 (10)
C7—N2—H2	115.5 (14)	C9—C8—C13	120.31 (13)
C8—N2—H2	114.6 (14)	C9—C8—N2	122.50 (12)
C2—C1—C6	121.44 (14)	C13—C8—N2	117.05 (12)
C2—C1—Cl1	119.44 (13)	C8—C9—C10	119.78 (14)
C6—C1—Cl1	119.12 (13)	C8—C9—H9	120.1
C1—C2—C3	119.03 (15)	C10—C9—H9	120.1
C1—C2—H2A	120.5	C11—C10—C9	119.25 (14)
C3—C2—H2A	120.5	C11—C10—H10	120.4
C2—C3—C4	120.34 (14)	C9—C10—H10	120.4
C2—C3—H3	119.8	C12—C11—C10	121.38 (14)
C4—C3—H3	119.8	C12—C11—Cl2	118.66 (12)
C3—C4—C5	120.02 (13)	C10—C11—Cl2	119.96 (12)
C3—C4—N1	117.60 (12)	C11—C12—C13	119.04 (14)
C5—C4—N1	122.26 (13)	C11—C12—H12	120.5
C4—C5—C6	119.71 (14)	C13—C12—H12	120.5
C4—C5—H5	120.1	C8—C13—C12	120.21 (13)
C6—C5—H5	120.1	C8—C13—H13	119.9
C1—C6—C5	119.45 (14)	C12—C13—H13	119.9
C1—C6—H6	120.3
C6—C1—C2—C3	0.8 (2)	C8—N2—C7—N1	−173.04 (12)
Cl1—C1—C2—C3	−178.82 (13)	C8—N2—C7—S1	4.5 (2)
C1—C2—C3—C4	−0.2 (2)	C7—N2—C8—C9	−57.4 (2)
C2—C3—C4—C5	−0.6 (2)	C7—N2—C8—C13	126.95 (15)
C2—C3—C4—N1	−176.71 (14)	C13—C8—C9—C10	−2.3 (2)
C7—N1—C4—C3	−135.00 (15)	N2—C8—C9—C10	−177.77 (14)
C7—N1—C4—C5	49.0 (2)	C8—C9—C10—C11	1.5 (2)
C3—C4—C5—C6	0.8 (2)	C9—C10—C11—C12	0.3 (3)
N1—C4—C5—C6	176.74 (13)	C9—C10—C11—Cl2	−179.21 (13)
C2—C1—C6—C5	−0.6 (2)	C10—C11—C12—C13	−1.3 (2)
Cl1—C1—C6—C5	179.04 (12)	Cl2—C11—C12—C13	178.17 (12)
C4—C5—C6—C1	−0.2 (2)	C9—C8—C13—C12	1.2 (2)
C4—N1—C7—N2	178.20 (13)	N2—C8—C13—C12	176.96 (13)
C4—N1—C7—S1	0.6 (2)	C11—C12—C13—C8	0.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1^i	0.83 (2)	2.58 (2)	3.3787 (13)	159.5 (16)
N2—H2···S1^i	0.85 (2)	2.50 (2)	3.3272 (13)	163.2 (18)

Symmetry code: (i) −x+1, y+1/2, −z+3/2.