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Acta Cryst. (2009). E65, o234    [ doi:10.1107/S1600536808043444 ]

1-(3-Chlorophenyl)-3-(2,6-dichlorobenzoyl)thiourea

M. Khawar Rauf, M. Bolte and A. Rauf

Abstract top

The structure of the title compound, C14H9Cl3N2OS, is composed of discrete molecules with bond lengths and angles quite typical for thiourea compounds of this class. The plane containing the thiocarbonyl and carbonyl groups subtends dihedral angles of 48.19 (3) and 87.51 (3)° with the planes formed by the 3-chloro and 2,6-dichlorophenyl rings, respectively; the dihedral angle between the two benzene ring planes is 45.32 (3)°. An intramolecular N-H...O hydrogen bond stabilizes the molecular conformation and the molecules form intermolecular N-H...S and N-H...O hydrogen bonds, generating a sheet along the a axis.

Comment top

The background to this study has been set out in our previous work on the structural chemistry of N,N'-disubstituted thioureas (Khawar Rauf et al., 2006a, 2007). Herein, as a continuation of these studies, the structure of the title compound, (I), is described.

In the structure of the title compound (Fig. 1), bond lengths and bond angles can be regarded as typical for N,N'-disubstituted thiourea compounds as found in the Cambridge Structural Database v5.28 (Allen, 2002) and some related structures (Khawar Rauf et al., 2006b). The molecule exists in the thione form with typical thiourea C—S and C—O bonds, as well as shortened C—N bonds. The thiocarbonyl and carbonyl groups are almost coplanar. The molecule features an intramolecular N—H···O hydrogen bond in the crystal structure. The molecules lying about inversions centers associate via N—H···S intermolecular hydrogen bonds to form dimers on one side and a similar association via N—H···O hydrogen bonding on the other side thus result in a sheet of molecules of (I) along the a<ι>-axis (Table 1; Fig. 2).

Related literature top

For related structures, see: Khawar Rauf et al., (2006a,b; 2007). For a description of the Cambridge structural Database, see: Allen (2002).

Experimental top

Freshly prepared and steam distillated 2,6-dichlorobenzoyl isothiocyanate (2.32 g, 10 mmol) was stirred in acetone (30 ml) for 20 minutes. Neat 3-chloroaniline (1.27 g, 10 mmol) was then added and the resulting mixture was stirred for 1 h. The reaction mixture was then poured into acidified (pH 4) water (approx. 300 ml) and stirred well. The solid product was separated, washed with deionized water and purified by recrystallization from methanol/1,1-dichloromethane (1:10 v/v) to give fine crystals of (I), with an overall yield of 85%.

Refinement top

Hydrogen atoms bonded to C were included in calculated positions and refined as riding on their parent C atom with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C). The H atoms bonded to N were freely refined.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003) and XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2003) and SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of (I) showing atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A view of the unit cell of (I) showing hydrogen bonds as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.
1-(3-Chlorophenyl)-3-(2,6-dichlorobenzoyl)thiourea top
Crystal data top
C14H9Cl3N2OSF(000) = 728
Mr = 359.64Dx = 1.527 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 37695 reflections
a = 10.6589 (5) Åθ = 3.7–31.2°
b = 11.2114 (5) ŵ = 0.72 mm−1
c = 13.2919 (6) ÅT = 173 K
β = 99.942 (3)°Block, colourless
V = 1564.55 (12) Å30.47 × 0.47 × 0.45 mm
Z = 4
Data collection top
Stoe IPDS-II two-circle
diffractometer		5066 independent reflections
Radiation source: fine-focus sealed tube4674 reflections with I > 2σ(I)
graphiteRint = 0.046
ω scansθmax = 31.3°, θmin = 3.6°
Absorption correction: multi-scan
(MULABS; Spek, 2003; Blessing, 1995)		h = −15→15
Tmin = 0.729, Tmax = 0.739k = −16→16
39690 measured reflectionsl = −19→19
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)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.094 w = 1/[σ2(Fo2) + (0.0404P)2 + 0.9365P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
5066 reflectionsΔρmax = 0.65 e Å−3
199 parametersΔρmin = −0.66 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0111 (12)
Crystal data top
C14H9Cl3N2OSV = 1564.55 (12) Å3
Mr = 359.64Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.6589 (5) ŵ = 0.72 mm−1
b = 11.2114 (5) ÅT = 173 K
c = 13.2919 (6) Å0.47 × 0.47 × 0.45 mm
β = 99.942 (3)°
Data collection top
Stoe IPDS-II two-circle
diffractometer		5066 independent reflections
Absorption correction: multi-scan
(MULABS; Spek, 2003; Blessing, 1995)		4674 reflections with I > 2σ(I)
Tmin = 0.729, Tmax = 0.739Rint = 0.046
39690 measured reflectionsθmax = 31.3°
Refinement top
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.094Δρmax = 0.65 e Å−3
S = 1.06Δρmin = −0.66 e Å−3
5066 reflectionsAbsolute structure: ?
199 parametersFlack parameter: ?
0 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
S10.09625 (3)0.60027 (3)0.62517 (2)0.02474 (9)
Cl10.19574 (4)0.61905 (4)0.23352 (3)0.03999 (11)
Cl20.22323 (4)0.18815 (4)0.41908 (3)0.03969 (11)
Cl30.33122 (7)0.61484 (7)0.99688 (3)0.0735 (2)
C10.27158 (11)0.45474 (11)0.41547 (8)0.0182 (2)
O10.38737 (8)0.46303 (10)0.43625 (7)0.0285 (2)
N10.19003 (9)0.49493 (10)0.47738 (8)0.01915 (19)
H10.1105 (19)0.4841 (18)0.4559 (15)0.030 (5)*
C20.21866 (10)0.55197 (10)0.57210 (8)0.0174 (2)
N20.34238 (9)0.56439 (10)0.61243 (8)0.01918 (19)
H20.394 (2)0.5442 (19)0.5770 (15)0.032 (5)*
C110.20320 (10)0.39859 (11)0.31773 (8)0.0179 (2)
C120.16489 (13)0.46736 (13)0.23029 (10)0.0251 (2)
C130.09985 (17)0.41613 (18)0.14040 (11)0.0394 (4)
H130.07450.46390.08140.047*
C140.07264 (17)0.29526 (19)0.13789 (12)0.0421 (4)
H140.02750.26060.07700.051*
C150.11043 (15)0.22420 (15)0.22299 (12)0.0337 (3)
H150.09230.14120.22080.040*
C160.17558 (12)0.27683 (12)0.31200 (10)0.0232 (2)
C210.39003 (11)0.62132 (11)0.70818 (9)0.0195 (2)
C220.34464 (15)0.58955 (14)0.79662 (10)0.0289 (3)
H220.28220.52880.79530.035*
C230.39279 (16)0.64880 (16)0.88702 (10)0.0340 (3)
C240.48645 (15)0.73570 (15)0.89168 (11)0.0332 (3)
H240.51800.77520.95410.040*
C250.53305 (14)0.76367 (15)0.80313 (11)0.0318 (3)
H250.59840.82180.80530.038*
C260.48479 (12)0.70721 (13)0.71106 (10)0.0246 (2)
H260.51640.72730.65070.030*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.01676 (13)0.03383 (17)0.02412 (15)−0.00159 (11)0.00495 (10)−0.01452 (12)
Cl10.0485 (2)0.02974 (18)0.0415 (2)−0.00112 (15)0.00718 (16)0.00931 (14)
Cl20.0507 (2)0.02793 (17)0.0402 (2)0.00109 (15)0.00724 (16)0.00754 (14)
Cl30.1095 (5)0.0945 (5)0.02015 (18)−0.0585 (4)0.0216 (2)−0.0165 (2)
C10.0160 (4)0.0228 (5)0.0156 (4)0.0010 (4)0.0018 (4)−0.0044 (4)
O10.0144 (4)0.0461 (6)0.0246 (4)0.0004 (4)0.0023 (3)−0.0134 (4)
N10.0133 (4)0.0275 (5)0.0163 (4)−0.0008 (3)0.0016 (3)−0.0081 (4)
C20.0171 (5)0.0197 (5)0.0152 (4)−0.0009 (4)0.0018 (4)−0.0037 (4)
N20.0153 (4)0.0266 (5)0.0152 (4)−0.0008 (4)0.0015 (3)−0.0061 (4)
C110.0160 (4)0.0231 (5)0.0147 (4)−0.0007 (4)0.0030 (4)−0.0051 (4)
C120.0247 (6)0.0317 (6)0.0185 (5)−0.0009 (5)0.0023 (4)0.0000 (4)
C130.0408 (8)0.0571 (10)0.0173 (6)−0.0037 (7)−0.0037 (5)−0.0014 (6)
C140.0391 (8)0.0612 (11)0.0243 (6)−0.0127 (8)0.0002 (6)−0.0189 (7)
C150.0315 (7)0.0355 (7)0.0350 (7)−0.0098 (6)0.0080 (5)−0.0185 (6)
C160.0225 (5)0.0246 (6)0.0236 (5)−0.0020 (4)0.0070 (4)−0.0059 (4)
C210.0185 (5)0.0235 (5)0.0151 (4)−0.0003 (4)−0.0005 (4)−0.0049 (4)
C220.0358 (7)0.0330 (7)0.0168 (5)−0.0123 (5)0.0015 (5)−0.0041 (5)
C230.0446 (8)0.0414 (8)0.0156 (5)−0.0123 (7)0.0041 (5)−0.0064 (5)
C240.0341 (7)0.0410 (8)0.0222 (6)−0.0079 (6)−0.0016 (5)−0.0123 (5)
C250.0265 (6)0.0382 (8)0.0300 (6)−0.0108 (5)0.0027 (5)−0.0129 (6)
C260.0206 (5)0.0305 (6)0.0229 (5)−0.0044 (5)0.0038 (4)−0.0076 (5)
Geometric parameters (Å, °) top
S1—C21.6766 (12)C13—H130.9500
Cl1—C121.7313 (15)C14—C151.385 (3)
Cl2—C161.7386 (14)C14—H140.9500
Cl3—C231.7433 (15)C15—C161.3951 (18)
C1—O11.2209 (14)C15—H150.9500
C1—N11.3721 (14)C21—C261.3912 (18)
C1—C111.5128 (15)C21—C221.3925 (18)
N1—C21.3980 (14)C22—C231.3912 (18)
N1—H10.86 (2)C22—H220.9500
C2—N21.3423 (14)C23—C241.389 (2)
N2—C211.4360 (14)C24—C251.390 (2)
N2—H20.82 (2)C24—H240.9500
C11—C121.3957 (17)C25—C261.3947 (17)
C11—C161.3957 (17)C25—H250.9500
C12—C131.3971 (19)C26—H260.9500
C13—C141.385 (3)
O1—C1—N1124.03 (10)C14—C15—C16118.77 (14)
O1—C1—C11122.98 (10)C14—C15—H15120.6
N1—C1—C11112.99 (9)C16—C15—H15120.6
C1—N1—C2128.90 (10)C15—C16—C11121.96 (13)
C1—N1—H1116.6 (13)C15—C16—Cl2118.99 (11)
C2—N1—H1114.5 (13)C11—C16—Cl2119.05 (9)
N2—C2—N1116.98 (10)C26—C21—C22120.68 (11)
N2—C2—S1125.50 (9)C26—C21—N2118.43 (11)
N1—C2—S1117.52 (8)C22—C21—N2120.88 (11)
C2—N2—C21124.95 (10)C23—C22—C21118.48 (13)
C2—N2—H2117.2 (14)C23—C22—H22120.8
C21—N2—H2117.5 (14)C21—C22—H22120.8
C12—C11—C16117.79 (11)C24—C23—C22121.91 (13)
C12—C11—C1120.90 (11)C24—C23—Cl3119.18 (10)
C16—C11—C1121.31 (11)C22—C23—Cl3118.89 (12)
C11—C12—C13121.04 (14)C23—C24—C25118.67 (12)
C11—C12—Cl1119.67 (10)C23—C24—H24120.7
C13—C12—Cl1119.28 (12)C25—C24—H24120.7
C14—C13—C12119.59 (15)C24—C25—C26120.60 (13)
C14—C13—H13120.2C24—C25—H25119.7
C12—C13—H13120.2C26—C25—H25119.7
C13—C14—C15120.85 (13)C21—C26—C25119.62 (12)
C13—C14—H14119.6C21—C26—H26120.2
C15—C14—H14119.6C25—C26—H26120.2
O1—C1—N1—C20.6 (2)C14—C15—C16—C110.2 (2)
C11—C1—N1—C2−179.35 (12)C14—C15—C16—Cl2179.98 (12)
C1—N1—C2—N2−4.11 (19)C12—C11—C16—C15−0.86 (18)
C1—N1—C2—S1175.27 (11)C1—C11—C16—C15178.74 (12)
N1—C2—N2—C21179.40 (11)C12—C11—C16—Cl2179.39 (9)
S1—C2—N2—C210.07 (18)C1—C11—C16—Cl2−1.01 (16)
O1—C1—C11—C12−90.46 (16)C2—N2—C21—C26−130.55 (14)
N1—C1—C11—C1289.48 (14)C2—N2—C21—C2250.86 (18)
O1—C1—C11—C1689.95 (16)C26—C21—C22—C232.4 (2)
N1—C1—C11—C16−90.11 (14)N2—C21—C22—C23−179.07 (14)
C16—C11—C12—C130.68 (19)C21—C22—C23—C24−1.7 (3)
C1—C11—C12—C13−178.93 (13)C21—C22—C23—Cl3176.96 (13)
C16—C11—C12—Cl1179.53 (10)C22—C23—C24—C25−0.1 (3)
C1—C11—C12—Cl1−0.07 (16)Cl3—C23—C24—C25−178.76 (14)
C11—C12—C13—C140.1 (2)C23—C24—C25—C261.3 (3)
Cl1—C12—C13—C14−178.73 (14)C22—C21—C26—C25−1.2 (2)
C12—C13—C14—C15−0.8 (3)N2—C21—C26—C25−179.82 (13)
C13—C14—C15—C160.6 (2)C24—C25—C26—C21−0.6 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O10.82 (2)2.07 (2)2.7190 (13)136.0 (18)
N2—H2···O1i0.82 (2)2.37 (2)3.0749 (14)145.5 (18)
N1—H1···S1ii0.86 (2)2.47 (2)3.2974 (10)163.6 (18)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O10.82 (2)2.07 (2)2.7190 (13)136.0 (18)
N2—H2···O1i0.82 (2)2.37 (2)3.0749 (14)145.5 (18)
N1—H1···S1ii0.86 (2)2.47 (2)3.2974 (10)163.6 (18)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1.
Acknowledgements top

MKR is grateful to the HEC-Pakistan for financial support for the PhD program under scholarship No. [ILC–0363104].

references
References top

Allen, F. H. (2002). Acta Cryst. B58, 380–388.

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Khawar Rauf, M., Badshah, A. & Bolte, M. (2006b). Acta Cryst. E62, o4296–o4298.

Khawar Rauf, M., Badshah, A. & Bolte, M. (2007). Acta Cryst. E63, o2665–o2666.

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Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.

Stoe & Cie (2001). X-AREA. Stoe & Cie, Darmstadt, Germany.