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Acta Crystallogr Sect E Struct Rep Online. 2009 January 1; 65(Pt 1): o177.
Published online 2008 December 20. doi:  10.1107/S1600536808042736
PMCID: PMC2968087

1-(2,6-Dichloro­benzo­yl)-3-(3,5-dichloro­phen­yl)thio­urea

Abstract

The crystal structure of the title compound, C14H8Cl4N2OS, is composed of discrete mol­ecules with bond lengths and angles quite typical for thio­urea compounds of this class. The plane containing the central SONNCC atom set subtends a dihedral angle of 31.47 (3)° with the benzene ring. An intra­molecular N—H(...)O hydrogen bond stabilizes the mol­ecular conformation and the mol­ecules form centrosymmetric dimers via inter­molecular N—H(...)S hydrogen bonds.

Related literature

For general background, see: Upadlgaya & Srivastava (1982 [triangle]); Wegner et al. (1986 [triangle]); Krishnamurthy et al. (1999 [triangle]). For related structures, see: Khawar Rauf et al. (2006a [triangle], 2007 [triangle]). For a description of the Cambridge Structural Database, see: Allen (2002 [triangle]). For bond lengths and angles in N,N′-disubstituted thio­urea compounds, see: Arslan et al. (2004 [triangle]); Khawar Rauf et al. (2006b [triangle]); Yamin & Yusof, (2003 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o177-scheme1.jpg

Experimental

Crystal data

  • C14H8Cl4N2OS
  • M r = 394.08
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o177-efi1.jpg
  • a = 14.7737 (13) Å
  • b = 10.3744 (6) Å
  • c = 10.6935 (11) Å
  • β = 97.250 (7)°
  • V = 1625.9 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.86 mm−1
  • T = 173 (2) K
  • 0.42 × 0.38 × 0.21 mm

Data collection

  • Stoe IPDSII two-circle diffractometer
  • Absorption correction: multi-scan (MULABS; Spek, 2003 [triangle]; Blessing, 1995 [triangle]) T min = 0.715, T max = 0.841
  • 12823 measured reflections
  • 3724 independent reflections
  • 3306 reflections with I > 2σ(I)
  • R int = 0.046

Refinement

  • R[F 2 > 2σ(F 2)] = 0.032
  • wR(F 2) = 0.087
  • S = 1.05
  • 3724 reflections
  • 208 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.44 e Å−3
  • Δρmin = −0.36 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808042736/fl2225sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808042736/fl2225Isup2.hkl

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

Acknowledgments

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

supplementary crystallographic information

Comment

Aliphatic and acylthioureas are well known for their fungicidal,antiviral, pesticidal and plant-growth regulating activities (Upadlgaya & Srivastava, 1982; Wegner et al., 1986). Symmetrical and unsymmetrical thioureas have shown antifungal activity against the plant pathogens Pyricularia oryzae and Drechslera oryzae (Krishnamurthy et al., 1999). The background to this study has been set out in our previous work on the structural and biological chemistry of chloro substituted N,N'-disubstituted thioureas (Khawar Rauf et al., 2006a; 2007).The biological studies of these thiourea derivatives are under investigation. Herein, as a continuation of these studies, the structure of the title compound (I) is described (Fig. 1). Bond lengths and angles, can be regarded as typical for N,N'-disubstituted thiourea compounds as found in the Cambridge Structural Database v5.28 (Allen, 2002; Khawar Rauf et al., 2006b; Arslan et al., 2004; Yamin & Yusof, 2003).The molecule exists in the thione form with typical thiourea C—S and C—O bonds, as well as shortened C—N bond lengths. The thiocarbonyl and carbonyl groups are almost coplanar. The molecule features an intramolecular N—H···O hydrogen bond and in the crystal structure, molecules associate via N—H···S intermolecular hydrogen bonds to form centrosymmetric dimers (Table 1; Fig 2).In addition to the intramolecular hydrogen bond, O1 is involved in a short O···Cl contact [O1···Cl2i: 3.0936 (14) Å, symmetry operator i: 1 - x, 1 - y, 1 - z].

Experimental

Freshly prepared 2,6-dichlorobenzoyl isothiocyanate (2.32 g, 10 mmol) was stirred in acetone (40 ml) for 20 minutes. Neat 3,5-dichloroaniline (1.62 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 and stirred well. The solid product was separated and 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 80%.

Refinement

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 Uiso(H) = 1.2Ueq(C). The H atoms bonded to N were freely refined.

Figures

Fig. 1.
Molecular structure of (I) showing atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
Partial packing diagram of (I) with view onto the ac plane. Hydrogen bonds shown as dashed lines.

Crystal data

C14H8Cl4N2OSF(000) = 792
Mr = 394.08Dx = 1.610 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 13230 reflections
a = 14.7737 (13) Åθ = 3.8–27.8°
b = 10.3744 (6) ŵ = 0.86 mm1
c = 10.6935 (11) ÅT = 173 K
β = 97.250 (7)°Plate, colourless
V = 1625.9 (2) Å30.42 × 0.38 × 0.21 mm
Z = 4

Data collection

Stoe IPDSII two-circle diffractometer3724 independent reflections
Radiation source: fine-focus sealed tube3306 reflections with I > 2σ(I)
graphiteRint = 0.046
ω scansθmax = 27.5°, θmin = 3.7°
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995)h = −19→19
Tmin = 0.715, Tmax = 0.841k = −13→13
12823 measured reflectionsl = −10→13

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.087w = 1/[σ2(Fo2) + (0.0525P)2 + 0.486P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
3724 reflectionsΔρmax = 0.44 e Å3
208 parametersΔρmin = −0.36 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0246 (15)

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 (Å2)

xyzUiso*/Ueq
Cl10.35875 (3)0.16745 (4)0.09234 (4)0.02939 (13)
Cl20.39163 (3)0.58457 (4)0.39696 (4)0.02796 (12)
Cl30.93189 (3)0.14605 (4)0.52460 (4)0.03065 (13)
Cl40.97033 (3)0.59117 (4)0.27286 (4)0.02639 (12)
C10.46669 (10)0.35599 (15)0.26849 (14)0.0171 (3)
O10.50255 (7)0.29825 (13)0.36158 (11)0.0257 (3)
N10.51344 (8)0.40910 (14)0.17722 (13)0.0185 (3)
H10.4844 (15)0.443 (2)0.115 (2)0.028 (5)*
S10.64669 (2)0.48065 (5)0.04928 (4)0.02559 (13)
C20.60770 (10)0.41647 (15)0.17586 (15)0.0168 (3)
N20.65773 (8)0.36848 (14)0.27949 (13)0.0178 (3)
H20.6248 (15)0.327 (2)0.333 (2)0.033 (6)*
C110.36443 (10)0.37608 (15)0.24447 (14)0.0170 (3)
C120.30851 (10)0.29239 (16)0.16745 (15)0.0196 (3)
C130.21408 (11)0.30756 (19)0.14814 (18)0.0265 (4)
H130.17710.25060.09410.032*
C140.17491 (11)0.40754 (19)0.2093 (2)0.0300 (4)
H140.11050.41770.19780.036*
C150.22860 (12)0.49305 (18)0.28705 (18)0.0270 (4)
H150.20140.56100.32880.032*
C160.32308 (10)0.47701 (16)0.30247 (15)0.0195 (3)
C210.75373 (10)0.37152 (16)0.31296 (14)0.0170 (3)
C220.79148 (10)0.27196 (16)0.39134 (15)0.0196 (3)
H220.75390.20540.41750.024*
C230.88510 (10)0.27226 (16)0.43034 (15)0.0208 (3)
C240.94227 (10)0.36829 (17)0.39447 (15)0.0217 (3)
H241.00620.36660.42050.026*
C250.90178 (10)0.46720 (16)0.31857 (15)0.0189 (3)
C260.80870 (10)0.47105 (16)0.27637 (15)0.0184 (3)
H260.78320.53940.22420.022*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0285 (2)0.0291 (2)0.0314 (2)−0.00172 (16)0.00678 (17)−0.00990 (17)
Cl20.0319 (2)0.0247 (2)0.0269 (2)−0.00439 (15)0.00228 (17)−0.00444 (16)
Cl30.0275 (2)0.0330 (2)0.0291 (2)0.00629 (16)−0.00562 (16)0.01025 (18)
Cl40.01753 (19)0.0297 (2)0.0324 (2)−0.00597 (14)0.00488 (15)0.00171 (16)
C10.0145 (6)0.0204 (8)0.0165 (7)−0.0021 (5)0.0017 (5)0.0004 (6)
O10.0169 (5)0.0394 (7)0.0207 (6)−0.0008 (5)0.0015 (4)0.0116 (5)
N10.0121 (6)0.0269 (7)0.0160 (6)0.0004 (5)0.0005 (5)0.0066 (5)
S10.01402 (18)0.0436 (3)0.0194 (2)0.00106 (16)0.00325 (14)0.01158 (17)
C20.0135 (6)0.0201 (8)0.0168 (7)0.0008 (5)0.0018 (5)0.0010 (6)
N20.0120 (6)0.0237 (7)0.0177 (6)−0.0012 (5)0.0014 (5)0.0037 (5)
C110.0138 (6)0.0216 (8)0.0158 (7)−0.0009 (5)0.0032 (5)0.0048 (6)
C120.0172 (7)0.0226 (8)0.0192 (8)−0.0013 (6)0.0035 (5)0.0014 (6)
C130.0169 (7)0.0316 (9)0.0298 (9)−0.0065 (6)−0.0021 (6)0.0016 (7)
C140.0135 (7)0.0371 (10)0.0391 (10)0.0025 (7)0.0016 (7)0.0051 (8)
C150.0222 (8)0.0267 (9)0.0330 (10)0.0065 (6)0.0065 (7)0.0029 (7)
C160.0191 (7)0.0205 (8)0.0186 (7)−0.0009 (6)0.0015 (6)0.0028 (6)
C210.0126 (6)0.0226 (8)0.0157 (7)0.0014 (5)0.0009 (5)−0.0016 (6)
C220.0178 (7)0.0232 (8)0.0178 (7)−0.0002 (6)0.0016 (5)0.0013 (6)
C230.0213 (7)0.0244 (8)0.0157 (7)0.0050 (6)−0.0010 (6)0.0017 (6)
C240.0142 (6)0.0298 (9)0.0204 (8)0.0020 (6)−0.0009 (5)−0.0026 (7)
C250.0150 (7)0.0242 (8)0.0178 (7)−0.0024 (6)0.0027 (5)−0.0019 (6)
C260.0147 (6)0.0213 (8)0.0188 (7)0.0007 (5)0.0011 (5)0.0005 (6)

Geometric parameters (Å, °)

Cl1—C121.7397 (17)C13—C141.390 (3)
Cl2—C161.7417 (17)C13—H130.9500
Cl3—C231.7414 (17)C14—C151.393 (3)
Cl4—C251.7445 (16)C14—H140.9500
C1—O11.224 (2)C15—C161.395 (2)
C1—N11.3796 (19)C15—H150.9500
C1—C111.5146 (19)C21—C261.400 (2)
N1—C21.3967 (18)C21—C221.401 (2)
N1—H10.82 (2)C22—C231.393 (2)
S1—C21.6745 (16)C22—H220.9500
C2—N21.347 (2)C23—C241.391 (2)
N2—C211.4186 (18)C24—C251.395 (2)
N2—H20.91 (2)C24—H240.9500
C11—C121.394 (2)C25—C261.393 (2)
C11—C161.396 (2)C26—H260.9500
C12—C131.393 (2)
O1—C1—N1124.54 (14)C14—C15—C16118.71 (16)
O1—C1—C11121.70 (13)C14—C15—H15120.6
N1—C1—C11113.75 (13)C16—C15—H15120.6
C1—N1—C2128.18 (14)C15—C16—C11121.63 (15)
C1—N1—H1118.9 (15)C15—C16—Cl2119.48 (13)
C2—N1—H1112.9 (15)C11—C16—Cl2118.89 (12)
N2—C2—N1114.54 (13)C26—C21—C22120.66 (14)
N2—C2—S1127.07 (11)C26—C21—N2122.87 (14)
N1—C2—S1118.38 (11)C22—C21—N2116.38 (14)
C2—N2—C21128.79 (13)C23—C22—C21118.86 (15)
C2—N2—H2114.5 (15)C23—C22—H22120.6
C21—N2—H2116.7 (15)C21—C22—H22120.6
C12—C11—C16118.01 (13)C24—C23—C22122.24 (15)
C12—C11—C1121.24 (14)C24—C23—Cl3119.19 (12)
C16—C11—C1120.72 (14)C22—C23—Cl3118.57 (13)
C13—C12—C11121.66 (15)C23—C24—C25117.16 (14)
C13—C12—Cl1119.56 (13)C23—C24—H24121.4
C11—C12—Cl1118.78 (11)C25—C24—H24121.4
C14—C13—C12118.88 (16)C26—C25—C24122.87 (15)
C14—C13—H13120.6C26—C25—Cl4118.19 (13)
C12—C13—H13120.6C24—C25—Cl4118.93 (12)
C13—C14—C15121.08 (15)C25—C26—C21118.19 (14)
C13—C14—H14119.5C25—C26—H26120.9
C15—C14—H14119.5C21—C26—H26120.9
O1—C1—N1—C2−4.9 (3)C14—C15—C16—Cl2178.83 (14)
C11—C1—N1—C2174.63 (15)C12—C11—C16—C151.5 (2)
C1—N1—C2—N2−2.2 (2)C1—C11—C16—C15−176.47 (15)
C1—N1—C2—S1177.27 (14)C12—C11—C16—Cl2−178.89 (12)
N1—C2—N2—C21−173.75 (15)C1—C11—C16—Cl23.2 (2)
S1—C2—N2—C216.9 (3)C2—N2—C21—C2630.3 (3)
O1—C1—C11—C12−95.3 (2)C2—N2—C21—C22−152.93 (16)
N1—C1—C11—C1285.17 (19)C26—C21—C22—C23−1.2 (2)
O1—C1—C11—C1682.6 (2)N2—C21—C22—C23−178.08 (14)
N1—C1—C11—C16−96.94 (18)C21—C22—C23—C240.2 (2)
C16—C11—C12—C13−0.1 (2)C21—C22—C23—Cl3−178.45 (12)
C1—C11—C12—C13177.83 (15)C22—C23—C24—C251.1 (2)
C16—C11—C12—Cl1179.03 (12)Cl3—C23—C24—C25179.77 (12)
C1—C11—C12—Cl1−3.0 (2)C23—C24—C25—C26−1.5 (2)
C11—C12—C13—C14−1.1 (3)C23—C24—C25—Cl4179.11 (12)
Cl1—C12—C13—C14179.72 (14)C24—C25—C26—C210.5 (2)
C12—C13—C14—C151.1 (3)Cl4—C25—C26—C21179.94 (12)
C13—C14—C15—C160.2 (3)C22—C21—C26—C250.9 (2)
C14—C15—C16—C11−1.5 (3)N2—C21—C26—C25177.49 (14)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2···O10.91 (2)1.89 (2)2.6581 (17)141 (2)
N1—H1···S1i0.82 (2)2.57 (2)3.3653 (14)163 (2)

Symmetry codes: (i) −x+1, −y+1, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FL2225).

References

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  • Khawar Rauf, M., Badshah, A. & Bolte, M. (2007). Acta Cryst. E63, o2665–o2666.
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  • Wegner, P., Hans, R., Frank, H. & Joppien, H. (1986). Eur. Patent No. 190 611.
  • Yamin, B. M. & Yusof, M. S. M. (2003). Acta Cryst. E59, o151–o152.

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