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

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

Experimental

Crystal data

• C₁₄H₈Cl₄N₂OS

• M_r = 394.08

• Monoclinic, P 2₁ /c

• a = 14.7737 (13) Å

• b = 10.3744 (6) Å

• c = 10.6935 (11) Å

• β = 97.250 (7)°

• V = 1625.9 (2) ų

• 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; Blessing, 1995) 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[F² > 2σ(F²)] = 0.032

• wR(F²) = 0.087

• S = 1.05

• 3724 reflections

• 208 parameters

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

• Δρ_max = 0.44 e Å⁻³

• Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1	0.91 (2)	1.89 (2)	2.6581 (17)	141 (2)
N1—H1⋯S1^i	0.82 (2)	2.57 (2)	3.3653 (14)	163 (2)
Symmetry code: (i) -x+1, -y+1, -z.

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

Supporting information

S1. 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].

Related literature

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

S2. 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%.

S3. 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 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 (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: XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

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.

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

Crystal data

C14H8Cl4N2OS	F(000) = 792
Mr = 394.08	Dx = 1.610 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 13230 reflections
a = 14.7737 (13) Å	θ = 3.8–27.8°
b = 10.3744 (6) Å	µ = 0.86 mm^−1
c = 10.6935 (11) Å	T = 173 K
β = 97.250 (7)°	Plate, colourless
V = 1625.9 (2) Å^3	0.42 × 0.38 × 0.21 mm
Z = 4

Data collection

Stoe IPDSII two-circle diffractometer	3724 independent reflections
Radiation source: fine-focus sealed tube	3306 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
ω scans	θmax = 27.5°, θmin = 3.7°
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995)	h = −19→19
Tmin = 0.715, Tmax = 0.841	k = −13→13
12823 measured reflections	l = −10→13

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) = 0.087	w = 1/[σ^2(Fo^2) + (0.0525P)^2 + 0.486P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
3724 reflections	Δρmax = 0.44 e Å^−3
208 parameters	Δρmin = −0.36 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction 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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.35875 (3)	0.16745 (4)	0.09234 (4)	0.02939 (13)
Cl2	0.39163 (3)	0.58457 (4)	0.39696 (4)	0.02796 (12)
Cl3	0.93189 (3)	0.14605 (4)	0.52460 (4)	0.03065 (13)
Cl4	0.97033 (3)	0.59117 (4)	0.27286 (4)	0.02639 (12)
C1	0.46669 (10)	0.35599 (15)	0.26849 (14)	0.0171 (3)
O1	0.50255 (7)	0.29825 (13)	0.36158 (11)	0.0257 (3)
N1	0.51344 (8)	0.40910 (14)	0.17722 (13)	0.0185 (3)
H1	0.4844 (15)	0.443 (2)	0.115 (2)	0.028 (5)*
S1	0.64669 (2)	0.48065 (5)	0.04928 (4)	0.02559 (13)
C2	0.60770 (10)	0.41647 (15)	0.17586 (15)	0.0168 (3)
N2	0.65773 (8)	0.36848 (14)	0.27949 (13)	0.0178 (3)
H2	0.6248 (15)	0.327 (2)	0.333 (2)	0.033 (6)*
C11	0.36443 (10)	0.37608 (15)	0.24447 (14)	0.0170 (3)
C12	0.30851 (10)	0.29239 (16)	0.16745 (15)	0.0196 (3)
C13	0.21408 (11)	0.30756 (19)	0.14814 (18)	0.0265 (4)
H13	0.1771	0.2506	0.0941	0.032*
C14	0.17491 (11)	0.40754 (19)	0.2093 (2)	0.0300 (4)
H14	0.1105	0.4177	0.1978	0.036*
C15	0.22860 (12)	0.49305 (18)	0.28705 (18)	0.0270 (4)
H15	0.2014	0.5610	0.3288	0.032*
C16	0.32308 (10)	0.47701 (16)	0.30247 (15)	0.0195 (3)
C21	0.75373 (10)	0.37152 (16)	0.31296 (14)	0.0170 (3)
C22	0.79148 (10)	0.27196 (16)	0.39134 (15)	0.0196 (3)
H22	0.7539	0.2054	0.4175	0.024*
C23	0.88510 (10)	0.27226 (16)	0.43034 (15)	0.0208 (3)
C24	0.94227 (10)	0.36829 (17)	0.39447 (15)	0.0217 (3)
H24	1.0062	0.3666	0.4205	0.026*
C25	0.90178 (10)	0.46720 (16)	0.31857 (15)	0.0189 (3)
C26	0.80870 (10)	0.47105 (16)	0.27637 (15)	0.0184 (3)
H26	0.7832	0.5394	0.2242	0.022*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0285 (2)	0.0291 (2)	0.0314 (2)	−0.00172 (16)	0.00678 (17)	−0.00990 (17)
Cl2	0.0319 (2)	0.0247 (2)	0.0269 (2)	−0.00439 (15)	0.00228 (17)	−0.00444 (16)
Cl3	0.0275 (2)	0.0330 (2)	0.0291 (2)	0.00629 (16)	−0.00562 (16)	0.01025 (18)
Cl4	0.01753 (19)	0.0297 (2)	0.0324 (2)	−0.00597 (14)	0.00488 (15)	0.00171 (16)
C1	0.0145 (6)	0.0204 (8)	0.0165 (7)	−0.0021 (5)	0.0017 (5)	0.0004 (6)
O1	0.0169 (5)	0.0394 (7)	0.0207 (6)	−0.0008 (5)	0.0015 (4)	0.0116 (5)
N1	0.0121 (6)	0.0269 (7)	0.0160 (6)	0.0004 (5)	0.0005 (5)	0.0066 (5)
S1	0.01402 (18)	0.0436 (3)	0.0194 (2)	0.00106 (16)	0.00325 (14)	0.01158 (17)
C2	0.0135 (6)	0.0201 (8)	0.0168 (7)	0.0008 (5)	0.0018 (5)	0.0010 (6)
N2	0.0120 (6)	0.0237 (7)	0.0177 (6)	−0.0012 (5)	0.0014 (5)	0.0037 (5)
C11	0.0138 (6)	0.0216 (8)	0.0158 (7)	−0.0009 (5)	0.0032 (5)	0.0048 (6)
C12	0.0172 (7)	0.0226 (8)	0.0192 (8)	−0.0013 (6)	0.0035 (5)	0.0014 (6)
C13	0.0169 (7)	0.0316 (9)	0.0298 (9)	−0.0065 (6)	−0.0021 (6)	0.0016 (7)
C14	0.0135 (7)	0.0371 (10)	0.0391 (10)	0.0025 (7)	0.0016 (7)	0.0051 (8)
C15	0.0222 (8)	0.0267 (9)	0.0330 (10)	0.0065 (6)	0.0065 (7)	0.0029 (7)
C16	0.0191 (7)	0.0205 (8)	0.0186 (7)	−0.0009 (6)	0.0015 (6)	0.0028 (6)
C21	0.0126 (6)	0.0226 (8)	0.0157 (7)	0.0014 (5)	0.0009 (5)	−0.0016 (6)
C22	0.0178 (7)	0.0232 (8)	0.0178 (7)	−0.0002 (6)	0.0016 (5)	0.0013 (6)
C23	0.0213 (7)	0.0244 (8)	0.0157 (7)	0.0050 (6)	−0.0010 (6)	0.0017 (6)
C24	0.0142 (6)	0.0298 (9)	0.0204 (8)	0.0020 (6)	−0.0009 (5)	−0.0026 (7)
C25	0.0150 (7)	0.0242 (8)	0.0178 (7)	−0.0024 (6)	0.0027 (5)	−0.0019 (6)
C26	0.0147 (6)	0.0213 (8)	0.0188 (7)	0.0007 (5)	0.0011 (5)	0.0005 (6)

Geometric parameters (Å, º)

Cl1—C12	1.7397 (17)	C13—C14	1.390 (3)
Cl2—C16	1.7417 (17)	C13—H13	0.9500
Cl3—C23	1.7414 (17)	C14—C15	1.393 (3)
Cl4—C25	1.7445 (16)	C14—H14	0.9500
C1—O1	1.224 (2)	C15—C16	1.395 (2)
C1—N1	1.3796 (19)	C15—H15	0.9500
C1—C11	1.5146 (19)	C21—C26	1.400 (2)
N1—C2	1.3967 (18)	C21—C22	1.401 (2)
N1—H1	0.82 (2)	C22—C23	1.393 (2)
S1—C2	1.6745 (16)	C22—H22	0.9500
C2—N2	1.347 (2)	C23—C24	1.391 (2)
N2—C21	1.4186 (18)	C24—C25	1.395 (2)
N2—H2	0.91 (2)	C24—H24	0.9500
C11—C12	1.394 (2)	C25—C26	1.393 (2)
C11—C16	1.396 (2)	C26—H26	0.9500
C12—C13	1.393 (2)
O1—C1—N1	124.54 (14)	C14—C15—C16	118.71 (16)
O1—C1—C11	121.70 (13)	C14—C15—H15	120.6
N1—C1—C11	113.75 (13)	C16—C15—H15	120.6
C1—N1—C2	128.18 (14)	C15—C16—C11	121.63 (15)
C1—N1—H1	118.9 (15)	C15—C16—Cl2	119.48 (13)
C2—N1—H1	112.9 (15)	C11—C16—Cl2	118.89 (12)
N2—C2—N1	114.54 (13)	C26—C21—C22	120.66 (14)
N2—C2—S1	127.07 (11)	C26—C21—N2	122.87 (14)
N1—C2—S1	118.38 (11)	C22—C21—N2	116.38 (14)
C2—N2—C21	128.79 (13)	C23—C22—C21	118.86 (15)
C2—N2—H2	114.5 (15)	C23—C22—H22	120.6
C21—N2—H2	116.7 (15)	C21—C22—H22	120.6
C12—C11—C16	118.01 (13)	C24—C23—C22	122.24 (15)
C12—C11—C1	121.24 (14)	C24—C23—Cl3	119.19 (12)
C16—C11—C1	120.72 (14)	C22—C23—Cl3	118.57 (13)
C13—C12—C11	121.66 (15)	C23—C24—C25	117.16 (14)
C13—C12—Cl1	119.56 (13)	C23—C24—H24	121.4
C11—C12—Cl1	118.78 (11)	C25—C24—H24	121.4
C14—C13—C12	118.88 (16)	C26—C25—C24	122.87 (15)
C14—C13—H13	120.6	C26—C25—Cl4	118.19 (13)
C12—C13—H13	120.6	C24—C25—Cl4	118.93 (12)
C13—C14—C15	121.08 (15)	C25—C26—C21	118.19 (14)
C13—C14—H14	119.5	C25—C26—H26	120.9
C15—C14—H14	119.5	C21—C26—H26	120.9
O1—C1—N1—C2	−4.9 (3)	C14—C15—C16—Cl2	178.83 (14)
C11—C1—N1—C2	174.63 (15)	C12—C11—C16—C15	1.5 (2)
C1—N1—C2—N2	−2.2 (2)	C1—C11—C16—C15	−176.47 (15)
C1—N1—C2—S1	177.27 (14)	C12—C11—C16—Cl2	−178.89 (12)
N1—C2—N2—C21	−173.75 (15)	C1—C11—C16—Cl2	3.2 (2)
S1—C2—N2—C21	6.9 (3)	C2—N2—C21—C26	30.3 (3)
O1—C1—C11—C12	−95.3 (2)	C2—N2—C21—C22	−152.93 (16)
N1—C1—C11—C12	85.17 (19)	C26—C21—C22—C23	−1.2 (2)
O1—C1—C11—C16	82.6 (2)	N2—C21—C22—C23	−178.08 (14)
N1—C1—C11—C16	−96.94 (18)	C21—C22—C23—C24	0.2 (2)
C16—C11—C12—C13	−0.1 (2)	C21—C22—C23—Cl3	−178.45 (12)
C1—C11—C12—C13	177.83 (15)	C22—C23—C24—C25	1.1 (2)
C16—C11—C12—Cl1	179.03 (12)	Cl3—C23—C24—C25	179.77 (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—Cl4	179.11 (12)
Cl1—C12—C13—C14	179.72 (14)	C24—C25—C26—C21	0.5 (2)
C12—C13—C14—C15	1.1 (3)	Cl4—C25—C26—C21	179.94 (12)
C13—C14—C15—C16	0.2 (3)	C22—C21—C26—C25	0.9 (2)
C14—C15—C16—C11	−1.5 (3)	N2—C21—C26—C25	177.49 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.91 (2)	1.89 (2)	2.6581 (17)	141 (2)
N1—H1···S1^i	0.82 (2)	2.57 (2)	3.3653 (14)	163 (2)

Symmetry code: (i) −x+1, −y+1, −z.