1-(4-Chlorophenyl)-3-(3-chloro­pro­pionyl)thio­urea

Yamin, B.M.; Soh, S.K.C.; Yusoff, S.F.M.

doi:10.1107/S1600536813028511

organic compounds

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Volume 69| Part 11| November 2013| Page o1696

doi:10.1107/S1600536813028511

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1-(4-Chlorophenyl)-3-(3-chloropropionyl)thiourea

Bohari M. Yamin,^a Siti K. C. Soh ^a and Siti Fairus M. Yusoff ^a ^*

^aSchool of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia
^*Correspondence e-mail: ctfairus@ukm.my

(Received 20 September 2013; accepted 17 October 2013; online 23 October 2013)

In the title compound, C₁₀H₁₀Cl₂N₂OS, the molecule adopts a trans–cis conformation with respect to the position of the carbonyl group and the chlorophenyl groups relative to the thiono group across the C—N bonds. The molecule is stabilized by an N—H⋯O hydrogen bond. In the crystal, molecules are linked by N—H⋯S and C—H⋯O hydrogen bonds, forming zigzag chains along the b-axis direction. C—H⋯π interactions are also present.

CCDC reference: 966877

Related literature

For bond-length data, see: Allen et al. (1987 ). For related thiourea derivatives, see: Othman et al. (2010 ); Yamin et al. (2011 ); Yamin & Othman (2011 ); Yusof et al. (2011 ).

Experimental

Crystal data

C₁₀H₁₀Cl₂N₂OS
M_r = 277.16
Triclinic, $[P \overline 1]$
a = 5.5151 (16) Å
b = 9.045 (3) Å
c = 12.387 (4) Å
α = 101.000 (5)°
β = 94.027 (5)°
γ = 94.780 (5)°
V = 602.1 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.69 mm⁻¹
T = 298 K
0.47 × 0.21 × 0.08 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.737, T_max = 0.947
5947 measured reflections
2227 independent reflections
1698 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.116
S = 1.22
2227 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C5–C10 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1	0.86	1.92	2.646 (4)	141
N1—H1A⋯S1ⁱ	0.86	2.52	3.367 (3)	169
C9—H9A⋯O1ⁱⁱ	0.93	2.55	3.402 (5)	152
C1—H1B⋯Cg1ⁱⁱⁱ	0.97	2.92	3.690 (4)	137
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x-1, -y, -z+1; (iii) -x, -y, -z+1.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 966877

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813028511/lr2115sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813028511/lr2115Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813028511/lr2115Isup3.cml

checkCIF report

Comment top

There are not many halogenocarbonyl reported compare to other aroyl or alkoyl-thioureas. N-(4-chlorobutanoyl)-N'-phenylthiourea (Yamin et al., 2011), N-(4-chlorobutanoyl)-N'-(2-fluorophenyl)thiourea (Yusof et al., 2011) and N-(4-bromobutanoyl)-N'-phenylthiourea (Yamin & Othman, 2011) are some examples of halogenobutanoyl thiourea. The title compound is a 3-chloropropionyl thiourea similar to N-(3-chloropropionyl)-N'- phenylthiourea (Othman et al. 2010) except the presence of chlorine atom at the para-position of the phenyl ring.

The whole molecule is not planar (Fig. 1) because of the dihedral angle of 14.36 (12)° between chlorophenylamine, Cl2/(C5-C10)/N2, and thiourea C5/N2/C4/N1/S1 fragments. Both fragments are each planar with maximum deviation of 0.015 (3)Å for N2 atom from the least square plane of the thiourea fragment. The bond lengths and angles are in normal ranges (Allen et al. 1987). The molecule maintains trans-cis configuration with respect to the position of chloropropionyl and chlorophenyl against the thiono group about N1-C4 and N2-C4 bonds, respectively.

There is an intramolecular N2-H2A···O1 hydrogen bonds . In the crystal packing, the molecules are linked by N1-H1A···S1 and C9-H9A···O1 intermolecular hydrogen bonds (symmetry codes as in Table 1) to form zigzag linear chains extended along b axis (Fig. 2). In addition, there is also a C1-H1B···π bond with the centroid benzene ring Cg1, (C5-C10) (Table 2).

Related literature top

For bond-length data, see: Allen et al. (1987). For related thiourea derivatives, see: Othman et al. (2010); Yamin et al. (2011); Yamin & Othman (2011); Yusof et al. (2011).

Experimental top

4-chloroaniline (1.27 g, 0.01 mol) disolved in 30 ml of acetone was added into a solution of 3-chloropropionyl isothiocyanate (1.49 g, 0.01 mol) in 30 ml acetone. The mixture was refluxed for 2 hours. The solution was filtered and left to evaporate at room temperature. The white precipitate obtained after a few days, was washed with water and cold ethanol. The colorless crystals were obtained by recrystallization from ethanol.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular structure of (I) with 50% probability displacement ellipsoids
	Fig. 2. Molecular packing of (I) in the unit cell viewed down the a axis

1-(4-Chlorophenyl)-3-(3-chloropropionyl)thiourea top

Crystal data top

C₁₀H₁₀Cl₂N₂OS	V = 602.1 (3) Å³
M_r = 277.16	Z = 2
Triclinic, P1	F(000) = 284
Hall symbol: -P 1	D_x = 1.529 Mg m⁻³
a = 5.5151 (16) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.045 (3) Å	µ = 0.69 mm⁻¹
c = 12.387 (4) Å	T = 298 K
α = 101.000 (5)°	Block, colourless
β = 94.027 (5)°	0.47 × 0.21 × 0.08 mm
γ = 94.780 (5)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2227 independent reflections
Radiation source: fine-focus sealed tube	1698 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
Detector resolution: 83.66 pixels mm^-1	θ_max = 25.5°, θ_min = 1.7°
ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −10→10
T_min = 0.737, T_max = 0.947	l = −14→14
5947 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H-atom parameters constrained
S = 1.22	w = 1/[σ²(F_o²) + (0.0289P)² + 0.4821P] where P = (F_o² + 2F_c²)/3
2227 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₀H₁₀Cl₂N₂OS	γ = 94.780 (5)°
M_r = 277.16	V = 602.1 (3) Å³
Triclinic, P1	Z = 2
a = 5.5151 (16) Å	Mo Kα radiation
b = 9.045 (3) Å	µ = 0.69 mm⁻¹
c = 12.387 (4) Å	T = 298 K
α = 101.000 (5)°	0.47 × 0.21 × 0.08 mm
β = 94.027 (5)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2227 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1698 reflections with I > 2σ(I)
T_min = 0.737, T_max = 0.947	R_int = 0.035
5947 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.22	Δρ_max = 0.25 e Å⁻³
2227 reflections	Δρ_min = −0.29 e Å⁻³
145 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	−0.1359 (2)	0.15827 (13)	0.11875 (8)	0.0690 (3)
Cl2	−0.63977 (19)	0.26746 (13)	0.95531 (9)	0.0666 (3)
S1	0.27725 (18)	0.51842 (10)	0.63440 (8)	0.0481 (3)
O1	−0.0306 (5)	0.1007 (3)	0.3804 (2)	0.0569 (7)
N1	0.2306 (5)	0.3097 (3)	0.4537 (2)	0.0405 (7)
H1A	0.3596	0.3612	0.4406	0.049*
N2	−0.0333 (5)	0.2657 (3)	0.5811 (2)	0.0422 (7)
H2A	−0.0743	0.1856	0.5312	0.051*
C1	0.1271 (7)	0.0805 (4)	0.1674 (3)	0.0491 (9)
H1B	0.0777	−0.0151	0.1878	0.059*
H1C	0.2346	0.0610	0.1087	0.059*
C2	0.2629 (7)	0.1865 (4)	0.2656 (3)	0.0465 (9)
H2B	0.4247	0.1547	0.2774	0.056*
H2C	0.2824	0.2874	0.2494	0.056*
C3	0.1378 (6)	0.1931 (4)	0.3701 (3)	0.0419 (8)
C4	0.1477 (6)	0.3573 (4)	0.5567 (3)	0.0369 (8)
C5	−0.1697 (6)	0.2764 (4)	0.6739 (3)	0.0382 (8)
C6	−0.1040 (7)	0.3699 (4)	0.7750 (3)	0.0503 (10)
H6A	0.0389	0.4351	0.7854	0.060*
C7	−0.2499 (7)	0.3672 (4)	0.8611 (3)	0.0522 (10)
H7A	−0.2060	0.4310	0.9291	0.063*
C8	−0.4593 (6)	0.2700 (4)	0.8458 (3)	0.0436 (9)
C9	−0.5279 (6)	0.1755 (4)	0.7458 (3)	0.0467 (9)
H9A	−0.6708	0.1104	0.7358	0.056*
C10	−0.3824 (6)	0.1788 (4)	0.6610 (3)	0.0442 (9)
H10A	−0.4269	0.1143	0.5932	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0701 (7)	0.0818 (8)	0.0521 (6)	0.0101 (6)	0.0018 (5)	0.0059 (5)
Cl2	0.0648 (7)	0.0843 (8)	0.0560 (6)	0.0065 (6)	0.0285 (5)	0.0192 (5)
S1	0.0518 (6)	0.0429 (5)	0.0431 (5)	−0.0112 (4)	0.0107 (4)	−0.0034 (4)
O1	0.0667 (18)	0.0535 (16)	0.0418 (14)	−0.0241 (14)	0.0165 (12)	−0.0041 (12)
N1	0.0400 (16)	0.0419 (16)	0.0347 (16)	−0.0095 (13)	0.0090 (12)	−0.0012 (12)
N2	0.0476 (17)	0.0416 (16)	0.0320 (15)	−0.0097 (13)	0.0099 (13)	−0.0027 (12)
C1	0.054 (2)	0.049 (2)	0.039 (2)	−0.0039 (18)	0.0112 (17)	−0.0030 (16)
C2	0.053 (2)	0.049 (2)	0.0352 (19)	−0.0072 (18)	0.0104 (17)	0.0039 (16)
C3	0.049 (2)	0.040 (2)	0.0351 (19)	−0.0011 (17)	0.0060 (16)	0.0035 (15)
C4	0.0367 (19)	0.0363 (19)	0.0359 (18)	−0.0024 (15)	0.0017 (14)	0.0057 (14)
C5	0.0395 (19)	0.043 (2)	0.0315 (18)	0.0014 (16)	0.0052 (14)	0.0053 (15)
C6	0.044 (2)	0.062 (2)	0.039 (2)	−0.0111 (18)	0.0075 (16)	0.0024 (18)
C7	0.057 (2)	0.063 (3)	0.033 (2)	−0.001 (2)	0.0095 (17)	0.0000 (17)
C8	0.041 (2)	0.052 (2)	0.042 (2)	0.0070 (17)	0.0135 (16)	0.0141 (17)
C9	0.040 (2)	0.048 (2)	0.052 (2)	−0.0045 (17)	0.0088 (17)	0.0114 (18)
C10	0.045 (2)	0.045 (2)	0.040 (2)	−0.0032 (17)	0.0050 (16)	0.0028 (16)

Geometric parameters (Å, º) top

Cl1—C1	1.780 (4)	C2—C3	1.502 (4)
Cl2—C8	1.741 (3)	C2—H2B	0.9700
S1—C4	1.660 (3)	C2—H2C	0.9700
O1—C3	1.227 (4)	C5—C6	1.376 (5)
N1—C3	1.366 (4)	C5—C10	1.388 (5)
N1—C4	1.389 (4)	C6—C7	1.383 (5)
N1—H1A	0.8600	C6—H6A	0.9300
N2—C4	1.332 (4)	C7—C8	1.370 (5)
N2—C5	1.410 (4)	C7—H7A	0.9300
N2—H2A	0.8600	C8—C9	1.373 (5)
C1—C2	1.506 (4)	C9—C10	1.369 (5)
C1—H1B	0.9700	C9—H9A	0.9300
C1—H1C	0.9700	C10—H10A	0.9300

C3—N1—C4	129.6 (3)	N2—C4—N1	114.4 (3)
C3—N1—H1A	115.2	N2—C4—S1	127.3 (3)
C4—N1—H1A	115.2	N1—C4—S1	118.3 (2)
C4—N2—C5	131.6 (3)	C6—C5—C10	118.7 (3)
C4—N2—H2A	114.2	C6—C5—N2	125.5 (3)
C5—N2—H2A	114.2	C10—C5—N2	115.7 (3)
C2—C1—Cl1	111.2 (3)	C5—C6—C7	120.2 (3)
C2—C1—H1B	109.4	C5—C6—H6A	119.9
Cl1—C1—H1B	109.4	C7—C6—H6A	119.9
C2—C1—H1C	109.4	C8—C7—C6	119.7 (3)
Cl1—C1—H1C	109.4	C8—C7—H7A	120.1
H1B—C1—H1C	108.0	C6—C7—H7A	120.1
C3—C2—C1	113.6 (3)	C7—C8—C9	121.0 (3)
C3—C2—H2B	108.8	C7—C8—Cl2	119.1 (3)
C1—C2—H2B	108.8	C9—C8—Cl2	119.9 (3)
C3—C2—H2C	108.8	C10—C9—C8	118.9 (3)
C1—C2—H2C	108.8	C10—C9—H9A	120.6
H2B—C2—H2C	107.7	C8—C9—H9A	120.6
O1—C3—N1	122.7 (3)	C9—C10—C5	121.4 (3)
O1—C3—C2	123.2 (3)	C9—C10—H10A	119.3
N1—C3—C2	114.1 (3)	C5—C10—H10A	119.3

Cl1—C1—C2—C3	73.9 (4)	C10—C5—C6—C7	−0.8 (6)
C4—N1—C3—O1	−7.3 (6)	N2—C5—C6—C7	−178.1 (3)
C4—N1—C3—C2	173.8 (3)	C5—C6—C7—C8	0.5 (6)
C1—C2—C3—O1	13.7 (5)	C6—C7—C8—C9	−0.4 (6)
C1—C2—C3—N1	−167.4 (3)	C6—C7—C8—Cl2	179.7 (3)
C5—N2—C4—N1	−177.7 (3)	C7—C8—C9—C10	0.4 (6)
C5—N2—C4—S1	1.6 (6)	Cl2—C8—C9—C10	−179.6 (3)
C3—N1—C4—N2	7.8 (5)	C8—C9—C10—C5	−0.7 (6)
C3—N1—C4—S1	−171.5 (3)	C6—C5—C10—C9	0.9 (5)
C4—N2—C5—C6	−17.2 (6)	N2—C5—C10—C9	178.4 (3)
C4—N2—C5—C10	165.4 (3)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C5–C10 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.86	1.92	2.646 (4)	141
C6—H6A···S1	0.93	2.55	3.193 (4)	126
N1—H1A···S1ⁱ	0.86	2.52	3.367 (3)	169
C9—H9A···O1ⁱⁱ	0.93	2.55	3.402 (5)	152
C1—H1B···Cg1ⁱⁱⁱ	0.97	2.92	3.690 (4)	137

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x−1, −y, −z+1; (iii) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C5–C10 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.86	1.92	2.646 (4)	141
N1—H1A···S1ⁱ	0.86	2.52	3.367 (3)	169
C9—H9A···O1ⁱⁱ	0.93	2.55	3.402 (5)	152
C1—H1B···Cg1ⁱⁱⁱ	0.97	2.92	3.690 (4)	137

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x−1, −y, −z+1; (iii) −x, −y, −z+1.

Acknowledgements

The authors would like to thank Universiti Kebangsaan Malaysia and the Ministry of Science and Technology, Malaysia for research grants GGPM-2012-015 and DIP-2012-11, and the Centre of Research and Instrumentation (CRIM) for research facilities.

References

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doi:10.1107/S1600536813028511

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