N-(3-Chloro­propion­yl)-N′-phenyl­thio­urea

Othman, E.A.; Soh, S.K.C.; Yamin, B.M.

doi:10.1107/S1600536810005271

organic compounds

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Volume 66| Part 3| March 2010| Page o628

doi:10.1107/S1600536810005271

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N-(3-Chloropropionyl)-N′-phenylthiourea

Eliyanti A. Othman,^a Siti K. C. Soh ^a and Bohari M. Yamin ^a ^*

^aSchool of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, UKM 43500 Bangi Selangor, Malaysia
^*Correspondence e-mail: bohari@ukm.my

(Received 27 January 2010; accepted 9 February 2010; online 13 February 2010)

The title compound, C₁₀H₁₁ClN₂OS, adopts a cis-trans configuration with respect to the position of the phenyl and 3-chloropropionyl groups relative to the thiono group across the C—N bonds. The benzene ring is perpendicular to the propionyl thiourea fragment with a dihedral angle of 82.62 (10)°. An intramolecular N—H⋯O interaction occurs. The crystal structure is stabilized by intermolecular N—H⋯S hydrogen bonds, which link pairs of molecules, building up R₂²(8) ring motifs, and C—H.. π interactions.

Related literature

For related structures, see: Ismail et al. (2007 ); Ismail & Yamin (2009 ). For hydrogen-bond motifs, see: Etter et al.(1990 ); Bernstein et al. (1995 ). For reference bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₀H₁₁ClN₂OS
M_r = 242.72
Triclinic, $[P \overline 1]$
a = 5.8088 (12) Å
b = 10.467 (2) Å
c = 10.660 (2) Å
α = 112.811 (3)°
β = 101.855 (3)°
γ = 95.483 (3)°
V = 573.6 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.49 mm⁻¹
T = 298 K
0.49 × 0.45 × 0.27 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.795, T_max = 0.879
5617 measured reflections
2103 independent reflections
1798 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.113
S = 1.04
2103 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C5–C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1	0.86	2.01	2.677 (3)	134
N1—H1A⋯S1ⁱ	0.86	2.53	3.3709 (19)	165
C1—H1C⋯Cg1ⁱⁱ	0.97	2.84	3.466	123
Symmetry codes: (i) -x+2, -y+2, -z+1; (ii) -x+2, -y+1, -z.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810005271/dn2535sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810005271/dn2535Isup2.hkl

checkCIF report

Comment top

The presence of both alpha and ipso chlorine atoms in 2-chloropropionyl chloride could lead to a complicated reaction when reacted with a nucleophile such as thiocyanate depending on the solvent used. For example, the reaction of 2-chloropropionyl chloride with ammonium thiocyanate and succeedingly with aniline in acetone was found to give 4,5,6-trimethyl-1- phenyl-3,4-dihydropyrimidine-2(1H)-thione (Ismail et al., 2007) instead of the expected N-phenyl-N'-(2-chloropropionyl) thiourea. However, in the present study, the same reaction but with 3-chloropropionyl chloride, the expected N-phenyl-N'-(3-chloropropionyl)thiourea (I) was indeed obtained.

The whole molecule is not planar (Fig.1). The benzene (C5—C10) ring and propionylthiourea fragment, S1/N1/N2/(C1—C4) are each planar with maximum deviation of 0.062 (2)Å for C3 atom from the least square plane. The benzene ring is roughly perpendicular to the propionylthiourea fragment with dihedral angle between the two planes of 82.62 (10)°. A smaller dihedral angle of 12.68 (7)° was observed in an analogous compound of N-(3-chloropropionyl)-N'(4-fluorophenyl) thiourea (II) (Ismail & Yamin, 2009).The trans-cis configuration of the propionyl and phenyl groups relative to the thiono group respectively, across their C—N bonds, is maintained. The bond lengths and angles are in normal range (Allen et al.,1987) and comparable to those in (II).

There is one intrahydrogen bond, N2—H2A···O1 forming the pseudo-six membered ring, N2/C4/N1/C3/O1···H2A. In the crystal structure, the molecules are linked by N1—H1A···S1 intermolecular hydrogen bond forming dimers through a R₂²(8) ring (Etter et al., 1990 ; Bernstein et al., 1995) extending along the c-axis (Table 1, Fig.2). In addition, there is also a C1—H1C.,.π bond with the benzene (C5—C10) ring (Table 1).

Related literature top

For related structures, see: Ismail et al. (2007); Ismail & Yamin (2009). For hydrogen-bond motifs, see: Etter et al.(1990); Bernstein et al. (1995). For reference bond lengths, see: Allen et al. (1987).

Experimental top

30 ml acetone solution of aniline was added into 30 ml acetone containing 3-chloropropionyl isothiocyanate (1.49, 0.01 mol). 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 crsytals were obtained by recrystallization from ethanol. Yield 90%; m.p 389.7-391.2 K; ¹H NMR (400 MHz, CDCl₃-d₆):δ (ppm)= 12.32 (s,1H), 9.99 (s,1H), 7.63 (m,4H, H_Ar), 7.41 (s,1H, H_Ar), 3.8 (d,2H,Cl—CH₂), 2.9 (d,2H,CH₂). ¹³C NMR (400 MHz, CDCl₃-d₆):δ (ppm)= 38.32, 39.76, 124.70, 127.35, 127.35, 129.08, 129.08, 137.30, 171.22, 178.49.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (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. The molecular structure of (I),with displacement ellipsods drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. A packing diagram of (I) viewed down the a axis. Hydrogen bonds are shown by dashed lines. H atoms not involved in hydrogen bondings have been omitted for clarity. [Symmetry code: (i) -x+2, -y+2, -z+1]

N-(3-chloropropionyl)-N'-phenylthiourea top

Crystal data top

C₁₀H₁₁ClN₂OS	Z = 2
M_r = 242.72	F(000) = 252
Triclinic, P1	D_x = 1.405 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.8088 (12) Å	Cell parameters from 3405 reflections
b = 10.467 (2) Å	θ = 2.1–25.5°
c = 10.660 (2) Å	µ = 0.49 mm⁻¹
α = 112.811 (3)°	T = 298 K
β = 101.855 (3)°	Block, colourless
γ = 95.483 (3)°	0.49 × 0.45 × 0.27 mm
V = 573.6 (2) Å³

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2103 independent reflections
Radiation source: fine-focus sealed tube	1798 reflections with I > 2σ(I)
Detector resolution: 83.66 pixels mm^-1	R_int = 0.016
ω scan	θ_max = 25.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −7→7
T_min = 0.795, T_max = 0.879	k = −12→12
5617 measured reflections	l = −12→12

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0559P)² + 0.2663P] where P = (F_o² + 2F_c²)/3
2103 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.54 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

C₁₀H₁₁ClN₂OS	γ = 95.483 (3)°
M_r = 242.72	V = 573.6 (2) Å³
Triclinic, P1	Z = 2
a = 5.8088 (12) Å	Mo Kα radiation
b = 10.467 (2) Å	µ = 0.49 mm⁻¹
c = 10.660 (2) Å	T = 298 K
α = 112.811 (3)°	0.49 × 0.45 × 0.27 mm
β = 101.855 (3)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2103 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1798 reflections with I > 2σ(I)
T_min = 0.795, T_max = 0.879	R_int = 0.016
5617 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.113	H-atom parameters constrained
S = 1.04	Δρ_max = 0.54 e Å⁻³
2103 reflections	Δρ_min = −0.43 e Å⁻³
136 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 > 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

	x	y	z	U_iso*/U_eq
Cl1	0.23811 (13)	1.37819 (8)	0.50799 (7)	0.0777 (3)
S1	1.10045 (13)	0.86771 (7)	0.31949 (6)	0.0653 (2)
O1	0.5152 (3)	1.07380 (16)	0.16725 (14)	0.0539 (4)
N1	0.7823 (3)	1.03263 (18)	0.32922 (17)	0.0497 (4)
H1A	0.8413	1.0614	0.4186	0.060*
N2	0.7847 (3)	0.87565 (18)	0.10659 (17)	0.0484 (4)
H2A	0.6781	0.9154	0.0753	0.058*
C1	0.3405 (4)	1.2689 (3)	0.3640 (2)	0.0594 (6)
H1B	0.2091	1.1935	0.2967	0.071*
H1C	0.3931	1.3244	0.3167	0.071*
C2	0.5422 (4)	1.2067 (2)	0.4124 (2)	0.0539 (5)
H2B	0.4968	1.1623	0.4707	0.065*
H2C	0.6809	1.2815	0.4696	0.065*
C3	0.6079 (4)	1.0991 (2)	0.2902 (2)	0.0434 (5)
C4	0.8769 (4)	0.9252 (2)	0.2443 (2)	0.0452 (5)
C5	0.8541 (4)	0.7586 (2)	0.00691 (19)	0.0435 (5)
C6	1.0500 (4)	0.7804 (2)	−0.0412 (2)	0.0543 (5)
H6A	1.1404	0.8707	−0.0087	0.065*
C7	1.1101 (5)	0.6653 (3)	−0.1391 (3)	0.0618 (6)
H7A	1.2421	0.6787	−0.1725	0.074*
C8	0.9790 (5)	0.5329 (3)	−0.1872 (2)	0.0635 (7)
H8A	1.0221	0.4565	−0.2524	0.076*
C9	0.7837 (5)	0.5125 (2)	−0.1393 (3)	0.0646 (7)
H9A	0.6934	0.4221	−0.1724	0.078*
C10	0.7203 (4)	0.6258 (2)	−0.0418 (2)	0.0541 (5)
H10A	0.5872	0.6120	−0.0094	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0802 (5)	0.0871 (5)	0.0664 (4)	0.0432 (4)	0.0358 (4)	0.0181 (4)
S1	0.0877 (5)	0.0664 (4)	0.0387 (3)	0.0470 (3)	0.0082 (3)	0.0157 (3)
O1	0.0636 (9)	0.0576 (9)	0.0367 (8)	0.0276 (7)	0.0084 (7)	0.0145 (7)
N1	0.0632 (11)	0.0471 (10)	0.0316 (8)	0.0248 (8)	0.0058 (7)	0.0090 (7)
N2	0.0596 (11)	0.0462 (10)	0.0345 (9)	0.0255 (8)	0.0069 (7)	0.0110 (7)
C1	0.0641 (14)	0.0675 (15)	0.0476 (12)	0.0343 (12)	0.0188 (11)	0.0180 (11)
C2	0.0604 (13)	0.0556 (13)	0.0400 (11)	0.0260 (11)	0.0097 (10)	0.0126 (10)
C3	0.0480 (11)	0.0397 (10)	0.0384 (11)	0.0137 (9)	0.0082 (8)	0.0125 (8)
C4	0.0560 (12)	0.0387 (10)	0.0384 (10)	0.0162 (9)	0.0102 (9)	0.0130 (8)
C5	0.0524 (11)	0.0440 (11)	0.0313 (9)	0.0205 (9)	0.0066 (8)	0.0126 (8)
C6	0.0513 (12)	0.0552 (13)	0.0508 (12)	0.0123 (10)	0.0090 (10)	0.0182 (10)
C7	0.0600 (14)	0.0798 (18)	0.0559 (14)	0.0321 (13)	0.0245 (11)	0.0301 (13)
C8	0.0891 (18)	0.0620 (15)	0.0459 (13)	0.0419 (14)	0.0251 (12)	0.0194 (11)
C9	0.0920 (19)	0.0416 (12)	0.0555 (14)	0.0182 (12)	0.0218 (13)	0.0130 (10)
C10	0.0650 (14)	0.0484 (12)	0.0517 (12)	0.0169 (10)	0.0219 (11)	0.0192 (10)

Geometric parameters (Å, º) top

Cl1—C1	1.778 (2)	C2—H2B	0.9700
S1—C4	1.669 (2)	C2—H2C	0.9700
O1—C3	1.221 (2)	C5—C10	1.369 (3)
N1—C3	1.367 (3)	C5—C6	1.375 (3)
N1—C4	1.386 (3)	C6—C7	1.385 (3)
N1—H1A	0.8600	C6—H6A	0.9300
N2—C4	1.320 (3)	C7—C8	1.361 (4)
N2—C5	1.433 (2)	C7—H7A	0.9300
N2—H2A	0.8600	C8—C9	1.367 (4)
C1—C2	1.490 (3)	C8—H8A	0.9300
C1—H1B	0.9700	C9—C10	1.381 (3)
C1—H1C	0.9700	C9—H9A	0.9300
C2—C3	1.503 (3)	C10—H10A	0.9300

C3—N1—C4	128.77 (17)	N2—C4—N1	117.03 (18)
C3—N1—H1A	115.6	N2—C4—S1	123.88 (16)
C4—N1—H1A	115.6	N1—C4—S1	119.09 (15)
C4—N2—C5	122.97 (17)	C10—C5—C6	120.60 (19)
C4—N2—H2A	118.5	C10—C5—N2	119.22 (19)
C5—N2—H2A	118.5	C6—C5—N2	120.17 (19)
C2—C1—Cl1	111.32 (16)	C5—C6—C7	118.7 (2)
C2—C1—H1B	109.4	C5—C6—H6A	120.7
Cl1—C1—H1B	109.4	C7—C6—H6A	120.7
C2—C1—H1C	109.4	C8—C7—C6	121.0 (2)
Cl1—C1—H1C	109.4	C8—C7—H7A	119.5
H1B—C1—H1C	108.0	C6—C7—H7A	119.5
C1—C2—C3	111.71 (17)	C7—C8—C9	119.9 (2)
C1—C2—H2B	109.3	C7—C8—H8A	120.1
C3—C2—H2B	109.3	C9—C8—H8A	120.1
C1—C2—H2C	109.3	C8—C9—C10	120.1 (2)
C3—C2—H2C	109.3	C8—C9—H9A	119.9
H2B—C2—H2C	107.9	C10—C9—H9A	119.9
O1—C3—N1	122.97 (18)	C5—C10—C9	119.7 (2)
O1—C3—C2	123.17 (18)	C5—C10—H10A	120.1
N1—C3—C2	113.86 (17)	C9—C10—H10A	120.1

Cl1—C1—C2—C3	172.29 (17)	C4—N2—C5—C6	−86.1 (3)
C4—N1—C3—O1	−3.2 (4)	C10—C5—C6—C7	−0.5 (3)
C4—N1—C3—C2	177.1 (2)	N2—C5—C6—C7	−179.04 (19)
C1—C2—C3—O1	4.3 (3)	C5—C6—C7—C8	−0.1 (3)
C1—C2—C3—N1	−176.1 (2)	C6—C7—C8—C9	0.4 (4)
C5—N2—C4—N1	−175.79 (19)	C7—C8—C9—C10	−0.3 (4)
C5—N2—C4—S1	5.2 (3)	C6—C5—C10—C9	0.6 (3)
C3—N1—C4—N2	−2.1 (3)	N2—C5—C10—C9	179.2 (2)
C3—N1—C4—S1	176.94 (18)	C8—C9—C10—C5	−0.2 (4)
C4—N2—C5—C10	95.3 (3)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C5–C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.86	2.01	2.677 (3)	134
N1—H1A···S1ⁱ	0.86	2.53	3.3709 (19)	165
C1—H1C···Cg1ⁱⁱ	0.97	2.84	3.466	123

Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x+2, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₁ClN₂OS
M_r	242.72
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	5.8088 (12), 10.467 (2), 10.660 (2)
α, β, γ (°)	112.811 (3), 101.855 (3), 95.483 (3)
V (Å³)	573.6 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.49
Crystal size (mm)	0.49 × 0.45 × 0.27

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.795, 0.879
No. of measured, independent and observed [I > 2σ(I)] reflections	5617, 2103, 1798
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.113, 1.04
No. of reflections	2103
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.43

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008, PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C5–C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.86	2.01	2.677 (3)	134
N1—H1A···S1ⁱ	0.86	2.53	3.3709 (19)	165
C1—H1C···Cg1ⁱⁱ	0.97	2.84	3.466	123

Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x+2, −y+1, −z.

Acknowledgements

The authors thank the Ministry of Higher Education of Malaysia for the research grant UKM-OUP-NBT-27–144 and Universiti Kebangsaan Malaysia for the research facilities.

References

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