3-Acetyl-1-(3-chloro­phen­yl)thio­urea

Shahwar, D.; Tahir, M.N.; Chohan, M.M.; Ahmad, N.; Raza, M.A.

doi:10.1107/S1600536812012147

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1189

doi:10.1107/S1600536812012147

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3-Acetyl-1-(3-chlorophenyl)thiourea

Durre Shahwar,^a M. Nawaz Tahir,^b ^* Muhammad Mansha Chohan,^a Naeem Ahmad ^a and M. Asam Raza ^c

^aDepartment of Chemistry, Government College University, Lahore, Pakistan, ^bUniversity of Sargodha, Department of Physics, Sargodha, Pakistan, and ^cDepartment of Chemistry, University of Gujrat, Gujrat, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 18 March 2012; accepted 21 March 2012; online 24 March 2012)

In the title compound, C₉H₉ClN₂OS, the 3-chlorophenyl and acetylthiourea fragments are oriented at a dihedral angle of 62.68 (5)°. An intramolecular N—H⋯O hydrogen bond generates an S(6) ring motif. Molecules are linked into dimers via a cyclic R₂²(8) motif of N—H⋯S hydrogen bonds. These dimers are further connected through C—H⋯S interactions, completing an R₂²(12) motif, into chains along [010].

Related literature

For related structures, see: Shahwar et al. (2012a ,b ).; For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₉H₉ClN₂OS
M_r = 228.69
Monoclinic, C 2/c
a = 28.3980 (14) Å
b = 4.1768 (2) Å
c = 20.2635 (11) Å
β = 122.651 (2)°
V = 2023.69 (18) Å³
Z = 8
Mo Kα radiation
μ = 0.55 mm⁻¹
T = 296 K
0.35 × 0.22 × 0.22 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.868, T_max = 0.872
7045 measured reflections
1775 independent reflections
1450 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.109
S = 1.11
1775 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.86	1.96	2.648 (3)	136
N2—H2⋯S1ⁱ	0.86	2.56	3.4095 (18)	170
C9—H9A⋯S1ⁱⁱ	0.96	2.85	3.799 (3)	170
Symmetry codes: (i) -x, -y+1, -z; (ii) -x, -y+2, -z.

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812012147/gk2470sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812012147/gk2470Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812012147/gk2470Isup3.cml

checkCIF report

Comment top

The title compound (Fig. 1) has been synthesized as a continuation of our work to find new enzyme inhibitors.

The crystal structures of N-(2-methylphenylcarbamothioyl)acetamide (Shahwar et al., 2012a) and N-(phenylcarbamothioyl)acetamide (Shahwar et al., 2012b) have been reported which are related to the title compound.

In the title compound, the 3-chlorophenyl group A (C1–C6/Cl1) and the N-carbamothioylacetamide moiety B (N1/C7/S1/N2/C8/O1/C9) are planar with r. m. s. deviation of 0.0055 Å and 0.0060 Å, respectively. The dihedral angle between A/B is 62.68 (5)°. There exist intramolecular H–bonding of N—H···O type (Table 1, Fig. 1) with S(6) ring motif (Bernstein et al., 1995). The molecules are dimerized due to N—H···S type of hydrogen bonds with R₂²(8) ring motifs (Table 1, Fig. 2). The dimers are interlinked due to C—H···S H–bondings (Table 1, Fig. 2) and complete R₂²(12) ring motifs.

Related literature top

For related structures, see: Shahwar et al. (2012a,b).; For graph-set notation, see: Bernstein et al. (1995).

Experimental top

The title compound was synthesized by adding (0.1 mol, 7.13 ml) of acetylchloride dropwise to a stirred solution of KSCN (0.11 mol) in dry acetone (50 ml), followed by slow addition of 3-chloroaniline (0.1 mol) in dry acetone (25 ml). The mixture was refluxed for 5–10 min, then poured on ice cooled water, which resulted in crude precipitate. Recrystallization of the precipitate from ethyl acetate yielded colorless rods (m.p. 374 K).

Structure description top

The title compound (Fig. 1) has been synthesized as a continuation of our work to find new enzyme inhibitors.

For related structures, see: Shahwar et al. (2012a,b).; For graph-set notation, see: Bernstein et al. (1995).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the title compound with displacement ellipsoids drawn at the 50% probability level. The dotted lines represent the intramolecular hydrogen bond.
	Fig. 2. The partial packing (PLATON; Spek, 2009) showing molecules connected via N-H···O and C-H···S interactions.

3-Acetyl-1-(3-chlorophenyl)thiourea top

Crystal data top

C₉H₉ClN₂OS	F(000) = 944
M_r = 228.69	D_x = 1.501 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1464 reflections
a = 28.3980 (14) Å	θ = 2.1–25.1°
b = 4.1768 (2) Å	µ = 0.55 mm⁻¹
c = 20.2635 (11) Å	T = 296 K
β = 122.651 (2)°	Rod, colorless
V = 2023.69 (18) Å³	0.35 × 0.22 × 0.22 mm
Z = 8

Data collection top

Bruker Kappa APEXII CCD diffractometer	1745 independent reflections
Radiation source: fine-focus sealed tube	1450 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 8.10 pixels mm^-1	θ_max = 25.1°, θ_min = 2.1°
ω scans	h = −33→27
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −4→3
T_min = 0.868, T_max = 0.872	l = −19→24
7045 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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0527P)² + 1.9073P] where P = (F_o² + 2F_c²)/3
1775 reflections	(Δ/σ)_max < 0.001
128 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₉H₉ClN₂OS	V = 2023.69 (18) Å³
M_r = 228.69	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 28.3980 (14) Å	µ = 0.55 mm⁻¹
b = 4.1768 (2) Å	T = 296 K
c = 20.2635 (11) Å	0.35 × 0.22 × 0.22 mm
β = 122.651 (2)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	1745 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1450 reflections with I > 2σ(I)
T_min = 0.868, T_max = 0.872	R_int = 0.029
7045 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 1.11	Δρ_max = 0.23 e Å⁻³
1775 reflections	Δρ_min = −0.23 e Å⁻³
128 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	0.27943 (3)	0.9289 (2)	0.34233 (4)	0.0593 (3)
S1	0.08011 (2)	0.46913 (17)	0.10724 (3)	0.0436 (2)
O1	−0.03091 (7)	1.0496 (5)	0.16023 (11)	0.0610 (7)
N1	0.06728 (7)	0.7792 (5)	0.21108 (10)	0.0383 (6)
N2	−0.00930 (7)	0.7704 (5)	0.08375 (10)	0.0353 (6)
C1	0.12315 (9)	0.7158 (6)	0.27507 (12)	0.0334 (7)
C2	0.16843 (9)	0.8388 (6)	0.27522 (13)	0.0375 (8)
C3	0.22127 (9)	0.7785 (6)	0.33950 (13)	0.0375 (7)
C4	0.22942 (10)	0.6054 (7)	0.40248 (14)	0.0461 (8)
C5	0.18373 (11)	0.4900 (7)	0.40138 (16)	0.0520 (9)
C6	0.13025 (10)	0.5409 (6)	0.33725 (14)	0.0422 (8)
C7	0.04606 (9)	0.6845 (5)	0.13794 (12)	0.0328 (7)
C8	−0.04474 (9)	0.9441 (6)	0.09596 (14)	0.0395 (8)
C9	−0.10196 (10)	0.9910 (7)	0.02487 (15)	0.0480 (9)
H1	0.04591	0.88682	0.22087	0.0459*
H2	−0.02292	0.70566	0.03650	0.0424*
H3	0.16340	0.95861	0.23319	0.0450*
H4	0.26537	0.56692	0.44526	0.0553*
H5	0.18883	0.37642	0.44424	0.0624*
H6	0.09947	0.45780	0.33622	0.0506*
H9A	−0.09942	1.10785	−0.01390	0.0720*
H9B	−0.12438	1.10907	0.03877	0.0720*
H9C	−0.11887	0.78623	0.00402	0.0720*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0285 (4)	0.0836 (6)	0.0561 (5)	−0.0088 (3)	0.0164 (3)	0.0058 (4)
S1	0.0301 (4)	0.0600 (4)	0.0331 (4)	0.0091 (3)	0.0120 (3)	−0.0070 (3)
O1	0.0378 (11)	0.0981 (16)	0.0396 (11)	0.0147 (10)	0.0159 (9)	−0.0173 (10)
N1	0.0223 (10)	0.0590 (13)	0.0290 (10)	0.0031 (9)	0.0109 (8)	−0.0061 (9)
N2	0.0231 (9)	0.0509 (12)	0.0251 (10)	0.0023 (8)	0.0086 (8)	−0.0049 (8)
C1	0.0248 (11)	0.0434 (13)	0.0262 (12)	0.0014 (9)	0.0099 (9)	−0.0051 (9)
C2	0.0303 (13)	0.0479 (14)	0.0283 (12)	−0.0001 (10)	0.0119 (10)	0.0032 (10)
C3	0.0250 (12)	0.0480 (14)	0.0334 (12)	−0.0038 (10)	0.0117 (10)	−0.0051 (10)
C4	0.0302 (13)	0.0605 (16)	0.0342 (14)	0.0060 (11)	0.0085 (11)	0.0070 (12)
C5	0.0439 (16)	0.0684 (18)	0.0374 (14)	0.0033 (13)	0.0178 (13)	0.0173 (13)
C6	0.0340 (14)	0.0545 (15)	0.0383 (14)	−0.0041 (11)	0.0196 (11)	0.0004 (11)
C7	0.0242 (12)	0.0400 (13)	0.0298 (12)	−0.0014 (9)	0.0116 (10)	−0.0003 (10)
C8	0.0274 (13)	0.0504 (15)	0.0371 (14)	0.0019 (10)	0.0150 (11)	−0.0017 (11)
C9	0.0304 (14)	0.0653 (17)	0.0412 (14)	0.0124 (12)	0.0146 (12)	−0.0002 (12)

Geometric parameters (Å, º) top

Cl1—C3	1.739 (3)	C3—C4	1.373 (4)
S1—C7	1.667 (3)	C4—C5	1.373 (5)
O1—C8	1.222 (3)	C5—C6	1.382 (4)
N1—C1	1.431 (3)	C8—C9	1.493 (4)
N1—C7	1.324 (3)	C2—H3	0.9300
N2—C7	1.394 (3)	C4—H4	0.9300
N2—C8	1.367 (4)	C5—H5	0.9300
N1—H1	0.8600	C6—H6	0.9300
N2—H2	0.8600	C9—H9A	0.9600
C1—C6	1.374 (3)	C9—H9B	0.9600
C1—C2	1.383 (4)	C9—H9C	0.9600
C2—C3	1.379 (4)

C1—N1—C7	124.9 (2)	N1—C7—N2	116.3 (2)
C7—N2—C8	128.42 (19)	O1—C8—C9	122.5 (3)
C1—N1—H1	118.00	N2—C8—C9	114.8 (2)
C7—N1—H1	118.00	O1—C8—N2	122.7 (2)
C7—N2—H2	116.00	C1—C2—H3	121.00
C8—N2—H2	116.00	C3—C2—H3	121.00
N1—C1—C2	120.5 (2)	C3—C4—H4	120.00
N1—C1—C6	118.1 (3)	C5—C4—H4	120.00
C2—C1—C6	121.3 (2)	C4—C5—H5	120.00
C1—C2—C3	118.1 (2)	C6—C5—H5	120.00
Cl1—C3—C4	118.6 (2)	C1—C6—H6	120.00
C2—C3—C4	121.7 (3)	C5—C6—H6	120.00
Cl1—C3—C2	119.68 (19)	C8—C9—H9A	109.00
C3—C4—C5	119.1 (3)	C8—C9—H9B	109.00
C4—C5—C6	120.7 (3)	C8—C9—H9C	109.00
C1—C6—C5	119.2 (3)	H9A—C9—H9B	109.00
S1—C7—N1	125.0 (2)	H9A—C9—H9C	109.00
S1—C7—N2	118.65 (16)	H9B—C9—H9C	109.00

C7—N1—C1—C2	63.5 (3)	C6—C1—C2—C3	0.6 (4)
C7—N1—C1—C6	−119.0 (3)	N1—C1—C6—C5	−176.9 (2)
C1—N1—C7—S1	1.1 (4)	C2—C1—C6—C5	0.6 (4)
C1—N1—C7—N2	−179.9 (2)	C1—C2—C3—Cl1	−179.9 (2)
C8—N2—C7—S1	179.9 (2)	C1—C2—C3—C4	−0.8 (4)
C8—N2—C7—N1	0.8 (4)	Cl1—C3—C4—C5	179.0 (2)
C7—N2—C8—O1	−0.3 (4)	C2—C3—C4—C5	−0.1 (4)
C7—N2—C8—C9	−179.5 (2)	C3—C4—C5—C6	1.3 (4)
N1—C1—C2—C3	178.0 (2)	C4—C5—C6—C1	−1.6 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	1.96	2.648 (3)	136
N2—H2···S1ⁱ	0.86	2.56	3.4095 (18)	170
C9—H9A···S1ⁱⁱ	0.96	2.85	3.799 (3)	170

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

Experimental details

Crystal data
Chemical formula	C₉H₉ClN₂OS
M_r	228.69
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	28.3980 (14), 4.1768 (2), 20.2635 (11)
β (°)	122.651 (2)
V (Å³)	2023.69 (18)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.55
Crystal size (mm)	0.35 × 0.22 × 0.22

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.868, 0.872
No. of measured, independent and observed [I > 2σ(I)] reflections	7045, 1745, 1450
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.109, 1.11
No. of reflections	1775
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.23

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	1.96	2.648 (3)	136
N2—H2···S1ⁱ	0.86	2.56	3.4095 (18)	170
C9—H9A···S1ⁱⁱ	0.96	2.85	3.799 (3)	170

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

Acknowledgements

The authors acknowledge the provision of funds for the purchase of the diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan. The authors also acknowledge the technical support provided by Syed Muhammad Hussain Rizvi of Bana International, Karachi, Pakistan.

References

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