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

Abstract

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 R ₂ ²(8) motif of N—H⋯S hydrogen bonds. These dimers are further connected through C—H⋯S inter­actions, completing an R ₂ ²(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,

• a = 28.3980 (14) Å

• b = 4.1768 (2) Å

• c = 20.2635 (11) Å

• β = 122.651 (2)°

• V = 2023.69 (18) ų

• 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[F ² > 2σ(F ²)] = 0.034

• wR(F ²) = 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

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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812012147/gk2470Isup3.cml

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

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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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).

Refinement

The H atoms were positioned geometrically (C—H = 0.93–0.96 Å, N—H = 0.86 Å) and refined as riding with U_iso(H) = xU_eq(C, N), where x = 1.5 for methyl groups and x = 1.2 for other H atoms.

Figures

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.

Crystal data

C9H9ClN2OS	F(000) = 944
Mr = 228.69	Dx = 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

Bruker Kappa APEXII CCD diffractometer	1745 independent reflections
Radiation source: fine-focus sealed tube	1450 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 8.10 pixels mm-1	θmax = 25.1°, θmin = 2.1°
ω scans	h = −33→27
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −4→3
Tmin = 0.868, Tmax = 0.872	l = −19→24
7045 measured reflections

Refinement

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(Fo2) + (0.0527P)2 + 1.9073P] where P = (Fo2 + 2Fc2)/3
1775 reflections	(Δ/σ)max < 0.001
128 parameters	Δρmax = 0.23 e Å−3
0 restraints	Δρmin = −0.23 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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.