3-Acetyl-1-(2-methylphenyl)thiourea

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

doi:10.1107/S1600536812011658

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1160

doi:10.1107/S1600536812011658

Open

access

3-Acetyl-1-(2-methylphenyl)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 17 March 2012; accepted 18 March 2012; online 24 March 2012)

In the title compound, C₁₀H₁₂N₂OS, the toluene and the N-carbamothioylacetamide units are oriented at dihedral angle of 78.75 (5)°. An intramolecular N—H⋯O hydrogen bond generates an S(6) ring. In the crystal, molecules are linked into [101] chains by pairs of N—H⋯S hydrogen bonds [which generate R₂²(8) loops] and pairs of O—H⋯O hydrogen bonds [which generate R₂²(4) loops]. The two motifs alternate in the chain.

Related literature

For related structures, see: Shahwar et al. (2012 ). For graph–set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₀H₁₂N₂OS
M_r = 208.28
Monoclinic, P 2₁ /c
a = 5.0444 (2) Å
b = 20.7019 (9) Å
c = 9.9464 (4) Å
β = 95.116 (2)°
V = 1034.55 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 296 K
0.35 × 0.15 × 0.13 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.915, T_max = 0.938
7696 measured reflections
1812 independent reflections
1512 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.088
S = 1.17
1812 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.20 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	1.99	2.664 (2)	135
N1—H1⋯O1ⁱ	0.86	2.50	3.172 (2)	135
N2—H2⋯S1ⁱⁱ	0.86	2.52	3.3747 (17)	171
Symmetry codes: (i) -x+2, -y, -z+1; (ii) -x+1, -y, -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/S1600536812011658/hb6692sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812011658/hb6692Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812011658/hb6692Isup3.cml

checkCIF report

Comment top

The title compound I (Fig. 1) has been synthesized in continuation of our efforts to find new enzyme inhibitors.

The crystal structures of N-(phenylcarbamothioyl)acetamide (Shahwar et al., 2012) has been published which is related to the title compound (I).

In (I), the toluene group A (C1–C7) and the N-carbamothioylacetamide moiety B (N1/C8/S1/N2/C9/O1/C10) are planar with r. m. s. deviation of 0.0058 Å and 0.0278 Å, respectively. The dihedral angle between A/B is 78.75 (5)°. There exist classical 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 from S(6) ring motifs due to strong N—H···O H–bondings (Table 1, Fig. 2) with centrosymmetric four membered ring motif (—O···H···O···H···O—) (Table 1, Fig. 2). The polymeric chains extend along the base vector [101].

Related literature top

For related structures, see: Shahwar et al. (2012). For graph–set notation, see: Bernstein et al. (1995).

Experimental top

The title compound (I) 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 toluidine (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 in ethylacetate yielded colourless needles.

Structure description top

The title compound I (Fig. 1) has been synthesized in continuation of our efforts to find new enzyme inhibitors.

The crystal structures of N-(phenylcarbamothioyl)acetamide (Shahwar et al., 2012) has been published which is related to the title compound (I).

For related structures, see: Shahwar et al. (2012). 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 are drawn at the 50% probability level. The dotted lines represent the intra-molecular H-bondings.
	Fig. 2. The partial packing (PLATON; Spek, 2009) which shows that molecules form polymeric chains extending along [1 0 1] direction.

3-Acetyl-1-(2-methylphenyl)thiourea top

Crystal data top

C₁₀H₁₂N₂OS	F(000) = 440
M_r = 208.28	D_x = 1.337 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1513 reflections
a = 5.0444 (2) Å	θ = 2.0–25.2°
b = 20.7019 (9) Å	µ = 0.28 mm⁻¹
c = 9.9464 (4) Å	T = 296 K
β = 95.116 (2)°	Needle, white
V = 1034.55 (7) Å³	0.35 × 0.15 × 0.13 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	1812 independent reflections
Radiation source: fine-focus sealed tube	1512 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 8.00 pixels mm^-1	θ_max = 25.2°, θ_min = 2.0°
ω scans	h = −5→6
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −24→22
T_min = 0.915, T_max = 0.938	l = −11→11
7696 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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	H-atom parameters constrained
S = 1.17	w = 1/[σ²(F_o²) + (0.0311P)² + 0.355P] where P = (F_o² + 2F_c²)/3
1812 reflections	(Δ/σ)_max < 0.001
129 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₀H₁₂N₂OS	V = 1034.55 (7) Å³
M_r = 208.28	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.0444 (2) Å	µ = 0.28 mm⁻¹
b = 20.7019 (9) Å	T = 296 K
c = 9.9464 (4) Å	0.35 × 0.15 × 0.13 mm
β = 95.116 (2)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	1812 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1512 reflections with I > 2σ(I)
T_min = 0.915, T_max = 0.938	R_int = 0.028
7696 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.088	H-atom parameters constrained
S = 1.17	Δρ_max = 0.18 e Å⁻³
1812 reflections	Δρ_min = −0.20 e Å⁻³
129 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
S1	0.39407 (11)	0.07983 (3)	0.11730 (5)	0.0401 (2)
O1	1.0674 (3)	−0.02473 (7)	0.36353 (14)	0.0456 (5)
N1	0.7141 (3)	0.07120 (8)	0.34350 (16)	0.0337 (5)
N2	0.7701 (3)	−0.00655 (8)	0.18163 (16)	0.0326 (5)
C1	0.5997 (4)	0.12750 (10)	0.40024 (19)	0.0312 (6)
C2	0.6773 (4)	0.18879 (10)	0.3631 (2)	0.0348 (7)
C3	0.5651 (4)	0.24080 (11)	0.4260 (2)	0.0440 (8)
C4	0.3876 (4)	0.23224 (12)	0.5219 (2)	0.0493 (8)
C5	0.3150 (5)	0.17099 (12)	0.5564 (2)	0.0491 (8)
C6	0.4207 (4)	0.11826 (11)	0.4958 (2)	0.0399 (7)
C7	0.8746 (4)	0.19878 (12)	0.2608 (2)	0.0462 (8)
C8	0.6379 (4)	0.04791 (9)	0.22219 (19)	0.0294 (6)
C9	0.9799 (4)	−0.03869 (10)	0.2492 (2)	0.0334 (7)
C10	1.0907 (4)	−0.09266 (11)	0.1711 (2)	0.0456 (8)
H1	0.83956	0.05146	0.39124	0.0404*
H2	0.71344	−0.02218	0.10425	0.0391*
H3	0.61134	0.28255	0.40262	0.0528*
H4	0.31710	0.26787	0.56314	0.0591*
H5	0.19428	0.16508	0.62076	0.0589*
H6	0.37200	0.07669	0.51911	0.0478*
H7A	0.79640	0.18600	0.17331	0.0692*
H7B	1.03029	0.17317	0.28474	0.0692*
H7C	0.92326	0.24358	0.25886	0.0692*
H10A	1.21650	−0.11680	0.22928	0.0684*
H10B	1.17794	−0.07517	0.09732	0.0684*
H10C	0.94861	−0.12060	0.13674	0.0684*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0437 (3)	0.0418 (3)	0.0328 (3)	0.0132 (3)	−0.0077 (2)	−0.0084 (3)
O1	0.0543 (9)	0.0469 (10)	0.0337 (9)	0.0164 (7)	−0.0069 (7)	−0.0033 (7)
N1	0.0381 (9)	0.0333 (10)	0.0284 (9)	0.0089 (7)	−0.0038 (7)	−0.0049 (7)
N2	0.0363 (9)	0.0318 (10)	0.0289 (9)	0.0056 (7)	−0.0007 (7)	−0.0084 (7)
C1	0.0328 (10)	0.0321 (11)	0.0272 (10)	0.0042 (9)	−0.0048 (8)	−0.0054 (9)
C2	0.0321 (11)	0.0369 (12)	0.0346 (11)	−0.0007 (9)	−0.0013 (9)	−0.0017 (10)
C3	0.0483 (13)	0.0303 (12)	0.0527 (14)	−0.0017 (10)	0.0010 (11)	−0.0058 (11)
C4	0.0546 (14)	0.0419 (14)	0.0519 (15)	0.0060 (11)	0.0082 (12)	−0.0167 (12)
C5	0.0532 (14)	0.0556 (16)	0.0409 (13)	0.0045 (12)	0.0173 (11)	−0.0064 (12)
C6	0.0462 (12)	0.0376 (13)	0.0361 (12)	−0.0007 (10)	0.0057 (10)	0.0002 (10)
C7	0.0451 (13)	0.0466 (14)	0.0474 (14)	−0.0053 (11)	0.0077 (10)	0.0029 (11)
C8	0.0316 (10)	0.0289 (11)	0.0278 (10)	−0.0013 (9)	0.0041 (8)	−0.0022 (8)
C9	0.0357 (11)	0.0322 (11)	0.0326 (12)	0.0035 (9)	0.0043 (9)	0.0022 (9)
C10	0.0503 (13)	0.0436 (14)	0.0429 (13)	0.0158 (11)	0.0041 (10)	−0.0044 (11)

Geometric parameters (Å, º) top

S1—C8	1.676 (2)	C4—C5	1.372 (3)
O1—C9	1.217 (2)	C5—C6	1.377 (3)
N1—C1	1.438 (3)	C9—C10	1.497 (3)
N1—C8	1.324 (2)	C3—H3	0.9300
N2—C8	1.388 (3)	C4—H4	0.9300
N2—C9	1.374 (3)	C5—H5	0.9300
N1—H1	0.8600	C6—H6	0.9300
N2—H2	0.8600	C7—H7A	0.9600
C1—C2	1.388 (3)	C7—H7B	0.9600
C1—C6	1.381 (3)	C7—H7C	0.9600
C2—C7	1.500 (3)	C10—H10A	0.9600
C2—C3	1.391 (3)	C10—H10B	0.9600
C3—C4	1.377 (3)	C10—H10C	0.9600

C1—N1—C8	123.96 (16)	O1—C9—N2	122.77 (19)
C8—N2—C9	128.34 (17)	C2—C3—H3	119.00
C1—N1—H1	118.00	C4—C3—H3	119.00
C8—N1—H1	118.00	C3—C4—H4	120.00
C8—N2—H2	116.00	C5—C4—H4	120.00
C9—N2—H2	116.00	C4—C5—H5	120.00
N1—C1—C2	120.27 (17)	C6—C5—H5	120.00
N1—C1—C6	117.88 (18)	C1—C6—H6	120.00
C2—C1—C6	121.80 (19)	C5—C6—H6	120.00
C3—C2—C7	121.32 (19)	C2—C7—H7A	109.00
C1—C2—C3	116.90 (18)	C2—C7—H7B	109.00
C1—C2—C7	121.79 (19)	C2—C7—H7C	109.00
C2—C3—C4	121.9 (2)	H7A—C7—H7B	109.00
C3—C4—C5	119.8 (2)	H7A—C7—H7C	109.00
C4—C5—C6	120.1 (2)	H7B—C7—H7C	109.00
C1—C6—C5	119.6 (2)	C9—C10—H10A	109.00
S1—C8—N1	124.12 (15)	C9—C10—H10B	109.00
S1—C8—N2	118.97 (14)	C9—C10—H10C	109.00
N1—C8—N2	116.91 (17)	H10A—C10—H10B	109.00
O1—C9—C10	122.74 (18)	H10A—C10—H10C	109.00
N2—C9—C10	114.49 (17)	H10B—C10—H10C	110.00

C8—N1—C1—C2	−79.9 (3)	C6—C1—C2—C3	−0.4 (3)
C8—N1—C1—C6	102.7 (2)	C6—C1—C2—C7	179.11 (19)
C1—N1—C8—S1	−0.9 (3)	N1—C1—C6—C5	177.42 (18)
C1—N1—C8—N2	179.42 (17)	C2—C1—C6—C5	0.1 (3)
C9—N2—C8—S1	177.45 (16)	C1—C2—C3—C4	0.8 (3)
C9—N2—C8—N1	−2.8 (3)	C7—C2—C3—C4	−178.76 (19)
C8—N2—C9—O1	5.5 (3)	C2—C3—C4—C5	−0.8 (3)
C8—N2—C9—C10	−175.01 (18)	C3—C4—C5—C6	0.4 (3)
N1—C1—C2—C3	−177.70 (17)	C4—C5—C6—C1	−0.1 (3)
N1—C1—C2—C7	1.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	1.99	2.664 (2)	135
N1—H1···O1ⁱ	0.86	2.50	3.172 (2)	135
N2—H2···S1ⁱⁱ	0.86	2.52	3.3747 (17)	171

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂N₂OS
M_r	208.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	5.0444 (2), 20.7019 (9), 9.9464 (4)
β (°)	95.116 (2)
V (Å³)	1034.55 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.35 × 0.15 × 0.13

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.915, 0.938
No. of measured, independent and observed [I > 2σ(I)] reflections	7696, 1812, 1512
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.088, 1.17
No. of reflections	1812
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.20

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	1.99	2.664 (2)	135
N1—H1···O1ⁱ	0.86	2.50	3.172 (2)	135
N2—H2···S1ⁱⁱ	0.86	2.52	3.3747 (17)	171

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

Acknowledgements

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

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Shahwar, D., Tahir, M. N., Chohan, M. M., Ahmad, N. & Samiullah (2012). Acta Cryst. E68, o508. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar