1-(4-Chloro­benzo­yl)-3-(3-methyl­pyridin-2-yl)thio­urea

Yusof, M.S.M.; Mushtari, N.A.; Kadir, M.A.; Yamin, B.M.

doi:10.1107/S1600536811032375

organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2367

doi:10.1107/S1600536811032375

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1-(4-Chlorobenzoyl)-3-(3-methylpyridin-2-yl)thiourea

M.Sukeri M. Yusof,^a ^* Nurwahyuni A. Mushtari,^a Maisara A. Kadir ^a and Bohari M. Yamin ^b

^aDepartment of Chemical Sciences, Faculty of Science and Technology, Universiti Malaysia Terengganu, 21030 Kuala Terengganu, Terengganu, Malaysia, and ^bSchool of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, UKM 43500 Bangi Selangor, Malaysia
^*Correspondence e-mail: mohdsukeri@umt.edu.my

(Received 17 July 2011; accepted 10 August 2011; online 17 August 2011)

The molecule of the title compound, C₁₄H₁₂ClN₃OS, consists of three approximately planar fragments: the central thiourea group, the chlorophenyl group and the picolyl (3-methylpyridin-2-yl) group with a maximum of 0.035 (2)° for an N atom from the mean square plane of the central thiourea group. The central fragment forms dihedral angles of 33.30 (8) and 76.78 (8)° with the chlorophenyl and picolyl groups, respectively. With respect to the thiourea C—N bonds, the 4-chlorobenzoyl group is positioned trans to the thiono S atoms, whereas the picolyl group lies in a cis position to it. The molecular conformation is stabilized by an intramolecular N—H⋯O hydrogen bond. In the crystal, molecules are linked by intermolecular C—H⋯N hydrogen bonds, forming chains along the a axis.

Related literature

For applications of thiourea derivatives, see: Cunha et al. (2007 ); Srivastava et al. (2010 ); Manjula et al. (2009 ); Chen et al. (2006 ). For related structures, see: Estévez-Hernández et al. (2009 ); Binzet et al. (2009 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₄H₁₂ClN₃OS
M_r = 305.78
Monoclinic, P 2₁ /c
a = 7.8417 (15) Å
b = 7.1058 (13) Å
c = 25.585 (5) Å
β = 93.405 (4)°
V = 1423.1 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 298 K
0.44 × 0.31 × 0.14 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.839, T_max = 0.944
9917 measured reflections
3421 independent reflections
2188 reflections with I > 2/s(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.139
S = 1.04
3421 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1	0.86	1.98	2.655 (2)	135
C2—H2B⋯N3ⁱ	0.93	2.59	3.417 (3)	148
Symmetry code: (i) x+1, y, z.

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); 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/S1600536811032375/yk2015sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811032375/yk2015Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811032375/yk2015Isup3.cml

checkCIF report

Comment top

The synthesis of new thiourea derivatives has attracted great interest because of their wide range applications in research and technology, such as in pharmacology (Cunha et al., 2007), catalysis (Chen et al., 2006) and agriculture (Srivastava et al., 2010). The title compound, (I), is an isomer of the previously reported compound, 4-chloro-N-[N-(6-methyl-2-pyridyl)-carbamothioyl]benzamide (Binzet et al., 2009) except the methyl group is attached at the third position of the pyridine ring. The molecule adopts trans-cis configuration with respect to the position of 4-chlorobenzoyl and 2-picolyl groups relative to the thiono S atom across the thiourea C—N bonds. The bond lengths and angles are within normal ranges (Allen et al., 1987) and agree with previously reported analogous molecules (Estévez-Hernández et al., 2009; Binzet et al., 2009). The molecule consists of central thiourea fragment (N2/C8/S1/N1), pyridine (C9—C13/N3) and phenyl (C1—C6) rings which are nearly planar with largest deviation from the least square plane of 0.035 (2)Å for N1 atom.

The molecule is stabilized by intramolecular hydrogen bond, O1···H2A—N2, forming a pseudo-six membered ring, O1···H2A—N2—C8—N1—C7—O1 (Table 1). In crystal the molecules are linked by intermolecular hydrogen bond C2—H2···N3ⁱ, forming chains along the a axis (Fig. 2).

Related literature top

For applications of thiourea derivatives, see: Cunha et al. (2007); Srivastava et al. (2010); Manjula et al. (2009); Chen et al. (2006). For related structures, see: Estévez-Hernández et al. (2009); Binzet et al. (2009). For standard bond lengths, see: Allen et al. (1987).

Experimental top

2-amino-3-picoline (1.0 g, 0.5 mmol) was added dropwise into the mixture of ammonium thiocyanate (0.62 g, 0.5 mmol) and 4-chlorobenzoyl chloride (0.44 g, 0.5 mmol) diluted by 50 ml of dry acetone. The reaction mixture was refluxed with permanent stirring for 3 h. The resulting precipitate was filtered off and washed with cold methanol. The colorless crystals were obtained by recrystallization from acetonitrile. Yield: 46%; m.p. 170.1–171.1°C

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); 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.
	Fig. 2. A packing diagram of (I) viewed down the b axis. Hydrogen bonds are shown by dashed lines.

1-(4-Chlorobenzoyl)-3-(3-methylpyridin-2-yl)thiourea top

Crystal data top

C₁₄H₁₂ClN₃OS	F(000) = 632
M_r = 305.78	D_x = 1.427 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 699 reflections
a = 7.8417 (15) Å	θ = 1.6–28.0°
b = 7.1058 (13) Å	µ = 0.41 mm⁻¹
c = 25.585 (5) Å	T = 298 K
β = 93.405 (4)°	Slab, colourless
V = 1423.1 (5) Å³	0.44 × 0.31 × 0.14 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3421 independent reflections
Radiation source: fine-focus sealed tube	2188 reflections with I > 2/s(I)
Graphite monochromator	R_int = 0.030
Detector resolution: 83.66 pixels mm^-1	θ_max = 28.0°, θ_min = 1.6°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2003)	k = −9→9
T_min = 0.839, T_max = 0.944	l = −30→33
9917 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) = 0.139	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0722P)² + 0.0755P] where P = (F_o² + 2F_c²)/3
3421 reflections	(Δ/σ)_max = 0.001
181 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₄H₁₂ClN₃OS	V = 1423.1 (5) Å³
M_r = 305.78	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.8417 (15) Å	µ = 0.41 mm⁻¹
b = 7.1058 (13) Å	T = 298 K
c = 25.585 (5) Å	0.44 × 0.31 × 0.14 mm
β = 93.405 (4)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3421 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	2188 reflections with I > 2/s(I)
T_min = 0.839, T_max = 0.944	R_int = 0.030
9917 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.139	H-atom parameters constrained
S = 1.04	Δρ_max = 0.37 e Å⁻³
3421 reflections	Δρ_min = −0.17 e Å⁻³
181 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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	1.21606 (9)	0.54075 (13)	0.35489 (3)	0.0897 (3)
S1	0.45565 (8)	0.34425 (9)	0.08001 (2)	0.0597 (2)
O1	0.4546 (2)	0.6680 (3)	0.23221 (6)	0.0657 (5)
N1	0.5639 (2)	0.4758 (3)	0.17178 (7)	0.0496 (5)
H1A	0.6480	0.4014	0.1669	0.060*
N2	0.3126 (2)	0.6067 (3)	0.13694 (7)	0.0501 (5)
H2A	0.3116	0.6688	0.1658	0.060*
N3	0.0289 (2)	0.5707 (3)	0.10740 (8)	0.0604 (5)
C2	0.8891 (3)	0.5112 (3)	0.23027 (9)	0.0485 (5)
H2B	0.8932	0.4886	0.1946	0.058*
C3	1.0381 (3)	0.5047 (3)	0.26218 (10)	0.0537 (6)
H3A	1.1421	0.4772	0.2483	0.064*
C4	1.0291 (3)	0.5398 (3)	0.31489 (9)	0.0552 (6)
C5	0.8769 (3)	0.5791 (3)	0.33639 (9)	0.0582 (6)
H5A	0.8734	0.6016	0.3721	0.070*
C6	0.7299 (3)	0.5850 (3)	0.30452 (8)	0.0537 (6)
H6A	0.6264	0.6120	0.3188	0.064*
C1	0.7344 (3)	0.5511 (3)	0.25111 (8)	0.0429 (5)
C7	0.5720 (3)	0.5711 (3)	0.21855 (8)	0.0465 (5)
C8	0.4375 (3)	0.4836 (3)	0.13118 (8)	0.0446 (5)
C9	0.1793 (3)	0.6406 (3)	0.09725 (8)	0.0437 (5)
C10	−0.0985 (3)	0.6033 (4)	0.07152 (12)	0.0758 (8)
H10A	−0.2062	0.5565	0.0777	0.091*
C11	−0.0802 (4)	0.7006 (4)	0.02671 (12)	0.0784 (9)
H11A	−0.1723	0.7180	0.0026	0.094*
C12	0.0767 (4)	0.7723 (4)	0.01786 (10)	0.0689 (7)
H12A	0.0919	0.8398	−0.0127	0.083*
C13	0.2135 (3)	0.7461 (3)	0.05369 (8)	0.0508 (5)
C14	0.3859 (4)	0.8282 (4)	0.04571 (12)	0.0781 (8)
H14A	0.3823	0.8960	0.0132	0.117*
H14B	0.4686	0.7289	0.0448	0.117*
H14C	0.4172	0.9125	0.0740	0.117*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0655 (5)	0.1158 (7)	0.0829 (5)	−0.0260 (4)	−0.0364 (4)	0.0270 (4)
S1	0.0599 (4)	0.0634 (4)	0.0533 (4)	0.0146 (3)	−0.0178 (3)	−0.0192 (3)
O1	0.0578 (10)	0.0846 (13)	0.0529 (10)	0.0209 (9)	−0.0111 (8)	−0.0216 (9)
N1	0.0472 (10)	0.0533 (11)	0.0462 (10)	0.0133 (8)	−0.0145 (8)	−0.0115 (8)
N2	0.0474 (10)	0.0602 (12)	0.0416 (10)	0.0094 (9)	−0.0065 (8)	−0.0091 (8)
N3	0.0439 (11)	0.0756 (14)	0.0614 (12)	0.0035 (10)	0.0013 (9)	0.0011 (10)
C2	0.0529 (13)	0.0471 (13)	0.0443 (12)	−0.0004 (10)	−0.0076 (10)	−0.0045 (9)
C3	0.0443 (13)	0.0532 (14)	0.0629 (15)	−0.0014 (10)	−0.0043 (11)	0.0023 (11)
C4	0.0547 (14)	0.0499 (14)	0.0579 (14)	−0.0154 (11)	−0.0227 (12)	0.0120 (11)
C5	0.0666 (16)	0.0654 (16)	0.0411 (12)	−0.0146 (13)	−0.0087 (11)	0.0011 (11)
C6	0.0521 (13)	0.0615 (15)	0.0467 (13)	−0.0054 (11)	−0.0057 (10)	−0.0036 (11)
C1	0.0483 (12)	0.0382 (11)	0.0408 (11)	−0.0016 (9)	−0.0078 (9)	−0.0026 (9)
C7	0.0478 (12)	0.0487 (13)	0.0423 (12)	0.0026 (10)	−0.0046 (10)	−0.0046 (10)
C8	0.0431 (12)	0.0467 (12)	0.0429 (11)	0.0010 (9)	−0.0068 (9)	−0.0021 (9)
C9	0.0426 (12)	0.0454 (12)	0.0422 (11)	0.0077 (9)	−0.0047 (9)	−0.0048 (9)
C10	0.0441 (14)	0.092 (2)	0.090 (2)	0.0071 (14)	−0.0097 (14)	−0.0119 (18)
C11	0.074 (2)	0.083 (2)	0.0737 (19)	0.0307 (16)	−0.0323 (15)	−0.0139 (16)
C12	0.096 (2)	0.0565 (16)	0.0528 (15)	0.0230 (15)	−0.0098 (14)	0.0027 (12)
C13	0.0644 (15)	0.0406 (12)	0.0471 (12)	0.0067 (11)	0.0003 (11)	−0.0024 (10)
C14	0.088 (2)	0.0666 (18)	0.0811 (19)	−0.0112 (15)	0.0187 (16)	0.0070 (15)

Geometric parameters (Å, º) top

Cl1—C4	1.738 (2)	C5—C6	1.372 (3)
S1—C8	1.654 (2)	C5—H5A	0.9300
O1—C7	1.218 (3)	C6—C1	1.390 (3)
N1—C7	1.373 (3)	C6—H6A	0.9300
N1—C8	1.394 (2)	C1—C7	1.487 (3)
N1—H1A	0.8600	C9—C13	1.382 (3)
N2—C8	1.328 (3)	C10—C11	1.354 (4)
N2—C9	1.434 (3)	C10—H10A	0.9300
N2—H2A	0.8600	C11—C12	1.363 (4)
N3—C9	1.320 (3)	C11—H11A	0.9300
N3—C10	1.337 (3)	C12—C13	1.382 (3)
C2—C3	1.385 (3)	C12—H12A	0.9300
C2—C1	1.383 (3)	C13—C14	1.498 (4)
C2—H2B	0.9300	C14—H14A	0.9600
C3—C4	1.377 (3)	C14—H14B	0.9600
C3—H3A	0.9300	C14—H14C	0.9600
C4—C5	1.372 (4)

C7—N1—C8	128.59 (18)	O1—C7—C1	122.05 (18)
C7—N1—H1A	115.7	N1—C7—C1	115.77 (19)
C8—N1—H1A	115.7	N2—C8—N1	116.12 (18)
C8—N2—C9	122.93 (17)	N2—C8—S1	125.52 (16)
C8—N2—H2A	118.5	N1—C8—S1	118.34 (15)
C9—N2—H2A	118.5	N3—C9—C13	125.6 (2)
C9—N3—C10	116.1 (2)	N3—C9—N2	114.81 (19)
C3—C2—C1	120.5 (2)	C13—C9—N2	119.6 (2)
C3—C2—H2B	119.7	N3—C10—C11	123.9 (3)
C1—C2—H2B	119.7	N3—C10—H10A	118.1
C4—C3—C2	118.7 (2)	C11—C10—H10A	118.1
C4—C3—H3A	120.6	C10—C11—C12	118.3 (3)
C2—C3—H3A	120.6	C10—C11—H11A	120.9
C3—C4—C5	121.7 (2)	C12—C11—H11A	120.9
C3—C4—Cl1	119.1 (2)	C11—C12—C13	120.8 (2)
C5—C4—Cl1	119.12 (19)	C11—C12—H12A	119.6
C6—C5—C4	119.2 (2)	C13—C12—H12A	119.6
C6—C5—H5A	120.4	C9—C13—C12	115.3 (2)
C4—C5—H5A	120.4	C9—C13—C14	122.8 (2)
C5—C6—C1	120.6 (2)	C12—C13—C14	121.9 (2)
C5—C6—H6A	119.7	C13—C14—H14A	109.5
C1—C6—H6A	119.7	C13—C14—H14B	109.5
C6—C1—C2	119.2 (2)	H14A—C14—H14B	109.5
C6—C1—C7	117.6 (2)	C13—C14—H14C	109.5
C2—C1—C7	123.05 (19)	H14A—C14—H14C	109.5
O1—C7—N1	122.2 (2)	H14B—C14—H14C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.86	1.98	2.655 (2)	135
C2—H2B···N3ⁱ	0.93	2.59	3.417 (3)	148

Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂ClN₃OS
M_r	305.78
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	7.8417 (15), 7.1058 (13), 25.585 (5)
β (°)	93.405 (4)
V (Å³)	1423.1 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.41
Crystal size (mm)	0.44 × 0.31 × 0.14

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.839, 0.944
No. of measured, independent and observed [I > 2/s(I)] reflections	9917, 3421, 2188
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.139, 1.04
No. of reflections	3421
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.17

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.86	1.98	2.655 (2)	135
C2—H2B···N3ⁱ	0.93	2.59	3.417 (3)	148

Symmetry code: (i) x+1, y, z.

Acknowledgements

The authors thank the Malaysian Government, Universiti Kebangsaan Malaysia, Faculty of Science and Technology, Universiti Malaysia Terengganu and the Ministry of Higher Education, Malaysia, for research grants UKM-GUP-NBT-08–27–110 and FRGS 59178.

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