4-Chloro­benzothio­amide

Khan, M.-H.; Hameed, S.; Akhtar, T.; Masuda, J.D.

doi:10.1107/S1600536809014640

organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1128

doi:10.1107/S1600536809014640

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4-Chlorobenzothioamide

Mahmood-ul-Hassan Khan,^a Shahid Hameed,^a ^* Tashfeen Akhtar ^a and Jason D. Masuda ^b

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, and ^bDepartment of Chemistry, Saint Mary's University, Halifax, Nova Scotia, Canada B3H 3C3
^*Correspondence e-mail: shameed@qau.edu.pk

(Received 17 April 2009; accepted 20 April 2009; online 25 April 2009)

In the title compound, C₇H₆ClNS, the dihedral angle between the aromatic ring and the thioamide fragment is 28.1 (2)°. The structure features a π-stacking interaction between the aromatic rings with a slight offset of the rings, giving a centroid–centroid separation of 3.7942 (2) Å. There are intermolecular hydrogen-bonding interactions between the amino group and the S atoms.

Related literature

For the uses of thioamides, see: Akhtar et al. (2006 , 2007 , 2008 ); Jagodzinski (2003 ); Lebana et al. (2008 ). For the biological activity of thioamides, see: Wei et al. (2006 ). For the synthesis of thioamides, see: Bauer & Kuhlein (1985 ); Cava & Levinson (1985 ); Manaka & Sato (2005 ). For a comparable structure, see: Jian et al. (2006 ).

Experimental

Crystal data

C₇H₆ClNS
M_r = 171.64
Monoclinic, P 2₁ /c
a = 8.1592 (4) Å
b = 9.0934 (5) Å
c = 10.8915 (6) Å
β = 100.113 (10°
V = 795.54 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.66 mm⁻¹
T = 296 K
0.40 × 0.36 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.778, T_max = 0.889
6337 measured reflections
1901 independent reflections
1667 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.105
S = 1.06
1901 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯S1ⁱ	0.86	2.64	3.3769 (15)	145
N1—H1B⋯S1ⁱⁱ	0.86	2.63	3.4527 (15)	160
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x, -y, -z+1.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); 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 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809014640/bt2933sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809014640/bt2933Isup2.hkl

checkCIF report

Comment top

Thioamides are important precursors/intermediates in the synthesis of various heterocycles (Jagodzinski et al., 2003). Besides being used as synthetic intermediates, they exhibit numerous biological activities (Wei et al., 2006). In addition, thioamides have found use as important ligands in coordination chemistry (Lebana et al., 2008). Several methods for their synthesis have been published involving the uses of Lawesson's regent (Cava et al., 1985) and phosphorus pentasulphide (Bauer et al., 1985). The title compound, 4-chlorobenzothioamide was synthesized in continuation of our previous work on the synthesis and biological screenings of five membered heterocycles (Akhtar et al., 2006, 2007, 2008). In this article the crystal structure of 4-chlorobenzothioamide is being reported. The title compound was synthesized by treating 4-chlorobenzonitrile with 70% sodium hydrogen sulfide hydrate and magnesium chloride hexahydrate in dimethylformamide (Manaka & Sato, 2005) as an intermediate for the synthesis of thiazoles.

The hydrogen bonding interactions between the nitrogen and sulfur atoms are in the range of those seen in p-trifluoromethylbenzothioamide where the corresponding interactions are between 3.3735Å and 3.5133Å (Jian et al., 2006).

Related literature top

For the uses of thioamides, see: Akhtar et al. (2006, 2007, 2008); Jagodzinski et al. (2003); Lebana et al. (2008). For the biological activity of thioamides, see: Wei et al. (2006). For the synthesis of thioamides, see: Bauer et al. (1985); Cava et al. (1985); Manaka & Sato (2005). For a comparable structure, see: Jian et al. (2006).

Experimental top

4-Chlorobenzonitrile (14.5 mmol) was added to a slurry of sodium hydrogen sulfide hydrate (70%, 29 mmol) and magnesium chloride hexahydrate (14.5 mmol) in DMF (40 mL) and the mixture stirred at room temperature for 2 h. The resulting green slurry was poured into water (100 mL) and the precipitated solid collected by filtration. The product obtained was resuspended in 1 N HCl (50 ml), stirred for another 30 min, filtered and washed with excess of water. The recrystallization of the residue from chloroform afforded the crystals of the title compound suitable for X-ray analysis.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of 4-chlorobenzothioamide showing displacement ellipsoids at the 50% probability level (for non-H atoms).
	Fig. 2. Packing diagram of 4-chlorobenzothioamide as viewed down the b axis. Displacement ellipsoids are shown at the 50% probability level (for non-H atoms).

4-Chlorobenzothioamide top

Crystal data top

C₇H₆ClNS	F(000) = 352
M_r = 171.64	D_x = 1.433 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3894 reflections
a = 8.1592 (4) Å	θ = 2.5–28.5°
b = 9.0934 (5) Å	µ = 0.66 mm⁻¹
c = 10.8915 (6) Å	T = 296 K
β = 100.113 (1)°	Block, yellow
V = 795.54 (7) Å³	0.40 × 0.36 × 0.18 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1901 independent reflections
Radiation source: fine-focus sealed tube	1667 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ϕ and ω scans	θ_max = 28.5°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −10→10
T_min = 0.778, T_max = 0.889	k = −12→12
6337 measured reflections	l = −9→14

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) = 0.105	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0539P)² + 0.2817P] where P = (F_o² + 2F_c²)/3
1901 reflections	(Δ/σ)_max < 0.001
91 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₇H₆ClNS	V = 795.54 (7) Å³
M_r = 171.64	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.1592 (4) Å	µ = 0.66 mm⁻¹
b = 9.0934 (5) Å	T = 296 K
c = 10.8915 (6) Å	0.40 × 0.36 × 0.18 mm
β = 100.113 (1)°

Data collection top

Bruker APEXII CCD diffractometer	1901 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1667 reflections with I > 2σ(I)
T_min = 0.778, T_max = 0.889	R_int = 0.017
6337 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.06	Δρ_max = 0.33 e Å⁻³
1901 reflections	Δρ_min = −0.38 e Å⁻³
91 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
S1	0.08443 (7)	0.15260 (5)	0.36191 (4)	0.05425 (18)
Cl1	0.41127 (8)	0.84764 (5)	0.55354 (7)	0.0767 (2)
N1	0.1431 (2)	0.16063 (15)	0.60516 (12)	0.0479 (4)
H1A	0.1776	0.2025	0.6758	0.058*
H1B	0.1046	0.0724	0.6028	0.058*
C1	0.14913 (18)	0.23175 (17)	0.50045 (13)	0.0367 (3)
C2	0.21721 (18)	0.38334 (16)	0.51285 (13)	0.0346 (3)
C7	0.16710 (19)	0.48716 (18)	0.41971 (14)	0.0402 (3)
H7A	0.0925	0.4603	0.3485	0.048*
C5	0.3367 (2)	0.66844 (17)	0.53788 (18)	0.0466 (4)
C6	0.2270 (2)	0.62963 (18)	0.43192 (17)	0.0462 (4)
H6A	0.1937	0.6984	0.3693	0.055*
C3	0.3294 (2)	0.42569 (19)	0.61821 (15)	0.0448 (4)
H3A	0.3647	0.3573	0.6808	0.054*
C4	0.3893 (2)	0.5685 (2)	0.63118 (17)	0.0515 (4)
H4A	0.4641	0.5963	0.7020	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0851 (4)	0.0495 (3)	0.0281 (2)	−0.0239 (2)	0.0096 (2)	−0.00374 (15)
Cl1	0.0841 (4)	0.0399 (3)	0.1008 (5)	−0.0176 (2)	0.0012 (3)	−0.0009 (2)
N1	0.0790 (10)	0.0363 (7)	0.0299 (7)	−0.0104 (6)	0.0134 (6)	−0.0014 (5)
C1	0.0449 (7)	0.0369 (7)	0.0291 (7)	−0.0020 (6)	0.0091 (6)	−0.0005 (5)
C2	0.0393 (7)	0.0345 (7)	0.0307 (7)	−0.0002 (5)	0.0085 (5)	−0.0002 (5)
C7	0.0438 (7)	0.0415 (8)	0.0341 (8)	0.0001 (6)	0.0030 (6)	0.0029 (6)
C5	0.0457 (8)	0.0337 (7)	0.0604 (11)	−0.0048 (6)	0.0095 (7)	−0.0024 (7)
C6	0.0489 (8)	0.0383 (8)	0.0504 (10)	0.0020 (7)	0.0056 (7)	0.0095 (7)
C3	0.0520 (9)	0.0422 (8)	0.0374 (8)	−0.0029 (7)	−0.0002 (6)	0.0040 (6)
C4	0.0539 (9)	0.0483 (9)	0.0477 (10)	−0.0087 (7)	−0.0036 (7)	−0.0042 (7)

Geometric parameters (Å, º) top

S1—C1	1.6714 (15)	C7—C6	1.383 (2)
Cl1—C5	1.7374 (16)	C7—H7A	0.9300
N1—C1	1.3195 (19)	C5—C4	1.375 (3)
N1—H1A	0.8600	C5—C6	1.376 (3)
N1—H1B	0.8600	C6—H6A	0.9300
C1—C2	1.483 (2)	C3—C4	1.386 (2)
C2—C3	1.391 (2)	C3—H3A	0.9300
C2—C7	1.393 (2)	C4—H4A	0.9300

C1—N1—H1A	120.0	C4—C5—C6	121.55 (15)
C1—N1—H1B	120.0	C4—C5—Cl1	119.26 (14)
H1A—N1—H1B	120.0	C6—C5—Cl1	119.19 (14)
N1—C1—C2	116.55 (13)	C5—C6—C7	119.19 (15)
N1—C1—S1	121.02 (12)	C5—C6—H6A	120.4
C2—C1—S1	122.42 (11)	C7—C6—H6A	120.4
C3—C2—C7	118.65 (14)	C4—C3—C2	120.85 (15)
C3—C2—C1	120.94 (14)	C4—C3—H3A	119.6
C7—C2—C1	120.40 (13)	C2—C3—H3A	119.6
C6—C7—C2	120.74 (15)	C5—C4—C3	119.02 (15)
C6—C7—H7A	119.6	C5—C4—H4A	120.5
C2—C7—H7A	119.6	C3—C4—H4A	120.5

S1—C1—C2—C7	28.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1ⁱ	0.86	2.64	3.3769 (15)	145
N1—H1B···S1ⁱⁱ	0.86	2.63	3.4527 (15)	160

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

Experimental details

Crystal data
Chemical formula	C₇H₆ClNS
M_r	171.64
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.1592 (4), 9.0934 (5), 10.8915 (6)
β (°)	100.113 (1)
V (Å³)	795.54 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.66
Crystal size (mm)	0.40 × 0.36 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.778, 0.889
No. of measured, independent and observed [I > 2σ(I)] reflections	6337, 1901, 1667
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.672

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.105, 1.06
No. of reflections	1901
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.38

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1ⁱ	0.86	2.64	3.3769 (15)	144.6
N1—H1B···S1ⁱⁱ	0.86	2.63	3.4527 (15)	160.3

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

Acknowledgements

MuHK is thankful to the HEC, Pakistan, for a PhD fellowship under the indigenous PhD Program. JDM thanks Saint Mary's Univeristy for funding.

References

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