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Acta Crystallogr Sect E Struct Rep Online. 2009 May 1; 65(Pt 5): o1128.
Published online 2009 April 25. doi:  10.1107/S1600536809014640
PMCID: PMC2977801

4-Chloro­benzothio­amide

Abstract

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

An external file that holds a picture, illustration, etc.
Object name is e-65-o1128-scheme1.jpg

Experimental

Crystal data

  • C7H6ClNS
  • M r = 171.64
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1128-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.105
  • S = 1.06
  • 1901 reflections
  • 91 parameters
  • H-atom parameters constrained
  • Δρmax = 0.33 e Å−3
  • Δρmin = −0.38 e Å−3

Data collection: APEX2 (Bruker, 2008 [triangle]); cell refinement: SAINT (Bruker, 2008 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

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

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

The hydrogen atoms were placed in geometrically idealized positions of 0.93Å (aromatic C—H) and 0.86Å (amide N—H) and constrained to ride on the parent atom with Uiso(H) = 1.2 Ueq(C,N).

Figures

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).

Crystal data

C7H6ClNSF(000) = 352
Mr = 171.64Dx = 1.433 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3894 reflections
a = 8.1592 (4) Åθ = 2.5–28.5°
b = 9.0934 (5) ŵ = 0.66 mm1
c = 10.8915 (6) ÅT = 296 K
β = 100.113 (1)°Block, yellow
V = 795.54 (7) Å30.40 × 0.36 × 0.18 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer1901 independent reflections
Radiation source: fine-focus sealed tube1667 reflections with I > 2σ(I)
graphiteRint = 0.017
[var phi] and ω scansθmax = 28.5°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2008)h = −10→10
Tmin = 0.778, Tmax = 0.889k = −12→12
6337 measured reflectionsl = −9→14

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105H-atom parameters constrained
S = 1.06w = 1/[σ2(Fo2) + (0.0539P)2 + 0.2817P] where P = (Fo2 + 2Fc2)/3
1901 reflections(Δ/σ)max < 0.001
91 parametersΔρmax = 0.33 e Å3
0 restraintsΔρmin = −0.38 e Å3

Special details

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)

xyzUiso*/Ueq
S10.08443 (7)0.15260 (5)0.36191 (4)0.05425 (18)
Cl10.41127 (8)0.84764 (5)0.55354 (7)0.0767 (2)
N10.1431 (2)0.16063 (15)0.60516 (12)0.0479 (4)
H1A0.17760.20250.67580.058*
H1B0.10460.07240.60280.058*
C10.14913 (18)0.23175 (17)0.50045 (13)0.0367 (3)
C20.21721 (18)0.38334 (16)0.51285 (13)0.0346 (3)
C70.16710 (19)0.48716 (18)0.41971 (14)0.0402 (3)
H7A0.09250.46030.34850.048*
C50.3367 (2)0.66844 (17)0.53788 (18)0.0466 (4)
C60.2270 (2)0.62963 (18)0.43192 (17)0.0462 (4)
H6A0.19370.69840.36930.055*
C30.3294 (2)0.42569 (19)0.61821 (15)0.0448 (4)
H3A0.36470.35730.68080.054*
C40.3893 (2)0.5685 (2)0.63118 (17)0.0515 (4)
H4A0.46410.59630.70200.062*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0851 (4)0.0495 (3)0.0281 (2)−0.0239 (2)0.0096 (2)−0.00374 (15)
Cl10.0841 (4)0.0399 (3)0.1008 (5)−0.0176 (2)0.0012 (3)−0.0009 (2)
N10.0790 (10)0.0363 (7)0.0299 (7)−0.0104 (6)0.0134 (6)−0.0014 (5)
C10.0449 (7)0.0369 (7)0.0291 (7)−0.0020 (6)0.0091 (6)−0.0005 (5)
C20.0393 (7)0.0345 (7)0.0307 (7)−0.0002 (5)0.0085 (5)−0.0002 (5)
C70.0438 (7)0.0415 (8)0.0341 (8)0.0001 (6)0.0030 (6)0.0029 (6)
C50.0457 (8)0.0337 (7)0.0604 (11)−0.0048 (6)0.0095 (7)−0.0024 (7)
C60.0489 (8)0.0383 (8)0.0504 (10)0.0020 (7)0.0056 (7)0.0095 (7)
C30.0520 (9)0.0422 (8)0.0374 (8)−0.0029 (7)−0.0002 (6)0.0040 (6)
C40.0539 (9)0.0483 (9)0.0477 (10)−0.0087 (7)−0.0036 (7)−0.0042 (7)

Geometric parameters (Å, °)

S1—C11.6714 (15)C7—C61.383 (2)
Cl1—C51.7374 (16)C7—H7A0.9300
N1—C11.3195 (19)C5—C41.375 (3)
N1—H1A0.8600C5—C61.376 (3)
N1—H1B0.8600C6—H6A0.9300
C1—C21.483 (2)C3—C41.386 (2)
C2—C31.391 (2)C3—H3A0.9300
C2—C71.393 (2)C4—H4A0.9300
C1—N1—H1A120.0C4—C5—C6121.55 (15)
C1—N1—H1B120.0C4—C5—Cl1119.26 (14)
H1A—N1—H1B120.0C6—C5—Cl1119.19 (14)
N1—C1—C2116.55 (13)C5—C6—C7119.19 (15)
N1—C1—S1121.02 (12)C5—C6—H6A120.4
C2—C1—S1122.42 (11)C7—C6—H6A120.4
C3—C2—C7118.65 (14)C4—C3—C2120.85 (15)
C3—C2—C1120.94 (14)C4—C3—H3A119.6
C7—C2—C1120.40 (13)C2—C3—H3A119.6
C6—C7—C2120.74 (15)C5—C4—C3119.02 (15)
C6—C7—H7A119.6C5—C4—H4A120.5
C2—C7—H7A119.6C3—C4—H4A120.5
S1—C1—C2—C728.1 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···S1i0.862.643.3769 (15)145
N1—H1B···S1ii0.862.633.4527 (15)160

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT2933).

References

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Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography