organic compounds
4-Methylbenzenecarbothioamide
aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, and bDepartment of Chemistry, The University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4
*Correspondence e-mail: drsa54@yahoo.com
In the title molecule, C8H9NS, the mean plane of the carbothioamide group is twisted slightly with respect to the mean plane of the benzene ring, making a dihedral angle of 17.03 (10)°. The is stabilized by intermolecular N—H⋯S hydrogen bonds, resulting in the formation of eight-membered rings lying about inversion centers and representing R22(8) and R42(8) motifs. Futhermore, these hydrogen bonds build up chains parallel to the b axis.
Related literature
For the use of thioamides as intermediates in the synthesis of various et al. (2009). For the uses of thioamides, see: Lebana et al. (2008). For the biological activity of thioamides, see: Jagodzinski (2003); Klimesova et al. (1999). For related structures, see: Khan et al. (2009a,b,c); Jian et al. (2006); Ali et al. (2010). For graph-set notation, see: Etter et al. (1990); Bernstein et al. (1994).
see: ZahidExperimental
Crystal data
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Refinement
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Data collection: COLLECT (Hooft, 1998); cell DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); 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: SHELXL97.
Supporting information
https://doi.org/10.1107/S1600536810015813/dn2557sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810015813/dn2557Isup2.hkl
4-Methylbenzonitrile (13.2 mmol) was added to a slurry of magnesium cholride hexahydrate (13.2 mmol) and sodium hydrogen sulphide hydrate (70%, 26.4 mmol) in dimethylformamide (35 ml) and the reaction mixture was stirred at room temperature for 4 h. The reaction mixture was poured into water (100 ml) and the resulting precipitates were collected by filtration. The product obtained was resuspended in 1 N HCl (50 ml), stirred for another 25 min, the precipitated solid filtered and washed with water. Recrystallization of the product from chloroform afforded the crystals of the title compound suitable for X-ray analysis.
Though all the H atoms could be distinguished in the difference Fourier map the H-atoms were included at geometrically idealized positions and refined in riding-model approximation with N—H = 0.88 Å and C—H = 0.95 and 0.98 Å for aryl and methyl H-atoms, respectively. The Uiso(H) were allowed at 1.2/1.5Ueq(N/C). The final difference map was essentially featurless.
Thioamides are not only used as intermediates in the synthesis of various
(Zahid et al., 2009), they are important biologically active agents (Jagodzinski, 2003; Klimesova et al., 1999). In addition, they are important ligands in the field of coordination chemistry (Lebana et al., 2008). In continuation to our work on thioamides (Khan et al., 2009a; 2009b; 2009c; Ali et al., 2010), we have synthesized 4-methylbenzenecarbothioamide, (I). In this article we report the of the title compound.In the title molecule (Fig. 1), the bond distances and angles agree with the corresponding bond distances and angles reported in closely related compounds (Khan et al., 2009a; 2009b; 2009c; Jian et al., 2006; Ali et al., 2010). In the title compound, the mean-plane of the carbothioamide group (S1/N1/C7) is slightly twisted with respect to the mean-plane of the phenyl ring (C1–C6), making a dihedral angle of 17.03 (10)°.
The structure is stabilized by intermolecular N—H···S hydrogen bonds resulting in the formation of eight membered rings lying about inversion centers (Tab. 1 and Fig. 2). In the graph set notation (Etter et al., 1990; Bernstein et al., 1994) the hydrogen bonded rings may be best described as representing R22(8) and R42(8) motifs.Futhermore, these hydrogen bonds build up chains parallel to the b axis.
For the synthesis and background to the use of thioamides as intermediates in the synthesis of various
see: Zahid et al. (2009). For the uses of thioamide, see: Lebana et al. (2008). For the biological activity of thioamides, see: Jagodzinski (2003); Klimesova et al. (1999). For related structures, see: Khan et al. (2009a,b,c); Jian et al. (2006); Ali et al. (2010). For graph-set notation, see: Etter et al. (1990); Bernstein et al. (1994).Data collection: COLLECT (Hooft, 1998); cell
DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); 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: SHELXL97 (Sheldrick, 2008).C8H9NS | F(000) = 320 |
Mr = 151.22 | Dx = 1.315 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1473 reflections |
a = 9.7341 (5) Å | θ = 1.0–26.0° |
b = 5.8391 (2) Å | µ = 0.34 mm−1 |
c = 13.9055 (6) Å | T = 123 K |
β = 104.946 (3)° | Block, yellow |
V = 763.63 (6) Å3 | 0.10 × 0.06 × 0.06 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 1482 independent reflections |
Radiation source: fine-focus sealed tube | 1399 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ω and φ scans | θmax = 26.0°, θmin = 3.8° |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | h = −11→11 |
Tmin = 0.967, Tmax = 0.980 | k = −7→7 |
2741 measured reflections | l = −16→16 |
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: difference Fourier map |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0373P)2 + 0.5912P] where P = (Fo2 + 2Fc2)/3 |
1482 reflections | (Δ/σ)max < 0.001 |
92 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C8H9NS | V = 763.63 (6) Å3 |
Mr = 151.22 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.7341 (5) Å | µ = 0.34 mm−1 |
b = 5.8391 (2) Å | T = 123 K |
c = 13.9055 (6) Å | 0.10 × 0.06 × 0.06 mm |
β = 104.946 (3)° |
Nonius KappaCCD diffractometer | 1482 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | 1399 reflections with I > 2σ(I) |
Tmin = 0.967, Tmax = 0.980 | Rint = 0.025 |
2741 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.27 e Å−3 |
1482 reflections | Δρmin = −0.24 e Å−3 |
92 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.15464 (4) | 0.79266 (7) | 0.03136 (3) | 0.02316 (16) | |
N1 | 0.19369 (15) | 0.3538 (2) | 0.06514 (10) | 0.0219 (3) | |
H1A | 0.2463 | 0.2313 | 0.0844 | 0.026* | |
H1B | 0.1007 | 0.3410 | 0.0440 | 0.026* | |
C1 | 0.41221 (16) | 0.5673 (3) | 0.10461 (11) | 0.0168 (3) | |
C2 | 0.48580 (17) | 0.7599 (3) | 0.08529 (11) | 0.0189 (3) | |
H2 | 0.4344 | 0.8849 | 0.0496 | 0.023* | |
C3 | 0.63277 (18) | 0.7714 (3) | 0.11743 (12) | 0.0207 (4) | |
H3 | 0.6805 | 0.9045 | 0.1037 | 0.025* | |
C4 | 0.71154 (17) | 0.5908 (3) | 0.16965 (11) | 0.0203 (4) | |
C5 | 0.63795 (18) | 0.3995 (3) | 0.19021 (11) | 0.0211 (4) | |
H5 | 0.6897 | 0.2753 | 0.2264 | 0.025* | |
C6 | 0.49105 (17) | 0.3872 (3) | 0.15894 (11) | 0.0196 (3) | |
H6 | 0.4433 | 0.2557 | 0.1744 | 0.023* | |
C7 | 0.25443 (17) | 0.5571 (3) | 0.06803 (11) | 0.0177 (3) | |
C8 | 0.87114 (18) | 0.6011 (3) | 0.20278 (13) | 0.0280 (4) | |
H8A | 0.9033 | 0.7532 | 0.1883 | 0.042* | |
H8B | 0.9114 | 0.4848 | 0.1671 | 0.042* | |
H8C | 0.9028 | 0.5719 | 0.2745 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0174 (2) | 0.0146 (2) | 0.0353 (3) | 0.00051 (14) | 0.00272 (18) | 0.00029 (16) |
N1 | 0.0160 (7) | 0.0155 (7) | 0.0332 (8) | −0.0010 (6) | 0.0045 (6) | 0.0019 (6) |
C1 | 0.0192 (8) | 0.0154 (8) | 0.0163 (7) | −0.0005 (6) | 0.0055 (6) | −0.0017 (6) |
C2 | 0.0205 (8) | 0.0156 (7) | 0.0204 (7) | 0.0009 (6) | 0.0050 (6) | 0.0019 (6) |
C3 | 0.0215 (8) | 0.0192 (8) | 0.0221 (8) | −0.0032 (6) | 0.0066 (6) | −0.0004 (6) |
C4 | 0.0193 (8) | 0.0229 (8) | 0.0182 (7) | 0.0001 (6) | 0.0041 (6) | −0.0033 (6) |
C5 | 0.0240 (8) | 0.0203 (8) | 0.0180 (7) | 0.0042 (6) | 0.0037 (6) | 0.0024 (6) |
C6 | 0.0234 (8) | 0.0158 (8) | 0.0202 (7) | −0.0018 (6) | 0.0068 (6) | 0.0009 (6) |
C7 | 0.0204 (8) | 0.0161 (8) | 0.0170 (7) | −0.0007 (6) | 0.0057 (6) | −0.0007 (6) |
C8 | 0.0194 (9) | 0.0328 (10) | 0.0299 (9) | 0.0000 (7) | 0.0026 (7) | 0.0007 (8) |
S1—C7 | 1.6852 (16) | C3—H3 | 0.9500 |
N1—C7 | 1.322 (2) | C4—C5 | 1.396 (2) |
N1—H1A | 0.8800 | C4—C8 | 1.503 (2) |
N1—H1B | 0.8800 | C5—C6 | 1.385 (2) |
C1—C2 | 1.396 (2) | C5—H5 | 0.9500 |
C1—C6 | 1.403 (2) | C6—H6 | 0.9500 |
C1—C7 | 1.489 (2) | C8—H8A | 0.9800 |
C2—C3 | 1.386 (2) | C8—H8B | 0.9800 |
C2—H2 | 0.9500 | C8—H8C | 0.9800 |
C3—C4 | 1.393 (2) | ||
C7—N1—H1A | 120.0 | C6—C5—C4 | 121.35 (15) |
C7—N1—H1B | 120.0 | C6—C5—H5 | 119.3 |
H1A—N1—H1B | 120.0 | C4—C5—H5 | 119.3 |
C2—C1—C6 | 118.11 (15) | C5—C6—C1 | 120.48 (15) |
C2—C1—C7 | 120.12 (14) | C5—C6—H6 | 119.8 |
C6—C1—C7 | 121.77 (14) | C1—C6—H6 | 119.8 |
C3—C2—C1 | 121.02 (15) | N1—C7—C1 | 117.39 (14) |
C3—C2—H2 | 119.5 | N1—C7—S1 | 120.35 (12) |
C1—C2—H2 | 119.5 | C1—C7—S1 | 122.26 (12) |
C2—C3—C4 | 120.99 (15) | C4—C8—H8A | 109.5 |
C2—C3—H3 | 119.5 | C4—C8—H8B | 109.5 |
C4—C3—H3 | 119.5 | H8A—C8—H8B | 109.5 |
C3—C4—C5 | 118.04 (15) | C4—C8—H8C | 109.5 |
C3—C4—C8 | 121.05 (15) | H8A—C8—H8C | 109.5 |
C5—C4—C8 | 120.91 (15) | H8B—C8—H8C | 109.5 |
C6—C1—C2—C3 | 1.0 (2) | C4—C5—C6—C1 | 0.6 (2) |
C7—C1—C2—C3 | −179.07 (14) | C2—C1—C6—C5 | −1.4 (2) |
C1—C2—C3—C4 | 0.3 (2) | C7—C1—C6—C5 | 178.65 (14) |
C2—C3—C4—C5 | −1.1 (2) | C2—C1—C7—N1 | 162.91 (15) |
C2—C3—C4—C8 | 178.76 (15) | C6—C1—C7—N1 | −17.2 (2) |
C3—C4—C5—C6 | 0.7 (2) | C2—C1—C7—S1 | −17.1 (2) |
C8—C4—C5—C6 | −179.18 (15) | C6—C1—C7—S1 | 162.78 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···S1i | 0.88 | 2.56 | 3.4178 (14) | 166 |
N1—H1A···S1ii | 0.88 | 2.75 | 3.3179 (15) | 124 |
Symmetry codes: (i) −x, −y+1, −z; (ii) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | C8H9NS |
Mr | 151.22 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 123 |
a, b, c (Å) | 9.7341 (5), 5.8391 (2), 13.9055 (6) |
β (°) | 104.946 (3) |
V (Å3) | 763.63 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.34 |
Crystal size (mm) | 0.10 × 0.06 × 0.06 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Multi-scan (SORTAV; Blessing, 1997) |
Tmin, Tmax | 0.967, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2741, 1482, 1399 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.089, 1.06 |
No. of reflections | 1482 |
No. of parameters | 92 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.24 |
Computer programs: COLLECT (Hooft, 1998), DENZO (Otwinowski & Minor, 1997), SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···S1i | 0.88 | 2.56 | 3.4178 (14) | 166 |
N1—H1A···S1ii | 0.88 | 2.75 | 3.3179 (15) | 124 |
Symmetry codes: (i) −x, −y+1, −z; (ii) x, y−1, z. |
References
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Thioamides are not only used as intermediates in the synthesis of various heterocyclic compounds (Zahid et al., 2009), they are important biologically active agents (Jagodzinski, 2003; Klimesova et al., 1999). In addition, they are important ligands in the field of coordination chemistry (Lebana et al., 2008). In continuation to our work on thioamides (Khan et al., 2009a; 2009b; 2009c; Ali et al., 2010), we have synthesized 4-methylbenzenecarbothioamide, (I). In this article we report the crystal structure of the title compound.
In the title molecule (Fig. 1), the bond distances and angles agree with the corresponding bond distances and angles reported in closely related compounds (Khan et al., 2009a; 2009b; 2009c; Jian et al., 2006; Ali et al., 2010). In the title compound, the mean-plane of the carbothioamide group (S1/N1/C7) is slightly twisted with respect to the mean-plane of the phenyl ring (C1–C6), making a dihedral angle of 17.03 (10)°.
The structure is stabilized by intermolecular N—H···S hydrogen bonds resulting in the formation of eight membered rings lying about inversion centers (Tab. 1 and Fig. 2). In the graph set notation (Etter et al., 1990; Bernstein et al., 1994) the hydrogen bonded rings may be best described as representing R22(8) and R42(8) motifs.Futhermore, these hydrogen bonds build up chains parallel to the b axis.