3-Methyl­thio­benzamide

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

doi:10.1107/S1600536809019849

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1446

doi:10.1107/S1600536809019849

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3-Methylthiobenzamide

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 23 May 2009; accepted 25 May 2009; online 29 May 2009)

In the title compound, C₈H₉NS, the dihedral angle between the aromatic ring and the thioamide fragment is 36.0 (2)°. There are π-stacking interactions between coplanar aryl fragments, with a centroid–centroid separation of 3.658 (2) Å. In addition, there are intermolecular hydrogen bonds between the amino group and the S atoms.

Related literature

For our previous work on the synthesis and biological screening of five-membered heterocycles, see: Akhtar et al. (2006 , 2007 , 2008 ); Serwar et al. (2009 ). For related structures, see: Jian et al. (2006 ); Khan et al. (2009a ,b ).

Experimental

Crystal data

C₈H₉NS
M_r = 151.22
Monoclinic, P 2₁ /c
a = 7.717 (5) Å
b = 10.267 (7) Å
c = 10.100 (7) Å
β = 97.186 (9)°
V = 794.0 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 296 K
0.37 × 0.27 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.793, T_max = 0.930
6234 measured reflections
1797 independent reflections
1447 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.112
S = 1.08
1797 reflections
92 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.29 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	2.66	3.455 (2)	155
N1—H1B⋯S1ⁱⁱ	0.86	2.58	3.422 (3)	165
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x, -y+1, -z.

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/S1600536809019849/bt2967sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809019849/bt2967Isup2.hkl

checkCIF report

Comment top

Thioamides are not only important intermediates in the synthesis of heterocyclic compounds but they also possess enormous biologically activities as reported in our previous articles (Khan et al., 2009a). In the present article, we report the crystal structure of 3-methylthiobenzamide, synthesized as a continuation of our previous work on the synthesis and biological screenings of five membered heterocycles (Akhtar et al., 2006, 2007, 2008; Serwar et al., 2009).

There are two distinct hydrogen bonding interactions between the nitrogen and sulfur atoms. The first arranges the dimer with N···S distances of 3.422 (3)Å and the second links two thioamide dimers through another N···S interaction on the order of 3.455 (2) Å. These N—H···S hydrogen bonding interactions are similar to those seen in p-trifluoromethylbenzothioamide where the corresponding interactions are between 3.3735Å and 3.5133Å (Jian et al., 2006), in 4-chlorobenzothioamide where the N···S distances are 3.3769 (15)Å and 3.4527 (15)Å (Khan et al., 2009a) and in 4-bromobenzothioamide where the N···S distances are between 3.500 (2)Å and 3.605 (3) Å (Khan et al., 2009b).

Related literature top

For our previous work on the synthesis and biological screening of five-membered heterocycles, see: Akhtar et al. (2006, 2007, 2008); Serwar et al. (2009). For related structures, see: Jian et al. (2006); Khan et al. (2009a,b).

Experimental top

The title compound was synthesized from 3-methylbenzonitrile according to a reported procedure (Khan et al., 2009a). The recrystallization of the product from chloroform afforded crystals 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 3-methylthiobenzamide showing displacement ellipsoids at the 50% probability level (for non-H atoms).
	Fig. 2. Packing diagram of 3-methylthiobenzamide. Hydrogen bonds shown as dashed lines.

3-Methylthiobenzamide top

Crystal data top

C₈H₉NS	F(000) = 320
M_r = 151.22	D_x = 1.265 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2572 reflections
a = 7.717 (5) Å	θ = 2.7–27.1°
b = 10.267 (7) Å	µ = 0.33 mm⁻¹
c = 10.100 (7) Å	T = 296 K
β = 97.186 (9)°	Block, yellow
V = 794.0 (9) Å³	0.37 × 0.27 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1797 independent reflections
Radiation source: fine-focus sealed tube	1447 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −10→9
T_min = 0.793, T_max = 0.930	k = −13→13
6234 measured reflections	l = −11→13

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0556P)² + 0.242P] where P = (F_o² + 2F_c²)/3
1797 reflections	(Δ/σ)_max < 0.001
92 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₈H₉NS	V = 794.0 (9) Å³
M_r = 151.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.717 (5) Å	µ = 0.33 mm⁻¹
b = 10.267 (7) Å	T = 296 K
c = 10.100 (7) Å	0.37 × 0.27 × 0.20 mm
β = 97.186 (9)°

Data collection top

Bruker APEXII CCD diffractometer	1797 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1447 reflections with I > 2σ(I)
T_min = 0.793, T_max = 0.930	R_int = 0.021
6234 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.112	H-atom parameters constrained
S = 1.08	Δρ_max = 0.22 e Å⁻³
1797 reflections	Δρ_min = −0.29 e Å⁻³
92 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	0.13324 (7)	0.62675 (4)	0.16035 (4)	0.05023 (19)
N1	0.0243 (2)	0.38549 (15)	0.17149 (16)	0.0521 (4)
H1A	0.0187	0.3113	0.2103	0.063*
H1B	−0.0260	0.3963	0.0914	0.063*
C2	0.1933 (2)	0.45618 (15)	0.37261 (16)	0.0358 (4)
C1	0.1099 (2)	0.48241 (16)	0.23470 (16)	0.0379 (4)
C3	0.2661 (2)	0.33439 (17)	0.40481 (18)	0.0406 (4)
H3A	0.2535	0.2683	0.3414	0.049*
C7	0.2072 (2)	0.55347 (17)	0.46931 (18)	0.0435 (4)
H7A	0.1589	0.6352	0.4492	0.052*
C4	0.3569 (2)	0.30980 (18)	0.52939 (19)	0.0455 (4)
C5	0.3695 (2)	0.4084 (2)	0.62387 (18)	0.0500 (5)
H5A	0.4303	0.3935	0.7079	0.060*
C6	0.2927 (3)	0.5286 (2)	0.59491 (19)	0.0501 (5)
H6A	0.2989	0.5927	0.6604	0.060*
C8	0.4466 (3)	0.1803 (2)	0.5575 (2)	0.0671 (6)
H8A	0.3710	0.1115	0.5210	0.101*
H8B	0.4729	0.1686	0.6522	0.101*
H8C	0.5529	0.1786	0.5173	0.101*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0774 (4)	0.0330 (2)	0.0387 (3)	0.0000 (2)	0.0007 (2)	0.00264 (17)
N1	0.0726 (11)	0.0435 (8)	0.0363 (8)	−0.0142 (7)	−0.0089 (7)	0.0048 (6)
C2	0.0384 (8)	0.0362 (8)	0.0329 (8)	−0.0031 (6)	0.0046 (6)	0.0001 (6)
C1	0.0439 (9)	0.0345 (8)	0.0351 (9)	0.0016 (6)	0.0042 (7)	−0.0013 (6)
C3	0.0461 (9)	0.0380 (8)	0.0379 (9)	−0.0003 (7)	0.0066 (7)	0.0007 (7)
C7	0.0508 (10)	0.0396 (9)	0.0398 (9)	−0.0018 (7)	0.0045 (8)	−0.0032 (7)
C4	0.0433 (9)	0.0492 (10)	0.0446 (10)	0.0012 (7)	0.0078 (7)	0.0129 (8)
C5	0.0482 (10)	0.0674 (12)	0.0332 (9)	−0.0082 (9)	−0.0003 (8)	0.0076 (8)
C6	0.0576 (11)	0.0554 (11)	0.0369 (10)	−0.0097 (9)	0.0040 (8)	−0.0083 (8)
C8	0.0737 (14)	0.0647 (14)	0.0630 (14)	0.0205 (11)	0.0093 (11)	0.0223 (11)

Geometric parameters (Å, º) top

S1—C1	1.6811 (19)	C7—H7A	0.9300
N1—C1	1.315 (2)	C4—C5	1.386 (3)
N1—H1A	0.8600	C4—C8	1.509 (3)
N1—H1B	0.8600	C5—C6	1.384 (3)
C2—C7	1.392 (2)	C5—H5A	0.9300
C2—C3	1.393 (2)	C6—H6A	0.9300
C2—C1	1.484 (2)	C8—H8A	0.9600
C3—C4	1.385 (3)	C8—H8B	0.9600
C3—H3A	0.9300	C8—H8C	0.9600
C7—C6	1.379 (3)

C1—N1—H1A	120.0	C3—C4—C5	118.45 (17)
C1—N1—H1B	120.0	C3—C4—C8	119.99 (18)
H1A—N1—H1B	120.0	C5—C4—C8	121.49 (19)
C7—C2—C3	119.16 (16)	C6—C5—C4	120.95 (18)
C7—C2—C1	120.98 (15)	C6—C5—H5A	119.5
C3—C2—C1	119.80 (15)	C4—C5—H5A	119.5
N1—C1—C2	116.80 (15)	C7—C6—C5	120.17 (17)
N1—C1—S1	121.71 (14)	C7—C6—H6A	119.9
C2—C1—S1	121.41 (12)	C5—C6—H6A	119.9
C4—C3—C2	121.29 (17)	C4—C8—H8A	109.5
C4—C3—H3A	119.4	C4—C8—H8B	109.5
C2—C3—H3A	119.4	H8A—C8—H8B	109.5
C6—C7—C2	119.91 (17)	C4—C8—H8C	109.5
C6—C7—H7A	120.0	H8A—C8—H8C	109.5
C2—C7—H7A	120.0	H8B—C8—H8C	109.5

N1—C1—C2—C3	36.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1ⁱ	0.86	2.66	3.455 (2)	155
N1—H1B···S1ⁱⁱ	0.86	2.58	3.422 (3)	165

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

Experimental details

Crystal data
Chemical formula	C₈H₉NS
M_r	151.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	7.717 (5), 10.267 (7), 10.100 (7)
β (°)	97.186 (9)
V (Å³)	794.0 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.37 × 0.27 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.793, 0.930
No. of measured, independent and observed [I > 2σ(I)] reflections	6234, 1797, 1447
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.112, 1.08
No. of reflections	1797
No. of parameters	92
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.29

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	2.66	3.455 (2)	155.0
N1—H1B···S1ⁱⁱ	0.86	2.58	3.422 (3)	164.9

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

Acknowledgements

The authors thank the HEC, Pakistan for a PhD fellowship awarded to MuHK under the indigenous PhD Program. JDM thanks Saint Mary's University for funding.

References

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