N-[(Methyl­sulfan­yl)meth­yl]benzamide

Khan, M.R.; Khan, A.; Tahir, M.N.; Adeel, M.; Ahmad, S.

doi:10.1107/S1600536812004515

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o653

doi:10.1107/S1600536812004515

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N-[(Methylsulfanyl)methyl]benzamide

Muhammad Riaz Khan,^a Azim Khan,^a M. Nawaz Tahir,^b ^* Muhammad Adeel ^a and Saeed Ahmad ^a

^aDepartment of Chemistry, Gomal University, Dera Ismail Khan, K.P.K., Pakistan, and ^bUniversity of Sargodha, Department of Physics, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 1 February 2012; accepted 2 February 2012; online 10 February 2012)

In the title compound, C₉H₁₁NOS, the phenyl ring and formamide unit make a dihedral angle of 23.93 (14)°, whereas the (methylsulfanyl)methyl group is oriented at a dihedral angle of 61.31 (8)° with respect to the phenyl ring. There are intermolecular N—H⋯O hydrogen bonds, forming C(4) chains along the [010] direction. These polymeric chains are linked by C—H⋯O hydrogen bonds to form polymeric sheets in the (110) plane.

Related literature

For crystal structures containing the 1-(methylsulfanyl)methanamine grouping, see: Siddiqui et al. (2008 ); Noroozi Pesyan et al. (2009 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₉H₁₁NOS
M_r = 181.25
Orthorhombic, P b c a
a = 9.7841 (4) Å
b = 9.2116 (4) Å
c = 21.2663 (8) Å
V = 1916.67 (14) Å³
Z = 8
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 296 K
0.26 × 0.20 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.932, T_max = 0.950
9379 measured reflections
2371 independent reflections
1722 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.116
S = 1.07
2371 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	2.02	2.8438 (17)	160
C8—H8B⋯O1ⁱⁱ	0.97	2.53	3.434 (2)	154
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812004515/wn2467sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812004515/wn2467Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812004515/wn2467Isup3.cml

checkCIF report

Comment top

The title compound (Fig. 1) was prepared in an attempt to synthesize a different compound from benzamide and phthalic anhydride in dimethyl sulphoxide.

The crystal structures of 2-((methylsulfanyl)methyl)-1,2-benzisothiazol-3(2H)-one 1,1-dioxide (Siddiqui et al., 2008) and 5-(2,6-dimethoxyphenoxy)-2-methylsulfanylmethyl-2H-tetrazole (Noroozi Pesyan et al., 2009) have been published; these contain the 1-(methylsulfanyl)methanamine grouping.

Let A, B, C denote the planes defined by the phenyl ring (C1–C6), the formamide unit (O1/C7/N1) and the (methylsulfanyl)methane grouping (C8/S1/C9), respectively. The dihedral angles between A/B, A/C and B/C are 23.93 (14)°, 61.31 (8)° and 67.92 (13)°, respectively.

There are intermolecular N—H···O hydrogen bonds (Table 1, Fig. 2), forming C(4) chains (Bernstein et al., 1995) along the [010] direction. These polymeric chains are linked by C—H···O hydrogen bonds (Table 1, Fig. 2) to form polymeric sheets in the (110) plane.

Related literature top

For crystal structures containing the 1-(methylsulfanyl)methanamine grouping, see: Siddiqui et al. (2008); Noroozi Pesyan et al. (2009). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

The title compound was prepared by adding a solution of benzamide (0.1 g, 0.078 mmol) in 3 ml of dimethyl sulphoxide (DMSO) to a solution of phthalic anhydride (0.1 g, 0.078 mmol) in DMSO (3 ml). The reaction mixture was heated to 353 K for 6 h. The organic and aqueous layers were separated and the latter was extracted with chloroform (3×15 ml). The organic layer was concentrated in vacuo and the residue was purified by chromatography (silica gel, EtOAc/hexane= 1:4). The title compound was obtained as a colorless crystalline solid. Yield = 0.14 g, 70%, m.p = 365 K. Crystallization from a saturated chloroform solution at ambient temperature gave colourless prisms.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the title compound, with displacement ellipsoids drawn at the 50% probability level. H-atoms are shown as small circles of arbitrary radius.
	Fig. 2. Packing diagram of the title compound (PLATON: Spek, 2009) showing that molecules form one dimensional polymeric chains along [010] and are interlinked. H atoms not involved in hydrogen bonding have been omitted for clarity.

N-[(methylsulfanyl)methyl]benzamide top

Crystal data top

C₉H₁₁NOS	F(000) = 768
M_r = 181.25	D_x = 1.256 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1722 reflections
a = 9.7841 (4) Å	θ = 1.9–28.3°
b = 9.2116 (4) Å	µ = 0.29 mm⁻¹
c = 21.2663 (8) Å	T = 296 K
V = 1916.67 (14) Å³	Prism, colorless
Z = 8	0.26 × 0.20 × 0.18 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2371 independent reflections
Radiation source: fine-focus sealed tube	1722 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Detector resolution: 7.50 pixels mm^-1	θ_max = 28.3°, θ_min = 1.9°
ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −12→12
T_min = 0.932, T_max = 0.950	l = −27→28
9379 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0531P)² + 0.2845P] where P = (F_o² + 2F_c²)/3
2371 reflections	(Δ/σ)_max < 0.001
110 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₉H₁₁NOS	V = 1916.67 (14) Å³
M_r = 181.25	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 9.7841 (4) Å	µ = 0.29 mm⁻¹
b = 9.2116 (4) Å	T = 296 K
c = 21.2663 (8) Å	0.26 × 0.20 × 0.18 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2371 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1722 reflections with I > 2σ(I)
T_min = 0.932, T_max = 0.950	R_int = 0.022
9379 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.07	Δρ_max = 0.18 e Å⁻³
2371 reflections	Δρ_min = −0.26 e Å⁻³
110 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	0.20155 (6)	0.43391 (6)	−0.09248 (2)	0.0717 (2)
O1	0.14747 (12)	0.17375 (11)	0.05060 (5)	0.0537 (4)
N1	0.25653 (14)	0.38548 (15)	0.03218 (5)	0.0493 (4)
C1	0.15800 (14)	0.34302 (14)	0.13470 (7)	0.0427 (4)
C2	0.04865 (18)	0.28086 (18)	0.16623 (8)	0.0562 (5)
C3	0.0203 (2)	0.3207 (2)	0.22745 (9)	0.0710 (7)
C4	0.1003 (2)	0.4214 (2)	0.25775 (9)	0.0709 (7)
C5	0.2082 (2)	0.4838 (2)	0.22691 (8)	0.0648 (6)
C6	0.23778 (18)	0.44502 (17)	0.16551 (7)	0.0525 (5)
C7	0.18659 (14)	0.29393 (15)	0.06896 (7)	0.0424 (4)
C8	0.29981 (18)	0.3490 (2)	−0.03071 (7)	0.0559 (6)
C9	0.0467 (2)	0.3318 (3)	−0.08796 (11)	0.0905 (9)
H1	0.27659	0.46996	0.04670	0.0592*
H2	−0.00569	0.21226	0.14612	0.0674*
H3	−0.05341	0.27902	0.24832	0.0852*
H4	0.08116	0.44708	0.29912	0.0851*
H5	0.26188	0.55253	0.24731	0.0778*
H6	0.31140	0.48753	0.14487	0.0630*
H8A	0.29434	0.24449	−0.03582	0.0670*
H8B	0.39487	0.37666	−0.03557	0.0670*
H9A	0.00311	0.34980	−0.04829	0.1358*
H9B	0.06706	0.23019	−0.09169	0.1358*
H9C	−0.01321	0.36045	−0.12147	0.1358*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0957 (4)	0.0699 (4)	0.0496 (3)	−0.0010 (3)	−0.0003 (2)	0.0110 (2)
O1	0.0662 (7)	0.0395 (6)	0.0553 (6)	−0.0005 (5)	−0.0022 (5)	−0.0059 (5)
N1	0.0605 (8)	0.0426 (7)	0.0448 (7)	−0.0021 (6)	0.0027 (6)	−0.0046 (5)
C1	0.0465 (8)	0.0375 (7)	0.0440 (7)	0.0072 (6)	−0.0033 (6)	0.0001 (6)
C2	0.0588 (10)	0.0498 (9)	0.0600 (9)	−0.0024 (7)	0.0056 (8)	−0.0074 (7)
C3	0.0765 (13)	0.0686 (11)	0.0679 (12)	−0.0042 (10)	0.0239 (9)	−0.0067 (9)
C4	0.0883 (14)	0.0736 (12)	0.0509 (10)	0.0057 (11)	0.0117 (9)	−0.0129 (9)
C5	0.0733 (12)	0.0685 (11)	0.0526 (10)	−0.0033 (9)	−0.0067 (8)	−0.0134 (9)
C6	0.0541 (9)	0.0566 (9)	0.0468 (8)	−0.0028 (7)	−0.0045 (7)	−0.0024 (7)
C7	0.0445 (8)	0.0372 (7)	0.0454 (8)	0.0059 (6)	−0.0057 (6)	−0.0001 (6)
C8	0.0568 (10)	0.0632 (10)	0.0476 (9)	0.0011 (8)	0.0064 (7)	−0.0031 (8)
C9	0.0826 (15)	0.0997 (17)	0.0893 (15)	0.0017 (13)	−0.0291 (12)	0.0092 (12)

Geometric parameters (Å, º) top

S1—C8	1.8060 (17)	C5—C6	1.384 (2)
S1—C9	1.786 (2)	C2—H2	0.9300
O1—C7	1.2347 (17)	C3—H3	0.9300
N1—C7	1.3384 (19)	C4—H4	0.9300
N1—C8	1.4426 (19)	C5—H5	0.9300
N1—H1	0.8600	C6—H6	0.9300
C1—C6	1.386 (2)	C8—H8A	0.9700
C1—C7	1.496 (2)	C8—H8B	0.9700
C1—C2	1.386 (2)	C9—H9A	0.9600
C2—C3	1.381 (3)	C9—H9B	0.9600
C3—C4	1.374 (3)	C9—H9C	0.9600
C4—C5	1.369 (3)

C8—S1—C9	100.62 (10)	C4—C3—H3	120.00
C7—N1—C8	123.03 (14)	C3—C4—H4	120.00
C8—N1—H1	118.00	C5—C4—H4	120.00
C7—N1—H1	118.00	C4—C5—H5	120.00
C2—C1—C7	118.13 (13)	C6—C5—H5	120.00
C2—C1—C6	119.07 (14)	C1—C6—H6	120.00
C6—C1—C7	122.78 (13)	C5—C6—H6	120.00
C1—C2—C3	120.08 (16)	S1—C8—H8A	109.00
C2—C3—C4	120.47 (18)	S1—C8—H8B	109.00
C3—C4—C5	119.86 (18)	N1—C8—H8A	109.00
C4—C5—C6	120.31 (17)	N1—C8—H8B	109.00
C1—C6—C5	120.20 (16)	H8A—C8—H8B	108.00
O1—C7—N1	122.59 (14)	S1—C9—H9A	109.00
O1—C7—C1	120.58 (13)	S1—C9—H9B	109.00
N1—C7—C1	116.83 (12)	S1—C9—H9C	109.00
S1—C8—N1	114.66 (12)	H9A—C9—H9B	109.00
C1—C2—H2	120.00	H9A—C9—H9C	109.00
C3—C2—H2	120.00	H9B—C9—H9C	109.00
C2—C3—H3	120.00

C9—S1—C8—N1	−73.54 (15)	C2—C1—C7—O1	−23.5 (2)
C8—N1—C7—O1	−3.9 (2)	C2—C1—C7—N1	157.05 (14)
C8—N1—C7—C1	175.55 (13)	C6—C1—C7—O1	155.07 (15)
C7—N1—C8—S1	105.09 (16)	C6—C1—C7—N1	−24.4 (2)
C6—C1—C2—C3	0.0 (2)	C1—C2—C3—C4	−0.4 (3)
C7—C1—C2—C3	178.63 (15)	C2—C3—C4—C5	0.6 (3)
C2—C1—C6—C5	0.0 (2)	C3—C4—C5—C6	−0.5 (3)
C7—C1—C6—C5	−178.51 (15)	C4—C5—C6—C1	0.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.02	2.8438 (17)	160
C8—H8B···O1ⁱⁱ	0.97	2.53	3.434 (2)	154

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

Experimental details

Crystal data
Chemical formula	C₉H₁₁NOS
M_r	181.25
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	9.7841 (4), 9.2116 (4), 21.2663 (8)
V (Å³)	1916.67 (14)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.26 × 0.20 × 0.18

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.932, 0.950
No. of measured, independent and observed [I > 2σ(I)] reflections	9379, 2371, 1722
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.116, 1.07
No. of reflections	2371
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.26

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.02	2.8438 (17)	160
C8—H8B···O1ⁱⁱ	0.97	2.53	3.434 (2)	154

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

Acknowledgements

The authors acknowledge the provision of funds for the purchase of the diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan. The authors also acknowledge the technical support provided by Syed Muhammad Hussain Rizvi of Bana International, Karachi, Pakistan.

References

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