organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

N-[(Methyl­sulfan­yl)meth­yl]benzamide

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[Siddiqui, W. A., Ahmad, S., Siddiqui, H. L., Hussain, R. A. & Parvez, M. (2008). Acta Cryst. E64, o1897.]); Noroozi Pesyan et al. (2009[Noroozi Pesyan, N., Omidkhah, N., Maghsoodi, M. & Patrick, B. O. (2009). Acta Cryst. E65, o655.]). For graph-set notation, see: Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]).

[Scheme 1]

Experimental

Crystal data
  • C9H11NOS

  • Mr = 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[Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.932, Tmax = 0.950

  • 9379 measured reflections

  • 2371 independent reflections

  • 1722 reflections with I > 2σ(I)

  • Rint = 0.022

Refinement
  • R[F2 > 2σ(F2)] = 0.041

  • wR(F2) = 0.116

  • S = 1.07

  • 2371 reflections

  • 110 parameters

  • H-atom parameters constrained

  • Δρmax = 0.18 e Å−3

  • Δρmin = −0.26 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]) and PLATON.

Supporting information


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.

Refinement top

The H-atoms were positioned geometrically (N—H = 0.86 Å, C—H = 0.93–0.97 Å) and refined as riding with Uiso(H) = xUeq(C, N), where x = 1.5 for methyl groups and x = 1.2 for all other H-atoms.

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
[Figure 1] 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.
[Figure 2] 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
C9H11NOSF(000) = 768
Mr = 181.25Dx = 1.256 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 1722 reflections
a = 9.7841 (4) Åθ = 1.9–28.3°
b = 9.2116 (4) ŵ = 0.29 mm1
c = 21.2663 (8) ÅT = 296 K
V = 1916.67 (14) Å3Prism, colorless
Z = 80.26 × 0.20 × 0.18 mm
Data collection top
Bruker Kappa APEXII CCD
diffractometer
2371 independent reflections
Radiation source: fine-focus sealed tube1722 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
Detector resolution: 7.50 pixels mm-1θmax = 28.3°, θmin = 1.9°
ω scansh = 1212
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
k = 1212
Tmin = 0.932, Tmax = 0.950l = 2728
9379 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0531P)2 + 0.2845P]
where P = (Fo2 + 2Fc2)/3
2371 reflections(Δ/σ)max < 0.001
110 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C9H11NOSV = 1916.67 (14) Å3
Mr = 181.25Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 9.7841 (4) ŵ = 0.29 mm1
b = 9.2116 (4) ÅT = 296 K
c = 21.2663 (8) Å0.26 × 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)
Tmin = 0.932, Tmax = 0.950Rint = 0.022
9379 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.116H-atom parameters constrained
S = 1.07Δρmax = 0.18 e Å3
2371 reflectionsΔρmin = 0.26 e Å3
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
xyzUiso*/Ueq
S10.20155 (6)0.43391 (6)0.09248 (2)0.0717 (2)
O10.14747 (12)0.17375 (11)0.05060 (5)0.0537 (4)
N10.25653 (14)0.38548 (15)0.03218 (5)0.0493 (4)
C10.15800 (14)0.34302 (14)0.13470 (7)0.0427 (4)
C20.04865 (18)0.28086 (18)0.16623 (8)0.0562 (5)
C30.0203 (2)0.3207 (2)0.22745 (9)0.0710 (7)
C40.1003 (2)0.4214 (2)0.25775 (9)0.0709 (7)
C50.2082 (2)0.4838 (2)0.22691 (8)0.0648 (6)
C60.23778 (18)0.44502 (17)0.16551 (7)0.0525 (5)
C70.18659 (14)0.29393 (15)0.06896 (7)0.0424 (4)
C80.29981 (18)0.3490 (2)0.03071 (7)0.0559 (6)
C90.0467 (2)0.3318 (3)0.08796 (11)0.0905 (9)
H10.276590.469960.046700.0592*
H20.005690.212260.146120.0674*
H30.053410.279020.248320.0852*
H40.081160.447080.299120.0851*
H50.261880.552530.247310.0778*
H60.311400.487530.144870.0630*
H8A0.294340.244490.035820.0670*
H8B0.394870.376660.035570.0670*
H9A0.003110.349800.048290.1358*
H9B0.067060.230190.091690.1358*
H9C0.013210.360450.121470.1358*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0957 (4)0.0699 (4)0.0496 (3)0.0010 (3)0.0003 (2)0.0110 (2)
O10.0662 (7)0.0395 (6)0.0553 (6)0.0005 (5)0.0022 (5)0.0059 (5)
N10.0605 (8)0.0426 (7)0.0448 (7)0.0021 (6)0.0027 (6)0.0046 (5)
C10.0465 (8)0.0375 (7)0.0440 (7)0.0072 (6)0.0033 (6)0.0001 (6)
C20.0588 (10)0.0498 (9)0.0600 (9)0.0024 (7)0.0056 (8)0.0074 (7)
C30.0765 (13)0.0686 (11)0.0679 (12)0.0042 (10)0.0239 (9)0.0067 (9)
C40.0883 (14)0.0736 (12)0.0509 (10)0.0057 (11)0.0117 (9)0.0129 (9)
C50.0733 (12)0.0685 (11)0.0526 (10)0.0033 (9)0.0067 (8)0.0134 (9)
C60.0541 (9)0.0566 (9)0.0468 (8)0.0028 (7)0.0045 (7)0.0024 (7)
C70.0445 (8)0.0372 (7)0.0454 (8)0.0059 (6)0.0057 (6)0.0001 (6)
C80.0568 (10)0.0632 (10)0.0476 (9)0.0011 (8)0.0064 (7)0.0031 (8)
C90.0826 (15)0.0997 (17)0.0893 (15)0.0017 (13)0.0291 (12)0.0092 (12)
Geometric parameters (Å, º) top
S1—C81.8060 (17)C5—C61.384 (2)
S1—C91.786 (2)C2—H20.9300
O1—C71.2347 (17)C3—H30.9300
N1—C71.3384 (19)C4—H40.9300
N1—C81.4426 (19)C5—H50.9300
N1—H10.8600C6—H60.9300
C1—C61.386 (2)C8—H8A0.9700
C1—C71.496 (2)C8—H8B0.9700
C1—C21.386 (2)C9—H9A0.9600
C2—C31.381 (3)C9—H9B0.9600
C3—C41.374 (3)C9—H9C0.9600
C4—C51.369 (3)
C8—S1—C9100.62 (10)C4—C3—H3120.00
C7—N1—C8123.03 (14)C3—C4—H4120.00
C8—N1—H1118.00C5—C4—H4120.00
C7—N1—H1118.00C4—C5—H5120.00
C2—C1—C7118.13 (13)C6—C5—H5120.00
C2—C1—C6119.07 (14)C1—C6—H6120.00
C6—C1—C7122.78 (13)C5—C6—H6120.00
C1—C2—C3120.08 (16)S1—C8—H8A109.00
C2—C3—C4120.47 (18)S1—C8—H8B109.00
C3—C4—C5119.86 (18)N1—C8—H8A109.00
C4—C5—C6120.31 (17)N1—C8—H8B109.00
C1—C6—C5120.20 (16)H8A—C8—H8B108.00
O1—C7—N1122.59 (14)S1—C9—H9A109.00
O1—C7—C1120.58 (13)S1—C9—H9B109.00
N1—C7—C1116.83 (12)S1—C9—H9C109.00
S1—C8—N1114.66 (12)H9A—C9—H9B109.00
C1—C2—H2120.00H9A—C9—H9C109.00
C3—C2—H2120.00H9B—C9—H9C109.00
C2—C3—H3120.00
C9—S1—C8—N173.54 (15)C2—C1—C7—O123.5 (2)
C8—N1—C7—O13.9 (2)C2—C1—C7—N1157.05 (14)
C8—N1—C7—C1175.55 (13)C6—C1—C7—O1155.07 (15)
C7—N1—C8—S1105.09 (16)C6—C1—C7—N124.4 (2)
C6—C1—C2—C30.0 (2)C1—C2—C3—C40.4 (3)
C7—C1—C2—C3178.63 (15)C2—C3—C4—C50.6 (3)
C2—C1—C6—C50.0 (2)C3—C4—C5—C60.5 (3)
C7—C1—C6—C5178.51 (15)C4—C5—C6—C10.2 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.862.022.8438 (17)160
C8—H8B···O1ii0.972.533.434 (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 formulaC9H11NOS
Mr181.25
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)296
a, b, c (Å)9.7841 (4), 9.2116 (4), 21.2663 (8)
V3)1916.67 (14)
Z8
Radiation typeMo Kα
µ (mm1)0.29
Crystal size (mm)0.26 × 0.20 × 0.18
Data collection
DiffractometerBruker Kappa APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2005)
Tmin, Tmax0.932, 0.950
No. of measured, independent and
observed [I > 2σ(I)] reflections
9379, 2371, 1722
Rint0.022
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.116, 1.07
No. of reflections2371
No. of parameters110
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N1—H1···O1i0.862.022.8438 (17)160
C8—H8B···O1ii0.972.533.434 (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

First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science Google Scholar
First citationBruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationFarrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.  CrossRef CAS IUCr Journals Google Scholar
First citationNoroozi Pesyan, N., Omidkhah, N., Maghsoodi, M. & Patrick, B. O. (2009). Acta Cryst. E65, o655.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSiddiqui, W. A., Ahmad, S., Siddiqui, H. L., Hussain, R. A. & Parvez, M. (2008). Acta Cryst. E64, o1897.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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