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The title compound, C8H9NS, was obtained by the reaction of N-methyl­benzamide with phospho­rus penta­sulfide in toluene. In the crystal structure, mol­ecules related by translation along the c axis are linked into linear chains by weak inter­molecular N—H...S hydrogen bonds [N...S = 3.338 (2) Å].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807043723/cv2299sup1.cif
Contains datablocks I, New_Global_Publ_Block

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807043723/cv2299Isup2.hkl
Contains datablock I

CCDC reference: 663744

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C)= 0.003 Å
  • R factor = 0.038
  • wR factor = 0.128
  • Data-to-parameter ratio = 14.7

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Comment top

Our group concerns measurements of the IR spectra using polarized light and theoretical analysis of the results (e.g. the dichroic effects, temperature effects), observed in the spectra of the hydrogen and deuterium bond at the frequency ranges of νN—H and νN—D bands, see: Flakus & Chełmicki (2004); Flakus & Michta (2004, 2005). The spectral studies were preceded by the crystal structure determination of the title compound, (I) (Fig. 1).

In the crystal, molecules of (I) are linked into linear chains along the c axis by the intermolecular N—H···S hydrogen bonds (Table 1, Fig. 2). The values of the H—A and D···A distances and the D—H···A angle characterize this bond as a weak hydrogen bond, see: Desiraju & Steiner (1999). The weakening of intermolecular hydrogen bonds in (I) is also supported by the IR spectroscopic data.

Related literature top

For related literature, see: Flakus & Miros (2001); Flakus & Chełmicki (2004); Flakus & Michta (2004, 2005); Perregaard et al. (1975). For discussion of weak hydrogen bonding, see: Desiraju & Steiner (1999).

Experimental top

Phosphorus pentasulfide (1.02 g, 0.1 mol) was added small portions of N-methylbenzamide (1.152 g, 0.5 mol) in toluene (4.42 ml) at 348 K with stirring. The reaction mixture was then brought to reflux for 2 h. After heating the hot reaction mixture was decanted and the solution was concentrated to give a yellow precipitate. The precipitate was dissolved in petroleum ether and the solution was left for crystallization at room temperature. Yellow crystals of (I) suitable for X-ray analysis were obtained upon recrystallization from petroleum ether and acetone [yield: 0.999 g, 77.70%; m.p. 350–351 K, literature m.p. 350–351 K (Perregaard et al., 1975)]. The IR spectra of N-methylthiobenzamide crystals and polycrystalline sample were measured using the method described by Flakus et al. (2001, 2004).

Refinement top

The C-bound hydrogen atoms were introduced in geometrically idealized positions [C—H = 0.95 Å (aromatic C) or 0.98 Å (methyl C)] and refined as riding, with Uiso(H) = 1.2–1.5Ueq(C). Atom H1 was located in a difference Fourier map and isotropically refined.

Structure description top

Our group concerns measurements of the IR spectra using polarized light and theoretical analysis of the results (e.g. the dichroic effects, temperature effects), observed in the spectra of the hydrogen and deuterium bond at the frequency ranges of νN—H and νN—D bands, see: Flakus & Chełmicki (2004); Flakus & Michta (2004, 2005). The spectral studies were preceded by the crystal structure determination of the title compound, (I) (Fig. 1).

In the crystal, molecules of (I) are linked into linear chains along the c axis by the intermolecular N—H···S hydrogen bonds (Table 1, Fig. 2). The values of the H—A and D···A distances and the D—H···A angle characterize this bond as a weak hydrogen bond, see: Desiraju & Steiner (1999). The weakening of intermolecular hydrogen bonds in (I) is also supported by the IR spectroscopic data.

For related literature, see: Flakus & Miros (2001); Flakus & Chełmicki (2004); Flakus & Michta (2004, 2005); Perregaard et al. (1975). For discussion of weak hydrogen bonding, see: Desiraju & Steiner (1999).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis CCD (Oxford Diffraction, 2007); data reduction: CrysAlis CCD (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. The conformation of (I) molecule with the atom numbering scheme. Atomic displacement ellipsoids represent 50% probability level.
[Figure 2] Fig. 2. The arrangement of the molecules of (I) in the unit cell. The intermolecular N—H···S interactions are represented by dashed lines. C-bound H atoms have been omitted for clarity.
N-methylthiobenzamide top
Crystal data top
C8H9NSF(000) = 320
Mr = 151.22Dx = 1.263 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1706 reflections
a = 9.3355 (19) Åθ = 3.6–32.6°
b = 14.707 (3) ŵ = 0.33 mm1
c = 5.9504 (12) ÅT = 298 K
β = 103.22 (3)°Polyhedron, colourless
V = 795.3 (3) Å30.6 × 0.16 × 0.04 mm
Z = 4
Data collection top
Kuma KM-4 Sapphire3 CCD
diffractometer
976 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.017
Graphite monochromatorθmax = 25.1°, θmin = 3.6°
θ–scanh = 1111
4859 measured reflectionsk = 1717
1396 independent reflectionsl = 37
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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129H atoms treated by a mixture of independent and constrained refinement
S = 1.31 w = 1/[σ2(Fo2) + (0.0641P)2]
where P = (Fo2 + 2Fc2)/3
1396 reflections(Δ/σ)max < 0.001
95 parametersΔρmax = 0.12 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C8H9NSV = 795.3 (3) Å3
Mr = 151.22Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.3355 (19) ŵ = 0.33 mm1
b = 14.707 (3) ÅT = 298 K
c = 5.9504 (12) Å0.6 × 0.16 × 0.04 mm
β = 103.22 (3)°
Data collection top
Kuma KM-4 Sapphire3 CCD
diffractometer
976 reflections with I > 2σ(I)
4859 measured reflectionsRint = 0.017
1396 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.129H atoms treated by a mixture of independent and constrained refinement
S = 1.31Δρmax = 0.12 e Å3
1396 reflectionsΔρmin = 0.18 e Å3
95 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
xyzUiso*/Ueq
S10.17075 (7)0.12453 (6)0.74687 (10)0.0709 (3)
N10.1751 (2)0.12580 (15)0.3094 (3)0.0566 (6)
C10.4155 (2)0.12438 (14)0.5570 (3)0.0417 (5)
C20.5044 (2)0.08673 (17)0.7560 (4)0.0503 (6)
H20.46140.06320.86990.060*
C30.6559 (3)0.08405 (19)0.7860 (4)0.0623 (7)
H30.71360.05800.91870.075*
C40.7213 (3)0.11936 (18)0.6221 (5)0.0624 (7)
H40.82310.11730.64300.075*
C50.6355 (3)0.15831 (18)0.4245 (5)0.0648 (7)
H50.67960.18300.31310.078*
C60.4846 (3)0.16044 (16)0.3934 (4)0.0542 (6)
H60.42780.18660.26020.065*
C70.2528 (2)0.12432 (14)0.5264 (3)0.0436 (5)
C80.0156 (3)0.1290 (2)0.2426 (4)0.0757 (9)
H8A0.02410.07420.29200.114*
H8B0.01540.13420.07780.114*
H8C0.01910.18050.31370.114*
H10.228 (4)0.1267 (19)0.208 (6)0.091*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0564 (4)0.1257 (7)0.0336 (4)0.0012 (4)0.0164 (3)0.0032 (3)
N10.0461 (11)0.0927 (16)0.0313 (9)0.0032 (10)0.0094 (8)0.0007 (10)
C10.0472 (12)0.0462 (12)0.0323 (10)0.0019 (10)0.0101 (10)0.0012 (9)
C20.0479 (13)0.0634 (15)0.0396 (13)0.0010 (10)0.0097 (11)0.0076 (10)
C30.0559 (15)0.0744 (17)0.0522 (15)0.0082 (12)0.0033 (12)0.0066 (12)
C40.0429 (13)0.0802 (18)0.0632 (16)0.0025 (12)0.0102 (12)0.0057 (14)
C50.0610 (17)0.0803 (19)0.0575 (16)0.0124 (14)0.0230 (13)0.0041 (13)
C60.0555 (14)0.0668 (15)0.0411 (12)0.0024 (11)0.0126 (11)0.0093 (11)
C70.0491 (13)0.0513 (12)0.0309 (10)0.0008 (10)0.0100 (9)0.0022 (10)
C80.0497 (15)0.133 (3)0.0423 (13)0.0043 (15)0.0051 (12)0.0056 (14)
Geometric parameters (Å, º) top
S1—C71.663 (2)C3—H30.9300
N1—C71.329 (3)C4—C51.386 (4)
N1—C81.451 (3)C4—H40.9300
N1—H10.86 (4)C5—C61.379 (3)
C1—C61.390 (3)C5—H50.9300
C1—C21.396 (3)C6—H60.9300
C1—C71.488 (3)C8—H8A0.9600
C2—C31.385 (3)C8—H8B0.9600
C2—H20.9300C8—H8C0.9600
C3—C41.366 (4)
C7—N1—C8124.4 (2)C6—C5—C4119.8 (2)
C7—N1—H1114 (2)C6—C5—H5120.1
C8—N1—H1121 (2)C4—C5—H5120.1
C6—C1—C2117.68 (19)C5—C6—C1121.4 (2)
C6—C1—C7122.61 (18)C5—C6—H6119.3
C2—C1—C7119.71 (18)C1—C6—H6119.3
C3—C2—C1120.8 (2)N1—C7—C1115.70 (18)
C3—C2—H2119.6N1—C7—S1121.28 (17)
C1—C2—H2119.6C1—C7—S1123.01 (15)
C4—C3—C2120.5 (2)N1—C8—H8A109.5
C4—C3—H3119.8N1—C8—H8B109.5
C2—C3—H3119.8H8A—C8—H8B109.5
C3—C4—C5119.8 (2)N1—C8—H8C109.5
C3—C4—H4120.1H8A—C8—H8C109.5
C5—C4—H4120.1H8B—C8—H8C109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S1i0.86 (4)2.67 (3)3.338 (2)135 (3)
Symmetry code: (i) x, y, z1.

Experimental details

Crystal data
Chemical formulaC8H9NS
Mr151.22
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)9.3355 (19), 14.707 (3), 5.9504 (12)
β (°) 103.22 (3)
V3)795.3 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.33
Crystal size (mm)0.6 × 0.16 × 0.04
Data collection
DiffractometerKuma KM-4 Sapphire3 CCD
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4859, 1396, 976
Rint0.017
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.129, 1.31
No. of reflections1396
No. of parameters95
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.12, 0.18

Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), publCIF (Westrip, 2007).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S1i0.86 (4)2.67 (3)3.338 (2)135 (3)
Symmetry code: (i) x, y, z1.
 

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