supplementary materials


rk2046 scheme

Acta Cryst. (2007). E63, o4161    [ doi:10.1107/S1600536807046582 ]

N-(m-Tolyl)thioacetamide

W. Smiszek-Lindert, M. Nowak and J. Kusz

Abstract top

The crystal structure of the title compound, C9H11NS, is stabilized by weak intermolecular N-H...S hydrogen bonds.

Comment top

The objective of our research were measurements and a theoretical interpretation of the polarized IR–spectra of the hydrogen bond in N–(m–tolyl)thioacetamide crystals. The spectral studies were preceded by determination of the crystal X–ray structure of this compound. We interpret spectroscopic effects, which are observed in the frequency ranges of the proton and deuteron stretching vibrations for the associated molecules, see: Flakus & Miros, 2001; Flakus & Pyzik, 2006; Flakus et al. (2002, 2003, 2007).

The structure of N–(m–tolyl)thioacetamide with the atomic numbering scheme is presented on Fig. 1. The molecules of (I) form an intermolecular N—H···S hydrogen bonds. These intermolecular hydrogen bonds link the molecules of N–(m–tolyl)thioacetamide giving infinite zigzag chains parallel to the c axis (Fig. 2). The values of the H···S (2.520 (16) Å) and N···S (3.3233 (14) Å) distances and N—H···S (173.0 (15)°) angle characterize this bond as a weak hydrogen bond: Desiraju & Steiner, (1999). The strength of the hydrogen bond in (I) was investigated by IR. The band of the isolated N—H stretching vibration, νN—H, is located in the 3200–2850 cm−1 frequency range.

For related literature, see: Flakus & Miros (2001); Flakus & Pyzik, 2006; Flakus et al. (2002, 2003, 2007); Hopkins & Hunter (1942). For discussion of hydrogen bonding, see: Desiraju & Steiner (1999).

Related literature top

For related literature, see: Desiraju & Steiner (1999); Flakus & Miros (2001); Flakus & Pyzik (2006); Flakus et al. (2002, 2003, 2007); Hopkins & Hunter (1942).

Experimental top

Phosphorus pentasulfide (0.31 g, 0.1 mol) was added small portions to m–acetotoluidide (1.03 g, 0.5 mol) in toluene (3.45 ml) at 343–353 K with stirring. The reaction mixture was then brought to reflux for 2.5 h. After heating the hot reaction mixture was decanted and the solution was concentrated to give a yellow precipitate. The precipitate was dissolved in ethanol and the solution was left for crystallization at room temperature. After one month, the deposited yellow crystals were collected and recrystallized from acetone and petroleum ether, giving needle–shaped crystals of quality suitable for X–ray measurement. Yeld: 0.78 g (69.57%). M.p. 316–317 K [literature m.p. 315–316 K, see: Hopkins & Hunter (1942)].

The IR–spectra of (I) crystals were measured by a transmission method, with the help of the FT–IR Nicolet Magna spectrometer, for two different, mutually perpendicular polarizations of IR–beam. The spectra were measured for the νN—H and νN—D band frequency ranges at temperatures of 298 and 77 K.

Refinement top

The amide H atom was located in a difference Fourier map and refined freely; The hydrogen atoms attached on C atoms were introduced in geometrically idealized positions and refined with an appropriate riding model, with C—H = 0.95Å (for aromatic C) or 0.98Å (for methyl C). Their isotropic displacement parameters were constrained with Uiso(H) values of 1.2Ueq (C) for H atoms in CH groups and 1.5Ueq(C) for the methyl H atoms.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); 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. Displacement ellipsoids are presented with 50% probability level. H atoms are depicted as small circles of arbitrary radii.
[Figure 2] Fig. 2. The crystal packing of the (I) in the unit cell. The intermolecular N—H···S interactions are represented by dashed lines.
N-(m-Tolyl)thioacetamide top
Crystal data top
C9H11NSF000 = 352
Mr = 165.25Dx = 1.249 Mg m3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1296 reflections
a = 16.023 (3) Åθ = 3.2–32.9º
b = 6.9877 (14) ŵ = 0.30 mm1
c = 8.0670 (16) ÅT = 100 (2) K
β = 103.35 (3)ºNeedle, yellow
V = 878.8 (3) Å30.6 × 0.04 × 0.03 mm
Z = 4
Data collection top
Oxford Diffraction KM-4 CCD Sapphire3
diffractometer
1480 reflections with I > 2σ(I)
Radiation source: fine–focus sealed tubeRint = 0.046
Monochromator: graphiteθmax = 32.9º
T = 100(2) Kθmin = 3.2º
θ scansh = 24→23
Absorption correction: nonek = 10→10
8311 measured reflectionsl = 5→12
2963 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.086  w = 1/[σ2(Fo2) + (0.0405P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.81(Δ/σ)max = 0.001
2963 reflectionsΔρmax = 0.34 e Å3
105 parametersΔρmin = 0.27 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C9H11NSV = 878.8 (3) Å3
Mr = 165.25Z = 4
Monoclinic, P21/cMo Kα
a = 16.023 (3) ŵ = 0.30 mm1
b = 6.9877 (14) ÅT = 100 (2) K
c = 8.0670 (16) Å0.6 × 0.04 × 0.03 mm
β = 103.35 (3)º
Data collection top
Oxford Diffraction KM-4 CCD Sapphire3
diffractometer
2963 independent reflections
Absorption correction: none1480 reflections with I > 2σ(I)
8311 measured reflectionsRint = 0.046
Refinement top
R[F2 > 2σ(F2)] = 0.039105 parameters
wR(F2) = 0.086H atoms treated by a mixture of
independent and constrained refinement
S = 0.81Δρmax = 0.34 e Å3
2963 reflectionsΔρmin = 0.27 e Å3
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 > 2σ(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
S10.37438 (3)0.45335 (6)0.42670 (5)0.02406 (12)
N10.33040 (8)0.74590 (18)0.21414 (15)0.0190 (3)
H10.3414 (10)0.810 (2)0.139 (2)0.023*
C10.26269 (9)0.8204 (2)0.28248 (17)0.0202 (3)
C20.26115 (10)1.0164 (2)0.30967 (19)0.0253 (4)
H20.30411.09710.28360.030*
C30.19587 (11)1.0919 (2)0.3755 (2)0.0328 (4)
H30.19451.22530.39720.039*
C40.13338 (11)0.9758 (3)0.4094 (2)0.0307 (4)
H40.08911.03040.45470.037*
C50.13278 (10)0.7807 (2)0.37947 (19)0.0270 (4)
C60.19927 (9)0.7042 (2)0.31496 (18)0.0229 (3)
H60.20060.57070.29340.027*
C70.06452 (11)0.6518 (3)0.4158 (2)0.0386 (5)
H7A0.08250.60240.53230.058*
H7B0.05540.54470.33520.058*
H7C0.01100.72390.40370.058*
C80.37891 (9)0.5926 (2)0.26284 (18)0.0185 (3)
C90.44358 (10)0.5519 (2)0.15960 (18)0.0231 (3)
H9A0.42880.43170.09710.035*
H9B0.50070.54080.23560.035*
H9C0.44350.65660.07870.035*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0297 (2)0.0214 (2)0.0216 (2)0.00168 (18)0.00700 (16)0.00134 (18)
N10.0233 (7)0.0201 (7)0.0145 (6)0.0011 (6)0.0062 (5)0.0021 (5)
C10.0202 (8)0.0263 (8)0.0131 (7)0.0035 (7)0.0021 (6)0.0017 (6)
C20.0288 (9)0.0238 (9)0.0238 (8)0.0023 (7)0.0073 (7)0.0015 (7)
C30.0403 (11)0.0283 (10)0.0309 (9)0.0083 (8)0.0104 (8)0.0001 (7)
C40.0268 (9)0.0414 (11)0.0247 (8)0.0111 (8)0.0076 (7)0.0003 (8)
C50.0197 (9)0.0424 (11)0.0173 (7)0.0013 (7)0.0008 (7)0.0047 (7)
C60.0219 (8)0.0270 (9)0.0171 (8)0.0004 (7)0.0008 (6)0.0018 (6)
C70.0273 (10)0.0553 (13)0.0333 (10)0.0071 (9)0.0069 (8)0.0004 (9)
C80.0193 (8)0.0178 (8)0.0163 (7)0.0024 (6)0.0002 (6)0.0042 (6)
C90.0242 (8)0.0230 (8)0.0222 (8)0.0034 (7)0.0053 (6)0.0022 (7)
Geometric parameters (Å, °) top
S1—C81.6565 (15)C4—H40.9500
N1—C81.3283 (18)C5—C61.396 (2)
N1—C11.4241 (18)C5—C71.497 (2)
N1—H10.808 (15)C6—H60.9500
C1—C61.372 (2)C7—H7A0.9800
C1—C21.389 (2)C7—H7B0.9800
C2—C31.382 (2)C7—H7C0.9800
C2—H20.9500C8—C91.499 (2)
C3—C41.364 (2)C9—H9A0.9800
C3—H30.9500C9—H9B0.9800
C4—C51.384 (2)C9—H9C0.9800
C8—N1—C1128.77 (13)C1—C6—C5120.47 (15)
C8—N1—H1117.2 (11)C1—C6—H6119.8
C1—N1—H1113.9 (11)C5—C6—H6119.8
C6—C1—C2120.84 (14)C5—C7—H7A109.5
C6—C1—N1121.43 (14)C5—C7—H7B109.5
C2—C1—N1117.69 (13)H7A—C7—H7B109.5
C3—C2—C1118.66 (15)C5—C7—H7C109.5
C3—C2—H2120.7H7A—C7—H7C109.5
C1—C2—H2120.7H7B—C7—H7C109.5
C4—C3—C2120.38 (16)N1—C8—C9114.90 (12)
C4—C3—H3119.8N1—C8—S1125.40 (11)
C2—C3—H3119.8C9—C8—S1119.68 (11)
C3—C4—C5121.77 (15)C8—C9—H9A109.5
C3—C4—H4119.1C8—C9—H9B109.5
C5—C4—H4119.1H9A—C9—H9B109.5
C4—C5—C6117.85 (15)C8—C9—H9C109.5
C4—C5—C7122.30 (15)H9A—C9—H9C109.5
C6—C5—C7119.85 (16)H9B—C9—H9C109.5
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S1i0.808 (15)2.520 (16)3.3233 (14)173.0 (15)
Symmetry codes: (i) x, −y+3/2, z−1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S1i0.808 (15)2.520 (16)3.3233 (14)173.0 (15)
Symmetry codes: (i) x, −y+3/2, z−1/2.
references
References top

Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond in Structural Chemistry and Biology. Oxford University Press.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Flakus, H., Miros, A. & Jones, P. G. (2002). Spectrochim. Acta Part A, 58, 225–237.

Flakus, H., Śmiszek-Lindert, W. & Stadnicka, K. (2007). Chem. Phys. 335, 221–232.

Flakus, H., Tyl, A. & Jones, P. G. (2003). Vib. Spectrosc. 33, 163–175.

Flakus, H. & Miros, A. (2001). Spectrochim. Acta Part A, 57, 2391–2401.

Flakus, H. & Pyzik, A. (2006). Chem. Phys. 323, 479–489.

Hopkins, G. & Hunter, L. (1942). J. Chem. Soc. 133, 638–642.

Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Version 1.171.29.2. Oxford Diffraction Ltd, Wrocław, Poland.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Westrip, S. P. (2007). publCIF. In preparation.