Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807046582/rk2046sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807046582/rk2046Isup2.hkl |
CCDC reference: 663836
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C)= 0.002 Å
- R factor = 0.039
- wR factor = 0.086
- Data-to-parameter ratio = 28.2
checkCIF/PLATON results
No syntax errors found No errors found in this datablock
For related literature, see: Desiraju & Steiner (1999); Flakus & Miros (2001); Flakus & Pyzik (2006); Flakus et al. (2002, 2003, 2007); Hopkins & Hunter (1942).
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.
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 = 0.95 Å (for aromatic C) or 0.98 Å (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.
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).
For related literature, see: Desiraju & Steiner (1999); Flakus & Miros (2001); Flakus & Pyzik (2006); Flakus et al. (2002, 2003, 2007); Hopkins & Hunter (1942).
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).
C9H11NS | F(000) = 352 |
Mr = 165.25 | Dx = 1.249 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1296 reflections |
a = 16.023 (3) Å | θ = 3.2–32.9° |
b = 6.9877 (14) Å | µ = 0.30 mm−1 |
c = 8.0670 (16) Å | T = 100 K |
β = 103.35 (3)° | Needle, yellow |
V = 878.8 (3) Å3 | 0.6 × 0.04 × 0.03 mm |
Z = 4 |
Oxford Diffraction KM-4 CCD Sapphire3 diffractometer | 1480 reflections with I > 2σ(I) |
Radiation source: fine–focus sealed tube | Rint = 0.046 |
Graphite monochromator | θmax = 32.9°, θmin = 3.2° |
θ scans | h = −24→23 |
8311 measured reflections | k = −10→10 |
2963 independent reflections | l = −5→12 |
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) = 0.086 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.81 | w = 1/[σ2(Fo2) + (0.0405P)2] where P = (Fo2 + 2Fc2)/3 |
2963 reflections | (Δ/σ)max = 0.001 |
105 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
C9H11NS | V = 878.8 (3) Å3 |
Mr = 165.25 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.023 (3) Å | µ = 0.30 mm−1 |
b = 6.9877 (14) Å | T = 100 K |
c = 8.0670 (16) Å | 0.6 × 0.04 × 0.03 mm |
β = 103.35 (3)° |
Oxford Diffraction KM-4 CCD Sapphire3 diffractometer | 1480 reflections with I > 2σ(I) |
8311 measured reflections | Rint = 0.046 |
2963 independent reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.086 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.81 | Δρmax = 0.34 e Å−3 |
2963 reflections | Δρmin = −0.27 e Å−3 |
105 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.37438 (3) | 0.45335 (6) | 0.42670 (5) | 0.02406 (12) | |
N1 | 0.33040 (8) | 0.74590 (18) | 0.21414 (15) | 0.0190 (3) | |
H1 | 0.3414 (10) | 0.810 (2) | 0.139 (2) | 0.023* | |
C1 | 0.26269 (9) | 0.8204 (2) | 0.28248 (17) | 0.0202 (3) | |
C2 | 0.26115 (10) | 1.0164 (2) | 0.30967 (19) | 0.0253 (4) | |
H2 | 0.3041 | 1.0971 | 0.2836 | 0.030* | |
C3 | 0.19587 (11) | 1.0919 (2) | 0.3755 (2) | 0.0328 (4) | |
H3 | 0.1945 | 1.2253 | 0.3972 | 0.039* | |
C4 | 0.13338 (11) | 0.9758 (3) | 0.4094 (2) | 0.0307 (4) | |
H4 | 0.0891 | 1.0304 | 0.4547 | 0.037* | |
C5 | 0.13278 (10) | 0.7807 (2) | 0.37947 (19) | 0.0270 (4) | |
C6 | 0.19927 (9) | 0.7042 (2) | 0.31496 (18) | 0.0229 (3) | |
H6 | 0.2006 | 0.5707 | 0.2934 | 0.027* | |
C7 | 0.06452 (11) | 0.6518 (3) | 0.4158 (2) | 0.0386 (5) | |
H7A | 0.0825 | 0.6024 | 0.5323 | 0.058* | |
H7B | 0.0554 | 0.5447 | 0.3352 | 0.058* | |
H7C | 0.0110 | 0.7239 | 0.4037 | 0.058* | |
C8 | 0.37891 (9) | 0.5926 (2) | 0.26284 (18) | 0.0185 (3) | |
C9 | 0.44358 (10) | 0.5519 (2) | 0.15960 (18) | 0.0231 (3) | |
H9A | 0.4288 | 0.4317 | 0.0971 | 0.035* | |
H9B | 0.5007 | 0.5408 | 0.2356 | 0.035* | |
H9C | 0.4435 | 0.6566 | 0.0787 | 0.035* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0297 (2) | 0.0214 (2) | 0.0216 (2) | 0.00168 (18) | 0.00700 (16) | 0.00134 (18) |
N1 | 0.0233 (7) | 0.0201 (7) | 0.0145 (6) | 0.0011 (6) | 0.0062 (5) | 0.0021 (5) |
C1 | 0.0202 (8) | 0.0263 (8) | 0.0131 (7) | 0.0035 (7) | 0.0021 (6) | 0.0017 (6) |
C2 | 0.0288 (9) | 0.0238 (9) | 0.0238 (8) | 0.0023 (7) | 0.0073 (7) | 0.0015 (7) |
C3 | 0.0403 (11) | 0.0283 (10) | 0.0309 (9) | 0.0083 (8) | 0.0104 (8) | −0.0001 (7) |
C4 | 0.0268 (9) | 0.0414 (11) | 0.0247 (8) | 0.0111 (8) | 0.0076 (7) | 0.0003 (8) |
C5 | 0.0197 (9) | 0.0424 (11) | 0.0173 (7) | −0.0013 (7) | 0.0008 (7) | 0.0047 (7) |
C6 | 0.0219 (8) | 0.0270 (9) | 0.0171 (8) | 0.0004 (7) | −0.0008 (6) | 0.0018 (6) |
C7 | 0.0273 (10) | 0.0553 (13) | 0.0333 (10) | −0.0071 (9) | 0.0069 (8) | 0.0004 (9) |
C8 | 0.0193 (8) | 0.0178 (8) | 0.0163 (7) | −0.0024 (6) | −0.0002 (6) | −0.0042 (6) |
C9 | 0.0242 (8) | 0.0230 (8) | 0.0222 (8) | 0.0034 (7) | 0.0053 (6) | −0.0022 (7) |
S1—C8 | 1.6565 (15) | C4—H4 | 0.9500 |
N1—C8 | 1.3283 (18) | C5—C6 | 1.396 (2) |
N1—C1 | 1.4241 (18) | C5—C7 | 1.497 (2) |
N1—H1 | 0.808 (15) | C6—H6 | 0.9500 |
C1—C6 | 1.372 (2) | C7—H7A | 0.9800 |
C1—C2 | 1.389 (2) | C7—H7B | 0.9800 |
C2—C3 | 1.382 (2) | C7—H7C | 0.9800 |
C2—H2 | 0.9500 | C8—C9 | 1.499 (2) |
C3—C4 | 1.364 (2) | C9—H9A | 0.9800 |
C3—H3 | 0.9500 | C9—H9B | 0.9800 |
C4—C5 | 1.384 (2) | C9—H9C | 0.9800 |
C8—N1—C1 | 128.77 (13) | C1—C6—C5 | 120.47 (15) |
C8—N1—H1 | 117.2 (11) | C1—C6—H6 | 119.8 |
C1—N1—H1 | 113.9 (11) | C5—C6—H6 | 119.8 |
C6—C1—C2 | 120.84 (14) | C5—C7—H7A | 109.5 |
C6—C1—N1 | 121.43 (14) | C5—C7—H7B | 109.5 |
C2—C1—N1 | 117.69 (13) | H7A—C7—H7B | 109.5 |
C3—C2—C1 | 118.66 (15) | C5—C7—H7C | 109.5 |
C3—C2—H2 | 120.7 | H7A—C7—H7C | 109.5 |
C1—C2—H2 | 120.7 | H7B—C7—H7C | 109.5 |
C4—C3—C2 | 120.38 (16) | N1—C8—C9 | 114.90 (12) |
C4—C3—H3 | 119.8 | N1—C8—S1 | 125.40 (11) |
C2—C3—H3 | 119.8 | C9—C8—S1 | 119.68 (11) |
C3—C4—C5 | 121.77 (15) | C8—C9—H9A | 109.5 |
C3—C4—H4 | 119.1 | C8—C9—H9B | 109.5 |
C5—C4—H4 | 119.1 | H9A—C9—H9B | 109.5 |
C4—C5—C6 | 117.85 (15) | C8—C9—H9C | 109.5 |
C4—C5—C7 | 122.30 (15) | H9A—C9—H9C | 109.5 |
C6—C5—C7 | 119.85 (16) | H9B—C9—H9C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S1i | 0.808 (15) | 2.520 (16) | 3.3233 (14) | 173.0 (15) |
Symmetry code: (i) x, −y+3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C9H11NS |
Mr | 165.25 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 16.023 (3), 6.9877 (14), 8.0670 (16) |
β (°) | 103.35 (3) |
V (Å3) | 878.8 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.30 |
Crystal size (mm) | 0.6 × 0.04 × 0.03 |
Data collection | |
Diffractometer | Oxford Diffraction KM-4 CCD Sapphire3 |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8311, 2963, 1480 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.764 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.086, 0.81 |
No. of reflections | 2963 |
No. of parameters | 105 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.34, −0.27 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), publCIF (Westrip, 2007).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S1i | 0.808 (15) | 2.520 (16) | 3.3233 (14) | 173.0 (15) |
Symmetry code: (i) x, −y+3/2, z−1/2. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
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).