Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807053767/rk2054sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807053767/rk2054Isup2.hkl |
CCDC reference: 672853
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C)= 0.002 Å
- R factor = 0.037
- wR factor = 0.102
- Data-to-parameter ratio = 29.5
checkCIF/PLATON results
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The title compound (I) was prepared by the reaction of the phosphorus pentasulfide (0.180 g, 0.1 mol) with N-benzylformamide (0.557 g, 0.5 mol) in toluene (1.650 ml) as a solvent. The reaction mixture was then brought to reflux for 2 h at 343–353 K with stirring. After heating the hot reaction mixture was decanted and the solution was concentrated to give a creamy precipitate. The precipitate was dissolved in petroleum ether and the solution was left for crystallization at room temperature. Single crystals of the title compound suitable for X-ray analysis were obtained by a slow evaporation of petroleum ether and acetone solution. Yield: 0.478 g (76.76%). M.p. 338–339 K [literature m.p. 338–339 K (Imrie et al., 1993)]. 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. Spectra were measured for the νN—H and νN—D band frequency ranges at temperatures of 298 and 77 K.
The hydrogen atom based on nitrogen atom was located in a difference Fourier map and was refined freely; other hydrogen atoms were introduced in geometrically idealized positions and refined with an appropriate riding model, with C—H = 0.95 Å (aromatic C) and C—H = 0.99 Å (CH2 group). Their isotropic displacement parameters were constrained with Uiso(H) values of 1.2Ueq(C) for H atoms in all groups.
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 (Version 1.9_c; Westrip, 2007).
C8H9NS | Dx = 1.248 Mg m−3 |
Mr = 151.22 | Melting point: 339 K |
Orthorhombic, Pccn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ab 2ac | Cell parameters from 6843 reflections |
a = 17.421 (4) Å | θ = 3.2–32.7° |
b = 9.5509 (19) Å | µ = 0.32 mm−1 |
c = 9.6729 (19) Å | T = 150 K |
V = 1609.5 (6) Å3 | Needle, colourless |
Z = 8 | 0.60 × 0.17 × 0.08 mm |
F(000) = 640 |
Kuma KM4 CCD Sapphire3 diffractometer | 2777 independent reflections |
Radiation source: Fine–focus sealed tube | 1847 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
θ scans | θmax = 32.7°, θmin = 3.2° |
Absorption correction: analytical (CrysAlis CCD; Oxford Diffraction, 2006) Analytical numerical absorption correction using a multifaceted crystal model based on expressions derived by Clark & Reid (1995). | h = −25→26 |
Tmin = 0.967, Tmax = 0.993 | k = −14→14 |
14474 measured reflections | l = −14→8 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.102 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0614P)2] where P = (Fo2 + 2Fc2)/3 |
2777 reflections | (Δ/σ)max = 0.001 |
94 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
C8H9NS | V = 1609.5 (6) Å3 |
Mr = 151.22 | Z = 8 |
Orthorhombic, Pccn | Mo Kα radiation |
a = 17.421 (4) Å | µ = 0.32 mm−1 |
b = 9.5509 (19) Å | T = 150 K |
c = 9.6729 (19) Å | 0.60 × 0.17 × 0.08 mm |
Kuma KM4 CCD Sapphire3 diffractometer | 2777 independent reflections |
Absorption correction: analytical (CrysAlis CCD; Oxford Diffraction, 2006) Analytical numerical absorption correction using a multifaceted crystal model based on expressions derived by Clark & Reid (1995). | 1847 reflections with I > 2σ(I) |
Tmin = 0.967, Tmax = 0.993 | Rint = 0.048 |
14474 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.102 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.29 e Å−3 |
2777 reflections | Δρmin = −0.32 e Å−3 |
94 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 | 0.665841 (16) | 0.07223 (3) | 0.11629 (3) | 0.03143 (11) | |
N1 | 0.69486 (6) | 0.08107 (10) | 0.38624 (9) | 0.0299 (2) | |
H1 | 0.7292 (8) | 0.0826 (13) | 0.4483 (15) | 0.036* | |
C1 | 0.60240 (6) | 0.01605 (13) | 0.56620 (10) | 0.0275 (2) | |
C2 | 0.62914 (8) | −0.11766 (14) | 0.59359 (12) | 0.0375 (3) | |
H2 | 0.6556 | −0.1683 | 0.5237 | 0.045* | |
C3 | 0.61756 (8) | −0.17825 (14) | 0.72271 (13) | 0.0440 (3) | |
H3 | 0.6361 | −0.2700 | 0.7407 | 0.053* | |
C4 | 0.57927 (8) | −0.10556 (13) | 0.82450 (12) | 0.0384 (3) | |
H4 | 0.5713 | −0.1472 | 0.9125 | 0.046* | |
C5 | 0.55260 (6) | 0.02737 (14) | 0.79845 (11) | 0.0326 (3) | |
H5 | 0.5262 | 0.0774 | 0.8688 | 0.039* | |
C6 | 0.56401 (6) | 0.08897 (12) | 0.66989 (11) | 0.0293 (2) | |
H6 | 0.5456 | 0.1810 | 0.6528 | 0.035* | |
C7 | 0.61376 (7) | 0.08306 (14) | 0.42613 (12) | 0.0363 (3) | |
H7A | 0.5832 | 0.0319 | 0.3562 | 0.044* | |
H7B | 0.5953 | 0.1810 | 0.4289 | 0.044* | |
C8 | 0.71943 (6) | 0.07808 (11) | 0.25872 (11) | 0.0264 (2) | |
H8 | 0.7735 | 0.0794 | 0.2459 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.02432 (15) | 0.0501 (2) | 0.01989 (14) | −0.00018 (12) | 0.00029 (9) | 0.00021 (11) |
N1 | 0.0214 (4) | 0.0468 (6) | 0.0215 (4) | −0.0054 (4) | −0.0028 (3) | 0.0005 (4) |
C1 | 0.0220 (5) | 0.0387 (6) | 0.0219 (4) | −0.0064 (4) | −0.0012 (4) | −0.0012 (4) |
C2 | 0.0440 (7) | 0.0348 (6) | 0.0337 (6) | −0.0063 (5) | 0.0049 (5) | −0.0102 (5) |
C3 | 0.0574 (8) | 0.0285 (6) | 0.0462 (7) | −0.0058 (6) | 0.0024 (6) | 0.0036 (5) |
C4 | 0.0443 (7) | 0.0419 (7) | 0.0289 (6) | −0.0136 (5) | 0.0015 (5) | 0.0060 (5) |
C5 | 0.0277 (5) | 0.0450 (7) | 0.0251 (5) | −0.0078 (5) | 0.0043 (4) | −0.0041 (5) |
C6 | 0.0221 (5) | 0.0381 (6) | 0.0277 (5) | −0.0003 (4) | 0.0011 (4) | 0.0005 (4) |
C7 | 0.0229 (5) | 0.0627 (9) | 0.0233 (5) | 0.0003 (5) | 0.0005 (4) | 0.0048 (5) |
C8 | 0.0215 (5) | 0.0325 (6) | 0.0253 (5) | −0.0016 (4) | 0.0005 (4) | −0.0001 (4) |
S1—C8 | 1.6652 (11) | C3—H3 | 0.9500 |
N1—C8 | 1.3059 (14) | C4—C5 | 1.3752 (18) |
N1—C7 | 1.4648 (15) | C4—H4 | 0.9500 |
N1—H1 | 0.848 (14) | C5—C6 | 1.3899 (16) |
C1—C2 | 1.3849 (18) | C5—H5 | 0.9500 |
C1—C6 | 1.3923 (15) | C6—H6 | 0.9500 |
C1—C7 | 1.5114 (15) | C7—H7A | 0.9900 |
C2—C3 | 1.3912 (16) | C7—H7B | 0.9900 |
C2—H2 | 0.9500 | C8—H8 | 0.9500 |
C3—C4 | 1.3771 (18) | ||
C8—N1—C7 | 124.42 (9) | C4—C5—C6 | 120.42 (11) |
C8—N1—H1 | 116.0 (9) | C4—C5—H5 | 119.8 |
C7—N1—H1 | 119.6 (9) | C6—C5—H5 | 119.8 |
C2—C1—C6 | 119.01 (10) | C5—C6—C1 | 120.10 (11) |
C2—C1—C7 | 121.20 (10) | C5—C6—H6 | 120.0 |
C6—C1—C7 | 119.79 (11) | C1—C6—H6 | 120.0 |
C1—C2—C3 | 120.44 (11) | N1—C7—C1 | 110.91 (9) |
C1—C2—H2 | 119.8 | N1—C7—H7A | 109.5 |
C3—C2—H2 | 119.8 | C1—C7—H7A | 109.5 |
C4—C3—C2 | 120.16 (13) | N1—C7—H7B | 109.5 |
C4—C3—H3 | 119.9 | C1—C7—H7B | 109.5 |
C2—C3—H3 | 119.9 | H7A—C7—H7B | 108.0 |
C5—C4—C3 | 119.87 (11) | N1—C8—S1 | 126.76 (9) |
C5—C4—H4 | 120.1 | N1—C8—H8 | 116.6 |
C3—C4—H4 | 120.1 | S1—C8—H8 | 116.6 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S1i | 0.848 (14) | 2.448 (15) | 3.2937 (11) | 175.2 (12) |
Symmetry code: (i) −x+3/2, y, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C8H9NS |
Mr | 151.22 |
Crystal system, space group | Orthorhombic, Pccn |
Temperature (K) | 150 |
a, b, c (Å) | 17.421 (4), 9.5509 (19), 9.6729 (19) |
V (Å3) | 1609.5 (6) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.32 |
Crystal size (mm) | 0.60 × 0.17 × 0.08 |
Data collection | |
Diffractometer | Kuma KM4 CCD Sapphire3 diffractometer |
Absorption correction | Analytical (CrysAlis CCD; Oxford Diffraction, 2006) Analytical numerical absorption correction using a multifaceted crystal model based on expressions derived by Clark & Reid (1995). |
Tmin, Tmax | 0.967, 0.993 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14474, 2777, 1847 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.760 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.102, 1.00 |
No. of reflections | 2777 |
No. of parameters | 94 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.29, −0.32 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), publCIF (Version 1.9_c; Westrip, 2007).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S1i | 0.848 (14) | 2.448 (15) | 3.2937 (11) | 175.2 (12) |
Symmetry code: (i) −x+3/2, y, z+1/2. |
We present here the synthesis and molecular structure of the N-benzylthioformamide (I), which was obtained by the reaction of N-benzylformamide with phosphorus pentasulfide. Determination the crystal structure of (I) was necessary for our spectral studies. Hydrogen bond in the N-benzylthioformamide is interesting because our group observe important effects in the spectra of the hydrogen and deuterium bond at the frequency ranges of νN—H and νN—D bands (Flakus & Michta, 2004, 2005). The molecular structure of the (I) is illustrated in Fig. 1. The crystal packing is stabilized by intermolecular N—H···S hydrogen bonds which link the molecules into infinite zigzag chains running along the crystallographic c axis of the unit cell (Fig. 2). The values of the H···S and N···S distances and the N—H···S angle characterize this intermolecular interactions as a weak (Desiraju & Steiner, 1999).
For related literature, see: Desiraju & Steiner (1999); Flakus & Michta (2004,2005); Imrie et al. (1993)