Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807043723/cv2299sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807043723/cv2299Isup2.hkl |
CCDC reference: 663744
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C)= 0.003 Å
- R factor = 0.038
- wR factor = 0.128
- Data-to-parameter ratio = 14.7
checkCIF/PLATON results
No syntax errors found No errors found in this datablock
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).
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).
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.
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).
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).
C8H9NS | F(000) = 320 |
Mr = 151.22 | Dx = 1.263 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1706 reflections |
a = 9.3355 (19) Å | θ = 3.6–32.6° |
b = 14.707 (3) Å | µ = 0.33 mm−1 |
c = 5.9504 (12) Å | T = 298 K |
β = 103.22 (3)° | Polyhedron, colourless |
V = 795.3 (3) Å3 | 0.6 × 0.16 × 0.04 mm |
Z = 4 |
Kuma KM-4 Sapphire3 CCD diffractometer | 976 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.017 |
Graphite monochromator | θmax = 25.1°, θmin = 3.6° |
θ–scan | h = −11→11 |
4859 measured reflections | k = −17→17 |
1396 independent reflections | l = −3→7 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.129 | H 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 parameters | Δρmax = 0.12 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C8H9NS | V = 795.3 (3) Å3 |
Mr = 151.22 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.3355 (19) Å | µ = 0.33 mm−1 |
b = 14.707 (3) Å | T = 298 K |
c = 5.9504 (12) Å | 0.6 × 0.16 × 0.04 mm |
β = 103.22 (3)° |
Kuma KM-4 Sapphire3 CCD diffractometer | 976 reflections with I > 2σ(I) |
4859 measured reflections | Rint = 0.017 |
1396 independent reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.129 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.31 | Δρmax = 0.12 e Å−3 |
1396 reflections | Δρmin = −0.18 e Å−3 |
95 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 > 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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.17075 (7) | 0.12453 (6) | 0.74687 (10) | 0.0709 (3) | |
N1 | 0.1751 (2) | 0.12580 (15) | 0.3094 (3) | 0.0566 (6) | |
C1 | 0.4155 (2) | 0.12438 (14) | 0.5570 (3) | 0.0417 (5) | |
C2 | 0.5044 (2) | 0.08673 (17) | 0.7560 (4) | 0.0503 (6) | |
H2 | 0.4614 | 0.0632 | 0.8699 | 0.060* | |
C3 | 0.6559 (3) | 0.08405 (19) | 0.7860 (4) | 0.0623 (7) | |
H3 | 0.7136 | 0.0580 | 0.9187 | 0.075* | |
C4 | 0.7213 (3) | 0.11936 (18) | 0.6221 (5) | 0.0624 (7) | |
H4 | 0.8231 | 0.1173 | 0.6430 | 0.075* | |
C5 | 0.6355 (3) | 0.15831 (18) | 0.4245 (5) | 0.0648 (7) | |
H5 | 0.6796 | 0.1830 | 0.3131 | 0.078* | |
C6 | 0.4846 (3) | 0.16044 (16) | 0.3934 (4) | 0.0542 (6) | |
H6 | 0.4278 | 0.1866 | 0.2602 | 0.065* | |
C7 | 0.2528 (2) | 0.12432 (14) | 0.5264 (3) | 0.0436 (5) | |
C8 | 0.0156 (3) | 0.1290 (2) | 0.2426 (4) | 0.0757 (9) | |
H8A | −0.0241 | 0.0742 | 0.2920 | 0.114* | |
H8B | −0.0154 | 0.1342 | 0.0778 | 0.114* | |
H8C | −0.0191 | 0.1805 | 0.3137 | 0.114* | |
H1 | 0.228 (4) | 0.1267 (19) | 0.208 (6) | 0.091* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0564 (4) | 0.1257 (7) | 0.0336 (4) | 0.0012 (4) | 0.0164 (3) | 0.0032 (3) |
N1 | 0.0461 (11) | 0.0927 (16) | 0.0313 (9) | −0.0032 (10) | 0.0094 (8) | 0.0007 (10) |
C1 | 0.0472 (12) | 0.0462 (12) | 0.0323 (10) | −0.0019 (10) | 0.0101 (10) | −0.0012 (9) |
C2 | 0.0479 (13) | 0.0634 (15) | 0.0396 (13) | 0.0010 (10) | 0.0097 (11) | 0.0076 (10) |
C3 | 0.0559 (15) | 0.0744 (17) | 0.0522 (15) | 0.0082 (12) | 0.0033 (12) | 0.0066 (12) |
C4 | 0.0429 (13) | 0.0802 (18) | 0.0632 (16) | −0.0025 (12) | 0.0102 (12) | −0.0057 (14) |
C5 | 0.0610 (17) | 0.0803 (19) | 0.0575 (16) | −0.0124 (14) | 0.0230 (13) | 0.0041 (13) |
C6 | 0.0555 (14) | 0.0668 (15) | 0.0411 (12) | −0.0024 (11) | 0.0126 (11) | 0.0093 (11) |
C7 | 0.0491 (13) | 0.0513 (12) | 0.0309 (10) | 0.0008 (10) | 0.0100 (9) | 0.0022 (10) |
C8 | 0.0497 (15) | 0.133 (3) | 0.0423 (13) | −0.0043 (15) | 0.0051 (12) | 0.0056 (14) |
S1—C7 | 1.663 (2) | C3—H3 | 0.9300 |
N1—C7 | 1.329 (3) | C4—C5 | 1.386 (4) |
N1—C8 | 1.451 (3) | C4—H4 | 0.9300 |
N1—H1 | 0.86 (4) | C5—C6 | 1.379 (3) |
C1—C6 | 1.390 (3) | C5—H5 | 0.9300 |
C1—C2 | 1.396 (3) | C6—H6 | 0.9300 |
C1—C7 | 1.488 (3) | C8—H8A | 0.9600 |
C2—C3 | 1.385 (3) | C8—H8B | 0.9600 |
C2—H2 | 0.9300 | C8—H8C | 0.9600 |
C3—C4 | 1.366 (4) | ||
C7—N1—C8 | 124.4 (2) | C6—C5—C4 | 119.8 (2) |
C7—N1—H1 | 114 (2) | C6—C5—H5 | 120.1 |
C8—N1—H1 | 121 (2) | C4—C5—H5 | 120.1 |
C6—C1—C2 | 117.68 (19) | C5—C6—C1 | 121.4 (2) |
C6—C1—C7 | 122.61 (18) | C5—C6—H6 | 119.3 |
C2—C1—C7 | 119.71 (18) | C1—C6—H6 | 119.3 |
C3—C2—C1 | 120.8 (2) | N1—C7—C1 | 115.70 (18) |
C3—C2—H2 | 119.6 | N1—C7—S1 | 121.28 (17) |
C1—C2—H2 | 119.6 | C1—C7—S1 | 123.01 (15) |
C4—C3—C2 | 120.5 (2) | N1—C8—H8A | 109.5 |
C4—C3—H3 | 119.8 | N1—C8—H8B | 109.5 |
C2—C3—H3 | 119.8 | H8A—C8—H8B | 109.5 |
C3—C4—C5 | 119.8 (2) | N1—C8—H8C | 109.5 |
C3—C4—H4 | 120.1 | H8A—C8—H8C | 109.5 |
C5—C4—H4 | 120.1 | H8B—C8—H8C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S1i | 0.86 (4) | 2.67 (3) | 3.338 (2) | 135 (3) |
Symmetry code: (i) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | C8H9NS |
Mr | 151.22 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 9.3355 (19), 14.707 (3), 5.9504 (12) |
β (°) | 103.22 (3) |
V (Å3) | 795.3 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.33 |
Crystal size (mm) | 0.6 × 0.16 × 0.04 |
Data collection | |
Diffractometer | Kuma KM-4 Sapphire3 CCD |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4859, 1396, 976 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.129, 1.31 |
No. of reflections | 1396 |
No. of parameters | 95 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.12, −0.18 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), 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 | 0.86 (4) | 2.67 (3) | 3.338 (2) | 135 (3) |
Symmetry code: (i) x, y, z−1. |
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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.