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Acta Cryst. (2008). E64, o1743    [ doi:10.1107/S1600536808025142 ]

N-Phenylpiperidine-1-carbothioamide

Y.-F. Li and F.-F. Jian

Abstract top

The title compound, C12H16N2S, was prepared by the reaction of with phenyl isothiocyanate and piperidine. In the crystal structure, the molecule exhibits intermolecular N-H...S hydrogen bonds and weak intramolecular C-H...S and C-H...N hydrogen-bonding interactions.

Comment top

Thioamide have received considerable attention in the literature. They are attractive from several points of view in application (Toshiaki et al., 2003). As part of our search for new thioamide compounds we synthesized the title compound (I), and describe its structure here.

The C6—S1 bond length of 1.7056 (17)Å is comparable with C—S bond [1.688 (2) Å] reported (Cowley et al., 2002). The distance of N1—C6 [1.349 (2) Å] is similar to the distance of reported [1.349 (1) Å] (Casas et al., 2002). The crystal strucure is stabilized by an intermolecular N—H···S hydrogen bond, and weak intramolecular C—H···S and C—H···N hydrogen bonding interactions (Table 1). Fig. 2 shows the intermolecular N—H···S hydrogen bonds between the neighbour molecules in the unit cell.

Related literature top

For related literature, see: Casas et al. (2002); Cowley et al. (2002); Toshiaki et al. (2003).

Experimental top

A mixture of the phenyl isothiocyanate (0.1 mol), and piperidine (0.1 mol) was stirred in refluxing ethanol (20 mL) for 4 h to afford the title compound (0.086 mol, yield 86%). Single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.

Refinement top

H atoms were fixed geometrically and allowed to ride on their attached atoms, with C—H distances = 0.93 - 0.97 Å, and with Uiso=1.2 or 1.5Ueq.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The structure of the title compound showing 30% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. A view of the intermolecular N—H···S hydrogen bonds between the neighbour molecules in the unit cell.
N-Phenylpiperidine-1-carbothioamide top
Crystal data top
C12H16N2SF000 = 472
Mr = 220.33Dx = 1.227 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 11.661 (2) Åθ = 1.8–27.0º
b = 9.5220 (19) ŵ = 0.24 mm−1
c = 10.989 (2) ÅT = 293 (2) K
β = 102.15 (3)ºBlock, colourless
V = 1192.8 (4) Å30.25 × 0.20 × 0.18 mm
Z = 4
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.009
Radiation source: fine-focus sealed tubeθmax = 27.0º
Monochromator: graphiteθmin = 1.8º
T = 293(2) Kh = −13→13
ω scansk = −11→0
Absorption correction: nonel = 0→13
2681 measured reflections3 standard reflections
2547 independent reflections every 100 reflections
1972 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of
independent and constrained refinement
R[F2 > 2σ(F2)] = 0.040  w = 1/[σ2(Fo2) + (0.0738P)2 + 0.2418P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.123(Δ/σ)max < 0.001
S = 1.03Δρmax = 0.26 e Å−3
2547 reflectionsΔρmin = −0.38 e Å−3
149 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.129 (8)
Secondary atom site location: difference Fourier map
Crystal data top
C12H16N2SV = 1192.8 (4) Å3
Mr = 220.33Z = 4
Monoclinic, P21/cMo Kα
a = 11.661 (2) ŵ = 0.24 mm−1
b = 9.5220 (19) ÅT = 293 (2) K
c = 10.989 (2) Å0.25 × 0.20 × 0.18 mm
β = 102.15 (3)º
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.009
Absorption correction: none3 standard reflections
2681 measured reflections every 100 reflections
2547 independent reflections intensity decay: none
1972 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.040149 parameters
wR(F2) = 0.123H atoms treated by a mixture of
independent and constrained refinement
S = 1.03Δρmax = 0.26 e Å−3
2547 reflectionsΔρmin = −0.38 e Å−3
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
S10.48254 (4)0.19137 (5)0.42566 (4)0.04595 (19)
N10.33547 (12)0.37786 (15)0.29140 (15)0.0441 (4)
N20.53031 (12)0.41101 (18)0.29001 (15)0.0465 (4)
C10.23443 (15)0.2923 (2)0.3048 (2)0.0507 (5)
H1A0.18780.34310.35370.061*
H1B0.26150.20600.34840.061*
C20.15982 (19)0.2580 (2)0.1783 (2)0.0655 (6)
H2B0.09000.20830.18900.079*
H2C0.20340.19660.13410.079*
C30.1237 (2)0.3906 (2)0.1007 (3)0.0701 (7)
H3A0.08370.36420.01730.084*
H3B0.06960.44500.13770.084*
C40.23033 (19)0.4800 (2)0.09364 (19)0.0558 (5)
H4A0.27940.43080.04650.067*
H4B0.20510.56760.05120.067*
C50.29967 (16)0.51043 (19)0.22297 (19)0.0449 (4)
C60.44703 (14)0.33344 (17)0.33069 (15)0.0362 (4)
C70.65404 (14)0.39270 (17)0.32415 (16)0.0388 (4)
C80.71647 (15)0.38347 (18)0.23028 (18)0.0439 (4)
H8A0.67720.38410.14730.053*
C90.83783 (16)0.3733 (2)0.2604 (2)0.0522 (5)
H9A0.87970.36730.19730.063*
C100.89689 (16)0.3721 (2)0.3832 (2)0.0538 (5)
H10A0.97820.36460.40300.065*
C110.83420 (16)0.3822 (2)0.4765 (2)0.0533 (5)
H11A0.87370.38140.55940.064*
C120.71314 (16)0.3935 (2)0.44777 (18)0.0481 (4)
H12A0.67160.40150.51100.058*
H5A0.3633 (19)0.566 (2)0.220 (2)0.055 (6)*
H5B0.2457 (19)0.561 (2)0.267 (2)0.056 (6)*
H20.5075 (17)0.463 (2)0.230 (2)0.051 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0424 (3)0.0424 (3)0.0520 (3)0.00420 (18)0.00770 (19)0.01026 (19)
N10.0343 (7)0.0404 (8)0.0576 (9)−0.0006 (6)0.0095 (6)0.0122 (7)
N20.0336 (7)0.0551 (9)0.0494 (9)−0.0004 (7)0.0058 (6)0.0162 (7)
C10.0344 (9)0.0481 (10)0.0717 (13)0.0002 (7)0.0158 (8)0.0176 (9)
C20.0502 (11)0.0419 (11)0.0962 (17)−0.0057 (9)−0.0033 (11)0.0036 (11)
C30.0613 (13)0.0556 (13)0.0792 (16)−0.0016 (10)−0.0179 (11)0.0042 (11)
C40.0655 (12)0.0503 (11)0.0525 (11)0.0128 (9)0.0142 (9)0.0097 (9)
C50.0370 (8)0.0355 (9)0.0631 (12)0.0021 (7)0.0124 (8)0.0092 (8)
C60.0351 (8)0.0369 (8)0.0367 (8)−0.0014 (6)0.0078 (6)−0.0016 (6)
C70.0335 (8)0.0343 (8)0.0475 (9)−0.0029 (6)0.0059 (7)0.0017 (7)
C80.0418 (9)0.0420 (10)0.0474 (10)−0.0041 (7)0.0081 (7)0.0007 (7)
C90.0434 (10)0.0475 (11)0.0706 (13)−0.0022 (8)0.0233 (9)−0.0035 (9)
C100.0320 (9)0.0451 (10)0.0814 (14)−0.0008 (7)0.0052 (9)0.0032 (9)
C110.0435 (10)0.0539 (12)0.0556 (11)−0.0051 (8)−0.0054 (8)0.0008 (9)
C120.0428 (9)0.0536 (11)0.0466 (10)−0.0036 (8)0.0066 (8)−0.0027 (8)
Geometric parameters (Å, °) top
S1—C61.7056 (17)C4—C51.508 (3)
N1—C61.349 (2)C4—H4A0.9700
N1—C11.465 (2)C4—H4B0.9700
N1—C51.484 (2)C5—H5A0.92 (2)
N2—C61.368 (2)C5—H5B0.99 (2)
N2—C71.423 (2)C7—C81.385 (3)
N2—H20.82 (2)C7—C121.388 (2)
C1—C21.512 (3)C8—C91.387 (3)
C1—H1A0.9700C8—H8A0.9300
C1—H1B0.9700C9—C101.380 (3)
C2—C31.533 (3)C9—H9A0.9300
C2—H2B0.9700C10—C111.383 (3)
C2—H2C0.9700C10—H10A0.9300
C3—C41.522 (3)C11—C121.384 (3)
C3—H3A0.9700C11—H11A0.9300
C3—H3B0.9700C12—H12A0.9300
C6—N1—C1122.35 (14)H4A—C4—H4B108.2
C6—N1—C5125.33 (14)N1—C5—C4110.63 (16)
C1—N1—C5112.18 (14)N1—C5—H5A111.5 (13)
C6—N2—C7126.72 (15)C4—C5—H5A110.9 (13)
C6—N2—H2117.1 (14)N1—C5—H5B107.9 (13)
C7—N2—H2115.0 (14)C4—C5—H5B106.3 (12)
N1—C1—C2110.30 (17)H5A—C5—H5B109.3 (18)
N1—C1—H1A109.6N1—C6—N2115.41 (15)
C2—C1—H1A109.6N1—C6—S1122.54 (12)
N1—C1—H1B109.6N2—C6—S1122.05 (12)
C2—C1—H1B109.6C8—C7—C12119.93 (16)
H1A—C1—H1B108.1C8—C7—N2118.31 (16)
C1—C2—C3111.80 (18)C12—C7—N2121.62 (16)
C1—C2—H2B109.3C7—C8—C9119.78 (18)
C3—C2—H2B109.3C7—C8—H8A120.1
C1—C2—H2C109.3C9—C8—H8A120.1
C3—C2—H2C109.3C10—C9—C8120.50 (19)
H2B—C2—H2C107.9C10—C9—H9A119.7
C4—C3—C2110.95 (18)C8—C9—H9A119.7
C4—C3—H3A109.4C9—C10—C11119.48 (17)
C2—C3—H3A109.4C9—C10—H10A120.3
C4—C3—H3B109.4C11—C10—H10A120.3
C2—C3—H3B109.4C10—C11—C12120.59 (18)
H3A—C3—H3B108.0C10—C11—H11A119.7
C5—C4—C3109.95 (18)C12—C11—H11A119.7
C5—C4—H4A109.7C11—C12—C7119.70 (18)
C3—C4—H4A109.7C11—C12—H12A120.1
C5—C4—H4B109.7C7—C12—H12A120.1
C3—C4—H4B109.7
C6—N1—C1—C2−117.8 (2)C7—N2—C6—N1175.49 (17)
C5—N1—C1—C258.1 (2)C7—N2—C6—S1−3.9 (3)
N1—C1—C2—C3−54.1 (2)C6—N2—C7—C8129.22 (19)
C1—C2—C3—C452.7 (3)C6—N2—C7—C12−55.1 (3)
C2—C3—C4—C5−53.8 (3)C12—C7—C8—C90.8 (3)
C6—N1—C5—C4115.4 (2)N2—C7—C8—C9176.49 (16)
C1—N1—C5—C4−60.4 (2)C7—C8—C9—C100.1 (3)
C3—C4—C5—N157.2 (2)C8—C9—C10—C11−0.5 (3)
C1—N1—C6—N2167.41 (17)C9—C10—C11—C120.0 (3)
C5—N1—C6—N2−8.0 (3)C10—C11—C12—C70.9 (3)
C1—N1—C6—S1−13.2 (2)C8—C7—C12—C11−1.3 (3)
C5—N1—C6—S1171.48 (14)N2—C7—C12—C11−176.82 (17)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···S1i0.82 (2)2.78 (2)3.5520 (19)156.1 (18)
C1—H1B···S10.972.543.073 (2)114
C5—H5A···N20.92 (2)2.44 (2)2.800 (2)103.8 (14)
Symmetry codes: (i) −x+1, y+1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···S1i0.82 (2)2.78 (2)3.5520 (19)156.1 (18)
C1—H1B···S10.972.543.073 (2)114
C5—H5A···N20.92 (2)2.44 (2)2.800 (2)103.8 (14)
Symmetry codes: (i) −x+1, y+1/2, −z+1/2.
references
References top

Casas, J. S., Castano, M. V. & Castellano, E. E. (2002). Inorg. Chem. 41, 1550–1557.

Cowley, A. R., Dilworth, J. R. & Dorinelly, P. S. (2002). J. Am. Chem. Soc. 124, 5270–5271.

Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.

Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst. 22, 384–387.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Toshiaki, M., Hideo, A. & Yoshiharu, Y. (2003). J. Org. Chem. 68, 8514–8519.