N-Phenyl­piperidine-1-carbothio­amide

Li, Y.-F.; Jian, F.-F.

doi:10.1107/S1600536808025142

organic compounds

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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1743

doi:10.1107/S1600536808025142

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N-Phenylpiperidine-1-carbothioamide

Yu-Feng Li ^a and Fang-Fang Jian ^a ^*

^aMicroscale Science Institute, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: ffjian2008@163.com

(Received 23 July 2008; accepted 5 August 2008; online 13 August 2008)

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.

Related literature

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

Experimental

Crystal data

C₁₂H₁₆N₂S
M_r = 220.33
Monoclinic, P 2₁ /c
a = 11.661 (2) Å
b = 9.5220 (19) Å
c = 10.989 (2) Å
β = 102.15 (3)°
V = 1192.8 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 293 (2) K
0.25 × 0.20 × 0.18 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
2681 measured reflections
2547 independent reflections
1972 reflections with I > 2σ(I)
R_int = 0.009
3 standard reflections every 100 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.123
S = 1.02
2547 reflections
149 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯S1ⁱ	0.82 (2)	2.78 (2)	3.5520 (19)	156.1 (18)
C1—H1B⋯S1	0.97	2.54	3.073 (2)	114
C5—H5A⋯N2	0.92 (2)	2.44 (2)	2.800 (2)	103.8 (14)
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808025142/at2604sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808025142/at2604Isup2.hkl

checkCIF report

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.

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

	Fig. 1. The structure of the title compound showing 30% probability displacement ellipsoids and the atom-numbering scheme.
	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

C₁₂H₁₆N₂S	F(000) = 472
M_r = 220.33	D_x = 1.227 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 11.661 (2) Å	θ = 1.8–27.0°
b = 9.5220 (19) Å	µ = 0.24 mm⁻¹
c = 10.989 (2) Å	T = 293 K
β = 102.15 (3)°	Block, colourless
V = 1192.8 (4) Å³	0.25 × 0.20 × 0.18 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.009
Radiation source: fine-focus sealed tube	θ_max = 27.0°, θ_min = 1.8°
Graphite monochromator	h = −13→13
ω scans	k = −11→0
2681 measured reflections	l = 0→13
2547 independent reflections	3 standard reflections every 100 reflections
1972 reflections with I > 2σ(I)	intensity decay: none

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.123	w = 1/[σ²(F_o²) + (0.0738P)² + 0.2418P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2547 reflections	Δρ_max = 0.26 e Å⁻³
149 parameters	Δρ_min = −0.38 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.129 (8)

Crystal data top

C₁₂H₁₆N₂S	V = 1192.8 (4) Å³
M_r = 220.33	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.661 (2) Å	µ = 0.24 mm⁻¹
b = 9.5220 (19) Å	T = 293 K
c = 10.989 (2) Å	0.25 × 0.20 × 0.18 mm
β = 102.15 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.009
2681 measured reflections	3 standard reflections every 100 reflections
2547 independent reflections	intensity decay: none
1972 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.26 e Å⁻³
2547 reflections	Δρ_min = −0.38 e Å⁻³
149 parameters

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

	x	y	z	U_iso*/U_eq
S1	0.48254 (4)	0.19137 (5)	0.42566 (4)	0.04595 (19)
N1	0.33547 (12)	0.37786 (15)	0.29140 (15)	0.0441 (4)
N2	0.53031 (12)	0.41101 (18)	0.29001 (15)	0.0465 (4)
C1	0.23443 (15)	0.2923 (2)	0.3048 (2)	0.0507 (5)
H1A	0.1878	0.3431	0.3537	0.061*
H1B	0.2615	0.2060	0.3484	0.061*
C2	0.15982 (19)	0.2580 (2)	0.1783 (2)	0.0655 (6)
H2B	0.0900	0.2083	0.1890	0.079*
H2C	0.2034	0.1966	0.1341	0.079*
C3	0.1237 (2)	0.3906 (2)	0.1007 (3)	0.0701 (7)
H3A	0.0837	0.3642	0.0173	0.084*
H3B	0.0696	0.4450	0.1377	0.084*
C4	0.23033 (19)	0.4800 (2)	0.09364 (19)	0.0558 (5)
H4A	0.2794	0.4308	0.0465	0.067*
H4B	0.2051	0.5676	0.0512	0.067*
C5	0.29967 (16)	0.51043 (19)	0.22297 (19)	0.0449 (4)
C6	0.44703 (14)	0.33344 (17)	0.33069 (15)	0.0362 (4)
C7	0.65404 (14)	0.39270 (17)	0.32415 (16)	0.0388 (4)
C8	0.71647 (15)	0.38347 (18)	0.23028 (18)	0.0439 (4)
H8A	0.6772	0.3841	0.1473	0.053*
C9	0.83783 (16)	0.3733 (2)	0.2604 (2)	0.0522 (5)
H9A	0.8797	0.3673	0.1973	0.063*
C10	0.89689 (16)	0.3721 (2)	0.3832 (2)	0.0538 (5)
H10A	0.9782	0.3646	0.4030	0.065*
C11	0.83420 (16)	0.3822 (2)	0.4765 (2)	0.0533 (5)
H11A	0.8737	0.3814	0.5594	0.064*
C12	0.71314 (16)	0.3935 (2)	0.44777 (18)	0.0481 (4)
H12A	0.6716	0.4015	0.5110	0.058*
H5A	0.3633 (19)	0.566 (2)	0.220 (2)	0.055 (6)*
H5B	0.2457 (19)	0.561 (2)	0.267 (2)	0.056 (6)*
H2	0.5075 (17)	0.463 (2)	0.230 (2)	0.051 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0424 (3)	0.0424 (3)	0.0520 (3)	0.00420 (18)	0.00770 (19)	0.01026 (19)
N1	0.0343 (7)	0.0404 (8)	0.0576 (9)	−0.0006 (6)	0.0095 (6)	0.0122 (7)
N2	0.0336 (7)	0.0551 (9)	0.0494 (9)	−0.0004 (7)	0.0058 (6)	0.0162 (7)
C1	0.0344 (9)	0.0481 (10)	0.0717 (13)	0.0002 (7)	0.0158 (8)	0.0176 (9)
C2	0.0502 (11)	0.0419 (11)	0.0962 (17)	−0.0057 (9)	−0.0033 (11)	0.0036 (11)
C3	0.0613 (13)	0.0556 (13)	0.0792 (16)	−0.0016 (10)	−0.0179 (11)	0.0042 (11)
C4	0.0655 (12)	0.0503 (11)	0.0525 (11)	0.0128 (9)	0.0142 (9)	0.0097 (9)
C5	0.0370 (8)	0.0355 (9)	0.0631 (12)	0.0021 (7)	0.0124 (8)	0.0092 (8)
C6	0.0351 (8)	0.0369 (8)	0.0367 (8)	−0.0014 (6)	0.0078 (6)	−0.0016 (6)
C7	0.0335 (8)	0.0343 (8)	0.0475 (9)	−0.0029 (6)	0.0059 (7)	0.0017 (7)
C8	0.0418 (9)	0.0420 (10)	0.0474 (10)	−0.0041 (7)	0.0081 (7)	0.0007 (7)
C9	0.0434 (10)	0.0475 (11)	0.0706 (13)	−0.0022 (8)	0.0233 (9)	−0.0035 (9)
C10	0.0320 (9)	0.0451 (10)	0.0814 (14)	−0.0008 (7)	0.0052 (9)	0.0032 (9)
C11	0.0435 (10)	0.0539 (12)	0.0556 (11)	−0.0051 (8)	−0.0054 (8)	0.0008 (9)
C12	0.0428 (9)	0.0536 (11)	0.0466 (10)	−0.0036 (8)	0.0066 (8)	−0.0027 (8)

Geometric parameters (Å, º) top

S1—C6	1.7056 (17)	C4—C5	1.508 (3)
N1—C6	1.349 (2)	C4—H4A	0.9700
N1—C1	1.465 (2)	C4—H4B	0.9700
N1—C5	1.484 (2)	C5—H5A	0.92 (2)
N2—C6	1.368 (2)	C5—H5B	0.99 (2)
N2—C7	1.423 (2)	C7—C8	1.385 (3)
N2—H2	0.82 (2)	C7—C12	1.388 (2)
C1—C2	1.512 (3)	C8—C9	1.387 (3)
C1—H1A	0.9700	C8—H8A	0.9300
C1—H1B	0.9700	C9—C10	1.380 (3)
C2—C3	1.533 (3)	C9—H9A	0.9300
C2—H2B	0.9700	C10—C11	1.383 (3)
C2—H2C	0.9700	C10—H10A	0.9300
C3—C4	1.522 (3)	C11—C12	1.384 (3)
C3—H3A	0.9700	C11—H11A	0.9300
C3—H3B	0.9700	C12—H12A	0.9300

C6—N1—C1	122.35 (14)	H4A—C4—H4B	108.2
C6—N1—C5	125.33 (14)	N1—C5—C4	110.63 (16)
C1—N1—C5	112.18 (14)	N1—C5—H5A	111.5 (13)
C6—N2—C7	126.72 (15)	C4—C5—H5A	110.9 (13)
C6—N2—H2	117.1 (14)	N1—C5—H5B	107.9 (13)
C7—N2—H2	115.0 (14)	C4—C5—H5B	106.3 (12)
N1—C1—C2	110.30 (17)	H5A—C5—H5B	109.3 (18)
N1—C1—H1A	109.6	N1—C6—N2	115.41 (15)
C2—C1—H1A	109.6	N1—C6—S1	122.54 (12)
N1—C1—H1B	109.6	N2—C6—S1	122.05 (12)
C2—C1—H1B	109.6	C8—C7—C12	119.93 (16)
H1A—C1—H1B	108.1	C8—C7—N2	118.31 (16)
C1—C2—C3	111.80 (18)	C12—C7—N2	121.62 (16)
C1—C2—H2B	109.3	C7—C8—C9	119.78 (18)
C3—C2—H2B	109.3	C7—C8—H8A	120.1
C1—C2—H2C	109.3	C9—C8—H8A	120.1
C3—C2—H2C	109.3	C10—C9—C8	120.50 (19)
H2B—C2—H2C	107.9	C10—C9—H9A	119.7
C4—C3—C2	110.95 (18)	C8—C9—H9A	119.7
C4—C3—H3A	109.4	C9—C10—C11	119.48 (17)
C2—C3—H3A	109.4	C9—C10—H10A	120.3
C4—C3—H3B	109.4	C11—C10—H10A	120.3
C2—C3—H3B	109.4	C10—C11—C12	120.59 (18)
H3A—C3—H3B	108.0	C10—C11—H11A	119.7
C5—C4—C3	109.95 (18)	C12—C11—H11A	119.7
C5—C4—H4A	109.7	C11—C12—C7	119.70 (18)
C3—C4—H4A	109.7	C11—C12—H12A	120.1
C5—C4—H4B	109.7	C7—C12—H12A	120.1
C3—C4—H4B	109.7

C6—N1—C1—C2	−117.8 (2)	C7—N2—C6—N1	175.49 (17)
C5—N1—C1—C2	58.1 (2)	C7—N2—C6—S1	−3.9 (3)
N1—C1—C2—C3	−54.1 (2)	C6—N2—C7—C8	129.22 (19)
C1—C2—C3—C4	52.7 (3)	C6—N2—C7—C12	−55.1 (3)
C2—C3—C4—C5	−53.8 (3)	C12—C7—C8—C9	0.8 (3)
C6—N1—C5—C4	115.4 (2)	N2—C7—C8—C9	176.49 (16)
C1—N1—C5—C4	−60.4 (2)	C7—C8—C9—C10	0.1 (3)
C3—C4—C5—N1	57.2 (2)	C8—C9—C10—C11	−0.5 (3)
C1—N1—C6—N2	167.41 (17)	C9—C10—C11—C12	0.0 (3)
C5—N1—C6—N2	−8.0 (3)	C10—C11—C12—C7	0.9 (3)
C1—N1—C6—S1	−13.2 (2)	C8—C7—C12—C11	−1.3 (3)
C5—N1—C6—S1	171.48 (14)	N2—C7—C12—C11	−176.82 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1ⁱ	0.82 (2)	2.78 (2)	3.5520 (19)	156.1 (18)
C1—H1B···S1	0.97	2.54	3.073 (2)	114
C5—H5A···N2	0.92 (2)	2.44 (2)	2.800 (2)	103.8 (14)

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₆N₂S
M_r	220.33
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.661 (2), 9.5220 (19), 10.989 (2)
β (°)	102.15 (3)
V (Å³)	1192.8 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.25 × 0.20 × 0.18

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2681, 2547, 1972
R_int	0.009
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.123, 1.03
No. of reflections	2547
No. of parameters	149
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.38

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1ⁱ	0.82 (2)	2.78 (2)	3.5520 (19)	156.1 (18)
C1—H1B···S1	0.97	2.54	3.073 (2)	114
C5—H5A···N2	0.92 (2)	2.44 (2)	2.800 (2)	103.8 (14)

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

References

Casas, J. S., Castano, M. V. & Castellano, E. E. (2002). Inorg. Chem. 41, 1550–1557. Web of Science CSD CrossRef PubMed CAS Google Scholar
Cowley, A. R., Dilworth, J. R. & Dorinelly, P. S. (2002). J. Am. Chem. Soc. 124, 5270–5271. Web of Science CSD CrossRef PubMed CAS Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst. 22, 384–387. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Toshiaki, M., Hideo, A. & Yoshiharu, Y. (2003). J. Org. Chem. 68, 8514–8519. Web of Science PubMed Google Scholar

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doi:10.1107/S1600536808025142

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