N-Phenyl­piperidine-1-carbothio­amide

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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.041
• wR factor = 0.124
• Data-to-parameter ratio = 17.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT414_ALERT_2_C Short Intra D-H..H-X       H2     ..  H5A     ..       1.93 Ang.

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

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

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

S2. Experimental

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.

S3. Refinement

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

Computing details

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

	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

Crystal data

C12H16N2S	F(000) = 472
Mr = 220.33	Dx = 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) Å^3	0.25 × 0.20 × 0.18 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.009
Radiation source: fine-focus sealed tube	θmax = 27.0°, θmin = 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

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

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1^i	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.