4-Methyl-N-phenyl­piperidine-1-thio­amide

The title compound, C₁₃H₁₈N₂S, was prepared by the reaction of phenyl isothio­cyanate and 4-methyl­piperidine. The crystal structure is stabilized by inter­molecular N—H...S hydrogen-bonding inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.038
• wR factor = 0.096
• Data-to-parameter ratio = 16.8

checkCIF/PLATON results

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Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           26.31
           From the CIF: _reflns_number_total               2500
           Count of symmetry unique reflns         1387
           Completeness (_total/calc)            180.25%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1113
           Fraction of Friedel pairs measured     0.802
           Are heavy atom types Z>Si present        yes
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

   0 ALERT level A = In general: serious problem
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S1. Comment

Thiourea derivatives have been used extensively as organical intermediate in the field of high polymer chemistry (Ballabeni et al., 1999). As part of our search for new compounds we synthesized the title compound (I), and describe its structure here.

Bond lengths and angles in (I) are generally normal. The C1—S1 distance of 1.679 (3) Å is shorter than the reported distance [1.700 Å] (Ramnathan et al.,1996). The C1—N2 distance of 1.338 (3)Å is longer than the reported distance [1.339 Å] (Guzman et al., 1991).

In the crystal structure, there is an intermolecular N—H···S hydrogen bonding interactions.

Related literature

For related literature, see: Ballabeni et al. (1999); Guzman & Rodriguez (1991); Ramnathan et al. (1996).

S2. Experimental

A mixture of the phenyl isothiocyanate (0.1 mol), and 4-methylpiperidine (0.1 mol) was stirred in refluxing ethanol (30 ml) for 5 h to afford the title compound (0.085 mol, yield 85%). Single crystals (I) suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.

S3. Refinement

The H atom bonded to N atom were found from a difference Fourier map and refined freely. The other H atoms were fixed geometrically and allowed to ride on their attached atoms, with C—H = 0.93 - 0.97 Å, and U_iso=1.2 - 1.5U_eq(C).

Computing details

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, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures

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

4-Methyl-N-phenylpiperidine-1-thioamide

Crystal data

C13H18N2S	F(000) = 504
Mr = 234.35	Dx = 1.219 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 2276 reflections
a = 11.654 (6) Å	θ = 2.5–24.7°
b = 11.335 (6) Å	µ = 0.23 mm^−1
c = 9.711 (5) Å	T = 294 K
V = 1282.7 (12) Å^3	Block, colourless
Z = 4	0.22 × 0.20 × 0.12 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	2500 independent reflections
Radiation source: fine-focus sealed tube	1842 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
φ and ω scans	θmax = 26.3°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→11
Tmin = 0.951, Tmax = 0.973	k = −14→13
6919 measured reflections	l = −11→12

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)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.096	w = 1/[σ^2(Fo^2) + (0.0494P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.004
2500 reflections	Δρmax = 0.16 e Å^−3
149 parameters	Δρmin = −0.20 e Å^−3
2 restraints	Absolute structure: Flack (1983), 1113 Freidel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (9)

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	0.15114 (6)	0.85016 (5)	0.69896 (7)	0.0586 (2)
N1	0.21408 (18)	0.7337 (2)	0.4733 (2)	0.0561 (6)
H1	0.230 (3)	0.750 (3)	0.393 (3)	0.084*
N2	0.06394 (17)	0.86019 (17)	0.4473 (2)	0.0553 (5)
C1	0.14138 (18)	0.8122 (2)	0.5322 (2)	0.0449 (5)
C2	−0.0131 (3)	0.9545 (2)	0.4919 (3)	0.0666 (8)
H2A	−0.0173	1.0149	0.4213	0.080*
H2B	0.0163	0.9905	0.5754	0.080*
C3	−0.1314 (2)	0.9046 (3)	0.5182 (3)	0.0714 (8)
H3A	−0.1823	0.9678	0.5465	0.086*
H3B	−0.1272	0.8480	0.5930	0.086*
C4	−0.1804 (2)	0.8449 (2)	0.3921 (3)	0.0625 (7)
H4	−0.1920	0.9052	0.3211	0.075*
C5	−0.0940 (2)	0.7553 (3)	0.3370 (3)	0.0618 (7)
H5A	−0.0902	0.6890	0.4000	0.074*
H5B	−0.1210	0.7258	0.2489	0.074*
C6	0.0251 (2)	0.8056 (3)	0.3187 (3)	0.0662 (7)
H6A	0.0777	0.7432	0.2925	0.079*
H6B	0.0244	0.8641	0.2458	0.079*
C7	−0.2953 (2)	0.7869 (3)	0.4205 (5)	0.1005 (12)
H7A	−0.2837	0.7163	0.4734	0.151*
H7B	−0.3318	0.7672	0.3349	0.151*
H7C	−0.3433	0.8403	0.4712	0.151*
C8	0.28608 (18)	0.65270 (19)	0.5418 (2)	0.0442 (6)
C9	0.24709 (19)	0.58503 (19)	0.6493 (3)	0.0507 (6)
H9	0.1727	0.5952	0.6820	0.061*
C10	0.3175 (2)	0.5026 (2)	0.7084 (4)	0.0651 (7)
H10	0.2910	0.4583	0.7826	0.078*
C11	0.4265 (2)	0.4845 (2)	0.6598 (3)	0.0712 (8)
H11	0.4733	0.4272	0.6992	0.085*
C12	0.4657 (2)	0.5516 (3)	0.5526 (3)	0.0671 (7)
H12	0.5397	0.5398	0.5194	0.081*
C13	0.3969 (2)	0.6364 (2)	0.4931 (3)	0.0559 (6)
H13	0.4246	0.6823	0.4210	0.067*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0768 (4)	0.0630 (4)	0.0360 (3)	0.0054 (3)	−0.0046 (4)	−0.0083 (3)
N1	0.0530 (11)	0.0858 (14)	0.0296 (11)	0.0221 (11)	0.0020 (9)	0.0003 (11)
N2	0.0546 (12)	0.0706 (13)	0.0408 (12)	0.0157 (11)	−0.0036 (10)	0.0008 (10)
C1	0.0474 (13)	0.0556 (12)	0.0317 (13)	0.0012 (11)	0.0009 (10)	0.0042 (10)
C2	0.0763 (19)	0.0518 (14)	0.0717 (19)	0.0145 (13)	−0.0087 (15)	0.0011 (14)
C3	0.0698 (18)	0.0628 (16)	0.082 (2)	0.0265 (15)	0.0112 (15)	−0.0144 (16)
C4	0.0566 (16)	0.0542 (16)	0.077 (2)	0.0135 (13)	0.0042 (14)	0.0066 (14)
C5	0.0646 (18)	0.0712 (16)	0.0496 (16)	0.0164 (14)	−0.0044 (13)	−0.0074 (13)
C6	0.0600 (16)	0.103 (2)	0.0356 (14)	0.0166 (16)	−0.0064 (12)	0.0019 (14)
C7	0.066 (2)	0.093 (2)	0.142 (4)	0.0042 (18)	0.015 (2)	−0.007 (2)
C8	0.0398 (12)	0.0587 (14)	0.0341 (12)	0.0052 (11)	−0.0069 (9)	−0.0092 (11)
C9	0.0404 (12)	0.0553 (13)	0.0563 (16)	−0.0050 (12)	0.0013 (11)	−0.0005 (12)
C10	0.0597 (16)	0.0615 (13)	0.0740 (18)	−0.0040 (13)	0.0020 (16)	0.0146 (17)
C11	0.0607 (16)	0.0774 (17)	0.076 (2)	0.0143 (14)	−0.0046 (14)	0.0198 (16)
C12	0.0456 (14)	0.0969 (19)	0.0589 (16)	0.0173 (15)	−0.0021 (13)	0.0030 (17)
C13	0.0440 (13)	0.0821 (18)	0.0417 (13)	0.0086 (12)	0.0043 (11)	0.0049 (13)

Geometric parameters (Å, º)

S1—C1	1.679 (3)	C5—H5B	0.9700
N1—C1	1.355 (3)	C6—H6A	0.9700
N1—C8	1.411 (3)	C6—H6B	0.9700
N1—H1	0.83 (2)	C7—H7A	0.9600
N2—C1	1.338 (3)	C7—H7B	0.9600
N2—C2	1.462 (3)	C7—H7C	0.9600
N2—C6	1.466 (3)	C8—C9	1.373 (3)
C2—C3	1.511 (4)	C8—C13	1.388 (3)
C2—H2A	0.9700	C9—C10	1.370 (3)
C2—H2B	0.9700	C9—H9	0.9300
C3—C4	1.512 (4)	C10—C11	1.371 (4)
C3—H3A	0.9700	C10—H10	0.9300
C3—H3B	0.9700	C11—C12	1.368 (4)
C4—C7	1.518 (4)	C11—H11	0.9300
C4—C5	1.527 (4)	C12—C13	1.378 (4)
C4—H4	0.9800	C12—H12	0.9300
C5—C6	1.511 (4)	C13—H13	0.9300
C5—H5A	0.9700
C1—N1—C8	126.9 (2)	H5A—C5—H5B	107.7
C1—N1—H1	113 (2)	N2—C6—C5	110.1 (2)
C8—N1—H1	118 (2)	N2—C6—H6A	109.6
C1—N2—C2	122.0 (2)	C5—C6—H6A	109.6
C1—N2—C6	124.2 (2)	N2—C6—H6B	109.6
C2—N2—C6	111.8 (2)	C5—C6—H6B	109.6
N2—C1—N1	115.4 (2)	H6A—C6—H6B	108.2
N2—C1—S1	122.40 (18)	C4—C7—H7A	109.5
N1—C1—S1	122.20 (18)	C4—C7—H7B	109.5
N2—C2—C3	109.7 (2)	H7A—C7—H7B	109.5
N2—C2—H2A	109.7	C4—C7—H7C	109.5
C3—C2—H2A	109.7	H7A—C7—H7C	109.5
N2—C2—H2B	109.7	H7B—C7—H7C	109.5
C3—C2—H2B	109.7	C9—C8—C13	119.5 (2)
H2A—C2—H2B	108.2	C9—C8—N1	121.7 (2)
C2—C3—C4	112.0 (2)	C13—C8—N1	118.7 (2)
C2—C3—H3A	109.2	C10—C9—C8	120.1 (2)
C4—C3—H3A	109.2	C10—C9—H9	119.9
C2—C3—H3B	109.2	C8—C9—H9	119.9
C4—C3—H3B	109.2	C9—C10—C11	120.8 (3)
H3A—C3—H3B	107.9	C9—C10—H10	119.6
C3—C4—C7	112.3 (3)	C11—C10—H10	119.6
C3—C4—C5	109.4 (2)	C12—C11—C10	119.2 (3)
C7—C4—C5	110.9 (2)	C12—C11—H11	120.4
C3—C4—H4	108.0	C10—C11—H11	120.4
C7—C4—H4	108.0	C11—C12—C13	120.8 (2)
C5—C4—H4	108.0	C11—C12—H12	119.6
C6—C5—C4	113.3 (2)	C13—C12—H12	119.6
C6—C5—H5A	108.9	C12—C13—C8	119.5 (3)
C4—C5—H5A	108.9	C12—C13—H13	120.3
C6—C5—H5B	108.9	C8—C13—H13	120.3
C4—C5—H5B	108.9
C2—N2—C1—N1	−174.0 (2)	C1—N2—C6—C5	105.0 (3)
C6—N2—C1—N1	23.7 (3)	C2—N2—C6—C5	−58.9 (3)
C2—N2—C1—S1	3.8 (3)	C4—C5—C6—N2	53.6 (3)
C6—N2—C1—S1	−158.5 (2)	C1—N1—C8—C9	45.6 (3)
C8—N1—C1—N2	−165.4 (2)	C1—N1—C8—C13	−138.4 (3)
C8—N1—C1—S1	16.8 (3)	C13—C8—C9—C10	0.4 (4)
C1—N2—C2—C3	−103.0 (3)	N1—C8—C9—C10	176.4 (2)
C6—N2—C2—C3	61.3 (3)	C8—C9—C10—C11	−1.5 (4)
N2—C2—C3—C4	−58.1 (3)	C9—C10—C11—C12	1.4 (5)
C2—C3—C4—C7	175.9 (2)	C10—C11—C12—C13	−0.2 (4)
C2—C3—C4—C5	52.2 (3)	C11—C12—C13—C8	−0.8 (4)
C3—C4—C5—C6	−50.4 (3)	C9—C8—C13—C12	0.7 (4)
C7—C4—C5—C6	−174.9 (3)	N1—C8—C13—C12	−175.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1^i	0.83 (2)	2.60 (2)	3.362 (3)	155 (3)

Symmetry code: (i) −x+1/2, y, z−1/2.