Crystal structure of S-(4-methyl­benz­yl) piperidine­dithio­carbamate

Abstract

The title compound, C₁₄H₁₉NS₂, crystallizes in the thione form with the presence of a C=S bond. The piperidine ring adopts a chair conformation. The dihedral angle between the essentially planar di­thio­carbamate and p-tolyl fragments is 74.46 (10)°

Related literature  

For the synthesis and related structures, see: Nabipour (2011 ▸); Kumar et al. (2013 ▸); Kotresh et al. (2012 ▸). For the various applications of di­thio­carbamates, see: Hogarth (2005 ▸).

Experimental  

Crystal data  

• C₁₄H₁₉NS₂

• M _r = 265.42

• Monoclinic,

• a = 6.3081 (4) Å

• b = 11.2191 (7) Å

• c = 19.8399 (13) Å

• β = 96.133 (5)°

• V = 1396.06 (15) ų

• Z = 4

• Mo Kα radiation

• μ = 0.36 mm⁻¹

• T = 100 K

• 0.4 × 0.2 × 0.1 mm

Data collection  

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2012 ▸) T _min = 0.666, T _max = 0.746

• 13322 measured reflections

• 3278 independent reflections

• 1866 reflections with I > 2σ(I)

• R _int = 0.105

Refinement  

• R[F ² > 2σ(F ²)] = 0.053

• wR(F ²) = 0.114

• S = 1.01

• 3278 reflections

• 155 parameters

• H-atom parameters constrained

• Δρ_max = 0.32 e Å⁻³

• Δρ_min = −0.34 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT (Bruker, 2009 ▸); data reduction: SAINT; program(s) used to solve structure: SIR2004 (Burla et al., 2007 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: pubICIF (Westrip, 2010 ▸).

Supplementary Material

CCDC reference: 975555

Additional supporting information: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

S1. Comment

Di­thio­carbamates are well known to possess various properties with a wide range of applications (Hogarth, 2005). In our attempt to modify the substituents of piperidine di­thio­carbamate we have formed the title compound. It is likely that this compound is bioactive and will be an inter­est for further research.

The C6—S2 bond is 1.664 (3) Å, which is an inter­mediate of the standard value for C═S (1.56 Å) and shorter than a C—S single bond (1.82 Å). This is attributed to a slight delocalization of negative charge over the C—N—C—S chain.

The piperidine ring shows a chair conformation with Cremer-Pople puckering parameters Q= 0.583 (3) Å, θ= 2.9 (3)°, φ= 355 (6)°. The dihedral angle between the planar di­thio­carbamate moiety S1/S2/N1/C6 and the planar p-tolyl frgament C7/C8/C9/C10/C11/C12/C13/C14 is 74.46 (10)°. The C7–S1–C6–S2 fragment adopts a cis conformation with the torsion angle of -6.6 (2)° comparable to previous literature (Kumar et al., 2013; Kotresh et al., 2012). The arrangement of the molecules in the crystal are dominated by the presence of the crystallographic 2-fold rotation axis. There are no significant pi–pi inter­actions or other specific inter­molecular inter­actions in the crystal structure.

S2. Experimental

Sodium piperidine di­thio­carbamate was pre-synthesized in accordance to the method of Nabipour (2011). Sodium piperidine di­thio­carbamate (5.5 mmol) in absolute ethanol (30 ml) was stirred continuously with dropwise addition of equimolar amounts of 4-methyl­benzyl chloride until a precipitation occurred. The precipitate (sodium chloride) was filtered off and the filtrate was reduced to half the volume and left to stand at room temperature to give colourless crystals. Yield= 63.11%, m.p.= 348.15–349.15 K. IR (KBr pellets, cm^–1): 1477 (s, ν N–CSS), 1224 (s, ν C=S) and 978 (s, ν C–S). UV–Vis in CH₃OH [λ_max/nm, with ε (L mol^–1 cm^–1)]: 277 (2.05), 255 (4.09), 245 (4.20). ¹H–NMR [DMSO–d₆]: δ (ppm) = 4.46 (s, 2H, S–CH₂–Bz); 4.22 (s, 2H, N–CH₂), 3.85 (s, 2H, N–CH₂); 7.11–7.27 (m, 4H, C₆H₄); 2.27 (s, 3H, CH₃). ¹³C–NMR [DMSO–d₆]: δ (ppm) = 193.82 (NCSS); 41.17 (S–CH₂–Bz); 52.77, 51.33 (N–CH₂); 129.49–137.03 (C aromatic); 21.18 (CH₃).

S2.1. Refinement

H-atoms were placed in calculated positions (C—H 0.93–0.97 Å) and were included in the refinement in a riding-model approximation with U_iso(H) = 1.2U_eq(C) or 1.2U_eq(C_methyl).

Figures

Fig. 1.

The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radius.

Crystal data

C14H19NS2	F(000) = 568
Mr = 265.42	Dx = 1.263 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.3081 (4) Å	Cell parameters from 883 reflections
b = 11.2191 (7) Å	θ = 3.6–20.8°
c = 19.8399 (13) Å	µ = 0.36 mm−1
β = 96.133 (5)°	T = 100 K
V = 1396.06 (15) Å3	Block, colourless
Z = 4	0.4 × 0.2 × 0.1 mm

Data collection

Bruker APEXII CCD diffractometer	3278 independent reflections
Radiation source: sealed tube	1866 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.105
Detector resolution: 8 pixels mm-1	θmax = 27.9°, θmin = 2.1°
φ and ω scans	h = −8→8
Absorption correction: multi-scan SADABS (Bruker, 2012)	k = −14→14
Tmin = 0.666, Tmax = 0.746	l = −25→25
13322 measured reflections

Refinement

Refinement on F2	Primary atom site location: iterative
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.036P)2 + 0.1195P] where P = (Fo2 + 2Fc2)/3
3278 reflections	(Δ/σ)max < 0.001
155 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.34 e Å−3

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	0.60407 (11)	0.46509 (6)	0.32887 (4)	0.0264 (2)
S2	0.40927 (14)	0.70252 (7)	0.35563 (4)	0.0347 (2)
N1	0.3416 (3)	0.5804 (2)	0.24001 (12)	0.0255 (6)
C7	0.7321 (5)	0.5087 (3)	0.41139 (15)	0.0339 (8)
H7A	0.8107	0.5824	0.4080	0.041*
H7B	0.6267	0.5204	0.4430	0.041*
C13	1.0788 (5)	0.3979 (3)	0.41109 (14)	0.0297 (7)
H13	1.1215	0.4545	0.3811	0.036*
C8	0.8810 (5)	0.4086 (2)	0.43476 (14)	0.0266 (7)
C6	0.4390 (4)	0.5890 (2)	0.30345 (14)	0.0240 (7)
C12	1.2139 (5)	0.3046 (3)	0.43127 (14)	0.0298 (7)
H12	1.3454	0.2991	0.4143	0.036*
C3	−0.0478 (5)	0.4953 (3)	0.16795 (17)	0.0382 (8)
H3A	−0.1839	0.4561	0.1702	0.046*
H3B	−0.0354	0.5148	0.1209	0.046*
C9	0.8232 (5)	0.3239 (3)	0.48066 (15)	0.0305 (7)
H9	0.6921	0.3301	0.4979	0.037*
C14	1.3055 (5)	0.1182 (3)	0.49932 (17)	0.0429 (9)
H14A	1.3890	0.0976	0.4633	0.064*
H14B	1.2243	0.0502	0.5108	0.064*
H14C	1.3983	0.1429	0.5383	0.064*
C5	0.1796 (4)	0.6661 (3)	0.21235 (15)	0.0299 (7)
H5A	0.2074	0.6898	0.1671	0.036*
H5B	0.1853	0.7368	0.2407	0.036*
C1	0.3454 (5)	0.4735 (3)	0.19726 (15)	0.0305 (7)
H1A	0.4574	0.4201	0.2160	0.037*
H1B	0.3747	0.4960	0.1520	0.037*
C2	0.1319 (5)	0.4110 (3)	0.19406 (16)	0.0345 (8)
H2A	0.1086	0.3829	0.2389	0.041*
H2B	0.1320	0.3425	0.1643	0.041*
C11	1.1563 (5)	0.2185 (3)	0.47668 (14)	0.0283 (7)
C10	0.9587 (5)	0.2306 (3)	0.50101 (14)	0.0307 (7)
H10	0.9166	0.1748	0.5316	0.037*
C4	−0.0398 (5)	0.6094 (3)	0.20983 (16)	0.0344 (8)
H4A	−0.1466	0.6648	0.1899	0.041*
H4B	−0.0716	0.5913	0.2555	0.041*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.0309 (4)	0.0220 (4)	0.0259 (4)	0.0032 (3)	0.0012 (3)	−0.0015 (3)
S2	0.0515 (5)	0.0223 (4)	0.0299 (5)	0.0053 (4)	0.0030 (4)	−0.0025 (3)
N1	0.0258 (13)	0.0230 (13)	0.0272 (14)	0.0022 (11)	0.0009 (11)	−0.0022 (11)
C7	0.0435 (19)	0.0309 (18)	0.0250 (17)	0.0050 (15)	−0.0067 (14)	−0.0050 (14)
C13	0.0354 (18)	0.0271 (17)	0.0255 (17)	−0.0063 (14)	−0.0015 (14)	0.0020 (13)
C8	0.0323 (17)	0.0218 (16)	0.0247 (16)	−0.0006 (14)	−0.0019 (13)	−0.0047 (13)
C6	0.0267 (16)	0.0218 (15)	0.0243 (16)	−0.0014 (13)	0.0066 (13)	0.0020 (12)
C12	0.0280 (16)	0.0341 (18)	0.0271 (17)	−0.0025 (15)	0.0023 (13)	−0.0009 (14)
C3	0.0307 (17)	0.0354 (19)	0.047 (2)	−0.0068 (14)	−0.0010 (15)	0.0049 (16)
C9	0.0315 (17)	0.0338 (18)	0.0260 (17)	−0.0003 (15)	0.0016 (13)	−0.0018 (14)
C14	0.048 (2)	0.0357 (19)	0.041 (2)	0.0072 (17)	−0.0157 (17)	−0.0013 (16)
C5	0.0329 (17)	0.0254 (16)	0.0306 (18)	0.0045 (14)	−0.0009 (14)	0.0040 (14)
C1	0.0332 (17)	0.0306 (17)	0.0264 (17)	0.0035 (15)	−0.0022 (13)	−0.0069 (14)
C2	0.0395 (19)	0.0282 (17)	0.0341 (19)	−0.0037 (15)	−0.0041 (15)	−0.0013 (14)
C11	0.0303 (17)	0.0277 (16)	0.0247 (17)	−0.0011 (14)	−0.0073 (13)	−0.0037 (13)
C10	0.0408 (19)	0.0262 (17)	0.0240 (17)	−0.0052 (15)	−0.0017 (14)	0.0056 (13)
C4	0.0304 (17)	0.0333 (18)	0.039 (2)	0.0040 (15)	0.0025 (14)	0.0084 (15)

Geometric parameters (Å, º)

S1—C7	1.814 (3)	C9—H9	0.9300
S1—C6	1.778 (3)	C9—C10	1.384 (4)
S2—C6	1.664 (3)	C14—H14A	0.9600
N1—C6	1.344 (3)	C14—H14B	0.9600
N1—C5	1.466 (3)	C14—H14C	0.9600
N1—C1	1.471 (3)	C14—C11	1.504 (4)
C7—H7A	0.9700	C5—H5A	0.9700
C7—H7B	0.9700	C5—H5B	0.9700
C7—C8	1.505 (4)	C5—C4	1.519 (4)
C13—H13	0.9300	C1—H1A	0.9700
C13—C8	1.384 (4)	C1—H1B	0.9700
C13—C12	1.382 (4)	C1—C2	1.513 (4)
C8—C9	1.392 (4)	C2—H2A	0.9700
C12—H12	0.9300	C2—H2B	0.9700
C12—C11	1.395 (4)	C11—C10	1.391 (4)
C3—H3A	0.9700	C10—H10	0.9300
C3—H3B	0.9700	C4—H4A	0.9700
C3—C2	1.523 (4)	C4—H4B	0.9700
C3—C4	1.524 (4)
C6—S1—C7	103.63 (13)	C11—C14—H14A	109.5
C6—N1—C5	122.3 (2)	C11—C14—H14B	109.5
C6—N1—C1	124.4 (2)	C11—C14—H14C	109.5
C5—N1—C1	111.9 (2)	N1—C5—H5A	109.8
S1—C7—H7A	110.5	N1—C5—H5B	109.8
S1—C7—H7B	110.5	N1—C5—C4	109.5 (2)
H7A—C7—H7B	108.7	H5A—C5—H5B	108.2
C8—C7—S1	106.24 (19)	C4—C5—H5A	109.8
C8—C7—H7A	110.5	C4—C5—H5B	109.8
C8—C7—H7B	110.5	N1—C1—H1A	109.8
C8—C13—H13	119.4	N1—C1—H1B	109.8
C12—C13—H13	119.4	N1—C1—C2	109.4 (2)
C12—C13—C8	121.2 (3)	H1A—C1—H1B	108.2
C13—C8—C7	121.1 (3)	C2—C1—H1A	109.8
C13—C8—C9	118.1 (3)	C2—C1—H1B	109.8
C9—C8—C7	120.8 (3)	C3—C2—H2A	109.5
S2—C6—S1	121.57 (17)	C3—C2—H2B	109.5
N1—C6—S1	113.9 (2)	C1—C2—C3	110.7 (2)
N1—C6—S2	124.6 (2)	C1—C2—H2A	109.5
C13—C12—H12	119.4	C1—C2—H2B	109.5
C13—C12—C11	121.1 (3)	H2A—C2—H2B	108.1
C11—C12—H12	119.4	C12—C11—C14	120.9 (3)
H3A—C3—H3B	108.1	C10—C11—C12	117.5 (3)
C2—C3—H3A	109.5	C10—C11—C14	121.6 (3)
C2—C3—H3B	109.5	C9—C10—C11	121.4 (3)
C2—C3—C4	110.8 (3)	C9—C10—H10	119.3
C4—C3—H3A	109.5	C11—C10—H10	119.3
C4—C3—H3B	109.5	C3—C4—H4A	109.6
C8—C9—H9	119.6	C3—C4—H4B	109.6
C10—C9—C8	120.7 (3)	C5—C4—C3	110.3 (3)
C10—C9—H9	119.6	C5—C4—H4A	109.6
H14A—C14—H14B	109.5	C5—C4—H4B	109.6
H14A—C14—H14C	109.5	H4A—C4—H4B	108.1
H14B—C14—H14C	109.5
S1—C7—C8—C13	79.9 (3)	C6—N1—C1—C2	104.9 (3)
S1—C7—C8—C9	−99.8 (3)	C12—C13—C8—C7	−178.5 (3)
N1—C5—C4—C3	−57.0 (3)	C12—C13—C8—C9	1.3 (4)
N1—C1—C2—C3	56.7 (3)	C12—C11—C10—C9	0.5 (4)
C7—S1—C6—S2	−6.6 (2)	C14—C11—C10—C9	179.1 (3)
C7—S1—C6—N1	174.4 (2)	C5—N1—C6—S1	172.6 (2)
C7—C8—C9—C10	178.7 (3)	C5—N1—C6—S2	−6.4 (4)
C13—C8—C9—C10	−1.1 (4)	C5—N1—C1—C2	−61.5 (3)
C13—C12—C11—C14	−179.0 (3)	C1—N1—C6—S1	7.5 (3)
C13—C12—C11—C10	−0.3 (4)	C1—N1—C6—S2	−171.5 (2)
C8—C13—C12—C11	−0.6 (4)	C1—N1—C5—C4	61.8 (3)
C8—C9—C10—C11	0.3 (4)	C2—C3—C4—C5	53.9 (3)
C6—S1—C7—C8	−178.0 (2)	C4—C3—C2—C1	−53.9 (3)
C6—N1—C5—C4	−105.1 (3)