N-Phenyl­pyrrolidine-1-carbothio­amide

Jiang, J.-H.

doi:10.1107/S1600536808040907

organic compounds

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doi:10.1107/S1600536808040907

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N-Phenylpyrrolidine-1-carbothioamide

Jin-He Jiang ^a ^*

^aDepartment of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: weifangjjh@126.com

(Received 2 December 2008; accepted 4 December 2008; online 10 December 2008)

The title compound, C₁₁H₁₄N₂S, was prepared by the reaction of 1-isothiocyanatobenzene and pyrrolidine. In the crystal structure, intermolecular N—H⋯S interactions are present.

Related literature

For the applications of thioamides, see: Toshiaki et al. (2003 ). For related structures, see: Casas et al. (2002 ); Cowley et al. (2002 );

Experimental

Crystal data

C₁₁H₁₄N₂S
M_r = 206.30
Monoclinic, P 2₁ /c
a = 11.195 (2) Å
b = 8.5694 (17) Å
c = 11.414 (2) Å
β = 108.03 (3)°
V = 1041.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 293 (2) K
0.25 × 0.20 × 0.18 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
4554 measured reflections
2393 independent reflections
2214 reflections with I > 2σ(I)
R_int = 0.018
3 standard reflections every 100 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.119
S = 1.30
2393 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯S1ⁱ	0.86	2.64	3.4359 (17)	155
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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/S1600536808040907/at2689sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808040907/at2689Isup2.hkl

checkCIF report

Comment top

Thioamides 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.

In (I) (Fig. 1), the C6—S1 bond length of 1.689 (2)Å is comparable with C—S bond [1.688 (2) Å] reported (Cowley et al., 2002). The distance of N1—C6 [1.332 (2) Å] is similar to the distance of reported [1.349 (1) Å] (Casas et al., 2002). The crystal strucure is stabilized by intermolecular C—H···S interactions.

Related literature top

For the applications of thioamides, see: Toshiaki et al. (2003). For related structures, see: Casas et al. (2002); Cowley et al. (2002);

Experimental top

A mixture of the 1-isothiocyanatobenzene (0.1 mol), and pyrrolidine (0.1 mol) was stirred in refluxing ethanol (20 mL) for 4 h to afford the title compound (0.080 mol, yield 80%). 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.

N-Phenylpyrrolidine-1-carbothioamide top

Crystal data top

C₁₁H₁₄N₂S	F(000) = 440
M_r = 206.30	D_x = 1.316 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 11.195 (2) Å	θ = 1.8–27.0°
b = 8.5694 (17) Å	µ = 0.27 mm⁻¹
c = 11.414 (2) Å	T = 293 K
β = 108.03 (3)°	Block, colourless
V = 1041.2 (4) Å³	0.25 × 0.20 × 0.18 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.018
Radiation source: fine-focus sealed tube	θ_max = 27.5°, θ_min = 1.9°
Graphite monochromator	h = −14→14
ω scans	k = −11→11
4554 measured reflections	l = −14→14
2393 independent reflections	3 standard reflections every 100 reflections
2214 reflections with I > 2σ(I)	intensity decay: none

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H-atom parameters constrained
S = 1.30	w = 1/[σ²(F_o²) + (0.0574P)² + 0.3194P] where P = (F_o² + 2F_c²)/3
2393 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

C₁₁H₁₄N₂S	V = 1041.2 (4) Å³
M_r = 206.30	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.195 (2) Å	µ = 0.27 mm⁻¹
b = 8.5694 (17) Å	T = 293 K
c = 11.414 (2) Å	0.25 × 0.20 × 0.18 mm
β = 108.03 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.018
4554 measured reflections	3 standard reflections every 100 reflections
2393 independent reflections	intensity decay: none
2214 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 1.30	Δρ_max = 0.30 e Å⁻³
2393 reflections	Δρ_min = −0.46 e Å⁻³
127 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	0.50030 (4)	0.12695 (5)	0.27663 (4)	0.01992 (15)
N2	0.34546 (13)	0.29432 (17)	0.09833 (13)	0.0162 (3)
N1	0.53176 (13)	0.23342 (19)	0.06683 (13)	0.0183 (3)
H1A	0.4979	0.2678	−0.0068	0.022*
C7	0.45718 (15)	0.2256 (2)	0.14190 (15)	0.0152 (3)
C5	0.66016 (16)	0.1894 (2)	0.10058 (16)	0.0177 (4)
C8	0.30485 (17)	0.3898 (2)	−0.01429 (16)	0.0200 (4)
H8A	0.2822	0.3248	−0.0874	0.024*
H8B	0.3704	0.4617	−0.0182	0.024*
C11	0.25255 (16)	0.2964 (2)	0.16519 (16)	0.0203 (4)
H11A	0.2806	0.3614	0.2382	0.024*
H11B	0.2364	0.1919	0.1892	0.024*
C4	0.70097 (18)	0.0997 (2)	0.01900 (18)	0.0225 (4)
H4A	0.6439	0.0646	−0.0541	0.027*
C9	0.19114 (17)	0.4771 (2)	−0.00189 (18)	0.0245 (4)
H9A	0.1312	0.4984	−0.0821	0.029*
H9B	0.2158	0.5748	0.0418	0.029*
C6	0.74613 (17)	0.2436 (2)	0.20885 (17)	0.0241 (4)
H6A	0.7196	0.3065	0.2624	0.029*
C2	0.91276 (19)	0.1125 (3)	0.1562 (2)	0.0337 (5)
H2A	0.9971	0.0854	0.1755	0.040*
C3	0.82751 (19)	0.0628 (2)	0.0475 (2)	0.0307 (5)
H3A	0.8551	0.0038	−0.0075	0.037*
C10	0.13624 (17)	0.3649 (2)	0.07178 (18)	0.0243 (4)
H10A	0.0844	0.4197	0.1124	0.029*
H10B	0.0865	0.2841	0.0193	0.029*
C1	0.87165 (18)	0.2032 (3)	0.23648 (19)	0.0309 (5)
H1B	0.9289	0.2375	0.3098	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0211 (2)	0.0247 (3)	0.0136 (2)	0.00322 (17)	0.00489 (16)	0.00532 (16)
N2	0.0159 (7)	0.0202 (7)	0.0125 (6)	0.0012 (6)	0.0045 (5)	0.0028 (5)
N1	0.0162 (7)	0.0264 (8)	0.0124 (6)	0.0025 (6)	0.0049 (5)	0.0027 (6)
C7	0.0164 (8)	0.0160 (8)	0.0127 (7)	−0.0019 (6)	0.0036 (6)	−0.0021 (6)
C5	0.0180 (8)	0.0180 (8)	0.0175 (8)	0.0006 (7)	0.0060 (7)	0.0036 (6)
C8	0.0204 (8)	0.0248 (9)	0.0150 (8)	0.0033 (7)	0.0056 (6)	0.0049 (7)
C11	0.0174 (8)	0.0270 (10)	0.0181 (8)	−0.0008 (7)	0.0078 (7)	0.0009 (7)
C4	0.0254 (9)	0.0195 (9)	0.0248 (9)	0.0001 (7)	0.0108 (7)	−0.0009 (7)
C9	0.0204 (9)	0.0264 (10)	0.0264 (9)	0.0051 (7)	0.0070 (7)	0.0076 (8)
C6	0.0223 (9)	0.0304 (10)	0.0192 (9)	−0.0014 (8)	0.0057 (7)	0.0016 (7)
C2	0.0200 (9)	0.0385 (12)	0.0436 (12)	0.0075 (8)	0.0111 (9)	0.0164 (10)
C3	0.0298 (10)	0.0266 (10)	0.0423 (12)	0.0080 (8)	0.0206 (9)	0.0029 (9)
C10	0.0176 (8)	0.0299 (10)	0.0262 (9)	0.0017 (7)	0.0078 (7)	0.0028 (8)
C1	0.0201 (9)	0.0415 (12)	0.0264 (10)	−0.0039 (8)	0.0002 (8)	0.0098 (9)

Geometric parameters (Å, º) top

S1—C7	1.6892 (17)	C4—C3	1.388 (3)
N2—C7	1.332 (2)	C4—H4A	0.9300
N2—C11	1.468 (2)	C9—C10	1.527 (3)
N2—C8	1.472 (2)	C9—H9A	0.9700
N1—C7	1.371 (2)	C9—H9B	0.9700
N1—C5	1.419 (2)	C6—C1	1.385 (3)
N1—H1A	0.8600	C6—H6A	0.9300
C5—C4	1.389 (2)	C2—C3	1.379 (3)
C5—C6	1.390 (3)	C2—C1	1.384 (3)
C8—C9	1.520 (2)	C2—H2A	0.9300
C8—H8A	0.9700	C3—H3A	0.9300
C8—H8B	0.9700	C10—H10A	0.9700
C11—C10	1.522 (3)	C10—H10B	0.9700
C11—H11A	0.9700	C1—H1B	0.9300
C11—H11B	0.9700

C7—N2—C11	123.08 (14)	C5—C4—H4A	120.2
C7—N2—C8	124.92 (14)	C8—C9—C10	103.46 (15)
C11—N2—C8	111.72 (13)	C8—C9—H9A	111.1
C7—N1—C5	125.40 (15)	C10—C9—H9A	111.1
C7—N1—H1A	117.3	C8—C9—H9B	111.1
C5—N1—H1A	117.3	C10—C9—H9B	111.1
N2—C7—N1	115.37 (15)	H9A—C9—H9B	109.0
N2—C7—S1	122.14 (13)	C1—C6—C5	119.56 (19)
N1—C7—S1	122.40 (13)	C1—C6—H6A	120.2
C4—C5—C6	119.98 (17)	C5—C6—H6A	120.2
C4—C5—N1	118.73 (16)	C3—C2—C1	119.36 (19)
C6—C5—N1	121.13 (16)	C3—C2—H2A	120.3
N2—C8—C9	103.50 (14)	C1—C2—H2A	120.3
N2—C8—H8A	111.1	C2—C3—C4	120.80 (19)
C9—C8—H8A	111.1	C2—C3—H3A	119.6
N2—C8—H8B	111.1	C4—C3—H3A	119.6
C9—C8—H8B	111.1	C11—C10—C9	103.05 (15)
H8A—C8—H8B	109.0	C11—C10—H10A	111.2
N2—C11—C10	103.34 (14)	C9—C10—H10A	111.2
N2—C11—H11A	111.1	C11—C10—H10B	111.2
C10—C11—H11A	111.1	C9—C10—H10B	111.2
N2—C11—H11B	111.1	H10A—C10—H10B	109.1
C10—C11—H11B	111.1	C2—C1—C6	120.7 (2)
H11A—C11—H11B	109.1	C2—C1—H1B	119.6
C3—C4—C5	119.51 (18)	C6—C1—H1B	119.6
C3—C4—H4A	120.2

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1ⁱ	0.86	2.64	3.4359 (17)	155

Symmetry code: (i) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₄N₂S
M_r	206.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.195 (2), 8.5694 (17), 11.414 (2)
β (°)	108.03 (3)
V (Å³)	1041.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
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	4554, 2393, 2214
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.119, 1.30
No. of reflections	2393
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.46

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
N1—H1A···S1ⁱ	0.86	2.64	3.4359 (17)	155

Symmetry code: (i) x, −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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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o52

doi:10.1107/S1600536808040907

Open

access