N-(2-Furylcarbon­yl)piperidine-1-carbo­thio­amide

Duque, J.; Estévez-Hernández, O.; Mascarenhas, Y.; Ellena, J.; Corrêa, R.S.

doi:10.1107/S1600536808020977

organic compounds

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Volume 64| Part 8| August 2008| Page o1457

doi:10.1107/S1600536808020977

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N-(2-Furylcarbonyl)piperidine-1-carbothioamide

J. Duque,^a ^* O. Estévez-Hernández,^a Yvonne Mascarenhas,^b J. Ellena ^b and Rodrigo S. Corrêa ^b

^aDepartment of Structure Analysis, Institute of Materials, University of Havana, Cuba, and ^bGrupo de Cristalografía, Instituto de Física de São Carlos, Universidade de São Paulo, São Carlos, Brazil
^*Correspondence e-mail: duque@imre.oc.uh.cu

(Received 9 May 2008; accepted 7 July 2008; online 12 July 2008)

The title compound, C₁₁H₁₄N₂O₂S, was synthesized from furoyl isothiocyanate and piperidine in dry acetone. The thiourea group is in the thioamide form. The thiourea group makes a dihedral angle of 53.9 (1)° with the furan carbonyl group. In the crystal structure, molecules are linked by intermolecular N—H⋯O hydrogen bonds, forming one-dimensional chains along the c axis. An intramolecular N—H⋯O hydrogen bond is also present.

Related literature

For general background, see: Aly et al. (2007 ); Estévez-Hernández et al. (2006 , 2007 ); Koch (2001 ). For related structures, see: Dago et al. (1987 ); Plutin et al. (2000 ); Pérez et al. (2008 ); Duque et al. (2008 ). For the synthesis, see: Otazo-Sánchez et al. (2001 ).

Experimental

Crystal data

C₁₁H₁₄N₂O₂S
M_r = 238.3
Orthorhombic, P b c a
a = 31.6377 (15) Å
b = 8.6787 (4) Å
c = 8.5308 (3) Å
V = 2342.34 (18) Å³
Z = 8
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 294 K
0.15 × 0.13 × 0.06 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
4308 measured reflections
2387 independent reflections
1550 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.205
S = 1.10
2387 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.86	2.38	2.756 (3)	107
N1—H1⋯O1ⁱ	0.86	2.18	2.994 (4)	157
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: COLLECT (Enraf–Nonius, 2000 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808020977/ww2121sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808020977/ww2121Isup2.hkl

checkCIF report

Comment top

Thiourea and its derivatives form a versatile family of ligands that are suitable to form complexes with ions of transition and post-transition metal through the S atom (Koch et al., 2001; Aly et al., 2007). The title compound shows outstanding complexation properties (Estévez-Hernández et al., 2006). The potential applications of this class of ligands as ionophores or chemical modifiers in amperometric sensors (Estévez-Hernández et al., 2007) have stimulated our interest in their crystal structure. The title compound crystallizes in the thioamide form. The main bond lengths and torsion angles are within the ranges obtained for similar compounds (Dago et al., 1987; Plutin et al., 2000). All the C–N bonds of thiourea fragment C1–N1, C2–N1 and C2–N2 (Table1) are in the range 1.415 (4)–1.327 (4) Å, intermediate between those expected for single and double C–N bonds (1.47 and 1.27 Å respectively). These results can be explained by the existence of resonance in this part of molecule (Pérez et al., 2008; Duque et al., 2008). The central thiourea fragment (N1—C2—S1—N2) makes dihedral angle of 53.9 (1)° with the furan carbonyl (C1—C3—C4—C5—C6—O2) group. The trans-cis geometry in the thiourea moiety is stabilized by the N1–H1···O2 intramolecular hydrogen bond (Fig.1 and Table 2). In the crystal structure symmetry related molecules are linked by N1–H1···O1 intermolecular hydrogen bonds to form one-dimensional chains along c axis (Figs. 2 and Table 2).

Related literature top

For general background, see: Aly et al. (2007); Estévez-Hernández et al. (2006, 2007); Koch (2001). For related structures, see: Dago et al. (1987); Plutin et al. (2000); Pérez et al. (2008); Duque et al. (2008). For the synthesis, see: Otazo-Sánchez et al. (2001).

Experimental top

The title compound was synthesized according to a previous report (Otazo-Sánchez et al., 2001), by converting furoyl choride into furoyl isothiocyanate and then condensing with piperidine. The resulting solid product was crystallized from ethanol yielding X-ray quality single crystals (m.p 120–121°C). Elemental analysis (%) for C₁₁H₁₄N₂O₂S calculated: C 55.46, H 5.88, N 11.76, S 13.45; found: C 55.23, H 5.90, N 11.63, S 13.32.

Computing details top

Data collection: COLLECT (Enraf–Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. View of the molecular structure of the title compound (50% probability displacement ellipsoids). Intramolecular Hydrogen bonds (N1–H1···O2) are shown as dashed lines.
	Fig. 2. View of the crystal packing of the title compound projected down the b axis. Intermolecular hydrogen bonds (N1–H1···O1) form one-dimensional chains along c axis. The hydrogen bonds are shown as dotted lines.

N-(2-Furylcarbonyl)piperidine-1-carbothioamide top

Crystal data top

C₁₁H₁₄N₂O₂S	F(000) = 1008
M_r = 238.3	D_x = 1.352 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2684 reflections
a = 31.6377 (15) Å	θ = 2.9–26.4°
b = 8.6787 (4) Å	µ = 0.26 mm⁻¹
c = 8.5308 (3) Å	T = 294 K
V = 2342.34 (18) Å³	Prism, colourless
Z = 8	0.15 × 0.13 × 0.06 mm

Data collection top

Nonius KappaCCD diffractometer	R_int = 0.039
CCD rotation images, thick slices scans	θ_max = 26.4°, θ_min = 3.4°
4308 measured reflections	h = −39→39
2387 independent reflections	k = −10→10
1550 reflections with I > 2σ(I)	l = −10→10

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.067	w = 1/[σ²(F_o²) + (0.1017P)² + 1.0533P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.205	(Δ/σ)_max < 0.001
S = 1.11	Δρ_max = 0.35 e Å⁻³
2387 reflections	Δρ_min = −0.35 e Å⁻³
145 parameters

Crystal data top

C₁₁H₁₄N₂O₂S	V = 2342.34 (18) Å³
M_r = 238.3	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 31.6377 (15) Å	µ = 0.26 mm⁻¹
b = 8.6787 (4) Å	T = 294 K
c = 8.5308 (3) Å	0.15 × 0.13 × 0.06 mm

Data collection top

Nonius KappaCCD diffractometer	1550 reflections with I > 2σ(I)
4308 measured reflections	R_int = 0.039
2387 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.067	0 restraints
wR(F²) = 0.205	H-atom parameters constrained
S = 1.11	Δρ_max = 0.35 e Å⁻³
2387 reflections	Δρ_min = −0.35 e Å⁻³
145 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.05964 (9)	0.3587 (4)	0.2251 (4)	0.0455 (7)
C2	0.13205 (9)	0.2817 (4)	0.2882 (3)	0.0456 (8)
C3	0.01610 (9)	0.3667 (3)	0.2812 (3)	0.0442 (7)
C4	−0.01794 (10)	0.4368 (4)	0.2179 (4)	0.0561 (9)
H4	−0.0191	0.4904	0.1237	0.067*
C5	−0.05161 (11)	0.4118 (4)	0.3246 (5)	0.0678 (11)
H5	−0.0792	0.4468	0.314	0.081*
C6	−0.03631 (12)	0.3293 (5)	0.4421 (5)	0.0776 (12)
H6	−0.0521	0.2957	0.5275	0.093*
C7	0.13358 (12)	0.5686 (4)	0.2859 (5)	0.0627 (10)
H7A	0.1051	0.5591	0.3268	0.075*
H7B	0.1321	0.6226	0.1865	0.075*
C8	0.16045 (13)	0.6593 (4)	0.3996 (5)	0.0743 (11)
H8A	0.1586	0.6123	0.5026	0.089*
H8B	0.1495	0.7633	0.4075	0.089*
C9	0.20640 (14)	0.6656 (5)	0.3497 (6)	0.0890 (13)
H9A	0.209	0.7254	0.2541	0.107*
H9B	0.223	0.7157	0.4305	0.107*
C10	0.22286 (12)	0.5045 (5)	0.3226 (6)	0.0849 (13)
H10A	0.2515	0.5098	0.2827	0.102*
H10B	0.2235	0.4492	0.4213	0.102*
C11	0.19565 (11)	0.4186 (5)	0.2081 (5)	0.0703 (11)
H11A	0.197	0.4688	0.1065	0.084*
H11B	0.2062	0.3143	0.1962	0.084*
N1	0.08854 (7)	0.2942 (3)	0.3243 (3)	0.0458 (7)
H1	0.0799	0.2594	0.4131	0.055*
N2	0.15184 (8)	0.4140 (3)	0.2619 (3)	0.0527 (7)
O1	0.06909 (7)	0.4111 (3)	0.0970 (2)	0.0569 (7)
O2	0.00546 (7)	0.3001 (3)	0.4214 (3)	0.0651 (7)
S1	0.15400 (3)	0.10814 (10)	0.28587 (13)	0.0661 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0424 (16)	0.0478 (17)	0.0462 (19)	0.0006 (13)	−0.0034 (13)	−0.0070 (15)
C2	0.0397 (15)	0.056 (2)	0.0412 (17)	−0.0007 (14)	−0.0028 (13)	−0.0054 (15)
C3	0.0435 (16)	0.0484 (17)	0.0406 (16)	0.0015 (13)	−0.0001 (13)	0.0006 (14)
C4	0.0547 (19)	0.0541 (19)	0.060 (2)	0.0076 (16)	−0.0086 (16)	0.0046 (17)
C5	0.0423 (18)	0.070 (2)	0.091 (3)	0.0139 (17)	0.0037 (18)	−0.004 (2)
C6	0.050 (2)	0.092 (3)	0.090 (3)	0.018 (2)	0.023 (2)	0.017 (2)
C7	0.057 (2)	0.049 (2)	0.082 (3)	0.0016 (16)	0.0006 (18)	0.0000 (18)
C8	0.089 (3)	0.048 (2)	0.086 (3)	−0.0092 (19)	−0.006 (2)	−0.005 (2)
C9	0.082 (3)	0.074 (3)	0.111 (3)	−0.027 (2)	−0.018 (3)	0.002 (3)
C10	0.053 (2)	0.084 (3)	0.118 (4)	−0.017 (2)	−0.011 (2)	0.009 (3)
C11	0.0438 (19)	0.079 (3)	0.088 (3)	−0.0093 (18)	0.0112 (18)	−0.006 (2)
N1	0.0374 (13)	0.0569 (17)	0.0430 (14)	0.0020 (11)	0.0016 (10)	0.0006 (12)
N2	0.0419 (15)	0.0509 (16)	0.0655 (18)	−0.0043 (12)	0.0023 (12)	−0.0071 (13)
O1	0.0537 (13)	0.0760 (17)	0.0411 (13)	−0.0015 (11)	0.0017 (10)	0.0051 (11)
O2	0.0520 (13)	0.0813 (18)	0.0619 (15)	0.0160 (12)	0.0121 (11)	0.0164 (13)
S1	0.0485 (5)	0.0536 (6)	0.0962 (8)	0.0069 (4)	−0.0001 (4)	−0.0080 (5)

Geometric parameters (Å, º) top

C1—O1	1.221 (4)	C7—H7A	0.97
C1—N1	1.366 (4)	C7—H7B	0.97
C1—C3	1.460 (4)	C8—C9	1.516 (6)
C2—N2	1.327 (4)	C8—H8A	0.97
C2—N1	1.415 (4)	C8—H8B	0.97
C2—S1	1.659 (3)	C9—C10	1.510 (7)
C3—C4	1.349 (4)	C9—H9A	0.97
C3—O2	1.371 (4)	C9—H9B	0.97
C4—C5	1.418 (5)	C10—C11	1.500 (5)
C4—H4	0.93	C10—H10A	0.97
C5—C6	1.323 (5)	C10—H10B	0.97
C5—H5	0.93	C11—N2	1.461 (4)
C6—O2	1.357 (4)	C11—H11A	0.97
C6—H6	0.93	C11—H11B	0.97
C7—N2	1.475 (4)	N1—H1	0.86
C7—C8	1.511 (5)

O1—C1—N1	122.9 (3)	C9—C8—H8B	109.2
O1—C1—C3	120.4 (3)	H8A—C8—H8B	107.9
N1—C1—C3	116.6 (3)	C10—C9—C8	109.9 (3)
N2—C2—N1	115.5 (3)	C10—C9—H9A	109.7
N2—C2—S1	125.9 (2)	C8—C9—H9A	109.7
N1—C2—S1	118.6 (2)	C10—C9—H9B	109.7
C4—C3—O2	110.1 (3)	C8—C9—H9B	109.7
C4—C3—C1	130.1 (3)	H9A—C9—H9B	108.2
O2—C3—C1	119.8 (3)	C11—C10—C9	111.2 (3)
C3—C4—C5	105.9 (3)	C11—C10—H10A	109.4
C3—C4—H4	127	C9—C10—H10A	109.4
C5—C4—H4	127	C11—C10—H10B	109.4
C6—C5—C4	107.1 (3)	C9—C10—H10B	109.4
C6—C5—H5	126.5	H10A—C10—H10B	108
C4—C5—H5	126.5	N2—C11—C10	110.7 (3)
C5—C6—O2	111.0 (3)	N2—C11—H11A	109.5
C5—C6—H6	124.5	C10—C11—H11A	109.5
O2—C6—H6	124.5	N2—C11—H11B	109.5
N2—C7—C8	110.0 (3)	C10—C11—H11B	109.5
N2—C7—H7A	109.7	H11A—C11—H11B	108.1
C8—C7—H7A	109.7	C1—N1—C2	123.2 (3)
N2—C7—H7B	109.7	C1—N1—H1	118.4
C8—C7—H7B	109.7	C2—N1—H1	118.4
H7A—C7—H7B	108.2	C2—N2—C11	121.6 (3)
C7—C8—C9	112.2 (4)	C2—N2—C7	125.4 (3)
C7—C8—H8A	109.2	C11—N2—C7	113.0 (3)
C9—C8—H8A	109.2	C6—O2—C3	105.9 (3)
C7—C8—H8B	109.2

O1—C1—C3—C4	−5.9 (5)	N2—C2—N1—C1	59.9 (4)
N1—C1—C3—C4	172.5 (3)	S1—C2—N1—C1	−121.4 (3)
O1—C1—C3—O2	176.5 (3)	N1—C2—N2—C11	−173.8 (3)
N1—C1—C3—O2	−5.2 (4)	S1—C2—N2—C11	7.6 (5)
O2—C3—C4—C5	−0.2 (4)	N1—C2—N2—C7	7.8 (4)
C1—C3—C4—C5	−178.0 (3)	S1—C2—N2—C7	−170.8 (3)
C3—C4—C5—C6	−0.5 (5)	C10—C11—N2—C2	−120.6 (4)
C4—C5—C6—O2	1.0 (5)	C10—C11—N2—C7	58.1 (4)
N2—C7—C8—C9	54.0 (5)	C8—C7—N2—C2	122.3 (4)
C7—C8—C9—C10	−53.7 (5)	C8—C7—N2—C11	−56.3 (4)
C8—C9—C10—C11	54.5 (5)	C5—C6—O2—C3	−1.1 (5)
C9—C10—C11—N2	−56.8 (5)	C4—C3—O2—C6	0.8 (4)
O1—C1—N1—C2	−0.1 (5)	C1—C3—O2—C6	178.8 (3)
C3—C1—N1—C2	−178.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	2.38	2.756 (3)	107
N1—H1···O1ⁱ	0.86	2.18	2.994 (4)	157

Symmetry code: (i) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₄N₂O₂S
M_r	238.3
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	294
a, b, c (Å)	31.6377 (15), 8.6787 (4), 8.5308 (3)
V (Å³)	2342.34 (18)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.15 × 0.13 × 0.06

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4308, 2387, 1550
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.205, 1.11
No. of reflections	2387
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.35

Computer programs: COLLECT (Enraf–Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

C1—N1	1.366 (4)	C2—N1	1.415 (4)
C2—N2	1.327 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	2.38	2.756 (3)	107
N1—H1···O1ⁱ	0.86	2.18	2.994 (4)	157

Symmetry code: (i) x, −y+1/2, z+1/2.

Acknowledgements

The authors thank the Crystallography Group, São Carlos Physics Institute, USP, and acknowledge financial support from the Brazilian agency CNPq.

References

Aly, A. A., Ahmed, E. K., El-Mokadem, K. M. & Hegazy, M. E. F. (2007). J. Sulfur Chem. 28, 73–93. CrossRef CAS Google Scholar
Dago, A., Simonov, M. A., Pobedimskaya, E. A., Martin, A. & Macías, A. (1987). Kristallografiya, 32, 1024–1026. CAS Google Scholar
Duque, J., Estevez-Hernandez, O., Reguera, E., Corrêa, R. S. & Gutierrez Maria, P. (2008). Acta Cryst. E64, o1068. Web of Science CSD CrossRef IUCr Journals Google Scholar
Enraf–Nonius (2000). COLLECT. Enraf–Nonius BV, Delft, The Netherlands. Google Scholar
Estévez-Hernández, O., Naranjo-Rodríguez, I., Hidalgo-Hidalgo de Cisneros, J. L. & Reguera, E. (2007). Sens. Actuators B, 123, 488–494. Google Scholar
Estévez-Hernández, O., Otazo-Sánchez, E., Hidalgo-Hidalgo de Cisneros, J. L., Naranjo-Rodríguez, I. & Reguera, E. (2006). Spectrochim. Acta A, 64, 961–971. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Koch, K. R. (2001). Coord. Chem. Rev. 216–217, 473–488. Web of Science CrossRef CAS Google Scholar
Otazo-Sánchez, E., Pérez-Marín, L., Estévez-Hernández, O., Rojas-Lima, S. & Alonso-Chamorro, J. (2001). J. Chem. Soc. Perkin Trans. 2, pp. 2211–2218. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Pérez, H., Mascarenhas, Y., Estévez-Hernández, O., Santos, S. Jr & Duque, J. (2008). Acta Cryst. E64, o695–695. Web of Science CSD CrossRef IUCr Journals Google Scholar
Plutin, A. M., Marquez, H., Ochoa, E., Morales, M., Sosa, M., Moran, L., Rodíguez, Y., Suarez, M., Martín, N. & Seoane, C. (2000). Tetrahedron, 56, 1533–1539. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar