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

Abstract

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,

• a = 31.6377 (15) Å

• b = 8.6787 (4) Å

• c = 8.5308 (3) Å

• V = 2342.34 (18) ų

• 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[F ² > 2σ(F ²)] = 0.067

• wR(F ²) = 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

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 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

All H atoms were refined with U_iso(H)=1.2U_eq(C/N).

Figures

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.

Crystal data

C11H14N2O2S1	F000 = 1008
Mr = 238.3	Dx = 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 = 2.9–26.4º
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

Nonius KappaCCD diffractometer	Rint = 0.039
CCD rotation images, thick slices scans	θmax = 26.4º
Absorption correction: none	θmin = 3.4º
4308 measured reflections	h = −39→39
2387 independent reflections	k = −10→10
1550 reflections with I > 2σ(I)	l = −10→10

Refinement

Refinement on F2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.1017P)2 + 1.0533P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.067	(Δ/σ)max < 0.001
wR(F2) = 0.205	Δρmax = 0.35 e Å−3
S = 1.11	Δρmin = −0.35 e Å−3
2387 reflections	Extinction correction: none
145 parameters

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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 codes: (i) x, −y+1/2, z+1/2.