1-Furfuryl-3-furoylthio­urea

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

doi:10.1107/S1600536808015250

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1157

doi:10.1107/S1600536808015250

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1-Furfuryl-3-furoylthiourea

O. Estévez-Hernández,^a ^* J. Duque,^a 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: osvaldo@imre.oc.uh.cu

(Received 6 May 2008; accepted 20 May 2008; online 24 May 2008)

The title compound, C₁₁H₁₀N₂O₃S, was synthesized from furoyl isothiocyanate and furfurylamine in dry acetone. The thiourea group is in the thioamide form. The trans–cis geometry of the thiourea group is stabilized by intramolecular hydrogen bonding between the carbonyl and cis-thioamide and results in a pseudo-S(6) planar ring which makes dihedral angles of 2.5 (3) and 88.1 (2)° with the furoyl and furfuryl groups, respectively. There is also an intramolecular hydrogen bond between the furan O atom and the other thioamide H atom. In the crystal structure, molecules are linked by two intermolecular N—H⋯O hydrogen bonds, forming dimers. These dimers are stacked within the crystal structure along the [010] direction.

Related literature

For general background, see: Dhooghe et al. (2005 ); Aly et al. (2007 ); Estévez-Hernández et al. (2007 ). For related structures, see: Koch (2001 ); Yamin & Hassan (2004 ). For the synthesis, see: Otazo et al. (2001 ).

Experimental

Crystal data

C₁₁H₁₀N₂O₃S
M_r = 250.27
Triclinic, $[P \overline 1]$
a = 4.5999 (2) Å
b = 11.3792 (6) Å
c = 12.0556 (5) Å
α = 68.351 (3)°
β = 83.187 (4)°
γ = 89.367 (3)°
V = 582.01 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 294 K
0.16 × 0.15 × 0.08 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
4433 measured reflections
2427 independent reflections
1753 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.135
S = 1.05
2427 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.28 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	2.24	2.672 (3)	111
N2—H2⋯O1	0.86	2.00	2.677 (3)	135
N2—H2⋯O1ⁱ	0.86	2.43	3.091 (3)	133
Symmetry code: (i) -x, -y, -z+1.

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/S1600536808015250/xu2426sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808015250/xu2426Isup2.hkl

checkCIF report

Comment top

Thiourea and its derivatives have found extensive applications in the fields of medicine, agriculture and analytical chemistry. Thioureas are also widely used in heterocyclic syntheses (Dhooghe et al., 2005). Aroylthioureas have also been found to have applications in metal complexes and molecular electronics (Aly et al., 2007). The title compound (Fig. 1), has been successfully used as ionophore in amperometric sensors for Cd(II) (Estévez-Hernández et al., 2007).

The title compound crystallizes in the thioamide form. The furoyl and furfuryl groups are trans and cis, respectively, to the S atom across the thiourea C—N bonds (Fig. 1). The main bond lengths and torsion angles are within the ranges obtained for similar compounds (Koch et al., 2001). The C2—S1 and C1—O1 bonds show a typical double bond character with bond lengths (Table 1) of 1.661 (2) and 1.227 (2) Å respectively, closely related to other thiourea derivatives (Yamin & Hassan, 2004). However, all the C—N bonds (Table 1) of thiourea fragment C1—N1, C2—N1 and C2—N2 are in the range 1.392 (3)–1,327 (3) Å, intermediate between those expected for single and double C—N bonds (1.47 and 1.27 Å respectively). It is deduced that this thiourea moiety makes up a multi-electron conjugated π bond. The central thiourea fragment makes torsion angles of 2.5 (3)° and 88.1 (2)° with the furan carbonyl ring (O2-C3-C1-N1) and the furfuryl group (C2-N2-C7-C8), respectively. The trans-cis geometry in the thiourea moiety is stabilized by the N2—H2···O1 intramolecular hydrogen bond (Fig.1 and Table 2). An additional intramolecular hydrogen bond N1—H1···O2 is observed. In the crystal structure symmetry related molecules are linked by two N2—H2···O1 intermolecular hydrogen bonds to form dimers along the [010] direction (Fig. 2 and Table 2).

Related literature top

For general background, see: Dhooghe et al. (2005); Aly et al. (2007); Estévez-Hernández et al. (2007). For related structures, see: Koch (2001); Yamin & Hassan (2004). For the synthesis, see: Otazo et al. (2001).

Experimental top

The title compound was synthesized according to a previous report (Otazo et al., 2001), by converting furoyl chloride into furoyl isothiocyanate and then condensing with furfurylamine. The resulting solid product was crystallized from ethanol yielding X-ray quality single crystals (m.p 79–80 ° C). Elemental analysis (%) for C₁₁H₁₀N₂O₃S calculated: C 52.80, H 4.00, N 11.20, S 12.80; found: C 52.83, H 4.07, N 11.21, S 12.81.

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. Molecular structure (50% probability displacement ellipsoids). Intramolecular hydrogen bonds are shown as dashed lines.
	Fig. 2. View of the crystal packing of the title compound. Intermolecular hydrogen bonds are shown as dashed lines.

1-Furfuryl-3-furoylthiourea top

Crystal data top

C₁₁H₁₀N₂O₃S	Z = 2
M_r = 250.27	F(000) = 260
Triclinic, P1	D_x = 1.428 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.5999 (2) Å	Cell parameters from 2356 reflections
b = 11.3792 (6) Å	θ = 2.9–26.7°
c = 12.0556 (5) Å	µ = 0.28 mm⁻¹
α = 68.351 (3)°	T = 294 K
β = 83.187 (4)°	Prism, colourless
γ = 89.367 (3)°	0.16 × 0.15 × 0.08 mm
V = 582.01 (5) Å³

Data collection top

Nonius KappaCCD diffractometer	R_int = 0.028
ω scans	θ_max = 26.6°, θ_min = 3.1°
4433 measured reflections	h = −5→5
2427 independent reflections	k = −14→14
1753 reflections with I > 2σ(I)	l = −15→13

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.048	w = 1/[σ²(F_o²) + (0.0698P)² + 0.1199P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.135	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.32 e Å⁻³
2427 reflections	Δρ_min = −0.28 e Å⁻³
154 parameters

Crystal data top

C₁₁H₁₀N₂O₃S	γ = 89.367 (3)°
M_r = 250.27	V = 582.01 (5) Å³
Triclinic, P1	Z = 2
a = 4.5999 (2) Å	Mo Kα radiation
b = 11.3792 (6) Å	µ = 0.28 mm⁻¹
c = 12.0556 (5) Å	T = 294 K
α = 68.351 (3)°	0.16 × 0.15 × 0.08 mm
β = 83.187 (4)°

Data collection top

Nonius KappaCCD diffractometer	1753 reflections with I > 2σ(I)
4433 measured reflections	R_int = 0.028
2427 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.135	H-atom parameters constrained
S = 1.05	Δρ_max = 0.32 e Å⁻³
2427 reflections	Δρ_min = −0.28 e Å⁻³
154 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
S1	−0.16463 (15)	0.45844 (5)	0.35901 (6)	0.0578 (2)
O1	0.1719 (4)	0.07028 (14)	0.56626 (15)	0.0540 (4)
O2	0.4479 (4)	0.28509 (15)	0.68097 (15)	0.0565 (4)
N2	−0.1523 (4)	0.21274 (16)	0.39894 (15)	0.0417 (4)
H2	−0.0911	0.139	0.4381	0.05*
O3	0.0164 (5)	0.1731 (2)	0.16872 (17)	0.0793 (6)
N1	0.1109 (4)	0.28290 (16)	0.51574 (15)	0.0421 (4)
H1	0.1601	0.3461	0.5332	0.05*
C8	−0.1860 (5)	0.2555 (2)	0.1856 (2)	0.0476 (5)
C7	−0.3440 (5)	0.2252 (2)	0.30733 (19)	0.0461 (5)
H7A	−0.4809	0.2911	0.3054	0.055*
H7B	−0.4567	0.1465	0.3299	0.055*
C3	0.3974 (5)	0.17197 (19)	0.67285 (18)	0.0415 (5)
C1	0.2185 (5)	0.16912 (19)	0.58107 (18)	0.0411 (5)
C2	−0.0679 (5)	0.30996 (19)	0.42464 (18)	0.0396 (5)
C4	0.5302 (6)	0.0818 (2)	0.7549 (2)	0.0606 (7)
H4	0.5303	−0.004	0.7676	0.073*
C9	−0.2028 (7)	0.3500 (3)	0.0816 (3)	0.0771 (9)
H9	−0.3219	0.4193	0.068	0.092*
C6	0.6146 (6)	0.2632 (3)	0.7713 (2)	0.0611 (7)
H6	0.6806	0.325	0.7966	0.073*
C5	0.6702 (6)	0.1424 (3)	0.8184 (2)	0.0607 (7)
H5	0.7805	0.1043	0.8814	0.073*
C10	0.0005 (8)	0.3236 (4)	−0.0059 (3)	0.0850 (10)
H10	0.0366	0.3725	−0.0875	0.102*
C11	0.1238 (8)	0.2192 (4)	0.0502 (3)	0.0893 (10)
H11	0.2657	0.1811	0.0144	0.107*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0793 (5)	0.0362 (3)	0.0594 (4)	0.0082 (3)	−0.0299 (3)	−0.0131 (3)
O1	0.0709 (11)	0.0387 (8)	0.0580 (10)	0.0093 (7)	−0.0252 (8)	−0.0195 (7)
O2	0.0688 (11)	0.0463 (9)	0.0608 (10)	0.0043 (8)	−0.0235 (8)	−0.0225 (8)
N2	0.0499 (10)	0.0363 (9)	0.0390 (9)	0.0019 (7)	−0.0114 (8)	−0.0122 (7)
O3	0.0938 (15)	0.0759 (13)	0.0589 (12)	0.0162 (11)	0.0080 (10)	−0.0197 (10)
N1	0.0512 (10)	0.0335 (8)	0.0426 (9)	0.0010 (7)	−0.0137 (8)	−0.0128 (7)
C8	0.0536 (13)	0.0444 (12)	0.0467 (12)	−0.0013 (10)	−0.0165 (10)	−0.0158 (10)
C7	0.0458 (12)	0.0479 (12)	0.0472 (12)	0.0008 (9)	−0.0131 (10)	−0.0185 (10)
C3	0.0437 (11)	0.0406 (11)	0.0420 (11)	0.0019 (9)	−0.0077 (9)	−0.0167 (9)
C1	0.0428 (11)	0.0400 (11)	0.0384 (11)	0.0012 (9)	−0.0034 (9)	−0.0125 (9)
C2	0.0413 (11)	0.0399 (11)	0.0350 (10)	0.0013 (9)	−0.0052 (8)	−0.0107 (9)
C4	0.0782 (17)	0.0469 (13)	0.0612 (15)	0.0147 (12)	−0.0309 (13)	−0.0189 (11)
C9	0.098 (2)	0.0648 (17)	0.0581 (17)	−0.0002 (16)	−0.0300 (16)	−0.0041 (14)
C6	0.0649 (16)	0.0689 (17)	0.0599 (15)	−0.0010 (13)	−0.0212 (13)	−0.0317 (13)
C5	0.0655 (16)	0.0704 (17)	0.0512 (14)	0.0123 (13)	−0.0272 (12)	−0.0229 (12)
C10	0.102 (2)	0.106 (3)	0.0390 (15)	−0.034 (2)	−0.0080 (15)	−0.0166 (16)
C11	0.108 (3)	0.098 (3)	0.0561 (19)	−0.010 (2)	0.0174 (18)	−0.0309 (19)

Geometric parameters (Å, º) top

S1—C2	1.661 (2)	C7—H7A	0.97
O1—C1	1.227 (2)	C7—H7B	0.97
O2—C3	1.351 (3)	C3—C4	1.336 (3)
O2—C6	1.353 (3)	C3—C1	1.465 (3)
N2—C2	1.327 (3)	C4—C5	1.412 (4)
N2—C7	1.460 (3)	C4—H4	0.93
N2—H2	0.86	C9—C10	1.439 (5)
O3—C11	1.359 (3)	C9—H9	0.93
O3—C8	1.366 (3)	C6—C5	1.314 (4)
N1—C1	1.367 (3)	C6—H6	0.93
N1—C2	1.392 (3)	C5—H5	0.93
N1—H1	0.86	C10—C11	1.294 (5)
C8—C9	1.327 (3)	C10—H10	0.93
C8—C7	1.476 (3)	C11—H11	0.93

C3—O2—C6	106.57 (19)	N1—C1—C3	115.07 (18)
C2—N2—C7	123.03 (18)	N2—C2—N1	116.40 (17)
C2—N2—H2	118.5	N2—C2—S1	125.21 (16)
C7—N2—H2	118.5	N1—C2—S1	118.38 (15)
C11—O3—C8	107.1 (2)	C3—C4—C5	106.4 (2)
C1—N1—C2	128.53 (18)	C3—C4—H4	126.8
C1—N1—H1	115.7	C5—C4—H4	126.8
C2—N1—H1	115.7	C8—C9—C10	106.1 (3)
C9—C8—O3	109.2 (2)	C8—C9—H9	126.9
C9—C8—C7	132.7 (3)	C10—C9—H9	126.9
O3—C8—C7	118.09 (19)	C5—C6—O2	110.6 (2)
N2—C7—C8	113.74 (18)	C5—C6—H6	124.7
N2—C7—H7A	108.8	O2—C6—H6	124.7
C8—C7—H7A	108.8	C6—C5—C4	106.7 (2)
N2—C7—H7B	108.8	C6—C5—H5	126.6
C8—C7—H7B	108.8	C4—C5—H5	126.6
H7A—C7—H7B	107.7	C11—C10—C9	107.2 (3)
C4—C3—O2	109.73 (19)	C11—C10—H10	126.4
C4—C3—C1	132.6 (2)	C9—C10—H10	126.4
O2—C3—C1	117.69 (18)	C10—C11—O3	110.3 (3)
O1—C1—N1	123.86 (19)	C10—C11—H11	124.8
O1—C1—C3	121.08 (19)	O3—C11—H11	124.8

C11—O3—C8—C9	−0.4 (3)	C7—N2—C2—S1	0.2 (3)
C11—O3—C8—C7	178.2 (2)	C1—N1—C2—N2	1.8 (3)
C2—N2—C7—C8	88.1 (2)	C1—N1—C2—S1	−179.47 (17)
C9—C8—C7—N2	−122.7 (3)	O2—C3—C4—C5	0.4 (3)
O3—C8—C7—N2	59.2 (3)	C1—C3—C4—C5	−179.9 (2)
C6—O2—C3—C4	−0.5 (3)	O3—C8—C9—C10	0.7 (3)
C6—O2—C3—C1	179.72 (19)	C7—C8—C9—C10	−177.6 (2)
C2—N1—C1—O1	0.9 (4)	C3—O2—C6—C5	0.4 (3)
C2—N1—C1—C3	−178.86 (19)	O2—C6—C5—C4	−0.2 (3)
C4—C3—C1—O1	−2.1 (4)	C3—C4—C5—C6	−0.1 (3)
O2—C3—C1—O1	177.7 (2)	C8—C9—C10—C11	−0.7 (3)
C4—C3—C1—N1	177.7 (2)	C9—C10—C11—O3	0.5 (4)
O2—C3—C1—N1	−2.5 (3)	C8—O3—C11—C10	−0.1 (4)
C7—N2—C2—N1	178.88 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	2.24	2.672 (3)	111
N2—H2···O1	0.86	2.00	2.677 (3)	135
N2—H2···O1ⁱ	0.86	2.43	3.091 (3)	133

Symmetry code: (i) −x, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₀N₂O₃S
M_r	250.27
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	4.5999 (2), 11.3792 (6), 12.0556 (5)
α, β, γ (°)	68.351 (3), 83.187 (4), 89.367 (3)
V (Å³)	582.01 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.16 × 0.15 × 0.08

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4433, 2427, 1753
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.630

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.135, 1.05
No. of reflections	2427
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.28

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

S1—C2	1.661 (2)	N2—C7	1.460 (3)
O1—C1	1.227 (2)	N1—C1	1.367 (3)
N2—C2	1.327 (3)	N1—C2	1.392 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	2.24	2.672 (3)	111
N2—H2···O1	0.86	2.00	2.677 (3)	135
N2—H2···O1ⁱ	0.86	2.43	3.091 (3)	133

Symmetry code: (i) −x, −y, −z+1.

Acknowledgements

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

References

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