1-(3-Cyano­phen­yl)-3-(2-furo­yl)thio­urea

Theodoro, J.E.; Mascarenhas, Y.; Ellena, J.; Estévez-Hernández, O.; Duque, J.

doi:10.1107/S1600536808016012

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1193

doi:10.1107/S1600536808016012

Open

access

1-(3-Cyanophenyl)-3-(2-furoyl)thiourea

Jahyr E. Theodoro,^a Yvonne Mascarenhas,^b Javier Ellena,^a Osvaldo Estévez-Hernández ^c and Julio Duque ^c ^*

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

(Received 16 May 2008; accepted 27 May 2008; online 7 June 2008)

The title compound, C₁₃H₉N₃O₂S, was synthesized from furoyl isothiocyanate and 3-aminobenzonitrile in dry acetone. The thiourea group is in the thioamide form. The thiourea fragment makes dihedral angles of 3.91 (16) and 37.83 (12)° with the ketofuran group and the benzene ring, respectively. The molecular geometry is stabilized by N—H⋯O hydrogen bonds. In the crystal structure, centrosymmetrically related molecules are linked by two intermolecular N—H⋯S hydrogen bonds to form dimers.

Related literature

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

Experimental

Crystal data

C₁₃H₉N₃O₂S
M_r = 271.29
Monoclinic, P 2₁ /n
a = 16.7375 (5) Å
b = 3.8789 (1) Å
c = 19.6739 (5) Å
β = 96.956 (1)°
V = 1267.89 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 294 K
0.16 × 0.04 × 0.03 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
4807 measured reflections
2684 independent reflections
1908 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.070
wR(F²) = 0.208
S = 1.08
2684 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.34 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	2.28	2.701 (5)	110
N1—H1⋯S1ⁱ	0.86	2.80	3.629 (4)	163
N2—H2⋯O1	0.86	1.90	2.622 (4)	141
Symmetry code: (i) -x, -y+1, -z.

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/S1600536808016012/rz2219sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808016012/rz2219Isup2.hkl

checkCIF report

Comment top

The importance of aroylthioureas is found largely in heterocyclic syntheses and many of these substrates have interesting biological activities. Aroylthioureas have also been found to have applications in metal complexes and molecular electronics (Aly et al., 2007). Structural determinations of this kind of derivatives shed more light on the chemistry of aroylthiourea compounds and their wide variety of applications. The title compound (Fig. 1) is another example of our newly synthesized furoylthiourea derivatives.

The title compound crystallizes in the thioamide form. The bond lengths are within the ranges observed for similar compounds (Koch, 2001). The C2—S1 and C1—O1 bonds (Table 1) both show the expected double-bond character. The short values of the C2—N1 (1.347 (5) Å), C2—N2 (1.348 (5) Å) and C1—N1 (1.368 (5) Å) bonds indicate partial double bond character. These results can be explained by the existence of resonance in this part of the molecule. The furan carbonyl group is nearly coplanar with the plane of the thiourea fragment (dihedral angle 3.39(16°), whereas the benzene ring is inclined by 37.83 (12)°. The geometry in the thiourea group is stabilized by the N2—H2···O1 and N1—H1···O2 intramolecular hydrogen bonds (Fig. 1 and Table 2). The crystal structure is stabilized by two intermolecular N1—H1···S1 hydrogen bonds (Fig. 2 and Table 2) between centrosymmetrically related molecules forming dimers stacked along the [010] direction.

Related literature top

For general background, see: Aly et al. (2007); Koch (2001). For related structures, see: Dago et al. (1987); Otazo-Sánchez et al. (2001); Pérez et al. (2008); Duque et al. (2008). For 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 chloride into furoyl isothiocyanate and then condensing with 3-aminobenzonitrile. The resulting solid product was crystallized from ethanol yielding X-ray quality single crystals (m.p 148–149 °C). Elemental analysis (%) for C₁₃H₉N₃O₂S calculated: C 57.56, H 3.32, N 15.50, S 11.81; found: C 57.77, H 3.34, N 15.79, S 11.73.

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 molecule (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-(3-Cyanophenyl)-3-(2-furoyl)thiourea top

Crystal data top

C₁₃H₉N₃O₂S	F(000) = 560
M_r = 271.29	D_x = 1.421 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3051 reflections
a = 16.7375 (5) Å	θ = 2.9–26.7°
b = 3.8789 (1) Å	µ = 0.26 mm⁻¹
c = 19.6739 (5) Å	T = 294 K
β = 96.956 (1)°	Prism, colourless
V = 1267.89 (6) Å³	0.16 × 0.04 × 0.03 mm
Z = 4

Data collection top

Enraf–Nonius KappaCCD diffractometer	R_int = 0.040
CCD rotation images, thick slices scans	θ_max = 26.9°, θ_min = 3.9°
4807 measured reflections	h = −20→21
2684 independent reflections	k = −4→4
1908 reflections with I > 2σ(I)	l = −25→24

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.071	w = 1/[σ²(F_o²) + (0.0641P)² + 3.4802P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.208	(Δ/σ)_max < 0.001
S = 1.08	Δρ_max = 0.51 e Å⁻³
2684 reflections	Δρ_min = −0.34 e Å⁻³
172 parameters

Crystal data top

C₁₃H₉N₃O₂S	V = 1267.89 (6) Å³
M_r = 271.29	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 16.7375 (5) Å	µ = 0.26 mm⁻¹
b = 3.8789 (1) Å	T = 294 K
c = 19.6739 (5) Å	0.16 × 0.04 × 0.03 mm
β = 96.956 (1)°

Data collection top

Enraf–Nonius KappaCCD diffractometer	1908 reflections with I > 2σ(I)
4807 measured reflections	R_int = 0.040
2684 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.071	0 restraints
wR(F²) = 0.208	H-atom parameters constrained
S = 1.08	Δρ_max = 0.51 e Å⁻³
2684 reflections	Δρ_min = −0.34 e Å⁻³
172 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	0.10993 (6)	0.7197 (3)	−0.00840 (5)	0.0465 (3)
O1	0.08926 (19)	0.9883 (11)	0.21366 (15)	0.0699 (11)
C13	0.3735 (3)	1.3099 (15)	−0.0369 (3)	0.0617 (13)
N3	0.3872 (3)	1.4227 (17)	−0.0884 (3)	0.0909 (17)
N1	0.0452 (2)	0.7949 (10)	0.10538 (16)	0.0457 (9)
H1	0.0031	0.7186	0.0805	0.055*
O2	−0.10121 (19)	0.6665 (10)	0.14431 (15)	0.0643 (10)
N2	0.17909 (19)	0.9396 (11)	0.11374 (17)	0.0482 (9)
H2	0.1712	0.991	0.1549	0.058*
C7	0.2586 (2)	0.9846 (11)	0.0976 (2)	0.0415 (9)
C5	−0.1517 (3)	0.7102 (15)	0.2424 (3)	0.0676 (15)
H5	−0.1872	0.6986	0.2752	0.081*
C2	0.1143 (2)	0.8261 (11)	0.07249 (19)	0.0398 (9)
C9	0.3556 (2)	1.1694 (12)	0.0263 (2)	0.0474 (10)
C8	0.2756 (2)	1.1209 (12)	0.0366 (2)	0.0456 (10)
H8	0.2342	1.1798	0.0026	0.055*
C3	−0.0430 (2)	0.7960 (12)	0.1925 (2)	0.0471 (10)
C10	0.4180 (3)	1.0819 (14)	0.0767 (2)	0.0571 (12)
H10	0.4714	1.1093	0.069	0.068*
C1	0.0355 (3)	0.8694 (13)	0.1719 (2)	0.0495 (11)
C11	0.3993 (3)	0.9541 (15)	0.1381 (3)	0.0633 (14)
H11	0.4403	0.9026	0.1729	0.076*
C4	−0.0724 (3)	0.8274 (14)	0.2531 (2)	0.0581 (13)
H4	−0.0452	0.9105	0.2938	0.07*
C6	−0.1676 (3)	0.6183 (17)	0.1772 (3)	0.0705 (15)
H6	−0.2168	0.5335	0.1569	0.085*
C12	0.3204 (3)	0.9022 (13)	0.1483 (2)	0.0535 (11)
H12	0.3084	0.8109	0.1895	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0410 (6)	0.0603 (8)	0.0382 (5)	−0.0046 (5)	0.0050 (4)	−0.0056 (5)
O1	0.0528 (19)	0.112 (3)	0.0457 (17)	−0.021 (2)	0.0093 (14)	−0.0222 (19)
C13	0.049 (3)	0.074 (4)	0.063 (3)	−0.004 (2)	0.015 (2)	0.004 (3)
N3	0.088 (4)	0.115 (5)	0.073 (3)	−0.013 (3)	0.025 (3)	0.017 (3)
N1	0.0389 (17)	0.061 (2)	0.0367 (17)	−0.0055 (17)	0.0040 (14)	−0.0029 (17)
O2	0.0536 (18)	0.096 (3)	0.0440 (16)	−0.0177 (19)	0.0072 (14)	−0.0081 (18)
N2	0.0393 (18)	0.069 (3)	0.0355 (17)	−0.0083 (18)	0.0028 (13)	−0.0001 (17)
C7	0.039 (2)	0.041 (2)	0.045 (2)	−0.0045 (18)	0.0045 (16)	0.0001 (18)
C5	0.058 (3)	0.075 (4)	0.075 (3)	0.001 (3)	0.031 (3)	−0.004 (3)
C2	0.0358 (19)	0.043 (2)	0.040 (2)	−0.0019 (17)	0.0049 (16)	0.0019 (18)
C9	0.044 (2)	0.046 (3)	0.053 (2)	−0.0032 (19)	0.0071 (18)	0.003 (2)
C8	0.039 (2)	0.052 (3)	0.044 (2)	−0.0024 (19)	0.0022 (17)	0.0050 (19)
C3	0.042 (2)	0.058 (3)	0.042 (2)	−0.004 (2)	0.0073 (17)	−0.003 (2)
C10	0.036 (2)	0.071 (3)	0.064 (3)	−0.005 (2)	0.005 (2)	0.002 (3)
C1	0.047 (2)	0.060 (3)	0.042 (2)	−0.005 (2)	0.0072 (18)	−0.001 (2)
C11	0.043 (2)	0.081 (4)	0.062 (3)	−0.001 (2)	−0.011 (2)	0.010 (3)
C4	0.059 (3)	0.073 (4)	0.045 (2)	−0.003 (3)	0.016 (2)	−0.009 (2)
C6	0.045 (3)	0.094 (4)	0.073 (3)	−0.014 (3)	0.013 (2)	0.009 (3)
C12	0.051 (2)	0.060 (3)	0.047 (2)	−0.008 (2)	−0.0041 (19)	0.006 (2)

Geometric parameters (Å, º) top

S1—C2	1.637 (4)	C5—C4	1.395 (7)
O1—C1	1.233 (5)	C5—H5	0.93
C13—N3	1.153 (6)	C9—C8	1.392 (6)
C13—C9	1.422 (6)	C9—C10	1.392 (6)
N1—C1	1.368 (5)	C8—H8	0.93
N1—C2	1.397 (5)	C3—C4	1.348 (6)
N1—H1	0.86	C3—C1	1.450 (6)
O2—C6	1.365 (6)	C10—C11	1.377 (7)
O2—C3	1.369 (5)	C10—H10	0.93
N2—C2	1.348 (5)	C11—C12	1.375 (6)
N2—C7	1.416 (5)	C11—H11	0.93
N2—H2	0.86	C4—H4	0.93
C7—C8	1.373 (6)	C6—H6	0.93
C7—C12	1.383 (6)	C12—H12	0.93
C5—C6	1.326 (7)

N3—C13—C9	179.3 (6)	C9—C8—H8	120.5
C1—N1—C2	128.7 (3)	C4—C3—O2	109.9 (4)
C1—N1—H1	115.6	C4—C3—C1	132.0 (4)
C2—N1—H1	115.6	O2—C3—C1	118.1 (4)
C6—O2—C3	105.9 (4)	C11—C10—C9	118.9 (4)
C2—N2—C7	128.0 (3)	C11—C10—H10	120.6
C2—N2—H2	116	C9—C10—H10	120.6
C7—N2—H2	116	O1—C1—N1	123.7 (4)
C8—C7—C12	120.2 (4)	O1—C1—C3	120.0 (4)
C8—C7—N2	122.9 (4)	N1—C1—C3	116.3 (4)
C12—C7—N2	116.8 (4)	C12—C11—C10	120.3 (4)
C6—C5—C4	108.0 (4)	C12—C11—H11	119.9
C6—C5—H5	126	C10—C11—H11	119.9
C4—C5—H5	126	C3—C4—C5	106.3 (4)
N2—C2—N1	113.6 (3)	C3—C4—H4	126.9
N2—C2—S1	127.3 (3)	C5—C4—H4	126.9
N1—C2—S1	119.1 (3)	C5—C6—O2	110.0 (4)
C8—C9—C10	121.1 (4)	C5—C6—H6	125
C8—C9—C13	119.1 (4)	O2—C6—H6	125
C10—C9—C13	119.8 (4)	C11—C12—C7	120.6 (4)
C7—C8—C9	118.9 (4)	C11—C12—H12	119.7
C7—C8—H8	120.5	C7—C12—H12	119.7

C2—N2—C7—C8	41.1 (7)	C2—N1—C1—C3	−177.3 (4)
C2—N2—C7—C12	−142.4 (5)	C4—C3—C1—O1	−1.2 (9)
C7—N2—C2—N1	176.9 (4)	O2—C3—C1—O1	179.5 (5)
C7—N2—C2—S1	−1.9 (7)	C4—C3—C1—N1	177.9 (5)
C1—N1—C2—N2	1.3 (7)	O2—C3—C1—N1	−1.3 (7)
C1—N1—C2—S1	−179.8 (4)	C9—C10—C11—C12	2.4 (8)
C12—C7—C8—C9	0.9 (7)	O2—C3—C4—C5	0.5 (6)
N2—C7—C8—C9	177.3 (4)	C1—C3—C4—C5	−178.8 (5)
C10—C9—C8—C7	0.1 (7)	C6—C5—C4—C3	−0.7 (7)
C13—C9—C8—C7	179.9 (5)	C4—C5—C6—O2	0.7 (7)
C6—O2—C3—C4	−0.1 (6)	C3—O2—C6—C5	−0.4 (6)
C6—O2—C3—C1	179.3 (5)	C10—C11—C12—C7	−1.5 (8)
C8—C9—C10—C11	−1.7 (8)	C8—C7—C12—C11	−0.3 (7)
C13—C9—C10—C11	178.4 (5)	N2—C7—C12—C11	−176.8 (5)
C2—N1—C1—O1	1.8 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	2.28	2.701 (5)	110
N1—H1···S1ⁱ	0.86	2.80	3.629 (4)	163
N2—H2···O1	0.86	1.90	2.622 (4)	141

Symmetry code: (i) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₃H₉N₃O₂S
M_r	271.29
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	294
a, b, c (Å)	16.7375 (5), 3.8789 (1), 19.6739 (5)
β (°)	96.956 (1)
V (Å³)	1267.89 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.16 × 0.04 × 0.03

Data collection
Diffractometer	Enraf–Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4807, 2684, 1908
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.635

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.071, 0.208, 1.08
No. of reflections	2684
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.34

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 geometric parameters (Å, º) top

S1—C2	1.637 (4)	N1—C1	1.368 (5)
O1—C1	1.233 (5)	N1—C2	1.397 (5)
C13—N3	1.153 (6)	N2—C2	1.348 (5)

C2—N2—C7—C8	41.1 (7)	O2—C3—C1—O1	179.5 (5)
C2—N2—C7—C12	−142.4 (5)	O2—C3—C1—N1	−1.3 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	2.28	2.701 (5)	110
N1—H1···S1ⁱ	0.86	2.80	3.629 (4)	163
N2—H2···O1	0.86	1.90	2.622 (4)	141

Symmetry code: (i) −x, −y+1, −z.

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., Martín, 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
Nonius (2000). COLLECT. Nonius BV, Delft, The Netherlands. 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 Jr, S. & Duque, J. (2008). Acta Cryst. E64, o695. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar