1-(2-Furo­yl)-3-(o-tol­yl)thio­urea

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

doi:10.1107/S1600536808020114

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1414

doi:10.1107/S1600536808020114

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1-(2-Furoyl)-3-(o-tolyl)thiourea

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

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

(Received 27 June 2008; accepted 1 July 2008; online 5 July 2008)

The title compound, C₁₃H₁₂N₂O₂S, was synthesized from furoyl isothiocyanate and o-toluidine in dry acetone. The thiourea group is in the thioamide form. The central thiourea fragment makes dihedral angles of 2.6 (1) and 22.4 (1)° with the ketofuran group and the benzene ring, respectively. The molecular structure is stabilized by N—H⋯O hydrogen bonds. In the crystal structure, centrosymmetrically related molecules are linked by a pair of N—H⋯S hydrogen bonds to form a dimer with an R₂²(6) ring motif.

Related literature

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

Experimental

Crystal data

C₁₃H₁₂N₂O₂S
M_r = 260.31
Monoclinic, P 2₁ /c
a = 6.0976 (1) Å
b = 16.6689 (6) Å
c = 13.1462 (4) Å
β = 108.765 (2)°
V = 1265.16 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 294 K
0.50 × 0.08 × 0.07 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: Gaussian (Coppens et al., 1965 ) T_min = 0.925, T_max = 0.983
8242 measured reflections
2408 independent reflections
1594 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.130
S = 1.02
2408 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.30 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	2.26	2.682 (3)	110
N1—H1⋯S1ⁱ	0.86	2.80	3.639 (2)	165
N2—H2⋯O1	0.86	1.92	2.649 (2)	141
Symmetry code: (i) -x, -y, -z.

Data collection: COLLECT (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/S1600536808020114/ci2623sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808020114/ci2623Isup2.hkl

checkCIF report

Comment top

Thiourea and its derivatives form a versatile family of ligands suitable to form complexes with ions of transition metals through the S atom (Aly et al., 2007). Of analytical interest is the potential application of these compounds as ionophores or chemical modifiers in potenciometric and amperometric sensors (Estévez-Hernández et al., 2007). The derived crystal structures help to understand the behaviour of these ligands as ionophores and also the complex formation with salts of the heavy metals. 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 and angles are within the ranges observed for similar compounds (Koch, 2001). The C2—S1 [1.652 (2) Å] and C1—O1 [1.221 (2) Å] bonds both show the expected double-bond character. The short values of the C2—N1 [1.400 (3) Å], C2—N2 [1.330 (3) Å] and C1—N1 [1.377 (2) 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 [O1/O2/C1/C3-C6] is nearly coplanar with the plane of the thiourea fragment [N1/N2/C2/S1, dihedral angle 2.6 (1)°], whereas the C7-C12 benzene ring is inclined by 22.4 (1)°. The trans-cis geometry in the thiourea group is stabilized by the N2—H2···O1 and N1—H1···O2 intramolecular hydrogen bonds (Fig.1 and Table 1). The crystal structure is stabilized by two intermolecular N1—H1···S1 hydrogen bonds (Fig.2 and Table 1) between centrosymmetrically related molecules forming dimers stacked along the [100] direction.

Related literature top

For general background, see: Aly et al. (2007); Koch (2001); Estévez-Hernández et al. (2007). For related structures, see: Theodoro 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 chloride into furoyl isothiocyanate and then condensing with o-toluidine. The resulting solid product was crystallized from ethanol yielding X-ray quality single crystals (m.p 387–388 K).

Computing details top

Data collection: COLLECT (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. The molecular structure of the title compound, showing 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-(2-Furoyl)-3-(o-tolyl)thiourea top

Crystal data top

C₁₃H₁₂N₂O₂S	F(000) = 544
M_r = 260.31	D_x = 1.367 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 20621 reflections
a = 6.0976 (1) Å	θ = 2.9–25.7°
b = 16.6689 (6) Å	µ = 0.25 mm⁻¹
c = 13.1462 (4) Å	T = 294 K
β = 108.765 (2)°	Needle, colourless
V = 1265.16 (6) Å³	0.50 × 0.08 × 0.07 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	1594 reflections with I > 2σ(I)
ω scans	R_int = 0.048
Absorption correction: gaussian (Coppens et al., 1965)	θ_max = 25.7°, θ_min = 2.9°
T_min = 0.925, T_max = 0.983	h = −6→7
8242 measured reflections	k = −19→20
2408 independent reflections	l = −16→16

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.046	w = 1/[σ²(F_o²) + (0.0702P)² + 0.1015P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.130	(Δ/σ)_max < 0.001
S = 1.03	Δρ_max = 0.26 e Å⁻³
2408 reflections	Δρ_min = −0.30 e Å⁻³
164 parameters

Crystal data top

C₁₃H₁₂N₂O₂S	V = 1265.16 (6) Å³
M_r = 260.31	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.0976 (1) Å	µ = 0.25 mm⁻¹
b = 16.6689 (6) Å	T = 294 K
c = 13.1462 (4) Å	0.50 × 0.08 × 0.07 mm
β = 108.765 (2)°

Data collection top

Nonius KappaCCD diffractometer	2408 independent reflections
Absorption correction: gaussian (Coppens et al., 1965)	1594 reflections with I > 2σ(I)
T_min = 0.925, T_max = 0.983	R_int = 0.048
8242 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.130	H-atom parameters constrained
S = 1.03	Δρ_max = 0.26 e Å⁻³
2408 reflections	Δρ_min = −0.30 e Å⁻³
164 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	0.22254 (12)	0.09680 (4)	0.04759 (5)	0.0800 (3)
N2	0.4198 (3)	0.09229 (10)	0.26210 (13)	0.0561 (4)
H2	0.408	0.0712	0.3198	0.067*
O2	−0.2979 (3)	−0.06394 (9)	0.17467 (12)	0.0679 (4)
O1	0.1899 (3)	0.01628 (10)	0.37313 (12)	0.0757 (5)
N1	0.0880 (3)	0.01904 (10)	0.18967 (13)	0.0578 (5)
H1	−0.0083	−0.0016	0.1328	0.069*
C7	0.6105 (3)	0.14441 (12)	0.27881 (15)	0.0528 (5)
C2	0.2552 (4)	0.07008 (12)	0.17262 (17)	0.0556 (5)
C1	0.0568 (4)	−0.00258 (13)	0.28515 (17)	0.0587 (5)
C12	0.7138 (4)	0.16151 (13)	0.20141 (17)	0.0631 (6)
H12	0.6557	0.1389	0.1333	0.076*
C3	−0.1472 (4)	−0.05056 (13)	0.27543 (17)	0.0594 (5)
C8	0.7009 (4)	0.17683 (13)	0.38190 (17)	0.0609 (6)
C9	0.8905 (4)	0.22716 (14)	0.40236 (19)	0.0728 (6)
H9	0.9524	0.2494	0.4705	0.087*
C4	−0.2232 (5)	−0.08806 (15)	0.3482 (2)	0.0774 (7)
H4	−0.1528	−0.0881	0.4224	0.093*
C10	0.9905 (4)	0.24531 (14)	0.3252 (2)	0.0737 (6)
H10	1.1166	0.2799	0.3409	0.088*
C11	0.9035 (4)	0.21225 (14)	0.2256 (2)	0.0703 (6)
H11	0.9719	0.2238	0.1734	0.084*
C13	0.5994 (4)	0.15856 (18)	0.46916 (17)	0.0835 (8)
H13A	0.671	0.1921	0.5303	0.125*
H13B	0.6264	0.1032	0.4896	0.125*
H13C	0.4357	0.1687	0.4435	0.125*
C6	−0.4688 (4)	−0.11084 (14)	0.1874 (2)	0.0769 (7)
H6	−0.5959	−0.1291	0.1316	0.092*
C5	−0.4295 (5)	−0.12709 (15)	0.2904 (2)	0.0831 (8)
H5	−0.5214	−0.1585	0.319	0.1*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0983 (5)	0.0930 (5)	0.0458 (4)	−0.0272 (4)	0.0189 (3)	0.0060 (3)
N2	0.0625 (10)	0.0623 (10)	0.0453 (10)	−0.0051 (9)	0.0199 (9)	0.0046 (8)
O2	0.0709 (10)	0.0737 (10)	0.0649 (10)	−0.0096 (8)	0.0302 (8)	−0.0045 (7)
O1	0.0788 (10)	0.0981 (13)	0.0498 (9)	−0.0183 (9)	0.0201 (8)	0.0072 (8)
N1	0.0627 (10)	0.0649 (11)	0.0469 (9)	−0.0066 (9)	0.0192 (8)	0.0012 (8)
C7	0.0572 (11)	0.0511 (12)	0.0512 (12)	0.0023 (10)	0.0190 (9)	0.0062 (9)
C2	0.0664 (13)	0.0525 (12)	0.0508 (13)	−0.0005 (10)	0.0231 (11)	0.0011 (9)
C1	0.0652 (13)	0.0602 (13)	0.0542 (13)	0.0000 (11)	0.0240 (11)	0.0040 (10)
C12	0.0688 (13)	0.0661 (14)	0.0583 (13)	0.0001 (11)	0.0262 (11)	0.0032 (10)
C3	0.0642 (13)	0.0624 (14)	0.0553 (13)	0.0021 (11)	0.0245 (11)	0.0016 (10)
C8	0.0639 (13)	0.0641 (14)	0.0541 (13)	−0.0005 (11)	0.0184 (10)	0.0032 (10)
C9	0.0739 (14)	0.0746 (16)	0.0652 (15)	−0.0132 (12)	0.0158 (12)	−0.0037 (12)
C4	0.0832 (17)	0.0879 (17)	0.0700 (16)	−0.0091 (14)	0.0370 (14)	0.0092 (13)
C10	0.0684 (14)	0.0705 (16)	0.0810 (17)	−0.0085 (12)	0.0223 (13)	0.0066 (13)
C11	0.0675 (14)	0.0750 (15)	0.0765 (17)	0.0015 (12)	0.0343 (13)	0.0164 (13)
C13	0.0874 (17)	0.113 (2)	0.0507 (13)	−0.0239 (15)	0.0226 (12)	−0.0079 (13)
C6	0.0716 (15)	0.0789 (17)	0.0887 (19)	−0.0192 (13)	0.0376 (14)	−0.0161 (14)
C5	0.0880 (18)	0.0825 (18)	0.094 (2)	−0.0170 (14)	0.0506 (16)	0.0027 (15)

Geometric parameters (Å, º) top

S1—C2	1.652 (2)	C8—C9	1.383 (3)
N2—C2	1.330 (3)	C8—C13	1.500 (3)
N2—C7	1.411 (2)	C9—C10	1.375 (3)
N2—H2	0.86	C9—H9	0.93
O2—C6	1.355 (3)	C4—C5	1.403 (4)
O2—C3	1.366 (3)	C4—H4	0.93
O1—C1	1.221 (2)	C10—C11	1.361 (3)
N1—C1	1.377 (2)	C10—H10	0.93
N1—C2	1.400 (3)	C11—H11	0.93
N1—H1	0.86	C13—H13A	0.96
C7—C12	1.388 (3)	C13—H13B	0.96
C7—C8	1.397 (3)	C13—H13C	0.96
C1—C3	1.449 (3)	C6—C5	1.325 (4)
C12—C11	1.385 (3)	C6—H6	0.93
C12—H12	0.93	C5—H5	0.93
C3—C4	1.344 (3)

C2—N2—C7	131.21 (17)	C10—C9—C8	122.1 (2)
C2—N2—H2	114.4	C10—C9—H9	118.9
C7—N2—H2	114.4	C8—C9—H9	118.9
C6—O2—C3	106.19 (18)	C3—C4—C5	106.5 (2)
C1—N1—C2	128.76 (18)	C3—C4—H4	126.7
C1—N1—H1	115.6	C5—C4—H4	126.7
C2—N1—H1	115.6	C11—C10—C9	119.5 (2)
C12—C7—C8	120.07 (19)	C11—C10—H10	120.2
C12—C7—N2	123.93 (19)	C9—C10—H10	120.2
C8—C7—N2	115.95 (17)	C10—C11—C12	120.4 (2)
N2—C2—N1	114.13 (17)	C10—C11—H11	119.8
N2—C2—S1	128.33 (16)	C12—C11—H11	119.8
N1—C2—S1	117.52 (16)	C8—C13—H13A	109.5
O1—C1—N1	123.5 (2)	C8—C13—H13B	109.5
O1—C1—C3	121.03 (19)	H13A—C13—H13B	109.5
N1—C1—C3	115.5 (2)	C8—C13—H13C	109.5
C11—C12—C7	120.0 (2)	H13A—C13—H13C	109.5
C11—C12—H12	120	H13B—C13—H13C	109.5
C7—C12—H12	120	C5—C6—O2	110.5 (2)
C4—C3—O2	109.6 (2)	C5—C6—H6	124.7
C4—C3—C1	132.6 (2)	O2—C6—H6	124.7
O2—C3—C1	117.80 (18)	C6—C5—C4	107.1 (2)
C9—C8—C7	117.88 (19)	C6—C5—H5	126.4
C9—C8—C13	120.0 (2)	C4—C5—H5	126.4
C7—C8—C13	122.15 (19)

C2—N2—C7—C12	−24.6 (3)	N1—C1—C3—O2	−5.5 (3)
C2—N2—C7—C8	158.1 (2)	C12—C7—C8—C9	1.5 (3)
C7—N2—C2—N1	−177.53 (18)	N2—C7—C8—C9	178.90 (19)
C7—N2—C2—S1	0.8 (3)	C12—C7—C8—C13	−178.4 (2)
C1—N1—C2—N2	8.7 (3)	N2—C7—C8—C13	−1.0 (3)
C1—N1—C2—S1	−169.87 (17)	C7—C8—C9—C10	−0.3 (3)
C2—N1—C1—O1	−6.2 (4)	C13—C8—C9—C10	179.6 (2)
C2—N1—C1—C3	174.14 (18)	O2—C3—C4—C5	0.5 (3)
C8—C7—C12—C11	−1.5 (3)	C1—C3—C4—C5	−178.3 (2)
N2—C7—C12—C11	−178.73 (18)	C8—C9—C10—C11	−0.9 (4)
C6—O2—C3—C4	−0.1 (2)	C9—C10—C11—C12	0.9 (4)
C6—O2—C3—C1	178.91 (18)	C7—C12—C11—C10	0.3 (3)
O1—C1—C3—C4	−6.4 (4)	C3—O2—C6—C5	−0.3 (3)
N1—C1—C3—C4	173.3 (2)	O2—C6—C5—C4	0.6 (3)
O1—C1—C3—O2	174.84 (19)	C3—C4—C5—C6	−0.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	2.26	2.682 (3)	110
N1—H1···S1ⁱ	0.86	2.80	3.639 (2)	165
N2—H2···O1	0.86	1.92	2.649 (2)	141

Symmetry code: (i) −x, −y, −z.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₂N₂O₂S
M_r	260.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	6.0976 (1), 16.6689 (6), 13.1462 (4)
β (°)	108.765 (2)
V (Å³)	1265.16 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.50 × 0.08 × 0.07

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Gaussian (Coppens et al., 1965)
T_min, T_max	0.925, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	8242, 2408, 1594
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.130, 1.03
No. of reflections	2408
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.30

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	2.26	2.682 (3)	110
N1—H1···S1ⁱ	0.86	2.80	3.639 (2)	165
N2—H2···O1	0.86	1.92	2.649 (2)	141

Symmetry code: (i) −x, −y, −z.

Acknowledgements

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

References

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