1-Benzyl-3-(2-furo­yl)thio­urea

Pérez, H.; Mascarenhas, Y.; Estévez-Hernández, O.; Santos Jr, S.; Duque, J.

doi:10.1107/S1600536808006181

organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page o695

doi:10.1107/S1600536808006181

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

Hiram Pérez,^a ^* Yvonne Mascarenhas,^b Osvaldo Estévez-Hernández,^c Sauli Santos Jr ^d and Julio Duque ^c

^aDepartamento de Química Inorgánica, Facultad de Química, Universidad de la Habana, Habana 10400, Cuba, ^bInstituto de Física de São Carlos, Universidade de São Paulo, São Carlos, Brazil, ^cInstituto de Ciencia y Tecnología de Materiales, Universidad de la Habana, Habana 10400, Cuba, and ^dLaboratório de Física, Universidade Federal do Tocantins, CEP 77020-120, Palmas, Tocantins, Brazil
^*Correspondence e-mail: hperez@fq.uh.cu

(Received 29 January 2008; accepted 6 March 2008; online 12 March 2008)

In the title compound, C₁₃H₁₂N₂O₂S, the dihedral angle between the two aromatic ring planes is 87.52 (12)°. The molecule shows an intramolecular N—H⋯O hydrogen bond. The crystal structure is stabilized by intermolecular N—H⋯S and C—H⋯O hydrogen bonding.

Related literature

For general background, see: Estévez-Hernández et al. (2007 ); Otazo et al. (2001 ). For related structures, see: Arslan et al. (2004 ); Khawar Rauf et al. (2007 ). For the synthesis, see: Otazo et al. (2001).

Experimental

Crystal data

C₁₃H₁₂N₂O₂S
M_r = 260.31
Tetragonal, P 4₁ 2₁ 2
a = 9.445 (3) Å
c = 27.107 (6) Å
V = 2418.2 (12) Å³
Z = 8
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 150 (2) K
0.3 × 0.1 × 0.08 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
12492 measured reflections
2120 independent reflections
1922 reflections with I > 2σ(I)
R_int = 0.092

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.085
S = 1.06
2120 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.19 e Å⁻³
Absolute structure: Flack (1983 ), 802 Friedel pairs
Flack parameter: −0.16 (10)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.88	2.00	2.697 (3)	135
N2—H2⋯S1ⁱ	0.88	2.70	3.578 (2)	174
C7—H7⋯O1ⁱⁱ	0.95	2.58	3.423 (3)	148
Symmetry codes: (i) y, x, -z; (ii) $[y+{\script{1\over 2}}, -x+{\script{3\over 2}}, z-{\script{1\over 4}}]$ .

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/S1600536808006181/xu2401sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808006181/xu2401Isup2.hkl

checkCIF report

Comment top

Substituted N-acylthioureas have been a subject of investigations, due to their ability to form stable metal complexes and as ionophores in potenciometric and amperometric sensors for Cd(II), Hg(II) and Pb(II) (Otazo et al., 2001; Estévez-Hernández et al., 2007). The title compound, (I) (Fig. 1), is another example of our newly synthesized furoylthiourea derivatives, which show outstanding complexation properties.

Compound (I) is a typical N,N'-disubstituted thiourea derivative with normal geometric parameters. The C2—S1 and C3—O1 bonds (Table 1) both show the expected double-bond character. The short values of the C2—N1, C2—N2 and C3—N2 bonds indicate partial double bond character.

The dihedral angle between the aromatic rings is 87.52 (12)°, and the angles with the thiourea plane are 86.67 (19)° for the benzene ring and 4.81 (12)° for the furan ring. An intramolecular N–H···O hydrogen bond is present (Table 2), forming a six-membered ring commonly observed in this type of compounds (Arslan et al., 2004; Khawar Rauf et al., 2007). The crystal structure of (I) is stabilized by intermolecular N—H···S and C—H···O hydrogen bonding (Table 2).

Related literature top

For general background, see: Estévez-Hernández et al. (2007); Otazo et al. (2001). For related structures, see: Arslan et al. (2004); Khawar Rauf et al. (2007). For thesynthesis, see: Otazo et al. (2001).

Experimental top

The title compound, (I), was synthesized according to a procedure described by Otazo et al. (2001) by converting furoyl chloride into furoyl isothiocyanate and then condensing with the appropriate amine. The resulting solid product was crystallized from a dichlorometane-methanol (1:1) mixture yielding X-ray quality single crystals. Elemental analysis for C₁₃H₁₂N₂O₂S found: C 67.73, H 4.75, N 8.23, S 9.34%; calculated: C 67.86, H 4.46, N 8.33, S 9.52%

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. The molecular structure of title compound. Displacement ellipsoids are drawn at the 50% probability level. The intramolecular N—H···O hydrogen bond is shown as a dashed line.

1-Benzyl-3-(2-furoyl)thiourea top

Crystal data top

C₁₃H₁₂N₂O₂S	D_x = 1.43 Mg m⁻³
M_r = 260.31	Melting point: 402.5 K
Tetragonal, P4₁2₁2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 4abw 2nw	Cell parameters from 9761 reflections
a = 9.445 (3) Å	θ = 2.9–26.0°
c = 27.107 (6) Å	µ = 0.26 mm⁻¹
V = 2418.2 (12) Å³	T = 150 K
Z = 8	Block, colourless
F(000) = 1088	0.3 × 0.1 × 0.08 mm

Data collection top

Nonius KappaCCD diffractometer	R_int = 0.092
ω scans	θ_max = 25.0°, θ_min = 3.7°
12492 measured reflections	h = −11→9
2120 independent reflections	k = −8→11
1922 reflections with I > 2σ(I)	l = −32→24

Refinement top

Refinement on F²	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0402P)² + 0.4478P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.035	(Δ/σ)_max < 0.001
wR(F²) = 0.085	Δρ_max = 0.17 e Å⁻³
S = 1.06	Δρ_min = −0.19 e Å⁻³
2120 reflections	Absolute structure: Flack (1983), 802 Friedel pairs
163 parameters	Absolute structure parameter: −0.16 (10)
0 restraints

Crystal data top

C₁₃H₁₂N₂O₂S	Z = 8
M_r = 260.31	Mo Kα radiation
Tetragonal, P4₁2₁2	µ = 0.26 mm⁻¹
a = 9.445 (3) Å	T = 150 K
c = 27.107 (6) Å	0.3 × 0.1 × 0.08 mm
V = 2418.2 (12) Å³

Data collection top

Nonius KappaCCD diffractometer	1922 reflections with I > 2σ(I)
12492 measured reflections	R_int = 0.092
2120 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.085	Δρ_max = 0.17 e Å⁻³
S = 1.06	Δρ_min = −0.19 e Å⁻³
2120 reflections	Absolute structure: Flack (1983), 802 Friedel pairs
163 parameters	Absolute structure parameter: −0.16 (10)
0 restraints

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	0.7270 (2)	0.4402 (2)	0.16180 (8)	0.0311 (6)
H1A	0.7104	0.3494	0.1791	0.037*
H1B	0.6351	0.4904	0.1597	0.037*
C2	0.7259 (2)	0.4740 (2)	0.07225 (7)	0.0251 (5)
C3	0.8761 (2)	0.3236 (2)	0.01767 (8)	0.0260 (5)
C4	0.9003 (2)	0.2913 (2)	−0.03448 (8)	0.0270 (5)
C5	0.9858 (2)	0.1962 (2)	−0.05694 (8)	0.0316 (5)
H5	1.0486	0.1313	−0.0415	0.038*
C6	0.9623 (2)	0.2131 (2)	−0.10836 (8)	0.0336 (6)
H6	1.0069	0.1616	−0.1341	0.04*
C7	0.8651 (2)	0.3157 (2)	−0.11361 (8)	0.0330 (6)
H7	0.8296	0.3482	−0.1444	0.04*
C8	0.8284 (2)	0.5288 (2)	0.19216 (8)	0.0272 (5)
C9	0.9223 (2)	0.6243 (2)	0.17099 (9)	0.0320 (5)
H9	0.9287	0.6313	0.1361	0.038*
C10	1.0065 (3)	0.7093 (3)	0.20046 (10)	0.0389 (6)
H10	1.0706	0.7739	0.1855	0.047*
C11	0.9987 (3)	0.7014 (3)	0.25126 (10)	0.0388 (6)
H11	1.0563	0.7606	0.2713	0.047*
C12	0.9063 (3)	0.6063 (3)	0.27252 (9)	0.0388 (6)
H12	0.9001	0.6	0.3074	0.047*
C13	0.8222 (2)	0.5198 (3)	0.24330 (8)	0.0333 (6)
H13	0.7598	0.4539	0.2584	0.04*
O1	0.94160 (17)	0.26029 (17)	0.04999 (6)	0.0314 (4)
O2	0.82422 (16)	0.36671 (15)	−0.06877 (5)	0.0309 (4)
N1	0.7763 (2)	0.41033 (19)	0.11201 (6)	0.0275 (4)
H1	0.8432	0.3465	0.1081	0.033*
N2	0.77589 (19)	0.42680 (19)	0.02701 (6)	0.0262 (4)
H2	0.739	0.4679	0.0009	0.031*
S1	0.60657 (6)	0.60581 (6)	0.072955 (19)	0.03259 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0337 (12)	0.0375 (13)	0.0220 (11)	−0.0027 (11)	0.0039 (9)	0.0008 (10)
C2	0.0253 (11)	0.0269 (11)	0.0231 (11)	−0.0052 (9)	0.0015 (9)	−0.0028 (9)
C3	0.0227 (11)	0.0265 (11)	0.0289 (12)	−0.0054 (10)	0.0013 (9)	−0.0005 (9)
C4	0.0289 (12)	0.0274 (12)	0.0248 (11)	−0.0019 (10)	−0.0021 (9)	0.0017 (9)
C5	0.0310 (13)	0.0319 (12)	0.0318 (12)	0.0041 (10)	0.0005 (10)	−0.0019 (10)
C6	0.0396 (14)	0.0353 (13)	0.0260 (12)	0.0033 (11)	0.0041 (10)	−0.0041 (10)
C7	0.0411 (14)	0.0380 (13)	0.0200 (11)	0.0024 (11)	0.0016 (10)	−0.0032 (10)
C8	0.0304 (12)	0.0266 (12)	0.0246 (11)	0.0077 (10)	0.0000 (9)	−0.0018 (9)
C9	0.0354 (13)	0.0324 (12)	0.0283 (12)	0.0043 (11)	0.0009 (10)	0.0006 (11)
C10	0.0381 (14)	0.0358 (13)	0.0427 (15)	−0.0012 (12)	−0.0005 (11)	−0.0003 (11)
C11	0.0399 (14)	0.0381 (13)	0.0385 (14)	0.0034 (12)	−0.0058 (12)	−0.0074 (12)
C12	0.0451 (15)	0.0452 (15)	0.0261 (12)	0.0097 (13)	−0.0045 (11)	−0.0035 (11)
C13	0.0376 (13)	0.0347 (13)	0.0277 (13)	0.0048 (11)	0.0023 (11)	0.0020 (10)
O1	0.0327 (9)	0.0354 (9)	0.0262 (8)	0.0035 (7)	−0.0005 (7)	0.0009 (7)
O2	0.0354 (9)	0.0319 (9)	0.0253 (8)	0.0060 (7)	−0.0011 (7)	−0.0017 (7)
N1	0.0303 (10)	0.0287 (10)	0.0236 (9)	0.0027 (8)	0.0016 (8)	−0.0010 (8)
N2	0.0288 (10)	0.0291 (10)	0.0208 (9)	0.0010 (8)	−0.0008 (8)	−0.0012 (8)
S1	0.0371 (3)	0.0324 (3)	0.0283 (3)	0.0066 (3)	0.0013 (3)	−0.0021 (2)

Geometric parameters (Å, º) top

C1—N1	1.456 (3)	C7—O2	1.363 (2)
C1—C8	1.515 (3)	C7—H7	0.95
C1—H1A	0.99	C8—C9	1.389 (3)
C1—H1B	0.99	C8—C13	1.390 (3)
C2—N1	1.323 (3)	C9—C10	1.384 (3)
C2—N2	1.388 (3)	C9—H9	0.95
C2—S1	1.679 (2)	C10—C11	1.381 (4)
C3—O1	1.228 (3)	C10—H10	0.95
C3—N2	1.382 (3)	C11—C12	1.379 (4)
C3—C4	1.464 (3)	C11—H11	0.95
C4—C5	1.353 (3)	C12—C13	1.387 (4)
C4—O2	1.374 (2)	C12—H12	0.95
C5—C6	1.420 (3)	C13—H13	0.95
C5—H5	0.95	N1—H1	0.88
C6—C7	1.342 (3)	N2—H2	0.88
C6—H6	0.95

N1—C1—C8	114.11 (18)	C9—C8—C1	122.5 (2)
N1—C1—H1A	108.7	C13—C8—C1	118.8 (2)
C8—C1—H1A	108.7	C10—C9—C8	120.3 (2)
N1—C1—H1B	108.7	C10—C9—H9	119.8
C8—C1—H1B	108.7	C8—C9—H9	119.8
H1A—C1—H1B	107.6	C11—C10—C9	120.9 (2)
N1—C2—N2	116.84 (18)	C11—C10—H10	119.6
N1—C2—S1	124.70 (16)	C9—C10—H10	119.6
N2—C2—S1	118.46 (15)	C12—C11—C10	119.1 (2)
O1—C3—N2	123.90 (19)	C12—C11—H11	120.5
O1—C3—C4	120.59 (19)	C10—C11—H11	120.5
N2—C3—C4	115.51 (18)	C11—C12—C13	120.5 (2)
C5—C4—O2	110.61 (18)	C11—C12—H12	119.8
C5—C4—C3	131.8 (2)	C13—C12—H12	119.8
O2—C4—C3	117.63 (18)	C12—C13—C8	120.6 (2)
C4—C5—C6	105.9 (2)	C12—C13—H13	119.7
C4—C5—H5	127.1	C8—C13—H13	119.7
C6—C5—H5	127.1	C7—O2—C4	105.78 (17)
C7—C6—C5	107.0 (2)	C2—N1—C1	123.51 (18)
C7—C6—H6	126.5	C2—N1—H1	118.2
C5—C6—H6	126.5	C1—N1—H1	118.2
C6—C7—O2	110.8 (2)	C3—N2—C2	128.43 (18)
C6—C7—H7	124.6	C3—N2—H2	115.8
O2—C7—H7	124.6	C2—N2—H2	115.8
C9—C8—C13	118.6 (2)

O1—C3—C4—C5	1.4 (4)	C10—C11—C12—C13	0.0 (4)
N2—C3—C4—C5	−178.1 (2)	C11—C12—C13—C8	−0.8 (3)
O1—C3—C4—O2	−179.53 (19)	C9—C8—C13—C12	1.1 (3)
N2—C3—C4—O2	1.0 (3)	C1—C8—C13—C12	−175.5 (2)
O2—C4—C5—C6	0.2 (3)	C6—C7—O2—C4	−0.1 (2)
C3—C4—C5—C6	179.3 (2)	C5—C4—O2—C7	−0.1 (2)
C4—C5—C6—C7	−0.2 (3)	C3—C4—O2—C7	−179.4 (2)
C5—C6—C7—O2	0.2 (3)	N2—C2—N1—C1	−175.32 (19)
N1—C1—C8—C9	27.7 (3)	S1—C2—N1—C1	4.4 (3)
N1—C1—C8—C13	−155.8 (2)	C8—C1—N1—C2	−104.7 (2)
C13—C8—C9—C10	−0.6 (3)	O1—C3—N2—C2	−3.1 (3)
C1—C8—C9—C10	175.9 (2)	C4—C3—N2—C2	176.4 (2)
C8—C9—C10—C11	−0.3 (4)	N1—C2—N2—C3	−2.3 (3)
C9—C10—C11—C12	0.6 (4)	S1—C2—N2—C3	178.05 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.88	2.00	2.697 (3)	135
N2—H2···S1ⁱ	0.88	2.70	3.578 (2)	174
C7—H7···O1ⁱⁱ	0.95	2.58	3.423 (3)	148

Symmetry codes: (i) y, x, −z; (ii) y+1/2, −x+3/2, z−1/4.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₂N₂O₂S
M_r	260.31
Crystal system, space group	Tetragonal, P4₁2₁2
Temperature (K)	150
a, c (Å)	9.445 (3), 27.107 (6)
V (Å³)	2418.2 (12)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.3 × 0.1 × 0.08

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	12492, 2120, 1922
R_int	0.092
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.085, 1.06
No. of reflections	2120
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.19
Absolute structure	Flack (1983), 802 Friedel pairs
Absolute structure parameter	−0.16 (10)

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

C2—N1	1.323 (3)	C3—O1	1.228 (3)
C2—N2	1.388 (3)	C3—N2	1.382 (3)
C2—S1	1.679 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.88	2.00	2.697 (3)	135
N2—H2···S1ⁱ	0.88	2.70	3.578 (2)	174
C7—H7···O1ⁱⁱ	0.95	2.58	3.423 (3)	148

Symmetry codes: (i) y, x, −z; (ii) y+1/2, −x+3/2, z−1/4.

Acknowledgements

The authors thank the Crystallography Group, São Carlos Physics Institute, USP, Brazil, for allowing the X-ray data collection. The authors acknowledge financial support from the Brazilian agency CAPES (Project 018/05).

References

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