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Acta Cryst. (2008). E64, o695    [ doi:10.1107/S1600536808006181 ]

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

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

Abstract top

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.

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%

Refinement top

H atoms were placed in calculated positions with C–H = 0.95 Å (aromatic), N–H = 0.88 Å and C–H = 0.99 Å (methylene), and refined in riding model, Uiso(H) = 1.2Ueq(C,N).

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
[Figure 1] 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
C13H12N2O2SZ = 8
Mr = 260.31F000 = 1088
Tetragonal, P41212Dx = 1.43 Mg m−3
Hall symbol: P 4abw 2nwMelting point: 402.5 K
a = 9.445 (3) ÅMo Kα radiation
λ = 0.71073 Å
b = 9.445 (3) ÅCell parameters from 9761 reflections
c = 27.107 (6) Åθ = 2.9–26.0º
α = 90ºµ = 0.26 mm−1
β = 90ºT = 150 (2) K
γ = 90ºBlock, colourless
V = 2418.2 (12) Å30.3 × 0.1 × 0.08 mm
Data collection top
Nonius KappaCCD
diffractometer		Rint = 0.092
ω scansθmax = 25.0º
Absorption correction: noneθmin = 3.7º
12492 measured reflectionsh = −11→9
2120 independent reflectionsk = −8→11
1922 reflections with I > 2σ(I)l = −32→24
Refinement top
Refinement on F2  w = 1/[σ2(Fo2) + (0.0402P)2 + 0.4478P]
where P = (Fo2 + 2Fc2)/3
Least-squares matrix: full(Δ/σ)max < 0.001
R[F2 > 2σ(F2)] = 0.035Δρmax = 0.17 e Å−3
wR(F2) = 0.085Δρmin = −0.19 e Å−3
S = 1.06Extinction correction: none
2120 reflectionsAbsolute structure: Flack (1983), 802 Friedel pairs
163 parametersFlack parameter: −0.16 (10)
H-atom parameters constrained
Crystal data top
C13H12N2O2Sγ = 90º
Mr = 260.31V = 2418.2 (12) Å3
Tetragonal, P41212Z = 8
a = 9.445 (3) ÅMo Kα
b = 9.445 (3) ŵ = 0.26 mm−1
c = 27.107 (6) ÅT = 150 (2) K
α = 90º0.3 × 0.1 × 0.08 mm
β = 90º
Data collection top
Nonius KappaCCD
diffractometer		2120 independent reflections
Absorption correction: none1922 reflections with I > 2σ(I)
12492 measured reflectionsRint = 0.092
Refinement top
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.085Δρmax = 0.17 e Å−3
S = 1.06Δρmin = −0.19 e Å−3
2120 reflectionsAbsolute structure: Flack (1983), 802 Friedel pairs
163 parametersFlack parameter: −0.16 (10)
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
xyzUiso*/Ueq
C10.7270 (2)0.4402 (2)0.16180 (8)0.0311 (6)
H1A0.71040.34940.17910.037*
H1B0.63510.49040.15970.037*
C20.7259 (2)0.4740 (2)0.07225 (7)0.0251 (5)
C30.8761 (2)0.3236 (2)0.01767 (8)0.0260 (5)
C40.9003 (2)0.2913 (2)−0.03448 (8)0.0270 (5)
C50.9858 (2)0.1962 (2)−0.05694 (8)0.0316 (5)
H51.04860.1313−0.04150.038*
C60.9623 (2)0.2131 (2)−0.10836 (8)0.0336 (6)
H61.00690.1616−0.13410.04*
C70.8651 (2)0.3157 (2)−0.11361 (8)0.0330 (6)
H70.82960.3482−0.14440.04*
C80.8284 (2)0.5288 (2)0.19216 (8)0.0272 (5)
C90.9223 (2)0.6243 (2)0.17099 (9)0.0320 (5)
H90.92870.63130.13610.038*
C101.0065 (3)0.7093 (3)0.20046 (10)0.0389 (6)
H101.07060.77390.18550.047*
C110.9987 (3)0.7014 (3)0.25126 (10)0.0388 (6)
H111.05630.76060.27130.047*
C120.9063 (3)0.6063 (3)0.27252 (9)0.0388 (6)
H120.90010.60.30740.047*
C130.8222 (2)0.5198 (3)0.24330 (8)0.0333 (6)
H130.75980.45390.25840.04*
O10.94160 (17)0.26029 (17)0.04999 (6)0.0314 (4)
O20.82422 (16)0.36671 (15)−0.06877 (5)0.0309 (4)
N10.7763 (2)0.41033 (19)0.11201 (6)0.0275 (4)
H10.84320.34650.10810.033*
N20.77589 (19)0.42680 (19)0.02701 (6)0.0262 (4)
H20.7390.46790.00090.031*
S10.60657 (6)0.60581 (6)0.072955 (19)0.03259 (18)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0337 (12)0.0375 (13)0.0220 (11)−0.0027 (11)0.0039 (9)0.0008 (10)
C20.0253 (11)0.0269 (11)0.0231 (11)−0.0052 (9)0.0015 (9)−0.0028 (9)
C30.0227 (11)0.0265 (11)0.0289 (12)−0.0054 (10)0.0013 (9)−0.0005 (9)
C40.0289 (12)0.0274 (12)0.0248 (11)−0.0019 (10)−0.0021 (9)0.0017 (9)
C50.0310 (13)0.0319 (12)0.0318 (12)0.0041 (10)0.0005 (10)−0.0019 (10)
C60.0396 (14)0.0353 (13)0.0260 (12)0.0033 (11)0.0041 (10)−0.0041 (10)
C70.0411 (14)0.0380 (13)0.0200 (11)0.0024 (11)0.0016 (10)−0.0032 (10)
C80.0304 (12)0.0266 (12)0.0246 (11)0.0077 (10)0.0000 (9)−0.0018 (9)
C90.0354 (13)0.0324 (12)0.0283 (12)0.0043 (11)0.0009 (10)0.0006 (11)
C100.0381 (14)0.0358 (13)0.0427 (15)−0.0012 (12)−0.0005 (11)−0.0003 (11)
C110.0399 (14)0.0381 (13)0.0385 (14)0.0034 (12)−0.0058 (12)−0.0074 (12)
C120.0451 (15)0.0452 (15)0.0261 (12)0.0097 (13)−0.0045 (11)−0.0035 (11)
C130.0376 (13)0.0347 (13)0.0277 (13)0.0048 (11)0.0023 (11)0.0020 (10)
O10.0327 (9)0.0354 (9)0.0262 (8)0.0035 (7)−0.0005 (7)0.0009 (7)
O20.0354 (9)0.0319 (9)0.0253 (8)0.0060 (7)−0.0011 (7)−0.0017 (7)
N10.0303 (10)0.0287 (10)0.0236 (9)0.0027 (8)0.0016 (8)−0.0010 (8)
N20.0288 (10)0.0291 (10)0.0208 (9)0.0010 (8)−0.0008 (8)−0.0012 (8)
S10.0371 (3)0.0324 (3)0.0283 (3)0.0066 (3)0.0013 (3)−0.0021 (2)
Geometric parameters (Å, °) top
C1—N11.456 (3)C7—O21.363 (2)
C1—C81.515 (3)C7—H70.95
C1—H1A0.99C8—C91.389 (3)
C1—H1B0.99C8—C131.390 (3)
C2—N11.323 (3)C9—C101.384 (3)
C2—N21.388 (3)C9—H90.95
C2—S11.679 (2)C10—C111.381 (4)
C3—O11.228 (3)C10—H100.95
C3—N21.382 (3)C11—C121.379 (4)
C3—C41.464 (3)C11—H110.95
C4—C51.353 (3)C12—C131.387 (4)
C4—O21.374 (2)C12—H120.95
C5—C61.420 (3)C13—H130.95
C5—H50.95N1—H10.88
C6—C71.342 (3)N2—H20.88
C6—H60.95
N1—C1—C8114.11 (18)C9—C8—C1122.5 (2)
N1—C1—H1A108.7C13—C8—C1118.8 (2)
C8—C1—H1A108.7C10—C9—C8120.3 (2)
N1—C1—H1B108.7C10—C9—H9119.8
C8—C1—H1B108.7C8—C9—H9119.8
H1A—C1—H1B107.6C11—C10—C9120.9 (2)
N1—C2—N2116.84 (18)C11—C10—H10119.6
N1—C2—S1124.70 (16)C9—C10—H10119.6
N2—C2—S1118.46 (15)C12—C11—C10119.1 (2)
O1—C3—N2123.90 (19)C12—C11—H11120.5
O1—C3—C4120.59 (19)C10—C11—H11120.5
N2—C3—C4115.51 (18)C11—C12—C13120.5 (2)
C5—C4—O2110.61 (18)C11—C12—H12119.8
C5—C4—C3131.8 (2)C13—C12—H12119.8
O2—C4—C3117.63 (18)C12—C13—C8120.6 (2)
C4—C5—C6105.9 (2)C12—C13—H13119.7
C4—C5—H5127.1C8—C13—H13119.7
C6—C5—H5127.1C7—O2—C4105.78 (17)
C7—C6—C5107.0 (2)C2—N1—C1123.51 (18)
C7—C6—H6126.5C2—N1—H1118.2
C5—C6—H6126.5C1—N1—H1118.2
C6—C7—O2110.8 (2)C3—N2—C2128.43 (18)
C6—C7—H7124.6C3—N2—H2115.8
O2—C7—H7124.6C2—N2—H2115.8
C9—C8—C13118.6 (2)
O1—C3—C4—C51.4 (4)C10—C11—C12—C130.0 (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—C121.1 (3)
N2—C3—C4—O21.0 (3)C1—C8—C13—C12−175.5 (2)
O2—C4—C5—C60.2 (3)C6—C7—O2—C4−0.1 (2)
C3—C4—C5—C6179.3 (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—O20.2 (3)N2—C2—N1—C1−175.32 (19)
N1—C1—C8—C927.7 (3)S1—C2—N1—C14.4 (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—C10175.9 (2)C4—C3—N2—C2176.4 (2)
C8—C9—C10—C11−0.3 (4)N1—C2—N2—C3−2.3 (3)
C9—C10—C11—C120.6 (4)S1—C2—N2—C3178.05 (17)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.882.002.697 (3)135
N2—H2···S1i0.882.703.578 (2)174
C7—H7···O1ii0.952.583.423 (3)148
Symmetry codes: (i) y, x, −z; (ii) y+1/2, −x+3/2, z−1/4.
Table 1
Selected geometric parameters (Å) top
C2—N11.323 (3)C3—O11.228 (3)
C2—N21.388 (3)C3—N21.382 (3)
C2—S11.679 (2)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.882.002.697 (3)135
N2—H2···S1i0.882.703.578 (2)174
C7—H7···O1ii0.952.583.423 (3)148
Symmetry codes: (i) y, x, −z; (ii) y+1/2, −x+3/2, z−1/4.
Acknowledgements top

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
References top

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