1-Benzyl-3-(2-furo­yl)thio­urea

Abstract

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,

• a = 9.445 (3) Å

• c = 27.107 (6) Å

• V = 2418.2 (12) ų

• 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[F ² > 2σ(F ²)] = 0.035

• wR(F ²) = 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)

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 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

Comment

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).

Experimental

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

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, U_iso(H) = 1.2U_eq(C,N).

Figures

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.

Crystal data

C13H12N2O2S	Z = 8
Mr = 260.31	F000 = 1088
Tetragonal, P41212	Dx = 1.43 Mg m−3
Hall symbol: P 4abw 2nw	Melting point: 402.5 K
a = 9.445 (3) Å	Mo Kα radiation λ = 0.71073 Å
b = 9.445 (3) Å	Cell parameters from 9761 reflections
c = 27.107 (6) Å	θ = 2.9–26.0º
α = 90º	µ = 0.26 mm−1
β = 90º	T = 150 (2) K
γ = 90º	Block, colourless
V = 2418.2 (12) Å3	0.3 × 0.1 × 0.08 mm

Data collection

Nonius KappaCCD diffractometer	Rint = 0.092
ω scans	θmax = 25.0º
Absorption correction: none	θmin = 3.7º
12492 measured reflections	h = −11→9
2120 independent reflections	k = −8→11
1922 reflections with I > 2σ(I)	l = −32→24

Refinement

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)] = 0.035	Δρmax = 0.17 e Å−3
wR(F2) = 0.085	Δρmin = −0.19 e Å−3
S = 1.06	Extinction correction: none
2120 reflections	Absolute structure: Flack (1983), 802 Friedel pairs
163 parameters	Flack parameter: −0.16 (10)
H-atom parameters constrained

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.