1-(4-Fluoro­phen­yl)thio­urea

Saeed, A.; Shaheen, U.; Flörke, U.

doi:10.1107/S1600536810020246

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1558

doi:10.1107/S1600536810020246

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1-(4-Fluorophenyl)thiourea

Aamer Saeed,^a ^* Uzma Shaheen ^a and Ulrich Flörke ^b

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, and ^bDepartment Chemie, Fakultät für Naturwissenschaften, Universität Paderborn, Warburgerstr. 100, D-33098 Paderborn, Germany
^*Correspondence e-mail: aamersaeed@yahoo.com

(Received 14 April 2010; accepted 28 May 2010; online 5 June 2010)

In the title compound, C₇H₇FN₂S, the aromatic ring plane and the thiourea unit are twisted with a torsion angle C—C—N—C7 of 44.6 (2)°. In the crystal, N—H⋯S and N—H⋯F intermolecular hydrogen bonds link the molecules into infinite sheets that are stacked along the c axis.

Related literature

For the biological activity of fluorinated thioureas, see: Sun et al. (2006 ); Saeed et al. (2009 ); Xu et al. (2003 ). For the use of fluorinated thioureas in organic synthesis, see: Nosova et al. (2006 , 2007 ); Lipunova et al. (2008 ); Berkessel et al. (2006 ). N′-(2-fluorobenzoyl)thiourea derivatives are suitable substrates for studying intramolecular hydrogen bonds and Fermi resonance, see: Hritzová & Koščík (2008 ).

Experimental

Crystal data

C₇H₇FN₂S
M_r = 170.21
Monoclinic, P 2₁ /c
a = 9.1384 (8) Å
b = 8.4338 (7) Å
c = 10.5334 (9) Å
β = 109.796 (2)°
V = 763.85 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 120 K
0.43 × 0.39 × 0.29 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.857, T_max = 0.900
6816 measured reflections
1814 independent reflections
1645 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.097
S = 1.05
1814 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯S1ⁱ	0.88	2.43	3.2841 (12)	163
N2—H2B⋯F1ⁱⁱ	0.88	2.30	3.0989 (15)	152
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) -x+1, -y+1, -z+2.

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810020246/pb2028sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810020246/pb2028Isup2.hkl

checkCIF report

Comment top

Fluorinated thioureas are an imoprtant class of thioureas. Theser are versatile synthons for various fluorine-containing heterocycles: [1,3]-benzothiazin-4-ones (Nosova et al.,2006, 2007) 1-aryl-2-ethylthio-quinazolin-4-one, thiazolidine and 1H-1,2,4-triazoles (Lipunova et al., 2008). Fluorinated thioureas exhibit a variety of biological activities: potent influenza virus neuraminidase inhibitors (Sun et al., 2006), antimicrobial (Saeed et al., 2009) and insecticidal activities (Xu et al., 2003). Moreover, fluorinated bis-thiourea derivatives are also used as organocatalyst in Morita-Baylis-Hillman reaction (Berkessel et al., 2006) and N-Substituted N'-(2-fluorobenzoyl)thiourea derivatives are suitable substrates for studying Intramolecular Hydrogen Bonds and Fermi Resonance (Hritzová & Koščík 2008). The aromatic ring plane and the thiourea moiety are twisted with a torsion angle C2–C1–N1–C7 of 44.6 (2)°. N(1)–H···S and N(2)–H···F intermolecular hydrogen bonds link molecules to endless 2D sheets that are stacked along the c axis.

Related literature top

For the biological activity of fluorinated thioureas, see: Sun et al. (2006); Saeed et al. (2009); Xu et al. (2003). For the use of fluorinated thioureas in organic synthesis, see: Nosova et al. (2006, 2007); Lipunova et al. (2008); Berkessel et al. (2006). N'-(2-fluorobenzoyl)thiourea derivatives are suitable substrates for studying intramolecular hydrogen bonds and Fermi resonance, see: Hritzová & Koščík (2008).

Experimental top

4-Fluorobenzoylisothiocyante (1 mmol) in acetone was treated with ammonia (1 mmol) under a nitrogen atmosphere at reflux for 3 h. Upon cooling, the reaction mixture was poured into aq HCl and the precipitated product was rerystallized from in methanol to afforded the title compound (78 %) as colourless crystals: Anal. calcd. for C₇H₇N₂O₂FS: C, 49.40; H, 4.15; N, 16.46; S, 18.84%; found: C, 49.02; H, 4.17; N, 16.41; S, 18.91%.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Crystal packing viewed along [001] with intermolecular hydrogen bonds indicated as dashed lines. H-atoms not involved in hydrogen bonding are omitted.

1-(4-Fluorophenyl)thiourea top

Crystal data top

C₇H₇FN₂S	F(000) = 352
M_r = 170.21	D_x = 1.480 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.1384 (8) Å	Cell parameters from 3596 reflections
b = 8.4338 (7) Å	θ = 3.2–28.3°
c = 10.5334 (9) Å	µ = 0.37 mm⁻¹
β = 109.796 (2)°	T = 120 K
V = 763.85 (11) Å³	Block, colourless
Z = 4	0.43 × 0.39 × 0.29 mm

Data collection top

Bruker SMART APEX diffractometer	1814 independent reflections
Radiation source: sealed tube	1645 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ϕ and ω scans	θ_max = 27.9°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −12→12
T_min = 0.857, T_max = 0.900	k = −10→11
6816 measured reflections	l = −13→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.097	w = 1/[σ²(F_o²) + (0.0546P)² + 0.3192P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
1814 reflections	Δρ_max = 0.44 e Å⁻³
101 parameters	Δρ_min = −0.31 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.009 (3)

Crystal data top

C₇H₇FN₂S	V = 763.85 (11) Å³
M_r = 170.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.1384 (8) Å	µ = 0.37 mm⁻¹
b = 8.4338 (7) Å	T = 120 K
c = 10.5334 (9) Å	0.43 × 0.39 × 0.29 mm
β = 109.796 (2)°

Data collection top

Bruker SMART APEX diffractometer	1814 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1645 reflections with I > 2σ(I)
T_min = 0.857, T_max = 0.900	R_int = 0.026
6816 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.05	Δρ_max = 0.44 e Å⁻³
1814 reflections	Δρ_min = −0.31 e Å⁻³
101 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	1.02935 (4)	0.53586 (4)	0.71645 (4)	0.02753 (15)
F1	0.35073 (11)	0.23014 (12)	0.98827 (10)	0.0374 (3)
N1	0.84161 (13)	0.39046 (13)	0.81980 (12)	0.0224 (3)
H1A	0.8874	0.3066	0.8006	0.027*
N2	0.85423 (14)	0.66261 (14)	0.84570 (13)	0.0257 (3)
H2B	0.7864	0.6574	0.8882	0.031*
H2C	0.8920	0.7550	0.8332	0.031*
C1	0.71613 (14)	0.35888 (15)	0.86719 (13)	0.0195 (3)
C2	0.57627 (15)	0.44244 (16)	0.81997 (14)	0.0214 (3)
H2A	0.5656	0.5286	0.7594	0.026*
C3	0.45251 (16)	0.39984 (17)	0.86130 (14)	0.0247 (3)
H3A	0.3572	0.4568	0.8308	0.030*
C4	0.47151 (16)	0.27309 (18)	0.94755 (14)	0.0254 (3)
C5	0.60776 (17)	0.18705 (17)	0.99488 (14)	0.0261 (3)
H5A	0.6167	0.0995	1.0538	0.031*
C6	0.73102 (16)	0.23144 (17)	0.95434 (14)	0.0233 (3)
H6A	0.8262	0.1745	0.9863	0.028*
C7	0.89954 (15)	0.53115 (15)	0.80043 (14)	0.0206 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0258 (2)	0.0168 (2)	0.0483 (3)	−0.00188 (12)	0.02351 (17)	−0.00191 (14)
F1	0.0391 (5)	0.0376 (5)	0.0475 (6)	−0.0133 (4)	0.0304 (4)	−0.0076 (4)
N1	0.0228 (5)	0.0154 (5)	0.0330 (6)	0.0021 (4)	0.0145 (5)	0.0018 (4)
N2	0.0267 (6)	0.0174 (6)	0.0386 (7)	−0.0017 (4)	0.0184 (5)	−0.0025 (5)
C1	0.0198 (6)	0.0188 (6)	0.0207 (6)	−0.0022 (5)	0.0080 (5)	−0.0014 (5)
C2	0.0233 (6)	0.0190 (6)	0.0222 (6)	0.0008 (5)	0.0080 (5)	0.0007 (5)
C3	0.0218 (6)	0.0250 (7)	0.0284 (7)	−0.0005 (5)	0.0101 (5)	−0.0055 (5)
C4	0.0272 (7)	0.0276 (7)	0.0262 (7)	−0.0106 (5)	0.0154 (5)	−0.0091 (5)
C5	0.0353 (7)	0.0230 (7)	0.0207 (6)	−0.0069 (6)	0.0103 (6)	0.0000 (5)
C6	0.0250 (6)	0.0201 (6)	0.0235 (6)	−0.0010 (5)	0.0066 (5)	0.0013 (5)
C7	0.0164 (6)	0.0189 (6)	0.0261 (7)	0.0003 (4)	0.0066 (5)	0.0014 (5)

Geometric parameters (Å, º) top

S1—C7	1.7035 (14)	C1—C2	1.3954 (18)
F1—C4	1.3616 (15)	C2—C3	1.3897 (19)
N1—C7	1.3427 (17)	C2—H2A	0.9500
N1—C1	1.4222 (15)	C3—C4	1.375 (2)
N1—H1A	0.8800	C3—H3A	0.9500
N2—C7	1.3274 (17)	C4—C5	1.380 (2)
N2—H2B	0.8800	C5—C6	1.3846 (19)
N2—H2C	0.8800	C5—H5A	0.9500
C1—C6	1.3899 (19)	C6—H6A	0.9500

C7—N1—C1	128.69 (11)	C2—C3—H3A	120.9
C7—N1—H1A	115.7	F1—C4—C3	118.71 (13)
C1—N1—H1A	115.7	F1—C4—C5	118.34 (13)
C7—N2—H2B	120.0	C3—C4—C5	122.95 (13)
C7—N2—H2C	120.0	C4—C5—C6	118.37 (13)
H2B—N2—H2C	120.0	C4—C5—H5A	120.8
C6—C1—C2	119.93 (12)	C6—C5—H5A	120.8
C6—C1—N1	117.80 (12)	C5—C6—C1	120.32 (13)
C2—C1—N1	122.03 (12)	C5—C6—H6A	119.8
C3—C2—C1	120.14 (13)	C1—C6—H6A	119.8
C3—C2—H2A	119.9	N2—C7—N1	119.76 (12)
C1—C2—H2A	119.9	N2—C7—S1	121.59 (10)
C4—C3—C2	118.28 (13)	N1—C7—S1	118.64 (10)
C4—C3—H3A	120.9

C7—N1—C1—C6	−141.01 (15)	F1—C4—C5—C6	−179.50 (12)
C7—N1—C1—C2	44.6 (2)	C3—C4—C5—C6	0.5 (2)
C6—C1—C2—C3	0.9 (2)	C4—C5—C6—C1	−0.5 (2)
N1—C1—C2—C3	175.14 (12)	C2—C1—C6—C5	−0.1 (2)
C1—C2—C3—C4	−0.9 (2)	N1—C1—C6—C5	−174.66 (12)
C2—C3—C4—F1	−179.79 (12)	C1—N1—C7—N2	10.3 (2)
C2—C3—C4—C5	0.2 (2)	C1—N1—C7—S1	−169.25 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1ⁱ	0.88	2.43	3.2841 (12)	163
N2—H2B···F1ⁱⁱ	0.88	2.30	3.0989 (15)	152

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

Experimental details

Crystal data
Chemical formula	C₇H₇FN₂S
M_r	170.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	120
a, b, c (Å)	9.1384 (8), 8.4338 (7), 10.5334 (9)
β (°)	109.796 (2)
V (Å³)	763.85 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.37
Crystal size (mm)	0.43 × 0.39 × 0.29

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.857, 0.900
No. of measured, independent and observed [I > 2σ(I)] reflections	6816, 1814, 1645
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.097, 1.05
No. of reflections	1814
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.31

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1ⁱ	0.88	2.43	3.2841 (12)	163.1
N2—H2B···F1ⁱⁱ	0.88	2.30	3.0989 (15)	151.8

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

Acknowledgements

The authors gratefully acknowledge a research grant from the Higher Education Commission of Pakistan under project No. 20-Miscel/R&D/00/3834.

References

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