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Acta Cryst. (2011). E67, o1849    [ doi:10.1107/S1600536811024743 ]

N-(4-Chlorobutanoyl)-N'-(2-fluorophenyl)thiourea

M. S. M. Yusof, N. F. Embong, E. A. Othman and B. M. Yamin

Abstract top

In the title compound, C11H12ClFN2OS, the asymmetric unit consists of two indenpendent molecules. Both molecules maintain a trans-cis configuration of the positions of the butanoyl and fluorophenyl groups with respect to the thiono group across their C-N bonds and are stabilized by classical intramolecular N-H...O hydrogen bonds. In the crystal, intermolecular N-H...O, C-H...S and N-H...S hydrogen bonds link the molecules into infinite chains along the c axis.

Comment top

The title compound, is analogous to the previously reported N-(4-chlorobutanoyl)-N'-(phenyl)thiourea (Yamin et al., 2011) except the fluoro atom is attached at the ortho-position of the phenyl ring. The asymmetric unit consists of two independent molecules (Fig. 1). The whole molecule is not planar. However, the thiourea N1/C5/S1/N2/C6, N3/C16/S2/N4/C17 fragments and the benzene rings, (C6–C11) and (C17–C22) are each planar with maximum deviation of 0.020 (3)Å for N4 atom from the least square plane. In each molecule, the benzene ring and thiourea moiety forms dihedral angle of 74.78 (19)° and 82.3 (2)°, respectively. The same dihedral angle in N-(4-chlorobutanoyl)-N'-(phenyl)thiourea are 72.98 (12)° and 81.47 (14)°, respectively. The bond lengths and angles are in normal ranges (Allen et al., 1987) and comparable to those in the analog. Both molecules maintain their trans–cis-configuration with respect to the position of the butanoyl and fluorophenyl groups against the thiono C═S-group bond across the C—N bonds. Like in most of the carbonylthiourea derivatives, the classical intramolecular hydrogen bonds between the carbonyl oxygen atom and thioamide hydrogen atom, N2—H2···O1 and N4—H4···O2, in both molecules are present. In the crystal packing, the molecules are linked by N3—H3···S1iii and N1—H1···S2iii; N2—H2···O2i and N4—H4···O1ii; C14—H14A···S1iii and C14—H14B···S2iv intermolecular hydrogen bonds (symmetry codes as in Table 1) and form infinite chains along the c-axis (Fig. 2).

Related literature top

For a related structure, see: Yamin et al. (2011). For standard bond lengths, see: Allen et al. (1987).

Experimental top

A solution of 4-chlorobutanoylisothiocyanate (1.25 g, 6.33 mmol) in 30 ml acetone was added into a flask containing 30 ml acetone solution of 2-floroaniline (0.71 g, 6.33 mmol. The mixture was refluxed for 1 h. Then, the solution was filtered-off and left to evaporate at room temperature. The colourless solid was obtained after one day of evaporation (yield 83%, m.p. 411.7 K–415.5 K)

Refinement top

All H atoms attached to C and N atoms were fixed geometrically and treated as riding with C—H = 0.93Å or 0.97Å (aromatic and methylene) and N—H = 0.86Å (amino) with Uiso(H) = 1.2Ueq(C, N).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as a small spheres of arbitrary radius. intramolecular H bonds are presented by dashed lines.
[Figure 2] Fig. 2. A packing diagram of title compound viewed down the a-axis. H bonds are shown by dashed lines.
N-(4-Chlorobutanoyl)-N'-(2-fluorophenyl)thiourea top
Crystal data top
C11H12ClFN2OSF(000) = 1136
Mr = 274.75Dx = 1.425 Mg m−3
Monoclinic, P21/cMelting point = 411.7–415.5 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 14.818 (7) ÅCell parameters from 1404 reflections
b = 10.291 (5) Åθ = 1.5–25.0°
c = 18.201 (9) ŵ = 0.46 mm−1
β = 112.599 (12)°T = 298 K
V = 2562 (2) Å3Plate, colourless
Z = 80.50 × 0.22 × 0.07 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		4501 independent reflections
Radiation source: fine-focus sealed tube2231 reflections with I > 2σ(I)
graphiteRint = 0.119
Detector resolution: 83.66 pixels mm-1θmax = 25.0°, θmin = 1.5°
ω scansh = −17→16
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		k = −12→12
Tmin = 0.803, Tmax = 0.969l = −13→21
13771 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.063Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.138H-atom parameters constrained
S = 0.89 w = 1/[σ2(Fo2) + (0.0451P)2]
where P = (Fo2 + 2Fc2)/3
4501 reflections(Δ/σ)max < 0.001
307 parametersΔρmax = 0.34 e Å−3
0 restraintsΔρmin = −0.30 e Å−3
Crystal data top
C11H12ClFN2OSV = 2562 (2) Å3
Mr = 274.75Z = 8
Monoclinic, P21/cMo Kα radiation
a = 14.818 (7) ŵ = 0.46 mm−1
b = 10.291 (5) ÅT = 298 K
c = 18.201 (9) Å0.50 × 0.22 × 0.07 mm
β = 112.599 (12)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		4501 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		2231 reflections with I > 2σ(I)
Tmin = 0.803, Tmax = 0.969Rint = 0.119
13771 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.063H-atom parameters constrained
wR(F2) = 0.138Δρmax = 0.34 e Å−3
S = 0.89Δρmin = −0.30 e Å−3
4501 reflectionsAbsolute structure: ?
307 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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
xyzUiso*/Ueq
Cl10.49078 (11)0.21242 (19)0.00799 (10)0.1269 (7)
F11.0669 (2)−0.1688 (3)0.35144 (16)0.0795 (9)
F20.3894 (2)0.7354 (3)0.12270 (17)0.0868 (9)
S11.02276 (8)−0.03047 (12)0.17159 (6)0.0509 (3)
S20.24427 (8)1.01331 (12)0.02342 (6)0.0502 (3)
Cl2−0.23288 (9)0.68710 (13)−0.21630 (7)0.0804 (5)
O10.80228 (19)0.1449 (3)0.26210 (18)0.0562 (9)
O20.0637 (2)0.6917 (3)0.07106 (17)0.0552 (9)
N10.8543 (2)0.0465 (3)0.17333 (18)0.0424 (9)
H10.83350.02120.12460.051*
N20.9869 (2)0.0693 (3)0.29214 (19)0.0428 (9)
H20.94670.10330.31030.051*
N30.0918 (2)0.8641 (3)0.00426 (18)0.0421 (9)
H30.06580.9086−0.03880.051*
N40.2217 (2)0.8449 (3)0.12431 (18)0.0447 (9)
H40.18830.78600.13600.054*
C10.5036 (3)0.1269 (6)0.0958 (3)0.0858 (19)
H1A0.45710.16080.11670.103*
H1B0.48850.03590.08310.103*
C20.6047 (3)0.1386 (5)0.1580 (3)0.0718 (16)
H2A0.61950.22990.17000.086*
H2B0.60650.09660.20630.086*
C30.6818 (3)0.0806 (5)0.1350 (2)0.0547 (13)
H3A0.67900.12080.08600.066*
H3B0.6682−0.01130.12460.066*
C40.7839 (3)0.0961 (4)0.1974 (3)0.0453 (11)
C50.9539 (3)0.0312 (4)0.2162 (2)0.0410 (11)
C61.0875 (3)0.0553 (4)0.3442 (2)0.0407 (11)
C71.1249 (3)−0.0633 (5)0.3737 (3)0.0522 (12)
C81.2206 (4)−0.0794 (6)0.4252 (3)0.0739 (16)
H81.2448−0.16130.44450.089*
C91.2793 (4)0.0285 (7)0.4472 (3)0.0822 (19)
H91.34430.01980.48160.099*
C101.2431 (3)0.1484 (6)0.4192 (3)0.0786 (17)
H101.28350.22100.43460.094*
C111.1459 (3)0.1625 (5)0.3675 (3)0.0610 (14)
H111.12090.24440.34890.073*
C12−0.2143 (3)0.6210 (5)−0.1206 (3)0.0691 (15)
H12A−0.25320.6696−0.09770.083*
H12B−0.23690.5316−0.12690.083*
C13−0.1093 (3)0.6249 (4)−0.0646 (2)0.0530 (13)
H13A−0.07130.5723−0.08650.064*
H13B−0.10360.5862−0.01450.064*
C14−0.0659 (3)0.7590 (4)−0.0487 (2)0.0490 (12)
H14A−0.06390.7934−0.09770.059*
H14B−0.10860.8147−0.03340.059*
C150.0351 (3)0.7652 (4)0.0149 (2)0.0418 (11)
C160.1846 (3)0.9006 (4)0.0537 (2)0.0386 (10)
C170.3156 (3)0.8794 (4)0.1821 (2)0.0453 (12)
C180.3983 (3)0.8244 (5)0.1795 (3)0.0566 (13)
C190.4902 (3)0.8541 (6)0.2342 (3)0.0781 (17)
H190.54570.81510.23190.094*
C200.4970 (4)0.9431 (7)0.2921 (4)0.091 (2)
H200.55840.96570.32910.109*
C210.4160 (4)0.9992 (5)0.2966 (3)0.0777 (17)
H210.42211.05880.33660.093*
C220.3243 (3)0.9664 (4)0.2409 (3)0.0571 (13)
H220.26861.00390.24380.069*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0706 (11)0.1612 (18)0.1063 (14)0.0426 (11)−0.0131 (9)0.0101 (12)
F10.077 (2)0.0548 (19)0.098 (2)0.0034 (15)0.0232 (16)0.0093 (16)
F20.068 (2)0.111 (3)0.081 (2)0.0213 (17)0.0283 (16)−0.0051 (19)
S10.0373 (6)0.0695 (9)0.0458 (7)0.0083 (6)0.0157 (5)−0.0007 (6)
S20.0383 (6)0.0665 (9)0.0432 (7)−0.0099 (6)0.0128 (5)0.0030 (6)
Cl20.0695 (9)0.0838 (10)0.0632 (9)−0.0010 (7)−0.0020 (7)−0.0005 (7)
O10.0393 (18)0.072 (2)0.051 (2)0.0063 (15)0.0105 (15)−0.0195 (17)
O20.0491 (19)0.050 (2)0.053 (2)−0.0104 (15)0.0043 (15)0.0103 (16)
N10.0292 (19)0.059 (2)0.035 (2)0.0022 (17)0.0072 (16)−0.0047 (16)
N20.0299 (19)0.052 (2)0.041 (2)0.0042 (16)0.0075 (16)−0.0039 (17)
N30.032 (2)0.052 (2)0.036 (2)−0.0023 (17)0.0056 (16)0.0003 (16)
N40.031 (2)0.054 (2)0.043 (2)−0.0076 (16)0.0067 (16)0.0077 (17)
C10.030 (3)0.135 (5)0.086 (4)−0.007 (3)0.014 (3)−0.035 (4)
C20.037 (3)0.110 (5)0.065 (3)−0.002 (3)0.017 (2)−0.014 (3)
C30.031 (2)0.078 (4)0.051 (3)0.006 (2)0.011 (2)−0.003 (2)
C40.037 (3)0.051 (3)0.045 (3)0.003 (2)0.013 (2)−0.001 (2)
C50.033 (2)0.040 (3)0.045 (3)−0.0013 (19)0.009 (2)0.003 (2)
C60.032 (2)0.053 (3)0.033 (2)0.004 (2)0.0073 (18)−0.004 (2)
C70.046 (3)0.055 (3)0.051 (3)0.007 (3)0.013 (2)−0.002 (2)
C80.058 (4)0.089 (4)0.061 (3)0.032 (3)0.007 (3)0.008 (3)
C90.034 (3)0.133 (6)0.063 (4)0.022 (3)0.001 (3)−0.007 (4)
C100.036 (3)0.100 (5)0.089 (4)−0.013 (3)0.011 (3)−0.026 (3)
C110.047 (3)0.055 (3)0.070 (3)0.003 (2)0.010 (2)−0.007 (3)
C120.050 (3)0.082 (4)0.068 (3)−0.022 (3)0.015 (3)−0.010 (3)
C130.046 (3)0.059 (3)0.048 (3)−0.012 (2)0.011 (2)−0.004 (2)
C140.032 (2)0.052 (3)0.060 (3)0.003 (2)0.014 (2)−0.004 (2)
C150.032 (2)0.042 (3)0.045 (3)0.000 (2)0.008 (2)−0.007 (2)
C160.028 (2)0.048 (3)0.038 (3)−0.0008 (19)0.0109 (19)−0.003 (2)
C170.031 (3)0.053 (3)0.043 (3)−0.005 (2)0.005 (2)0.010 (2)
C180.045 (3)0.069 (4)0.053 (3)0.000 (3)0.016 (2)0.005 (3)
C190.037 (3)0.104 (5)0.082 (4)0.006 (3)0.011 (3)0.025 (4)
C200.047 (4)0.105 (5)0.089 (5)−0.022 (4)−0.007 (3)0.022 (4)
C210.068 (4)0.077 (4)0.068 (4)−0.016 (3)0.005 (3)−0.013 (3)
C220.050 (3)0.053 (3)0.058 (3)0.001 (2)0.009 (2)0.000 (3)
Geometric parameters (Å, °) top
Cl1—C11.769 (6)C6—C71.361 (6)
F1—C71.347 (5)C6—C111.365 (5)
F2—C181.350 (5)C7—C81.377 (6)
S1—C51.654 (4)C8—C91.372 (7)
S2—C161.675 (4)C8—H80.9300
Cl2—C121.791 (5)C9—C101.364 (7)
O1—C41.212 (4)C9—H90.9300
O2—C151.210 (4)C10—C111.393 (6)
N1—C41.374 (5)C10—H100.9300
N1—C51.388 (4)C11—H110.9300
N1—H10.8600C12—C131.498 (5)
N2—C51.336 (5)C12—H12A0.9700
N2—C61.433 (5)C12—H12B0.9700
N2—H20.8600C13—C141.502 (5)
N3—C161.375 (4)C13—H13A0.9700
N3—C151.380 (5)C13—H13B0.9700
N3—H30.8600C14—C151.501 (5)
N4—C161.318 (4)C14—H14A0.9700
N4—C171.430 (5)C14—H14B0.9700
N4—H40.8600C17—C221.363 (6)
C1—C21.496 (5)C17—C181.366 (6)
C1—H1A0.9700C18—C191.377 (6)
C1—H1B0.9700C19—C201.369 (7)
C2—C31.485 (6)C19—H190.9300
C2—H2A0.9700C20—C211.363 (8)
C2—H2B0.9700C20—H200.9300
C3—C41.511 (5)C21—C221.389 (6)
C3—H3A0.9700C21—H210.9300
C3—H3B0.9700C22—H220.9300
C4—N1—C5129.5 (4)C9—C10—C11120.2 (5)
C4—N1—H1115.2C9—C10—H10119.9
C5—N1—H1115.2C11—C10—H10119.9
C5—N2—C6121.9 (4)C6—C11—C10119.5 (5)
C5—N2—H2119.0C6—C11—H11120.2
C6—N2—H2119.0C10—C11—H11120.2
C16—N3—C15128.2 (3)C13—C12—Cl2112.4 (4)
C16—N3—H3115.9C13—C12—H12A109.1
C15—N3—H3115.9Cl2—C12—H12A109.1
C16—N4—C17122.1 (3)C13—C12—H12B109.1
C16—N4—H4118.9Cl2—C12—H12B109.1
C17—N4—H4118.9H12A—C12—H12B107.8
C2—C1—Cl1111.9 (4)C12—C13—C14114.3 (4)
C2—C1—H1A109.2C12—C13—H13A108.7
Cl1—C1—H1A109.2C14—C13—H13A108.7
C2—C1—H1B109.2C12—C13—H13B108.7
Cl1—C1—H1B109.2C14—C13—H13B108.7
H1A—C1—H1B107.9H13A—C13—H13B107.6
C3—C2—C1114.2 (4)C15—C14—C13114.4 (3)
C3—C2—H2A108.7C15—C14—H14A108.7
C1—C2—H2A108.7C13—C14—H14A108.7
C3—C2—H2B108.7C15—C14—H14B108.7
C1—C2—H2B108.7C13—C14—H14B108.7
H2A—C2—H2B107.6H14A—C14—H14B107.6
C2—C3—C4113.7 (4)O2—C15—N3123.0 (4)
C2—C3—H3A108.8O2—C15—C14123.2 (4)
C4—C3—H3A108.8N3—C15—C14113.8 (4)
C2—C3—H3B108.8N4—C16—N3117.2 (4)
C4—C3—H3B108.8N4—C16—S2123.2 (3)
H3A—C3—H3B107.7N3—C16—S2119.7 (3)
O1—C4—N1123.3 (4)C22—C17—C18119.0 (4)
O1—C4—C3124.0 (4)C22—C17—N4120.8 (4)
N1—C4—C3112.6 (4)C18—C17—N4120.3 (4)
N2—C5—N1115.8 (4)F2—C18—C17118.9 (4)
N2—C5—S1124.8 (3)F2—C18—C19118.9 (5)
N1—C5—S1119.4 (3)C17—C18—C19122.2 (5)
C7—C6—C11119.3 (4)C20—C19—C18117.7 (5)
C7—C6—N2120.9 (4)C20—C19—H19121.2
C11—C6—N2119.8 (4)C18—C19—H19121.2
F1—C7—C6119.2 (4)C21—C20—C19121.6 (5)
F1—C7—C8118.6 (5)C21—C20—H20119.2
C6—C7—C8122.2 (5)C19—C20—H20119.2
C9—C8—C7118.2 (5)C20—C21—C22119.4 (5)
C9—C8—H8120.9C20—C21—H21120.3
C7—C8—H8120.9C22—C21—H21120.3
C10—C9—C8120.6 (5)C17—C22—C21120.2 (5)
C10—C9—H9119.7C17—C22—H22119.9
C8—C9—H9119.7C21—C22—H22119.9
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O10.862.022.691 (5)134
N2—H2···O2i0.862.403.128 (5)143
N4—H4···O20.862.022.676 (5)133
N4—H4···O1ii0.862.323.033 (5)141
N3—H3···S1iii0.862.593.447 (4)176
N1—H1···S2iii0.862.523.364 (4)169
C3—H3A···Cl10.972.763.189 (5)107
C14—H14A···Cl20.972.823.190 (4)103
C14—H14A···S1iii0.972.963.784 (5)143
C14—H14B···S2iv0.972.743.691 (5)168
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) −x+1, −y+1, −z; (iv) −x, −y+2, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O10.862.022.691 (5)134
N2—H2···O2i0.862.403.128 (5)143
N4—H4···O20.862.022.676 (5)133
N4—H4···O1ii0.862.323.033 (5)141
N3—H3···S1iii0.862.593.447 (4)176
N1—H1···S2iii0.862.523.364 (4)169
C3—H3A···Cl10.972.763.189 (5)107
C14—H14A···Cl20.972.823.190 (4)103
C14—H14A···S1iii0.972.963.784 (5)143
C14—H14B···S2iv0.972.743.691 (5)168
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) −x+1, −y+1, −z; (iv) −x, −y+2, −z.
Acknowledgements top

The authors thank the Malaysian Government, Universiti Kebangsaan Malaysia, Universiti Malaysia Terengganu and the Ministry of Higher Education, Malaysia, for research grants UKM–GUP–NBT–08–27–110 and FRGS 59178.

references
References top

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Spek, A. L. (2009). Acta Cryst. D65, 148–155.

Yamin, B. M., Othman, N. E. A., Yusof, M. S. M. & Embong, F. (2011). Acta Cryst. E67, o419.