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Acta Crystallogr Sect E Struct Rep Online. 2010 May 1; 66(Pt 5): o1018.
Published online 2010 April 2. doi:  10.1107/S1600536810011682
PMCID: PMC2979150

4-(2-Fluoro­phen­yl)-1-(2-oxoindolin-3-yl­idene)thio­semicarbazide

Abstract

The title compound, C15H11FN4OS, is almost planar, the dihedral angle between the aromatic ring systems being 5.00 (13)°. The conformation is stabilized by intra­molecular N—H(...)N and N—H(...)O hydrogen bonds, which generate S(5) and S(6) rings, respectively. N—H(...)F and C—H(...)S inter­actions also occur. In the crystal, inversion dimers linked by pairs of N—H(...)O hydrogen bonds occur, generating R 2 2(8) loops.

Related literature

For related structures and medicinal background, see: Pervez et al. (2009 [triangle], 2010 [triangle]). For graph-set theory, see: Bernstein et al. (1995 [triangle]).

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Object name is e-66-o1018-scheme1.jpg

Experimental

Crystal data

  • C15H11FN4OS
  • M r = 314.34
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1018-efi1.jpg
  • a = 5.7646 (3) Å
  • b = 18.4939 (12) Å
  • c = 13.6772 (8) Å
  • β = 91.212 (3)°
  • V = 1457.80 (15) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.24 mm−1
  • T = 296 K
  • 0.30 × 0.14 × 0.12 mm

Data collection

  • Bruker Kappa APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.963, T max = 0.971
  • 11407 measured reflections
  • 2626 independent reflections
  • 1437 reflections with I > 2σ(I)
  • R int = 0.068

Refinement

  • R[F 2 > 2σ(F 2)] = 0.047
  • wR(F 2) = 0.114
  • S = 0.96
  • 2626 reflections
  • 199 parameters
  • H-atom parameters constrained
  • Δρmax = 0.15 e Å−3
  • Δρmin = −0.22 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810011682/hb5381sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810011682/hb5381Isup2.hkl

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

Acknowledgments

HP, MY and MR wish to acknowledge partial financial assistance given by the MoST, Government of Pakistan, under Projects for the Strengthening of S&T Education in Universities (Project No. P&D/S&T/2001/231).

supplementary crystallographic information

Comment

As part of our ongoing studies of N4-arylsubstituted isatins-3-thiosemecarbazones with certain medicinal applications (Pervez et al., 2009, 2010), we now report the synthesis and crystal structure of the title compound (I, Fig. 1).

The crystal structure of (II) i.e. 1-(5-nitro-2-oxoindolino-3-ylidene)- 4-o-tolylthiosemicarbazide methanol monosolvate (Pervez et al., 2009) has been published. The title compound (I) differs from (II) due to the absence of nitro function at position-5 of the isatin scaffold and presence of fluoro instead of methyl group at position-2 of the phenyl ring substituted at N4 of the thiosemicarbazone moiety. In (I), the 2-oxoindolin A (C1–C8/N1/O1), thiosemicarbazide B (N2/N3/C9/S1/N4) and the 2-fluorophenyl C (C10—C15/F1) are planar with maximum r. m. s. deviations of 0.0289, 0.0261 and 0.0056 Å, respectively. Due to intramolecular H-bondings (Table 1, Fig. 1), two S(5) and two S(6) (Bernstein et al., 1995) ring motifs are formed. The molecules are dimerised due to intermolecular H-bonding of N—H···O type with R22(8) ring motifs.

Experimental

To a hot solution of isatin (0.74 g, 5.0 mmol) in ethanol (10 ml) containing a few drops of glacial acetic acid was added 4-o -fluorophenylthiosemicarbazide (0.93 g, 5.0 mmol) dissolved in ethanol (10 ml) under stirring. The reaction mixture was then heated under reflux for 2 h. The yellow crystalline solid formed during refluxing was collected by suction filtration. Thorough washing with hot ethanol followed by ether furnished the target compound (I) in pure form (1.20 g, 76 %), m.p. 505-507 K (d). The dark yellow needles of (I) were grown in ethyl acetate-petroleum ether (1:5) system by diffusion method at room temperature.

Figures

Fig. 1.
View of (I) with ellipsoids drawn at the 50% probability level. The dotted lines indicate the intramolecular H-bonds.
Fig. 2.
The partial packing of (I), which shows that molecules form inversion dimers.

Crystal data

C15H11FN4OSF(000) = 648
Mr = 314.34Dx = 1.432 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2626 reflections
a = 5.7646 (3) Åθ = 3.5–25.3°
b = 18.4939 (12) ŵ = 0.24 mm1
c = 13.6772 (8) ÅT = 296 K
β = 91.212 (3)°Needle, dark yellow
V = 1457.80 (15) Å30.30 × 0.14 × 0.12 mm
Z = 4

Data collection

Bruker Kappa APEXII CCD diffractometer2626 independent reflections
Radiation source: fine-focus sealed tube1437 reflections with I > 2σ(I)
graphiteRint = 0.068
Detector resolution: 7.80 pixels mm-1θmax = 25.3°, θmin = 3.5°
ω scansh = −6→6
Absorption correction: multi-scan (SADABS; Bruker, 2005)k = −21→22
Tmin = 0.963, Tmax = 0.971l = −16→16
11407 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114H-atom parameters constrained
S = 0.96w = 1/[σ2(Fo2) + (0.0467P)2] where P = (Fo2 + 2Fc2)/3
2626 reflections(Δ/σ)max < 0.001
199 parametersΔρmax = 0.15 e Å3
0 restraintsΔρmin = −0.22 e Å3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles
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)

xyzUiso*/Ueq
S10.09191 (15)0.20047 (5)0.00689 (6)0.0742 (3)
F1−0.0601 (3)0.14317 (12)0.37578 (11)0.0911 (9)
O10.7157 (3)0.04818 (11)0.01234 (13)0.0575 (8)
N10.9081 (4)−0.02584 (13)0.12316 (16)0.0547 (9)
N20.4000 (4)0.06836 (12)0.18384 (15)0.0489 (8)
N30.3340 (4)0.10541 (12)0.10344 (15)0.0510 (8)
N40.0393 (3)0.15113 (12)0.19057 (14)0.0499 (8)
C10.5848 (5)0.02916 (15)0.17922 (19)0.0474 (10)
C20.7385 (5)0.01971 (16)0.0932 (2)0.0494 (11)
C30.8851 (5)−0.04562 (15)0.2217 (2)0.0513 (10)
C41.0273 (5)−0.08819 (17)0.2785 (2)0.0696 (12)
C50.9689 (6)−0.09758 (19)0.3747 (3)0.0803 (14)
C60.7757 (6)−0.06518 (19)0.4128 (2)0.0774 (15)
C70.6305 (5)−0.02238 (17)0.3550 (2)0.0658 (11)
C80.6871 (4)−0.01264 (15)0.25825 (19)0.0494 (10)
C90.1480 (5)0.15218 (15)0.10471 (18)0.0486 (10)
C10−0.1520 (4)0.19126 (15)0.22268 (19)0.0479 (10)
C11−0.2029 (5)0.18597 (18)0.3198 (2)0.0626 (11)
C12−0.3861 (6)0.2210 (2)0.3614 (3)0.0864 (14)
C13−0.5248 (6)0.2633 (2)0.3026 (3)0.0849 (16)
C14−0.4818 (5)0.26920 (18)0.2062 (3)0.0743 (14)
C15−0.2977 (5)0.23337 (16)0.1658 (2)0.0623 (11)
H11.01726−0.040970.086430.0657*
H30.409140.099840.050300.0611*
H41.15840−0.109960.253130.0834*
H4A0.095730.121070.232750.0598*
H51.06218−0.126470.414990.0960*
H60.74193−0.072120.478280.0929*
H70.49911−0.000910.380650.0791*
H12−0.414960.216190.427760.1037*
H13−0.649120.288090.329020.1015*
H14−0.577700.297790.166680.0892*
H15−0.271610.237710.099190.0747*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0779 (6)0.0878 (7)0.0577 (5)0.0167 (5)0.0193 (4)0.0148 (5)
F10.0833 (14)0.1408 (19)0.0495 (10)0.0171 (13)0.0103 (9)−0.0024 (11)
O10.0453 (12)0.0735 (15)0.0543 (12)0.0021 (10)0.0167 (9)−0.0014 (11)
N10.0398 (14)0.0640 (17)0.0610 (15)0.0076 (12)0.0148 (11)−0.0042 (13)
N20.0410 (14)0.0541 (15)0.0519 (14)0.0019 (12)0.0100 (11)−0.0051 (12)
N30.0481 (14)0.0577 (16)0.0477 (14)0.0049 (12)0.0153 (11)−0.0039 (12)
N40.0460 (14)0.0585 (16)0.0455 (13)0.0098 (12)0.0118 (11)−0.0016 (11)
C10.0397 (16)0.0486 (18)0.0544 (17)−0.0033 (14)0.0127 (13)−0.0092 (14)
C20.0399 (17)0.055 (2)0.0537 (18)−0.0072 (15)0.0124 (13)−0.0104 (15)
C30.0417 (17)0.0550 (19)0.0574 (18)0.0009 (15)0.0072 (14)−0.0036 (16)
C40.054 (2)0.076 (2)0.079 (2)0.0149 (18)0.0073 (17)0.0046 (19)
C50.075 (2)0.089 (3)0.077 (2)0.017 (2)0.0008 (19)0.012 (2)
C60.086 (3)0.090 (3)0.0564 (19)0.010 (2)0.0068 (18)0.0090 (19)
C70.065 (2)0.077 (2)0.0558 (19)0.0075 (19)0.0142 (16)−0.0024 (17)
C80.0425 (17)0.0527 (19)0.0532 (17)0.0001 (14)0.0055 (13)−0.0062 (15)
C90.0448 (17)0.0512 (18)0.0504 (16)−0.0002 (15)0.0124 (13)−0.0052 (14)
C100.0404 (16)0.0517 (19)0.0518 (17)−0.0038 (15)0.0073 (13)−0.0137 (14)
C110.0508 (19)0.085 (2)0.0519 (18)0.0027 (18)0.0005 (15)−0.0134 (17)
C120.065 (2)0.131 (3)0.064 (2)0.001 (2)0.0214 (18)−0.036 (2)
C130.049 (2)0.106 (3)0.100 (3)0.008 (2)0.010 (2)−0.044 (2)
C140.053 (2)0.075 (2)0.095 (3)0.0098 (18)0.0041 (18)−0.016 (2)
C150.0504 (18)0.069 (2)0.068 (2)0.0058 (17)0.0099 (15)−0.0038 (17)

Geometric parameters (Å, °)

S1—C91.635 (3)C5—C61.377 (5)
F1—C111.365 (4)C6—C71.387 (4)
O1—C21.229 (3)C7—C81.381 (4)
N1—C21.348 (4)C10—C151.375 (4)
N1—C31.406 (4)C10—C111.370 (4)
N2—N31.344 (3)C11—C121.373 (5)
N2—C11.291 (4)C12—C131.368 (5)
N3—C91.378 (4)C13—C141.351 (6)
N4—C91.343 (3)C14—C151.377 (4)
N4—C101.407 (3)C4—H40.9300
N1—H10.8600C5—H50.9300
N3—H30.8600C6—H60.9300
N4—H4A0.8600C7—H70.9300
C1—C81.445 (4)C12—H120.9300
C1—C21.498 (4)C13—H130.9300
C3—C81.396 (4)C14—H140.9300
C3—C41.367 (4)C15—H150.9300
C4—C51.376 (5)
S1···C153.216 (3)C9···C2vi3.403 (4)
S1···C13i3.661 (4)C9···C14iii3.323 (4)
S1···C11ii3.696 (3)C9···O1vi3.372 (3)
S1···C12ii3.665 (4)C10···C1vi3.407 (4)
S1···H152.5600C11···S1vii3.696 (3)
S1···H13i2.8900C12···S1vii3.665 (4)
F1···N42.613 (2)C13···S1viii3.661 (4)
F1···H4A2.2100C14···C9vi3.323 (4)
O1···N23.022 (3)C15···N3vi3.280 (4)
O1···N32.762 (3)C15···S13.216 (3)
O1···C9iii3.372 (3)C2···H32.4700
O1···N3iv3.262 (3)C2···H3iv3.0600
O1···O1iv3.072 (3)C2···H1v2.8800
O1···N1v2.912 (3)C5···H14ix3.0200
O1···C2iv3.218 (3)C6···H14ix2.9800
O1···H32.0800C9···H152.8900
O1···H1v2.0700C14···H4x2.9600
N1···O1v2.912 (3)H1···O1v2.0700
N2···O13.022 (3)H1···C2v2.8800
N2···N42.585 (3)H3···O12.0800
N3···O1iv3.262 (3)H3···C22.4700
N3···O12.762 (3)H3···C2iv3.0600
N3···C15iii3.280 (4)H4···C14xi2.9600
N4···C2vi3.254 (4)H4A···F12.2100
N4···F12.613 (2)H4A···N22.1300
N4···N22.585 (3)H13···S1viii2.8900
N2···H4A2.1300H14···C5xii3.0200
C1···C10iii3.407 (4)H14···C6xii2.9800
C2···N4iii3.254 (4)H15···S12.5600
C2···C9iii3.403 (4)H15···C92.8900
C2···O1iv3.218 (3)
C2—N1—C3111.8 (2)S1—C9—N4129.5 (2)
N3—N2—C1117.8 (2)C11—C10—C15116.6 (2)
N2—N3—C9121.1 (2)N4—C10—C15126.6 (2)
C9—N4—C10130.4 (2)N4—C10—C11116.8 (2)
C3—N1—H1124.00C10—C11—C12123.4 (3)
C2—N1—H1124.00F1—C11—C10116.5 (2)
N2—N3—H3119.00F1—C11—C12120.1 (3)
C9—N3—H3119.00C11—C12—C13118.1 (4)
C10—N4—H4A115.00C12—C13—C14120.2 (3)
C9—N4—H4A115.00C13—C14—C15120.8 (3)
N2—C1—C2127.3 (2)C10—C15—C14120.8 (3)
C2—C1—C8106.6 (2)C3—C4—H4121.00
N2—C1—C8126.0 (2)C5—C4—H4121.00
N1—C2—C1105.8 (2)C4—C5—H5119.00
O1—C2—N1127.2 (3)C6—C5—H5119.00
O1—C2—C1127.1 (3)C5—C6—H6119.00
N1—C3—C4128.9 (3)C7—C6—H6119.00
N1—C3—C8108.9 (2)C6—C7—H7121.00
C4—C3—C8122.2 (3)C8—C7—H7121.00
C3—C4—C5117.4 (3)C11—C12—H12121.00
C4—C5—C6121.6 (3)C13—C12—H12121.00
C5—C6—C7121.1 (3)C12—C13—H13120.00
C6—C7—C8117.9 (3)C14—C13—H13120.00
C1—C8—C3106.9 (2)C13—C14—H14120.00
C3—C8—C7119.8 (2)C15—C14—H14120.00
C1—C8—C7133.3 (2)C10—C15—H15120.00
S1—C9—N3118.23 (19)C14—C15—H15120.00
N3—C9—N4112.3 (2)
C3—N1—C2—O1177.5 (3)C8—C3—C4—C5−0.2 (5)
C3—N1—C2—C1−1.8 (3)N1—C3—C8—C1−0.2 (3)
C2—N1—C3—C4−177.2 (3)N1—C3—C8—C7−178.3 (3)
C2—N1—C3—C81.3 (3)C4—C3—C8—C1178.5 (3)
C1—N2—N3—C9−175.5 (3)C4—C3—C8—C70.3 (4)
N3—N2—C1—C20.0 (4)C3—C4—C5—C6−0.4 (5)
N3—N2—C1—C8178.0 (2)C4—C5—C6—C70.8 (5)
N2—N3—C9—S1174.9 (2)C5—C6—C7—C8−0.7 (5)
N2—N3—C9—N4−4.4 (4)C6—C7—C8—C1−177.4 (3)
C10—N4—C9—S1−0.8 (4)C6—C7—C8—C30.1 (4)
C10—N4—C9—N3178.3 (2)N4—C10—C11—F11.1 (4)
C9—N4—C10—C11−170.6 (3)N4—C10—C11—C12−179.0 (3)
C9—N4—C10—C1511.8 (4)C15—C10—C11—F1179.0 (3)
N2—C1—C2—O10.6 (5)C15—C10—C11—C12−1.1 (5)
N2—C1—C2—N1180.0 (3)N4—C10—C15—C14179.0 (3)
C8—C1—C2—O1−177.7 (3)C11—C10—C15—C141.3 (4)
C8—C1—C2—N11.7 (3)F1—C11—C12—C13−180.0 (3)
N2—C1—C8—C3−179.2 (3)C10—C11—C12—C130.1 (5)
N2—C1—C8—C7−1.5 (5)C11—C12—C13—C140.7 (5)
C2—C1—C8—C3−0.9 (3)C12—C13—C14—C15−0.5 (5)
C2—C1—C8—C7176.9 (3)C13—C14—C15—C10−0.6 (5)
N1—C3—C4—C5178.1 (3)

Symmetry codes: (i) x+1, −y+1/2, z−1/2; (ii) x, −y+1/2, z−1/2; (iii) x+1, y, z; (iv) −x+1, −y, −z; (v) −x+2, −y, −z; (vi) x−1, y, z; (vii) x, −y+1/2, z+1/2; (viii) x−1, −y+1/2, z+1/2; (ix) −x, y−1/2, −z+1/2; (x) −x+1, y+1/2, −z+1/2; (xi) −x+1, y−1/2, −z+1/2; (xii) −x, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O1v0.862.072.912 (3)164
N3—H3···O10.862.082.762 (3)135
N4—H4A···F10.862.212.613 (2)109
N4—H4A···N20.862.132.585 (3)113
C15—H15···S10.932.563.216 (3)128

Symmetry codes: (v) −x+2, −y, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5381).

References

  • Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl.34, 1555-1573.
  • Bruker (2005). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Pervez, H., Manzoor, N., Yaqub, M., Khan, A., Khan, K. M., Nasim, F. H. & Choudhary, M. I. (2010). Lett. Drug Des. Discov. 7, 102-108.
  • Pervez, H., Yaqub, M., Manzoor, N., Tahir, M. N. & Iqbal, M. S. (2009). Acta Cryst. E65, o2858. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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