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Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1737.
Published online 2010 June 23. doi:  10.1107/S1600536810023354
PMCID: PMC3007081

2-(4-Fluoro­phen­yl)-3-[5-(4-nitro­phen­yl)-1,3,4-thia­diazol-2-yl]-1,3-thia­zolidin-4-one

Abstract

In the title compound, C17H11FN4O3S2, the five-membered thia­zolidinone and thia­diazole rings are almost planar, with r.m.s. deviations of 0.017 and 0.0019 Å, respectively. The 4-fluoro­phenyl ring is almost perpendicular to the thia­diazole ring, making a dihedral angle of 89.5 (3)°. The 4-nitro­phenyl ring is nearly coplanar with the thia­diazole ring, the dihedral angle being 7.9 (3)°. The crystal structure is stabilized by two inter­molecular C—H(...)O hydrogen bonds.

Related literature

For the chemical and pharmaceutical properties of thia­diazole derivatives, see: Arun et al. (1999 [triangle]); Chen et al. (2000 [triangle]); Kidwai et al. (2000 [triangle]); Vicentini et al. (1998 [triangle]); Wasfy et al. (1996 [triangle]). For a related structure, see: Wan et al. (2008 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1737-scheme1.jpg

Experimental

Crystal data

  • C17H11FN4O3S2
  • M r = 402.44
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1737-efi1.jpg
  • a = 7.2360 (14) Å
  • b = 9.1340 (18) Å
  • c = 14.464 (3) Å
  • α = 71.67 (2)°
  • β = 87.16 (3)°
  • γ = 75.69 (2)°
  • V = 878.9 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.34 mm−1
  • T = 293 K
  • 0.30 × 0.10 × 0.05 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.905, T max = 0.983
  • 3470 measured reflections
  • 3195 independent reflections
  • 1330 reflections with I > 2σ(I)
  • R int = 0.036
  • 3 standard reflections every 200 reflections intensity decay: 1%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.060
  • wR(F 2) = 0.086
  • S = 0.96
  • 3195 reflections
  • 244 parameters
  • 2 restraints
  • H-atom parameters constrained
  • Δρmax = 0.24 e Å−3
  • Δρmin = −0.16 e Å−3

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1989 [triangle]); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810023354/pv2286sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810023354/pv2286Isup2.hkl

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

Acknowledgments

The authors would like to thank Professor Hua-qin Wang of Nanjing University for carrying out the X-ray crystallographic analysis.

supplementary crystallographic information

Comment

1,3,4-Thiadiazole derivatives containing thiazolidinone unit are of great interest because of their chemical and pharmaceutical properties. Some derivatives have fungicidal activities and exhibit herbicidal activities (Chen et al., 2000; Kidwai et al., 2000; Vicentini et al., 1998). Some thiadiazole derivatives show insecticidal activities (Arun et al., 1999; Wasfy et al.,1996). We report here the crystal structure of the titled compound,(I).

The molecular strucutre of (I) is shown in Fig. 1. The bond distances and bond angles in (I) are normal (Allen et al., 1987). In the title structure, unlike the structure of a related compound reported previously (Wan et al., 2008), ring A (C7/S1/C8/C9/N1) is a planar five-mermbered ring and the mean deviation from the plane is 0.0170 Å. Rings B (C1—C6), C (S2/C10/N2/N3/C11) and D (C12—C17) are also individually planar. The dihedral angles between the mean-planes of the rings are: A/B = 85.2 (2) °, A/C = 7.3 (3) °, A/D = 1.1 (1) °, B/C = 89.5 (2) °, B/D = 85.6 (3)° and C/D = 7.9 (3) °. The intramolecular C—H···S hydrogen bond (Tab. 1) results in the formation of a planar five-membered ring (S2/C11/C12/C13/H13A). In the crystal structure, intermolecular C—H···O hydrogen bonds link the molecules to form a dimeric unit (Tab. 1 & Fig. 2), which may be effective in the stabilization of the structure.

Experimental

N-(4-Fluorobenzylidene)-5-(4-nitrophenyl)-1,3,4-thiadiazol-2-amine and mercapto-acetic acid (5 mmol) were added in toluene (50 ml). The water produced in the reaction was collected in a Dean-Stark water separator. The reaction mixture was left to cool to room temperature, filtered, and the filterate was crystallized from acetone to give pure compound (I) (m.p. 468–469 K). Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of an acetone solution.

Refinement

All H atoms were positioned geometrically, with C—H = 0.98, 0.97, 0.96 and 0.93 Å for methine, methylene, methyl and aromatic H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H atoms and x = 1.2 for all other H atoms.

Figures

Fig. 1.
A view of the molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate intramolecular C—H···S hydrogen bond.
Fig. 2.
A packing diagram for (I). Dashed lines indicate intramolecular C—H···S hydrogen bond, and intermolecular C—H···O hydrogen bonds.

Crystal data

C17H11FN4O3S2Z = 2
Mr = 402.44F(000) = 412
Triclinic, P1Dx = 1.521 Mg m3
Hall symbol: -P 1Melting point = 468–469 K
a = 7.2360 (14) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.1340 (18) ÅCell parameters from 25 reflections
c = 14.464 (3) Åθ = 8–12°
α = 71.67 (2)°µ = 0.34 mm1
β = 87.16 (3)°T = 293 K
γ = 75.69 (2)°Plate, colorless
V = 878.9 (3) Å30.30 × 0.10 × 0.05 mm

Data collection

Enraf–Nonius CAD-4 diffractometer1330 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.036
graphiteθmax = 25.3°, θmin = 1.5°
ω/2θ scansh = 0→8
Absorption correction: ψ scan (North et al., 1968)k = −10→10
Tmin = 0.905, Tmax = 0.983l = −17→17
3470 measured reflections3 standard reflections every 200 reflections
3195 independent reflections intensity decay: 1%

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)] = 0.060Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086H-atom parameters constrained
S = 0.96w = 1/[σ2(Fo2) + (0.010P)2] where P = (Fo2 + 2Fc2)/3
3195 reflections(Δ/σ)max < 0.001
244 parametersΔρmax = 0.24 e Å3
2 restraintsΔρmin = −0.16 e Å3

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.
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
S1−0.38553 (16)0.40768 (16)0.33761 (10)0.1076 (5)
S20.04152 (14)0.21307 (12)0.06830 (8)0.0692 (3)
F0.4006 (4)0.1694 (3)0.5770 (2)0.1367 (11)
O1−0.2824 (4)0.1676 (4)0.1585 (2)0.0930 (11)
O20.9132 (6)0.1639 (5)−0.2536 (3)0.1480 (18)
O30.7277 (6)0.0551 (5)−0.2946 (3)0.1517 (18)
N1−0.1477 (4)0.3266 (4)0.2108 (2)0.0661 (9)
N20.1157 (5)0.4161 (3)0.1383 (2)0.0683 (10)
N30.2535 (5)0.3935 (4)0.0692 (2)0.0762 (11)
N40.7610 (8)0.1341 (6)−0.2506 (4)0.1108 (18)
C10.0664 (6)0.1986 (6)0.3988 (3)0.0880 (15)
H1A0.01170.12880.38130.106*
C20.2070 (8)0.1378 (7)0.4716 (4)0.1105 (19)
H2B0.25810.02900.49850.133*
C30.2620 (7)0.2377 (9)0.4996 (4)0.105 (2)
C40.2190 (8)0.4000 (8)0.4583 (4)0.1027 (19)
H4A0.27630.46640.47800.123*
C50.0798 (7)0.4547 (6)0.3836 (4)0.0941 (16)
H5A0.03560.56370.35380.113*
C60.0073 (6)0.3531 (6)0.3532 (3)0.0699 (12)
C7−0.1554 (5)0.4201 (4)0.2769 (3)0.0673 (12)
H7A−0.15820.53080.23980.081*
C8−0.4389 (6)0.2787 (5)0.2801 (3)0.0997 (14)
H8A−0.44800.17990.32890.120*
H8B−0.56120.32700.24540.120*
C9−0.2846 (7)0.2443 (6)0.2088 (4)0.0880 (16)
C10−0.0012 (5)0.3287 (4)0.1446 (3)0.0618 (11)
C110.2339 (6)0.2965 (5)0.0283 (3)0.0618 (12)
C120.3617 (6)0.2569 (5)−0.0445 (3)0.0707 (12)
C130.3348 (6)0.1556 (5)−0.0957 (3)0.0773 (13)
H13A0.23040.1107−0.08280.093*
C140.4619 (7)0.1221 (5)−0.1651 (3)0.0899 (15)
H14A0.43810.0628−0.20290.108*
C150.6262 (7)0.1787 (5)−0.1773 (3)0.0748 (13)
C160.6601 (6)0.2724 (6)−0.1301 (3)0.0924 (15)
H16A0.76800.3127−0.14230.111*
C170.5285 (6)0.3094 (5)−0.0611 (3)0.0749 (13)
H17A0.55400.3712−0.02540.090*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0478 (7)0.1601 (13)0.1320 (12)−0.0182 (8)0.0108 (8)−0.0759 (11)
S20.0633 (7)0.0719 (8)0.0791 (8)−0.0314 (6)−0.0064 (6)−0.0202 (6)
F0.130 (3)0.152 (3)0.127 (2)−0.024 (2)−0.024 (2)−0.047 (2)
O10.080 (2)0.109 (3)0.109 (3)−0.049 (2)0.001 (2)−0.040 (2)
O20.150 (4)0.155 (4)0.172 (4)−0.060 (3)0.080 (4)−0.090 (3)
O30.139 (4)0.198 (4)0.144 (4)−0.012 (3)0.007 (3)−0.113 (3)
N10.051 (2)0.087 (3)0.063 (2)−0.024 (2)−0.0025 (19)−0.021 (2)
N20.069 (2)0.061 (2)0.078 (3)−0.015 (2)−0.004 (2)−0.027 (2)
N30.074 (3)0.089 (3)0.072 (3)−0.035 (2)0.010 (2)−0.025 (2)
N40.112 (4)0.113 (4)0.083 (4)0.012 (4)0.017 (4)−0.029 (3)
C10.069 (3)0.091 (4)0.076 (4)−0.004 (3)−0.002 (3)0.002 (3)
C20.099 (5)0.114 (5)0.092 (5)−0.009 (4)0.001 (3)−0.008 (4)
C30.066 (4)0.160 (7)0.091 (5)−0.011 (5)−0.013 (3)−0.054 (5)
C40.077 (4)0.151 (5)0.119 (5)−0.045 (4)0.019 (4)−0.085 (5)
C50.066 (3)0.126 (5)0.111 (4)−0.028 (3)0.027 (3)−0.065 (4)
C60.047 (3)0.106 (4)0.058 (3)−0.020 (3)0.004 (2)−0.028 (3)
C70.063 (3)0.079 (3)0.068 (3)−0.023 (3)0.004 (2)−0.029 (3)
C80.076 (3)0.146 (4)0.084 (4)−0.051 (3)0.008 (3)−0.027 (3)
C90.070 (3)0.110 (5)0.080 (4)−0.037 (3)−0.004 (3)−0.011 (3)
C100.046 (3)0.068 (3)0.073 (3)−0.013 (2)−0.013 (2)−0.024 (3)
C110.072 (3)0.066 (3)0.061 (3)−0.043 (2)0.004 (2)−0.020 (2)
C120.076 (3)0.067 (3)0.066 (3)−0.025 (3)−0.006 (3)−0.009 (3)
C130.081 (3)0.064 (3)0.093 (4)−0.017 (3)−0.003 (3)−0.032 (3)
C140.120 (5)0.079 (3)0.082 (4)−0.030 (3)−0.020 (3)−0.032 (3)
C150.079 (4)0.066 (3)0.071 (4)−0.027 (3)−0.001 (3)−0.002 (3)
C160.073 (4)0.111 (4)0.096 (4)−0.024 (3)−0.008 (3)−0.033 (3)
C170.066 (3)0.081 (3)0.087 (4)−0.036 (3)−0.002 (3)−0.025 (3)

Geometric parameters (Å, °)

S1—C81.761 (4)C4—C51.397 (6)
S1—C71.855 (3)C4—H4A0.9300
S2—C101.723 (4)C5—C61.360 (5)
S2—C111.738 (3)C5—H5A0.9300
F—C31.418 (5)C6—C71.526 (5)
O1—C91.155 (5)C7—H7A0.9800
O2—N41.194 (5)C8—C91.525 (5)
O3—N41.172 (5)C8—H8A0.9700
N1—C91.390 (5)C8—H8B0.9700
N1—C101.392 (4)C11—C121.439 (5)
N1—C71.460 (4)C12—C171.389 (5)
N2—C101.281 (4)C12—C131.406 (4)
N2—N31.401 (4)C13—C141.381 (5)
N3—C111.248 (4)C13—H13A0.9300
N4—C151.489 (6)C14—C151.391 (5)
C1—C61.324 (5)C14—H14A0.9300
C1—C21.382 (6)C15—C161.321 (5)
C1—H1A0.9300C16—C171.405 (5)
C2—C31.257 (6)C16—H16A0.9300
C2—H2B0.9300C17—H17A0.9300
C3—C41.373 (6)
C8—S1—C795.25 (18)C9—C8—S1110.5 (3)
C10—S2—C1186.21 (19)C9—C8—H8A109.6
C9—N1—C10120.0 (4)S1—C8—H8A109.6
C9—N1—C7122.6 (4)C9—C8—H8B109.6
C10—N1—C7117.3 (3)S1—C8—H8B109.6
C10—N2—N3110.6 (3)H8A—C8—H8B108.1
C11—N3—N2114.2 (3)O1—C9—N1124.8 (5)
O3—N4—O2121.2 (6)O1—C9—C8126.7 (5)
O3—N4—C15120.6 (6)N1—C9—C8108.5 (4)
O2—N4—C15117.5 (6)N2—C10—N1121.3 (4)
C6—C1—C2122.1 (5)N2—C10—S2115.0 (3)
C6—C1—H1A118.9N1—C10—S2123.6 (3)
C2—C1—H1A118.9N3—C11—C12122.5 (4)
C3—C2—C1116.3 (6)N3—C11—S2113.9 (3)
C3—C2—H2B121.8C12—C11—S2123.6 (3)
C1—C2—H2B121.8C17—C12—C13116.9 (4)
C2—C3—C4128.0 (6)C17—C12—C11119.8 (4)
C2—C3—F114.2 (7)C13—C12—C11123.2 (4)
C4—C3—F117.4 (6)C14—C13—C12120.7 (4)
C3—C4—C5112.7 (5)C14—C13—H13A119.7
C3—C4—H4A123.7C12—C13—H13A119.7
C5—C4—H4A123.7C13—C14—C15118.8 (4)
C6—C5—C4121.9 (5)C13—C14—H14A120.6
C6—C5—H5A119.1C15—C14—H14A120.6
C4—C5—H5A119.1C16—C15—C14122.9 (5)
C1—C6—C5118.4 (5)C16—C15—N4120.7 (5)
C1—C6—C7121.8 (5)C14—C15—N4116.4 (5)
C5—C6—C7119.4 (5)C15—C16—C17118.2 (5)
N1—C7—C6113.5 (3)C15—C16—H16A120.9
N1—C7—S1102.9 (2)C17—C16—H16A120.9
C6—C7—S1109.6 (3)C12—C17—C16122.3 (4)
N1—C7—H7A110.2C12—C17—H17A118.9
C6—C7—H7A110.2C16—C17—H17A118.9
S1—C7—H7A110.2
C10—N2—N3—C110.7 (5)N3—N2—C10—S2−0.5 (4)
C6—C1—C2—C37.2 (8)C9—N1—C10—N2173.0 (4)
C1—C2—C3—C4−9.5 (9)C7—N1—C10—N2−3.8 (5)
C1—C2—C3—F177.5 (4)C9—N1—C10—S2−8.7 (5)
C2—C3—C4—C57.9 (9)C7—N1—C10—S2174.5 (3)
F—C3—C4—C5−179.4 (4)C11—S2—C10—N20.2 (3)
C3—C4—C5—C6−3.8 (7)C11—S2—C10—N1−178.2 (3)
C2—C1—C6—C5−4.0 (7)N2—N3—C11—C12−179.7 (3)
C2—C1—C6—C7−176.6 (4)N2—N3—C11—S2−0.6 (5)
C4—C5—C6—C12.5 (6)C10—S2—C11—N30.2 (3)
C4—C5—C6—C7175.2 (4)C10—S2—C11—C12179.4 (4)
C9—N1—C7—C6113.8 (4)N3—C11—C12—C179.3 (6)
C10—N1—C7—C6−69.5 (4)S2—C11—C12—C17−169.8 (3)
C9—N1—C7—S1−4.6 (4)N3—C11—C12—C13−175.9 (4)
C10—N1—C7—S1172.1 (3)S2—C11—C12—C135.0 (6)
C1—C6—C7—N1−41.7 (5)C17—C12—C13—C14−5.3 (6)
C5—C6—C7—N1145.9 (4)C11—C12—C13—C14179.8 (4)
C1—C6—C7—S172.8 (5)C12—C13—C14—C155.7 (7)
C5—C6—C7—S1−99.7 (4)C13—C14—C15—C16−4.8 (7)
C8—S1—C7—N13.4 (3)C13—C14—C15—N4177.9 (4)
C8—S1—C7—C6−117.7 (3)O3—N4—C15—C16−177.6 (5)
C7—S1—C8—C9−2.0 (3)O2—N4—C15—C1611.9 (8)
C10—N1—C9—O14.3 (7)O3—N4—C15—C14−0.2 (7)
C7—N1—C9—O1−179.1 (5)O2—N4—C15—C14−170.8 (5)
C10—N1—C9—C8−173.2 (3)C14—C15—C16—C173.3 (7)
C7—N1—C9—C83.4 (5)N4—C15—C16—C17−179.5 (4)
S1—C8—C9—O1−177.7 (5)C13—C12—C17—C163.9 (6)
S1—C8—C9—N1−0.2 (5)C11—C12—C17—C16179.0 (4)
N3—N2—C10—N1177.9 (3)C15—C16—C17—C12−2.9 (7)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C5—H5A···O2i0.932.563.411 (7)152
C13—H13A···S20.932.813.184 (5)106
C14—H14A···O1ii0.932.523.198 (6)130

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2286).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Arun, K. P., Nag, V. L. & Panda, C. S. (1999). Indian J. Chem. Sect. B, 38, 998–1001.
  • Chen, H. S., Li, Z. M. & Han, Y. F. (2000). J. Agric. Food Chem.48, 5312–5315. [PubMed]
  • Enraf-Nonius (1989). CAD-4 EXPRESS Enraf-Nonius, Delft, The Netherlands.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • Kidwai, M., Negi, N. & Misra, P. (2000). J. Indian Chem. Soc.77, 46–48.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Vicentini, C. B., Manfrini, M., Veronese, A. C. & Guarneri, M. (1998). J. Heterocycl. Chem.35, 29–36.
  • Wan, R., Yin, L., Han, F., Wang, B. & Wang, J. (2008). Acta Cryst. E64, o260. [PMC free article] [PubMed]
  • Wasfy, A. A., Nassar, S. A. & Eissa, A. M. (1996). Indian J. Chem. Sect. B, 35, 1218–1220.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography