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Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): o1643.
Published online 2009 June 20. doi:  10.1107/S1600536809022314
PMCID: PMC2969331

4-Fluoro-N-[3-(2-fluoro­phen­yl)-4-methyl-2,3-dihydro-2-thienyl­idene]benzamide

Abstract

In the title compound, C17H12F2N2OS, the planar thia­zole ring (r.m.s. deviation = 0.012 Å) makes dihedral angles of 15.08 (9) and 81.81 (6)° with the 4-fluoro­phenyl and 2-fluoro­phenyl rings, respectively. The 2-fluoro­phenyl ring is disordered over two orientations with site-occupancy factors of 0.810 (3) and 0.190 (3). The structure contains inter­molecular C—H(...)O hydrogen bonds.

Related literature

For the biological activity of imino-1,3-thia­zoline derivatives, see: Kim et al. (2007 [triangle]); Vicini et al. (2006 [triangle]); Hosseinimehr et al. (2001 [triangle]); Zhang et al. (2000 [triangle]); Pietrancosta et al. (2006 [triangle]). For details of the synthesis, see: Saeed et al. (2008a [triangle]). For a related structure, see: Saeed et al. (2008b [triangle]).

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Object name is e-65-o1643-scheme1.jpg

Experimental

Crystal data

  • C17H12F2N2OS
  • M r = 330.35
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1643-efi1.jpg
  • a = 7.0982 (14) Å
  • b = 11.423 (2) Å
  • c = 18.949 (4) Å
  • V = 1536.5 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.24 mm−1
  • T = 173 K
  • 0.36 × 0.34 × 0.28 mm

Data collection

  • Stoe IPDS-II two-circle diffractometer
  • Absorption correction: multi-scan (MULABS; Spek, 2009 [triangle]; Blessing, 1995 [triangle]) T min = 0.920, T max = 0.937
  • 10484 measured reflections
  • 3531 independent reflections
  • 3213 reflections with I > 2σ(I)
  • R int = 0.046

Refinement

  • R[F 2 > 2σ(F 2)] = 0.034
  • wR(F 2) = 0.082
  • S = 0.99
  • 3531 reflections
  • 219 parameters
  • H-atom parameters constrained
  • Δρmax = 0.15 e Å−3
  • Δρmin = −0.26 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1491 Friedel pairs
  • Flack parameter: −0.15 (6)

Data collection: X-AREA (Stoe & Cie, 2001 [triangle]); cell refinement: X-AREA; data reduction: X-AREA; 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: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809022314/bi2375sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809022314/bi2375Isup2.hkl

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

supplementary crystallographic information

Comment

The imino-1,3-thiazoline group is found in a variety of biologically active natural products and finds extensive applications in medicinal chemistry. 2-Thiazolylimino-5-arylidene-4-thiazolidinones show noticeable antimicrobial activity against bacteria, yeasts and mould (Kim et al., 2007). 3-Substituted 2-(cyanoimino)thiazolidines can be used in agriculture due to their neonicotinoid insecticidal activity (Vicini et al., 2006). 3-Substituted thiazolidines show radioprotective properties against γ-radiation (Hosseinimehr et al., 2001). KHG22394, a 2-imino-1,3-thiazoline derivative, significantly inhibits melanin production in a dose-dependent manner, thus acting as a skin whitening agent (Zhang et al., 2000) and pifithrin-alpha, another iminothiazoline, is a reversible inhibitor of p53-mediated apoptosis and p53-dependent gene transcription (Pietrancosta et al., 2006).

Experimental

The title compound was prepared according to the procedure reported earlier (Saeed et al. (2008a). Crystallization of the residue in CHCl3 afforded the title compound (81%) as white needles: Anal. calcd. for C14H12ClNO1: C 68.44, H 4.92, N 5.70%; found: C 68.39, H 4.90, N 5.67%

Refinement

H atoms were geometrically positioned and refined using a riding model with fixed individual displacement parameters [Uiso(H) = 1.2 Ueq(C) or 1.5 Ueq(Cmethyl)] using a riding model with C—H(aromatic) = 0.95 Å or C—H(methyl) = 0.98 Å. The ortho-fluoro-phenyl ring is disordered over two positions with site occupation factors of 0.810 (3) and 0.190 (3).

Figures

Fig. 1.
Perspective view of the title compound with the atom numbering scheme; displacement ellipsoids are at the 50% probability level; H atoms are drawn as small spheres of arbitrary radii. The atoms of the minor occupied sites have been omitted for clarity. ...

Crystal data

C17H12F2N2OSF(000) = 680
Mr = 330.35Dx = 1.428 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 9675 reflections
a = 7.0982 (14) Åθ = 3.4–27.8°
b = 11.423 (2) ŵ = 0.24 mm1
c = 18.949 (4) ÅT = 173 K
V = 1536.5 (5) Å3Block, colourless
Z = 40.36 × 0.34 × 0.28 mm

Data collection

Stoe IPDS-II two-circle diffractometer3531 independent reflections
Radiation source: fine-focus sealed tube3213 reflections with I > 2σ(I)
graphiteRint = 0.046
ω scansθmax = 27.6°, θmin = 3.4°
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995)h = −8→9
Tmin = 0.920, Tmax = 0.937k = −12→14
10484 measured reflectionsl = −24→23

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H-atom parameters constrained
wR(F2) = 0.082w = 1/[σ2(Fo2) + (0.052P)2] where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max = 0.001
3531 reflectionsΔρmax = 0.15 e Å3
219 parametersΔρmin = −0.26 e Å3
0 restraintsAbsolute structure: Flack (1983), 1491 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.15 (6)

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*/UeqOcc. (<1)
S10.86255 (5)0.65177 (5)0.73205 (2)0.04103 (12)
N10.56925 (19)0.59033 (13)0.64274 (7)0.0316 (3)
O10.7594 (2)0.44060 (14)0.68401 (8)0.0520 (4)
F10.0840 (3)0.15356 (14)0.55262 (9)0.0825 (5)
F20.71228 (15)0.86728 (14)0.53579 (6)0.0406 (4)0.810 (3)
F2'0.2818 (7)0.7551 (6)0.7021 (3)0.048 (2)0.190 (3)
C10.6168 (2)0.47540 (16)0.65201 (8)0.0356 (4)
C20.67222 (19)0.66920 (16)0.67514 (8)0.0303 (3)
N30.63342 (18)0.78545 (13)0.66789 (7)0.0304 (3)
C40.7456 (2)0.86166 (18)0.70871 (8)0.0340 (4)
C50.8742 (2)0.80204 (19)0.74587 (9)0.0414 (4)
H50.96260.83810.77660.050*
C60.7117 (3)0.98996 (19)0.70565 (10)0.0436 (4)
H6A0.78341.02870.74320.065*
H6B0.57711.00560.71210.065*
H6C0.75231.02010.65970.065*
C110.4788 (3)0.39042 (17)0.62212 (8)0.0353 (4)
C120.5145 (3)0.27036 (19)0.62624 (10)0.0451 (4)
H120.63010.24350.64570.054*
C130.3827 (3)0.19005 (18)0.60216 (10)0.0513 (5)
H130.40620.10830.60520.062*
C140.2173 (3)0.2315 (2)0.57387 (11)0.0529 (5)
C150.1774 (3)0.3489 (2)0.56784 (11)0.0519 (5)
H150.06220.37470.54760.062*
C160.3098 (3)0.42878 (17)0.59203 (10)0.0405 (4)
H160.28540.51030.58810.049*
C210.48714 (19)0.82453 (15)0.62105 (8)0.0278 (3)
C220.5303 (2)0.86227 (15)0.55392 (8)0.0290 (3)
H220.65870.86610.54000.035*0.190 (3)
C230.3925 (2)0.89464 (15)0.50637 (8)0.0325 (3)
H230.42500.92010.46020.039*
C240.2054 (2)0.88918 (16)0.52746 (9)0.0348 (4)
H240.10850.91070.49540.042*
C250.1592 (2)0.8527 (2)0.59472 (9)0.0439 (4)
H250.03090.84990.60890.053*
C260.2997 (2)0.8203 (2)0.64164 (9)0.0403 (4)
H260.26750.79450.68770.048*0.810 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.02961 (17)0.0565 (3)0.0369 (2)0.00724 (19)−0.00870 (15)0.0061 (2)
N10.0334 (6)0.0324 (8)0.0290 (6)0.0029 (5)−0.0029 (5)0.0041 (6)
O10.0474 (7)0.0475 (9)0.0610 (8)0.0136 (6)−0.0158 (6)0.0073 (7)
F10.1076 (11)0.0365 (7)0.1034 (11)−0.0068 (8)−0.0504 (9)−0.0073 (8)
F20.0270 (6)0.0573 (10)0.0374 (6)−0.0039 (5)0.0046 (4)0.0079 (6)
F2'0.032 (3)0.074 (5)0.038 (3)0.005 (3)0.006 (2)0.014 (3)
C10.0391 (8)0.0375 (9)0.0302 (7)0.0106 (8)−0.0003 (6)0.0046 (7)
C20.0263 (6)0.0403 (10)0.0242 (6)0.0023 (6)−0.0005 (5)0.0036 (6)
N30.0260 (5)0.0362 (7)0.0290 (6)−0.0027 (6)−0.0054 (5)0.0023 (5)
C40.0269 (6)0.0454 (11)0.0299 (7)−0.0076 (7)−0.0004 (5)−0.0033 (7)
C50.0288 (7)0.0603 (12)0.0351 (8)−0.0059 (7)−0.0074 (6)−0.0013 (7)
C60.0402 (8)0.0462 (12)0.0443 (9)−0.0112 (8)−0.0037 (7)−0.0079 (8)
C110.0460 (9)0.0325 (9)0.0275 (7)0.0087 (7)−0.0001 (6)0.0021 (6)
C120.0590 (11)0.0372 (10)0.0391 (9)0.0129 (9)−0.0036 (8)−0.0004 (8)
C130.0751 (13)0.0302 (10)0.0485 (10)0.0111 (9)−0.0098 (10)−0.0064 (8)
C140.0751 (13)0.0332 (11)0.0504 (11)−0.0010 (10)−0.0168 (10)−0.0057 (9)
C150.0656 (11)0.0348 (10)0.0553 (11)0.0055 (9)−0.0237 (9)−0.0007 (10)
C160.0525 (10)0.0295 (9)0.0395 (8)0.0064 (7)−0.0111 (7)0.0015 (8)
C210.0262 (6)0.0285 (8)0.0288 (7)−0.0004 (6)−0.0037 (5)0.0016 (6)
C220.0280 (6)0.0278 (8)0.0314 (7)−0.0019 (6)0.0010 (5)0.0002 (6)
C230.0409 (8)0.0299 (8)0.0267 (7)−0.0024 (7)−0.0022 (6)0.0021 (6)
C240.0335 (7)0.0363 (9)0.0346 (8)0.0029 (7)−0.0097 (6)−0.0014 (7)
C250.0258 (6)0.0679 (13)0.0379 (8)0.0020 (8)−0.0020 (6)0.0010 (9)
C260.0290 (7)0.0615 (13)0.0305 (7)−0.0027 (8)−0.0009 (6)0.0070 (8)

Geometric parameters (Å, °)

S1—C51.738 (2)C12—C131.388 (3)
S1—C21.7400 (15)C12—H120.950
N1—C21.313 (2)C13—C141.375 (3)
N1—C11.367 (2)C13—H130.950
O1—C11.245 (2)C14—C151.376 (3)
F1—C141.360 (3)C15—C161.387 (3)
F2—C221.3379 (18)C15—H150.950
F2'—C261.373 (6)C16—H160.950
C1—C111.491 (3)C21—C221.378 (2)
C2—N31.363 (2)C21—C261.387 (2)
N3—C41.411 (2)C22—C231.380 (2)
N3—C211.4370 (18)C22—H220.950
C4—C51.339 (2)C23—C241.388 (2)
C4—C61.486 (3)C23—H230.950
C5—H50.950C24—C251.380 (2)
C6—H6A0.980C24—H240.950
C6—H6B0.980C25—C261.386 (2)
C6—H6C0.980C25—H250.950
C11—C121.397 (3)C26—H260.950
C11—C161.399 (2)
C5—S1—C290.99 (8)F1—C14—C13119.0 (2)
C2—N1—C1117.49 (14)F1—C14—C15118.1 (2)
O1—C1—N1124.75 (18)C13—C14—C15122.9 (2)
O1—C1—C11120.75 (17)C14—C15—C16118.31 (19)
N1—C1—C11114.48 (14)C14—C15—H15120.8
N1—C2—N3120.60 (13)C16—C15—H15120.8
N1—C2—S1130.07 (14)C15—C16—C11120.64 (18)
N3—C2—S1109.32 (12)C15—C16—H16119.7
C2—N3—C4115.58 (14)C11—C16—H16119.7
C2—N3—C21120.72 (13)C22—C21—C26118.93 (14)
C4—N3—C21123.70 (15)C22—C21—N3120.45 (13)
C5—C4—N3111.06 (17)C26—C21—N3120.56 (14)
C5—C4—C6129.23 (16)F2—C22—C21117.72 (14)
N3—C4—C6119.71 (15)F2—C22—C23120.34 (14)
C4—C5—S1113.00 (13)C21—C22—C23121.94 (14)
C4—C5—H5123.5C21—C22—H22118.9
S1—C5—H5123.5C23—C22—H22119.1
C4—C6—H6A109.5C22—C23—C24118.55 (15)
C4—C6—H6B109.5C22—C23—H23120.7
H6A—C6—H6B109.5C24—C23—H23120.7
C4—C6—H6C109.5C25—C24—C23120.43 (14)
H6A—C6—H6C109.5C25—C24—H24119.8
H6B—C6—H6C109.5C23—C24—H24119.8
C12—C11—C16119.08 (18)C24—C25—C26120.12 (14)
C12—C11—C1119.91 (16)C24—C25—H25119.9
C16—C11—C1120.96 (16)C26—C25—H25119.9
C13—C12—C11120.54 (18)F2'—C26—C25127.8 (3)
C13—C12—H12119.7F2'—C26—C21110.0 (3)
C11—C12—H12119.7C25—C26—C21120.02 (15)
C14—C13—C12118.5 (2)C25—C26—H26119.9
C14—C13—H13120.8C21—C26—H26120.0
C12—C13—H13120.8
C2—N1—C1—O1−6.3 (3)C12—C13—C14—C150.6 (3)
C2—N1—C1—C11171.87 (14)F1—C14—C15—C16177.5 (2)
C1—N1—C2—N3179.61 (14)C13—C14—C15—C16−0.6 (4)
C1—N1—C2—S1−2.0 (2)C14—C15—C16—C11−0.4 (3)
C5—S1—C2—N1−176.30 (15)C12—C11—C16—C151.3 (3)
C5—S1—C2—N32.19 (11)C1—C11—C16—C15−176.43 (18)
N1—C2—N3—C4176.05 (13)C2—N3—C21—C22−97.29 (18)
S1—C2—N3—C4−2.61 (15)C4—N3—C21—C2282.51 (19)
N1—C2—N3—C21−4.1 (2)C2—N3—C21—C2680.0 (2)
S1—C2—N3—C21177.21 (10)C4—N3—C21—C26−100.2 (2)
C2—N3—C4—C51.65 (19)C26—C21—C22—F2178.95 (18)
C21—N3—C4—C5−178.16 (13)N3—C21—C22—F2−3.7 (2)
C2—N3—C4—C6−178.75 (14)C26—C21—C22—C23−0.8 (3)
C21—N3—C4—C61.4 (2)N3—C21—C22—C23176.59 (16)
N3—C4—C5—S10.14 (17)F2—C22—C23—C24−179.43 (18)
C6—C4—C5—S1−179.40 (14)C21—C22—C23—C240.3 (3)
C2—S1—C5—C4−1.36 (13)C22—C23—C24—C250.4 (3)
O1—C1—C11—C12−3.8 (3)C23—C24—C25—C26−0.5 (3)
N1—C1—C11—C12177.96 (16)C24—C25—C26—F2'−161.8 (4)
O1—C1—C11—C16173.91 (17)C24—C25—C26—C210.0 (3)
N1—C1—C11—C16−4.3 (2)C22—C21—C26—F2'165.4 (3)
C16—C11—C12—C13−1.3 (3)N3—C21—C26—F2'−12.0 (4)
C1—C11—C12—C13176.43 (16)C22—C21—C26—C250.6 (3)
C11—C12—C13—C140.4 (3)N3—C21—C26—C25−176.76 (18)
C12—C13—C14—F1−177.5 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C5—H5···O1i0.952.413.322 (2)160

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BI2375).

References

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