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Acta Crystallogr Sect E Struct Rep Online. 2009 June 1; 65(Pt 6): o1437.
Published online 2009 May 29. doi:  10.1107/S1600536809019692
PMCID: PMC2969597

6-(1-Adamant­yl)-3-(2-fluoro­phen­yl)-1,2,4-triazolo[3,4-b][1,3,4]thia­diazole

Abstract

In the title compound, C19H19FN4S, the planes of the 2-fluoro­phenyl and 1,2,4-triazolo[3,4-b][1,3,4]thia­diazole ring systems are oriented at a dihedral angle of 48.98 (6)°. In the crystal, weak C—H(...)S and C—H(...)π inter­actions may help to establish the packing and π–π inter­actions between the centroids of the benzene rings at a distance of 3.8792 (13) Å occur.

Related literature

For a related structure, see: Holm et al. (2008 [triangle]). For our previous studies on related compounds, see: Akhtar et al. (2007 [triangle], 2008a [triangle],b [triangle]). For background to the biological activity of related compounds, see: El-Emam et al. (2004 [triangle]); Kadi et al. (2007 [triangle]); Zhang et al. (2002 [triangle]).

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Object name is e-65-o1437-scheme1.jpg

Experimental

Crystal data

  • C19H19FN4S
  • M r = 354.44
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1437-efi1.jpg
  • a = 13.2684 (9) Å
  • b = 12.4293 (9) Å
  • c = 20.2231 (15) Å
  • V = 3335.1 (4) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.21 mm−1
  • T = 296 K
  • 0.25 × 0.22 × 0.20 mm

Data collection

  • Bruker Kappa APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.945, T max = 0.956
  • 22695 measured reflections
  • 4486 independent reflections
  • 3116 reflections with I > 2σ(I)
  • R int = 0.031

Refinement

  • R[F 2 > 2σ(F 2)] = 0.047
  • wR(F 2) = 0.136
  • S = 1.04
  • 4486 reflections
  • 235 parameters
  • H-atom parameters constrained
  • Δρmax = 0.35 e Å−3
  • Δρmin = −0.28 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 (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/S1600536809019692/hb2984sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809019692/hb2984Isup2.hkl

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

Acknowledgments

The authors acknowledge the Higher Education Commission, Islamabad, Pakistan, and Bana International, Karachi, Pakistan, for funding the purchase of the diffractometer and for technical support, respectively.

supplementary crystallographic information

Comment

Five membered heterocycles bearing adamantyl moiety are gaining importance due to their promising biological activities (El-Emam et al., 2004; Kadi et al., 2007). On the other hand the condensed heterocyclic systems e.g., triazolothiadiazoles exhibit numerous biological activities (Zhang et al., 2002). In continuation of our previous studeis (Akhtar et al., 2007, 2008a, 2008b), the title compound, (I), (Fig. 1), has been synthesized with the hope that it will possess antiviral and anticancer activity. The crystal structure of (II) 3-(2-Fluorophenyl)-6-(phenoxymethyl)-1,2,4- triazolo(3,4 - b)(1,3,4)thiadiazole (Holm, et al., 2008) has been published which has a common moiety as in (I).

In (I), the ring A (C1—C6) along with F1-atom and two [(C7/N1/N2/C8/N3) & (C8/S1/C9/N4/N3)] fused heterocyclic rings B (C7/N1/N2/C8/S1/C9/N4/N3) are planar and oriented at a dihedral angle of 48.98 (6)°. There exist π—π interaction between the centroids, CgA—CgAi [symmetry code: i = 1 - x, -y, 1 - z], of benzene rings at a distance of 3.8792 (13) Å. In the crystal, the packing is consolidated by H-bonding (Fig 2) and C—H···π interactions (Table 1).

Experimental

A mixture of 4-amino-5-(2-fluorophenyl)-2H-1,2,4-triazole-3(4H)-thione (0.2 g, 0.56 mmol) and adamantane-1-carboxylic acid (0.10 g, 0.56 mmol) in the presence of POCl3 (5 ml) was refluxed for four hours. The reaction mixture was cooled to room temperature, poured into crushed ice and neutralized using solid potassium carbonate until pH was 8. The precipitated solid was filtered, washed with excess water and recrystallized from chloroform to yield colourless prisms of (I).

Refinement

H-atoms were positioned in calculated positions with C-H = 0.93–0.98 Å and refined as riding with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
View of (I) with displacement ellipsoids drawn at the 30% probability level. H-atoms are shown by small spheres of arbitrary radius.
Fig. 2.
Partial packing diagram for (I) showing the C—H···S interaction as a dashed line.

Crystal data

C19H19FN4SF(000) = 1488
Mr = 354.44Dx = 1.412 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 3116 reflections
a = 13.2684 (9) Åθ = 2.5–29.1°
b = 12.4293 (9) ŵ = 0.21 mm1
c = 20.2231 (15) ÅT = 296 K
V = 3335.1 (4) Å3Prism, colourless
Z = 80.25 × 0.22 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer4486 independent reflections
Radiation source: fine-focus sealed tube3116 reflections with I > 2σ(I)
graphiteRint = 0.031
Detector resolution: 7.40 pixels mm-1θmax = 29.1°, θmin = 2.5°
ω scansh = −12→18
Absorption correction: multi-scan (SADABS; Bruker, 2005)k = −17→14
Tmin = 0.945, Tmax = 0.956l = −26→27
22695 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) = 0.136H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.0579P)2 + 1.3259P] where P = (Fo2 + 2Fc2)/3
4486 reflections(Δ/σ)max < 0.001
235 parametersΔρmax = 0.35 e Å3
0 restraintsΔρmin = −0.28 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 e.s.d.'s 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
S10.25232 (4)−0.15058 (4)0.23126 (2)0.0517 (2)
F10.35571 (14)−0.27396 (11)0.52074 (7)0.0839 (6)
N10.20243 (13)−0.22822 (13)0.41446 (9)0.0543 (6)
N20.17459 (14)−0.24778 (14)0.34844 (9)0.0591 (6)
N30.29443 (10)−0.12526 (11)0.35182 (7)0.0360 (4)
N40.36117 (10)−0.05549 (11)0.32199 (7)0.0343 (4)
C10.32252 (13)−0.10525 (14)0.47314 (9)0.0392 (5)
C20.36251 (16)−0.16551 (17)0.52410 (10)0.0517 (6)
C30.41073 (19)−0.1200 (2)0.57717 (10)0.0639 (8)
C40.41784 (17)−0.0094 (2)0.58048 (10)0.0611 (8)
C50.37749 (16)0.05301 (18)0.53119 (10)0.0549 (7)
C60.33120 (14)0.00584 (15)0.47758 (9)0.0463 (6)
C70.27374 (13)−0.15494 (14)0.41576 (9)0.0403 (5)
C80.23167 (13)−0.18403 (14)0.31343 (10)0.0437 (5)
C90.34740 (12)−0.06062 (13)0.25887 (8)0.0348 (5)
C100.40431 (12)0.00535 (13)0.20943 (8)0.0337 (4)
C110.48759 (15)0.07039 (18)0.24376 (9)0.0504 (6)
C120.54359 (15)0.13979 (18)0.19241 (10)0.0543 (7)
C130.47109 (16)0.21626 (17)0.15982 (11)0.0581 (7)
C140.38813 (17)0.15387 (18)0.12638 (12)0.0626 (8)
C150.33138 (15)0.08502 (16)0.17677 (11)0.0527 (6)
C160.4512 (2)−0.06639 (17)0.15637 (11)0.0657 (8)
C170.5082 (3)0.0039 (2)0.10590 (12)0.0802 (9)
C180.59042 (18)0.0674 (2)0.14102 (13)0.0730 (9)
C190.4329 (3)0.0822 (2)0.07399 (11)0.0855 (10)
H30.43812−0.162930.610280.0767*
H40.450040.022860.616190.0733*
H50.381430.127570.534000.0658*
H60.305450.048880.443970.0555*
H11A0.458180.116290.277420.0604*
H11B0.534680.021850.265120.0604*
H120.596730.180970.214600.0651*
H13A0.442450.264090.192730.0697*
H13B0.506520.259660.127440.0697*
H140.340990.204330.105640.0751*
H15A0.301450.130910.210220.0633*
H15B0.277640.045950.154830.0633*
H16A0.49735−0.117050.176700.0789*
H16B0.39877−0.106920.134050.0789*
H170.53836−0.041910.071760.0963*
H18A0.627420.110320.109150.0876*
H18B0.637340.018260.162030.0876*
H19A0.379720.042080.052160.1027*
H19B0.466940.125700.041030.1027*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0578 (3)0.0481 (3)0.0492 (3)−0.0163 (2)−0.0141 (2)−0.0060 (2)
F10.1293 (14)0.0492 (8)0.0733 (9)0.0040 (8)−0.0198 (9)0.0189 (7)
N10.0552 (10)0.0455 (9)0.0623 (11)−0.0141 (8)−0.0018 (8)0.0070 (8)
N20.0611 (10)0.0483 (9)0.0678 (12)−0.0202 (8)−0.0068 (9)0.0020 (9)
N30.0342 (7)0.0312 (7)0.0427 (8)−0.0025 (5)−0.0031 (6)−0.0002 (6)
N40.0330 (7)0.0324 (7)0.0375 (7)−0.0016 (5)−0.0019 (6)−0.0014 (6)
C10.0351 (8)0.0425 (9)0.0401 (9)−0.0011 (7)0.0052 (7)0.0042 (7)
C20.0615 (12)0.0487 (11)0.0450 (10)0.0004 (9)0.0043 (9)0.0110 (9)
C30.0733 (15)0.0777 (16)0.0407 (10)0.0016 (12)−0.0069 (10)0.0148 (10)
C40.0616 (13)0.0810 (16)0.0406 (10)−0.0128 (12)0.0007 (9)−0.0047 (10)
C50.0585 (12)0.0528 (12)0.0533 (12)−0.0067 (10)0.0026 (10)−0.0077 (9)
C60.0470 (10)0.0432 (10)0.0487 (10)−0.0015 (8)−0.0022 (8)0.0024 (8)
C70.0390 (9)0.0342 (8)0.0478 (10)−0.0005 (7)0.0006 (7)0.0048 (7)
C80.0425 (9)0.0356 (9)0.0530 (10)−0.0064 (7)−0.0083 (8)−0.0036 (8)
C90.0338 (8)0.0313 (7)0.0394 (9)0.0013 (6)−0.0055 (7)−0.0054 (7)
C100.0355 (8)0.0340 (8)0.0315 (7)0.0043 (6)−0.0038 (6)−0.0048 (6)
C110.0423 (10)0.0682 (13)0.0406 (9)−0.0147 (9)−0.0045 (8)0.0014 (9)
C120.0401 (10)0.0728 (14)0.0499 (11)−0.0137 (9)−0.0001 (8)0.0052 (10)
C130.0550 (12)0.0478 (11)0.0716 (14)−0.0041 (9)0.0134 (11)0.0044 (10)
C140.0527 (12)0.0602 (13)0.0748 (15)0.0024 (10)−0.0127 (11)0.0291 (12)
C150.0402 (10)0.0453 (10)0.0727 (13)0.0009 (8)−0.0095 (9)0.0140 (10)
C160.0922 (18)0.0451 (11)0.0599 (13)0.0105 (11)0.0243 (12)−0.0122 (10)
C170.123 (2)0.0619 (15)0.0558 (13)0.0071 (15)0.0433 (15)−0.0135 (12)
C180.0537 (13)0.0819 (17)0.0834 (17)0.0217 (12)0.0285 (12)0.0241 (14)
C190.114 (2)0.105 (2)0.0374 (11)−0.0375 (19)−0.0114 (13)0.0115 (13)

Geometric parameters (Å, °)

S1—C81.735 (2)C14—C151.529 (3)
S1—C91.7758 (17)C14—C191.506 (4)
F1—C21.353 (3)C16—C171.542 (4)
N1—N21.407 (3)C17—C181.522 (4)
N1—C71.314 (2)C17—C191.537 (5)
N2—C81.305 (3)C3—H30.9300
N3—N41.3784 (19)C4—H40.9300
N3—C71.372 (2)C5—H50.9300
N3—C81.353 (2)C6—H60.9300
N4—C91.291 (2)C11—H11A0.9700
C1—C21.380 (3)C11—H11B0.9700
C1—C61.389 (3)C12—H120.9800
C1—C71.465 (3)C13—H13A0.9700
C2—C31.372 (3)C13—H13B0.9700
C3—C41.380 (4)C14—H140.9800
C4—C51.372 (3)C15—H15A0.9700
C5—C61.377 (3)C15—H15B0.9700
C9—C101.497 (2)C16—H16A0.9700
C10—C111.535 (3)C16—H16B0.9700
C10—C151.534 (3)C17—H170.9800
C10—C161.528 (3)C18—H18A0.9700
C11—C121.541 (3)C18—H18B0.9700
C12—C131.504 (3)C19—H19A0.9700
C12—C181.509 (3)C19—H19B0.9700
C13—C141.507 (3)
C8—S1—C987.82 (8)C2—C3—H3121.00
N2—N1—C7109.15 (16)C4—C3—H3121.00
N1—N2—C8104.93 (16)C3—C4—H4120.00
N4—N3—C7135.23 (14)C5—C4—H4120.00
N4—N3—C8118.95 (14)C4—C5—H5120.00
C7—N3—C8105.81 (14)C6—C5—H5120.00
N3—N4—C9108.10 (13)C1—C6—H6120.00
C2—C1—C6117.36 (17)C5—C6—H6120.00
C2—C1—C7122.17 (17)C10—C11—H11A110.00
C6—C1—C7120.47 (16)C10—C11—H11B110.00
F1—C2—C1118.53 (18)C12—C11—H11A110.00
F1—C2—C3118.78 (19)C12—C11—H11B110.00
C1—C2—C3122.7 (2)H11A—C11—H11B108.00
C2—C3—C4118.7 (2)C11—C12—H12109.00
C3—C4—C5120.1 (2)C13—C12—H12109.00
C4—C5—C6120.4 (2)C18—C12—H12109.00
C1—C6—C5120.75 (18)C12—C13—H13A110.00
N1—C7—N3108.16 (16)C12—C13—H13B110.00
N1—C7—C1128.78 (17)C14—C13—H13A110.00
N3—C7—C1122.99 (15)C14—C13—H13B110.00
S1—C8—N2139.20 (16)H13A—C13—H13B108.00
S1—C8—N3108.85 (13)C13—C14—H14109.00
N2—C8—N3111.95 (18)C15—C14—H14109.00
S1—C9—N4116.26 (12)C19—C14—H14109.00
S1—C9—C10119.54 (12)C10—C15—H15A110.00
N4—C9—C10124.18 (15)C10—C15—H15B110.00
C9—C10—C11110.45 (14)C14—C15—H15A110.00
C9—C10—C15108.84 (14)C14—C15—H15B110.00
C9—C10—C16110.78 (14)H15A—C15—H15B108.00
C11—C10—C15107.99 (15)C10—C16—H16A110.00
C11—C10—C16109.38 (16)C10—C16—H16B110.00
C15—C10—C16109.35 (15)C17—C16—H16A110.00
C10—C11—C12109.70 (15)C17—C16—H16B110.00
C11—C12—C13109.91 (17)H16A—C16—H16B108.00
C11—C12—C18109.21 (18)C16—C17—H17110.00
C13—C12—C18109.78 (18)C18—C17—H17110.00
C12—C13—C14109.79 (18)C19—C17—H17110.00
C13—C14—C15110.41 (19)C12—C18—H18A110.00
C13—C14—C19109.4 (2)C12—C18—H18B110.00
C15—C14—C19109.39 (19)C17—C18—H18A110.00
C10—C15—C14109.73 (16)C17—C18—H18B110.00
C10—C16—C17109.51 (17)H18A—C18—H18B108.00
C16—C17—C18109.7 (2)C14—C19—H19A110.00
C16—C17—C19108.5 (3)C14—C19—H19B110.00
C18—C17—C19109.5 (2)C17—C19—H19A110.00
C12—C18—C17109.6 (2)C17—C19—H19B110.00
C14—C19—C17109.61 (19)H19A—C19—H19B108.00
C9—S1—C8—N2−179.0 (2)C4—C5—C6—C11.5 (3)
C9—S1—C8—N31.05 (13)S1—C9—C10—C11−175.71 (12)
C8—S1—C9—N4−0.64 (14)S1—C9—C10—C1565.90 (17)
C8—S1—C9—C10−179.31 (14)S1—C9—C10—C16−54.36 (19)
C7—N1—N2—C8−0.1 (2)N4—C9—C10—C115.7 (2)
N2—N1—C7—N3−0.2 (2)N4—C9—C10—C15−112.66 (18)
N2—N1—C7—C1176.70 (17)N4—C9—C10—C16127.08 (18)
N1—N2—C8—S1−179.67 (17)C9—C10—C11—C12−178.63 (15)
N1—N2—C8—N30.3 (2)C15—C10—C11—C12−59.7 (2)
C7—N3—N4—C9179.60 (18)C16—C10—C11—C1259.2 (2)
C8—N3—N4—C90.9 (2)C9—C10—C15—C14179.60 (16)
N4—N3—C7—N1−178.48 (16)C11—C10—C15—C1459.7 (2)
N4—N3—C7—C14.4 (3)C16—C10—C15—C14−59.3 (2)
C8—N3—C7—N10.33 (19)C9—C10—C16—C17179.4 (2)
C8—N3—C7—C1−176.77 (16)C11—C10—C16—C17−58.6 (2)
N4—N3—C8—S1−1.38 (18)C15—C10—C16—C1759.5 (2)
N4—N3—C8—N2178.67 (15)C10—C11—C12—C1360.2 (2)
C7—N3—C8—S1179.58 (12)C10—C11—C12—C18−60.3 (2)
C7—N3—C8—N2−0.4 (2)C11—C12—C13—C14−59.2 (2)
N3—N4—C9—S10.02 (17)C18—C12—C13—C1461.0 (2)
N3—N4—C9—C10178.62 (14)C11—C12—C18—C1761.0 (2)
C6—C1—C2—F1−179.52 (18)C13—C12—C18—C17−59.6 (2)
C6—C1—C2—C3−1.0 (3)C12—C13—C14—C1559.4 (2)
C7—C1—C2—F1−0.3 (3)C12—C13—C14—C19−61.0 (2)
C7—C1—C2—C3178.2 (2)C13—C14—C15—C10−60.1 (2)
C2—C1—C6—C5−0.4 (3)C19—C14—C15—C1060.3 (2)
C7—C1—C6—C5−179.61 (18)C13—C14—C19—C1759.7 (3)
C2—C1—C7—N150.7 (3)C15—C14—C19—C17−61.4 (3)
C2—C1—C7—N3−132.83 (19)C10—C16—C17—C1859.5 (3)
C6—C1—C7—N1−130.1 (2)C10—C16—C17—C19−60.1 (2)
C6—C1—C7—N346.3 (3)C16—C17—C18—C12−60.8 (3)
F1—C2—C3—C4179.9 (2)C19—C17—C18—C1258.2 (3)
C1—C2—C3—C41.3 (3)C16—C17—C19—C1461.2 (3)
C2—C3—C4—C5−0.3 (3)C18—C17—C19—C14−58.5 (3)
C3—C4—C5—C6−1.1 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C15—H15A···S1i0.972.843.640 (2)140
C12—H12···Cg1ii0.982.903.713 (2)140
C18—H18B···Cg1iii0.972.833.787 (3)170

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2984).

References

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