Acta Cryst. (2009). E65, o2075-o2076 [ doi:10.1107/S1600536809029894 ]
In the title compound, C10H8Cl2N2O2S·0.5H2O, the atoms in the oxadiazole ring are essentially coplanar (r.m.s. deviation 0.010 Å). The crystal structure is stabilized by intermolecular N-H
O hydrogen bonds involving the water molecule, which is situated on an a twofold rotation axis, and two organic molecules, leading to a thione tautomer in the solid state. The C atom attached to the oxadiazole ring adopts a typical sp3 hybridization. The dihedral angle between the mean plane of the benzene ring of the dichlorophenyl group and the mean plane of the oxadiazole ring is 74.18 (4)°. The crystal structure is stabilized by intermolecular N-HO and O-HS hydrogen bonds.
3,4-dichlorophenoxy acid hydrazide (10.30 mmol) was stirred with KOH (12.37 mmol) dissolved in methanol (30 ml). Carbon disulfide (0.75 mL, 12.37 mmol) was added slowly with stirring. The yellow solution obtained was refluxed until the evolution of hydrogen sulfide had ceased (18h). The reaction mixture was then cooled to rt and filtered. The filtrate was then poured into ice cooled water and acidified with 6M HCl until the colour turned congo red. The precipitate that formed was filtered off and dried. Recrystallization from ethanol/water (1:1) afforded colorless block-like crystals, suitable for X-ray diffraction analysis.
The water H-atom was located from a difference electron-density map and refined (O-H = 0.846 (17) Å), with Uiso(H) = 1.3Ueq(O). The other H-atoms were placed in idealized positions and treated as riding atoms: N-H = 0.86 Å, C—H = 0.93 - 0.98 Å with Uiso(H) = 1.2Ueq(N,C) or 1.5Ueq(Cmethyl).
Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./su2129fig1thm.gif)
| Fig. 1. Molecular structure of the title compound, showing the atom-labelling scheme and displacement ellipsoids drawn at the 50% probability level. |
![[Figure 2]](./su2129fig2thm.gif)
| Fig. 2. Partial crystal packing diagram of the title compound, viewed along the a axis. Hydrogen bonds are shown as dashed pale-blue lines. |
| C10H8Cl2N2O2S·0.5H2O | F(000) = 1224 |
| Mr = 300.15 | Dx = 1.601 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 4427 reflections |
| a = 11.8725 (2) Å | θ = 3.1–28.3° |
| b = 7.8932 (1) Å | µ = 0.68 mm−1 |
| c = 26.6092 (4) Å | T = 123 K |
| β = 92.913 (1)° | Block, colorless |
| V = 2490.38 (6) Å3 | 0.40 × 0.30 × 0.25 mm |
| Z = 8 |
| Bruker SMART CCD area-detector diffractometer | 2490 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.019 |
| graphite | θmax = 28.3°, θmin = 3.1° |
| φ and ω scans | h = −15→15 |
| 10568 measured reflections | k = −10→10 |
| 3088 independent reflections | l = −35→35 |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.078 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.09 | w = 1/[σ2(Fo2) + (0.0399P)2 + 0.7008P] where P = (Fo2 + 2Fc2)/3 |
| 3088 reflections | (Δ/σ)max = 0.001 |
| 162 parameters | Δρmax = 0.22 e Å−3 |
| 0 restraints | Δρmin = −0.21 e Å−3 |
| C10H8Cl2N2O2S·0.5H2O | V = 2490.38 (6) Å3 |
| Mr = 300.15 | Z = 8 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 11.8725 (2) Å | µ = 0.68 mm−1 |
| b = 7.8932 (1) Å | T = 123 K |
| c = 26.6092 (4) Å | 0.40 × 0.30 × 0.25 mm |
| β = 92.913 (1)° |
| Bruker SMART CCD area-detector diffractometer | 2490 reflections with I > 2σ(I) |
| 10568 measured reflections | Rint = 0.019 |
| 3088 independent reflections | θmax = 28.3° |
| R[F2 > 2σ(F2)] = 0.027 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.078 | Δρmax = 0.22 e Å−3 |
| S = 1.09 | Δρmin = −0.21 e Å−3 |
| 3088 reflections | Absolute structure: ? |
| 162 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.25873 (7) | 0.32348 (12) | 0.33123 (4) | 0.0347 (2) | |
| C1 | 0.26630 (11) | 0.47444 (17) | 0.30643 (5) | 0.0321 (3) | |
| S1 | 0.15653 (3) | 0.59419 (5) | 0.290316 (15) | 0.04313 (11) | |
| N1 | 0.37606 (9) | 0.49544 (15) | 0.30057 (4) | 0.0373 (3) | |
| H1 | 0.4040 | 0.5814 | 0.2857 | 0.045* | |
| N2 | 0.44029 (9) | 0.36407 (16) | 0.32095 (5) | 0.0379 (3) | |
| C2 | 0.36727 (11) | 0.26539 (17) | 0.33892 (5) | 0.0330 (3) | |
| C3 | 0.38524 (12) | 0.09920 (18) | 0.36521 (5) | 0.0381 (3) | |
| H3 | 0.4630 | 0.0612 | 0.3616 | 0.046* | |
| C4 | 0.30442 (15) | −0.0347 (2) | 0.34486 (6) | 0.0495 (4) | |
| H4A | 0.3187 | −0.1393 | 0.3625 | 0.074* | |
| H4B | 0.3148 | −0.0510 | 0.3096 | 0.074* | |
| H4C | 0.2284 | 0.0010 | 0.3495 | 0.074* | |
| O2 | 0.36403 (8) | 0.11531 (14) | 0.41765 (4) | 0.0417 (2) | |
| C5 | 0.44340 (11) | 0.18810 (17) | 0.45029 (5) | 0.0351 (3) | |
| C6 | 0.54468 (11) | 0.25923 (18) | 0.43709 (5) | 0.0374 (3) | |
| H6 | 0.5649 | 0.2584 | 0.4038 | 0.045* | |
| C7 | 0.61526 (11) | 0.33147 (19) | 0.47429 (5) | 0.0379 (3) | |
| H7 | 0.6830 | 0.3797 | 0.4656 | 0.046* | |
| C8 | 0.58683 (11) | 0.33307 (17) | 0.52386 (5) | 0.0354 (3) | |
| Cl1 | 0.67766 (3) | 0.42681 (5) | 0.568937 (14) | 0.04480 (11) | |
| C9 | 0.48523 (12) | 0.26045 (17) | 0.53664 (5) | 0.0360 (3) | |
| Cl2 | 0.44427 (3) | 0.26092 (6) | 0.598122 (14) | 0.05328 (13) | |
| C10 | 0.41405 (11) | 0.18835 (18) | 0.50013 (5) | 0.0380 (3) | |
| H10 | 0.3464 | 0.1399 | 0.5089 | 0.046* | |
| O1W | 0.5000 | 0.75760 (19) | 0.2500 | 0.0457 (4) | |
| H1W | 0.5445 (15) | 0.817 (2) | 0.2687 (7) | 0.059* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0320 (4) | 0.0336 (5) | 0.0389 (5) | 0.0003 (4) | 0.0056 (4) | 0.0056 (4) |
| C1 | 0.0360 (6) | 0.0313 (7) | 0.0291 (6) | 0.0000 (5) | 0.0026 (5) | −0.0009 (5) |
| S1 | 0.03808 (18) | 0.0406 (2) | 0.0504 (2) | 0.00707 (14) | −0.00080 (15) | 0.00403 (16) |
| N1 | 0.0354 (5) | 0.0342 (6) | 0.0425 (6) | 0.0001 (5) | 0.0062 (5) | 0.0078 (5) |
| N2 | 0.0337 (5) | 0.0384 (6) | 0.0419 (6) | 0.0037 (5) | 0.0046 (5) | 0.0045 (5) |
| C2 | 0.0349 (6) | 0.0327 (7) | 0.0315 (6) | 0.0034 (5) | 0.0032 (5) | −0.0013 (5) |
| C3 | 0.0434 (7) | 0.0358 (7) | 0.0355 (7) | 0.0051 (6) | 0.0045 (6) | 0.0038 (6) |
| C4 | 0.0664 (10) | 0.0345 (8) | 0.0473 (9) | −0.0019 (7) | −0.0005 (7) | 0.0028 (7) |
| O2 | 0.0414 (5) | 0.0494 (6) | 0.0344 (5) | −0.0037 (4) | 0.0027 (4) | 0.0062 (4) |
| C5 | 0.0356 (6) | 0.0341 (7) | 0.0356 (7) | 0.0075 (5) | 0.0025 (5) | 0.0065 (6) |
| C6 | 0.0361 (7) | 0.0437 (8) | 0.0328 (7) | 0.0066 (6) | 0.0058 (5) | 0.0059 (6) |
| C7 | 0.0335 (6) | 0.0409 (8) | 0.0400 (7) | 0.0065 (6) | 0.0065 (5) | 0.0052 (6) |
| C8 | 0.0361 (6) | 0.0332 (7) | 0.0371 (7) | 0.0098 (5) | 0.0019 (5) | 0.0023 (6) |
| Cl1 | 0.04519 (19) | 0.0466 (2) | 0.0423 (2) | 0.00724 (15) | −0.00057 (14) | −0.00463 (16) |
| C9 | 0.0402 (7) | 0.0363 (7) | 0.0321 (7) | 0.0119 (6) | 0.0074 (5) | 0.0071 (6) |
| Cl2 | 0.0564 (2) | 0.0696 (3) | 0.03508 (19) | 0.00834 (19) | 0.01402 (16) | 0.00641 (18) |
| C10 | 0.0364 (7) | 0.0380 (8) | 0.0401 (7) | 0.0051 (6) | 0.0078 (6) | 0.0096 (6) |
| O1W | 0.0431 (8) | 0.0329 (8) | 0.0612 (10) | 0.000 | 0.0048 (7) | 0.000 |
| O1—C1 | 1.3672 (16) | O2—C5 | 1.3745 (17) |
| O1—C2 | 1.3733 (15) | C5—C10 | 1.3882 (19) |
| C1—N1 | 1.3306 (16) | C5—C6 | 1.3884 (19) |
| C1—S1 | 1.6489 (13) | C6—C7 | 1.387 (2) |
| N1—N2 | 1.3817 (16) | C6—H6 | 0.9300 |
| N1—H1 | 0.8600 | C7—C8 | 1.3783 (19) |
| N2—C2 | 1.2763 (18) | C7—H7 | 0.9300 |
| C2—C3 | 1.4967 (19) | C8—C9 | 1.3931 (19) |
| C3—O2 | 1.4363 (17) | C8—Cl1 | 1.7371 (15) |
| C3—C4 | 1.509 (2) | C9—C10 | 1.378 (2) |
| C3—H3 | 0.9800 | C9—Cl2 | 1.7302 (14) |
| C4—H4A | 0.9600 | C10—H10 | 0.9300 |
| C4—H4B | 0.9600 | O1W—H1W | 0.846 (17) |
| C4—H4C | 0.9600 | ||
| C1—O1—C2 | 106.18 (10) | H4A—C4—H4C | 109.5 |
| N1—C1—O1 | 104.71 (11) | H4B—C4—H4C | 109.5 |
| N1—C1—S1 | 131.59 (11) | C5—O2—C3 | 120.17 (10) |
| O1—C1—S1 | 123.69 (9) | O2—C5—C10 | 114.02 (12) |
| C1—N1—N2 | 112.63 (11) | O2—C5—C6 | 125.73 (12) |
| C1—N1—H1 | 123.7 | C10—C5—C6 | 120.25 (14) |
| N2—N1—H1 | 123.7 | C7—C6—C5 | 119.04 (13) |
| C2—N2—N1 | 103.48 (10) | C7—C6—H6 | 120.5 |
| N2—C2—O1 | 112.99 (12) | C5—C6—H6 | 120.5 |
| N2—C2—C3 | 128.79 (12) | C8—C7—C6 | 121.23 (13) |
| O1—C2—C3 | 118.20 (11) | C8—C7—H7 | 119.4 |
| O2—C3—C2 | 110.40 (11) | C6—C7—H7 | 119.4 |
| O2—C3—C4 | 105.72 (12) | C7—C8—C9 | 119.15 (13) |
| C2—C3—C4 | 111.92 (12) | C7—C8—Cl1 | 119.41 (11) |
| O2—C3—H3 | 109.6 | C9—C8—Cl1 | 121.44 (10) |
| C2—C3—H3 | 109.6 | C10—C9—C8 | 120.36 (12) |
| C4—C3—H3 | 109.6 | C10—C9—Cl2 | 118.41 (11) |
| C3—C4—H4A | 109.5 | C8—C9—Cl2 | 121.22 (11) |
| C3—C4—H4B | 109.5 | C9—C10—C5 | 119.97 (13) |
| H4A—C4—H4B | 109.5 | C9—C10—H10 | 120.0 |
| C3—C4—H4C | 109.5 | C5—C10—H10 | 120.0 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O1W | 0.86 | 2.06 | 2.9084 (16) | 168 |
| O1W—H1W···S1i | 0.846 (17) | 2.612 (18) | 3.3854 (13) | 152.5 (17) |
| Symmetry codes: (i) x+1/2, y+1/2, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O1W | 0.86 | 2.06 | 2.9084 (16) | 168 |
| O1W—H1W···S1i | 0.846 (17) | 2.612 (18) | 3.3854 (13) | 152.5 (17) |
| Symmetry codes: (i) x+1/2, y+1/2, z. |
The authors are grateful to Professor G. B. Jameson, Institute of Fundamental Sciences, Private Bag 11 222, Massey University, Palmerston North, New Zealand, for fruitful discussions.
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1,3,4-Oxadiazoles are an important class of five-membered heterocycles. They show diverse biological activities, for example, antifungal, antibacterial (Almasirad et al., 2004), anti-convulsant (Aboraia et al. 2006), antitumour (Akhtar, Hameed, Khan et al., 2008) and enzyme inhibitory activities (Khan et al., 2005). In continuation to our work on five membered heterocycles (Akhtar & Hameed et al., 2007), the title compound was synthesized and evaluated for its biological activities (Akhtar et al., 2008a). Herein, we report on the crystal structure of 5-[1-(3,4-dichlorophenoxy) ethyl]-1,3,4-oxadiazole-2(3H)-thione, derived from 3,4-dichlorophenoxy propionic acid (Akhtar & Rauf et al., 2007).
The molecular structure of the title compound is illustrated in Fig. 1. The dihedral angle between the mean planes of the benzene and 1,3,4-oxadiazole rings is 74.18 (4)°. The bond lengths and angles are in good agreement with the expected values (Allen et al., 1987; Thamotharan et al., 2005). The N1—N2 [1.3817 (16) A°] and C1=S1 [1.6489 (13) A°] bond lengths correspond to the usual single bond N—N distance and C=S distance.
1,3,4-Oxadizole-2-thiones/thiols can exist in two tautomeric forms (Aydogan et al., 2002). In the title compound the thione form is observed. The H-atom of the thiol group has been transferred to the adjacent N atom of the oxadiazole ring (Fig. 1).
The title compound crystallized as a hemihydrate, with the water molecule lieing on a crystallographic two-fold axis. The water molecule O-atom hydrogen bonds to the NH group, while the water H-atom hydrogen bonds to the S-atom of the S=C moiety (see Table 1 and Fig. 2).