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Acta Cryst. (2008). E64, o736    [ doi:10.1107/S1600536808007125 ]

Ethyl 2-(5-phenyl-1,3,4-oxadiazol-2-ylsulfanyl)acetate

M. Zareef, R. Iqbal, M. Arfan and M. Parvez

Abstract top

The title molecule, C12H12N2O3S, is composed of two individually planar units, viz. 5-phenyl-1,3,4-oxadiazol-2-yl-sulfanyl and ethyl acetate, which are oriented at almost right angles [80.07 (8)°] with respect to each other. The structure is stabilized by weak intermolecular C-H...O and C-H...N hydrogen bonds. The phenyl and oxadiazole rings show [pi]-[pi] stacking interactions [centroid-centroid distance = 3.846 (2) Å] and there is also a short [pi]-interaction between the carbonyl O atom and the oxadiazole ring [the distance from this O atom to the centroid of the oxadiazole ring is 3.156 (2) Å].

Comment top

Substituted-1,3,4-oxadiazole derivatives are of significant interest due to their chemotherapeutic effects (Kadi et al., 2007; Zareef et al., 2006; Zareef et al., 2007; Cao et al., 2002). Based on the known structures of the 2,5-disubstituted-1,3,4-oxadiazoles with diverse biological activities and their derivatives, we have designed and synthesized several new derivatives of 1,3,4-oxadiazole (Zareef et al., 2007). In this paper, we report the structure of one of these compounds.

The structure of the title compound (Fig. 1) is composed of two essentially planar moieties, C1—C8/N1/N2/O1/S1 and C9—C12/O2/O3 the least-square planes of which are inclined at 80.07 (8)°; the maximum deviations from the respective least square planes are: O1 = 0.037 (2) and C11 = 0.048 (2) Å. The structure is stabilized by two intermolecular interactions C4—H4···O2 and C9—H9B···N1 (Table 1). The shortest distance between the centroids of the phenyl and the oxadiazole rings of the adjacent molecules is 3.846 (2) Å which indicates the existence of π-π stacking interactions. In addition, there is a π-interaction between the carbonyl O-atom and the oxadiazole ring. (The distance from this O atom to the centroid of the oxadiazole ring is 3.156 (2) Å). The bond distances and angles in the title compound are in agreement with the corresponding ones reported in the similar structure of Ethyl 2-({5-[2-(benzoylamino)phenyl]-1,3,4-oxadiazol-2-yl}sulfanyl)acetate (Iqbal et al., 2007).

Related literature top

For related literature, see: Cao et al. (2002); Iqbal et al. (2007); Kadi et al. (2007); Mir & Siddiqui (1970); Zareef et al. (2006, 2007).

Experimental top

The title compound was prepared according to the procedure reported in the literature (Zareef et al., 2006; Mir & Siddiqui, 1970). To a solution of benzoic acid hydrazide (50 mmol) in ethanol (150 ml) was added carbon disulfide (55 mmol), followed by the addition of KOH (50 mmol) dissolved in 25 ml of water. The reaction mixture was stirred and subjected to reflux for 19 h. After reaction completion, excess ethanol was distilled off. The crude solid obtained was dissolved in water (50 ml) and acidified with 4 N HCl to pH 2–3. The product was filtered, washed with water and recrystallized from aqueous ethanol (20–30%). The resulting 5-phenyl-2-mercapto-1,3,4-oxadiazole (20 mmol) was dissolved in saturated aqueous sodium hydrogencarbonate solution while stirring. The required ethylbromoacetate (20 mmol) in absolute ethanol (10 ml) was added and the reaction mixture was stirred for 7 h at 325–335 K. After reaction completion, the resulting solid was filtered off, washed with water and recrystallized from aqueous ethanol (60%) (Yield = 75%; m.p. = 344–345 K). Prismatic crystals suitable for crystallographic study were grown from ethanol solution by slow evaporation at room temperature.

Refinement top

Though all the H atoms could be distinguished in the difference Fouries map the H-atoms were situated at the geometrically idealized positions and refined in riding-model approximation with the following constraints: aryl, methylene and methyl C—H distances were set to 0.95, 0.99 and 0.98 Å, respectively; in all these instances Uiso(H) = 1.2 Ueq(C).

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SAPI91 (Fan, 1991); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. ORTEP-3 (Farrugia, 1997) drawing of the title molecule with displacement ellipsoids plotted at 50% probability level.
Ethyl 2-(5-phenyl-1,3,4-oxadiazol-2-ylsulfanyl)acetate top
Crystal data top
C12H12N2O3SF000 = 552
Mr = 264.30Dx = 1.419 Mg m−3
Monoclinic, P21/cMelting point = 344–345 K
Hall symbol: -P 2ybcMo Kα radiation
λ = 0.71073 Å
a = 8.777 (3) ÅCell parameters from 5263 reflections
b = 11.008 (5) Åθ = 3.7–27.5º
c = 13.177 (6) ŵ = 0.26 mm−1
β = 103.59 (3)ºT = 173 (2) K
V = 1237.5 (9) Å3Prism, colourless
Z = 40.16 × 0.10 × 0.08 mm
Data collection top
Nonius KappaCCD
diffractometer		2820 independent reflections
Radiation source: fine-focus sealed tube1943 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.046
T = 173(2) Kθmax = 27.5º
ω and φ scansθmin = 3.7º
Absorption correction: multi-scan
(SORTAV; Blessing, 1997)		h = −11→11
Tmin = 0.959, Tmax = 0.979k = −13→14
5263 measured reflectionsl = −17→17
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.117  w = 1/[σ2(Fo2) + (0.058P)2 + 0.1P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
2820 reflectionsΔρmax = 0.25 e Å−3
165 parametersΔρmin = −0.27 e Å−3
47 constraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.021 (3)
Crystal data top
C12H12N2O3SV = 1237.5 (9) Å3
Mr = 264.30Z = 4
Monoclinic, P21/cMo Kα
a = 8.777 (3) ŵ = 0.26 mm−1
b = 11.008 (5) ÅT = 173 (2) K
c = 13.177 (6) Å0.16 × 0.10 × 0.08 mm
β = 103.59 (3)º
Data collection top
Nonius KappaCCD
diffractometer		2820 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1997)		1943 reflections with I > 2σ(I)
Tmin = 0.959, Tmax = 0.979Rint = 0.046
5263 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.045165 parameters
wR(F2) = 0.117H-atom parameters constrained
S = 1.02Δρmax = 0.25 e Å−3
2820 reflectionsΔρmin = −0.27 e Å−3
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.76489 (6)0.36024 (5)0.69782 (4)0.0336 (2)
O10.67313 (14)0.20172 (11)0.54296 (10)0.0264 (3)
O20.86894 (16)0.19182 (14)0.88791 (12)0.0412 (4)
O31.12555 (15)0.22664 (13)0.90282 (11)0.0354 (4)
N10.87361 (18)0.07562 (15)0.55872 (13)0.0307 (4)
N20.91309 (18)0.16477 (15)0.63754 (13)0.0319 (4)
C10.6404 (2)0.03494 (16)0.41660 (14)0.0245 (4)
C20.7088 (2)−0.06503 (17)0.37915 (15)0.0283 (5)
H20.8131−0.08820.41160.034*
C30.6246 (2)−0.13002 (18)0.29499 (16)0.0339 (5)
H30.6717−0.19720.26900.041*
C40.4712 (2)−0.09762 (19)0.24806 (16)0.0335 (5)
H40.4130−0.14290.19050.040*
C50.4040 (2)0.0005 (2)0.28557 (16)0.0342 (5)
H50.29910.02250.25340.041*
C60.4870 (2)0.06791 (19)0.36949 (15)0.0291 (5)
H60.43970.13570.39450.035*
C70.7333 (2)0.10069 (16)0.50595 (15)0.0245 (4)
C80.7925 (2)0.23515 (17)0.62486 (15)0.0266 (4)
C90.9529 (2)0.35400 (18)0.78938 (17)0.0337 (5)
H9A1.03580.34990.74980.040*
H9B0.96840.43020.83040.040*
C100.9730 (2)0.24772 (19)0.86414 (16)0.0311 (5)
C111.1623 (2)0.1290 (2)0.97896 (17)0.0392 (6)
H11A1.11050.05280.94920.047*
H11B1.12520.14981.04220.047*
C121.3366 (2)0.1135 (2)1.00597 (17)0.0421 (6)
H12A1.36550.04661.05580.051*
H12B1.38640.18871.03730.051*
H12C1.37220.09520.94250.051*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0300 (3)0.0316 (3)0.0369 (3)0.0048 (2)0.0031 (2)−0.0069 (2)
O10.0232 (7)0.0275 (7)0.0273 (7)0.0048 (6)0.0037 (5)−0.0008 (6)
O20.0280 (7)0.0554 (10)0.0392 (9)−0.0054 (7)0.0056 (7)−0.0009 (8)
O30.0235 (7)0.0397 (8)0.0407 (9)0.0003 (6)0.0026 (6)0.0013 (7)
N10.0292 (8)0.0333 (10)0.0278 (9)0.0061 (7)0.0031 (7)−0.0055 (8)
N20.0279 (9)0.0354 (10)0.0308 (10)0.0070 (8)0.0038 (7)−0.0050 (8)
C10.0265 (9)0.0261 (10)0.0219 (10)−0.0015 (8)0.0074 (8)0.0045 (8)
C20.0275 (10)0.0286 (10)0.0288 (11)0.0000 (9)0.0066 (8)0.0020 (9)
C30.0403 (12)0.0296 (11)0.0327 (12)−0.0022 (10)0.0103 (9)−0.0023 (9)
C40.0349 (11)0.0373 (12)0.0278 (11)−0.0128 (10)0.0061 (9)−0.0010 (9)
C50.0250 (10)0.0473 (13)0.0286 (11)−0.0036 (10)0.0031 (9)0.0057 (10)
C60.0265 (10)0.0354 (11)0.0264 (11)0.0028 (9)0.0085 (8)0.0044 (9)
C70.0241 (9)0.0235 (10)0.0278 (10)0.0056 (8)0.0101 (8)0.0034 (8)
C80.0243 (9)0.0283 (10)0.0267 (10)0.0011 (9)0.0050 (8)0.0005 (8)
C90.0269 (10)0.0336 (11)0.0382 (12)−0.0033 (9)0.0027 (9)−0.0088 (9)
C100.0241 (10)0.0381 (12)0.0300 (11)−0.0027 (9)0.0040 (8)−0.0111 (9)
C110.0353 (11)0.0437 (14)0.0387 (13)0.0012 (10)0.0089 (10)0.0031 (10)
C120.0356 (12)0.0534 (15)0.0360 (13)0.0066 (11)0.0056 (10)0.0033 (11)
Geometric parameters (Å, °) top
S1—C81.729 (2)C3—H30.9500
S1—C91.802 (2)C4—C51.377 (3)
O1—C81.366 (2)C4—H40.9500
O1—C71.369 (2)C5—C61.387 (3)
O2—C101.202 (2)C5—H50.9500
O3—C101.336 (2)C6—H60.9500
O3—C111.454 (3)C9—C101.513 (3)
N1—C71.294 (2)C9—H9A0.9900
N1—N21.412 (2)C9—H9B0.9900
N2—C81.291 (2)C11—C121.497 (3)
C1—C61.392 (2)C11—H11A0.9900
C1—C21.398 (3)C11—H11B0.9900
C1—C71.457 (3)C12—H12A0.9800
C2—C31.379 (3)C12—H12B0.9800
C2—H20.9500C12—H12C0.9800
C3—C41.390 (3)
C8—S1—C996.66 (9)O1—C7—C1120.13 (15)
C8—O1—C7102.24 (13)N2—C8—O1113.20 (17)
C10—O3—C11115.56 (16)N2—C8—S1128.61 (15)
C7—N1—N2106.58 (15)O1—C8—S1118.18 (13)
C8—N2—N1105.66 (15)C10—C9—S1114.43 (14)
C6—C1—C2119.91 (17)C10—C9—H9A108.7
C6—C1—C7121.99 (18)S1—C9—H9A108.7
C2—C1—C7118.10 (16)C10—C9—H9B108.7
C3—C2—C1119.90 (18)S1—C9—H9B108.7
C3—C2—H2120.0H9A—C9—H9B107.6
C1—C2—H2120.0O2—C10—O3124.49 (19)
C2—C3—C4120.3 (2)O2—C10—C9125.87 (18)
C2—C3—H3119.8O3—C10—C9109.62 (17)
C4—C3—H3119.8O3—C11—C12107.26 (18)
C5—C4—C3119.56 (18)O3—C11—H11A110.3
C5—C4—H4120.2C12—C11—H11A110.3
C3—C4—H4120.2O3—C11—H11B110.3
C4—C5—C6121.14 (18)C12—C11—H11B110.3
C4—C5—H5119.4H11A—C11—H11B108.5
C6—C5—H5119.4C11—C12—H12A109.5
C5—C6—C1119.2 (2)C11—C12—H12B109.5
C5—C6—H6120.4H12A—C12—H12B109.5
C1—C6—H6120.4C11—C12—H12C109.5
N1—C7—O1112.32 (16)H12A—C12—H12C109.5
N1—C7—C1127.55 (18)H12B—C12—H12C109.5
C7—N1—N2—C80.1 (2)C6—C1—C7—O1−3.2 (3)
C6—C1—C2—C30.6 (3)C2—C1—C7—O1177.68 (16)
C7—C1—C2—C3179.73 (18)N1—N2—C8—O1−0.3 (2)
C1—C2—C3—C4−0.9 (3)N1—N2—C8—S1178.66 (15)
C2—C3—C4—C50.5 (3)C7—O1—C8—N20.4 (2)
C3—C4—C5—C60.1 (3)C7—O1—C8—S1−178.68 (14)
C4—C5—C6—C1−0.3 (3)C9—S1—C8—N20.1 (2)
C2—C1—C6—C50.0 (3)C9—S1—C8—O1179.01 (15)
C7—C1—C6—C5−179.09 (18)C8—S1—C9—C10−69.82 (17)
N2—N1—C7—O10.2 (2)C11—O3—C10—O2−0.3 (3)
N2—N1—C7—C1−179.84 (18)C11—O3—C10—C9177.96 (16)
C8—O1—C7—N1−0.4 (2)S1—C9—C10—O2−22.7 (3)
C8—O1—C7—C1179.66 (16)S1—C9—C10—O3159.06 (14)
C6—C1—C7—N1176.80 (19)C10—O3—C11—C12175.61 (18)
C2—C1—C7—N1−2.3 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O2i0.952.513.268 (3)137
C9—H9B···N1ii0.992.383.293 (3)153
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+2, y+1/2, −z+3/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O2i0.952.513.268 (3)137
C9—H9B···N1ii0.992.383.293 (3)153
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+2, y+1/2, −z+3/2.
references
References top

Blessing, R. H. (1997). J. Appl. Cryst. 30, 421–426.

Cao, S., Qian, X., Song, G. & Huang, Q. C. (2002). J. Fluorine Chem. 117, 63–66.

Fan, H.-F. (1991). SAPI91. Rigaku Corporation, Tokyo, Japan.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Hooft, R. (1998). COLLECT. Nonius B V, Delft, The Netherlands.

Iqbal, R., Aziz, S., Ahmed, M. N., Qadeer, G. & Wong, W.-Y. (2007). Acta Cryst. E63, o1021–o1022.

Kadi, A. A., El-Brollosy, N. R., Al-Deeb, O. A., Habib, E. E., Ibrahim, T. M. & El-Emam, A. A. (2007). Eur. J. Med. Chem. 42, 235–242.

Mir, I. & Siddiqui, M. T. (1970). Tetrahedron, 26, 5235–5238.

Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr. and R. M. Sweet, pp. 307–326. New York: Academic Press.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Zareef, M., Innocenti, A., Iqbal, R., Zaidi, J. H., Arfan, M., Scozzafava, A. & Supuran, C. T. J. (2006). Enzym. Inhib. Med. Chem. 21, 351–359.

Zareef, M., Iqbal, R., Al-Masoudi, N. A., Zaidi, J. H., Arfan, M. & Shahzad, S. A. (2007). Phosphorus Sulfur Silicon Relat. Elem. 182, 281–298.