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Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): o1911.
Published online 2010 July 3. doi:  10.1107/S1600536810024967
PMCID: PMC3007562

5-(3,4,5-Trimeth­oxy­phen­yl)-1,3,4-oxadiazole-2(3H)-thione

Abstract

The two rings in the title compound, C11H12N2O4S, are roughly coplanar [dihedral angle = 6.77 (8)°]. Whereas the two outer methyl groups of the three meth­oxy groups are almost coplanar with the aromatic ring to which they are attached [C—C—O—C torsion angles = 8.5 (3) and −8.3 (3)°], the methyl group of the central meth­oxy substituent is not [C—C—C—C = −78.4 (3)°]. The crystal packing is stabilized by N—H(...)O hydrogen bonding.

Related literature

For background to the use of 1,3,4-oxadiazo­les, see: Erden et al. (2005 [triangle]); Smicius et al. (2002 [triangle]); Dutta & Kataky (1992 [triangle]). For details of the biological activity of 1,3,4-oxadiazo­les, see: Chen, et al. (2000 [triangle]); Mehuskiene, et al. (2003 [triangle]); El-Emam et al. (2004 [triangle]); Krasovshii et al. (2000 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1911-scheme1.jpg

Experimental

Crystal data

  • C11H12N2O4S
  • M r = 268.29
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1911-efi1.jpg
  • a = 12.506 (2) Å
  • b = 7.1577 (7) Å
  • c = 13.451 (2) Å
  • β = 96.558 (12)°
  • V = 1196.2 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.28 mm−1
  • T = 173 K
  • 0.37 × 0.33 × 0.32 mm

Data collection

  • Stoe IPDS II two-circle diffractometer
  • Absorption correction: multi-scan (MULABS; Spek, 2009 [triangle]; Blessing, 1995 [triangle]) T min = 0.904, T max = 0.916
  • 7121 measured reflections
  • 2235 independent reflections
  • 1679 reflections with I > 2σ(I)
  • R int = 0.075

Refinement

  • R[F 2 > 2σ(F 2)] = 0.044
  • wR(F 2) = 0.112
  • S = 0.94
  • 2235 reflections
  • 171 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.45 e Å−3
  • Δρmin = −0.27 e Å−3

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: XP (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/S1600536810024967/tk2682sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810024967/tk2682Isup2.hkl

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

supplementary crystallographic information

Comment

Substituted 1,3,4-oxadiazoles attract interest in materials science due to their important applications in industrial, agricultural and polymer chemistry (Erden et al., 2005, Smicius et al., 2002, Dutta & Kataky, 1992) and their wide range of biological activities, such as bactericidal, anti-inflammatory, antiviral, antimicrobial, tuberculostatic, anti convulsive and fungicidal activities (Chen et al., 2000; Mehuskiene et al., 2003; El-Emam et al., 2004; Krasovshii et al., 2000). The title compound was prepared by refluxing 3,4,5-trimethoxybenzohydrazide and potassium hydroxide with carbon disulfide in ethanol.

The two rings in the title compound, C11H12N2O4S, are coplanar [dihedral angle = 6.77 (8) °]. Whereas the two outer methyl groups of the three methoxy groups are coplanar with the aromatic ring to which they are attached [C—C—O—C torsion angles = 8.5 (3) and -8.3 (3) °], the methyl group of the central methoxy substituent is not [C—C—C—C = -78.4 (3) °]. The crystal packing is stabilized by N—H···O hydrogen bonding.

Experimental

A mixture of 3,4,5-trimethoxybenzohydrazide (0.03 mol) and potassium hydroxide (0.03 mol) was dissolved in ethanol, followed by addition of carbon disulfide (0.08 mol) drop wise under stirring. The reaction mixture was heated under reflux for 14 h. After completion of reaction as indicated by TLC, the reaction mixture was concentrated and residue was dissolved in H2O, filtered and acidified with dilute hydrochloric acid (pH = 2–3). The resulting precipitate was filtered and recrystallized from ethanol to give crystalline solid in 82% yield; m.p. = 453–455 K. IR (KBr, cm-1), 3227–3012 (NH), 2939 (Ar—CH), 1581 (Cδb N), 1503, 1454, 1447 (Cδb C, aromatic), 1359 (C═S), 1233–1163 (C—O—C).

Refinement

H atoms were located in a difference Fourier map. The H atom bonded to N was freely refined. The H atoms bonded to C were refined using a riding model with isotropic displacement parameters Uiso(H) set to 1.2Ueq(C) and with C—H = 0.95 Å or Uiso(H) set to 1.5Ueq(Cmethyl) and with C—H = 0.98 Å. The methyl groups were allowed to rotate but not to tip.

Figures

Fig. 1.
Molecular structure of title compound. Displacement ellipsoids are drawn at the 50% probability level.

Crystal data

C11H12N2O4SF(000) = 560
Mr = 268.29Dx = 1.490 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 5950 reflections
a = 12.506 (2) Åθ = 3.6–25.9°
b = 7.1577 (7) ŵ = 0.28 mm1
c = 13.451 (2) ÅT = 173 K
β = 96.558 (12)°Block, colourless
V = 1196.2 (3) Å30.37 × 0.33 × 0.32 mm
Z = 4

Data collection

Stoe IPDS II two-circle diffractometer2235 independent reflections
Radiation source: fine-focus sealed tube1679 reflections with I > 2σ(I)
graphiteRint = 0.075
ω scansθmax = 25.7°, θmin = 3.5°
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995)h = −12→15
Tmin = 0.904, Tmax = 0.916k = −7→8
7121 measured reflectionsl = −16→16

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.112w = 1/[σ2(Fo2) + (0.0699P)2] where P = (Fo2 + 2Fc2)/3
S = 0.94(Δ/σ)max < 0.001
2235 reflectionsΔρmax = 0.45 e Å3
171 parametersΔρmin = −0.27 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.024 (3)

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
S10.40007 (5)0.10396 (10)0.11859 (4)0.0358 (2)
O10.40507 (12)0.1537 (2)0.31509 (9)0.0258 (4)
C10.45909 (18)0.1504 (3)0.23147 (14)0.0260 (5)
N10.56078 (16)0.1912 (3)0.26552 (13)0.0278 (4)
H10.619 (2)0.211 (4)0.233 (2)0.040 (7)*
N20.57512 (15)0.2258 (3)0.36818 (12)0.0273 (4)
C20.48040 (17)0.2018 (3)0.39406 (14)0.0234 (5)
C110.44138 (17)0.2288 (3)0.49170 (14)0.0232 (5)
C120.33315 (17)0.2074 (3)0.49941 (14)0.0248 (5)
H120.28540.17020.44280.030*
C130.29410 (17)0.2409 (3)0.59106 (14)0.0234 (5)
C140.36466 (18)0.3006 (3)0.67290 (14)0.0238 (5)
C150.47369 (17)0.3228 (3)0.66338 (14)0.0239 (5)
C160.51427 (18)0.2840 (3)0.57291 (14)0.0246 (5)
H160.58900.29480.56690.030*
O170.18925 (12)0.2223 (2)0.60687 (10)0.0289 (4)
O180.32183 (13)0.3468 (2)0.75958 (10)0.0288 (4)
O190.53524 (12)0.3899 (2)0.74645 (10)0.0307 (4)
C170.11725 (18)0.1399 (4)0.52800 (16)0.0336 (6)
H17A0.10790.22520.47070.050*
H17B0.04730.11690.55200.050*
H17C0.14740.02150.50750.050*
C180.34058 (19)0.2114 (4)0.83861 (15)0.0328 (6)
H18A0.31030.09070.81530.049*
H18B0.30610.25310.89660.049*
H18C0.41820.19800.85780.049*
C190.64872 (18)0.3968 (4)0.74341 (16)0.0335 (6)
H19A0.67680.26960.73930.050*
H19B0.68300.45750.80420.050*
H19C0.66440.46820.68460.050*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0358 (4)0.0522 (4)0.0195 (3)−0.0034 (3)0.0042 (2)−0.0050 (2)
O10.0240 (8)0.0374 (10)0.0168 (7)−0.0006 (7)0.0050 (5)−0.0010 (6)
C10.0267 (12)0.0313 (13)0.0212 (10)0.0023 (10)0.0076 (8)0.0022 (8)
N10.0250 (10)0.0401 (12)0.0196 (8)0.0001 (9)0.0086 (7)−0.0011 (8)
N20.0262 (10)0.0376 (12)0.0186 (8)0.0003 (8)0.0050 (7)0.0000 (7)
C20.0231 (11)0.0263 (12)0.0208 (9)0.0004 (9)0.0018 (8)0.0015 (8)
C110.0273 (11)0.0243 (12)0.0186 (9)0.0029 (9)0.0051 (8)0.0017 (8)
C120.0249 (11)0.0317 (13)0.0179 (9)−0.0018 (10)0.0021 (8)−0.0004 (8)
C130.0218 (11)0.0284 (12)0.0203 (10)0.0009 (9)0.0037 (8)0.0013 (8)
C140.0281 (12)0.0278 (12)0.0161 (9)0.0046 (9)0.0046 (8)−0.0004 (8)
C150.0252 (11)0.0265 (11)0.0190 (9)0.0027 (9)−0.0012 (8)0.0010 (8)
C160.0213 (11)0.0289 (13)0.0239 (10)0.0018 (9)0.0038 (8)0.0021 (8)
O170.0209 (8)0.0453 (10)0.0212 (7)−0.0042 (7)0.0053 (6)−0.0041 (6)
O180.0321 (9)0.0370 (10)0.0183 (7)0.0087 (7)0.0064 (6)−0.0004 (6)
O190.0245 (8)0.0438 (10)0.0228 (7)0.0001 (7)−0.0020 (6)−0.0049 (6)
C170.0250 (12)0.0430 (16)0.0332 (12)−0.0056 (11)0.0043 (9)−0.0109 (10)
C180.0358 (13)0.0436 (15)0.0197 (10)0.0028 (11)0.0060 (9)0.0018 (9)
C190.0249 (12)0.0435 (15)0.0306 (11)−0.0001 (11)−0.0034 (9)−0.0019 (10)

Geometric parameters (Å, °)

S1—C11.645 (2)C15—O191.369 (2)
O1—C11.377 (2)C15—C161.399 (3)
O1—C21.381 (2)C16—H160.9500
C1—N11.334 (3)O17—C171.437 (3)
N1—N21.394 (2)O18—C181.438 (3)
N1—H10.90 (3)O19—C191.425 (3)
N2—C21.284 (3)C17—H17A0.9800
C2—C111.465 (3)C17—H17B0.9800
C11—C121.378 (3)C17—H17C0.9800
C11—C161.398 (3)C18—H18A0.9800
C12—C131.398 (3)C18—H18B0.9800
C12—H120.9500C18—H18C0.9800
C13—O171.359 (3)C19—H19A0.9800
C13—C141.397 (3)C19—H19B0.9800
C14—O181.378 (2)C19—H19C0.9800
C14—C151.393 (3)
C1—O1—C2106.11 (16)C14—C15—C16120.90 (18)
N1—C1—O1104.66 (17)C11—C16—C15117.8 (2)
N1—C1—S1132.15 (17)C11—C16—H16121.1
O1—C1—S1123.19 (17)C15—C16—H16121.1
C1—N1—N2112.87 (18)C13—O17—C17117.32 (16)
C1—N1—H1131.5 (16)C14—O18—C18114.68 (17)
N2—N1—H1115.3 (16)C15—O19—C19117.23 (17)
C2—N2—N1103.10 (17)O17—C17—H17A109.5
N2—C2—O1113.23 (17)O17—C17—H17B109.5
N2—C2—C11129.62 (18)H17A—C17—H17B109.5
O1—C2—C11117.04 (18)O17—C17—H17C109.5
C12—C11—C16122.09 (18)H17A—C17—H17C109.5
C12—C11—C2118.92 (18)H17B—C17—H17C109.5
C16—C11—C2118.92 (19)O18—C18—H18A109.5
C11—C12—C13119.51 (18)O18—C18—H18B109.5
C11—C12—H12120.2H18A—C18—H18B109.5
C13—C12—H12120.2O18—C18—H18C109.5
O17—C13—C14116.15 (18)H18A—C18—H18C109.5
O17—C13—C12124.19 (18)H18B—C18—H18C109.5
C14—C13—C12119.6 (2)O19—C19—H19A109.5
O18—C14—C15121.99 (18)O19—C19—H19B109.5
O18—C14—C13117.95 (19)H19A—C19—H19B109.5
C15—C14—C13119.95 (18)O19—C19—H19C109.5
O19—C15—C14115.45 (18)H19A—C19—H19C109.5
O19—C15—C16123.6 (2)H19B—C19—H19C109.5
C2—O1—C1—N11.4 (2)C12—C13—C14—O18174.8 (2)
C2—O1—C1—S1−178.55 (17)O17—C13—C14—C15179.80 (19)
O1—C1—N1—N2−1.4 (3)C12—C13—C14—C15−1.3 (3)
S1—C1—N1—N2178.49 (19)O18—C14—C15—O191.2 (3)
C1—N1—N2—C20.9 (3)C13—C14—C15—O19177.2 (2)
N1—N2—C2—O10.1 (2)O18—C14—C15—C16−176.7 (2)
N1—N2—C2—C11−175.9 (2)C13—C14—C15—C16−0.7 (3)
C1—O1—C2—N2−0.9 (2)C12—C11—C16—C15−1.8 (3)
C1—O1—C2—C11175.60 (19)C2—C11—C16—C15175.1 (2)
N2—C2—C11—C12175.1 (2)O19—C15—C16—C11−175.5 (2)
O1—C2—C11—C12−0.8 (3)C14—C15—C16—C112.2 (3)
N2—C2—C11—C16−1.9 (4)C14—C13—O17—C17−172.7 (2)
O1—C2—C11—C16−177.8 (2)C12—C13—O17—C178.5 (3)
C16—C11—C12—C13−0.2 (3)C15—C14—O18—C18−78.4 (3)
C2—C11—C12—C13−177.1 (2)C13—C14—O18—C18105.6 (2)
C11—C12—C13—O17−179.4 (2)C14—C15—O19—C19173.8 (2)
C11—C12—C13—C141.8 (3)C16—C15—O19—C19−8.3 (3)
O17—C13—C14—O18−4.1 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O17i0.90 (3)2.06 (3)2.881 (2)151 (2)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2682).

References

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  • Smicius, R., Jakubkiene, V., Burduliene, M. M. & Vainilavicius, P. (2002). Monatsh. Chem.133, 173–176.
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