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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): o1481.
Published online 2008 July 12. doi:  10.1107/S160053680802062X
PMCID: PMC2962111

6-(2-Methyl­phen­yl)-3-(3,4,5-trimethoxy­phen­yl)-1,2,4-triazolo[3,4-b][1,3,4]thia­diazole

Abstract

In the mol­ecule of the title compound, C19H18N4O3S, the planar central heterocylic ring system is oriented with respect to the trimethoxy­phenyl and 2-methyl­phenyl rings at dihedral angles of 4.43 (3) and 4.32 (3)°, respectively. The dihedral angle between the two benzene rings is 7.65 (4)°. In the crystal structure, inter­molecular C—H(...)N hydrogen bonds link the mol­ecules into centrosymmetric R 2 2(18) dimers. These dimers are connected via a C—H(...)π contact between the 2-methyl­phenyl and trimethoxy­phenyl rings, and a π–π contact between the thia­diazole and trimethoxy­phenyl rings [interplanar distance 3.51 Å, dihedral angles 4.17(4)°]. An intramolecular C—H(...)N hydrogen bond is also present.

Related literature

For general background, see: Karabasanagouda et al. (2007 [triangle]); Mathew et al. (2007 [triangle]). For ring motif details, see: Bernstein et al. (1995 [triangle]).

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Object name is e-64-o1481-scheme1.jpg

Experimental

Crystal data

  • C19H18N4O3S
  • M r = 382.43
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1481-efi1.jpg
  • a = 7.5108 (15) Å
  • b = 15.950 (3) Å
  • c = 14.096 (3) Å
  • β = 91.88 (3)°
  • V = 1687.7 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.22 mm−1
  • T = 113 (2) K
  • 0.24 × 0.20 × 0.16 mm

Data collection

  • Rigaku Saturn CCD area-detector diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 [triangle]) T min = 0.923, T max = 0.965
  • 11990 measured reflections
  • 3984 independent reflections
  • 3408 reflections with I > 2σ(I)
  • R int = 0.031

Refinement

  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.108
  • S = 1.07
  • 3984 reflections
  • 248 parameters
  • H-atom parameters constrained
  • Δρmax = 0.39 e Å−3
  • Δρmin = −0.35 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2005 [triangle]); 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]) and PLATON (Spek, 2003 [triangle]); software used to prepare material for publication: SHELXTL and PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680802062X/hk2487sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680802062X/hk2487Isup2.hkl

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

Acknowledgments

The authors thank Guiyang College (grant No. 2008012) for financial support.

supplementary crystallographic information

Comment

1,2,4-Triazole and 1,3,4-thiadiazole represent one of the most biologically active classes of compounds, possessing a wide spectrum of activities. Various substituted 1,2,4-triazolo[3,4-b]-1,3,4-thiadiazoles are associated with diverse pharmacological activities such as antimicrobial (Karabasanagouda et al., 2007) and anti-inflammatory activity (Mathew et al., 2007). We report herein the crystal structure of the title compound.

In the molecule of the title compound (Fig. 1) the bond lengths and angles are within normal ranges. Rings A (C1-C6), B (N1-N3/C10/C11), C (S1/N3/N4/C11/C12) and D (C13-C18) are, of course, planar, and the dihedral angles between them are A/B = 4.63 (4)°, A/C = 4.08 (3)°, A/D = 7.65 (4)°, B/C = 0.94 (3)°, B/D = 4.59 (4)° and C/D = 4.25 (4)°. So, rings B and C are nearly coplanar. The coplanar ring system is oriented with respect to rings A and D at dihedral angles of 4.43 (3)° and 4.32 (3)°, respectively. The intra- molecular C-H···N hydrogen bond (Table 1) results in the formation of a planar six-membered ring E (N3/N4/C1/C2/C10/H2), in which it is oriented with respect to the other rings at dihedral angles of A/E = 3.24 (4)°, B/E = 1.39 (3)°, C/E = 1.03 (3)° and D/E = 5.25 (4)°. So, rings A, B, C and E are also nearly coplanar.

In the crystal structure, intermolecular weak C-H···N hydrogen bonds (Table 1) link the molecules to form a R22(18) ring motif (Fig. 2) (Bernstein et al., 1995), in which they may be effective in the stabilization of the structure. The C—H···π contact (Table 1) between the 2-methylphenyl and trimethoxyphenyl rings and a π—π contact between the thiadiazole and trimethoxyphenyl rings CgC···CgAi [symmetry code: (i) 1 - x, 1 - y, 1 - z] further stabilize the structure, with centroid-centroid distance of 3.506 (1) Å.

Experimental

For the preparation of the title compound, 4-amino-5-(3,4,5-trimethoxyphenyl) -4H-1,2,4-triazole-3-thiol (0.01 M) and 2-methylbenzoic acid (0.01 M) were dissolved in dry phosphorous oxychloride (10 ml). The resulted solution was further heated under reflux for 7 h. The reaction mixture was cooled to room temperature and the mixture was gradually poured onto crushed ice with stirring. Finally, powdered potassium carbonate and the required amount of solid potassium hydroxide were added until the pH of the mixture was raised to 8, to remove the excess of phosphorous oxychloride. The mixture was allowed to stand overnight and the solid was separated. It was filtered, washed with cold water, and then dried. Crystals suitable for X-ray analysis were obtained by the recrystallization of the solid residue from a mixture of N,N-dimethyl- formamide/ethanol (1:1) by slow evaporation at room temperature.

Refinement

H atoms were positioned geometrically, with C-H = 0.95 and 0.98 Å for aromatic and methyl H, respectively, and constrained to ride on their parent atoms with Uiso(H) = xUeq(C), where x = 1.5 for methyl H and x = 1.2 for aromatic H atoms.

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
A partial packing diagram of the title compound [symmetry code: (') -x, -y, -z]. Hydrogen bonds are shown as dashed lines.

Crystal data

C19H18N4O3SF000 = 800
Mr = 382.43Dx = 1.505 Mg m3
Monoclinic, P21/cMelting point: 435 K
Hall symbol: -P 2ybcMo Kα radiation λ = 0.71073 Å
a = 7.5108 (15) ÅCell parameters from 4684 reflections
b = 15.950 (3) Åθ = 1.9–27.9º
c = 14.096 (3) ŵ = 0.22 mm1
β = 91.88 (3)ºT = 113 (2) K
V = 1687.7 (6) Å3Prism, colorless
Z = 40.24 × 0.20 × 0.16 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer3984 independent reflections
Radiation source: rotating anode3408 reflections with I > 2σ(I)
Monochromator: confocalRint = 0.031
Detector resolution: 7.31 pixels mm-1θmax = 27.9º
T = 113(2) Kθmin = 1.9º
ω and [var phi] scansh = −9→9
Absorption correction: multi-scan(CrystalClear; Rigaku/MSC, 2005)k = −20→20
Tmin = 0.923, Tmax = 0.965l = −17→18
11990 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.108  w = 1/[σ2(Fo2) + (0.0664P)2 + 0.1888P] where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.002
3984 reflectionsΔρmax = 0.39 e Å3
248 parametersΔρmin = −0.35 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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 > 2sigma(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
S10.45611 (5)0.68554 (2)0.69693 (2)0.02005 (12)
O10.04396 (14)0.40664 (6)0.30838 (7)0.0227 (2)
O20.03955 (14)0.24866 (6)0.34593 (7)0.0223 (2)
O30.17803 (14)0.18588 (6)0.51532 (7)0.0209 (2)
N10.43365 (17)0.44321 (7)0.69492 (9)0.0208 (3)
N20.48819 (18)0.51377 (8)0.74703 (9)0.0226 (3)
N30.36258 (15)0.55345 (7)0.61030 (8)0.0156 (2)
N40.31020 (15)0.61420 (7)0.54614 (8)0.0164 (2)
C10.27851 (18)0.41101 (8)0.54193 (10)0.0162 (3)
C20.20134 (19)0.44117 (8)0.45750 (10)0.0176 (3)
H20.20180.49950.44390.021*
C30.12374 (18)0.38475 (9)0.39346 (10)0.0173 (3)
C40.12199 (18)0.29857 (8)0.41238 (10)0.0170 (3)
C50.19617 (18)0.26966 (8)0.49906 (10)0.0169 (3)
C60.27654 (18)0.32539 (8)0.56254 (10)0.0174 (3)
H60.33030.30530.62010.021*
C70.0480 (2)0.49299 (9)0.28278 (11)0.0232 (3)
H7A−0.00990.52630.33140.035*
H7B−0.01520.50090.22150.035*
H7C0.17200.51120.27780.035*
C80.1222 (2)0.17048 (9)0.32363 (12)0.0276 (4)
H8A0.25130.17500.33490.041*
H8B0.09680.15680.25680.041*
H8C0.07510.12620.36390.041*
C90.2468 (2)0.15402 (9)0.60340 (11)0.0247 (3)
H9A0.37560.16390.60830.037*
H9B0.22320.09370.60690.037*
H9C0.18900.18260.65570.037*
C100.35879 (18)0.46709 (8)0.61313 (10)0.0164 (3)
C110.44294 (18)0.57788 (9)0.69380 (10)0.0182 (3)
C120.35200 (18)0.68710 (8)0.58207 (9)0.0159 (3)
C130.32100 (18)0.76838 (8)0.53561 (10)0.0167 (3)
C140.3639 (2)0.84107 (9)0.58780 (11)0.0212 (3)
H140.41010.83570.65100.025*
C150.3405 (2)0.92022 (9)0.54955 (11)0.0240 (3)
H150.37240.96860.58550.029*
C160.2700 (2)0.92787 (9)0.45800 (11)0.0245 (3)
H160.25210.98190.43090.029*
C170.22563 (19)0.85687 (9)0.40588 (11)0.0210 (3)
H170.17620.86340.34340.025*
C180.25090 (18)0.77609 (9)0.44191 (10)0.0174 (3)
C190.2042 (2)0.70232 (9)0.37935 (10)0.0206 (3)
H19A0.16330.72240.31660.031*
H19B0.10930.66970.40790.031*
H19C0.30960.66690.37270.031*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0259 (2)0.01750 (18)0.01647 (19)−0.00076 (13)−0.00384 (14)−0.00149 (12)
O10.0347 (6)0.0148 (5)0.0181 (5)0.0021 (4)−0.0071 (4)0.0011 (4)
O20.0258 (6)0.0165 (5)0.0242 (6)0.0014 (4)−0.0056 (4)−0.0036 (4)
O30.0278 (6)0.0142 (5)0.0203 (5)−0.0019 (4)−0.0035 (4)0.0032 (4)
N10.0244 (7)0.0189 (6)0.0190 (6)0.0012 (5)−0.0023 (5)−0.0002 (5)
N20.0287 (7)0.0196 (6)0.0193 (6)0.0012 (5)−0.0038 (5)−0.0006 (5)
N30.0173 (6)0.0158 (5)0.0136 (5)0.0000 (4)−0.0010 (4)0.0005 (4)
N40.0182 (6)0.0149 (5)0.0160 (6)0.0005 (4)−0.0002 (4)0.0024 (4)
C10.0154 (6)0.0170 (6)0.0164 (7)0.0007 (5)0.0026 (5)−0.0006 (5)
C20.0202 (7)0.0150 (6)0.0177 (7)0.0015 (5)0.0012 (5)−0.0004 (5)
C30.0200 (7)0.0179 (7)0.0140 (6)0.0031 (5)0.0005 (5)0.0003 (5)
C40.0171 (7)0.0155 (6)0.0184 (7)−0.0001 (5)0.0003 (5)−0.0022 (5)
C50.0167 (7)0.0142 (6)0.0199 (7)0.0010 (5)0.0034 (5)0.0014 (5)
C60.0168 (7)0.0190 (7)0.0165 (7)0.0019 (5)0.0005 (5)0.0020 (5)
C70.0316 (8)0.0161 (7)0.0217 (7)0.0028 (6)−0.0042 (6)0.0037 (5)
C80.0387 (9)0.0170 (7)0.0265 (8)0.0034 (6)−0.0065 (7)−0.0061 (6)
C90.0335 (9)0.0177 (7)0.0227 (8)−0.0002 (6)−0.0037 (6)0.0058 (6)
C100.0169 (7)0.0146 (6)0.0177 (7)0.0008 (5)0.0016 (5)0.0014 (5)
C110.0196 (7)0.0196 (6)0.0154 (7)−0.0006 (5)−0.0010 (5)−0.0013 (5)
C120.0147 (6)0.0180 (7)0.0149 (7)−0.0003 (5)0.0002 (5)−0.0013 (5)
C130.0161 (7)0.0163 (6)0.0176 (7)0.0005 (5)0.0006 (5)0.0000 (5)
C140.0233 (7)0.0198 (7)0.0204 (7)0.0001 (6)−0.0018 (6)−0.0023 (6)
C150.0287 (8)0.0161 (6)0.0271 (8)−0.0007 (6)−0.0012 (6)−0.0030 (6)
C160.0297 (8)0.0168 (7)0.0270 (8)0.0013 (6)0.0005 (6)0.0025 (6)
C170.0218 (7)0.0216 (7)0.0198 (7)0.0011 (6)0.0004 (5)0.0019 (5)
C180.0163 (7)0.0190 (7)0.0169 (7)0.0004 (5)0.0015 (5)0.0003 (5)
C190.0245 (8)0.0200 (7)0.0172 (7)−0.0012 (6)−0.0015 (5)−0.0009 (5)

Geometric parameters (Å, °)

S1—C111.7205 (15)C7—H7A0.9800
S1—C121.7749 (15)C7—H7B0.9800
O1—C31.3682 (17)C7—H7C0.9800
O1—C71.4244 (16)C8—H8A0.9800
O2—C41.3625 (16)C8—H8B0.9800
O2—C81.4325 (17)C8—H8C0.9800
O3—C51.3633 (16)C9—H9A0.9800
O3—C91.4229 (17)C9—H9B0.9800
N1—C101.3221 (18)C9—H9C0.9800
N1—N21.3978 (17)C12—C131.4677 (19)
N2—C111.3067 (18)C13—C141.4048 (19)
N3—C111.3619 (18)C13—C181.411 (2)
N3—N41.3742 (16)C14—C151.382 (2)
N3—C101.3783 (17)C14—H140.9500
N4—C121.3026 (17)C15—C161.384 (2)
C1—C21.392 (2)C15—H150.9500
C1—C61.3964 (19)C16—C171.385 (2)
C1—C101.4600 (19)C16—H160.9500
C2—C31.3893 (19)C17—C181.3956 (19)
C2—H20.9500C17—H170.9500
C3—C41.4003 (19)C18—C191.5050 (19)
C4—C51.404 (2)C19—H19A0.9800
C5—C61.3855 (19)C19—H19B0.9800
C6—H60.9500C19—H19C0.9800
C11—S1—C1288.13 (6)O3—C9—H9A109.5
C3—O1—C7117.15 (11)O3—C9—H9B109.5
C4—O2—C8117.97 (11)H9A—C9—H9B109.5
C5—O3—C9117.47 (11)O3—C9—H9C109.5
C10—N1—N2109.59 (11)H9A—C9—H9C109.5
C11—N2—N1105.19 (12)H9B—C9—H9C109.5
C11—N3—N4118.44 (11)N1—C10—N3107.73 (12)
C11—N3—C10105.66 (11)N1—C10—C1125.26 (12)
N4—N3—C10135.89 (12)N3—C10—C1126.93 (12)
C12—N4—N3108.26 (11)N2—C11—N3111.83 (13)
C2—C1—C6120.59 (13)N2—C11—S1138.82 (11)
C2—C1—C10121.79 (12)N3—C11—S1109.35 (10)
C6—C1—C10117.59 (12)N4—C12—C13125.61 (13)
C3—C2—C1119.05 (13)N4—C12—S1115.82 (10)
C3—C2—H2120.5C13—C12—S1118.57 (10)
C1—C2—H2120.5C14—C13—C18119.37 (13)
O1—C3—C2124.52 (12)C14—C13—C12117.71 (13)
O1—C3—C4114.26 (12)C18—C13—C12122.93 (12)
C2—C3—C4121.23 (13)C15—C14—C13121.71 (14)
O2—C4—C3116.72 (12)C15—C14—H14119.1
O2—C4—C5124.38 (12)C13—C14—H14119.1
C3—C4—C5118.83 (12)C14—C15—C16118.96 (14)
O3—C5—C6124.34 (13)C14—C15—H15120.5
O3—C5—C4115.42 (12)C16—C15—H15120.5
C6—C5—C4120.22 (12)C15—C16—C17120.04 (14)
C5—C6—C1120.03 (13)C15—C16—H16120.0
C5—C6—H6120.0C17—C16—H16120.0
C1—C6—H6120.0C16—C17—C18122.30 (14)
O1—C7—H7A109.5C16—C17—H17118.8
O1—C7—H7B109.5C18—C17—H17118.8
H7A—C7—H7B109.5C17—C18—C13117.60 (13)
O1—C7—H7C109.5C17—C18—C19118.83 (13)
H7A—C7—H7C109.5C13—C18—C19123.57 (12)
H7B—C7—H7C109.5C18—C19—H19A109.5
O2—C8—H8A109.5C18—C19—H19B109.5
O2—C8—H8B109.5H19A—C19—H19B109.5
H8A—C8—H8B109.5C18—C19—H19C109.5
O2—C8—H8C109.5H19A—C19—H19C109.5
H8A—C8—H8C109.5H19B—C19—H19C109.5
H8B—C8—H8C109.5
C10—N1—N2—C110.13 (16)C2—C1—C10—N1179.68 (13)
C11—N3—N4—C12−0.04 (16)C6—C1—C10—N11.6 (2)
C10—N3—N4—C12−178.51 (15)C2—C1—C10—N33.3 (2)
C6—C1—C2—C3−0.6 (2)C6—C1—C10—N3−174.73 (13)
C10—C1—C2—C3−178.64 (13)N1—N2—C11—N3−0.07 (16)
C7—O1—C3—C22.7 (2)N1—N2—C11—S1−179.34 (13)
C7—O1—C3—C4−177.29 (12)N4—N3—C11—N2−178.90 (12)
C1—C2—C3—O1−179.99 (13)C10—N3—C11—N2−0.01 (16)
C1—C2—C3—C40.0 (2)N4—N3—C11—S10.58 (15)
C8—O2—C4—C3138.95 (14)C10—N3—C11—S1179.48 (9)
C8—O2—C4—C5−44.2 (2)C12—S1—C11—N2178.60 (18)
O1—C3—C4—O2−1.28 (18)C12—S1—C11—N3−0.68 (10)
C2—C3—C4—O2178.74 (12)N3—N4—C12—C13179.15 (12)
O1—C3—C4—C5−178.28 (12)N3—N4—C12—S1−0.53 (14)
C2—C3—C4—C51.7 (2)C11—S1—C12—N40.74 (11)
C9—O3—C5—C6−0.1 (2)C11—S1—C12—C13−178.97 (11)
C9—O3—C5—C4−178.32 (12)N4—C12—C13—C14175.74 (13)
O2—C4—C5—O3−1.3 (2)S1—C12—C13—C14−4.59 (17)
C3—C4—C5—O3175.43 (12)N4—C12—C13—C18−4.3 (2)
O2—C4—C5—C6−179.60 (13)S1—C12—C13—C18175.39 (11)
C3—C4—C5—C6−2.9 (2)C18—C13—C14—C15−0.5 (2)
O3—C5—C6—C1−175.88 (13)C12—C13—C14—C15179.46 (13)
C4—C5—C6—C12.2 (2)C13—C14—C15—C161.2 (2)
C2—C1—C6—C5−0.5 (2)C14—C15—C16—C17−0.6 (2)
C10—C1—C6—C5177.61 (12)C15—C16—C17—C18−0.7 (2)
N2—N1—C10—N3−0.13 (15)C16—C17—C18—C131.3 (2)
N2—N1—C10—C1−177.07 (12)C16—C17—C18—C19−178.14 (14)
C11—N3—C10—N10.09 (15)C14—C13—C18—C17−0.7 (2)
N4—N3—C10—N1178.69 (14)C12—C13—C18—C17179.32 (13)
C11—N3—C10—C1176.96 (13)C14—C13—C18—C19178.70 (13)
N4—N3—C10—C1−4.4 (3)C12—C13—C18—C19−1.3 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C2—H2···N40.952.453.127 (3)128
C7—H7C···N2i0.982.623.524 (3)154
C19—H19B···CgAii0.982.903.808 (3)155

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2487).

References

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