supplementary materials


Acta Cryst. (2008). E64, o2040    [ doi:10.1107/S1600536808030936 ]

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

H.-T. Du, H.-J. Du and W. Zhou

Abstract top

In the molecule of the title compound, C19H18N4O3S, the central heterocylic ring system is oriented with respect to the trimethoxyphenyl and 4-methylphenyl rings at dihedral angles of 1.1 (5) and 15.1 (5)°, respectively. The dihedral angle between the two benzene rings is 16.1 (4)°. In the crystal structure, molecules are linked by intermolecular C-H...O hydrogen bonds, and an intramolecular C-H...N interaction also occurs.

Comment top

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 = 0.61 (3)°, A/C = 1.57 (3)°, A/D = 16.09 (4)°, B/C = 0.96 (4)°, B/D = 15.53 (4)° and C/D = 14.60 (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 1.36 (3)° and 14.77 (4)°.

In the crystal structure, intramolecular C—H···N hydrogen bond results in the formation of a six-membered ring, intermolecular C—H···O hydrogen bonds link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

For general background, see: Karabasanagouda et al. (2007); Mathew et al. (2007).

Experimental top

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 4-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-dimethylformamide/ ethanol (1:1) by slow evaporation at room temperature.

Refinement top

H atoms were positioned geometrically, with C—H = 0.93 and 0.96 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.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines. [Symmetry code: O3 (x+1/2, -y+3/2, z+1/2)].
6-(4-Methylphenyl)-3-(3,4,5-trimethoxyphenyl)-1,2,4- triazolo[3,4-b][1,3,4]thiadiazole top
Crystal data top
C19H18N4O3SF(000) = 800
Mr = 382.43Dx = 1.443 Mg m3
Monoclinic, P21/nMelting point: 461 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 7.2613 (15) ÅCell parameters from 4938 reflections
b = 18.519 (4) Åθ = 2.2–27.9°
c = 13.314 (3) ŵ = 0.21 mm1
β = 100.52 (3)°T = 113 K
V = 1760.2 (6) Å3Prism, colourless
Z = 40.20 × 0.18 × 0.12 mm
Data collection top
Rigaku Saturn
diffractometer
4184 independent reflections
Radiation source: rotating anode3593 reflections with I > 2σ(I)
confocalRint = 0.030
ω scansθmax = 27.9°, θmin = 2.2°
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)
h = 99
Tmin = 0.959, Tmax = 0.975k = 2124
12668 measured reflectionsl = 1417
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0558P)2 + 0.2342P]
where P = (Fo2 + 2Fc2)/3
4184 reflections(Δ/σ)max = 0.003
248 parametersΔρmax = 0.34 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C19H18N4O3SV = 1760.2 (6) Å3
Mr = 382.43Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.2613 (15) ŵ = 0.21 mm1
b = 18.519 (4) ÅT = 113 K
c = 13.314 (3) Å0.20 × 0.18 × 0.12 mm
β = 100.52 (3)°
Data collection top
Rigaku Saturn
diffractometer
3593 reflections with I > 2σ(I)
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)
Rint = 0.030
Tmin = 0.959, Tmax = 0.975θmax = 27.9°
12668 measured reflectionsStandard reflections: 0
4184 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.034H-atom parameters constrained
wR(F2) = 0.094Δρmax = 0.34 e Å3
S = 1.06Δρmin = 0.26 e Å3
4184 reflectionsAbsolute structure: ?
248 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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.

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) top
xyzUiso*/Ueq
S10.94253 (4)1.187575 (15)0.09160 (2)0.01899 (10)
O10.66918 (12)0.79479 (4)0.06276 (7)0.02001 (19)
O20.48496 (12)0.74823 (4)0.11902 (7)0.01879 (19)
O30.40808 (13)0.83645 (5)0.27867 (7)0.0217 (2)
N10.68396 (15)1.08768 (5)0.14953 (8)0.0197 (2)
N20.75719 (15)1.15421 (5)0.11050 (8)0.0215 (2)
N30.80820 (13)1.07072 (5)0.01101 (8)0.0154 (2)
N40.87889 (13)1.04929 (5)0.10918 (8)0.0161 (2)
C10.65260 (15)0.96291 (6)0.08603 (9)0.0147 (2)
C20.69065 (16)0.91670 (6)0.00221 (9)0.0157 (2)
H20.75240.93380.06070.019*
C30.63518 (16)0.84455 (6)0.01355 (9)0.0154 (2)
C40.54233 (16)0.81924 (6)0.10783 (9)0.0156 (2)
C50.50224 (16)0.86673 (6)0.19093 (9)0.0161 (2)
C60.55682 (16)0.93877 (6)0.18036 (9)0.0163 (2)
H60.52980.97030.23540.020*
C70.74671 (19)0.82186 (7)0.16222 (10)0.0222 (3)
H7A0.86750.84260.16120.033*
H7B0.75940.78300.21070.033*
H7C0.66520.85810.18140.033*
C80.62703 (18)0.70088 (7)0.14319 (11)0.0233 (3)
H8A0.65760.71450.20770.035*
H8B0.58160.65210.14700.035*
H8C0.73690.70430.09100.035*
C90.36549 (19)0.88121 (7)0.36669 (10)0.0235 (3)
H9A0.28940.92100.35270.035*
H9B0.29870.85360.42280.035*
H9C0.47960.89920.38400.035*
C100.71354 (16)1.03844 (6)0.07648 (9)0.0158 (2)
C110.82850 (17)1.14151 (6)0.01460 (10)0.0175 (2)
C120.95402 (16)1.10531 (6)0.15977 (10)0.0166 (2)
C131.04249 (16)1.10151 (6)0.26740 (9)0.0165 (2)
C141.08199 (17)1.16412 (7)0.32607 (10)0.0205 (3)
H141.05551.20910.29590.025*
C151.15986 (18)1.15957 (7)0.42833 (10)0.0221 (3)
H151.18341.20180.46630.026*
C161.20416 (18)1.09329 (7)0.47618 (10)0.0213 (3)
C171.16536 (18)1.03064 (7)0.41664 (10)0.0221 (3)
H171.19340.98570.44690.026*
C181.08647 (17)1.03423 (6)0.31419 (10)0.0200 (3)
H181.06250.99200.27620.024*
C191.2948 (2)1.08960 (8)0.58656 (11)0.0297 (3)
H19A1.41871.07000.59230.044*
H19B1.22171.05920.62260.044*
H19C1.30211.13720.61540.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.02085 (17)0.01264 (15)0.02384 (17)0.00229 (10)0.00504 (12)0.00188 (11)
O10.0277 (5)0.0151 (4)0.0155 (4)0.0007 (3)0.0008 (4)0.0016 (3)
O20.0206 (4)0.0136 (4)0.0223 (5)0.0038 (3)0.0040 (4)0.0029 (3)
O30.0277 (5)0.0203 (4)0.0149 (4)0.0055 (4)0.0020 (4)0.0003 (3)
N10.0231 (5)0.0157 (5)0.0206 (5)0.0005 (4)0.0047 (4)0.0002 (4)
N20.0271 (6)0.0150 (5)0.0233 (6)0.0019 (4)0.0068 (5)0.0005 (4)
N30.0157 (5)0.0125 (4)0.0183 (5)0.0004 (4)0.0042 (4)0.0001 (4)
N40.0158 (5)0.0161 (5)0.0164 (5)0.0004 (4)0.0030 (4)0.0008 (4)
C10.0130 (5)0.0144 (5)0.0175 (6)0.0004 (4)0.0049 (4)0.0013 (4)
C20.0155 (5)0.0155 (5)0.0158 (6)0.0000 (4)0.0020 (4)0.0020 (4)
C30.0154 (5)0.0148 (5)0.0160 (6)0.0016 (4)0.0030 (4)0.0009 (4)
C40.0150 (5)0.0137 (5)0.0186 (6)0.0021 (4)0.0040 (5)0.0022 (4)
C50.0139 (5)0.0196 (5)0.0149 (6)0.0012 (4)0.0028 (4)0.0019 (4)
C60.0154 (5)0.0176 (5)0.0161 (6)0.0002 (4)0.0038 (4)0.0015 (4)
C70.0280 (7)0.0206 (6)0.0152 (6)0.0018 (5)0.0034 (5)0.0011 (5)
C80.0247 (6)0.0166 (6)0.0274 (7)0.0015 (5)0.0011 (5)0.0029 (5)
C90.0249 (6)0.0302 (7)0.0146 (6)0.0042 (5)0.0016 (5)0.0024 (5)
C100.0158 (5)0.0159 (5)0.0163 (6)0.0012 (4)0.0047 (4)0.0013 (4)
C110.0183 (6)0.0124 (5)0.0231 (6)0.0007 (4)0.0069 (5)0.0001 (4)
C120.0151 (5)0.0138 (5)0.0223 (6)0.0002 (4)0.0065 (5)0.0015 (4)
C130.0139 (5)0.0176 (5)0.0188 (6)0.0012 (4)0.0052 (5)0.0037 (4)
C140.0208 (6)0.0159 (5)0.0250 (7)0.0001 (5)0.0048 (5)0.0036 (5)
C150.0236 (6)0.0194 (6)0.0234 (7)0.0032 (5)0.0047 (5)0.0080 (5)
C160.0206 (6)0.0240 (6)0.0202 (6)0.0031 (5)0.0062 (5)0.0042 (5)
C170.0266 (6)0.0177 (6)0.0227 (7)0.0017 (5)0.0064 (5)0.0004 (5)
C180.0229 (6)0.0166 (6)0.0211 (6)0.0029 (5)0.0059 (5)0.0038 (4)
C190.0365 (8)0.0299 (7)0.0217 (7)0.0041 (6)0.0029 (6)0.0034 (5)
Geometric parameters (Å, °) top
S1—C111.7276 (13)C7—H7A0.9600
S1—C121.7675 (13)C7—H7B0.9600
O1—C31.3604 (14)C7—H7C0.9600
O1—C71.4315 (15)C8—H8A0.9600
O2—C41.3792 (13)C8—H8B0.9600
O2—C81.4346 (15)C8—H8C0.9600
O3—C51.3619 (14)C9—H9A0.9600
O3—C91.4225 (15)C9—H9B0.9600
N1—C101.3218 (15)C9—H9C0.9600
N1—N21.4035 (14)C12—C131.4611 (18)
N2—C111.3085 (17)C13—C141.3983 (16)
N3—C111.3693 (15)C13—C181.4034 (17)
N3—N41.3727 (14)C14—C151.3781 (19)
N3—C101.3763 (15)C14—H140.9300
N4—C121.3012 (15)C15—C161.3931 (18)
C1—C21.3934 (16)C15—H150.9300
C1—C61.3935 (17)C16—C171.4044 (17)
C1—C101.4655 (16)C16—C191.4981 (19)
C2—C31.3959 (16)C17—C181.3812 (18)
C2—H20.9300C17—H170.9300
C3—C41.3931 (17)C18—H180.9300
C4—C51.4017 (16)C19—H19A0.9600
C5—C61.3915 (16)C19—H19B0.9600
C6—H60.9300C19—H19C0.9600
C11—S1—C1288.01 (6)O3—C9—H9A109.5
C3—O1—C7116.15 (9)O3—C9—H9B109.5
C4—O2—C8113.06 (9)H9A—C9—H9B109.5
C5—O3—C9117.79 (10)O3—C9—H9C109.5
C10—N1—N2109.48 (10)H9A—C9—H9C109.5
C11—N2—N1105.02 (10)H9B—C9—H9C109.5
C11—N3—N4118.38 (10)N1—C10—N3108.18 (10)
C11—N3—C10105.37 (10)N1—C10—C1126.06 (11)
N4—N3—C10136.25 (10)N3—C10—C1125.75 (11)
C12—N4—N3108.12 (10)N2—C11—N3111.94 (10)
C2—C1—C6121.21 (11)N2—C11—S1139.02 (9)
C2—C1—C10120.27 (11)N3—C11—S1109.04 (9)
C6—C1—C10118.52 (11)N4—C12—C13122.48 (11)
C1—C2—C3119.35 (11)N4—C12—S1116.44 (10)
C1—C2—H2120.3C13—C12—S1121.08 (9)
C3—C2—H2120.3C14—C13—C18118.77 (11)
O1—C3—C4115.91 (10)C14—C13—C12121.10 (11)
O1—C3—C2123.93 (11)C18—C13—C12120.12 (10)
C4—C3—C2120.15 (11)C15—C14—C13120.43 (12)
O2—C4—C3120.33 (10)C15—C14—H14119.8
O2—C4—C5119.86 (10)C13—C14—H14119.8
C3—C4—C5119.78 (10)C14—C15—C16121.63 (11)
O3—C5—C6124.79 (11)C14—C15—H15119.2
O3—C5—C4114.71 (10)C16—C15—H15119.2
C6—C5—C4120.50 (11)C15—C16—C17117.64 (12)
C5—C6—C1118.99 (11)C15—C16—C19120.81 (11)
C5—C6—H6120.5C17—C16—C19121.52 (12)
C1—C6—H6120.5C18—C17—C16121.46 (12)
O1—C7—H7A109.5C18—C17—H17119.3
O1—C7—H7B109.5C16—C17—H17119.3
H7A—C7—H7B109.5C17—C18—C13120.06 (11)
O1—C7—H7C109.5C17—C18—H18120.0
H7A—C7—H7C109.5C13—C18—H18120.0
H7B—C7—H7C109.5C16—C19—H19A109.5
O2—C8—H8A109.5C16—C19—H19B109.5
O2—C8—H8B109.5H19A—C19—H19B109.5
H8A—C8—H8B109.5C16—C19—H19C109.5
O2—C8—H8C109.5H19A—C19—H19C109.5
H8A—C8—H8C109.5H19B—C19—H19C109.5
H8B—C8—H8C109.5
C10—N1—N2—C110.10 (13)C2—C1—C10—N1179.02 (11)
C11—N3—N4—C120.36 (14)C6—C1—C10—N11.10 (18)
C10—N3—N4—C12179.17 (12)C2—C1—C10—N30.50 (18)
C6—C1—C2—C31.35 (17)C6—C1—C10—N3179.61 (10)
C10—C1—C2—C3178.53 (10)N1—N2—C11—N30.69 (13)
C7—O1—C3—C4173.70 (10)N1—N2—C11—S1179.31 (11)
C7—O1—C3—C27.59 (16)N4—N3—C11—N2179.15 (9)
C1—C2—C3—O1178.51 (10)C10—N3—C11—N21.19 (13)
C1—C2—C3—C40.15 (17)N4—N3—C11—S10.85 (13)
C8—O2—C4—C387.14 (13)C10—N3—C11—S1178.81 (7)
C8—O2—C4—C594.73 (13)C12—S1—C11—N2179.22 (15)
O1—C3—C4—O22.14 (16)C12—S1—C11—N30.79 (9)
C2—C3—C4—O2179.09 (10)N3—N4—C12—C13179.87 (10)
O1—C3—C4—C5179.73 (10)N3—N4—C12—S10.32 (12)
C2—C3—C4—C50.96 (17)C11—S1—C12—N40.68 (10)
C9—O3—C5—C61.35 (17)C11—S1—C12—C13179.76 (10)
C9—O3—C5—C4178.93 (10)N4—C12—C13—C14164.70 (11)
O2—C4—C5—O30.68 (16)S1—C12—C13—C1414.83 (16)
C3—C4—C5—O3178.82 (10)N4—C12—C13—C1814.20 (17)
O2—C4—C5—C6179.05 (10)S1—C12—C13—C18166.27 (9)
C3—C4—C5—C60.91 (17)C18—C13—C14—C151.05 (18)
O3—C5—C6—C1179.96 (11)C12—C13—C14—C15177.87 (11)
C4—C5—C6—C10.26 (17)C13—C14—C15—C160.95 (19)
C2—C1—C6—C51.40 (17)C14—C15—C16—C170.48 (19)
C10—C1—C6—C5178.49 (10)C14—C15—C16—C19177.87 (12)
N2—N1—C10—N30.83 (13)C15—C16—C17—C180.14 (19)
N2—N1—C10—C1177.90 (11)C19—C16—C17—C18178.20 (12)
C11—N3—C10—N11.20 (13)C16—C17—C18—C130.27 (19)
N4—N3—C10—N1179.23 (11)C14—C13—C18—C170.71 (17)
C11—N3—C10—C1177.54 (11)C12—C13—C18—C17178.21 (11)
N4—N3—C10—C12.0 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C2—H2···N40.932.373.059 (2)131
C6—H6···N10.932.612.913 (2)100
C14—H14···S10.932.723.131 (2)108
C7—H7B···O3i0.962.453.202 (2)135
Symmetry codes: (i) x+1/2, −y+3/2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °)
top
D—H···AD—HH···AD···AD—H···A
C2—H2···N40.932.373.059 (2)131
C6—H6···N10.932.612.913 (2)100
C14—H14···S10.932.723.131 (2)108
C7—H7B···O3i0.962.453.202 (2)135
Symmetry codes: (i) x+1/2, −y+3/2, z+1/2.
Acknowledgements top

The authors thank Guiyang College for financial support.

references
References top

Karabasanagouda, T., Adhikari, A. V. & Shetty, S. N. (2007). Eur. J. Med. Chem. 42, 521–529.

Mathew, V., Keshavayya, J., Vaidya, V. P. & Giles, D. (2007). Eur. J. Med. Chem. 42, 823–840.

Rigaku/MSC (2005). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA.

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