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Acta Cryst. (2009). E65, o469    [ doi:10.1107/S1600536809002645 ]

(E)-3-Allylsulfanyl-N-(4-methoxybenzylidene)-5-(3,4,5-trimethoxyphenyl)-4H-1,2,4-triazol-4-amine

Q.-Z. Li, B.-A. Song, S. Yang, Y.-G. Zheng and Q.-Q. Guo

Abstract top

The title compound, C22H24N4O4S, adopts a trans configuration with respect to the C=N double bond. A weak intramolecular C-H...N hydrogen bond is observed between the N atom of the C=N double bond and its neighboring phenyl H atom. The crystal structure is stabilized by intermolecular C-H...N hydrogen bonds and C-H...[pi] interactions.

Comment top

Triazole derivatives are of great interest in medicinal chemistry in relation to antibacterial bioactivities (Bekircan & Gumrukcuoglu, 2005; Ewiss et al., 1986; Ikizler et al., 1998). However, to date, only a few reports have been dedicated to the synthesis and antimicrobial activity evaluation of triazole derivatives with a 3,4,5-trimethoxyphenyl substituent. Herein, we want to report on the synthesis and structure such a compound, (E)-4-(4-methoxybenzylideneamino)-5-(3,4,5-trimethoxyphenyl)-4H-1,2,4-triazole-3-thiol.

The molecule of the title compound (Fig. 1), exists in an E configuration with respect to the C12=N4 double bond [1.278 (2) Å] with a N3–N4–C12–C13 torsion angle of 179.08 (13)°. The whole molecule is not planar as the dihedral angles between the triazole ring and the two phenyl rings are 25.3 (2)° and 113.8 (2)°, respectively. There is one weak intramolecular C–H···N hydrogen bond between C1 and N4 (Table 1).

In the crystal structure (Fig. 3), two neighboring molecules are linked by weak C12—H12···N2 intermolecular interactions into a centrosymmetric R22(12) ring motif (Bernstein et al., 1995) with two parallel trizole rings with a centroid-centroid separation of 3.650 (1) Å between them (Fig. 2). Moreover, an intermolecular C-H···N hydrogen bond (C19—H19A···N1) is also observed. The molecular packing is further stabilized by C—H···π interactions (Table 1, Cg1 and Cg2 are the centroids of the C1–C6 and C13–C18 rings, respectively).

Related literature top

For background on the biological activity of triazole compounds, see: Bekircan & Gumrukcuoglu (2005); Ewiss et al. (1986); Ikizler et al. (1998). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

A mixture of 3-bromoprop-1-ene (5 mmol) and methanol (3 mL) was added dropwise to a stirred solution of (E)-4-(4-methoxybenzylideneamino)-5-(3,4,5-trimethoxyphenyl)-4H-1,2,4-triazole-3-thiol (5 mmol) and sodium hydroxide (5 mmol) in water (15 mL). The resulting mixture was stirred at room temperature for 4 hours. After allowing the resulting solution to stand in air at room temperature for 2 days, colorless block-shaped crystals were formed at the bottom of the vessel on slow evaporation of the solvent. The crystals were isolated, washed with ethanol and dried.

Refinement top

H atoms were placed in calculated positions and were treated as riding on the parent C atoms with C—H = 0.93 - 0.97 Å, and with Uiso(H) = 1.5 Ueq(C) for methyl C atoms or Uiso(H) = 1.2 Ueq(C) for the other C atoms.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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 structure of the title compound showing displacement ellipsoids drawn at the 30% probability level.
[Figure 2] Fig. 2. A perspective view of the R22(12) ring motif formed through the intermolecular C12—H12···N2 hydrogen bond. Dashed lines indicate C-H···N hydrogen bonds and π-π stacking interactions.
[Figure 3] Fig. 3. Crystal structure of the title compound viewed along the a-axis. Hydrogen bonds are shown as dashed lines.
(E)-3-Allylsulfanyl-N-(4-methoxybenzylidene)-5-(3,4,5- trimethoxyphenyl)-4H-1,2,4-triazol-4-amine top
Crystal data top
C22H24N4O4SF(000) = 928
Mr = 440.51Dx = 1.307 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2895 reflections
a = 7.9414 (12) Åθ = 2.4–27.9°
b = 15.043 (2) ŵ = 0.18 mm−1
c = 19.047 (3) ÅT = 293 K
β = 100.385 (6)°Block, colorless
V = 2238.1 (6) Å30.36 × 0.30 × 0.26 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		3929 independent reflections
Radiation source: fine-focus sealed tube3354 reflections with I > 2σ(I)
graphiteRint = 0.028
φ and ω scansθmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −8→9
Tmin = 0.936, Tmax = 0.956k = −17→17
23323 measured reflectionsl = −22→22
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.103 w = 1/[σ2(Fo2) + (0.0532P)2 + 0.4889P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
3929 reflectionsΔρmax = 0.35 e Å−3
281 parametersΔρmin = −0.20 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0132 (12)
Crystal data top
C22H24N4O4SV = 2238.1 (6) Å3
Mr = 440.51Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.9414 (12) ŵ = 0.18 mm−1
b = 15.043 (2) ÅT = 293 K
c = 19.047 (3) Å0.36 × 0.30 × 0.26 mm
β = 100.385 (6)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		3929 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3354 reflections with I > 2σ(I)
Tmin = 0.936, Tmax = 0.956Rint = 0.028
23323 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.103Δρmax = 0.35 e Å−3
S = 1.07Δρmin = −0.20 e Å−3
3929 reflectionsAbsolute structure: ?
281 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
S1−0.32086 (5)0.40159 (3)0.50696 (2)0.05036 (16)
O20.53116 (15)0.34899 (8)0.80320 (6)0.0566 (3)
O40.63039 (17)0.63866 (9)0.73084 (7)0.0647 (4)
O10.27845 (18)−0.05796 (9)0.56221 (8)0.0737 (4)
N40.04176 (16)0.33704 (8)0.60779 (7)0.0419 (3)
N3−0.00642 (16)0.42733 (8)0.59683 (7)0.0392 (3)
O30.72831 (15)0.49408 (9)0.81168 (6)0.0614 (4)
N2−0.15075 (18)0.54951 (9)0.56327 (8)0.0505 (4)
N10.00133 (18)0.57222 (9)0.60765 (8)0.0493 (3)
C130.10497 (19)0.20262 (10)0.55230 (8)0.0412 (4)
C30.5743 (2)0.49373 (11)0.76468 (8)0.0461 (4)
C60.25403 (19)0.49468 (10)0.67595 (8)0.0394 (3)
C120.05405 (19)0.29577 (10)0.55028 (8)0.0426 (4)
H120.03030.32540.50680.051*
C140.1270 (2)0.15253 (11)0.61543 (9)0.0464 (4)
H140.10200.17780.65690.056*
C8−0.1542 (2)0.46257 (10)0.55731 (8)0.0431 (4)
C70.0855 (2)0.49833 (10)0.62810 (8)0.0398 (3)
C10.3077 (2)0.41986 (10)0.71705 (8)0.0415 (4)
H10.23680.37040.71500.050*
C20.4679 (2)0.41929 (11)0.76131 (8)0.0435 (4)
C50.3589 (2)0.56949 (10)0.67940 (8)0.0443 (4)
H50.32210.61960.65240.053*
C40.5188 (2)0.56862 (11)0.72351 (9)0.0463 (4)
C150.1852 (2)0.06656 (11)0.61640 (10)0.0517 (4)
H150.20130.03420.65870.062*
C160.2205 (2)0.02742 (11)0.55411 (10)0.0518 (4)
C180.1392 (2)0.16211 (12)0.49085 (9)0.0517 (4)
H180.12340.19430.44850.062*
C10−0.3730 (3)0.30522 (14)0.62529 (10)0.0633 (5)
H10−0.27350.31990.65690.076*
C9−0.4510 (2)0.37642 (12)0.57463 (10)0.0558 (4)
H9A−0.46450.43000.60140.067*
H9B−0.56390.35750.55110.067*
C190.4213 (3)0.27423 (13)0.80370 (12)0.0717 (6)
H19A0.47930.22940.83490.108*
H19B0.39120.25070.75620.108*
H19C0.31940.29220.82030.108*
C170.1965 (2)0.07488 (12)0.49092 (10)0.0561 (5)
H170.21840.04880.44920.067*
C210.5991 (3)0.70808 (15)0.68073 (15)0.0924 (8)
H21A0.68530.75310.69250.139*
H21B0.48840.73330.68160.139*
H21C0.60210.68520.63390.139*
C11−0.4301 (3)0.22612 (15)0.62922 (12)0.0764 (6)
H11A−0.52920.20830.59870.092*
H11B−0.37240.18650.66260.092*
C200.8754 (3)0.47977 (17)0.78013 (13)0.0797 (6)
H20A0.97620.48080.81650.120*
H20B0.88290.52580.74590.120*
H20C0.86640.42310.75660.120*
C220.3150 (3)−0.10321 (14)0.50050 (15)0.0858 (8)
H22A0.3545−0.16230.51350.129*
H22B0.4019−0.07140.48180.129*
H22C0.2129−0.10630.46480.129*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0433 (3)0.0626 (3)0.0420 (3)−0.00628 (19)−0.00102 (17)0.00451 (18)
O20.0536 (7)0.0571 (7)0.0529 (7)−0.0027 (6)−0.0065 (5)0.0096 (6)
O40.0612 (8)0.0609 (8)0.0682 (8)−0.0265 (6)0.0013 (6)−0.0029 (6)
O10.0718 (9)0.0497 (7)0.0989 (11)0.0117 (6)0.0139 (8)−0.0119 (7)
N40.0437 (7)0.0341 (7)0.0443 (7)−0.0016 (5)−0.0015 (6)0.0014 (5)
N30.0391 (7)0.0357 (6)0.0410 (7)−0.0017 (5)0.0026 (5)0.0035 (5)
O30.0438 (7)0.0890 (9)0.0478 (7)−0.0136 (6)−0.0018 (5)−0.0031 (6)
N20.0465 (8)0.0451 (8)0.0576 (9)0.0013 (6)0.0032 (6)0.0085 (6)
N10.0475 (8)0.0402 (7)0.0582 (9)−0.0013 (6)0.0036 (7)0.0031 (6)
C130.0378 (8)0.0434 (8)0.0413 (8)−0.0037 (6)0.0038 (6)−0.0012 (7)
C30.0399 (9)0.0610 (10)0.0365 (8)−0.0068 (7)0.0046 (7)−0.0069 (7)
C60.0382 (8)0.0426 (8)0.0378 (8)−0.0028 (6)0.0076 (6)−0.0048 (6)
C120.0397 (8)0.0447 (8)0.0421 (9)−0.0025 (7)0.0042 (7)0.0056 (7)
C140.0513 (9)0.0446 (9)0.0451 (9)−0.0001 (7)0.0137 (7)0.0000 (7)
C80.0408 (9)0.0453 (9)0.0423 (9)−0.0010 (7)0.0045 (7)0.0076 (7)
C70.0419 (8)0.0371 (8)0.0406 (8)−0.0032 (6)0.0083 (7)0.0002 (6)
C10.0415 (8)0.0427 (8)0.0396 (8)−0.0062 (6)0.0056 (7)−0.0025 (6)
C20.0440 (9)0.0486 (9)0.0376 (8)0.0000 (7)0.0063 (7)−0.0020 (7)
C50.0493 (9)0.0403 (8)0.0434 (9)−0.0051 (7)0.0087 (7)−0.0021 (7)
C40.0448 (9)0.0505 (9)0.0445 (9)−0.0136 (7)0.0101 (7)−0.0086 (7)
C150.0523 (10)0.0467 (9)0.0575 (10)0.0028 (8)0.0141 (8)0.0081 (8)
C160.0399 (9)0.0437 (9)0.0707 (12)−0.0015 (7)0.0068 (8)−0.0087 (8)
C180.0538 (10)0.0591 (10)0.0404 (9)−0.0002 (8)0.0038 (7)−0.0009 (7)
C100.0613 (12)0.0763 (13)0.0538 (11)−0.0111 (10)0.0142 (9)−0.0017 (9)
C90.0467 (10)0.0563 (10)0.0668 (12)−0.0027 (8)0.0169 (9)−0.0012 (9)
C190.0762 (14)0.0586 (11)0.0720 (13)−0.0088 (10)−0.0088 (10)0.0201 (10)
C170.0496 (10)0.0647 (11)0.0531 (11)0.0005 (8)0.0068 (8)−0.0199 (9)
C210.0758 (15)0.0691 (14)0.124 (2)−0.0331 (12)−0.0033 (14)0.0223 (14)
C110.0755 (14)0.0708 (14)0.0833 (15)0.0001 (11)0.0154 (12)0.0125 (11)
C200.0458 (11)0.1008 (17)0.0890 (16)0.0021 (11)0.0027 (11)−0.0133 (13)
C220.0673 (14)0.0626 (13)0.128 (2)0.0019 (10)0.0205 (14)−0.0384 (13)
Geometric parameters (Å, °) top
S1—C81.7477 (16)C1—H10.9300
S1—C91.8312 (18)C5—C41.391 (2)
O2—C21.3649 (19)C5—H50.9300
O2—C191.424 (2)C15—C161.397 (2)
O4—C41.3676 (19)C15—H150.9300
O4—C211.406 (3)C16—C171.383 (3)
O1—C161.364 (2)C18—C171.389 (2)
O1—C221.433 (3)C18—H180.9300
N4—C121.278 (2)C10—C111.280 (3)
N4—N31.4164 (17)C10—C91.499 (3)
N3—C71.3681 (19)C10—H100.9300
N3—C81.3810 (19)C9—H9A0.9700
O3—C31.3795 (19)C9—H9B0.9700
O3—C201.423 (2)C19—H19A0.9600
N2—C81.313 (2)C19—H19B0.9600
N2—N11.3863 (19)C19—H19C0.9600
N1—C71.319 (2)C17—H170.9300
C13—C181.389 (2)C21—H21A0.9600
C13—C141.403 (2)C21—H21B0.9600
C13—C121.457 (2)C21—H21C0.9600
C3—C21.397 (2)C11—H11A0.9300
C3—C41.398 (2)C11—H11B0.9300
C6—C11.393 (2)C20—H20A0.9600
C6—C51.394 (2)C20—H20B0.9600
C6—C71.478 (2)C20—H20C0.9600
C12—H120.9300C22—H22A0.9600
C14—C151.372 (2)C22—H22B0.9600
C14—H140.9300C22—H22C0.9600
C1—C21.394 (2)
C8—S1—C9100.95 (8)C16—C15—H15119.9
C2—O2—C19117.02 (13)O1—C16—C17125.13 (17)
C4—O4—C21118.08 (15)O1—C16—C15114.57 (17)
C16—O1—C22117.95 (17)C17—C16—C15120.29 (16)
C12—N4—N3113.56 (12)C17—C18—C13121.84 (16)
C7—N3—C8105.79 (12)C17—C18—H18119.1
C7—N3—N4125.15 (12)C13—C18—H18119.1
C8—N3—N4128.97 (12)C11—C10—C9126.3 (2)
C3—O3—C20115.13 (14)C11—C10—H10116.8
C8—N2—N1107.50 (13)C9—C10—H10116.8
C7—N1—N2108.17 (13)C10—C9—S1112.37 (13)
C18—C13—C14118.26 (15)C10—C9—H9A109.1
C18—C13—C12119.68 (14)S1—C9—H9A109.1
C14—C13—C12122.03 (14)C10—C9—H9B109.1
O3—C3—C2119.41 (15)S1—C9—H9B109.1
O3—C3—C4120.93 (15)H9A—C9—H9B107.9
C2—C3—C4119.56 (15)O2—C19—H19A109.5
C1—C6—C5120.38 (15)O2—C19—H19B109.5
C1—C6—C7121.86 (13)H19A—C19—H19B109.5
C5—C6—C7117.75 (14)O2—C19—H19C109.5
N4—C12—C13120.54 (14)H19A—C19—H19C109.5
N4—C12—H12119.7H19B—C19—H19C109.5
C13—C12—H12119.7C16—C17—C18118.84 (16)
C15—C14—C13120.48 (15)C16—C17—H17120.6
C15—C14—H14119.8C18—C17—H17120.6
C13—C14—H14119.8O4—C21—H21A109.5
N2—C8—N3109.43 (13)O4—C21—H21B109.5
N2—C8—S1124.92 (12)H21A—C21—H21B109.5
N3—C8—S1125.65 (12)O4—C21—H21C109.5
N1—C7—N3109.08 (14)H21A—C21—H21C109.5
N1—C7—C6124.59 (14)H21B—C21—H21C109.5
N3—C7—C6126.32 (13)C10—C11—H11A120.0
C6—C1—C2119.90 (14)C10—C11—H11B120.0
C6—C1—H1120.1H11A—C11—H11B120.0
C2—C1—H1120.1O3—C20—H20A109.5
O2—C2—C1123.92 (14)O3—C20—H20B109.5
O2—C2—C3115.99 (14)H20A—C20—H20B109.5
C1—C2—C3120.09 (15)O3—C20—H20C109.5
C4—C5—C6119.56 (15)H20A—C20—H20C109.5
C4—C5—H5120.2H20B—C20—H20C109.5
C6—C5—H5120.2O1—C22—H22A109.5
O4—C4—C5123.97 (16)O1—C22—H22B109.5
O4—C4—C3115.52 (15)H22A—C22—H22B109.5
C5—C4—C3120.51 (14)O1—C22—H22C109.5
C14—C15—C16120.28 (16)H22A—C22—H22C109.5
C14—C15—H15119.9H22B—C22—H22C109.5
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C1—H1···N40.932.382.960 (2)120
C12—H12···N2i0.932.593.359 (2)141
C19—H19A···N1ii0.962.603.477 (3)152
C9—H9A···Cg1iii0.972.793.616 (2)143
C11—H11A···Cg2iv0.932.833.703 (2)158
C15—H15···Cg1v0.932.703.514 (2)147
C22—H22C···Cg2vi0.962.943.747 (2)143
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1/2, y−1/2, −z+3/2; (iii) x−1, y, z; (iv) x−1, y−1, z; (v) −x+3/2, y+1/2, −z+1/2; (vi) −x+1, −y+1, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C1—H1···N40.932.382.960 (2)120
C12—H12···N2i0.932.593.359 (2)141
C19—H19A···N1ii0.962.603.477 (3)152
C9—H9A···Cg1iii0.972.793.616 (2)143
C11—H11A···Cg2iv0.932.833.703 (2)158
C15—H15···Cg1v0.932.703.514 (2)147
C22—H22C···Cg2vi0.962.943.747 (2)143
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1/2, y−1/2, −z+3/2; (iii) x−1, y, z; (iv) x−1, y−1, z; (v) −x+3/2, y+1/2, −z+1/2; (vi) −x+1, −y+1, −z.
Acknowledgements top

The authors acknowledge the National Key Technologies R&D Program of China (grant No. 2006BAE01A01-13) for supporting this work.

references
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