3-(3,5-Dimethoxy­phen­yl)-4-(2-methoxy­phen­yl)-1H-1,2,4-triazole-5(4H)-thione

Qadeer, G.; Rama, N.H.; Akhtar, J.; Malik, M.A.; Raftery, J.

doi:10.1107/S1600536807036471

3-(3,5-Dimethoxyphenyl)-4-(2-methoxyphenyl)-1H-1,2,4-triazole-5(4H)-thione

G. Qadeer, N. H. Rama, J. Akhtar, M. A. Malik and J. Raftery

The title compound, C₁₇H₁₇N₃O₃S, is an important biologically active heterocyclic compound containing one five-membered and two six-membered planar rings. The five-membered ring is oriented with respect to the six-membered rings at dihedral angles of 88.84 (2) and 78.69 (3)°. The structure is further stabilized by intermolecular N—H

S stacking interactions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807036471/bq2029sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807036471/bq2029Isup2.hkl Contains datablock I

CCDC reference: 657862

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Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.002 Å
R factor = 0.035
wR factor = 0.099
Data-to-parameter ratio = 16.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    S1     -   C1      ..       7.37 su

Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        100 Deg.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          6

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Substituted triazole derivatives display significant biological activity including antimicrobial (Holla et al., 1998), analgesic (Turan-Zitouni et al., 1999), antitumor (Demirbas et al., 2002), antihypertensive (Paulvannan et al., 2000) and antiviral activities (Kritsanida et al., 2002). The biological activity is closely related to the structure, possibly being due to the presence of the —N—C ═S unit (Omar et al., 1986). We are interested in the synthesis and biological activity of aryloxyacetyl hydrazide derivatives and report here the synthesis and crystal structure of the title compound, (I) (Fig. 1).

The C1═S1 bond length [1.6782 (14) Å] compares with 1.6773 (19) Å in 4-(4-chlorophenyl)-3-(furan-2-yl)-1H-1,2,4- triazole-5(4H)-thione (Ozturk et al., 2004a) and 1.668 (5) Å in 4-amino-3-(1,2,3,4,5-pentahydroxypentyl)-1H-1,2,4-triazole- 5(4H)-thione (Zhang et al., 2004). In the triazole ring, the N2 ═C1 bond [1.3385 (17) Å] shows double-bond character. In the crystal structure, all bond lengths and angles are comparable with those observed in related structures (Ozturk et al., 2004a and 2004b). The triazole ring is planar within 0.002 Å and 2-methoxyphenyl ring is almost perpendicular to this ring while 3,5-dimethoxy-phenyl ring is planar to. It forms inversion related dimers via N—H···S hydrogen bonds. The structure is further stabilized by intermolecular-stacking interactions down the b axis. N2—H2···S1 hydrogen bonds link molecules of title compound into infinite chains extending along the b axis of the unit cell (Fig. 2 and Table 1).

Related literature top

For related literature, see: Demirbas et al. (2002); Holla et al. (1998); Omar et al. (1986); Ozturk et al. (2004a,b); Paulvannan et al. (2000); Turan-Zitouni et al. (1999); Zhang et al. (2004).

For related literature, see: Kritsanida et al. (2002).

Experimental top

The synthesis of the title compound was carried out by refluxing a solution of 1-(3,5-dimethoxybenzoyl)-4-(2-methoxyphenyl)thiosemicarbazide (3.47 g, 10 mmol) in 2 M NaOH for 5 h. Single crystals suitable for X-ray measurements were obtained by recrystallization from an aqueous ethanol solution at room temperature (yield: 80%; m.p. 470–471 K).

Structure description top

For related literature, see: Kritsanida et al. (2002).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. The molecular structure of (I) with 50% probability displacement ellipsoids (arbitrary spheres for H atoms).
	Fig. 2. Crystal packing of (I), showing the formation of hydrogen bonds with the symmetry position -x + 1, -y + 1, -z + 1.
	Fig. 3. The formation of the title compound.

3-(3,5-Dimethoxyphenyl)-4-(2-methoxyphenyl)-1H-1,2,4-triazole-5(4H)-thione top

Crystal data top

C₁₇H₁₇N₃O₃S	Z = 2
M_r = 343.40	F(000) = 360
Triclinic, P1	D_x = 1.425 Mg m⁻³ D_m = 1.411 Mg m⁻³ D_m measured by not measured
Hall symbol: -P 1	Melting point: 470(1) K
a = 8.8950 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.3510 (8) Å	Cell parameters from 3874 reflections
c = 10.5510 (9) Å	θ = 2.3–28.3°
α = 94.365 (1)°	µ = 0.22 mm⁻¹
β = 102.452 (1)°	T = 100 K
γ = 108.924 (1)°	Block, white
V = 800.44 (12) Å³	0.35 × 0.30 × 0.25 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3963 independent reflections
Radiation source: fine-focus sealed tube	3136 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
φ and ω scans	θ_max = 28.3°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.926, T_max = 0.946	k = −12→12
6943 measured reflections	l = −13→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0582P)² + 0.033P] where P = (F_o² + 2F_c²)/3
3625 reflections	(Δ/σ)_max < 0.001
220 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₇H₁₇N₃O₃S	γ = 108.924 (1)°
M_r = 343.40	V = 800.44 (12) Å³
Triclinic, P1	Z = 2
a = 8.8950 (8) Å	Mo Kα radiation
b = 9.3510 (8) Å	µ = 0.22 mm⁻¹
c = 10.5510 (9) Å	T = 100 K
α = 94.365 (1)°	0.35 × 0.30 × 0.25 mm
β = 102.452 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3963 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3136 reflections with I > 2σ(I)
T_min = 0.926, T_max = 0.946	R_int = 0.031
6943 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.09	Δρ_max = 0.38 e Å⁻³
3625 reflections	Δρ_min = −0.29 e Å⁻³
220 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.55056 (15)	0.34243 (15)	0.35976 (13)	0.0149 (3)
C2	0.65598 (15)	0.41748 (15)	0.19148 (13)	0.0147 (3)
C3	0.67625 (16)	0.17140 (15)	0.27023 (13)	0.0145 (3)
C4	0.84064 (16)	0.19625 (15)	0.33053 (13)	0.0159 (3)
C5	0.89278 (17)	0.07165 (16)	0.33995 (14)	0.0196 (3)
H5	1.0041	0.0864	0.3804	0.024*
C6	0.77988 (17)	−0.07507 (16)	0.28931 (14)	0.0213 (3)
H6	0.8153	−0.1604	0.2961	0.026*
C7	0.61750 (17)	−0.09936 (15)	0.22939 (14)	0.0202 (3)
H7	0.5424	−0.2001	0.1946	0.024*
C8	0.56524 (16)	0.02510 (15)	0.22058 (13)	0.0178 (3)
H8	0.4536	0.0098	0.1806	0.021*
C9	1.10474 (16)	0.37350 (17)	0.44617 (14)	0.0206 (3)
H9A	1.1060	0.3194	0.5222	0.031*
H9B	1.1614	0.4837	0.4763	0.031*
H9C	1.1608	0.3367	0.3876	0.031*
C10	0.72473 (15)	0.42325 (15)	0.07657 (13)	0.0154 (3)
C11	0.75431 (16)	0.30133 (15)	0.01694 (13)	0.0161 (3)
H11	0.7375	0.2092	0.0533	0.019*
C12	0.80932 (16)	0.31619 (15)	−0.09758 (13)	0.0161 (3)
C13	0.83678 (16)	0.45016 (15)	−0.15064 (13)	0.0175 (3)
H13	0.8743	0.4590	−0.2284	0.021*
C14	0.80850 (16)	0.57224 (15)	−0.08796 (13)	0.0175 (3)
C15	0.75216 (16)	0.56080 (15)	0.02409 (13)	0.0167 (3)
H15	0.7322	0.6444	0.0653	0.020*
C16	0.85664 (19)	0.18902 (18)	−0.28188 (14)	0.0243 (3)
H16A	0.7674	0.2106	−0.3401	0.037*
H16B	0.8574	0.0885	−0.3149	0.037*
H16C	0.9620	0.2678	−0.2794	0.037*
C17	0.81545 (19)	0.82927 (16)	−0.08535 (15)	0.0247 (3)
H17A	0.7010	0.8006	−0.0800	0.037*
H17B	0.8398	0.9128	−0.1371	0.037*
H17C	0.8888	0.8630	0.0034	0.037*
N1	0.62267 (13)	0.30080 (12)	0.26679 (10)	0.0138 (2)
N2	0.54324 (13)	0.47840 (13)	0.33425 (11)	0.0164 (2)
H2	0.5009	0.5316	0.3790	0.020*
N3	0.60780 (14)	0.52693 (13)	0.23210 (11)	0.0168 (2)
O1	0.93818 (11)	0.34536 (11)	0.37661 (10)	0.0195 (2)
O2	0.83196 (12)	0.18925 (11)	−0.15200 (9)	0.0186 (2)
O3	0.83978 (13)	0.70006 (11)	−0.14709 (10)	0.0231 (2)
S1	0.48847 (4)	0.24514 (4)	0.47744 (3)	0.01896 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0121 (6)	0.0142 (6)	0.0167 (6)	0.0049 (5)	0.0009 (5)	−0.0004 (5)
C2	0.0132 (6)	0.0118 (6)	0.0171 (6)	0.0037 (5)	0.0011 (5)	0.0025 (5)
C3	0.0165 (6)	0.0135 (6)	0.0159 (6)	0.0076 (5)	0.0046 (5)	0.0037 (5)
C4	0.0164 (6)	0.0144 (6)	0.0158 (6)	0.0044 (5)	0.0036 (5)	0.0015 (5)
C5	0.0175 (6)	0.0193 (7)	0.0222 (7)	0.0085 (5)	0.0020 (5)	0.0031 (6)
C6	0.0245 (7)	0.0163 (7)	0.0265 (7)	0.0112 (6)	0.0061 (6)	0.0054 (6)
C7	0.0211 (7)	0.0117 (6)	0.0261 (7)	0.0040 (5)	0.0054 (6)	0.0029 (5)
C8	0.0158 (6)	0.0157 (7)	0.0213 (7)	0.0049 (5)	0.0044 (5)	0.0031 (5)
C9	0.0154 (6)	0.0217 (7)	0.0209 (7)	0.0053 (5)	−0.0005 (5)	0.0000 (6)
C10	0.0119 (6)	0.0153 (6)	0.0166 (6)	0.0031 (5)	0.0018 (5)	0.0020 (5)
C11	0.0145 (6)	0.0135 (6)	0.0187 (7)	0.0036 (5)	0.0030 (5)	0.0040 (5)
C12	0.0129 (6)	0.0153 (6)	0.0188 (7)	0.0049 (5)	0.0016 (5)	0.0011 (5)
C13	0.0164 (6)	0.0186 (7)	0.0164 (6)	0.0046 (5)	0.0040 (5)	0.0047 (5)
C14	0.0162 (6)	0.0147 (6)	0.0198 (7)	0.0044 (5)	0.0013 (5)	0.0058 (5)
C15	0.0165 (6)	0.0127 (6)	0.0200 (7)	0.0056 (5)	0.0023 (5)	0.0017 (5)
C16	0.0311 (8)	0.0261 (8)	0.0211 (7)	0.0145 (6)	0.0104 (6)	0.0043 (6)
C17	0.0302 (8)	0.0138 (7)	0.0296 (8)	0.0075 (6)	0.0056 (6)	0.0066 (6)
N1	0.0135 (5)	0.0118 (5)	0.0159 (5)	0.0046 (4)	0.0030 (4)	0.0024 (4)
N2	0.0185 (6)	0.0149 (5)	0.0184 (6)	0.0079 (4)	0.0069 (5)	0.0029 (4)
N3	0.0181 (6)	0.0149 (6)	0.0179 (6)	0.0059 (4)	0.0052 (5)	0.0034 (4)
O1	0.0142 (5)	0.0144 (5)	0.0253 (5)	0.0043 (4)	−0.0014 (4)	−0.0017 (4)
O2	0.0230 (5)	0.0164 (5)	0.0198 (5)	0.0089 (4)	0.0088 (4)	0.0038 (4)
O3	0.0321 (6)	0.0154 (5)	0.0249 (5)	0.0092 (4)	0.0101 (4)	0.0092 (4)
S1	0.0240 (2)	0.01631 (18)	0.02032 (19)	0.00884 (14)	0.00978 (14)	0.00527 (13)

Geometric parameters (Å, º) top

C1—N2	1.3385 (17)	C10—C11	1.3862 (19)
C1—N1	1.3785 (16)	C10—C15	1.4084 (18)
C1—S1	1.6782 (14)	C11—C12	1.3982 (19)
C2—N3	1.3083 (17)	C11—H11	0.9500
C2—N1	1.3905 (16)	C12—O2	1.3712 (16)
C2—C10	1.4680 (18)	C12—C13	1.3820 (19)
C3—C8	1.3830 (18)	C13—C14	1.3953 (19)
C3—C4	1.3974 (18)	C13—H13	0.9500
C3—N1	1.4374 (16)	C14—O3	1.3667 (16)
C4—O1	1.3651 (15)	C14—C15	1.3786 (19)
C4—C5	1.3896 (19)	C15—H15	0.9500
C5—C6	1.3928 (19)	C16—O2	1.4337 (16)
C5—H5	0.9500	C16—H16A	0.9800
C6—C7	1.3817 (19)	C16—H16B	0.9800
C6—H6	0.9500	C16—H16C	0.9800
C7—C8	1.3885 (18)	C17—O3	1.4289 (17)
C7—H7	0.9500	C17—H17A	0.9800
C8—H8	0.9500	C17—H17B	0.9800
C9—O1	1.4324 (15)	C17—H17C	0.9800
C9—H9A	0.9800	N2—N3	1.3674 (15)
C9—H9B	0.9800	N2—H2	0.8800
C9—H9C	0.9800

N2—C1—N1	103.64 (11)	C12—C11—H11	120.6
N2—C1—S1	128.55 (10)	O2—C12—C13	123.48 (12)
N1—C1—S1	127.81 (10)	O2—C12—C11	115.21 (12)
N3—C2—N1	110.19 (11)	C13—C12—C11	121.30 (13)
N3—C2—C10	121.30 (12)	C12—C13—C14	118.86 (13)
N1—C2—C10	128.40 (11)	C12—C13—H13	120.6
C8—C3—C4	121.02 (12)	C14—C13—H13	120.6
C8—C3—N1	120.42 (11)	O3—C14—C15	123.94 (12)
C4—C3—N1	118.48 (11)	O3—C14—C13	114.70 (12)
O1—C4—C5	125.09 (12)	C15—C14—C13	121.35 (12)
O1—C4—C3	115.70 (11)	C14—C15—C10	118.93 (12)
C5—C4—C3	119.22 (12)	C14—C15—H15	120.5
C4—C5—C6	119.21 (12)	C10—C15—H15	120.5
C4—C5—H5	120.4	O2—C16—H16A	109.5
C6—C5—H5	120.4	O2—C16—H16B	109.5
C7—C6—C5	121.47 (12)	H16A—C16—H16B	109.5
C7—C6—H6	119.3	O2—C16—H16C	109.5
C5—C6—H6	119.3	H16A—C16—H16C	109.5
C6—C7—C8	119.30 (13)	H16B—C16—H16C	109.5
C6—C7—H7	120.3	O3—C17—H17A	109.5
C8—C7—H7	120.3	O3—C17—H17B	109.5
C3—C8—C7	119.77 (12)	H17A—C17—H17B	109.5
C3—C8—H8	120.1	O3—C17—H17C	109.5
C7—C8—H8	120.1	H17A—C17—H17C	109.5
O1—C9—H9A	109.5	H17B—C17—H17C	109.5
O1—C9—H9B	109.5	C1—N1—C2	107.79 (11)
H9A—C9—H9B	109.5	C1—N1—C3	122.33 (11)
O1—C9—H9C	109.5	C2—N1—C3	128.97 (11)
H9A—C9—H9C	109.5	C1—N2—N3	113.65 (11)
H9B—C9—H9C	109.5	C1—N2—H2	123.2
C11—C10—C15	120.65 (13)	N3—N2—H2	123.2
C11—C10—C2	123.83 (12)	C2—N3—N2	104.73 (11)
C15—C10—C2	115.44 (12)	C4—O1—C9	116.91 (10)
C10—C11—C12	118.89 (12)	C12—O2—C16	116.63 (11)
C10—C11—H11	120.6	C14—O3—C17	116.86 (11)

C8—C3—C4—O1	−179.51 (12)	C11—C10—C15—C14	0.21 (19)
N1—C3—C4—O1	−2.65 (17)	C2—C10—C15—C14	−176.68 (11)
C8—C3—C4—C5	0.3 (2)	N2—C1—N1—C2	0.68 (13)
N1—C3—C4—C5	177.14 (12)	S1—C1—N1—C2	−178.90 (9)
O1—C4—C5—C6	179.63 (13)	N2—C1—N1—C3	170.67 (11)
C3—C4—C5—C6	−0.1 (2)	S1—C1—N1—C3	−8.90 (18)
C4—C5—C6—C7	0.3 (2)	N3—C2—N1—C1	−0.41 (14)
C5—C6—C7—C8	−0.6 (2)	C10—C2—N1—C1	−176.69 (12)
C4—C3—C8—C7	−0.6 (2)	N3—C2—N1—C3	−169.53 (12)
N1—C3—C8—C7	−177.40 (12)	C10—C2—N1—C3	14.2 (2)
C6—C7—C8—C3	0.8 (2)	C8—C3—N1—C1	81.84 (16)
N3—C2—C10—C11	−169.74 (12)	C4—C3—N1—C1	−95.05 (15)
N1—C2—C10—C11	6.2 (2)	C8—C3—N1—C2	−110.45 (15)
N3—C2—C10—C15	7.04 (18)	C4—C3—N1—C2	72.67 (17)
N1—C2—C10—C15	−177.05 (12)	N1—C1—N2—N3	−0.75 (14)
C15—C10—C11—C12	−1.05 (19)	S1—C1—N2—N3	178.82 (9)
C2—C10—C11—C12	175.56 (11)	N1—C2—N3—N2	−0.04 (14)
C10—C11—C12—O2	−178.55 (11)	C10—C2—N3—N2	176.55 (11)
C10—C11—C12—C13	0.99 (19)	C1—N2—N3—C2	0.51 (14)
O2—C12—C13—C14	179.44 (12)	C5—C4—O1—C9	−3.58 (19)
C11—C12—C13—C14	−0.07 (19)	C3—C4—O1—C9	176.19 (11)
C12—C13—C14—O3	179.68 (11)	C13—C12—O2—C16	−11.41 (18)
C12—C13—C14—C15	−0.8 (2)	C11—C12—O2—C16	168.12 (11)
O3—C14—C15—C10	−179.80 (12)	C15—C14—O3—C17	1.57 (19)
C13—C14—C15—C10	0.75 (19)	C13—C14—O3—C17	−178.94 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1ⁱ	0.88	2.45	3.2624 (12)	154

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₇N₃O₃S
M_r	343.40
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	8.8950 (8), 9.3510 (8), 10.5510 (9)
α, β, γ (°)	94.365 (1), 102.452 (1), 108.924 (1)
V (Å³)	800.44 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.35 × 0.30 × 0.25

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.926, 0.946
No. of measured, independent and observed [I > 2σ(I)] reflections	6943, 3963, 3136
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.099, 1.09
No. of reflections	3625
No. of parameters	220
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.29

Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1999), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1999), SHELXTL.