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Acta Crystallogr Sect E Struct Rep Online. 2009 September 1; 65(Pt 9): o2213.
Published online 2009 August 22. doi:  10.1107/S1600536809032607
PMCID: PMC2969966

4-Amino-3-[(4-methoxy­phen­yl)amino­meth­yl]-1H-1,2,4-triazole-5(4H)-thione

Abstract

The mol­ecule of the title compound, C10H13N5OS, is approximately planar, the dihedral angle between the triazole and benzene rings being 4.53 (10)°. The amino group adopts a pyramidal configuration. In the crystal structure, mol­ecules are linked into two-dimensional networks parallel to (001) by inter­molecular N—H(...)S and N—H(...)N hydrogen bonds. In addition, an S(...)S short contact of 3.3435 (7) Å is observed.

Related literature

For the pharmacological applications of 1,2,4-triazole derivatives, see: Amir et al. (2008 [triangle]); Isloor et al. (2009 [triangle]); Krzysztof et al. (2008 [triangle]); Kuş et al. (2008 [triangle]); Padmavathi et al. (2008 [triangle]). For the preparation, see: Holla & Udupa (1992 [triangle]). For related structures, see: Fun et al. (2009a [triangle],b [triangle]). For the stability of the temperature controller used for data collection, see: Cosier & Glazer (1986 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2213-scheme1.jpg

Experimental

Crystal data

  • C10H13N5OS
  • M r = 251.31
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2213-efi1.jpg
  • a = 11.5142 (2) Å
  • b = 5.8804 (1) Å
  • c = 16.6891 (3) Å
  • β = 95.292 (1)°
  • V = 1125.17 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.28 mm−1
  • T = 100 K
  • 0.33 × 0.18 × 0.02 mm

Data collection

  • Bruker SMART APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.913, T max = 0.994
  • 5827 measured reflections
  • 2365 independent reflections
  • 2126 reflections with I > 2σ(I)
  • R int = 0.024

Refinement

  • R[F 2 > 2σ(F 2)] = 0.031
  • wR(F 2) = 0.068
  • S = 1.04
  • 2365 reflections
  • 171 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.33 e Å−3
  • Δρmin = −0.26 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 588 Friedel pairs
  • Flack parameter: 0.03 (7)

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809032607/ci2889sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809032607/ci2889Isup2.hkl

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

Acknowledgments

HKF thanks Universiti Sains Malaysia (USM) for the Research University Golden Goose grant No. 1001/PFIZIK/811012. CSY thanks USM for the award of a USM fellowship. AMI is grateful to the Head of the Department of Chemistry and Director, NITK, Surathkal, India, for providing research facilities.

supplementary crystallographic information

Comment

1,2,4-triazole and its derivatives were reported to exhibit various pharmacological activities such as antimicrobial, analgesic, anti-inflammatory, anticancer and antioxidant properties (Amir et al., 2008; Krzysztof et al., 2008; Kuş et al., 2008; Padmavathi et al., 2008). A few derivatives of triazoles have exhibited antimicrobial activity (Isloor et al., 2009). Some of the present day drugs such as ribavirin (antiviral agent), rizatriptan (antimigraine agent), alprazolam (anxiolytic agent), fluconazole and itraconazole (antifungal agents) are the best examples for potent molecules possessing the triazole nucleus. The amino and mercapto groups of 1,2,4-triazoles serve as readily accessible nucleophilic centers for the preparation of N-bridged heterocycles. Keeping in view of the biological importance, we have synthesized the title compound and its crystal structure is reported here.

Bond lengths and angles in the title compound (Fig. 1) are comparable to those observed in related structures (Fun et al., 2009a,b). The molecule is approximately planar, with the dihedral angle between the triazole (N1/N2/C1/N3/C2) and benzene rings (C4-C9) being 4.53 (10)°.

In the crystal structure, the molecules are linked by intermolecular N2—H1N2···S1, N4—H1N4···N5 and N5—H1N5···N1 hydrogen bonds into a two-dimensional network parallel to ab plane (Fig. 2 and Table 1). In addition, a S···S(1-x, y, -z) short contact of 3.3435 (7) Å is observed.

Experimental

2-[(4-Methoxyphenyl)amino]acetohydrazide (19.5 g, 0.1 mol) was added slowly to a solution of potassium hydroxide (8.4 g, 0.15 mol) in ethanol (150 ml). The resulting mixture was stirred well till a clear solution was obtained. Carbon disulfide (11.4 g, 0.15 mol) was added dropwise and the contents were stirred vigorously. Further stirring was continued for 24 h. The resulting mixture (Holla & Udupa, 1992) was diluted with 100 ml of ether and the precipitate formed was collected by filtration, washed with dry ether and dried at 338 K under vacuum. It was used for the next step without any purification.

A mixture of above synthesized potassium dithiocarbazinate (30.9 g, 0.1 mol), hydrazine hydrate (99%, 0.2 mol) and water (2 ml) was gently heated to boil for 30 min. Heating was continued until the evaluation of hydrogen sulfide ceases. The reaction mixture was cooled to room temperature, diluted with water (100 ml) and acidified with 2 N HCl. The solid mass that separated was collected by filtration, washed with water and dried. Recrystallization was done from ethanol (yield: 15.1 g, 67.7%; m.p. 484–486 K).

Refinement

N-bound H atoms were located in a difference Fourier map and refined freely. The remaining H atoms were positioned geometrically [C-H = 0.93–0.97 Å] and refined using a riding model, with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(methyl C). A rotating group model was used for the methyl groups.

Figures

Fig. 1.
The molecular structure of the title compound, with atom labels and 50% probability ellipsoids for non-H atoms.
Fig. 2.
The crystal structure of the title compound, viewed down the b axis, showing two-dimensional networks parallel to ab plane. Intermolecular hydrogen bonds are shown as dashed lines.

Crystal data

C10H13N5OSF(000) = 528
Mr = 251.31Dx = 1.484 Mg m3
Monoclinic, C2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2yCell parameters from 2961 reflections
a = 11.5142 (2) Åθ = 3.6–32.2°
b = 5.8804 (1) ŵ = 0.28 mm1
c = 16.6891 (3) ÅT = 100 K
β = 95.292 (1)°Plate, colourless
V = 1125.17 (3) Å30.33 × 0.18 × 0.02 mm
Z = 4

Data collection

Bruker SMART APEXII CCD area-detector diffractometer2365 independent reflections
Radiation source: fine-focus sealed tube2126 reflections with I > 2σ(I)
graphiteRint = 0.024
[var phi] and ω scansθmax = 30.0°, θmin = 3.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −15→16
Tmin = 0.913, Tmax = 0.994k = −8→5
5827 measured reflectionsl = −23→23

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.068w = 1/[σ2(Fo2) + (0.0277P)2 + 0.6764P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
2365 reflectionsΔρmax = 0.33 e Å3
171 parametersΔρmin = −0.25 e Å3
1 restraintAbsolute structure: Flack (1983), 588 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.03 (7)

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.
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
S10.37035 (4)0.34412 (9)0.03759 (3)0.01571 (11)
O1−0.26796 (11)1.2919 (3)0.42305 (8)0.0248 (4)
N10.07536 (13)0.3929 (3)0.13658 (9)0.0171 (4)
N20.15394 (14)0.2872 (3)0.09067 (10)0.0164 (4)
N30.23563 (13)0.5947 (3)0.13167 (9)0.0136 (3)
N4−0.02128 (14)0.6826 (3)0.24608 (10)0.0167 (4)
N50.30984 (14)0.7845 (3)0.14247 (10)0.0171 (4)
C10.25184 (15)0.4074 (3)0.08580 (11)0.0144 (4)
C20.12844 (15)0.5803 (4)0.16083 (11)0.0138 (4)
C30.08129 (16)0.7617 (4)0.21027 (12)0.0158 (4)
H3A0.14040.80720.25240.019*
H3B0.06130.89330.17680.019*
C4−0.08548 (14)0.8413 (4)0.28707 (10)0.0146 (3)
C5−0.04122 (16)1.0556 (4)0.31036 (12)0.0174 (4)
H5A0.03071.10190.29500.021*
C6−0.10392 (16)1.1985 (4)0.35610 (12)0.0187 (4)
H6A−0.07321.33980.37150.022*
C7−0.21184 (16)1.1350 (4)0.37941 (11)0.0168 (4)
C8−0.25711 (16)0.9225 (4)0.35578 (11)0.0174 (4)
H8A−0.32950.87760.37080.021*
C9−0.19487 (15)0.7792 (4)0.31039 (11)0.0163 (4)
H9A−0.22610.63840.29490.020*
C10−0.37125 (17)1.2205 (4)0.45705 (12)0.0219 (5)
H10A−0.39821.34060.48960.033*
H10B−0.35451.08810.48970.033*
H10C−0.43051.18480.41470.033*
H1N20.1335 (18)0.175 (4)0.0617 (13)0.016 (6)*
H1N4−0.063 (2)0.601 (5)0.2156 (15)0.032 (7)*
H1N50.381 (2)0.728 (5)0.1550 (16)0.047 (8)*
H2N50.3141 (19)0.845 (6)0.0921 (15)0.042 (7)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.01344 (18)0.0157 (2)0.0184 (2)0.0019 (2)0.00344 (15)−0.0002 (2)
O10.0220 (7)0.0201 (9)0.0342 (8)−0.0015 (6)0.0123 (6)−0.0096 (7)
N10.0157 (7)0.0161 (10)0.0201 (8)−0.0007 (7)0.0052 (6)0.0000 (7)
N20.0186 (7)0.0117 (9)0.0197 (8)−0.0021 (6)0.0050 (6)−0.0030 (7)
N30.0126 (7)0.0149 (9)0.0135 (7)−0.0008 (6)0.0015 (6)−0.0003 (7)
N40.0150 (8)0.0149 (9)0.0208 (9)−0.0039 (7)0.0051 (7)−0.0033 (7)
N50.0142 (7)0.0148 (9)0.0220 (9)−0.0050 (6)0.0006 (6)−0.0019 (7)
C10.0143 (8)0.0155 (10)0.0135 (8)0.0025 (7)0.0011 (7)0.0001 (7)
C20.0132 (8)0.0156 (10)0.0126 (9)0.0022 (7)0.0015 (7)0.0029 (8)
C30.0151 (8)0.0140 (10)0.0183 (9)−0.0012 (7)0.0020 (7)0.0006 (8)
C40.0153 (7)0.0154 (9)0.0132 (7)0.0032 (9)0.0012 (6)0.0006 (10)
C50.0139 (9)0.0176 (11)0.0211 (10)−0.0015 (8)0.0043 (7)0.0005 (8)
C60.0188 (9)0.0146 (10)0.0228 (10)−0.0027 (8)0.0020 (8)−0.0037 (8)
C70.0174 (9)0.0165 (10)0.0167 (9)0.0015 (8)0.0030 (7)−0.0005 (8)
C80.0157 (9)0.0184 (10)0.0187 (9)−0.0014 (8)0.0044 (7)0.0013 (8)
C90.0163 (8)0.0121 (10)0.0203 (9)−0.0024 (7)0.0002 (7)−0.0006 (8)
C100.0177 (9)0.0258 (13)0.0228 (10)0.0016 (9)0.0057 (8)−0.0032 (9)

Geometric parameters (Å, °)

S1—C11.6883 (18)C3—H3A0.97
O1—C71.373 (2)C3—H3B0.97
O1—C101.427 (2)C4—C51.401 (3)
N1—C21.306 (3)C4—C91.401 (2)
N1—N21.386 (2)C5—C61.383 (3)
N2—C11.339 (2)C5—H5A0.93
N2—H1N20.84 (2)C6—C71.387 (3)
N3—C11.364 (3)C6—H6A0.93
N3—C21.370 (2)C7—C81.397 (3)
N3—N51.407 (2)C8—C91.377 (3)
N4—C41.407 (3)C8—H8A0.93
N4—C31.448 (2)C9—H9A0.93
N4—H1N40.82 (3)C10—H10A0.96
N5—H1N50.89 (3)C10—H10B0.96
N5—H2N50.92 (3)C10—H10C0.96
C2—C31.482 (3)
C7—O1—C10117.60 (17)H3A—C3—H3B108.1
C2—N1—N2103.83 (15)C5—C4—C9118.09 (18)
C1—N2—N1113.14 (16)C5—C4—N4122.53 (16)
C1—N2—H1N2125.0 (14)C9—C4—N4119.3 (2)
N1—N2—H1N2120.6 (14)C6—C5—C4120.33 (17)
C1—N3—C2108.88 (16)C6—C5—H5A119.8
C1—N3—N5126.84 (15)C4—C5—H5A119.8
C2—N3—N5124.04 (17)C5—C6—C7121.20 (19)
C4—N4—C3118.22 (18)C5—C6—H6A119.4
C4—N4—H1N4112.7 (18)C7—C6—H6A119.4
C3—N4—H1N4112.5 (17)O1—C7—C6116.46 (18)
N3—N5—H1N5105.8 (19)O1—C7—C8124.69 (17)
N3—N5—H2N5105.9 (18)C6—C7—C8118.83 (18)
H1N5—N5—H2N5103 (2)C9—C8—C7120.19 (17)
N2—C1—N3103.45 (15)C9—C8—H8A119.9
N2—C1—S1129.38 (15)C7—C8—H8A119.9
N3—C1—S1127.15 (15)C8—C9—C4121.4 (2)
N1—C2—N3110.68 (18)C8—C9—H9A119.3
N1—C2—C3126.50 (17)C4—C9—H9A119.3
N3—C2—C3122.78 (18)O1—C10—H10A109.5
N4—C3—C2110.69 (17)O1—C10—H10B109.5
N4—C3—H3A109.5H10A—C10—H10B109.5
C2—C3—H3A109.5O1—C10—H10C109.5
N4—C3—H3B109.5H10A—C10—H10C109.5
C2—C3—H3B109.5H10B—C10—H10C109.5
C2—N1—N2—C1−0.9 (2)N3—C2—C3—N4−168.35 (17)
N1—N2—C1—N31.1 (2)C3—N4—C4—C5−14.9 (3)
N1—N2—C1—S1179.40 (14)C3—N4—C4—C9169.36 (17)
C2—N3—C1—N2−0.9 (2)C9—C4—C5—C61.0 (3)
N5—N3—C1—N2−175.43 (17)N4—C4—C5—C6−174.84 (19)
C2—N3—C1—S1−179.25 (15)C4—C5—C6—C7−0.5 (3)
N5—N3—C1—S16.3 (3)C10—O1—C7—C6−171.73 (18)
N2—N1—C2—N30.2 (2)C10—O1—C7—C810.0 (3)
N2—N1—C2—C3177.94 (18)C5—C6—C7—O1−178.46 (18)
C1—N3—C2—N10.4 (2)C5—C6—C7—C8−0.1 (3)
N5—N3—C2—N1175.13 (17)O1—C7—C8—C9178.47 (18)
C1—N3—C2—C3−177.35 (17)C6—C7—C8—C90.2 (3)
N5—N3—C2—C3−2.7 (3)C7—C8—C9—C40.2 (3)
C4—N4—C3—C2−172.48 (15)C5—C4—C9—C8−0.8 (3)
N1—C2—C3—N414.2 (3)N4—C4—C9—C8175.13 (18)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H1N2···S1i0.84 (2)2.55 (2)3.3672 (18)164 (2)
N4—H1N4···N5ii0.82 (3)2.60 (3)3.410 (2)169 (3)
N5—H1N5···N1iii0.89 (2)2.48 (2)3.133 (2)130 (2)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2889).

References

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