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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2483.
Published online 2008 November 29. doi:  10.1107/S1600536808039688
PMCID: PMC2960044

4-Amino-3-(4-hydroxy­phen­yl)-1H-1,2,4-triazol-5(4H)-one

Abstract

The mol­ecule of the title compound, C8H8N4O2, is nearly planar, with a dihedral angle between the rings of 1.1 (1)°. Adjacent mol­ecules are linked into a layered structure by hydr­oxy–oxo O—H(...)O and triazol­yl–hydr­oxy N—H(...)O hydrogen bonds. Only one of the H atoms of the pyramidal amino group is engaged in building up the infinite layer. The second H atom of the amino group also shows hydrogen-bonding inter­actions, linking adjacent layers into a three-dimensional network.

Related literature

For a synthesis of the title compound using CS2 as a reactant, see: Chande & Singh-Jathar (1998 [triangle]). This product was obtained unexpectedly in the present study.

An external file that holds a picture, illustration, etc.
Object name is e-64-o2483-scheme1.jpg

Experimental

Crystal data

  • C8H8N4O2
  • M r = 192.18
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2483-efi1.jpg
  • a = 6.534 (1) Å
  • b = 7.330 (1) Å
  • c = 9.804 (1) Å
  • α = 106.69 (1)°
  • β = 102.328 (9)°
  • γ = 106.712 (2)°
  • V = 407.7 (1) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.12 mm−1
  • T = 295 (2) K
  • 0.25 × 0.16 × 0.04 mm

Data collection

  • Bruker APEXII area-detector diffractometer
  • Absorption correction: none
  • 3032 measured reflections
  • 1434 independent reflections
  • 1115 reflections with I > 2σ(I)
  • R int = 0.017

Refinement

  • R[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.109
  • S = 1.03
  • 1434 reflections
  • 143 parameters
  • 4 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.14 e Å−3
  • Δρmin = −0.19 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808039688/im2089sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808039688/im2089Isup2.hkl

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

Acknowledgments

We thank the Education Department of Henan Province, Zhengzhou University and the University of Malaya for supporting this work.

supplementary crystallographic information

Comment

In connection with our work on metal triazolates, we are interested in synthesizing 4-amino-bis(4-hydroxyphenyl)-1,2,4-triazole. The synthesis of this triazole yielded the title compound as an unexpected product. A specific procedure for the synthesis of the title compound is reported in the literature to start from carbonyl sulfide and 4-hydroxybenzohydrazide in potassium hydroxide to give a precursor that was subsequently reacted with hydrazine (Chande & Singh-Jathar, 1998).

Experimental

4-Hydroxybenzoic acid (2.76 g, 0.02 mol) and 80% hydrazine hydrate (1.55 g, 0.02 mol) were heated in a sealed tube at 439 K for three days. After cooling to room temperature, the mixture was centrifuged. The resulting white solid was suspended in water, and 6M hydrochloric acid was added until the pH was 3. The white product was collected and recrystallized from a DMSO–water mixture(10:1) to afford colorless crystals in 3% yield. CH&N elemental analysis. C 49.58 (calc. 49.99), H 4.19 (found 4.20), N 29.25% (29.15%).

Refinement

Carbon-bound H atoms were generated geometrically (C–H 0.93 Å), and were included in the refinement in the riding model approximation, with U(H) set to 1.2Ueq(C). The amino and hydroxy H atoms were located in a difference Fourier map, and were refined with distance restraints of N–H = O–H = 0.85±0.01 Å; their temperature factors were freely refined.

Figures

Fig. 1.
Thermal ellipsoid (Barbour, 2001) plot of C18H8N4O2 at the 70% probability level.
Fig. 2.
Thermal ellipsoid (Barbour, 2001) plot of the layered structure arising from O–Hhydroxy and N–Htriazolyl hydrogen bonds.

Crystal data

C8H8N4O2Z = 2
Mr = 192.18F000 = 200
Triclinic, P1Dx = 1.565 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 6.534 (1) ÅCell parameters from 986 reflections
b = 7.330 (1) Åθ = 2.3–26.7º
c = 9.804 (1) ŵ = 0.12 mm1
α = 106.69 (1)ºT = 295 (2) K
β = 102.328 (9)ºBlock, colorless
γ = 106.712 (2)º0.25 × 0.16 × 0.04 mm
V = 407.7 (1) Å3

Data collection

Bruker APEXII area-detector diffractometer1115 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.017
Monochromator: graphiteθmax = 25.0º
T = 295(2) Kθmin = 2.3º
[var phi] and ω scansh = −7→7
Absorption correction: Nonek = −8→8
3032 measured reflectionsl = −11→11
1434 independent 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)] = 0.039H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.109  w = 1/[σ2(Fo2) + (0.0565P)2 + 0.1018P] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
1434 reflectionsΔρmax = 0.14 e Å3
143 parametersΔρmin = −0.19 e Å3
4 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
O10.3462 (2)0.3381 (2)0.06978 (15)0.0481 (4)
O20.6706 (2)1.2219 (2)1.00449 (15)0.0456 (4)
N10.8848 (3)1.0137 (3)0.72942 (18)0.0423 (5)
N20.9057 (3)1.1419 (3)0.87015 (19)0.0444 (5)
N30.5523 (2)0.9858 (2)0.75552 (16)0.0319 (4)
N40.3171 (3)0.9141 (3)0.7256 (2)0.0420 (5)
C10.7075 (3)1.1281 (3)0.8902 (2)0.0361 (5)
C20.6672 (3)0.9197 (3)0.6610 (2)0.0314 (4)
C30.5739 (3)0.7693 (3)0.5056 (2)0.0302 (4)
C40.3450 (3)0.6652 (3)0.4264 (2)0.0373 (5)
H4A0.23980.69100.47190.045*
C50.2715 (3)0.5241 (3)0.2810 (2)0.0402 (5)
H50.11770.45710.22890.048*
C60.4261 (3)0.4820 (3)0.2127 (2)0.0342 (5)
C70.6551 (3)0.5851 (3)0.2893 (2)0.0387 (5)
H70.75980.55930.24320.046*
C80.7269 (3)0.7262 (3)0.4342 (2)0.0386 (5)
H80.88080.79420.48540.046*
H10.450 (3)0.301 (4)0.043 (3)0.067 (8)*
H21.037 (2)1.204 (3)0.937 (2)0.054 (7)*
H40.294 (5)0.881 (4)0.801 (2)0.076 (9)*
H400.273 (4)1.013 (3)0.732 (3)0.078 (10)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0338 (8)0.0580 (10)0.0293 (8)0.0155 (7)0.0038 (6)−0.0101 (7)
O20.0431 (9)0.0556 (9)0.0288 (8)0.0213 (7)0.0126 (6)−0.0008 (7)
N10.0305 (9)0.0498 (10)0.0295 (9)0.0122 (8)0.0071 (7)−0.0045 (8)
N20.0288 (9)0.0540 (11)0.0268 (9)0.0114 (8)0.0029 (7)−0.0095 (8)
N30.0271 (8)0.0396 (9)0.0245 (8)0.0135 (7)0.0099 (6)0.0032 (7)
N40.0295 (9)0.0559 (12)0.0343 (10)0.0172 (9)0.0124 (8)0.0053 (9)
C10.0347 (11)0.0406 (11)0.0262 (10)0.0156 (9)0.0081 (8)0.0025 (9)
C20.0301 (10)0.0349 (10)0.0259 (10)0.0132 (8)0.0097 (8)0.0051 (8)
C30.0312 (10)0.0325 (10)0.0255 (10)0.0135 (8)0.0103 (8)0.0061 (8)
C40.0309 (10)0.0442 (12)0.0320 (11)0.0165 (9)0.0111 (8)0.0042 (9)
C50.0264 (10)0.0472 (12)0.0343 (11)0.0120 (9)0.0056 (8)0.0023 (9)
C60.0339 (11)0.0380 (11)0.0246 (10)0.0136 (9)0.0075 (8)0.0043 (8)
C70.0316 (11)0.0476 (12)0.0297 (11)0.0153 (9)0.0124 (8)0.0019 (9)
C80.0276 (10)0.0450 (12)0.0310 (11)0.0110 (9)0.0067 (8)0.0017 (9)

Geometric parameters (Å, °)

O1—C61.368 (2)C2—C31.470 (2)
O1—H10.861 (10)C3—C41.389 (3)
O2—C11.247 (2)C3—C81.394 (3)
N1—C21.308 (2)C4—C51.381 (3)
N1—N21.381 (2)C4—H4A0.9300
N2—C11.331 (3)C5—C61.383 (3)
N2—H20.860 (10)C5—H50.9300
N3—C11.374 (2)C6—C71.385 (3)
N3—C21.380 (2)C7—C81.379 (3)
N3—N41.407 (2)C7—H70.9300
N4—H40.868 (10)C8—H80.9300
N4—H400.846 (10)
C6—O1—H1112.3 (18)C4—C3—C2124.64 (17)
C2—N1—N2104.87 (15)C8—C3—C2117.37 (17)
C1—N2—N1112.93 (16)C5—C4—C3120.93 (18)
C1—N2—H2127.2 (16)C5—C4—H4A119.5
N1—N2—H2119.0 (16)C3—C4—H4A119.5
C1—N3—C2108.48 (15)C4—C5—C6120.17 (18)
C1—N3—N4124.53 (15)C4—C5—H5119.9
C2—N3—N4126.90 (16)C6—C5—H5119.9
N3—N4—H4105.8 (19)O1—C6—C5118.31 (17)
N3—N4—H40109.5 (19)O1—C6—C7121.86 (17)
H4—N4—H40104 (3)C5—C6—C7119.83 (17)
O2—C1—N2128.18 (18)C8—C7—C6119.58 (18)
O2—C1—N3127.92 (18)C8—C7—H7120.2
N2—C1—N3103.90 (16)C6—C7—H7120.2
N1—C2—N3109.81 (15)C7—C8—C3121.49 (18)
N1—C2—C3121.80 (16)C7—C8—H8119.3
N3—C2—C3128.39 (16)C3—C8—H8119.3
C4—C3—C8117.99 (17)
C2—N1—N2—C10.4 (2)N3—C2—C3—C4−0.2 (3)
N1—N2—C1—O2179.29 (19)N1—C2—C3—C81.5 (3)
N1—N2—C1—N3−0.6 (2)N3—C2—C3—C8−179.08 (18)
C2—N3—C1—O2−179.4 (2)C8—C3—C4—C5−0.3 (3)
N4—N3—C1—O2−2.7 (3)C2—C3—C4—C5−179.17 (18)
C2—N3—C1—N20.5 (2)C3—C4—C5—C60.9 (3)
N4—N3—C1—N2177.19 (19)C4—C5—C6—O1178.66 (18)
N2—N1—C2—N3−0.1 (2)C4—C5—C6—C7−1.4 (3)
N2—N1—C2—C3179.42 (17)O1—C6—C7—C8−178.87 (18)
C1—N3—C2—N1−0.2 (2)C5—C6—C7—C81.2 (3)
N4—N3—C2—N1−176.86 (19)C6—C7—C8—C3−0.5 (3)
C1—N3—C2—C3−179.71 (18)C4—C3—C8—C70.1 (3)
N4—N3—C2—C33.7 (3)C2—C3—C8—C7179.05 (18)
N1—C2—C3—C4−179.6 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.86 (1)1.78 (1)2.633 (2)175 (3)
N2—H2···O1ii0.86 (1)1.93 (1)2.789 (2)173 (2)
N4—H4···O2iii0.87 (1)2.24 (1)3.077 (3)163 (2)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IM2089).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Winconsin, USA.
  • Chande, M. S. & Singh-Jathar, K. (1998). Indian J. Chem. Sect. B, 37, 352–357.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2008). publCIF In preparation.

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