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

Shi, K.-G.; Yang, G.; Ng, S.W.

doi:10.1107/S1600536808039688

organic compounds

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Volume 64| Part 12| December 2008| Page o2483

doi:10.1107/S1600536808039688

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

Kai-Ge Shi,^a Guang Yang ^a and Seik Weng Ng ^b ^*

^aDepartment of Chemistry, Zhengzhou University, Zhengzhou 450052, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 11 November 2008; accepted 25 November 2008; online 29 November 2008)

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 ). This product was obtained unexpectedly in the present study.

Experimental

Crystal data

C₈H₈N₄O₂
M_r = 192.18
Triclinic, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.039
wR(F²) = 0.109
S = 1.03
1434 reflections
143 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.86 (1)	1.78 (1)	2.633 (2)	175 (3)
N2—H2⋯O1ⁱⁱ	0.86 (1)	1.93 (1)	2.789 (2)	173 (2)
N4—H4⋯O2ⁱⁱⁱ	0.87 (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.

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

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

For the synthesis with carbonyl sulfide as reactant, see: Chande & Singh-Jathar (1998). This product was unexpectedly obtained in the present study.

Experimental top

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%).

Computing details top

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

Figures top

	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–H_hydroxy and N–H_triazolyl hydrogen bonds.

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

Crystal data top

C₈H₈N₄O₂	Z = 2
M_r = 192.18	F(000) = 200
Triclinic, P1	D_x = 1.565 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.534 (1) Å	Cell parameters from 986 reflections
b = 7.330 (1) Å	θ = 2.3–26.7°
c = 9.804 (1) Å	µ = 0.12 mm⁻¹
α = 106.69 (1)°	T = 295 K
β = 102.328 (9)°	Block, colorless
γ = 106.712 (2)°	0.25 × 0.16 × 0.04 mm
V = 407.7 (1) Å³

Data collection top

Bruker APEXII area-detector diffractometer	1115 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.017
Graphite monochromator	θ_max = 25.0°, θ_min = 2.3°
ϕ and ω scans	h = −7→7
3032 measured reflections	k = −8→8
1434 independent reflections	l = −11→11

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0565P)² + 0.1018P] where P = (F_o² + 2F_c²)/3
1434 reflections	(Δ/σ)_max = 0.001
143 parameters	Δρ_max = 0.14 e Å⁻³
4 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₈H₈N₄O₂	γ = 106.712 (2)°
M_r = 192.18	V = 407.7 (1) Å³
Triclinic, P1	Z = 2
a = 6.534 (1) Å	Mo Kα radiation
b = 7.330 (1) Å	µ = 0.12 mm⁻¹
c = 9.804 (1) Å	T = 295 K
α = 106.69 (1)°	0.25 × 0.16 × 0.04 mm
β = 102.328 (9)°

Data collection top

Bruker APEXII area-detector diffractometer	1115 reflections with I > 2σ(I)
3032 measured reflections	R_int = 0.017
1434 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	4 restraints
wR(F²) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.14 e Å⁻³
1434 reflections	Δρ_min = −0.19 e Å⁻³
143 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.3462 (2)	0.3381 (2)	0.06978 (15)	0.0481 (4)
O2	0.6706 (2)	1.2219 (2)	1.00449 (15)	0.0456 (4)
N1	0.8848 (3)	1.0137 (3)	0.72942 (18)	0.0423 (5)
N2	0.9057 (3)	1.1419 (3)	0.87015 (19)	0.0444 (5)
N3	0.5523 (2)	0.9858 (2)	0.75552 (16)	0.0319 (4)
N4	0.3171 (3)	0.9141 (3)	0.7256 (2)	0.0420 (5)
C1	0.7075 (3)	1.1281 (3)	0.8902 (2)	0.0361 (5)
C2	0.6672 (3)	0.9197 (3)	0.6610 (2)	0.0314 (4)
C3	0.5739 (3)	0.7693 (3)	0.5056 (2)	0.0302 (4)
C4	0.3450 (3)	0.6652 (3)	0.4264 (2)	0.0373 (5)
H4A	0.2398	0.6910	0.4719	0.045*
C5	0.2715 (3)	0.5241 (3)	0.2810 (2)	0.0402 (5)
H5	0.1177	0.4571	0.2289	0.048*
C6	0.4261 (3)	0.4820 (3)	0.2127 (2)	0.0342 (5)
C7	0.6551 (3)	0.5851 (3)	0.2893 (2)	0.0387 (5)
H7	0.7598	0.5593	0.2432	0.046*
C8	0.7269 (3)	0.7262 (3)	0.4342 (2)	0.0386 (5)
H8	0.8808	0.7942	0.4854	0.046*
H1	0.450 (3)	0.301 (4)	0.043 (3)	0.067 (8)*
H2	1.037 (2)	1.204 (3)	0.937 (2)	0.054 (7)*
H4	0.294 (5)	0.881 (4)	0.801 (2)	0.076 (9)*
H40	0.273 (4)	1.013 (3)	0.732 (3)	0.078 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0338 (8)	0.0580 (10)	0.0293 (8)	0.0155 (7)	0.0038 (6)	−0.0101 (7)
O2	0.0431 (9)	0.0556 (9)	0.0288 (8)	0.0213 (7)	0.0126 (6)	−0.0008 (7)
N1	0.0305 (9)	0.0498 (10)	0.0295 (9)	0.0122 (8)	0.0071 (7)	−0.0045 (8)
N2	0.0288 (9)	0.0540 (11)	0.0268 (9)	0.0114 (8)	0.0029 (7)	−0.0095 (8)
N3	0.0271 (8)	0.0396 (9)	0.0245 (8)	0.0135 (7)	0.0099 (6)	0.0032 (7)
N4	0.0295 (9)	0.0559 (12)	0.0343 (10)	0.0172 (9)	0.0124 (8)	0.0053 (9)
C1	0.0347 (11)	0.0406 (11)	0.0262 (10)	0.0156 (9)	0.0081 (8)	0.0025 (9)
C2	0.0301 (10)	0.0349 (10)	0.0259 (10)	0.0132 (8)	0.0097 (8)	0.0051 (8)
C3	0.0312 (10)	0.0325 (10)	0.0255 (10)	0.0135 (8)	0.0103 (8)	0.0061 (8)
C4	0.0309 (10)	0.0442 (12)	0.0320 (11)	0.0165 (9)	0.0111 (8)	0.0042 (9)
C5	0.0264 (10)	0.0472 (12)	0.0343 (11)	0.0120 (9)	0.0056 (8)	0.0023 (9)
C6	0.0339 (11)	0.0380 (11)	0.0246 (10)	0.0136 (9)	0.0075 (8)	0.0043 (8)
C7	0.0316 (11)	0.0476 (12)	0.0297 (11)	0.0153 (9)	0.0124 (8)	0.0019 (9)
C8	0.0276 (10)	0.0450 (12)	0.0310 (11)	0.0110 (9)	0.0067 (8)	0.0017 (9)

Geometric parameters (Å, º) top

O1—C6	1.368 (2)	C2—C3	1.470 (2)
O1—H1	0.861 (10)	C3—C4	1.389 (3)
O2—C1	1.247 (2)	C3—C8	1.394 (3)
N1—C2	1.308 (2)	C4—C5	1.381 (3)
N1—N2	1.381 (2)	C4—H4A	0.9300
N2—C1	1.331 (3)	C5—C6	1.383 (3)
N2—H2	0.860 (10)	C5—H5	0.9300
N3—C1	1.374 (2)	C6—C7	1.385 (3)
N3—C2	1.380 (2)	C7—C8	1.379 (3)
N3—N4	1.407 (2)	C7—H7	0.9300
N4—H4	0.868 (10)	C8—H8	0.9300
N4—H40	0.846 (10)

C6—O1—H1	112.3 (18)	C4—C3—C2	124.64 (17)
C2—N1—N2	104.87 (15)	C8—C3—C2	117.37 (17)
C1—N2—N1	112.93 (16)	C5—C4—C3	120.93 (18)
C1—N2—H2	127.2 (16)	C5—C4—H4A	119.5
N1—N2—H2	119.0 (16)	C3—C4—H4A	119.5
C1—N3—C2	108.48 (15)	C4—C5—C6	120.17 (18)
C1—N3—N4	124.53 (15)	C4—C5—H5	119.9
C2—N3—N4	126.90 (16)	C6—C5—H5	119.9
N3—N4—H4	105.8 (19)	O1—C6—C5	118.31 (17)
N3—N4—H40	109.5 (19)	O1—C6—C7	121.86 (17)
H4—N4—H40	104 (3)	C5—C6—C7	119.83 (17)
O2—C1—N2	128.18 (18)	C8—C7—C6	119.58 (18)
O2—C1—N3	127.92 (18)	C8—C7—H7	120.2
N2—C1—N3	103.90 (16)	C6—C7—H7	120.2
N1—C2—N3	109.81 (15)	C7—C8—C3	121.49 (18)
N1—C2—C3	121.80 (16)	C7—C8—H8	119.3
N3—C2—C3	128.39 (16)	C3—C8—H8	119.3
C4—C3—C8	117.99 (17)

C2—N1—N2—C1	0.4 (2)	N3—C2—C3—C4	−0.2 (3)
N1—N2—C1—O2	179.29 (19)	N1—C2—C3—C8	1.5 (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—N2	0.5 (2)	C3—C4—C5—C6	0.9 (3)
N4—N3—C1—N2	177.19 (19)	C4—C5—C6—O1	178.66 (18)
N2—N1—C2—N3	−0.1 (2)	C4—C5—C6—C7	−1.4 (3)
N2—N1—C2—C3	179.42 (17)	O1—C6—C7—C8	−178.87 (18)
C1—N3—C2—N1	−0.2 (2)	C5—C6—C7—C8	1.2 (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—C7	0.1 (3)
N4—N3—C2—C3	3.7 (3)	C2—C3—C8—C7	179.05 (18)
N1—C2—C3—C4	−179.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.86 (1)	1.78 (1)	2.633 (2)	175 (3)
N2—H2···O1ⁱⁱ	0.86 (1)	1.93 (1)	2.789 (2)	173 (2)
N4—H4···O2ⁱⁱⁱ	0.87 (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.

Experimental details

Crystal data
Chemical formula	C₈H₈N₄O₂
M_r	192.18
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	6.534 (1), 7.330 (1), 9.804 (1)
α, β, γ (°)	106.69 (1), 102.328 (9), 106.712 (2)
V (Å³)	407.7 (1)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.25 × 0.16 × 0.04

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3032, 1434, 1115
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.109, 1.03
No. of reflections	1434
No. of parameters	143
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.19

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.86 (1)	1.78 (1)	2.633 (2)	175 (3)
N2—H2···O1ⁱⁱ	0.86 (1)	1.93 (1)	2.789 (2)	173 (2)
N4—H4···O2ⁱⁱⁱ	0.87 (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.

Acknowledgements

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

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
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