organic compounds
4-Amino-3-(4-hydroxyphenyl)-1H-1,2,4-triazol-5(4H)-one
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
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
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Data collection
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Refinement
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Data collection: APEX2 (Bruker, 2007); cell 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
10.1107/S1600536808039688/im2089sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808039688/im2089Isup2.hkl
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%).
Carbon-bound H atoms were generated geometrically (C–H 0.93 Å), and were included in the
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.Data collection: APEX2 (Bruker, 2007); cell
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).C8H8N4O2 | Z = 2 |
Mr = 192.18 | F(000) = 200 |
Triclinic, P1 | Dx = 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 |
Bruker APEXII area-detector diffractometer | 1115 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.017 |
Graphite monochromator | θmax = 25.0°, θmin = 2.3° |
ϕ and ω scans | h = −7→7 |
3032 measured reflections | k = −8→8 |
1434 independent reflections | l = −11→11 |
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(Fo2) + (0.0565P)2 + 0.1018P] where P = (Fo2 + 2Fc2)/3 |
1434 reflections | (Δ/σ)max = 0.001 |
143 parameters | Δρmax = 0.14 e Å−3 |
4 restraints | Δρmin = −0.19 e Å−3 |
C8H8N4O2 | γ = 106.712 (2)° |
Mr = 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)° |
Bruker APEXII area-detector diffractometer | 1115 reflections with I > 2σ(I) |
3032 measured reflections | Rint = 0.017 |
1434 independent reflections |
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 | Δρmax = 0.14 e Å−3 |
1434 reflections | Δρmin = −0.19 e Å−3 |
143 parameters |
x | y | z | Uiso*/Ueq | ||
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)* |
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) |
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) |
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 |
Mr | 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 |
Rint | 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 |
Δρmax, Δρmin (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).
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
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Winconsin, USA. Google Scholar
Chande, M. S. & Singh-Jathar, K. (1998). Indian J. Chem. Sect. B, 37, 352–357. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2008). publCIF. In preparation. Google Scholar
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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).