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Acta Crystallogr Sect E Struct Rep Online. 2010 February 1; 66(Pt 2): o330.
Published online 2010 January 9. doi:  10.1107/S1600536809055536
PMCID: PMC2979808

2,2′-(4-Amino-4H-1,2,4-triazole-3,5-di­yl)diphenol

Abstract

The structure of the title compound, C14H12N4O2, was determined as part of a project on the coordination chemistry of 1,2,4-triazole derivatives. In the crystal structure, one of the two benzene rings is almost coplanar with the five-membered triazole ring (mean deviation = 0.019 Å), whereas the second benzene ring is rotated by 51.973 (2)°. The two N—C—N—N torsion angles [170.365 (2) and −170.942 (3)°] indicate that the amido group is slightly twisted away from the triazole plane. An intra­molecular O—H(...)N hydrogen bond occurs. In the crystal structure, inter­molecular N—H(...)O and O—H(...)N hydrogen bonding is found.

Related literature

For background information on tthe coordination chemistry of 1,2,4-triazole derivatives, see: Lavrenova et al. (1995 [triangle]).

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Object name is e-66-0o330-scheme1.jpg

Experimental

Crystal data

  • C14H12N4O2
  • M r = 268.28
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o330-efi1.jpg
  • a = 8.262 (2) Å
  • b = 9.384 (3) Å
  • c = 15.919 (4) Å
  • V = 1234.2 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 296 K
  • 0.10 × 0.10 × 0.08 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.980, T max = 0.992
  • 6343 measured reflections
  • 1276 independent reflections
  • 1143 reflections with I > 2σ(I)
  • R int = 0.043

Refinement

  • R[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.112
  • S = 1.10
  • 1276 reflections
  • 192 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.18 e Å−3
  • Δρmin = −0.17 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1997 [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: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809055536/nc2167sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809055536/nc2167Isup2.hkl

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

Acknowledgments

The authors thank the National Natural Science Foundation of China (grant No. 20573079) for financial support.

supplementary crystallographic information

Experimental

2-hydroxy-N-(2-hydroxybenzoyl)benzohydrazide and hydrazine monohydrate were purchased from Acros and used without further purification. 2-hydroxy-N-(2-hydroxybenzoyl)benzohydrazide (4.08 g, 0.15 mmol) and hydrazine monohydrate(7.27 ml, 0.15 mol) were transfered into a 50 ml round-bottom flask. The mixture was stirred and refluxed for 3 h. After cooling, the solution was poured into ice water and the resulting light pink precipitate was collected by filtration, and recrystallized from ethanol. colorless crystal, 1.812 g (46.6 %), 1H NMR (DMSO, 400 MHz, p.p.m.): 11.27 (s, 2H), 8.0 (q, 2H), 7.4 (m, 2H), 7.0 (q, 4H), 6.14 (s, 2H). m.p = 532.3–533.2 K. Anal. Calcd for C14H12O2N4: C, 62.69; H, 4.48; N, 20.90%, Found: C, 62.58; H, 4.42; N, 20.83 %. GC—MS(m/z): 268 (M+), 249, 221, 207, 117, 91, 77, 51, 32.

Refinement

All C-H H atoms were placed in geometrically idealized positions (methyl H atoms allowed to rotate but not to tip) and constrained to ride on their parent atoms with C—H distances in the range of 0.93–0.98 Å, and with Uiso(H) = 1.2 U eq for aryl H atoms and 1.5 Ueq for the methyl H atoms. The O-H and N-H H atoms were located in difference map and were refined isotropic with varying coordinates. Because no strong anomalous scaterring atoms are present the absolute structure cannot be determined, Therefore, Friedel-opposites were merged in the refinement and the absolute structure was selected arbitrarily.

Figures

Fig. 1.
Crystal structure of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

Crystal data

C14H12N4O2F(000) = 560
Mr = 268.28Dx = 1.444 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 2036 reflections
a = 8.262 (2) Åθ = 2.4–24.6°
b = 9.384 (3) ŵ = 0.10 mm1
c = 15.919 (4) ÅT = 296 K
V = 1234.2 (6) Å3Block, colorless
Z = 40.10 × 0.10 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer1276 independent reflections
Radiation source: fine-focus sealed tube1143 reflections with I > 2σ(I)
graphiteRint = 0.043
phi and ω scansθmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −9→9
Tmin = 0.980, Tmax = 0.992k = −9→11
6343 measured reflectionsl = −18→16

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.112w = 1/[σ2(Fo2) + (0.0693P)2 + 0.078P] where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max = 0.005
1276 reflectionsΔρmax = 0.18 e Å3
192 parametersΔρmin = −0.17 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.011 (4)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C10.5404 (4)0.5286 (4)0.49447 (17)0.0385 (7)
C20.4539 (4)0.4330 (4)0.54359 (19)0.0449 (8)
H20.34160.43860.54500.054*
C30.5310 (4)0.3309 (4)0.5899 (2)0.0457 (8)
H30.47110.26710.62200.055*
C40.6981 (4)0.3225 (4)0.5890 (2)0.0479 (8)
H40.75090.25360.62080.057*
C50.7861 (4)0.4166 (3)0.5408 (2)0.0442 (8)
H50.89850.41030.54060.053*
C60.7108 (4)0.5211 (3)0.49212 (17)0.0339 (7)
C70.7987 (4)0.6149 (3)0.43411 (18)0.0339 (7)
C80.9790 (3)0.7037 (3)0.34798 (17)0.0333 (7)
C91.1311 (3)0.7234 (3)0.30083 (17)0.0345 (7)
C101.1826 (4)0.8612 (3)0.2823 (2)0.0422 (8)
H101.12860.93880.30550.051*
C111.3126 (4)0.8838 (4)0.2298 (2)0.0521 (9)
H111.34820.97590.21860.062*
C121.3895 (4)0.7686 (4)0.1941 (2)0.0586 (10)
H121.47440.78370.15680.070*
C131.3427 (4)0.6316 (4)0.2127 (2)0.0482 (9)
H131.39810.55500.18940.058*
C141.2130 (4)0.6075 (3)0.26611 (18)0.0371 (7)
N10.7263 (3)0.7099 (3)0.38646 (15)0.0388 (6)
N20.8404 (3)0.7657 (3)0.33109 (15)0.0395 (6)
N30.9594 (3)0.6108 (3)0.41328 (15)0.0335 (6)
N41.0844 (3)0.5384 (4)0.45696 (19)0.0427 (7)
O10.4530 (3)0.6247 (3)0.44960 (15)0.0554 (7)
H10.51430.67340.42100.083*
O21.1615 (3)0.4745 (2)0.28606 (13)0.0458 (6)
H2A1.17850.42060.24650.069*
H4A1.167 (7)0.605 (5)0.471 (3)0.097 (16)*
H4B1.131 (5)0.486 (4)0.419 (2)0.059 (12)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0354 (17)0.0409 (17)0.0393 (15)0.0028 (14)−0.0007 (13)−0.0023 (14)
C20.0329 (17)0.052 (2)0.0500 (17)−0.0040 (15)0.0028 (15)0.0022 (16)
C30.0440 (19)0.0430 (19)0.0500 (18)−0.0045 (16)0.0092 (16)0.0025 (15)
C40.0438 (18)0.047 (2)0.0531 (18)0.0030 (16)0.0074 (15)0.0123 (16)
C50.0367 (17)0.0430 (19)0.0529 (18)0.0052 (15)0.0008 (14)0.0087 (16)
C60.0321 (16)0.0312 (16)0.0385 (15)−0.0029 (13)0.0013 (12)−0.0051 (13)
C70.0317 (15)0.0291 (16)0.0408 (15)0.0000 (14)0.0011 (12)−0.0003 (13)
C80.0326 (15)0.0280 (15)0.0391 (14)−0.0011 (13)−0.0007 (12)−0.0023 (13)
C90.0310 (15)0.0344 (17)0.0382 (15)−0.0025 (13)−0.0014 (12)−0.0009 (13)
C100.0392 (17)0.0343 (17)0.0530 (18)−0.0042 (14)−0.0030 (15)0.0003 (15)
C110.0391 (17)0.046 (2)0.071 (2)−0.0101 (18)−0.0009 (17)0.0159 (18)
C120.0346 (18)0.074 (3)0.067 (2)−0.0013 (19)0.0118 (16)0.013 (2)
C130.0326 (16)0.057 (2)0.0552 (19)0.0087 (16)0.0062 (15)−0.0016 (18)
C140.0336 (15)0.0377 (17)0.0400 (15)0.0003 (14)−0.0047 (13)0.0016 (14)
N10.0342 (13)0.0348 (15)0.0474 (13)0.0007 (12)0.0030 (11)0.0056 (12)
N20.0368 (14)0.0341 (14)0.0477 (14)0.0021 (11)0.0044 (11)0.0045 (12)
N30.0263 (12)0.0335 (13)0.0409 (12)0.0003 (11)0.0003 (10)0.0009 (11)
N40.0313 (15)0.0460 (17)0.0507 (17)0.0061 (13)−0.0032 (12)0.0065 (15)
O10.0302 (12)0.0693 (18)0.0666 (15)0.0058 (12)0.0032 (11)0.0211 (14)
O20.0577 (15)0.0305 (12)0.0493 (12)−0.0016 (11)0.0076 (11)−0.0071 (10)

Geometric parameters (Å, °)

C1—O11.358 (4)C9—C101.393 (4)
C1—C21.388 (4)C9—C141.395 (4)
C1—C61.410 (5)C10—C111.377 (5)
C2—C31.366 (5)C10—H100.9300
C2—H20.9300C11—C121.376 (5)
C3—C41.383 (5)C11—H110.9300
C3—H30.9300C12—C131.375 (5)
C4—C51.377 (5)C12—H120.9300
C4—H40.9300C13—C141.386 (4)
C5—C61.396 (4)C13—H130.9300
C5—H50.9300C14—O21.356 (4)
C6—C71.468 (4)N1—N21.393 (3)
C7—N11.314 (4)N3—N41.419 (3)
C7—N31.368 (4)N4—H4A0.95 (5)
C8—N21.312 (4)N4—H4B0.87 (4)
C8—N31.366 (4)O1—H10.8200
C8—C91.475 (4)O2—H2A0.8200
O1—C1—C2116.8 (3)C14—C9—C8121.2 (3)
O1—C1—C6123.4 (3)C11—C10—C9120.6 (3)
C2—C1—C6119.8 (3)C11—C10—H10119.7
C3—C2—C1121.1 (3)C9—C10—H10119.7
C3—C2—H2119.4C12—C11—C10119.3 (3)
C1—C2—H2119.4C12—C11—H11120.3
C2—C3—C4120.0 (3)C10—C11—H11120.3
C2—C3—H3120.0C13—C12—C11121.0 (3)
C4—C3—H3120.0C13—C12—H12119.5
C5—C4—C3119.8 (3)C11—C12—H12119.5
C5—C4—H4120.1C12—C13—C14120.1 (3)
C3—C4—H4120.1C12—C13—H13119.9
C4—C5—C6121.6 (3)C14—C13—H13119.9
C4—C5—H5119.2O2—C14—C13122.4 (3)
C6—C5—H5119.2O2—C14—C9118.2 (3)
C5—C6—C1117.7 (3)C13—C14—C9119.4 (3)
C5—C6—C7123.3 (3)C7—N1—N2108.2 (2)
C1—C6—C7118.7 (3)C8—N2—N1107.1 (2)
N1—C7—N3108.7 (2)C8—N3—C7106.4 (2)
N1—C7—C6123.0 (3)C8—N3—N4126.3 (2)
N3—C7—C6128.0 (3)C7—N3—N4126.9 (2)
N2—C8—N3109.6 (3)N3—N4—H4A109 (3)
N2—C8—C9125.7 (3)N3—N4—H4B105 (3)
N3—C8—C9124.6 (3)H4A—N4—H4B103 (4)
C10—C9—C14119.4 (3)C1—O1—H1109.5
C10—C9—C8119.0 (3)C14—O2—H2A109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N4—H4A···O1i0.95 (5)2.39 (6)3.153 (4)136 (4)
O1—H1···N10.821.872.598 (3)148
O2—H2A···N2ii0.821.912.705 (3)162

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NC2167).

References

  • Bruker (1997). SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (1999). SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Lavrenova, L. G., Yudina, N. G., Ikorskii, V. N., Varnek, V. A., Oglezneva, I. M. & Larionov, S. V. (1995). Polyhedron, 14, 1333–1337.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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