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

Chen, S.-H.; Zhang, G.-Y.; Dong, J.-F.

doi:10.1107/S1600536809055536

organic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page o330

https://doi.org/10.1107/S1600536809055536

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

Sheng-Hui Chen,^a Gao-Yong Zhang ^a and Jin-Feng Dong ^a ^*

^aCollege of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, People's Republic of China
^*Correspondence e-mail: whujfdong@yahoo.com.cn

(Received 5 November 2009; accepted 28 December 2009; online 9 January 2010)

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 ).

Experimental

Crystal data

C₁₄H₁₂N₄O₂
M_r = 268.28
Orthorhombic, P 2₁ 2₁ 2₁
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 ) 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[F² > 2σ(F²)] = 0.041
wR(F²) = 0.112
S = 1.10
1276 reflections
192 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯O1ⁱ	0.95 (5)	2.39 (6)	3.153 (4)	136 (4)
O1—H1⋯N1	0.82	1.87	2.598 (3)	148
O2—H2A⋯N2ⁱⁱ	0.82	1.91	2.705 (3)	162
Symmetry codes: (i) x+1, y, z; (ii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809055536/nc2167Isup2.hkl

checkCIF report

Related literature top

Provide at least one background reference.

Experimental top

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.

Structure description top

Provide at least one background reference.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

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

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

Crystal data top

C₁₄H₁₂N₄O₂	F(000) = 560
M_r = 268.28	D_x = 1.444 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2036 reflections
a = 8.262 (2) Å	θ = 2.4–24.6°
b = 9.384 (3) Å	µ = 0.10 mm⁻¹
c = 15.919 (4) Å	T = 296 K
V = 1234.2 (6) Å³	Block, colorless
Z = 4	0.10 × 0.10 × 0.08 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1276 independent reflections
Radiation source: fine-focus sealed tube	1143 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
phi and ω scans	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.980, T_max = 0.992	k = −9→11
6343 measured reflections	l = −18→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.112	w = 1/[σ²(F_o²) + (0.0693P)² + 0.078P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.005
1276 reflections	Δρ_max = 0.18 e Å⁻³
192 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.011 (4)

Crystal data top

C₁₄H₁₂N₄O₂	V = 1234.2 (6) Å³
M_r = 268.28	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.262 (2) Å	µ = 0.10 mm⁻¹
b = 9.384 (3) Å	T = 296 K
c = 15.919 (4) Å	0.10 × 0.10 × 0.08 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1276 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1143 reflections with I > 2σ(I)
T_min = 0.980, T_max = 0.992	R_int = 0.043
6343 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.18 e Å⁻³
1276 reflections	Δρ_min = −0.17 e Å⁻³
192 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
C1	0.5404 (4)	0.5286 (4)	0.49447 (17)	0.0385 (7)
C2	0.4539 (4)	0.4330 (4)	0.54359 (19)	0.0449 (8)
H2	0.3416	0.4386	0.5450	0.054*
C3	0.5310 (4)	0.3309 (4)	0.5899 (2)	0.0457 (8)
H3	0.4711	0.2671	0.6220	0.055*
C4	0.6981 (4)	0.3225 (4)	0.5890 (2)	0.0479 (8)
H4	0.7509	0.2536	0.6208	0.057*
C5	0.7861 (4)	0.4166 (3)	0.5408 (2)	0.0442 (8)
H5	0.8985	0.4103	0.5406	0.053*
C6	0.7108 (4)	0.5211 (3)	0.49212 (17)	0.0339 (7)
C7	0.7987 (4)	0.6149 (3)	0.43411 (18)	0.0339 (7)
C8	0.9790 (3)	0.7037 (3)	0.34798 (17)	0.0333 (7)
C9	1.1311 (3)	0.7234 (3)	0.30083 (17)	0.0345 (7)
C10	1.1826 (4)	0.8612 (3)	0.2823 (2)	0.0422 (8)
H10	1.1286	0.9388	0.3055	0.051*
C11	1.3126 (4)	0.8838 (4)	0.2298 (2)	0.0521 (9)
H11	1.3482	0.9759	0.2186	0.062*
C12	1.3895 (4)	0.7686 (4)	0.1941 (2)	0.0586 (10)
H12	1.4744	0.7837	0.1568	0.070*
C13	1.3427 (4)	0.6316 (4)	0.2127 (2)	0.0482 (9)
H13	1.3981	0.5550	0.1894	0.058*
C14	1.2130 (4)	0.6075 (3)	0.26611 (18)	0.0371 (7)
N1	0.7263 (3)	0.7099 (3)	0.38646 (15)	0.0388 (6)
N2	0.8404 (3)	0.7657 (3)	0.33109 (15)	0.0395 (6)
N3	0.9594 (3)	0.6108 (3)	0.41328 (15)	0.0335 (6)
N4	1.0844 (3)	0.5384 (4)	0.45696 (19)	0.0427 (7)
O1	0.4530 (3)	0.6247 (3)	0.44960 (15)	0.0554 (7)
H1	0.5143	0.6734	0.4210	0.083*
O2	1.1615 (3)	0.4745 (2)	0.28606 (13)	0.0458 (6)
H2A	1.1785	0.4206	0.2465	0.069*
H4A	1.167 (7)	0.605 (5)	0.471 (3)	0.097 (16)*
H4B	1.131 (5)	0.486 (4)	0.419 (2)	0.059 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0354 (17)	0.0409 (17)	0.0393 (15)	0.0028 (14)	−0.0007 (13)	−0.0023 (14)
C2	0.0329 (17)	0.052 (2)	0.0500 (17)	−0.0040 (15)	0.0028 (15)	0.0022 (16)
C3	0.0440 (19)	0.0430 (19)	0.0500 (18)	−0.0045 (16)	0.0092 (16)	0.0025 (15)
C4	0.0438 (18)	0.047 (2)	0.0531 (18)	0.0030 (16)	0.0074 (15)	0.0123 (16)
C5	0.0367 (17)	0.0430 (19)	0.0529 (18)	0.0052 (15)	0.0008 (14)	0.0087 (16)
C6	0.0321 (16)	0.0312 (16)	0.0385 (15)	−0.0029 (13)	0.0013 (12)	−0.0051 (13)
C7	0.0317 (15)	0.0291 (16)	0.0408 (15)	0.0000 (14)	0.0011 (12)	−0.0003 (13)
C8	0.0326 (15)	0.0280 (15)	0.0391 (14)	−0.0011 (13)	−0.0007 (12)	−0.0023 (13)
C9	0.0310 (15)	0.0344 (17)	0.0382 (15)	−0.0025 (13)	−0.0014 (12)	−0.0009 (13)
C10	0.0392 (17)	0.0343 (17)	0.0530 (18)	−0.0042 (14)	−0.0030 (15)	0.0003 (15)
C11	0.0391 (17)	0.046 (2)	0.071 (2)	−0.0101 (18)	−0.0009 (17)	0.0159 (18)
C12	0.0346 (18)	0.074 (3)	0.067 (2)	−0.0013 (19)	0.0118 (16)	0.013 (2)
C13	0.0326 (16)	0.057 (2)	0.0552 (19)	0.0087 (16)	0.0062 (15)	−0.0016 (18)
C14	0.0336 (15)	0.0377 (17)	0.0400 (15)	0.0003 (14)	−0.0047 (13)	0.0016 (14)
N1	0.0342 (13)	0.0348 (15)	0.0474 (13)	0.0007 (12)	0.0030 (11)	0.0056 (12)
N2	0.0368 (14)	0.0341 (14)	0.0477 (14)	0.0021 (11)	0.0044 (11)	0.0045 (12)
N3	0.0263 (12)	0.0335 (13)	0.0409 (12)	0.0003 (11)	0.0003 (10)	0.0009 (11)
N4	0.0313 (15)	0.0460 (17)	0.0507 (17)	0.0061 (13)	−0.0032 (12)	0.0065 (15)
O1	0.0302 (12)	0.0693 (18)	0.0666 (15)	0.0058 (12)	0.0032 (11)	0.0211 (14)
O2	0.0577 (15)	0.0305 (12)	0.0493 (12)	−0.0016 (11)	0.0076 (11)	−0.0071 (10)

Geometric parameters (Å, º) top

C1—O1	1.358 (4)	C9—C10	1.393 (4)
C1—C2	1.388 (4)	C9—C14	1.395 (4)
C1—C6	1.410 (5)	C10—C11	1.377 (5)
C2—C3	1.366 (5)	C10—H10	0.9300
C2—H2	0.9300	C11—C12	1.376 (5)
C3—C4	1.383 (5)	C11—H11	0.9300
C3—H3	0.9300	C12—C13	1.375 (5)
C4—C5	1.377 (5)	C12—H12	0.9300
C4—H4	0.9300	C13—C14	1.386 (4)
C5—C6	1.396 (4)	C13—H13	0.9300
C5—H5	0.9300	C14—O2	1.356 (4)
C6—C7	1.468 (4)	N1—N2	1.393 (3)
C7—N1	1.314 (4)	N3—N4	1.419 (3)
C7—N3	1.368 (4)	N4—H4A	0.95 (5)
C8—N2	1.312 (4)	N4—H4B	0.87 (4)
C8—N3	1.366 (4)	O1—H1	0.8200
C8—C9	1.475 (4)	O2—H2A	0.8200

O1—C1—C2	116.8 (3)	C14—C9—C8	121.2 (3)
O1—C1—C6	123.4 (3)	C11—C10—C9	120.6 (3)
C2—C1—C6	119.8 (3)	C11—C10—H10	119.7
C3—C2—C1	121.1 (3)	C9—C10—H10	119.7
C3—C2—H2	119.4	C12—C11—C10	119.3 (3)
C1—C2—H2	119.4	C12—C11—H11	120.3
C2—C3—C4	120.0 (3)	C10—C11—H11	120.3
C2—C3—H3	120.0	C13—C12—C11	121.0 (3)
C4—C3—H3	120.0	C13—C12—H12	119.5
C5—C4—C3	119.8 (3)	C11—C12—H12	119.5
C5—C4—H4	120.1	C12—C13—C14	120.1 (3)
C3—C4—H4	120.1	C12—C13—H13	119.9
C4—C5—C6	121.6 (3)	C14—C13—H13	119.9
C4—C5—H5	119.2	O2—C14—C13	122.4 (3)
C6—C5—H5	119.2	O2—C14—C9	118.2 (3)
C5—C6—C1	117.7 (3)	C13—C14—C9	119.4 (3)
C5—C6—C7	123.3 (3)	C7—N1—N2	108.2 (2)
C1—C6—C7	118.7 (3)	C8—N2—N1	107.1 (2)
N1—C7—N3	108.7 (2)	C8—N3—C7	106.4 (2)
N1—C7—C6	123.0 (3)	C8—N3—N4	126.3 (2)
N3—C7—C6	128.0 (3)	C7—N3—N4	126.9 (2)
N2—C8—N3	109.6 (3)	N3—N4—H4A	109 (3)
N2—C8—C9	125.7 (3)	N3—N4—H4B	105 (3)
N3—C8—C9	124.6 (3)	H4A—N4—H4B	103 (4)
C10—C9—C14	119.4 (3)	C1—O1—H1	109.5
C10—C9—C8	119.0 (3)	C14—O2—H2A	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O1ⁱ	0.95 (5)	2.39 (6)	3.153 (4)	136 (4)
O1—H1···N1	0.82	1.87	2.598 (3)	148
O2—H2A···N2ⁱⁱ	0.82	1.91	2.705 (3)	162

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂N₄O₂
M_r	268.28
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	8.262 (2), 9.384 (3), 15.919 (4)
V (Å³)	1234.2 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.10 × 0.10 × 0.08

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.980, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	6343, 1276, 1143
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.112, 1.10
No. of reflections	1276
No. of parameters	192
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.17

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O1ⁱ	0.95 (5)	2.39 (6)	3.153 (4)	136 (4)
O1—H1···N1	0.82	1.87	2.598 (3)	147.7
O2—H2A···N2ⁱⁱ	0.82	1.91	2.705 (3)	161.8

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

Acknowledgements

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

References

Bruker (1997). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (1999). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar