4-(2,3-Dihydroxybenzyl­ideneamino)-3-methyl-1H-1,2,4-triazol-5(4H)-one

Tanak, H.; Köysal, Y.; Yavuz, M.; Işık, Ş.; Gül, G.

doi:10.1107/S1600536809045772

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3039

doi:10.1107/S1600536809045772

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4-(2,3-Dihydroxybenzylideneamino)-3-methyl-1H-1,2,4-triazol-5(4H)-one

Hasan Tanak,^a ^* Yavuz Köysal,^b Metin Yavuz,^c Şamil Işık ^d and Gülşah Gül ^e

^aDepartment of Physics, Ondokuz Mayıs University, TR-55139 Samsun, Turkey, ^bSamsun Vocational School, Ondokuz Mayıs University, TR-55139 Samsun, Turkey, ^cDepartment of Physics, Faculty of Arts & Science, Ondokuz Mayıs University, TR-55139 Kurupelit-Samsun, Turkey, ^dDepartment of Physics, Ondokuz Mayıs University, TR-55139 Samsun, Turkey, and ^eDepartment of Chemistry, Karadeniz Tecnical University, Trabzon, Turkey
^*Correspondence e-mail: htanak@omu.edu.tr

(Received 26 October 2009; accepted 31 October 2009; online 7 November 2009)

All the non-H atoms of the title compound, C₁₀H₁₀N₄O₃, are almost coplanar, the maximum deviation from planarity being 0.065 (3) Å. The dihedral angle between the aromatic rings is 1.66 (6)°. The molecule adopts the enol–imine tautomeric form with an intramolecular hydrogen-bonding interaction between the Schiff base N atom and the hydroxy group. In the crystal, intermolecular N—H⋯O and O—H⋯O hydrogen bonds link the molecules into a three-dimensional network.

Related literature

For the synthesis of the title compound, see Ünver et al. (2008 ). For related compounds, see: Köysal et al. (2007 ); Tanak et al., (2009 ). For hydrogen-bond motifs, see Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₀H₁₀N₄O₃
M_r = 234.22
Monoclinic, C 2
a = 13.944 (3) Å
b = 6.2551 (7) Å
c = 11.882 (2) Å
β = 93.857 (17)°
V = 1034.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 296 K
0.60 × 0.42 × 0.20 mm

Data collection

Stoe IPDS II diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ) T_min = 0.944, T_max = 0.974
3000 measured reflections
1118 independent reflections
1058 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.116
S = 1.09
1118 reflections
159 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.82	2.11	2.842 (3)	148
N3—H3⋯O3ⁱⁱ	0.86	2.00	2.830 (3)	163
O1—H1⋯N1	0.87 (5)	1.85 (5)	2.634 (3)	148 (4)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+1]$ .

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809045772/bt5118sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809045772/bt5118Isup2.hkl

checkCIF report

Comment top

The 1,2,4-triazole ring is strictly planar and the dihedral angle between the aromatic ring systems [C1/C6 and C8/N2] is 1.66 (6)°. The phenol H atom forms a strong intramolecular hydrogen bond with the imine N atom which is consistent with related structures (Köysal et al., 2007; Tanak et al., 2009), Fig 2.

The torsion angle C1—C7—N1—N2, bridged the aromatic ring systems, is 178.5 (2)° shows that for the title compound, the side chain conformation induced by the anti conformations, respectively. The interatomic distances within the triazole ring of are not equal. The C9—N4 is double bond and shorter than the conjugated C8—N2 and C9—N2 bonds. The length of the C7=N1 double bond is 1.278 (3) Å, it is almost consistent with standars 1.28 value of C=N double bond. The imino group is coplanar with the hydroxyphenyl ring as it can be shown by the C6—C1—C7—N1 torsion angle is -1.6 (3) Å.

Compound (I) is stabilized by N—H···O and O—H···O intermolecular contacts which link the molecules infinite chain and O—H···O, C—H···O and C—H···N type intramolecular hydrogen bonds. N3—H3···O3 (symmetry code: -x + 3/2,y + 1/2,-z + 1) bond is generates eight-membered ring, producing a R₂²(8) motif (Bernstein, et al., 1995). An intramolecular O1—H1···N1 hydrogen bond generates a six-membered ring, producing a S(6) ring motif (Bernstein, et al., 1995), resulting in approximate planarity of the molecular skeleton [O···N= 2.636 (2) Å].

Related literature top

For the synthesis of the title compound, see Ünver et al. (2008). For related compounds, see: Köysal et al. (2007); Tanak et al., (2009). For hydrogen -bond motifs, see Bernstein et al. (1995).

Experimental top

The title compound, C₁₀H₁₀N₄O₃, was synthesized according to the method of Ünver et al. (2008).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. A view of the title compound, with the atom-numbering scheme and 50% probability displacement ellipsoids. The dashed line indicates the intramolecular hydrogen bond.
	Fig. 2. A partial packing of the title compound.

4-(2,3-Dihydroxybenzylideneamino)-3-methyl-1H-1,2,4-triazol- 5(4H)-one top

Crystal data top

C₁₀H₁₀N₄O₃	F(000) = 488
M_r = 234.22	D_x = 1.505 Mg m⁻³
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 4561 reflections
a = 13.944 (3) Å	θ = 1.7–28.0°
b = 6.2551 (7) Å	µ = 0.12 mm⁻¹
c = 11.882 (2) Å	T = 296 K
β = 93.857 (17)°	Prism., yellow
V = 1034.0 (3) Å³	0.60 × 0.42 × 0.20 mm
Z = 4

Data collection top

Stoe IPDS II diffractometer	1118 independent reflections
Radiation source: fine-focus sealed tube	1058 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
Detector resolution: 6.67 pixels mm^-1	θ_max = 26.0°, θ_min = 1.7°
rotation method scans	h = −17→17
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −7→7
T_min = 0.944, T_max = 0.974	l = −14→12
3000 measured reflections

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)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.116	w = 1/[σ²(F_o²) + (0.0817P)² + 0.2531P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
1118 reflections	Δρ_max = 0.31 e Å⁻³
159 parameters	Δρ_min = −0.27 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.014 (3)

Crystal data top

C₁₀H₁₀N₄O₃	V = 1034.0 (3) Å³
M_r = 234.22	Z = 4
Monoclinic, C2	Mo Kα radiation
a = 13.944 (3) Å	µ = 0.12 mm⁻¹
b = 6.2551 (7) Å	T = 296 K
c = 11.882 (2) Å	0.60 × 0.42 × 0.20 mm
β = 93.857 (17)°

Data collection top

Stoe IPDS II diffractometer	1118 independent reflections
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	1058 reflections with I > 2σ(I)
T_min = 0.944, T_max = 0.974	R_int = 0.036
3000 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	1 restraint
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.31 e Å⁻³
1118 reflections	Δρ_min = −0.27 e Å⁻³
159 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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	0.42468 (17)	0.3934 (5)	0.2738 (2)	0.0359 (6)
C2	0.4051 (2)	0.2125 (6)	0.3388 (2)	0.0437 (7)
H8	0.4384	0.1927	0.4084	0.052*
C3	0.3379 (2)	0.0655 (5)	0.3012 (3)	0.0468 (7)
H9	0.3259	−0.0535	0.3451	0.056*
C4	0.28754 (19)	0.0937 (5)	0.1977 (3)	0.0423 (7)
H44	0.2419	−0.0067	0.1722	0.051*
C5	0.30481 (17)	0.2698 (5)	0.1325 (2)	0.0367 (6)
C6	0.37377 (17)	0.4209 (5)	0.1696 (2)	0.0339 (6)
C7	0.49894 (18)	0.5409 (5)	0.3167 (2)	0.0375 (6)
H13	0.5301	0.5190	0.3874	0.045*
C8	0.64752 (17)	0.8427 (5)	0.3996 (2)	0.0369 (6)
C9	0.61215 (17)	1.0237 (5)	0.2381 (2)	0.0367 (6)
C10	0.5679 (2)	1.0718 (6)	0.1242 (2)	0.0463 (7)
H15A	0.5240	0.9595	0.1009	0.069*
H15B	0.6172	1.0821	0.0718	0.069*
H15C	0.5338	1.2049	0.1259	0.069*
N1	0.52117 (14)	0.7007 (4)	0.25680 (18)	0.0346 (5)
N2	0.58991 (14)	0.8440 (4)	0.29821 (17)	0.0347 (5)
N3	0.69709 (17)	1.0251 (5)	0.3919 (2)	0.0441 (6)
H3	0.7380	1.0693	0.4442	0.053*
N4	0.67653 (16)	1.1360 (5)	0.2924 (2)	0.0436 (6)
O1	0.38826 (15)	0.5879 (4)	0.09998 (18)	0.0464 (6)
O2	0.25821 (14)	0.3108 (4)	0.03004 (16)	0.0478 (6)
H2	0.2197	0.2146	0.0141	0.072*
O3	0.64859 (14)	0.7078 (4)	0.47417 (16)	0.0471 (5)
H1	0.438 (3)	0.656 (9)	0.131 (4)	0.074 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0356 (12)	0.0356 (15)	0.0357 (12)	−0.0006 (11)	−0.0031 (10)	−0.0023 (12)
C2	0.0501 (15)	0.0436 (17)	0.0362 (13)	−0.0019 (14)	−0.0062 (11)	0.0060 (14)
C3	0.0557 (16)	0.0408 (17)	0.0446 (15)	−0.0055 (14)	0.0084 (12)	0.0037 (13)
C4	0.0385 (13)	0.0375 (15)	0.0507 (16)	−0.0066 (12)	0.0007 (11)	−0.0069 (13)
C5	0.0301 (11)	0.0395 (16)	0.0396 (13)	0.0018 (11)	−0.0040 (10)	−0.0078 (11)
C6	0.0325 (11)	0.0311 (13)	0.0371 (12)	0.0012 (11)	−0.0041 (9)	−0.0008 (11)
C7	0.0393 (12)	0.0398 (16)	0.0322 (11)	0.0013 (12)	−0.0072 (9)	−0.0004 (12)
C8	0.0327 (11)	0.0408 (14)	0.0354 (12)	0.0039 (11)	−0.0101 (9)	−0.0046 (12)
C9	0.0360 (12)	0.0369 (14)	0.0365 (12)	0.0004 (11)	−0.0031 (9)	0.0007 (12)
C10	0.0431 (14)	0.0524 (19)	0.0420 (14)	−0.0001 (13)	−0.0081 (11)	0.0084 (14)
N1	0.0334 (10)	0.0329 (12)	0.0360 (10)	−0.0011 (9)	−0.0096 (8)	−0.0030 (10)
N2	0.0326 (10)	0.0359 (12)	0.0339 (10)	−0.0007 (9)	−0.0107 (8)	−0.0002 (10)
N3	0.0433 (11)	0.0432 (14)	0.0431 (12)	−0.0087 (11)	−0.0172 (9)	−0.0034 (12)
N4	0.0402 (11)	0.0448 (14)	0.0445 (12)	−0.0061 (11)	−0.0077 (9)	0.0013 (12)
O1	0.0493 (11)	0.0393 (12)	0.0472 (11)	−0.0091 (10)	−0.0206 (9)	0.0101 (9)
O2	0.0463 (10)	0.0471 (13)	0.0470 (12)	−0.0054 (10)	−0.0183 (9)	−0.0041 (10)
O3	0.0477 (10)	0.0514 (13)	0.0392 (10)	−0.0007 (10)	−0.0178 (8)	0.0063 (10)

Geometric parameters (Å, º) top

C1—C6	1.396 (4)	C8—O3	1.223 (4)
C1—C2	1.407 (4)	C8—N3	1.340 (4)
C1—C7	1.453 (4)	C8—N2	1.402 (3)
C2—C3	1.367 (4)	C9—N4	1.280 (4)
C2—H8	0.9300	C9—N2	1.378 (4)
C3—C4	1.386 (4)	C9—C10	1.480 (4)
C3—H9	0.9300	C10—H15A	0.9600
C4—C5	1.377 (4)	C10—H15B	0.9600
C4—H44	0.9300	C10—H15C	0.9600
C5—O2	1.365 (3)	N1—N2	1.379 (3)
C5—C6	1.398 (4)	N3—N4	1.384 (4)
C6—O1	1.356 (3)	N3—H3	0.8600
C7—N1	1.277 (4)	O1—H1	0.87 (5)
C7—H13	0.9300	O2—H2	0.8200

C6—C1—C2	118.7 (2)	O3—C8—N2	127.2 (3)
C6—C1—C7	122.7 (2)	N3—C8—N2	101.8 (2)
C2—C1—C7	118.6 (2)	N4—C9—N2	111.1 (2)
C3—C2—C1	121.1 (3)	N4—C9—C10	125.8 (3)
C3—C2—H8	119.5	N2—C9—C10	123.0 (3)
C1—C2—H8	119.5	C9—C10—H15A	109.5
C2—C3—C4	120.0 (3)	C9—C10—H15B	109.5
C2—C3—H9	120.0	H15A—C10—H15B	109.5
C4—C3—H9	120.0	C9—C10—H15C	109.5
C5—C4—C3	120.3 (3)	H15A—C10—H15C	109.5
C5—C4—H44	119.9	H15B—C10—H15C	109.5
C3—C4—H44	119.9	C7—N1—N2	119.9 (2)
O2—C5—C4	124.1 (2)	N1—N2—C9	121.4 (2)
O2—C5—C6	115.5 (3)	N1—N2—C8	130.3 (2)
C4—C5—C6	120.4 (2)	C9—N2—C8	108.3 (2)
O1—C6—C1	123.3 (2)	C8—N3—N4	114.0 (2)
O1—C6—C5	117.1 (2)	C8—N3—H3	123.0
C1—C6—C5	119.6 (3)	N4—N3—H3	123.0
N1—C7—C1	119.7 (2)	C9—N4—N3	104.7 (2)
N1—C7—H13	120.2	C6—O1—H1	105 (3)
C1—C7—H13	120.2	C5—O2—H2	109.5
O3—C8—N3	131.0 (2)

C6—C1—C2—C3	0.2 (4)	C1—C7—N1—N2	178.4 (2)
C7—C1—C2—C3	−178.2 (3)	C7—N1—N2—C9	−176.8 (2)
C1—C2—C3—C4	−0.2 (5)	C7—N1—N2—C8	3.3 (4)
C2—C3—C4—C5	−0.1 (4)	N4—C9—N2—N1	179.0 (2)
C3—C4—C5—O2	−179.6 (3)	C10—C9—N2—N1	−2.6 (4)
C3—C4—C5—C6	0.5 (4)	N4—C9—N2—C8	−1.1 (3)
C2—C1—C6—O1	−179.0 (2)	C10—C9—N2—C8	177.3 (3)
C7—C1—C6—O1	−0.7 (4)	O3—C8—N2—N1	0.5 (5)
C2—C1—C6—C5	0.2 (4)	N3—C8—N2—N1	−178.5 (3)
C7—C1—C6—C5	178.5 (2)	O3—C8—N2—C9	−179.4 (3)
O2—C5—C6—O1	−1.2 (4)	N3—C8—N2—C9	1.6 (3)
C4—C5—C6—O1	178.7 (2)	O3—C8—N3—N4	179.4 (3)
O2—C5—C6—C1	179.5 (2)	N2—C8—N3—N4	−1.7 (3)
C4—C5—C6—C1	−0.5 (4)	N2—C9—N4—N3	0.0 (3)
C6—C1—C7—N1	−1.6 (4)	C10—C9—N4—N3	−178.3 (3)
C2—C1—C7—N1	176.7 (3)	C8—N3—N4—C9	1.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.82	2.11	2.842 (3)	148
N3—H3···O3ⁱⁱ	0.86	2.00	2.830 (3)	163
O1—H1···N1	0.87 (5)	1.85 (5)	2.634 (3)	148 (4)

Symmetry codes: (i) −x+1/2, y−1/2, −z; (ii) −x+3/2, y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀N₄O₃
M_r	234.22
Crystal system, space group	Monoclinic, C2
Temperature (K)	296
a, b, c (Å)	13.944 (3), 6.2551 (7), 11.882 (2)
β (°)	93.857 (17)
V (Å³)	1034.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.60 × 0.42 × 0.20

Data collection
Diffractometer	Stoe IPDS II diffractometer
Absorption correction	Integration (X-RED32; Stoe & Cie, 2002)
T_min, T_max	0.944, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections	3000, 1118, 1058
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.116, 1.09
No. of reflections	1118
No. of parameters	159
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.27

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.82	2.11	2.842 (3)	148.4
N3—H3···O3ⁱⁱ	0.86	2.00	2.830 (3)	162.9
O1—H1···N1	0.87 (5)	1.85 (5)	2.634 (3)	148 (4)

Symmetry codes: (i) −x+1/2, y−1/2, −z; (ii) −x+3/2, y+1/2, −z+1.

Acknowledgements

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS II diffractometer

References

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