5-(4-Methyl­phen­yl)-1,3,4-oxadiazol-2-amine

Zheng, J.; Li, W.; Song, M.; Xu, Y.

doi:10.1107/S1600536812019617

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1668

doi:10.1107/S1600536812019617

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5-(4-Methylphenyl)-1,3,4-oxadiazol-2-amine

Juan Zheng,^a Wen-juan Li,^a Manman Song ^a and Yan Xu ^a ^*

^aDepartment of Chemistry, Zhengzhou University, Zhengzhou 450052, People's Republic of China
^*Correspondence e-mail: xuyan@zzu.edu.cn

(Received 9 March 2012; accepted 2 May 2012; online 12 May 2012)

In the crystal structure of the title compound, C₉H₉N₃O, adjacent molecules are linked through N—H⋯N hydrogen bonds into a three-dimensional network.

Related literature

For background to 1,3,4-oxadiazole derivatives, see: Lv et al. (2010 ); Bachwani & Sharma (2011 ); Padmavathi et al. (2009 ); Tang et al. (2007 ); Xue et al. (2007 ).

Experimental

Crystal data

C₉H₉N₃O
M_r = 175.19
Monoclinic, P 2₁ /n
a = 12.161 (2) Å
b = 5.9374 (3) Å
c = 12.8282 (15) Å
β = 108.012 (19)°
V = 880.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 291 K
0.38 × 0.35 × 0.30 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2006 ) T_min = 0.966, T_max = 0.973
3809 measured reflections
1800 independent reflections
1313 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.124
S = 1.03
1800 reflections
127 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N1ⁱ	0.88 (2)	2.11 (2)	2.979 (2)	165.7 (19)
N3—H3B⋯N2ⁱⁱ	0.93 (2)	2.05 (2)	2.964 (2)	167.6 (16)
Symmetry codes: (i) x, y+1, z; (ii) $[-x-{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku/MSC, 2006); cell refinement: CrystalClear; data reduction: CrystalClear; 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: 10.1107/S1600536812019617/zj2066sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812019617/zj2066Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812019617/zj2066Isup3.cml

checkCIF report

Comment top

Oxadiazole is a five-membered heterocyclic aromatic chemical compound having two carbons, two nitrogen, and one oxygen atoms and two double bonds. Up to now, a large number of oxadiazole derivatives have been prepared and a series of novel substituted 1,3,4-oxadiazole derivatives were synthesized (Bachwani et al., 2011). In addition, electron transporting 1,3,4-oxadiazole moiety has been connected to many chelating ligands to obtain luminescent complexes with more new function. (Lv et al., 2010) 1,3,4-oxadiazole, which has abundant N-donor and O-donor sites is easily to form single-crystal. However, there has been limited study about their crystal properties. To further explore these types of structures, we synthesized the title compound and its crystal structure is presented herein. The molecular structure of the title compound is represented in Fig. 1. As shown in figure 1, the bond length between O1 with C8 is 1.3608 (19) Å and is nearly the bond length between O1 with C7(1.3754) Å. The angle of C8—O1—C7 is 102.79 (11) Å. Similarly, the bond length of C7 with N1 is approximate the bond length of C8 with N2. They are 1.279 (2) Å, 1.296 (2) Å. The bond length between N1 with N2 is 1.4129 (19) Å. The dihedral angle between the phenyl and the Oxadiazole ring bonded to the imino group is 26.37 °. The torsion angle between C(7)—N(1)—N(2)—C(8) is -0.3 (2) °. As depicted in figure 2 and 3, intramolecular N—H···N hydrogen bonds stabilize the molecular configuration.

Related literature top

For background to 1,3,4-oxadiazole derivatives, see: Lv et al. (2010); Bachwani & Sharma (2011); Padmavathi et al. (2009); Tang et al. (2007); Xue et al. (2007).

Experimental top

The benzaldehyde (0.01 mol) and ethanol was added to semicarbazide hydrochloride (0.011 mol) refluxed 2 h. And then the obtained semicarbazone was oxidized by bromine liquid in acetic acid. The title compound (0.02 mmol) was dissolved in alcohol (3 ml) with a little aqueous solution. The resulting solution was allowed to stand at room temperature. Evaporation of the solvent, after three weeks yellow crystals with good quality were obtained from the filtrate and dried in air.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2006); cell refinement: CrystalClear (Rigaku/MSC, 2006); data reduction: CrystalClear (Rigaku/MSC, 2006); 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. View of the title complex, showing the labeling of the 30% probability ellipsoids. H atoms are omitted for clarity.
	Fig. 2. View of the title complex, showing the packing of the structure.
	Fig. 3. View of the title complex, showing the hydrogen bonding in the crystal structure.

5-(4-Methylphenyl)-1,3,4-oxadiazol-2-amine top

Crystal data top

C₉H₉N₃O	F(000) = 368
M_r = 175.19	D_x = 1.321 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.161 (2) Å	Cell parameters from 1122 reflections
b = 5.9374 (3) Å	θ = 3.3–26.3°
c = 12.8282 (15) Å	µ = 0.09 mm⁻¹
β = 108.012 (19)°	T = 291 K
V = 880.9 (2) Å³	Prism, yellow
Z = 4	0.38 × 0.35 × 0.30 mm

Data collection top

Rigaku Saturn diffractometer	1800 independent reflections
Radiation source: fine-focus sealed tube	1313 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Detector resolution: 28.5714 pixels mm^-1	θ_max = 26.4°, θ_min = 3.3°
ω scans	h = −15→15
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2006)	k = −7→6
T_min = 0.966, T_max = 0.973	l = −16→15
3809 measured reflections

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0612P)² + 0.0867P] where P = (F_o² + 2F_c²)/3
1800 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₉H₉N₃O	V = 880.9 (2) Å³
M_r = 175.19	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.161 (2) Å	µ = 0.09 mm⁻¹
b = 5.9374 (3) Å	T = 291 K
c = 12.8282 (15) Å	0.38 × 0.35 × 0.30 mm
β = 108.012 (19)°

Data collection top

Rigaku Saturn diffractometer	1800 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2006)	1313 reflections with I > 2σ(I)
T_min = 0.966, T_max = 0.973	R_int = 0.022
3809 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.20 e Å⁻³
1800 reflections	Δρ_min = −0.15 e Å⁻³
127 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
O1	0.00011 (9)	0.21279 (17)	0.19008 (10)	0.0417 (3)
N1	−0.06440 (12)	−0.1327 (2)	0.19144 (13)	0.0516 (4)
N2	−0.13933 (12)	0.0146 (2)	0.22353 (14)	0.0497 (4)
N3	−0.13387 (15)	0.4123 (3)	0.24629 (15)	0.0572 (5)
C1	0.29096 (15)	−0.2138 (3)	0.05483 (15)	0.0515 (5)
C2	0.19911 (16)	−0.3566 (3)	0.04961 (15)	0.0537 (5)
H2	0.1975	−0.4991	0.0191	0.064*
C3	0.11020 (16)	−0.2923 (3)	0.08861 (15)	0.0485 (5)
H3	0.0500	−0.3917	0.0847	0.058*
C4	0.11017 (13)	−0.0803 (3)	0.13353 (14)	0.0395 (4)
C5	0.20195 (15)	0.0649 (3)	0.14061 (16)	0.0497 (5)
H5	0.2036	0.2073	0.1712	0.060*
C6	0.29100 (15)	−0.0041 (3)	0.10172 (17)	0.0568 (5)
H6	0.3524	0.0933	0.1073	0.068*
C7	0.01433 (13)	−0.0122 (3)	0.17222 (14)	0.0388 (4)
C8	−0.09732 (14)	0.2145 (3)	0.22099 (15)	0.0411 (4)
C9	0.38709 (18)	−0.2859 (4)	0.0109 (2)	0.0749 (7)
H9A	0.4075	−0.4395	0.0312	0.112*
H9B	0.4533	−0.1910	0.0410	0.112*
H9C	0.3617	−0.2730	−0.0676	0.112*
H3A	−0.1032 (18)	0.535 (4)	0.2273 (17)	0.068 (6)*
H3B	−0.2065 (17)	0.421 (3)	0.2559 (16)	0.062 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0408 (6)	0.0300 (6)	0.0602 (8)	−0.0006 (5)	0.0243 (6)	0.0001 (5)
N1	0.0544 (9)	0.0322 (8)	0.0790 (11)	−0.0021 (6)	0.0363 (8)	−0.0008 (7)
N2	0.0521 (8)	0.0319 (8)	0.0768 (11)	−0.0014 (6)	0.0372 (8)	0.0020 (7)
N3	0.0563 (10)	0.0337 (9)	0.0968 (14)	0.0003 (7)	0.0460 (10)	−0.0007 (8)
C1	0.0468 (10)	0.0584 (12)	0.0530 (11)	0.0107 (9)	0.0209 (9)	0.0035 (9)
C2	0.0652 (12)	0.0437 (10)	0.0584 (12)	0.0078 (9)	0.0279 (10)	−0.0056 (9)
C3	0.0538 (10)	0.0393 (9)	0.0573 (11)	−0.0033 (8)	0.0244 (9)	−0.0043 (8)
C4	0.0400 (8)	0.0351 (9)	0.0447 (10)	0.0027 (7)	0.0148 (7)	0.0025 (7)
C5	0.0478 (9)	0.0390 (10)	0.0654 (12)	−0.0004 (8)	0.0222 (9)	−0.0041 (9)
C6	0.0439 (10)	0.0566 (12)	0.0758 (14)	−0.0018 (9)	0.0269 (10)	0.0005 (10)
C7	0.0431 (9)	0.0279 (8)	0.0472 (10)	0.0011 (7)	0.0165 (8)	0.0016 (7)
C8	0.0394 (8)	0.0348 (9)	0.0544 (11)	−0.0004 (7)	0.0223 (8)	0.0020 (8)
C9	0.0596 (12)	0.0929 (17)	0.0811 (16)	0.0168 (11)	0.0350 (12)	−0.0082 (13)

Geometric parameters (Å, º) top

O1—C8	1.3608 (19)	C2—H2	0.9300
O1—C7	1.3754 (18)	C3—C4	1.385 (2)
N1—C7	1.279 (2)	C3—H3	0.9300
N1—N2	1.4129 (19)	C4—C5	1.391 (2)
N2—C8	1.296 (2)	C4—C7	1.458 (2)
N3—C8	1.331 (2)	C5—C6	1.387 (2)
N3—H3A	0.88 (2)	C5—H5	0.9300
N3—H3B	0.93 (2)	C6—H6	0.9300
C1—C6	1.382 (3)	C9—H9A	0.9600
C1—C2	1.388 (3)	C9—H9B	0.9600
C1—C9	1.509 (3)	C9—H9C	0.9600
C2—C3	1.378 (2)

C8—O1—C7	102.79 (11)	C6—C5—C4	119.58 (16)
C7—N1—N2	107.39 (13)	C6—C5—H5	120.2
C8—N2—N1	105.34 (13)	C4—C5—H5	120.2
C8—N3—H3A	117.2 (13)	C1—C6—C5	121.82 (17)
C8—N3—H3B	119.0 (11)	C1—C6—H6	119.1
H3A—N3—H3B	119.1 (17)	C5—C6—H6	119.1
C6—C1—C2	117.61 (16)	N1—C7—O1	111.77 (14)
C6—C1—C9	121.48 (18)	N1—C7—C4	129.48 (15)
C2—C1—C9	120.92 (18)	O1—C7—C4	118.74 (13)
C3—C2—C1	121.55 (17)	N2—C8—N3	129.62 (16)
C3—C2—H2	119.2	N2—C8—O1	112.70 (14)
C1—C2—H2	119.2	N3—C8—O1	117.65 (14)
C2—C3—C4	120.28 (17)	C1—C9—H9A	109.5
C2—C3—H3	119.9	C1—C9—H9B	109.5
C4—C3—H3	119.9	H9A—C9—H9B	109.5
C3—C4—C5	119.15 (16)	C1—C9—H9C	109.5
C3—C4—C7	119.79 (15)	H9A—C9—H9C	109.5
C5—C4—C7	121.06 (15)	H9B—C9—H9C	109.5

C7—N1—N2—C8	−0.3 (2)	N2—N1—C7—C4	−177.86 (16)
C6—C1—C2—C3	0.6 (3)	C8—O1—C7—N1	−0.76 (19)
C9—C1—C2—C3	−179.45 (18)	C8—O1—C7—C4	177.94 (14)
C1—C2—C3—C4	0.6 (3)	C3—C4—C7—N1	14.9 (3)
C2—C3—C4—C5	−1.2 (3)	C5—C4—C7—N1	−165.33 (19)
C2—C3—C4—C7	178.60 (16)	C3—C4—C7—O1	−163.57 (15)
C3—C4—C5—C6	0.6 (3)	C5—C4—C7—O1	16.2 (2)
C7—C4—C5—C6	−179.16 (17)	N1—N2—C8—N3	−178.37 (19)
C2—C1—C6—C5	−1.2 (3)	N1—N2—C8—O1	−0.2 (2)
C9—C1—C6—C5	178.88 (19)	C7—O1—C8—N2	0.58 (19)
C4—C5—C6—C1	0.6 (3)	C7—O1—C8—N3	178.98 (16)
N2—N1—C7—O1	0.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N1ⁱ	0.88 (2)	2.11 (2)	2.979 (2)	165.7 (19)
N3—H3B···N2ⁱⁱ	0.93 (2)	2.05 (2)	2.964 (2)	167.6 (16)

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

Experimental details

Crystal data
Chemical formula	C₉H₉N₃O
M_r	175.19
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	291
a, b, c (Å)	12.161 (2), 5.9374 (3), 12.8282 (15)
β (°)	108.012 (19)
V (Å³)	880.9 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.38 × 0.35 × 0.30

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2006)
T_min, T_max	0.966, 0.973
No. of measured, independent and observed [I > 2σ(I)] reflections	3809, 1800, 1313
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.124, 1.03
No. of reflections	1800
No. of parameters	127
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.15

Computer programs: CrystalClear (Rigaku/MSC, 2006), 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
N3—H3A···N1ⁱ	0.88 (2)	2.11 (2)	2.979 (2)	165.7 (19)
N3—H3B···N2ⁱⁱ	0.93 (2)	2.05 (2)	2.964 (2)	167.6 (16)

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

Acknowledgements

We gratefully acknowledge financial support by the National Natural Science Foundation of China (No. 21171149).

References

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