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

Abstract

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,

• a = 12.161 (2) Å

• b = 5.9374 (3) Å

• c = 12.8282 (15) Å

• β = 108.012 (19)°

• V = 880.9 (2) ų

• 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[F ² > 2σ(F ²)] = 0.045

• wR(F ²) = 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

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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812019617/zj2066Isup3.cml

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

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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

All H atoms are positioned geometrically and refined as riding atoms, with C—H = 0.93-0.98 Å, N—H = 0.86 Å, O—H = 0.82 Å, and with U_iso = 1.2U_eq(C,N) or 1.5U_eq(O).

Figures

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.

Crystal data

C9H9N3O	F(000) = 368
Mr = 175.19	Dx = 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

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

Refinement

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(Fo2) + (0.0612P)2 + 0.0867P] where P = (Fo2 + 2Fc2)/3
1800 reflections	(Δ/σ)max < 0.001
127 parameters	Δρmax = 0.20 e Å−3
0 restraints	Δρmin = −0.15 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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.