5-Phenyl-1,3,4-oxadiazol-2-amine

Song, M.-M.; Wu, K.-L.; Zhu, L.; Zheng, J.; Xu, Y.

doi:10.1107/S1600536812040640

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 10| October 2012| Page o3058

https://doi.org/10.1107/S1600536812040640

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5-Phenyl-1,3,4-oxadiazol-2-amine

Man-Man Song,^a Kong-Li Wu,^a Lin Zhu,^a Juan Zheng ^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 5 June 2012; accepted 26 September 2012; online 29 September 2012)

In the title complex, C₈H₇N₃O, the C—O [1.369 (2) and 1.364 (3) Å] and C=N [1.285 (3) and 1.289 (3) Å] bond lengths in the oxadiazole ring are each almost identical within systematic errors, although different substituents are attached to the ring. The phenyl ring is inclined to the planar oxadiazole ring [r.m.s. deviation 0.002 Å] by 13.42 (18)°. In the crystal, molecules are linked via N—H⋯N hydrogen bonds, forming double-stranded chains propagating along [010].

Related literature

For background to 5-phenyl-1,3,4-oxadiazol-2-amines and the synthesis of the title compound, see: Bachwani et al. (2011 ); Lv et al. (2010 ); Tang et al. (2007 ).

Experimental

Crystal data

C₈H₇N₃O
M_r = 161.17
Monoclinic, P 2₁ /c
a = 11.194 (3) Å
b = 5.8990 (5) Å
c = 15.034 (5) Å
β = 130.193 (18)°
V = 758.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 291 K
0.26 × 0.24 × 0.22 mm

Data collection

Agilent Xcalibur Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.851, T_max = 1.000
2912 measured reflections
1551 independent reflections
877 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.137
S = 1.02
1551 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.17 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⋯N2ⁱ	0.89	2.12	2.997 (3)	169
N3—H3B⋯N1ⁱⁱ	0.95	2.12	3.054 (3)	168
Symmetry codes: (i) $[-x-1, y+{\script{1\over 2}}, -z-{\script{1\over 2}}]$ ; (ii) x, y+1, z.

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: OLEX2.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812040640/im2386sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812040640/im2386Isup2.hkl

checkCIF report

Comment top

Oxadiazole is the parent compound for a vast class of heterocyclic compounds. Oxadiazole derivatives have attracted considerable attention (Bachwani et al., 2011). Although 1,3,4-oxadiazole exhibit various N and O atoms that should allow to form single crystals due to their ability to act as hydrogen bond acceptor sites, there have been limited studies concerning their crystal properties. To further explore their crystal properties, in this communication, we report the crystal structure of the title compound. The molecular structure of the title compound is shown in Fig. 1. As shown in figure 1, the bond length between the O1 with C7 is nearly to the bond length between the O1 with C8, they are 1.369 (2) Å and 1.364 (3) Å. Similarly, the distance of the bond between the C7 and N1 is 1.285 (3) Å and the distance of the bond between the C8 and N2 is 1.289 (3) Å. The bond length between N1 with N2 is 1.413 (3) Å and the bond length between N3 with C8 is 1.328 (3) Å. In the crystal structure, the C7—N1—N2 and C8—N2—N1 angles are 106.97 (18) ° and 105.75 (19) °. The torsion angle between C(7)—N(1)—N(2)—C(8) is 0.2 (3) ° demonstrating the planarity of the heterocyclic moiety. Classical intermolecular N(1)—H···N(3) (3.054 Å) and N(2)—H···N(3) (2.997 Å) hydrogen bonds link the adjacent molecules into a two-dimensional structure.

Related literature top

For background to 5-phenyl-1,3,4-oxadiazol-2-amines and the synthesis of the title compound, see: Bachwani et al. (2011); Lv et al. (2010); Tang et al. (2007).

Experimental top

Benzaldehyde (0.01 mol) and ethanol (20 ml) were added to semicarbazide hydrochloride (0.011 mol) and the reaction mixture was refluxed for 2 h. Afterwards the obtained semicarbazone (0.01 mol) was dissolved in acetic acid together with bromine (0.65 ml) and the solution was stirred for 30 minutes. The resulting precipitate (0.02 mmol) was dissolved in a ethanol (3 ml) water (3 ml) mixture. The resulting solution was allowed to stand at room temperature for about two weeks days. Colourless crystals were obtained in a yield of 43%.

Structure description top

For background to 5-phenyl-1,3,4-oxadiazol-2-amines and the synthesis of the title compound, see: Bachwani et al. (2011); Lv et al. (2010); Tang et al. (2007).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. View of the title compound showing thermal ellipsoids at the 30% probability level. H atoms are omitted for clarity.
	Fig. 2. View of the title complex, showing the hydrogen bonding in the crystal structure.

5-Phenyl-1,3,4-oxadiazol-2-amine top

Crystal data top

C₈H₇N₃O	F(000) = 336
M_r = 161.17	D_x = 1.412 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.7107 Å
a = 11.194 (3) Å	Cell parameters from 656 reflections
b = 5.8990 (5) Å	θ = 3.5–26.3°
c = 15.034 (5) Å	µ = 0.10 mm⁻¹
β = 130.193 (18)°	T = 291 K
V = 758.3 (3) Å³	Prism, colourless
Z = 4	0.26 × 0.24 × 0.22 mm

Data collection top

Agilent Xcalibur Eos Gemini diffractometer	1551 independent reflections
Radiation source: Enhance (Mo) X-ray Source	877 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
Detector resolution: 16.2312 pixels mm^-1	θ_max = 26.4°, θ_min = 3.6°
ω scans	h = −13→12
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −4→7
T_min = 0.851, T_max = 1.000	l = −18→17
2912 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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.137	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.054P)²] where P = (F_o² + 2F_c²)/3
1551 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₈H₇N₃O	V = 758.3 (3) Å³
M_r = 161.17	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.194 (3) Å	µ = 0.10 mm⁻¹
b = 5.8990 (5) Å	T = 291 K
c = 15.034 (5) Å	0.26 × 0.24 × 0.22 mm
β = 130.193 (18)°

Data collection top

Agilent Xcalibur Eos Gemini diffractometer	1551 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	877 reflections with I > 2σ(I)
T_min = 0.851, T_max = 1.000	R_int = 0.040
2912 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.137	H-atom parameters constrained
S = 1.02	Δρ_max = 0.17 e Å⁻³
1551 reflections	Δρ_min = −0.15 e Å⁻³
109 parameters

Special details top

Experimental. CrysAlisPro, Agilent Technologies, Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET) (compiled Oct 27 2011,15:02:11) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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	−0.15541 (17)	0.6145 (2)	0.02276 (13)	0.0495 (5)
N1	−0.2177 (2)	0.2637 (3)	−0.04164 (18)	0.0617 (7)
N2	−0.3435 (2)	0.4062 (3)	−0.12624 (17)	0.0594 (7)
N3	−0.3795 (2)	0.8025 (3)	−0.12550 (17)	0.0622 (7)
H3A	−0.4628	0.8128	−0.2012	0.075*
H3B	−0.3161	0.9341	−0.0922	0.075*
C1	0.1056 (3)	0.1191 (4)	0.1680 (2)	0.0624 (8)
H1	0.0506	0.0125	0.1084	0.075*
C2	0.2512 (3)	0.0674 (4)	0.2723 (3)	0.0683 (9)
H2	0.2942	−0.0749	0.2825	0.082*
C3	0.3329 (3)	0.2221 (5)	0.3606 (2)	0.0714 (9)
H3	0.4308	0.1850	0.4303	0.086*
C4	0.2704 (3)	0.4311 (5)	0.3463 (2)	0.0720 (9)
H4	0.3259	0.5365	0.4065	0.086*
C5	0.1250 (3)	0.4866 (4)	0.2428 (2)	0.0578 (8)
H5	0.0828	0.6292	0.2336	0.069*
C6	0.0423 (3)	0.3320 (4)	0.1532 (2)	0.0457 (6)
C7	−0.1115 (3)	0.3912 (4)	0.0434 (2)	0.0450 (6)
C8	−0.3014 (3)	0.6083 (4)	−0.0839 (2)	0.0477 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0394 (10)	0.0366 (9)	0.0426 (9)	−0.0023 (7)	0.0129 (8)	−0.0024 (7)
N1	0.0457 (13)	0.0409 (11)	0.0551 (13)	−0.0007 (10)	0.0129 (11)	−0.0039 (10)
N2	0.0413 (12)	0.0417 (12)	0.0529 (13)	−0.0017 (10)	0.0112 (11)	−0.0038 (10)
N3	0.0462 (13)	0.0409 (12)	0.0514 (13)	0.0025 (10)	0.0097 (11)	0.0036 (10)
C1	0.0511 (17)	0.0476 (15)	0.0623 (17)	−0.0008 (13)	0.0247 (15)	−0.0049 (13)
C2	0.0508 (17)	0.0531 (16)	0.0730 (19)	0.0128 (14)	0.0273 (16)	0.0128 (14)
C3	0.0463 (16)	0.075 (2)	0.0537 (18)	0.0022 (15)	0.0143 (14)	0.0111 (15)
C4	0.0611 (19)	0.067 (2)	0.0468 (16)	−0.0069 (16)	0.0164 (15)	−0.0053 (14)
C5	0.0522 (17)	0.0457 (14)	0.0529 (16)	0.0005 (12)	0.0236 (15)	−0.0019 (12)
C6	0.0391 (14)	0.0415 (13)	0.0467 (14)	0.0012 (11)	0.0232 (12)	0.0037 (11)
C7	0.0404 (14)	0.0330 (12)	0.0487 (14)	−0.0002 (11)	0.0229 (12)	0.0003 (11)
C8	0.0365 (14)	0.0447 (14)	0.0422 (13)	−0.0044 (12)	0.0164 (12)	−0.0025 (12)

Geometric parameters (Å, º) top

O1—C7	1.369 (2)	C1—C6	1.387 (3)
O1—C8	1.364 (3)	C2—H2	0.9300
N1—N2	1.413 (3)	C2—C3	1.366 (4)
N1—C7	1.285 (3)	C3—H3	0.9300
N2—C8	1.289 (3)	C3—C4	1.364 (4)
N3—H3A	0.8936	C4—H4	0.9300
N3—H3B	0.9476	C4—C5	1.382 (3)
N3—C8	1.328 (3)	C5—H5	0.9300
C1—H1	0.9300	C5—C6	1.376 (3)
C1—C2	1.382 (3)	C6—C7	1.464 (3)

C8—O1—C7	102.89 (16)	C3—C4—H4	119.9
C7—N1—N2	106.97 (18)	C3—C4—C5	120.2 (2)
C8—N2—N1	105.75 (18)	C5—C4—H4	119.9
H3A—N3—H3B	115.3	C4—C5—H5	119.8
C8—N3—H3A	119.2	C6—C5—C4	120.3 (2)
C8—N3—H3B	114.6	C6—C5—H5	119.8
C2—C1—H1	120.4	C1—C6—C7	120.3 (2)
C2—C1—C6	119.2 (2)	C5—C6—C1	119.5 (2)
C6—C1—H1	120.4	C5—C6—C7	120.3 (2)
C1—C2—H2	119.5	O1—C7—C6	118.30 (19)
C3—C2—C1	121.0 (2)	N1—C7—O1	111.77 (19)
C3—C2—H2	119.5	N1—C7—C6	129.9 (2)
C2—C3—H3	120.1	N2—C8—O1	112.6 (2)
C4—C3—C2	119.8 (3)	N2—C8—N3	130.2 (2)
C4—C3—H3	120.1	N3—C8—O1	117.12 (19)

N1—N2—C8—O1	0.7 (3)	C4—C5—C6—C1	0.5 (4)
N1—N2—C8—N3	−176.1 (3)	C4—C5—C6—C7	−179.8 (2)
N2—N1—C7—O1	−0.4 (3)	C5—C6—C7—O1	13.9 (3)
N2—N1—C7—C6	−180.0 (2)	C5—C6—C7—N1	−166.5 (3)
C1—C2—C3—C4	0.1 (5)	C6—C1—C2—C3	0.3 (4)
C1—C6—C7—O1	−166.5 (2)	C7—O1—C8—N2	−0.9 (3)
C1—C6—C7—N1	13.1 (4)	C7—O1—C8—N3	176.4 (2)
C2—C1—C6—C5	−0.5 (4)	C7—N1—N2—C8	−0.2 (3)
C2—C1—C6—C7	179.8 (3)	C8—O1—C7—N1	0.8 (3)
C2—C3—C4—C5	−0.1 (5)	C8—O1—C7—C6	−179.6 (2)
C3—C4—C5—C6	−0.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N2ⁱ	0.89	2.12	2.997 (3)	169
N3—H3B···N1ⁱⁱ	0.95	2.12	3.054 (3)	168

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

Experimental details

Crystal data
Chemical formula	C₈H₇N₃O
M_r	161.17
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	11.194 (3), 5.8990 (5), 15.034 (5)
β (°)	130.193 (18)
V (Å³)	758.3 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.26 × 0.24 × 0.22

Data collection
Diffractometer	Agilent Xcalibur Eos Gemini
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.851, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	2912, 1551, 877
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.137, 1.02
No. of reflections	1551
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.15

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N2ⁱ	0.89	2.12	2.997 (3)	168.7
N3—H3B···N1ⁱⁱ	0.95	2.12	3.054 (3)	168.4

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

Acknowledgements

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

References

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