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

Naveen, S.; Naveen, P.; Zabiulla; Manjunath, H.R.; Lokanath, N.K.; Khanum, S.A.; Warad, I.

doi:10.1107/S2414314616018964

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 12| December 2016| x161896

https://doi.org/10.1107/S2414314616018964

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

S. Naveen,^a P. Naveen,^b Zabiulla,^b H. R. Manjunath,^c N. K. Lokanath,^d Shaukath Ara Khanum ^b and Ismail Warad ^e ^*

^aInstitution of Excellence, University of Mysore, Manasagangotri, Mysuru 570 006, India, ^bDepartment of Chemistry, Yuvaraja's College, University of Mysore, Mysuru 570 005, India, ^cDepartment of Physics, Acharya Institute of Technology, Soldevanahalli, Bengaluru 562 090, India, ^dDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysuru 570 006, India, and ^eDepartment of Chemistry, Science College, An-Najah National University, PO Box 7, Nablus, West Bank, Palestinian Territories
^*Correspondence e-mail: khalil.i@najah.edu

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 26 November 2016; accepted 27 November 2016; online 9 December 2016)

In the title compound, C₉H₉N₃O₂, the dihedral angle between the aromatic rings is 8.64 (10)°. The crystal structure features inversion-related dimers linked by pairs of N—H⋯N hydrogen bonds, generating R₂²(8) loops. A further N—H⋯N hydrogen bond links the dimers into (100) sheets.

Keywords: crystal structure; N—H⋯N hydrogen bonds; 1,3,4-oxadiazole derivative.

CCDC reference: 1520838

Structure description

Derivatives of 1,3,4-oxadiazole exhibit a broad spectrum of pharmaceutical applications such as antibacterial, anticonvulsant (Taha et al., 2016 ), anti-inflammatory, anticancer, analgesic and fungicidal. As a part of our ongoing research on such molecules (Yasser et al., 2016 ) we report herein on the synthesis and crystal structure of the title compound (Fig. 1).

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.

The molecule is approximately planar as indicated by the dihedral angle value of 8.64 (10)° between the aromatic rings. The methoxy group lies almost in the plane of the phenyl ring as indicated by the torsion angle value of −5.1 (3)° for C9—O2—C5—C6. The crystal structure features inversion-related dimers linked by pairs of N—H⋯N hydrogen bonds generating $[R_{2}^{2}]$ (8) loops (Table 1 and Fig. 2). A further N—H⋯N hydrogen bond links the dimers into (100) sheets.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N2ⁱ	0.86	2.09	2.924 (2)	163
N3—H3B⋯N1ⁱⁱ	0.86	2.13	2.969 (2)	164
Symmetry codes: (i) -x+2, -y+3, -z+2; (ii) $[x, -y+{\script{5\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
Inversion-related dimers linked by pairs of N—H⋯O hydrogen bonds, generating $[R_{2}^{2}]$ (8) loops. The right-hand molecule is generated by the symmetry operation 2 − x, 3 − y, 2 − z.

Synthesis and crystallization

To a solution of 1-(4-methoxybenzylidene)semicarbazide in ethanol, chloramine-T was added and refluxed. The reaction was monitored by TLC and the after completion of the reaction, the sodium chloride formed in the reaction was filtered and the filtrate was concentrated and extracted to dichloromethane. The organic layer was washed with 10% hydrochloric acid, the aqueous layer was neutralized with 10% sodium hydroxide and the white solid obtained was further purified. Colourless crystals formed after 3 days due to the slow evaporation of the solvent. Yield 84%, m.p. 246–248°C.

IR (KBr, γ/cm⁻¹): 3409–3490 (COOH), 3050 (CH), 1730 (CO of COOH), 1675 (CO of OCOCH₃). ¹H NMR (400 MHz, DMSO-d⁶): δ 3.9 (s, 3H,CH₃) 5.1 (s, 2H,NH₂), 7.1–08.1 (m, 4H, ArH), ¹³C NMR: 155.32, 150.06, 129.21, 125.43, 124.31, 54.32. LCMS (M⁺): (191). Analysis calculated for C₉H₉N₃O₂: C, 56.54; H, 4.74; N, 21.98; found: C, 56.01; H, 4.56; N, 21.68%.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₉H₉N₃O₂
M_r	191.19
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	16.2029 (9), 5.0730 (3), 11.1133 (6)
β (°)	108.096 (3)
V (Å³)	868.30 (9)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	0.90
Crystal size (mm)	0.28 × 0.26 × 0.23

Data collection
Diffractometer	Bruker X8 Proteum
Absorption correction	Multi-scan (SADABS; Bruker, 2013 )
T_min, T_max	0.788, 0.821
No. of measured, independent and observed [I > 2σ(I)] reflections	5230, 1430, 1308
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.587

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.142, 1.15
No. of reflections	1430
No. of parameters	129
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.31
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1520838

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314616018964/hb4101sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616018964/hb4101Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616018964/hb4101Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: Mercury (Macrae et al., 2008).

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

Crystal data top

C₉H₉N₃O₂	F(000) = 400
M_r = 191.19	D_x = 1.463 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 1308 reflections
a = 16.2029 (9) Å	θ = 8.0–64.8°
b = 5.0730 (3) Å	µ = 0.90 mm⁻¹
c = 11.1133 (6) Å	T = 296 K
β = 108.096 (3)°	Block, colourless
V = 868.30 (9) Å³	0.28 × 0.26 × 0.23 mm
Z = 4

Data collection top

Bruker X8 Proteum diffractometer	1430 independent reflections
Radiation source: Bruker MicroStar microfocus rotating anode	1308 reflections with I > 2σ(I)
Helios multilayer optics monochromator	R_int = 0.042
Detector resolution: 18.4 pixels mm^-1	θ_max = 64.8°, θ_min = 8.0°
φ and ω scans	h = −18→18
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −5→5
T_min = 0.788, T_max = 0.821	l = −12→12
5230 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)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.142	w = 1/[σ²(F_o²) + (0.0816P)² + 0.4652P] where P = (F_o² + 2F_c²)/3
S = 1.15	(Δ/σ)_max < 0.001
1430 reflections	Δρ_max = 0.32 e Å⁻³
129 parameters	Δρ_min = −0.31 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: 0.0050 (13)

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > 2sigma(F²) is used only for calculating -R-factor-obs 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.

H atoms were fixed geometrically (C—H = 0.93–0.96 Å) and allowed to ride on their parent atoms with U_iso(H) = 1.5U_eq(C) for the methyl H atoms and = 1.2U_eq(C) for the others.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.84349 (8)	1.0817 (3)	0.83232 (11)	0.0197 (4)
O2	0.58911 (9)	0.4726 (3)	0.65817 (13)	0.0230 (4)
N1	0.88643 (10)	1.0232 (3)	1.03973 (15)	0.0186 (5)
N2	0.93522 (10)	1.2299 (3)	1.01268 (14)	0.0190 (5)
N3	0.93358 (12)	1.4284 (4)	0.81916 (15)	0.0264 (6)
C1	0.90787 (12)	1.2572 (4)	0.88958 (17)	0.0183 (6)
C2	0.83441 (12)	0.9410 (4)	0.93398 (17)	0.0164 (6)
C3	0.76937 (12)	0.7335 (4)	0.91245 (17)	0.0186 (6)
C4	0.70870 (12)	0.6920 (4)	0.79427 (17)	0.0178 (6)
C5	0.64685 (12)	0.4939 (4)	0.77827 (18)	0.0190 (6)
C6	0.64528 (13)	0.3346 (4)	0.87986 (19)	0.0217 (6)
C7	0.70707 (13)	0.3786 (4)	0.99784 (18)	0.0223 (6)
C8	0.76843 (12)	0.5742 (4)	1.01542 (18)	0.0196 (6)
C9	0.52835 (14)	0.2595 (4)	0.6353 (2)	0.0267 (7)
H3A	0.97340	1.54120	0.85420	0.0320*
H3B	0.91050	1.42720	0.73820	0.0320*
H4	0.70950	0.79660	0.72590	0.0210*
H6	0.60400	0.20200	0.86940	0.0260*
H7	0.70660	0.27310	1.06610	0.0270*
H8	0.80890	0.60070	1.09470	0.0230*
H9A	0.55920	0.09510	0.65060	0.0400*
H9B	0.49150	0.26560	0.54900	0.0400*
H9C	0.49360	0.27480	0.69090	0.0400*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0222 (7)	0.0219 (8)	0.0132 (7)	−0.0060 (6)	0.0029 (5)	−0.0003 (5)
O2	0.0206 (8)	0.0251 (8)	0.0201 (7)	−0.0072 (6)	0.0016 (6)	−0.0015 (6)
N1	0.0196 (9)	0.0198 (9)	0.0157 (8)	−0.0016 (7)	0.0045 (7)	0.0003 (6)
N2	0.0197 (9)	0.0217 (9)	0.0149 (8)	−0.0040 (7)	0.0042 (6)	0.0002 (6)
N3	0.0309 (10)	0.0317 (11)	0.0131 (8)	−0.0154 (8)	0.0017 (7)	0.0001 (7)
C1	0.0177 (10)	0.0206 (11)	0.0151 (9)	−0.0029 (8)	0.0030 (7)	−0.0026 (7)
C2	0.0186 (10)	0.0176 (10)	0.0132 (9)	0.0007 (8)	0.0053 (7)	0.0016 (7)
C3	0.0193 (10)	0.0191 (11)	0.0178 (10)	0.0023 (8)	0.0065 (8)	−0.0003 (7)
C4	0.0199 (10)	0.0183 (11)	0.0161 (9)	−0.0009 (8)	0.0069 (8)	0.0016 (8)
C5	0.0192 (10)	0.0197 (11)	0.0176 (10)	0.0028 (8)	0.0050 (8)	−0.0025 (8)
C6	0.0208 (10)	0.0202 (11)	0.0254 (11)	−0.0012 (8)	0.0089 (8)	−0.0004 (8)
C7	0.0261 (11)	0.0212 (11)	0.0215 (10)	0.0033 (8)	0.0103 (8)	0.0047 (8)
C8	0.0199 (10)	0.0216 (11)	0.0172 (10)	0.0031 (8)	0.0058 (8)	0.0007 (8)
C9	0.0256 (11)	0.0225 (12)	0.0288 (11)	−0.0055 (9)	0.0039 (9)	−0.0034 (8)

Geometric parameters (Å, º) top

O1—C1	1.369 (2)	C3—C4	1.391 (3)
O1—C2	1.382 (2)	C4—C5	1.391 (3)
O2—C5	1.376 (2)	C5—C6	1.395 (3)
O2—C9	1.431 (3)	C6—C7	1.399 (3)
N1—N2	1.401 (2)	C7—C8	1.375 (3)
N1—C2	1.285 (2)	C4—H4	0.9300
N2—C1	1.308 (2)	C6—H6	0.9300
N3—C1	1.320 (3)	C7—H7	0.9300
N3—H3A	0.8600	C8—H8	0.9300
N3—H3B	0.8600	C9—H9A	0.9600
C2—C3	1.456 (3)	C9—H9B	0.9600
C3—C8	1.405 (3)	C9—H9C	0.9600

C1—O1—C2	102.42 (14)	O2—C5—C6	124.18 (18)
C5—O2—C9	117.05 (16)	C5—C6—C7	118.59 (19)
N2—N1—C2	107.48 (15)	C6—C7—C8	121.59 (18)
N1—N2—C1	105.86 (15)	C3—C8—C7	119.32 (18)
H3A—N3—H3B	120.00	C3—C4—H4	120.00
C1—N3—H3A	120.00	C5—C4—H4	120.00
C1—N3—H3B	120.00	C5—C6—H6	121.00
O1—C1—N2	112.28 (17)	C7—C6—H6	121.00
N2—C1—N3	128.53 (19)	C6—C7—H7	119.00
O1—C1—N3	119.18 (16)	C8—C7—H7	119.00
N1—C2—C3	128.38 (17)	C3—C8—H8	120.00
O1—C2—C3	119.63 (16)	C7—C8—H8	120.00
O1—C2—N1	111.96 (17)	O2—C9—H9A	109.00
C2—C3—C4	121.87 (17)	O2—C9—H9B	109.00
C2—C3—C8	118.20 (17)	O2—C9—H9C	109.00
C4—C3—C8	119.93 (18)	H9A—C9—H9B	109.00
C3—C4—C5	120.00 (18)	H9A—C9—H9C	109.00
C4—C5—C6	120.57 (18)	H9B—C9—H9C	109.00
O2—C5—C4	115.25 (17)

C2—O1—C1—N2	−0.4 (2)	N1—C2—C3—C4	170.2 (2)
C2—O1—C1—N3	−179.58 (19)	N1—C2—C3—C8	−9.3 (3)
C1—O1—C2—N1	0.5 (2)	C2—C3—C4—C5	−179.06 (19)
C1—O1—C2—C3	178.77 (18)	C8—C3—C4—C5	0.4 (3)
C9—O2—C5—C4	175.65 (18)	C2—C3—C8—C7	179.34 (19)
C9—O2—C5—C6	−5.1 (3)	C4—C3—C8—C7	−0.1 (3)
C2—N1—N2—C1	0.2 (2)	C3—C4—C5—O2	178.97 (18)
N2—N1—C2—O1	−0.5 (2)	C3—C4—C5—C6	−0.3 (3)
N2—N1—C2—C3	−178.51 (19)	O2—C5—C6—C7	−179.19 (19)
N1—N2—C1—O1	0.2 (2)	C4—C5—C6—C7	0.1 (3)
N1—N2—C1—N3	179.2 (2)	C5—C6—C7—C8	0.2 (3)
O1—C2—C3—C4	−7.8 (3)	C6—C7—C8—C3	−0.2 (3)
O1—C2—C3—C8	172.78 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N2ⁱ	0.86	2.09	2.924 (2)	163
N3—H3B···N1ⁱⁱ	0.86	2.13	2.969 (2)	164

Symmetry codes: (i) −x+2, −y+3, −z+2; (ii) x, −y+5/2, z−1/2.

Acknowledgements

The authors thank the Institution of Excellence, Vijnana Bhavana, University of Mysore, India, for providing the single-crystal X-ray diffractometer facility. NP gratefully acknowledges the financial support of UGC MRP(S)-0551–13-14/KAMY013/UGC-SWRO. Zabiulla gratefully acknowledges the financial support provided by the Department of Science and Technology, New Delhi, under the INSPIRE–Fellowship scheme. SAK thankfully acknowledges the financial support provided by VGST, Bangalore, under the CISEE Programme.

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