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ISSN: 2056-9890

5-(5′-Fluoro-2′-meth­­oxy­bi­phenyl-3-yl)-1,3,4-oxa­diazol-2-amine

aDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysore 570 006, India, bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri, Mangalore 574 199, India, and cPost-Graduate Department of Physics & Electronics, University of Jammu, Jammu Tawi 180 006, India
*Correspondence e-mail: dr@physics.uni-mysore.ac.in

(Received 24 October 2013; accepted 13 November 2013; online 20 November 2013)

In the title compound, C15H12FN3O2, the dihedral angles between the central benzene ring and the pendant benzene and oxa­diazole rings are 45.05 (13) and 15.60 (14)°, respectively. The C atom of the meth­oxy group is roughly coplanar with its attached ring [displacement = 0.178 (4) Å]. In the crystal, N—H⋯N hydrogen bonds link the mol­ecules into [010] chains. Weak C—H⋯π inter­actions are also observed.

Related literature

For background to the title compound, see: Ainsworth (1965[Ainsworth, C. (1965). J. Am. Chem. Soc. 87, 5800-5803.]); Paik et al. (2002[Paik, K. L., Baek, N. S., Kim, H. K., Lee, J. H. & Lee, Y. (2002). Macromolecules, 35, 6782-6791.]); Kulkarni et al. (2004[Kulkarni, A. P., Tonzola, C. J., Babel, A. & Jenekhe, S. A. (2004). Chem. Mater. 16, 4556-4573.]). For a related structure, see: Zheng et al. (2012[Zheng, J., Li, W., Song, M. & Xu, Y. (2012). Acta Cryst. E68, o1668.]).

[Scheme 1]

Experimental

Crystal data
  • C15H12FN3O2

  • Mr = 285.28

  • Monoclinic, P 21 /c

  • a = 12.9105 (9) Å

  • b = 6.1738 (4) Å

  • c = 16.9255 (11) Å

  • β = 90.341 (7)°

  • V = 1349.05 (16) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.11 mm−1

  • T = 293 K

  • 0.30 × 0.20 × 0.20 mm

Data collection
  • Oxford Diffraction Xcalibur Sapphire3 CCD diffractometer

  • Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010[Oxford Diffraction (2010). CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]) Tmin = 0.806, Tmax = 1.000

  • 5027 measured reflections

  • 2650 independent reflections

  • 1382 reflections with I > 2σ(I)

  • Rint = 0.048

Refinement
  • R[F2 > 2σ(F2)] = 0.054

  • wR(F2) = 0.135

  • S = 1.01

  • 2650 reflections

  • 191 parameters

  • H-atom parameters constrained

  • Δρmax = 0.18 e Å−3

  • Δρmin = −0.18 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

Cg3 is the centroid of the C13–C18 ring.

D—H⋯A D—H H⋯A DA D—H⋯A
N6—H6A⋯N3i 0.86 2.13 2.972 (3) 166
N6—H6B⋯N4ii 0.86 2.29 3.118 (3) 161
C17—H17⋯Cg3iii 0.93 2.72 3.53 146
Symmetry codes: (i) [-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]; (ii) x, y+1, z; (iii) [-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}].

Data collection: CrysAlis PRO (Oxford Diffraction, 2010[Oxford Diffraction (2010). CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]); software used to prepare material for publication: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Comment top

The title compound, C15H12FN3O2, a derivative of 1,3,4 oxadiazole (Ainsworth, 1965), has a wide variety of uses, particularly as a bioactive compound in medicine and agriculture, as a dye stuff, and used in UV absorbing and fluorescent materials, heat resistant polymers and scintillators (Paik et al., 2002; Kulkarni et al., 2004). As part of our studies in this area, we now report the structure of the title compound.

The bond distances in the title compound are comparable to the closely related structure 5-(4-Methylphenyl)-1,3,4-oxadiazol-2-amine (Zheng et al., 2012). The oxadiazole ring A makes dihedral angles of 15.64 (9)° and 55.84 (1)° respectively, with the phenyl rings B and C. The dihedral angle between the phenyl ring B and ring C is 45.19 (1)°. Classical N6—H6A···N3 and N6—H6B···N4 hydrogen bonds link the adjacent molecules into [010] chains. Weak C—H···π interactions are also observed.

Related literature top

For background to the title compound, see: Ainsworth (1965); Paik et al. (2002); Kulkarni et al. (2004). For a related structure, see: Zheng et al. (2012).

Experimental top

To a solution of 5'-fluoro-2'-methoxybiphenyl-3-carbohydrazide (3.84 mmol)in 1,4-dioxane (10 ml) cyanogen bromide (3.84 mmol) was added, followed by a solution of sodium bicarbonate (3.84 mmol) in water (10 ml). The resulting mixture was stirred at room temperature for 2 h. The reaction mixture was taken in ethyl acetate (100 ml), washed with water (20 ml) followed by saturated sodium chloride solution (20 ml) and dried over sodium sulfate. The resulting solution was concentrated and purified by column chromatography [30–40% ethyl acetate in petroleum ether] to afford the title compound (M.P. 223–226°C).

Refinement top

The H atoms were positioned geometrically and were refined as riding on their parent C and N atoms, with C—H distances of 0.88–0.95 Å, N—H distance of 0.86 Å and with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); 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, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. ORTEP view of the molecule with displacement ellipsoids drawn at the 40% probability level.
[Figure 2] Fig. 2. The packing arrangement of molecules viewed along the a axis.
5-(5'-Fluoro-2'-methoxybiphenyl-3-yl)-1,3,4-oxadiazol-2-amine top
Crystal data top
C15H12FN3O2F(000) = 592
Mr = 285.28Dx = 1.405 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1316 reflections
a = 12.9105 (9) Åθ = 4.1–28.0°
b = 6.1738 (4) ŵ = 0.11 mm1
c = 16.9255 (11) ÅT = 293 K
β = 90.341 (7)°Block, colourless
V = 1349.05 (16) Å30.30 × 0.20 × 0.20 mm
Z = 4
Data collection top
Oxford Diffraction Xcalibur Sapphire3 CCD
diffractometer
2650 independent reflections
Radiation source: fine-focus sealed tube1382 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.048
Detector resolution: 16.1049 pixels mm-1θmax = 26.0°, θmin = 3.5°
ω scansh = 815
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2010)
k = 74
Tmin = 0.806, Tmax = 1.000l = 1720
5027 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.135H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0316P)2]
where P = (Fo2 + 2Fc2)/3
2650 reflections(Δ/σ)max = 0.001
191 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C15H12FN3O2V = 1349.05 (16) Å3
Mr = 285.28Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.9105 (9) ŵ = 0.11 mm1
b = 6.1738 (4) ÅT = 293 K
c = 16.9255 (11) Å0.30 × 0.20 × 0.20 mm
β = 90.341 (7)°
Data collection top
Oxford Diffraction Xcalibur Sapphire3 CCD
diffractometer
2650 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2010)
1382 reflections with I > 2σ(I)
Tmin = 0.806, Tmax = 1.000Rint = 0.048
5027 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0540 restraints
wR(F2) = 0.135H-atom parameters constrained
S = 1.01Δρmax = 0.18 e Å3
2650 reflectionsΔρmin = 0.18 e Å3
191 parameters
Special details top

Experimental. CrysAlis PRO, Agilent Technologies, Version 1.171.36.28 (release 01–02-2013 CrysAlis171. NET) (compiled Feb 1 2013,16:14:44) 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
xyzUiso*/Ueq
O10.89022 (14)0.0443 (3)0.56943 (11)0.0411 (5)
C20.9336 (2)0.0508 (4)0.64301 (15)0.0357 (7)
N30.95451 (18)0.1405 (3)0.67077 (13)0.0435 (6)
N40.92173 (18)0.2865 (3)0.61121 (14)0.0440 (6)
C50.8848 (2)0.1745 (4)0.55387 (16)0.0361 (7)
N60.94739 (18)0.2434 (3)0.67575 (14)0.0522 (7)
H6A0.97380.25340.72240.063*
H6B0.92990.35860.65040.063*
C70.8429 (2)0.2443 (4)0.47839 (16)0.0394 (7)
C80.8602 (2)0.4578 (4)0.45329 (17)0.0454 (8)
H80.89590.55490.48540.054*
C90.8235 (2)0.5213 (4)0.38043 (18)0.0480 (8)
H90.83630.66150.36280.058*
C100.7682 (2)0.3804 (4)0.33300 (17)0.0466 (8)
H100.74390.42680.28400.056*
C110.7485 (2)0.1694 (4)0.35787 (16)0.0388 (7)
C120.7856 (2)0.1043 (4)0.43139 (16)0.0405 (7)
H120.77180.03520.44930.049*
C130.6929 (2)0.0182 (4)0.30377 (17)0.0411 (7)
C140.7207 (2)0.0126 (5)0.22425 (18)0.0506 (8)
H140.77310.10270.20590.061*
C150.6709 (2)0.1257 (5)0.17307 (18)0.0524 (9)
F150.70017 (16)0.1262 (3)0.09598 (11)0.0846 (7)
C160.5951 (3)0.2629 (5)0.19672 (19)0.0531 (9)
H160.56370.35740.16110.064*
C170.5654 (2)0.2585 (5)0.27592 (17)0.0517 (9)
H170.51220.34800.29320.062*
C180.6147 (2)0.1221 (4)0.32879 (17)0.0441 (8)
O190.58667 (17)0.1049 (3)0.40644 (12)0.0614 (7)
C200.5209 (3)0.2668 (6)0.4382 (2)0.0936 (14)
H20A0.55060.40710.42900.140*
H20B0.51340.24410.49400.140*
H20C0.45410.25880.41300.140*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0593 (13)0.0289 (9)0.0351 (11)0.0003 (9)0.0166 (10)0.0016 (9)
C20.0461 (17)0.0308 (14)0.0301 (16)0.0027 (12)0.0122 (14)0.0017 (13)
N30.0615 (17)0.0327 (12)0.0360 (15)0.0038 (11)0.0156 (13)0.0011 (12)
N40.0553 (16)0.0352 (13)0.0412 (15)0.0026 (11)0.0122 (14)0.0020 (11)
C50.0457 (17)0.0279 (14)0.0345 (17)0.0006 (12)0.0035 (14)0.0008 (13)
N60.0814 (19)0.0304 (12)0.0444 (16)0.0014 (12)0.0292 (15)0.0041 (12)
C70.0481 (17)0.0339 (15)0.0362 (18)0.0033 (13)0.0061 (15)0.0014 (14)
C80.0564 (19)0.0326 (14)0.0471 (19)0.0002 (14)0.0083 (16)0.0077 (14)
C90.061 (2)0.0363 (15)0.047 (2)0.0004 (14)0.0050 (17)0.0040 (15)
C100.060 (2)0.0403 (17)0.0391 (18)0.0048 (14)0.0127 (16)0.0072 (14)
C110.0448 (18)0.0384 (15)0.0331 (17)0.0026 (13)0.0104 (15)0.0035 (13)
C120.0461 (17)0.0359 (15)0.0393 (18)0.0002 (13)0.0103 (15)0.0027 (14)
C130.0440 (18)0.0432 (17)0.0359 (18)0.0017 (13)0.0122 (15)0.0060 (14)
C140.0465 (19)0.058 (2)0.047 (2)0.0030 (15)0.0033 (16)0.0008 (17)
C150.053 (2)0.066 (2)0.0376 (19)0.0013 (17)0.0043 (17)0.0113 (17)
F150.0898 (16)0.1211 (17)0.0430 (12)0.0135 (13)0.0050 (12)0.0220 (12)
C160.063 (2)0.052 (2)0.044 (2)0.0017 (17)0.0132 (18)0.0107 (17)
C170.056 (2)0.0550 (19)0.044 (2)0.0098 (16)0.0097 (17)0.0001 (17)
C180.0494 (19)0.0460 (17)0.0367 (18)0.0024 (14)0.0126 (16)0.0019 (15)
O190.0755 (17)0.0654 (15)0.0433 (14)0.0219 (12)0.0017 (13)0.0034 (12)
C200.131 (4)0.092 (3)0.059 (3)0.044 (3)0.005 (3)0.012 (2)
Geometric parameters (Å, º) top
O1—C21.363 (3)C11—C131.490 (4)
O1—C51.378 (3)C12—H120.9300
C2—N31.299 (3)C13—C141.396 (4)
C2—N61.323 (3)C13—C181.398 (4)
N3—N41.415 (3)C14—C151.374 (4)
N4—C51.281 (3)C14—H140.9300
C5—C71.450 (3)C15—C161.356 (4)
N6—H6A0.8600C15—F151.361 (3)
N6—H6B0.8600C16—C171.397 (4)
C7—C121.386 (3)C16—H160.9300
C7—C81.403 (3)C17—C181.381 (4)
C8—C91.375 (4)C17—H170.9300
C8—H80.9300C18—O191.369 (3)
C9—C101.380 (4)O19—C201.420 (3)
C9—H90.9300C20—H20A0.9600
C10—C111.393 (3)C20—H20B0.9600
C10—H100.9300C20—H20C0.9600
C11—C121.390 (3)
C2—O1—C5102.9 (2)C7—C12—H12119.6
N3—C2—N6129.7 (3)C11—C12—H12119.6
N3—C2—O1112.8 (2)C14—C13—C18117.9 (3)
N6—C2—O1117.5 (2)C14—C13—C11118.8 (3)
C2—N3—N4105.1 (2)C18—C13—C11123.3 (3)
C5—N4—N3107.7 (2)C15—C14—C13120.1 (3)
N4—C5—O1111.5 (2)C15—C14—H14120.0
N4—C5—C7130.0 (2)C13—C14—H14120.0
O1—C5—C7118.6 (2)C16—C15—F15119.1 (3)
C2—N6—H6A120.0C16—C15—C14122.6 (3)
C2—N6—H6B120.0F15—C15—C14118.3 (3)
H6A—N6—H6B120.0C15—C16—C17118.3 (3)
C12—C7—C8119.9 (3)C15—C16—H16120.9
C12—C7—C5121.0 (2)C17—C16—H16120.9
C8—C7—C5119.1 (2)C18—C17—C16120.4 (3)
C9—C8—C7119.0 (3)C18—C17—H17119.8
C9—C8—H8120.5C16—C17—H17119.8
C7—C8—H8120.5O19—C18—C17123.1 (3)
C8—C9—C10121.1 (3)O19—C18—C13116.0 (3)
C8—C9—H9119.5C17—C18—C13120.8 (3)
C10—C9—H9119.5C18—O19—C20118.1 (3)
C9—C10—C11120.6 (3)O19—C20—H20A109.5
C9—C10—H10119.7O19—C20—H20B109.5
C11—C10—H10119.7H20A—C20—H20B109.5
C12—C11—C10118.6 (3)O19—C20—H20C109.5
C12—C11—C13122.1 (2)H20A—C20—H20C109.5
C10—C11—C13119.3 (2)H20B—C20—H20C109.5
C7—C12—C11120.9 (2)
C5—O1—C2—N30.6 (3)C10—C11—C12—C71.3 (4)
C5—O1—C2—N6178.7 (2)C13—C11—C12—C7175.8 (3)
N6—C2—N3—N4178.8 (3)C12—C11—C13—C14133.5 (3)
O1—C2—N3—N40.4 (3)C10—C11—C13—C1443.7 (4)
C2—N3—N4—C50.0 (3)C12—C11—C13—C1845.5 (4)
N3—N4—C5—O10.4 (3)C10—C11—C13—C18137.3 (3)
N3—N4—C5—C7178.7 (3)C18—C13—C14—C150.8 (4)
C2—O1—C5—N40.6 (3)C11—C13—C14—C15179.8 (2)
C2—O1—C5—C7179.2 (2)C13—C14—C15—C161.0 (5)
N4—C5—C7—C12165.3 (3)C13—C14—C15—F15179.9 (3)
O1—C5—C7—C1216.4 (4)F15—C15—C16—C17179.4 (3)
N4—C5—C7—C814.2 (5)C14—C15—C16—C171.6 (5)
O1—C5—C7—C8164.1 (2)C15—C16—C17—C181.9 (5)
C12—C7—C8—C92.8 (4)C16—C17—C18—O19177.6 (3)
C5—C7—C8—C9177.7 (3)C16—C17—C18—C131.8 (5)
C7—C8—C9—C101.6 (4)C14—C13—C18—O19177.3 (3)
C8—C9—C10—C110.3 (4)C11—C13—C18—O193.7 (4)
C9—C10—C11—C120.1 (4)C14—C13—C18—C171.2 (4)
C9—C10—C11—C13177.2 (3)C11—C13—C18—C17179.8 (3)
C8—C7—C12—C112.7 (4)C17—C18—O19—C2014.6 (4)
C5—C7—C12—C11177.8 (3)C13—C18—O19—C20169.5 (3)
Hydrogen-bond geometry (Å, º) top
Cg3 is the centroid of the C13–C18 ring.
D—H···AD—HH···AD···AD—H···A
N6—H6A···N3i0.862.132.972 (3)166
N6—H6B···N4ii0.862.293.118 (3)161
C17—H17···Cg3iii0.932.723.53146
Symmetry codes: (i) x+2, y+1/2, z+3/2; (ii) x, y+1, z; (iii) x+1, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
Cg3 is the centroid of the C13–C18 ring.
D—H···AD—HH···AD···AD—H···A
N6—H6A···N3i0.862.1312.972 (3)166
N6—H6B···N4ii0.862.2923.118 (3)161
C17—H17···Cg3iii0.932.723.53146
Symmetry codes: (i) x+2, y+1/2, z+3/2; (ii) x, y+1, z; (iii) x+1, y+1/2, z+1/2.
 

Acknowledgements

RK acknowledges the DST, New Delhi, for the single-crystal X-ray diffractometer sanctioned as a National Facility under project No. SR/S2/CMP-47/2003. MKU thanks the DST, New Delhi, for the award of an INSPIRE Fellowship. VKG is thankful to the University of Jammu, Jammu, India, for financial support. DR acknowledges the UGC, New Delhi, for financial support under the Major Research Project- scheme [No. F.41-882/2012 (SR)].

References

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