2-Phenyl-5-(p-tol­yl)-1,3,4-oxadiazole

David B Cordes; Guoxiong Hua; Alexandra M Z Slawin; J Derek Woollins

doi:10.1107/S1600536811023579

. 2011 Jun 22;67(Pt 7):o1757. doi: 10.1107/S1600536811023579

2-Phenyl-5-(p-tolyl)-1,3,4-oxadiazole

David B Cordes ^a, Guoxiong Hua ^a, Alexandra M Z Slawin ^a,^*, J Derek Woollins ^a

PMCID: PMC3152068 PMID: 21837139

Abstract

The title compound, C₁₅H₁₂N₂O, adopts the expected near-planar geometry, the phenyl and tolyl rings being inclined relative to the oxadiazole ring by 3.8 (3) and 8.3 (2)°, respectively. This allows adjacent molecules to pack in a parallel fashion and form stacking along [010] via π–π interactions [centroid–centroid distances = 3.629 (2) and 3.723 (2) Å]. Further intermolecular interactions include C—H⋯π interactions and weak C—H⋯N hydrogen bonds, giving rise to a crossed herringbone packing motif.

Related literature

For synthesis of the starting material N′-benzoyl-4-methylbenzohydrazide, see: Hua et al. (2009 ▶). For a review of synthetic routes to the title compound, see: Weaver (2004 ▶). For related structures, see: Kuznetsov et al. (1998 ▶); Franco et al. (2003 ▶); Reck et al. (2003 ▶).

Experimental

Crystal data

C₁₅H₁₂N₂O
M _r = 236.27
Monoclinic,
a = 19.733 (5) Å
b = 5.1441 (12) Å
c = 12.436 (3) Å
β = 107.477 (6)°
V = 1204.1 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 93 K
0.20 × 0.04 × 0.02 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2010 ▶) T _min = 0.984, T _max = 0.998
7407 measured reflections
2256 independent reflections
1293 reflections with I > 2σ(I)
R _int = 0.207

Refinement

R[F ² > 2σ(F ²)] = 0.109
wR(F ²) = 0.307
S = 1.02
2256 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.85 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Data collection: CrystalClear (Rigaku, 2010 ▶); 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 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811023579/su2281sup1.cif

e-67-o1757-sup1.cif^{(21.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811023579/su2281Isup2.hkl

e-67-o1757-Isup2.hkl^{(110.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811023579/su2281Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 and Cg2 are the centroids of the C3–C8 and C10–C15 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯N2ⁱ	0.95	2.61	3.322 (4)	132
C9—H9B⋯Cg1ⁱⁱ	0.98	2.80	3.731 (4)	158
C14—H14⋯Cg2ⁱⁱⁱ	0.95	2.99	3.783 (4)	141

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The authors are grateful to the University of St. Andrews and the Engineering and Physical Science Research Council (EPSRC, UK) for financial support.

supplementary crystallographic information

Comment

The title compound (Fig. 1), previously prepared by a number of different routes (Weaver, 2004), has been prepared by a new method, reacting Woollins' reagent with N'-benzoyl-4-methylbenzohydrazide (Hua et al., 2009). It adopts an offset π-stacked packing motif, similar to those seen in related structures (Kuznetsov et al., 1998, Franco et al., 2003, and Reck et al., 2003), the oxadiazole ring interacting with both the tolyl (x, 1 + y, z) and the phenyl (x, -1 + y, z) rings of adjacent molecules [centroid-centroid distances of 3.629 (2) and 3.723 (2) Å, respectively]. As a result of this arrangement, one of the tolyl methyl H atoms forms a C—H···π interaction with the adjacent tolyl π-system (Table 1). The stacks run along the [0 1 0] direction, and form herringbone sheets in the (0 0 1) plane (Fig. 2), via further C—H···π interactions (Table 1). These sheets resemble the herringbone packing motif seen previously in the structures of 2,5-diphenyl-1,3,4-oxadiazole (Kuznetsov et al., 1998, and Franco et al., 2003). However, adjacent sheets do not align, and instead are offset, forming a crossed herringbone pattern (Fig. 3), interacting via C—H···N hydrogen bonds (Table 1).

Footnote to Table 1: Cg1 = centroid of ring (C3-C8); Cg2 = centroid of ring (C10-C15).

Experimental

A red suspension of N'-benzoyl-4-methylbenzohydrazide (0.25 g, 1.0 mmol, Hua et al., 2009) and Woollins' reagent (0.54 g, 1.0 mmol) in 20 ml of dry toluene was refluxed for 7 h. Following cooling to room temperature and removal of the solvent in vacuuo the residue was purified by silica gel column chromatography (1: 9 ethyl acetate/dichloromethane eluent) to give 2-phenyl-5-p-tolyl-1,3,4-selenadiazole as a dark yellow solid in good yield (0.270 g, 90%). The title compound was formed from this by air oxidation during the growth of X-ray quality crystals from the diffusion of hexane into a dichloromethane solution of 2-phenyl-5-p-tolyl-1,3,4-selenadiazole.