3-(m-Tol­yloxy)phthalonitrile

Xian-Fu Zhang; Dandan Jia; Qiang Liu; Aijun Song

doi:10.1107/S1600536807068225

. 2008 Jan 9;64(Pt 2):o401. doi: 10.1107/S1600536807068225

3-(m-Tolyloxy)phthalonitrile

Xian-Fu Zhang ^a,^*, Dandan Jia ^a, Qiang Liu ^b, Aijun Song ^a

PMCID: PMC2960461 PMID: 21201429

Abstract

In the molecule of the title compound, C₁₅H₁₀N₂O, the dihedral angle between the two benzene rings is 65.49 (9)°.

Related literature

For the synthesis of a related compound, see: Sharman & van Lier (2003 ▶). For the crystal structure of an isomer of the title compound see: Ocak Ískeleli (2007 ▶). For related literature, see: Atalay et al. (2003 ▶, 2004 ▶); Cave et al. (1986 ▶); Koysal et al. (2004 ▶); Leznoff & Lever (1989–1996 ▶); McKeown (1998 ▶); Ocak et al. (2003 ▶).

Experimental

Crystal data

C₁₅H₁₀N₂O
M _r = 234.25
Orthorhombic,
a = 25.514 (3) Å
b = 14.6064 (18) Å
c = 6.6109 (6) Å
V = 2463.7 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 295 (2) K
0.6 × 0.5 × 0.3 mm

Data collection

Bruker P4 diffractometer
Absorption correction: none
3094 measured reflections
2254 independent reflections
1372 reflections with I > 2σ(I)
R _int = 0.041
3 standard reflections every 97 reflections intensity decay: none

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.109
S = 1.04
2254 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: XSCANS (Bruker, 1997 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Bruker, 1997 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807068225/rk2070sup1.cif

e-64-0o401-sup1.cif^{(14.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807068225/rk2070Isup2.hkl

e-64-0o401-Isup2.hkl^{(110.9KB, hkl)}

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

Acknowledgments

The authors thank the HBUST for financial support.

supplementary crystallographic information

Comment

Phthalonitriles are among the most important precusors of phthalocyanine materials (Leznoff, 1989–1986). Mono phenyloxyphthalonitriles have been used for preparing symetrical phthalocyanines and subphthalocyanines which have been applied in many areas, such as laser printing, photocopying, optical data storage, catalyst etc. (McKeown, 1998). The 3–(m–tolyloxy)phthalonitrile (I), which contains an electron–donating moiety and a strong electron–accepting fragment linked by an oxygen atom, is also a good model suitable for the study of photoinduced electron transfer between the short linked donor and acceptor. The rate of such electron transfer process and the lifetime of the resultant charge separation state, however, are highly dependent on the relative orientation between the donor and the acceptor (Cave, 1986). The crystal structure of the title compound, (I), can therefore provide very helpful information for it.

The triple bond lengths between C and N, both 1.140 (3)Å and 1.133 (3) Å, as shown in Fig. 1, agree with literature values (Ocak et al., 2003). The geometry around the O atoms is in good agreement with the literature (Atalay et al., 2003, 2004; Koysal et al., 2004). The dihedral angle between the two aromatic rings planes is 65.49 (9)°. The crystal structure of compound involves extensive intermolecular π–π interactions, as can be seen from the packing diagram (Fig. 2). Phthalonitrile moieties are packed shoulder by shoulder along the a–axis which is stablized by the intermolecular dipole–dipole interactions and partial face–to–face π–π overlaping along the c–axis, while the toluene moieties are arranged by face to face π–π stacking along the b–axis and shouler by shoulder along the c–axis within the distance 4.15–4.20 Å. It is worth noting that the structure of the isomeric 4–(m–tolyloxy)phthalonitrile is monoclinic (Ocak Ískeleli, 2007) while the title compound report herein is orthorhombic.

Experimental

The m–cresol (1.56 g, 14.4 mmol) and 3–nitrophthalonitrile (1.60 g, 9.3 mmol) were dissolved in dry DMF (30 ml) with stirring under N₂. Dry fine–powdered potassium carbonate (2.5 g, 18.1 mmol) was added in portions evenly every 10 min. The reaction mixture was stirred for 48 h at room temperature and poured into iced water (150 g). The product was filtered off and washed with (10% w/w) NaOH solution and water until the filtrate was neutral. Recrystallization from ethanol gave a white product (yield 1.2 g, 55%). Single crystals were obtained from absolute ethanol at room temperature via slow evaporation (m.p. 374–375 K). IR data (ν_max/cm^-1): 3086 (Ar—H), 2980–2950 (CH₃), 2229 (CN). ¹H NMR data (p.p.m.): 2.34 (s,3H), 7.00–7.05 (d, 1H), 7.07 (s, 1H), 7.12–7.17 (d, 1H), 7.24–7.29 (dd, 1H), 7.35–7.42 (t, 1H), 7.81–7.84 (d, 1H), 7.84–7.85 (d, 1H).