3-(m-Tolyloxy)phthalonitrile

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

In the molecule of the title compound, C 15 H 10 N 2 O, the dihedral angle between the two benzene rings is 65.49 (9) .

3-(m-Tolyloxy)phthalonitrile
Xian-Fu Zhang, Dandan Jia, Qiang Liu and Aijun Song S1. Comment Phthalonitriles are among the most important precusors of phthalocyanine materials (Leznoff, 1989(Leznoff, -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(Atalay et al., , 2004Koysal 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 dipoledipole 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.

S2. 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 N 2 . 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%

S3. Refinement
All H atoms were positioned geometrically and refined using a riding model, with C-H = 0.96 Å (CH 3 ) and C-H = 0.93 Å (CH) with U iso (H) = 1.2U eq (parent C) (for CH) or U iso (H) = 1.5U eq (parent C) (for CH 3 ).   The packing of (I), viewed down the c-axis. where P = (F o 2 + 2F c 2 )/3 (Δ/σ) max < 0.001 Δρ max = 0.21 e Å −3 Δρ min = −0.23 e Å −3 Extinction correction: SHELXTL (Bruker, 1997), Fc * =kFc[1+0.001xFc 2 λ 3 /sin(2θ)] -1/4 Extinction coefficient: 0.00028 (6) Special details Geometry. All s.u.'s (except the s.u.'s in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes. Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F 2 , conventional R-factors R are based on F, with F set to zero for negative F 2 . The threshold expression of F 2 > 2σ(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.