3-(m-Tol­yloxy)phthalonitrile

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

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.054
• wR factor = 0.110
• Data-to-parameter ratio = 13.7

checkCIF/PLATON results

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Alert level C
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C1     -   C3     ...       1.45 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C2     -   C4     ...       1.42 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. 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.

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 (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).

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 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).

S3. Refinement

All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.96 Å (CH₃) 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 CH₃).

Computing details

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

Figures

	Fig. 1. The molecular structure of title compound with the atom numbering scheme. Displacement ellipsoids are drawn at 35% probability level. Hydrogen atoms are presented as spheres of arbitrary radius.
	Fig. 2. The packing of (I), viewed down the c–axis.

3-(m-Tolyloxy)phthalonitrile

Crystal data

C15H10N2O	Dx = 1.263 Mg m^−3
Mr = 234.25	Melting point: 374 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 58 reflections
a = 25.514 (3) Å	θ = 2.8–25.5°
b = 14.6064 (18) Å	µ = 0.08 mm^−1
c = 6.6109 (6) Å	T = 295 K
V = 2463.7 (5) Å^3	Prism, colourless
Z = 8	0.6 × 0.5 × 0.3 mm
F(000) = 976

Data collection

Bruker P4 diffractometer	Rint = 0.041
Radiation source: fine–focus sealed tube	θmax = 25.5°, θmin = 2.1°
Graphite monochromator	h = −30→1
ω scans	k = −17→1
3094 measured reflections	l = −1→8
2254 independent reflections	3 standard reflections every 97 reflections
1372 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.054	H-atom parameters constrained
wR(F^2) = 0.109	w = 1/[σ^2(Fo^2) + (0.001P)^2 + 2.2P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
2254 reflections	Δρmax = 0.21 e Å^−3
165 parameters	Δρmin = −0.23 e Å^−3
0 restraints	Extinction correction: SHELXTL (Bruker, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	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 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 > 2σ(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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.65134 (6)	0.53717 (13)	0.7428 (3)	0.0755 (6)
N1	0.43352 (8)	0.42711 (17)	0.7588 (4)	0.0682 (7)
N2	0.57804 (9)	0.33811 (18)	0.7422 (5)	0.0842 (8)
C1	0.46678 (9)	0.47844 (18)	0.7550 (4)	0.0532 (6)
C2	0.57161 (9)	0.41537 (19)	0.7437 (4)	0.0570 (7)
C3	0.50933 (9)	0.54397 (17)	0.7508 (4)	0.0510 (6)
C4	0.56143 (9)	0.51093 (16)	0.7447 (4)	0.0499 (6)
C5	0.60184 (9)	0.57428 (18)	0.7405 (4)	0.0568 (6)
C6	0.59127 (11)	0.66675 (19)	0.7441 (5)	0.0678 (8)
H6A	0.6187	0.7086	0.7429	0.081*
C7	0.54050 (11)	0.69742 (19)	0.7495 (5)	0.0708 (8)
H7A	0.5338	0.7600	0.7514	0.085*
C8	0.49907 (11)	0.63599 (19)	0.7523 (4)	0.0634 (7)
H8A	0.4647	0.6571	0.7551	0.076*
C9	0.69296 (10)	0.58418 (18)	0.6486 (5)	0.0641 (8)
C10	0.74003 (9)	0.58177 (18)	0.7517 (5)	0.0647 (7)
H10A	0.7423	0.5552	0.8792	0.078*
C11	0.78408 (10)	0.62010 (19)	0.6599 (6)	0.0757 (9)
C12	0.77921 (11)	0.6595 (2)	0.4711 (6)	0.0835 (10)
H12A	0.8085	0.6851	0.4096	0.100*
C13	0.73158 (12)	0.6617 (2)	0.3718 (6)	0.0822 (10)
H13A	0.7289	0.6891	0.2452	0.099*
C14	0.68779 (11)	0.6230 (2)	0.4610 (5)	0.0725 (8)
H14A	0.6556	0.6233	0.3951	0.087*
C15	0.83646 (11)	0.6162 (2)	0.7674 (7)	0.1120 (16)
H15A	0.8590	0.6632	0.7152	0.168*
H15B	0.8523	0.5574	0.7455	0.168*
H15C	0.8313	0.6255	0.9098	0.168*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0412 (9)	0.0688 (12)	0.1166 (18)	−0.0042 (8)	0.0010 (11)	0.0251 (12)
N1	0.0486 (12)	0.0869 (17)	0.0691 (16)	−0.0053 (12)	−0.0033 (12)	0.0028 (14)
N2	0.0641 (15)	0.0659 (16)	0.123 (3)	0.0005 (12)	0.0043 (16)	0.0054 (17)
C1	0.0453 (13)	0.0675 (16)	0.0469 (14)	0.0045 (12)	−0.0021 (12)	0.0014 (13)
C2	0.0411 (12)	0.0611 (16)	0.0688 (18)	−0.0028 (12)	0.0024 (13)	0.0046 (15)
C3	0.0461 (12)	0.0618 (15)	0.0452 (14)	0.0005 (11)	−0.0002 (12)	0.0005 (12)
C4	0.0433 (12)	0.0564 (14)	0.0500 (14)	0.0003 (11)	0.0015 (12)	0.0024 (13)
C5	0.0447 (12)	0.0627 (15)	0.0630 (17)	−0.0007 (11)	−0.0008 (13)	0.0029 (14)
C6	0.0603 (16)	0.0609 (16)	0.082 (2)	−0.0092 (13)	0.0012 (16)	0.0005 (16)
C7	0.0757 (18)	0.0554 (15)	0.081 (2)	0.0070 (14)	0.0064 (17)	−0.0022 (16)
C8	0.0555 (14)	0.0682 (17)	0.0665 (17)	0.0106 (13)	0.0057 (14)	0.0006 (15)
C9	0.0456 (13)	0.0553 (15)	0.091 (2)	−0.0074 (12)	0.0025 (15)	0.0055 (16)
C10	0.0458 (13)	0.0570 (15)	0.091 (2)	0.0012 (12)	−0.0044 (15)	0.0047 (16)
C11	0.0420 (14)	0.0559 (16)	0.129 (3)	0.0002 (12)	−0.0001 (17)	−0.0025 (19)
C12	0.0565 (17)	0.0668 (19)	0.127 (3)	−0.0029 (14)	0.0243 (19)	0.012 (2)
C13	0.075 (2)	0.075 (2)	0.097 (3)	−0.0020 (16)	0.0121 (19)	0.0110 (19)
C14	0.0572 (16)	0.0723 (19)	0.088 (2)	−0.0070 (14)	−0.0036 (16)	0.0037 (18)
C15	0.0446 (15)	0.090 (2)	0.202 (5)	−0.0048 (15)	−0.022 (2)	0.013 (3)

Geometric parameters (Å, º)

O1—C5	1.375 (3)	C9—C14	1.370 (4)
O1—C9	1.409 (3)	C9—C10	1.381 (4)
N1—C1	1.133 (3)	C10—C11	1.394 (4)
N2—C2	1.140 (3)	C10—H10A	0.9300
C1—C3	1.448 (3)	C11—C12	1.380 (5)
C2—C4	1.420 (4)	C11—C15	1.515 (4)
C3—C8	1.369 (4)	C12—C13	1.382 (4)
C3—C4	1.415 (3)	C12—H12A	0.9300
C4—C5	1.386 (3)	C13—C14	1.384 (4)
C5—C6	1.377 (4)	C13—H13A	0.9300
C6—C7	1.371 (4)	C14—H14A	0.9300
C6—H6A	0.9300	C15—H15A	0.9600
C7—C8	1.387 (4)	C15—H15B	0.9600
C7—H7A	0.9300	C15—H15C	0.9600
C8—H8A	0.9300
C5—O1—C9	119.7 (2)	C10—C9—O1	115.2 (3)
N1—C1—C3	179.8 (3)	C9—C10—C11	118.4 (3)
N2—C2—C4	177.7 (3)	C9—C10—H10A	120.8
C8—C3—C4	121.0 (2)	C11—C10—H10A	120.8
C8—C3—C1	120.4 (2)	C12—C11—C10	119.2 (3)
C4—C3—C1	118.7 (2)	C12—C11—C15	121.3 (3)
C5—C4—C3	118.2 (2)	C10—C11—C15	119.5 (3)
C5—C4—C2	121.3 (2)	C11—C12—C13	121.2 (3)
C3—C4—C2	120.5 (2)	C11—C12—H12A	119.4
O1—C5—C6	124.5 (2)	C13—C12—H12A	119.4
O1—C5—C4	114.8 (2)	C12—C13—C14	119.9 (3)
C6—C5—C4	120.6 (2)	C12—C13—H13A	120.1
C7—C6—C5	120.4 (2)	C14—C13—H13A	120.1
C7—C6—H6A	119.8	C9—C14—C13	118.5 (3)
C5—C6—H6A	119.8	C9—C14—H14A	120.8
C6—C7—C8	120.6 (3)	C13—C14—H14A	120.8
C6—C7—H7A	119.7	C11—C15—H15A	109.5
C8—C7—H7A	119.7	C11—C15—H15B	109.5
C3—C8—C7	119.3 (2)	H15A—C15—H15B	109.5
C3—C8—H8A	120.4	C11—C15—H15C	109.5
C7—C8—H8A	120.4	H15A—C15—H15C	109.5
C14—C9—C10	122.7 (3)	H15B—C15—H15C	109.5
C14—C9—O1	121.9 (3)