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Acta Cryst. (2008). E64, o401    [ doi:10.1107/S1600536807068225 ]

3-(m-Tolyloxy)phthalonitrile

X.-F. Zhang, D. Jia, Q. Liu and A. Song

Abstract top

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

Comment top

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 top

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).

Experimental top

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 (νmax/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).

Refinement top

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 Uiso(H) = 1.2Ueq (parent C) (for CH) or Uiso(H) = 1.5Ueq (parent C) (for CH3).

Computing details top

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 top
[Figure 1] 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.
[Figure 2] Fig. 2. The packing of (I), viewed down the c–axis.
3-(m-Tolyloxy)phthalonitrile top
Crystal data top
C15H10N2ODx = 1.263 Mg m−3
Mr = 234.25Melting point: 374 K
Orthorhombic, PbcaMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 58 reflections
a = 25.514 (3) Åθ = 2.8–25.5º
b = 14.6064 (18) ŵ = 0.08 mm−1
c = 6.6109 (6) ÅT = 295 (2) K
V = 2463.7 (5) Å3Prism, colourless
Z = 80.6 × 0.5 × 0.3 mm
F000 = 976
Data collection top
Bruker P4
diffractometer		Rint = 0.041
Radiation source: fine–focus sealed tubeθmax = 25.5º
Monochromator: graphiteθmin = 2.1º
T = 295(2) Kh = −30→1
ω scansk = −17→1
Absorption correction: nonel = −1→8
3094 measured reflections3 standard reflections
2254 independent reflections every 97 reflections
1372 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.054  w = 1/[σ2(Fo2) + (0.001P)2 + 2.2P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.109(Δ/σ)max < 0.001
S = 1.04Δρmax = 0.21 e Å−3
2254 reflectionsΔρmin = −0.23 e Å−3
165 parametersExtinction correction: SHELXTL (Bruker, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00028 (6)
Secondary atom site location: difference Fourier map
Crystal data top
C15H10N2OV = 2463.7 (5) Å3
Mr = 234.25Z = 8
Orthorhombic, PbcaMo Kα
a = 25.514 (3) ŵ = 0.08 mm−1
b = 14.6064 (18) ÅT = 295 (2) K
c = 6.6109 (6) Å0.6 × 0.5 × 0.3 mm
Data collection top
Bruker P4
diffractometer		Rint = 0.041
Absorption correction: none3 standard reflections
3094 measured reflections every 97 reflections
2254 independent reflections intensity decay: none
1372 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.054165 parameters
wR(F2) = 0.109H-atom parameters constrained
S = 1.04Δρmax = 0.21 e Å−3
2254 reflectionsΔρmin = −0.23 e Å−3
Special details top

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 (Å2) top
xyzUiso*/Ueq
O10.65134 (6)0.53717 (13)0.7428 (3)0.0755 (6)
N10.43352 (8)0.42711 (17)0.7588 (4)0.0682 (7)
N20.57804 (9)0.33811 (18)0.7422 (5)0.0842 (8)
C10.46678 (9)0.47844 (18)0.7550 (4)0.0532 (6)
C20.57161 (9)0.41537 (19)0.7437 (4)0.0570 (7)
C30.50933 (9)0.54397 (17)0.7508 (4)0.0510 (6)
C40.56143 (9)0.51093 (16)0.7447 (4)0.0499 (6)
C50.60184 (9)0.57428 (18)0.7405 (4)0.0568 (6)
C60.59127 (11)0.66675 (19)0.7441 (5)0.0678 (8)
H6A0.61870.70860.74290.081*
C70.54050 (11)0.69742 (19)0.7495 (5)0.0708 (8)
H7A0.53380.76000.75140.085*
C80.49907 (11)0.63599 (19)0.7523 (4)0.0634 (7)
H8A0.46470.65710.75510.076*
C90.69296 (10)0.58418 (18)0.6486 (5)0.0641 (8)
C100.74003 (9)0.58177 (18)0.7517 (5)0.0647 (7)
H10A0.74230.55520.87920.078*
C110.78408 (10)0.62010 (19)0.6599 (6)0.0757 (9)
C120.77921 (11)0.6595 (2)0.4711 (6)0.0835 (10)
H12A0.80850.68510.40960.100*
C130.73158 (12)0.6617 (2)0.3718 (6)0.0822 (10)
H13A0.72890.68910.24520.099*
C140.68779 (11)0.6230 (2)0.4610 (5)0.0725 (8)
H14A0.65560.62330.39510.087*
C150.83646 (11)0.6162 (2)0.7674 (7)0.1120 (16)
H15A0.85900.66320.71520.168*
H15B0.85230.55740.74550.168*
H15C0.83130.62550.90980.168*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0412 (9)0.0688 (12)0.1166 (18)−0.0042 (8)0.0010 (11)0.0251 (12)
N10.0486 (12)0.0869 (17)0.0691 (16)−0.0053 (12)−0.0033 (12)0.0028 (14)
N20.0641 (15)0.0659 (16)0.123 (3)0.0005 (12)0.0043 (16)0.0054 (17)
C10.0453 (13)0.0675 (16)0.0469 (14)0.0045 (12)−0.0021 (12)0.0014 (13)
C20.0411 (12)0.0611 (16)0.0688 (18)−0.0028 (12)0.0024 (13)0.0046 (15)
C30.0461 (12)0.0618 (15)0.0452 (14)0.0005 (11)−0.0002 (12)0.0005 (12)
C40.0433 (12)0.0564 (14)0.0500 (14)0.0003 (11)0.0015 (12)0.0024 (13)
C50.0447 (12)0.0627 (15)0.0630 (17)−0.0007 (11)−0.0008 (13)0.0029 (14)
C60.0603 (16)0.0609 (16)0.082 (2)−0.0092 (13)0.0012 (16)0.0005 (16)
C70.0757 (18)0.0554 (15)0.081 (2)0.0070 (14)0.0064 (17)−0.0022 (16)
C80.0555 (14)0.0682 (17)0.0665 (17)0.0106 (13)0.0057 (14)0.0006 (15)
C90.0456 (13)0.0553 (15)0.091 (2)−0.0074 (12)0.0025 (15)0.0055 (16)
C100.0458 (13)0.0570 (15)0.091 (2)0.0012 (12)−0.0044 (15)0.0047 (16)
C110.0420 (14)0.0559 (16)0.129 (3)0.0002 (12)−0.0001 (17)−0.0025 (19)
C120.0565 (17)0.0668 (19)0.127 (3)−0.0029 (14)0.0243 (19)0.012 (2)
C130.075 (2)0.075 (2)0.097 (3)−0.0020 (16)0.0121 (19)0.0110 (19)
C140.0572 (16)0.0723 (19)0.088 (2)−0.0070 (14)−0.0036 (16)0.0037 (18)
C150.0446 (15)0.090 (2)0.202 (5)−0.0048 (15)−0.022 (2)0.013 (3)
Geometric parameters (Å, °) top
O1—C51.375 (3)C9—C141.370 (4)
O1—C91.409 (3)C9—C101.381 (4)
N1—C11.133 (3)C10—C111.394 (4)
N2—C21.140 (3)C10—H10A0.9300
C1—C31.448 (3)C11—C121.380 (5)
C2—C41.420 (4)C11—C151.515 (4)
C3—C81.369 (4)C12—C131.382 (4)
C3—C41.415 (3)C12—H12A0.9300
C4—C51.386 (3)C13—C141.384 (4)
C5—C61.377 (4)C13—H13A0.9300
C6—C71.371 (4)C14—H14A0.9300
C6—H6A0.9300C15—H15A0.9600
C7—C81.387 (4)C15—H15B0.9600
C7—H7A0.9300C15—H15C0.9600
C8—H8A0.9300
C5—O1—C9119.7 (2)C10—C9—O1115.2 (3)
N1—C1—C3179.8 (3)C9—C10—C11118.4 (3)
N2—C2—C4177.7 (3)C9—C10—H10A120.8
C8—C3—C4121.0 (2)C11—C10—H10A120.8
C8—C3—C1120.4 (2)C12—C11—C10119.2 (3)
C4—C3—C1118.7 (2)C12—C11—C15121.3 (3)
C5—C4—C3118.2 (2)C10—C11—C15119.5 (3)
C5—C4—C2121.3 (2)C11—C12—C13121.2 (3)
C3—C4—C2120.5 (2)C11—C12—H12A119.4
O1—C5—C6124.5 (2)C13—C12—H12A119.4
O1—C5—C4114.8 (2)C12—C13—C14119.9 (3)
C6—C5—C4120.6 (2)C12—C13—H13A120.1
C7—C6—C5120.4 (2)C14—C13—H13A120.1
C7—C6—H6A119.8C9—C14—C13118.5 (3)
C5—C6—H6A119.8C9—C14—H14A120.8
C6—C7—C8120.6 (3)C13—C14—H14A120.8
C6—C7—H7A119.7C11—C15—H15A109.5
C8—C7—H7A119.7C11—C15—H15B109.5
C3—C8—C7119.3 (2)H15A—C15—H15B109.5
C3—C8—H8A120.4C11—C15—H15C109.5
C7—C8—H8A120.4H15A—C15—H15C109.5
C14—C9—C10122.7 (3)H15B—C15—H15C109.5
C14—C9—O1121.9 (3)
Acknowledgements top

The authors thank the HBUST for financial support.

references
References top

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