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Acta Crystallogr Sect E Struct Rep Online. 2009 May 1; 65(Pt 5): o1172.
Published online 2009 April 30. doi:  10.1107/S1600536809015402
PMCID: PMC2977837

4-{2-Meth­oxy-6-[(4-methyl­phen­yl)imino­meth­yl]phen­oxy}phthalonitrile

Abstract

In the mol­ecule of the title compound, C23H17N3O2, the methoxy­phenyl ring is oriented at dihedral angles of 13.34 (12) and 88.83 (12)° with respect to the methyl­phenyl and phthalonitrile rings, respectively; the dihedral angle between methyl­phenyl and phthalonitrile rings is 89.67 (10)°. In the crystal structure, weak inter­molecular C—H(...)N inter­actions link mol­ecules into chains. A weak C—H(...)π inter­action is also found..

Related literature

For a related structure, see: Ocak İskeleli et al. (2005 [triangle]). For general background to substituted phthalonitriles, see: McKeown (1998 [triangle]); Leznoff & Lever (1989–1996 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

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Object name is e-65-o1172-scheme1.jpg

Experimental

Crystal data

  • C23H17N3O2
  • M r = 367.40
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1172-efi1.jpg
  • a = 9.3549 (5) Å
  • b = 23.6606 (13) Å
  • c = 8.9317 (5) Å
  • β = 97.256 (4)°
  • V = 1961.13 (19) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 296 K
  • 0.67 × 0.36 × 0.20 mm

Data collection

  • Stoe IPDS-II diffractometer
  • Absorption correction: integration (X-RED32; Stoe & Cie, 2002 [triangle]) T min = 0.703, T max = 0.952
  • 10306 measured reflections
  • 3680 independent reflections
  • 1962 reflections with I > 2σ(I)
  • R int = 0.072

Refinement

  • R[F 2 > 2σ(F 2)] = 0.048
  • wR(F 2) = 0.122
  • S = 0.96
  • 3680 reflections
  • 253 parameters
  • H-atom parameters constrained
  • Δρmax = 0.12 e Å−3
  • Δρmin = −0.10 e Å−3

Data collection: X-AREA (Stoe & Cie, 2002 [triangle]); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809015402/hk2671sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809015402/hk2671Isup2.hkl

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

Acknowledgments

The authors wish to acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS-II diffractometer (purchased under grant No. F279 of the University Research Fund).

supplementary crystallographic information

Comment

Substituted phthalonitriles are generally used for preparing symmetrically and unsymmetrically peripherally and non-peripherally substituted phthalocyanines and subphthalocyanines (McKeown, 1998; Leznoff & Lever, 1989-1996). In addition to their extensive use as dyes and pigments, phthalocyanines have found widespread applications in catalysis, in optical recording, as photoconductive materials, in photo-dynamic therapy and as chemical sensors (Leznoff & Lever, 1989-1996). We report herein the crystal structure of the title compound.

In the molecule of the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. The N2[equivalent]C22 [1.133 (3) Å] and N3[equivalent]C23 [1.145 (3) Å] bonds show N[equivalent]C triple bond character and are in good agreement with the literature values (Ocak İskeleli et al., 2005). Rings A (C1-C6), B (C9-C14) and C (C16-C21) are, of course, planar, and they are oriented at dihedral angles of A/B = 13.34 (12), A/C = 88.83 (12) and B/C = 89.67 (10) °.

In the crystal structure, weak intermolecular C-H···N interactions (Table 1) link the molecules into chains (Fig. 2), in which they may be effective in the stabilization of the structure. There also exists a weak C-H···π interaction (Table 1).

Experimental

For the preparation of the title compound, potasium carbonato (0.9 g, 6.58 mmol) was added to a solution of solid o-vaniline (0.5 g, 3.29 mmol) in DMF. The mixture was stirred for 30 min under nitrogen atmosphere. 4-Nitrophtalonitrile solution in DMF was added. The mixture was stirred for 48 h at 323 K under nitrogen atmosphere and poured into ice-water (150 g). The product 2-(3,4-dicyanophenoxy)-3-methoxybenzaldehyde was filtered off and washed with water. The title compound was prepared by refluxing a mixture of a solution containing 2-(3,4-Dicyanophenoxy)-3-methoxybenzaldehyde (0.5 g, 1.799 mmol) in ethanol (20 ml) and a solution containing 4-methylaniline (0.218 g 1.799 mmol) in ethanol (20 ml). The reaction mixture was stirred for 1 h under reflux. Crystals suitable for X-ray analysis were obtained from ethylalcohol by slow evaporation (yield; 55%, m.p. 427-429 K).

Refinement

H atoms were positioned geometrically, with C-H = 0.93 and 0.96 Å for aromatic and methyl H, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H and x = 1.2 for aromatic H atoms.

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

Crystal data

C23H17N3O2F(000) = 768
Mr = 367.40Dx = 1.244 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 9188 reflections
a = 9.3549 (5) Åθ = 1.7–26.2°
b = 23.6606 (13) ŵ = 0.08 mm1
c = 8.9317 (5) ÅT = 296 K
β = 97.256 (4)°Prism, yellow
V = 1961.13 (19) Å30.67 × 0.36 × 0.20 mm
Z = 4

Data collection

Stoe IPDS-II diffractometer3680 independent reflections
Radiation source: fine-focus sealed tube1962 reflections with I > 2σ(I)
graphiteRint = 0.072
Detector resolution: 6.67 pixels mm-1θmax = 25.6°, θmin = 1.7°
ω scansh = −11→10
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)k = −28→28
Tmin = 0.703, Tmax = 0.952l = −10→10
10306 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122H-atom parameters constrained
S = 0.96w = 1/[σ2(Fo2) + (0.0491P)2] where P = (Fo2 + 2Fc2)/3
3680 reflections(Δ/σ)max < 0.001
253 parametersΔρmax = 0.12 e Å3
0 restraintsΔρmin = −0.10 e Å3

Special details

Experimental. 140 frames, detector distance = 130 mm
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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)

xyzUiso*/Ueq
O10.38836 (16)0.44741 (6)0.57255 (15)0.0725 (4)
O20.49525 (18)0.52245 (6)0.77461 (17)0.0879 (5)
N10.0395 (2)0.47793 (7)0.26224 (19)0.0737 (5)
N20.4483 (3)0.21068 (11)0.7035 (4)0.1657 (14)
N30.1213 (3)0.23410 (10)0.9455 (3)0.1180 (9)
C10.2188 (2)0.51464 (8)0.4521 (2)0.0659 (6)
C20.1712 (3)0.57046 (9)0.4401 (2)0.0768 (6)
H20.09690.58050.36570.092*
C30.2339 (3)0.61054 (9)0.5379 (2)0.0798 (7)
H30.20280.64780.52730.096*
C40.3424 (3)0.59675 (9)0.6520 (2)0.0760 (7)
H40.38280.62450.71810.091*
C50.3905 (2)0.54177 (9)0.6673 (2)0.0687 (6)
C60.3289 (2)0.50179 (8)0.5654 (2)0.0644 (5)
C70.5596 (3)0.56217 (11)0.8831 (3)0.1040 (9)
H7A0.62560.54290.95690.156*
H7B0.48590.58000.93200.156*
H7C0.61060.59030.83330.156*
C80.1525 (3)0.46997 (9)0.3529 (2)0.0727 (6)
H80.19540.43440.35680.087*
C9−0.0244 (2)0.43225 (9)0.1744 (2)0.0683 (6)
C10−0.0023 (3)0.37542 (10)0.2086 (2)0.0818 (7)
H100.06240.36490.29170.098*
C11−0.0759 (3)0.33451 (10)0.1202 (3)0.0872 (7)
H11−0.05990.29670.14500.105*
C12−0.1731 (3)0.34819 (11)−0.0046 (3)0.0870 (7)
C13−0.1944 (3)0.40459 (11)−0.0376 (3)0.0854 (7)
H13−0.25890.4149−0.12090.102*
C14−0.1221 (2)0.44613 (10)0.0501 (2)0.0761 (6)
H14−0.13910.48390.02540.091*
C15−0.2535 (4)0.30258 (13)−0.0997 (4)0.1312 (12)
H15A−0.28340.3170−0.19930.197*
H15B−0.33670.2913−0.05430.197*
H15C−0.19140.2706−0.10590.197*
C160.3328 (2)0.40673 (8)0.6576 (2)0.0626 (6)
C170.2221 (3)0.41613 (8)0.7412 (2)0.0674 (6)
H170.18230.45200.74520.081*
C180.1699 (3)0.37193 (9)0.8193 (2)0.0728 (6)
H180.09520.37840.87670.087*
C190.2270 (3)0.31831 (9)0.8135 (3)0.0745 (6)
C200.3403 (3)0.30971 (9)0.7282 (3)0.0793 (7)
C210.3937 (3)0.35393 (9)0.6509 (3)0.0776 (7)
H210.46990.34810.59510.093*
C220.4004 (3)0.25418 (11)0.7156 (4)0.1104 (10)
C230.1688 (3)0.27176 (10)0.8882 (3)0.0904 (8)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0718 (10)0.0594 (9)0.0864 (10)0.0058 (8)0.0110 (8)−0.0032 (7)
O20.0908 (12)0.0751 (10)0.0908 (10)−0.0005 (9)−0.0153 (9)−0.0078 (8)
N10.0850 (14)0.0644 (11)0.0691 (10)−0.0018 (10)−0.0001 (10)0.0018 (9)
N20.156 (3)0.0656 (15)0.262 (4)0.0429 (17)−0.026 (3)−0.0140 (19)
N30.159 (3)0.0703 (14)0.1152 (17)−0.0202 (15)−0.0180 (16)0.0176 (12)
C10.0758 (15)0.0581 (12)0.0637 (12)−0.0014 (11)0.0079 (11)−0.0006 (9)
C20.0941 (18)0.0625 (13)0.0720 (13)0.0039 (12)0.0039 (12)0.0086 (11)
C30.107 (2)0.0508 (12)0.0819 (15)0.0015 (12)0.0138 (14)0.0061 (11)
C40.0931 (19)0.0586 (13)0.0759 (14)−0.0114 (13)0.0091 (13)−0.0052 (10)
C50.0731 (15)0.0603 (13)0.0718 (13)−0.0069 (11)0.0056 (11)−0.0004 (10)
C60.0700 (14)0.0518 (11)0.0722 (13)0.0001 (11)0.0119 (11)0.0013 (10)
C70.101 (2)0.1008 (19)0.1020 (17)−0.0055 (16)−0.0182 (16)−0.0239 (15)
C80.0841 (17)0.0602 (13)0.0723 (13)0.0028 (12)0.0044 (13)−0.0034 (10)
C90.0737 (15)0.0658 (13)0.0644 (12)−0.0017 (11)0.0045 (11)0.0013 (10)
C100.0931 (19)0.0699 (15)0.0781 (14)−0.0045 (14)−0.0053 (13)0.0021 (11)
C110.098 (2)0.0698 (15)0.0914 (16)−0.0100 (14)0.0039 (14)−0.0001 (13)
C120.0813 (18)0.0915 (18)0.0861 (16)−0.0141 (14)0.0018 (14)−0.0090 (14)
C130.0804 (18)0.0994 (19)0.0735 (15)−0.0033 (15)−0.0012 (13)0.0018 (13)
C140.0740 (16)0.0793 (15)0.0734 (13)0.0026 (13)0.0026 (12)0.0045 (11)
C150.130 (3)0.120 (2)0.134 (2)−0.032 (2)−0.022 (2)−0.0259 (19)
C160.0624 (14)0.0501 (11)0.0714 (13)0.0010 (10)−0.0061 (11)−0.0064 (10)
C170.0770 (16)0.0477 (11)0.0750 (13)0.0066 (11)−0.0003 (12)−0.0028 (9)
C180.0842 (18)0.0575 (13)0.0750 (13)−0.0002 (12)0.0029 (12)0.0007 (10)
C190.0826 (17)0.0507 (13)0.0829 (14)−0.0001 (12)−0.0184 (13)0.0014 (10)
C200.0807 (17)0.0462 (12)0.1017 (17)0.0116 (12)−0.0253 (15)−0.0064 (11)
C210.0691 (16)0.0583 (13)0.1014 (16)0.0125 (12)−0.0047 (12)−0.0136 (12)
C220.104 (2)0.0576 (15)0.159 (3)0.0155 (15)−0.0258 (19)−0.0029 (15)
C230.113 (2)0.0544 (14)0.0954 (17)−0.0048 (14)−0.0198 (15)0.0066 (12)

Geometric parameters (Å, °)

C1—C61.384 (3)C11—H110.9300
C1—C21.393 (3)C12—C131.376 (3)
C1—C81.465 (3)C12—C151.513 (3)
C2—C31.370 (3)C13—C141.379 (3)
C2—H20.9300C13—H130.9300
C3—C41.384 (3)C14—H140.9300
C3—H30.9300C15—H15A0.9600
C4—C51.377 (3)C15—H15B0.9600
C4—H40.9300C15—H15C0.9600
C5—O21.361 (2)C16—O11.369 (2)
C5—C61.386 (3)C16—C171.369 (3)
C6—O11.400 (2)C16—C211.378 (3)
C7—O21.427 (3)C17—C181.381 (3)
C7—H7A0.9600C17—H170.9300
C7—H7B0.9600C18—C191.380 (3)
C7—H7C0.9600C18—H180.9300
C8—N11.262 (3)C19—C201.397 (3)
C8—H80.9300C19—C231.431 (4)
C9—C141.385 (3)C20—C211.381 (3)
C9—C101.389 (3)C20—C221.439 (3)
C9—N11.422 (3)C21—H210.9300
C10—C111.378 (3)C22—N21.133 (3)
C10—H100.9300C23—N31.145 (3)
C11—C121.385 (3)
C16—O1—C6119.67 (16)C10—C11—H11119.1
C5—O2—C7117.49 (18)C12—C11—H11119.1
C8—N1—C9120.00 (19)C13—C12—C11117.5 (2)
C6—C1—C2117.71 (19)C13—C12—C15121.6 (2)
C6—C1—C8120.19 (19)C11—C12—C15121.0 (3)
C2—C1—C8122.1 (2)C12—C13—C14121.5 (2)
C3—C2—C1120.1 (2)C12—C13—H13119.2
C3—C2—H2120.0C14—C13—H13119.2
C1—C2—H2120.0C13—C14—C9120.8 (2)
C2—C3—C4121.4 (2)C13—C14—H14119.6
C2—C3—H3119.3C9—C14—H14119.6
C4—C3—H3119.3C12—C15—H15A109.5
C5—C4—C3119.7 (2)C12—C15—H15B109.5
C5—C4—H4120.2H15A—C15—H15B109.5
C3—C4—H4120.2C12—C15—H15C109.5
O2—C5—C4125.72 (19)H15A—C15—H15C109.5
O2—C5—C6115.83 (19)H15B—C15—H15C109.5
C4—C5—C6118.5 (2)O1—C16—C17123.69 (18)
C1—C6—C5122.64 (19)O1—C16—C21115.2 (2)
C1—C6—O1119.32 (17)C17—C16—C21121.1 (2)
C5—C6—O1117.88 (19)C16—C17—C18119.5 (2)
O2—C7—H7A109.5C16—C17—H17120.2
O2—C7—H7B109.5C18—C17—H17120.2
H7A—C7—H7B109.5C19—C18—C17121.0 (2)
O2—C7—H7C109.5C19—C18—H18119.5
H7A—C7—H7C109.5C17—C18—H18119.5
H7B—C7—H7C109.5C18—C19—C20118.6 (2)
N1—C8—C1122.4 (2)C18—C19—C23121.2 (3)
N1—C8—H8118.8C20—C19—C23120.2 (2)
C1—C8—H8118.8C21—C20—C19120.6 (2)
C14—C9—C10118.1 (2)C21—C20—C22118.9 (3)
C14—C9—N1116.8 (2)C19—C20—C22120.4 (3)
C10—C9—N1125.02 (19)C16—C21—C20119.2 (2)
C11—C10—C9120.3 (2)C16—C21—H21120.4
C11—C10—H10119.9C20—C21—H21120.4
C9—C10—H10119.9N2—C22—C20178.9 (4)
C10—C11—C12121.8 (2)N3—C23—C19178.8 (3)
C1—C6—O1—C16−91.4 (2)C2—C1—C8—N1−7.8 (3)
C5—C6—O1—C1693.0 (2)C14—C9—C10—C110.2 (4)
C17—C16—O1—C6−1.5 (3)N1—C9—C10—C11176.3 (2)
C21—C16—O1—C6176.75 (18)C9—C10—C11—C120.1 (4)
C4—C5—O2—C71.3 (3)C10—C11—C12—C13−0.2 (4)
C6—C5—O2—C7−179.0 (2)C10—C11—C12—C15−179.6 (3)
C1—C8—N1—C9−176.67 (18)C11—C12—C13—C14−0.1 (4)
C14—C9—N1—C8−162.8 (2)C15—C12—C13—C14179.4 (3)
C10—C9—N1—C821.0 (4)C12—C13—C14—C90.4 (4)
C6—C1—C2—C30.5 (3)C10—C9—C14—C13−0.5 (3)
C8—C1—C2—C3178.3 (2)N1—C9—C14—C13−176.9 (2)
C1—C2—C3—C4−1.5 (4)O1—C16—C17—C18177.77 (19)
C2—C3—C4—C50.9 (4)C21—C16—C17—C18−0.4 (3)
C3—C4—C5—O2−179.5 (2)C16—C17—C18—C19−0.5 (3)
C3—C4—C5—C60.8 (3)C17—C18—C19—C200.8 (3)
C2—C1—C6—C51.2 (3)C17—C18—C19—C23−176.9 (2)
C8—C1—C6—C5−176.7 (2)C18—C19—C20—C21−0.2 (3)
C2—C1—C6—O1−174.27 (19)C23—C19—C20—C21177.5 (2)
C8—C1—C6—O17.9 (3)C18—C19—C20—C22−178.3 (2)
O2—C5—C6—C1178.4 (2)C23—C19—C20—C22−0.6 (3)
C4—C5—C6—C1−1.8 (3)O1—C16—C21—C20−177.32 (19)
O2—C5—C6—O1−6.1 (3)C17—C16—C21—C201.0 (3)
C4—C5—C6—O1173.70 (19)C19—C20—C21—C16−0.7 (3)
C6—C1—C8—N1169.9 (2)C22—C20—C21—C16177.4 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C4—H4···N2i0.932.623.483 (3)154
C18—H18···Cg2ii0.932.773.694 (3)171

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, y, z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2671).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Leznoff, C. C. & Lever, A. B. P. (1989–1996). Phthalocyanines: Properties and Applications, Vols. 1–4. Weinheim, New York: VCH Publishers Inc.
  • McKeown, N. B. (1998). In Phthalocyanine Materials: Synthesis, Structure and Function Cambridge University Press.
  • Ocak İskeleli, N., Atalay, S., Ağar, E. & Akdemir, N. (2005). Acta Cryst. E61, o2294–o2295.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]
  • Stoe & Cie (2002). X-AREA and X-RED Stoe & Cie, Darmstadt, Germany.

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