4-(4-Allyl-2-meth­oxyphen­oxy)benzene-1,2-dicarbonitrile

In the title compound, C₁₈H₁₄N₂O₂, the dihedral angle between the two benzene rings is 88.6 (1)°. The allyl group is disordered over two orientations, with refined occupancies of 0.695 (6) and 0.305 (6). The meth­oxy group is coplanar with the attached benzene ring. C—H...N inter­molecular hydrogen bonds link the mol­ecules into a C(6) chain along the a axis. The chain structure is further strengthened by C—H...π inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in main residue
• R factor = 0.035
• wR factor = 0.099
• Data-to-parameter ratio = 8.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.78 mm
PLAT301_ALERT_3_C Main Residue  Disorder .........................       8.00 Perc.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C3     -   C7     ...       1.43 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C4     -   C8     ...       1.43 Ang.

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.97
           From the CIF: _reflns_number_total               1930
           Count of symmetry unique reflns         1961
           Completeness (_total/calc)             98.42%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          3

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   2 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
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

Phthalonitriles have been used as starting materials for phthalocyanines (Leznoff & Lever, 1996), which are important components for dyes, pigments, gas sensors, optical limiters and liquid crystals, and which are also used in medicine, as singlet oxygen photosensitisers for photodynamic therapy (PDT) (McKeown, 1998). Some phthalocyanines have been used in the petroleum industry as catalysts, for the oxidation of sulfur compounds in the gasoline fraction. Applications as photoconductors in the xerographic double layers of laser printers and copying machines, and as active materials in writable data-storage disks, are also known (Wöhrle, 2001). The synthetic details of the title compound was published elsewhere (Agar et al., 1999). We report here the crystal structure of the title compound.

The benzene rings are essentially planar [the atoms having the largest deviations in the two benzene rings are C4 (0.009 (2) Å) and C12 (0.017 (2) Å)] and they form a dihedral angle of 88.6 (1)° (Fig. 1). The methoxy group is coplanar with the attached ring, with the C13—C14—O2—C15 torsion angle being 0.6 (4)°.

The crystal packing is stabilized by C—H···N intermolecular hydrogen bonds and C—H···π interactions (Table 1). The C—H···N hydrogen bonds link the molecules into a C(6) chain along the a axis (Fig. 2). The chain is further strengthened by C16—H16A···π interactions involving the C1—C6 benzene ring (centroid Cg1).

Related literature

For general background, see: Agar et al. (1999); Leznoff & Lever (1996); McKeown (1998); Wöhrle (2001).

S2. Experimental

The title compound was prepared using the method reported previously by Agar et al. (1999).

S3. Refinement

Atoms C17 and C18 of the allyl group are disordered over two sites, with refined occupancies of 0.695 (6) and 0.305 (6). The corresponding C—C distances involving the disordered atoms were restrained to be the same. The H atoms of the benzene rings were located in a difference map and refined freely, with U_iso(H) = 1.2U_eq(C). All other H atoms were placed in calculated positions and constrained to ride on their parent atoms, with C—H = 0.93–0.97 Å and U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C). 1315 Friedel pairs were merged before the final refinement.

Computing details

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

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. Both disorder components are shown.
	Fig. 2. A packing diagram for (I), showing a C—H···N hydrogen-bonded (dashed lines) chain. H atoms not involved in hydrogen bonding have been omitted for clarity.

4-(4-Allyl-2-methoxyphenoxy)benzene-1,2-dicarbonitrile

Crystal data

C18H14N2O2	F(000) = 608
Mr = 290.31	Dx = 1.265 Mg m^−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 11502 reflections
a = 14.7784 (13) Å	θ = 1.7–27.8°
b = 11.9726 (9) Å	µ = 0.08 mm^−1
c = 8.6133 (6) Å	T = 296 K
V = 1524.0 (2) Å^3	Prism, colourless
Z = 4	0.78 × 0.40 × 0.17 mm

Data collection

Stoe IPDSII diffractometer	1930 independent reflections
Radiation source: fine-focus sealed tube	1317 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.074
Detector resolution: 6.67 pixels mm^-1	θmax = 28.0°, θmin = 2.2°
ω scans	h = −19→19
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −15→15
Tmin = 0.969, Tmax = 0.989	l = −10→11
14749 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 0.91	w = 1/[σ^2(Fo^2) + (0.0656P)^2] where P = (Fo^2 + 2Fc^2)/3
1930 reflections	(Δ/σ)max = 0.001
225 parameters	Δρmax = 0.08 e Å^−3
3 restraints	Δρmin = −0.10 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.49053 (11)	0.51155 (13)	0.3686 (2)	0.0736 (5)
O2	0.53129 (11)	0.33713 (16)	0.1909 (2)	0.0828 (5)
N1	0.36210 (17)	0.1802 (2)	0.8284 (4)	0.1042 (9)
N2	0.12638 (15)	0.2620 (2)	0.6747 (4)	0.0956 (7)
C1	0.41981 (14)	0.45549 (17)	0.4342 (3)	0.0608 (5)
C2	0.42998 (15)	0.37518 (17)	0.5476 (3)	0.0617 (5)
H2	0.4858 (17)	0.352 (2)	0.584 (3)	0.074*
C3	0.35322 (14)	0.32673 (17)	0.6111 (3)	0.0613 (5)
C4	0.26687 (14)	0.35687 (18)	0.5590 (3)	0.0642 (5)
C5	0.25886 (15)	0.4388 (2)	0.4455 (3)	0.0708 (6)
H5	0.1964 (18)	0.462 (2)	0.410 (3)	0.085*
C6	0.33423 (16)	0.4874 (2)	0.3835 (3)	0.0682 (6)
H6	0.3309 (15)	0.543 (2)	0.302 (4)	0.082*
C7	0.36038 (15)	0.2447 (2)	0.7318 (3)	0.0740 (6)
C8	0.18843 (16)	0.3044 (2)	0.6234 (3)	0.0730 (6)
C9	0.57803 (13)	0.46782 (19)	0.3737 (3)	0.0642 (5)
C10	0.64291 (18)	0.5200 (2)	0.4616 (4)	0.0764 (6)
H10	0.6209 (17)	0.576 (2)	0.528 (4)	0.092*
C11	0.73302 (17)	0.4895 (2)	0.4442 (4)	0.0790 (7)
H11	0.7764 (19)	0.531 (2)	0.516 (4)	0.095*
C12	0.75807 (15)	0.4089 (2)	0.3391 (3)	0.0732 (6)
C13	0.69107 (16)	0.3541 (2)	0.2541 (3)	0.0710 (6)
H13	0.7080 (17)	0.296 (2)	0.174 (4)	0.085*
C14	0.60094 (15)	0.38315 (18)	0.2714 (3)	0.0669 (6)
C15	0.5531 (2)	0.2518 (2)	0.0813 (4)	0.0978 (9)
H15A	0.5949	0.2806	0.0061	0.147*
H15B	0.4989	0.2276	0.0297	0.147*
H15C	0.5801	0.1896	0.1344	0.147*
C16	0.85578 (17)	0.3797 (3)	0.3059 (4)	0.0944 (9)
H16A	0.8696	0.3101	0.3583	0.113*	0.695 (6)
H16C	0.8618	0.3665	0.1953	0.113*	0.695 (6)
H16D	0.8699	0.4052	0.2030	0.113*	0.305 (6)
H16B	0.8615	0.2999	0.3060	0.113*	0.305 (6)
C17A	0.9235 (3)	0.4622 (4)	0.3515 (7)	0.0994 (15)	0.695 (6)
H17A	0.9160	0.5350	0.3159	0.119*	0.695 (6)
C18A	0.9929 (3)	0.4418 (6)	0.4376 (8)	0.124 (2)	0.695 (6)
H18A	1.0026	0.3700	0.4754	0.148*	0.695 (6)
H18B	1.0333	0.4987	0.4618	0.148*	0.695 (6)
C17B	0.9235 (6)	0.4196 (9)	0.4153 (14)	0.0994 (15)	0.305 (6)
H17B	0.9228	0.3906	0.5155	0.119*	0.305 (6)
C18B	0.9847 (10)	0.4930 (13)	0.382 (3)	0.124 (2)	0.305 (6)
H18C	0.9872	0.5235	0.2825	0.148*	0.305 (6)
H18D	1.0263	0.5152	0.4567	0.148*	0.305 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0676 (8)	0.0717 (9)	0.0815 (12)	0.0061 (7)	0.0087 (8)	0.0191 (9)
O2	0.0739 (9)	0.0871 (11)	0.0874 (13)	−0.0033 (8)	−0.0090 (9)	−0.0118 (10)
N1	0.1000 (16)	0.1026 (17)	0.110 (2)	−0.0132 (13)	−0.0126 (14)	0.0421 (17)
N2	0.0752 (13)	0.1035 (16)	0.108 (2)	−0.0108 (12)	0.0071 (13)	−0.0001 (15)
C1	0.0660 (12)	0.0597 (11)	0.0568 (13)	0.0000 (9)	0.0044 (9)	−0.0005 (10)
C2	0.0622 (11)	0.0620 (11)	0.0607 (14)	0.0009 (9)	−0.0053 (10)	−0.0006 (10)
C3	0.0697 (12)	0.0576 (11)	0.0567 (13)	−0.0039 (9)	−0.0022 (9)	−0.0003 (10)
C4	0.0609 (11)	0.0682 (12)	0.0636 (14)	−0.0013 (9)	0.0013 (10)	−0.0050 (11)
C5	0.0656 (13)	0.0756 (13)	0.0711 (16)	0.0084 (10)	−0.0023 (11)	0.0017 (13)
C6	0.0718 (13)	0.0713 (14)	0.0616 (15)	0.0088 (10)	−0.0010 (11)	0.0061 (12)
C7	0.0703 (13)	0.0751 (13)	0.0766 (17)	−0.0089 (10)	−0.0071 (12)	0.0100 (13)
C8	0.0634 (12)	0.0784 (13)	0.0772 (17)	−0.0002 (11)	0.0007 (11)	−0.0007 (13)
C9	0.0631 (12)	0.0650 (12)	0.0646 (14)	−0.0006 (9)	0.0042 (10)	0.0100 (11)
C10	0.0858 (16)	0.0753 (14)	0.0680 (17)	−0.0058 (12)	0.0048 (13)	0.0063 (13)
C11	0.0739 (14)	0.0878 (15)	0.0753 (17)	−0.0131 (12)	−0.0074 (13)	0.0062 (14)
C12	0.0677 (12)	0.0778 (13)	0.0743 (18)	−0.0015 (11)	−0.0009 (11)	0.0156 (13)
C13	0.0700 (14)	0.0703 (13)	0.0727 (16)	0.0021 (11)	0.0026 (12)	0.0040 (13)
C14	0.0651 (11)	0.0704 (13)	0.0652 (14)	−0.0038 (10)	−0.0036 (10)	0.0089 (11)
C15	0.101 (2)	0.0907 (17)	0.102 (2)	−0.0066 (14)	−0.0140 (17)	−0.0210 (17)
C16	0.0680 (14)	0.104 (2)	0.111 (3)	−0.0034 (13)	−0.0023 (14)	0.0154 (19)
C17A	0.0668 (18)	0.090 (3)	0.141 (5)	0.000 (2)	−0.001 (2)	0.035 (3)
C18A	0.085 (2)	0.135 (6)	0.151 (7)	−0.016 (3)	−0.031 (3)	0.022 (4)
C17B	0.0668 (18)	0.090 (3)	0.141 (5)	0.000 (2)	−0.001 (2)	0.035 (3)
C18B	0.085 (2)	0.135 (6)	0.151 (7)	−0.016 (3)	−0.031 (3)	0.022 (4)

Geometric parameters (Å, º)

O1—C1	1.364 (3)	C11—H11	1.02 (3)
O1—C9	1.396 (3)	C12—C13	1.395 (4)
O2—C14	1.358 (3)	C12—C16	1.513 (4)
O2—C15	1.428 (3)	C13—C14	1.385 (3)
N1—C7	1.136 (3)	C13—H13	1.02 (3)
N2—C8	1.137 (3)	C15—H15A	0.96
C1—C2	1.379 (3)	C15—H15B	0.96
C1—C6	1.391 (3)	C15—H15C	0.96
C2—C3	1.386 (3)	C16—C17B	1.456 (9)
C2—H2	0.93 (3)	C16—C17A	1.460 (5)
C3—C4	1.400 (3)	C16—H16A	0.97
C3—C7	1.434 (4)	C16—H16C	0.97
C4—C5	1.390 (3)	C16—H16D	0.96
C4—C8	1.431 (3)	C16—H16B	0.96
C5—C6	1.366 (4)	C17A—C18A	1.289 (6)
C5—H5	1.01 (3)	C17A—H17A	0.93
C6—H6	0.97 (3)	C18A—H18A	0.93
C9—C10	1.372 (4)	C18A—H18B	0.93
C9—C14	1.385 (4)	C17B—C18B	1.294 (9)
C10—C11	1.389 (4)	C17B—H17B	0.93
C10—H10	0.94 (3)	C18B—H18C	0.93
C11—C12	1.374 (4)	C18B—H18D	0.93
C1—O1—C9	120.80 (16)	O2—C14—C13	124.9 (2)
C14—O2—C15	117.20 (19)	O2—C14—C9	115.89 (19)
O1—C1—C2	123.6 (2)	C13—C14—C9	119.2 (2)
O1—C1—C6	115.6 (2)	O2—C15—H15A	109.5
C2—C1—C6	120.8 (2)	O2—C15—H15B	109.5
C1—C2—C3	118.8 (2)	H15A—C15—H15B	109.5
C1—C2—H2	123.2 (16)	O2—C15—H15C	109.5
C3—C2—H2	118.0 (16)	H15A—C15—H15C	109.5
C2—C3—C4	120.8 (2)	H15B—C15—H15C	109.5
C2—C3—C7	120.8 (2)	C17B—C16—C12	117.3 (6)
C4—C3—C7	118.4 (2)	C17A—C16—C12	116.6 (3)
C5—C4—C3	119.0 (2)	C17A—C16—H16A	108.1
C5—C4—C8	120.9 (2)	C12—C16—H16A	108.1
C3—C4—C8	120.1 (2)	C17B—C16—H16C	128.8
C6—C5—C4	120.4 (2)	C17A—C16—H16C	108.1
C6—C5—H5	120.3 (15)	C12—C16—H16C	108.1
C4—C5—H5	119.2 (15)	H16A—C16—H16C	107.3
C5—C6—C1	120.1 (2)	C17B—C16—H16D	110.1
C5—C6—H6	122.4 (14)	C12—C16—H16D	108.0
C1—C6—H6	117.5 (14)	H16A—C16—H16D	131.0
N1—C7—C3	177.0 (3)	C17B—C16—H16B	105.4
N2—C8—C4	179.6 (3)	C17A—C16—H16B	127.8
C10—C9—C14	120.9 (2)	C12—C16—H16B	108.3
C10—C9—O1	119.6 (2)	H16D—C16—H16B	107.3
C14—C9—O1	118.8 (2)	C18A—C17A—C16	124.9 (5)
C9—C10—C11	119.4 (3)	C18A—C17A—H17A	117.6
C9—C10—H10	114.7 (17)	C16—C17A—H17A	117.6
C11—C10—H10	125.8 (16)	C17A—C18A—H18A	120.0
C12—C11—C10	120.9 (3)	C17A—C18A—H18B	120.0
C12—C11—H11	125.0 (17)	H18A—C18A—H18B	120.0
C10—C11—H11	114.0 (17)	C18B—C17B—C16	123.9 (13)
C11—C12—C13	119.0 (2)	C18B—C17B—H17B	118.0
C11—C12—C16	122.9 (2)	C16—C17B—H17B	118.0
C13—C12—C16	118.0 (3)	C17B—C18B—H18C	120.0
C14—C13—C12	120.5 (2)	C17B—C18B—H18D	120.0
C14—C13—H13	118.9 (15)	H18C—C18B—H18D	120.0
C12—C13—H13	120.4 (15)
C9—O1—C1—C2	21.1 (3)	C10—C11—C12—C13	−2.8 (4)
C9—O1—C1—C6	−161.3 (2)	C10—C11—C12—C16	174.6 (3)
O1—C1—C2—C3	177.3 (2)	C11—C12—C13—C14	2.3 (4)
C6—C1—C2—C3	−0.2 (3)	C16—C12—C13—C14	−175.3 (2)
C1—C2—C3—C4	1.3 (3)	C15—O2—C14—C13	0.6 (4)
C1—C2—C3—C7	−178.6 (2)	C15—O2—C14—C9	178.3 (2)
C2—C3—C4—C5	−1.9 (3)	C12—C13—C14—O2	178.0 (2)
C7—C3—C4—C5	178.0 (2)	C12—C13—C14—C9	0.3 (3)
C2—C3—C4—C8	178.7 (2)	C10—C9—C14—O2	179.7 (2)
C7—C3—C4—C8	−1.4 (3)	O1—C9—C14—O2	−10.3 (3)
C3—C4—C5—C6	1.4 (3)	C10—C9—C14—C13	−2.4 (4)
C8—C4—C5—C6	−179.2 (2)	O1—C9—C14—C13	167.6 (2)
C4—C5—C6—C1	−0.3 (4)	C11—C12—C16—C17B	14.8 (6)
O1—C1—C6—C5	−178.0 (2)	C13—C12—C16—C17B	−167.7 (5)
C2—C1—C6—C5	−0.3 (4)	C11—C12—C16—C17A	−18.7 (5)
C1—O1—C9—C10	−111.8 (2)	C13—C12—C16—C17A	158.7 (3)
C1—O1—C9—C14	78.0 (3)	C17B—C16—C17A—C18A	27.7 (11)
C14—C9—C10—C11	1.9 (4)	C12—C16—C17A—C18A	126.7 (6)
O1—C9—C10—C11	−168.0 (2)	C17A—C16—C17B—C18B	−17.3 (12)
C9—C10—C11—C12	0.8 (4)	C12—C16—C17B—C18B	−113.7 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N2^i	0.93 (3)	2.61 (3)	3.510 (3)	166 (2)
C16—H16A···Cg1^i	0.97	2.88	3.808 (4)	160

Symmetry code: (i) x+1/2, −y+1/2, z.