4,4′-(N-Phenyl-2,2′-imino­diethano­xy)­diphthalo­nitrile

The title compound, C₂₆H₁₉N₅O₂, contains three aromatic rings, which are not coplanar. The crystal structure is stabilized by intermolecular C—H...N contacts.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.044
• wR factor = 0.138
• Data-to-parameter ratio = 11.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           62.97
         From the CIF: _reflns_number_total               3484
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         3810
         Completeness (_total/calc)             91.44%
          Alert C: < 95% complete

THETM_01  Alert C The value of sine(theta_max)/wavelength is less than 0.590
          Calculated sin(theta_max)/wavelength =    0.5777

PLAT_371  Alert C Long   C(sp2)-C(sp1) Bond  C8     -   C24      =       1.44 Ang.

PLAT_371  Alert C Long   C(sp2)-C(sp1) Bond  C13    -   C23      =       1.44 Ang.

PLAT_371  Alert C Long   C(sp2)-C(sp1) Bond  C14    -   C26      =       1.43 Ang.

PLAT_371  Alert C Long   C(sp2)-C(sp1) Bond  C21    -   C25      =       1.44 Ang.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 6 Alert Level C = Please check

---

S1. Comment

Diphthalonitriles have been used as starting materials for network polymeric phthalocyanines (McKeown, 1998). Phthalocyanine compounds have been widely studied for over 50 years due to their varied applications (Moser et al., 1983). Polymeric phthalocyanines have been described for use as dyes and industrial high-tech materials and are also of additional interest because of their high thermostability (Leznoff & Lever, 1989–1996).

An ORTEPIII (Burnett & Johnson, 1996) plot of the title structure, (I), is shown in Fig. 1. The bond distances and angles in (I) are normal (Table 1). The average N≡C bond distance in cyano groups, 1.139 (4) Å, is short enough to indicate its triple- bond character. This value is in good agreement with those in 4,4'-[2,2-methylenebis(4-chlorophenoxy)]diphthalonitrile (Çoruh et al., 2002) and 4-(phenothiazin-10-yl)benzene-1,2-dicarbonitrile ("Oztürk et al., 1999). The O—C bond distances correspond to those in 4,4'-[2,2-methylenebis(4-chlorophenoxy)]diphthalonitrile (Çoruh et al., 2002)."

The three phenyl rings in the molecule are essentially planar. The dihedral angle between ring A (C13/C11/C4/C16/C15/C8) and ring B (C7/C21/C14/C17/C20/C12) planes is 70.73 (7)°, while the dihedral angle between ring A and ring C (C3/C18/C28/C29/C27/C5) planes is 73.54(0.10)°. The angle between B and C planes is 69.23(0.10)°.

The crystal structure is stabilized by intermolecular C—H···N contacts (Table 2).

S2. Experimental

N-Phenyl-2,2'-iminodiethanol (1.17 g, 6.46 mmol) was dissolved in dry DMF and 4-nitrophthalonitrile (2.15 g, 12.43 mmol) was added. After stirring for 30 min, finely ground anhydrous K₂CO₃ (2.76 g, 20 mmol) was added portionwise in 2 h with efficient stirring. The reaction mixture was stirred for 24 h at 333 K and then poured into ice water (200 g). The product filtered off and washed with water until the filtrate was neutral. The product was then refluxed in methanol, filtered and dried. The title compound (I), was crystallized from dimethylformamide via slow evaporation at room temperature (yield 0.29 g, 10.8%). M.p.: 433 K. IR (ν_max/cm^-1): 3100–3040 (Ar—CH), 2940–2900 (CH), 2220 (CN), 1660, 1588, 1556, 1484, 1452, 1424, 1388, 1360, 1288, 1240, 1192, 1168, 1116, 1092, 1028, 1016, 984, 952, 908, 888, 844, 828, 748, 725, 690, 640, 624, 590, 550, 520. ¹H NMR (acetone-d₆): 4.01 (t,2H), 4.47 (t,2H), 6.68–7.95 (m,6H). ¹³C NMR (acetone-d₆): 51.18 (CH₂—N), 68.17 (CH₂—O), 107.93, 113.52, 116.47, 117.06, 117.97, 120.75, 120.93, 130.19, 136.38, 147.94, 163.18. Analysis calculated for C₂₆H₁₉N₅O₂: C 72.04, H 4.42, N 16.16%; found: C 72.04, H 4.39, N 16.14%.

S3. Refinement

The H atoms were located geometrically and refined using a riding model.

Computing details

Data collection: COLLECT (Nonius, 1997-2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: WinGX (Farrugia, 1997) and PARST (Nardelli, 1995).

Figures

Fig. 1. An ORTEPIII drawing (burnett & Johnson, 1996) of the title compound, showing the atomic numbering scheme. Displacement ellipsoids of non-H atoms are shown at the 50% probability level.

4,4'-(N-Phenyl-2,2'-iminodiethanoxy)diphthalonitrile

Crystal data

C26H19N5O2	F(000) = 1808
Mr = 433.46	Dx = 1.222 Mg m^−3
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3683 reflections
a = 16.621 (5) Å	θ = 0.0–64.5°
b = 9.004 (5) Å	µ = 0.65 mm^−1
c = 31.494 (5) Å	T = 293 K
V = 4713 (3) Å^3	Prismatic, dark yellow
Z = 8	0.25 × 0.18 × 0.13 mm

Data collection

Nonius KappaCCD diffractometer	1872 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.001
Graphite monochromator	θmax = 63.0°, θmin = 3.9°
Detector resolution: 9 pixels mm^-1	h = −18→18
ω–2θ scans	k = −9→9
6338 measured reflections	l = −36→35
3484 independent 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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0507P)^2 + 0.7824P] where P = (Fo^2 + 2Fc^2)/3
3484 reflections	(Δ/σ)max < 0.001
298 parameters	Δρmax = 0.11 e Å^−3
0 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
O1	1.11340 (10)	0.54371 (19)	0.59502 (6)	0.0864 (6)
N2	0.99288 (12)	0.3341 (2)	0.62351 (7)	0.0787 (6)
C3	1.00467 (14)	0.1828 (3)	0.62566 (8)	0.0690 (7)
C4	1.18079 (16)	0.5885 (3)	0.57522 (9)	0.0763 (7)
C5	1.05667 (15)	0.1218 (3)	0.65566 (9)	0.0852 (8)
H5	1.0828	0.1838	0.6748	0.102*
O6	0.85398 (11)	0.4874 (2)	0.65186 (7)	0.1084 (7)
C7	0.79704 (17)	0.6020 (3)	0.71028 (10)	0.0908 (9)
H7	0.8484	0.6318	0.7184	0.109*
C8	1.31338 (18)	0.6958 (3)	0.53085 (10)	0.0880 (9)
C9	1.03740 (17)	0.4346 (3)	0.65037 (9)	0.0907 (9)
H9A	1.0406	0.3929	0.6787	0.109*
H9B	1.0085	0.5279	0.6523	0.109*
C10	1.12138 (16)	0.4644 (3)	0.63439 (9)	0.0875 (8)
H10A	1.1511	0.5234	0.6548	0.105*
H10B	1.1499	0.3718	0.6299	0.105*
C11	1.16970 (17)	0.6789 (3)	0.53976 (9)	0.0842 (8)
H11	1.1180	0.7031	0.5309	0.101*
C12	0.78608 (18)	0.5158 (3)	0.67405 (10)	0.0881 (8)
C13	1.23535 (18)	0.7325 (3)	0.51787 (9)	0.0843 (8)
C14	0.65391 (17)	0.5975 (3)	0.72282 (10)	0.0875 (8)
C15	1.32313 (17)	0.6049 (4)	0.56557 (10)	0.0958 (9)
H15	1.3748	0.5785	0.5740	0.115*
C16	1.25782 (17)	0.5516 (3)	0.58828 (9)	0.0891 (8)
H16	1.2656	0.4918	0.6120	0.107*
C17	0.64556 (17)	0.5084 (3)	0.68754 (10)	0.0959 (9)
H17	0.5945	0.4749	0.6801	0.115*
C18	0.96601 (16)	0.0857 (4)	0.59793 (9)	0.0909 (9)
H18	0.9301	0.1223	0.5779	0.109*
C19	0.84996 (17)	0.3978 (4)	0.61419 (10)	0.0999 (10)
H19A	0.8116	0.4392	0.5942	0.120*
H19B	0.8336	0.2973	0.6211	0.120*
C20	0.71044 (18)	0.4672 (3)	0.66285 (10)	0.0939 (9)
H20	0.7032	0.4077	0.6390	0.113*
C21	0.73120 (18)	0.6426 (3)	0.73402 (10)	0.0866 (8)
C22	0.93342 (17)	0.3988 (3)	0.59559 (9)	0.0980 (9)
H22A	0.9330	0.3441	0.5690	0.118*
H22B	0.9487	0.5004	0.5893	0.118*
C23	1.22418 (19)	0.8288 (4)	0.48186 (13)	0.1080 (11)
C24	1.3821 (2)	0.7532 (4)	0.50859 (11)	0.1144 (11)
C25	0.74284 (19)	0.7335 (4)	0.77131 (13)	0.1090 (11)
C26	0.5848 (2)	0.6437 (4)	0.74660 (10)	0.1051 (10)
C27	1.0698 (2)	−0.0271 (5)	0.65729 (14)	0.1229 (13)
H27	1.1044	−0.0653	0.6778	0.148*
C28	0.9811 (2)	−0.0658 (5)	0.60024 (14)	0.1262 (13)
H28	0.9554	−0.1303	0.5816	0.151*
C29	1.0335 (3)	−0.1208 (5)	0.62975 (19)	0.1436 (18)
H29	1.0441	−0.2221	0.6309	0.172*
N30	1.43768 (19)	0.7975 (4)	0.49135 (10)	0.1578 (13)
N31	1.21692 (18)	0.9059 (4)	0.45360 (11)	0.1447 (13)
N32	0.75208 (19)	0.8047 (4)	0.80074 (11)	0.1499 (13)
N33	0.52887 (18)	0.6815 (4)	0.76449 (10)	0.1413 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0728 (12)	0.0835 (13)	0.1028 (15)	−0.0038 (9)	0.0040 (10)	0.0121 (11)
N2	0.0726 (14)	0.0626 (15)	0.1008 (18)	0.0058 (11)	−0.0062 (12)	0.0022 (13)
C3	0.0611 (15)	0.0595 (17)	0.087 (2)	0.0032 (13)	0.0066 (14)	0.0035 (15)
C4	0.0698 (19)	0.0695 (18)	0.090 (2)	−0.0049 (14)	−0.0016 (16)	−0.0078 (16)
C5	0.0727 (18)	0.078 (2)	0.105 (2)	0.0000 (14)	0.0021 (16)	0.0188 (17)
O6	0.0786 (13)	0.1229 (17)	0.1237 (18)	0.0178 (11)	0.0018 (12)	−0.0206 (15)
C7	0.081 (2)	0.088 (2)	0.104 (2)	0.0054 (16)	−0.0099 (18)	0.0013 (19)
C8	0.080 (2)	0.102 (2)	0.083 (2)	−0.0168 (17)	0.0021 (17)	−0.0142 (19)
C9	0.101 (2)	0.0676 (18)	0.104 (2)	−0.0067 (16)	0.0154 (18)	−0.0056 (16)
C10	0.088 (2)	0.0780 (19)	0.096 (2)	−0.0096 (15)	−0.0038 (17)	0.0045 (17)
C11	0.080 (2)	0.082 (2)	0.091 (2)	−0.0069 (15)	−0.0068 (16)	0.0012 (17)
C12	0.074 (2)	0.090 (2)	0.100 (2)	0.0199 (16)	−0.0018 (18)	0.0029 (19)
C13	0.088 (2)	0.088 (2)	0.077 (2)	−0.0142 (17)	−0.0054 (17)	−0.0044 (17)
C14	0.076 (2)	0.100 (2)	0.087 (2)	0.0087 (16)	−0.0084 (17)	0.0042 (19)
C15	0.0679 (19)	0.112 (2)	0.107 (3)	−0.0072 (17)	−0.0114 (17)	−0.011 (2)
C16	0.0724 (19)	0.096 (2)	0.099 (2)	−0.0059 (16)	−0.0106 (17)	0.0026 (17)
C17	0.074 (2)	0.111 (2)	0.103 (3)	0.0093 (17)	−0.0156 (18)	−0.001 (2)
C18	0.0749 (18)	0.093 (2)	0.105 (2)	−0.0066 (16)	0.0077 (16)	−0.0163 (19)
C19	0.087 (2)	0.115 (2)	0.098 (2)	0.0336 (17)	−0.0096 (17)	0.000 (2)
C20	0.074 (2)	0.105 (2)	0.103 (2)	0.0201 (17)	−0.0148 (18)	−0.0103 (18)
C21	0.087 (2)	0.083 (2)	0.090 (2)	0.0065 (16)	−0.0061 (18)	0.0002 (17)
C22	0.101 (2)	0.091 (2)	0.102 (2)	0.0266 (17)	0.0050 (18)	0.0197 (17)
C23	0.103 (2)	0.124 (3)	0.097 (3)	−0.030 (2)	−0.004 (2)	0.007 (2)
C24	0.092 (2)	0.149 (3)	0.102 (3)	−0.028 (2)	0.011 (2)	−0.025 (2)
C25	0.094 (2)	0.119 (3)	0.115 (3)	0.009 (2)	−0.007 (2)	−0.008 (2)
C26	0.093 (2)	0.135 (3)	0.088 (3)	0.008 (2)	−0.0004 (19)	0.000 (2)
C27	0.090 (2)	0.094 (3)	0.185 (4)	0.015 (2)	0.019 (2)	0.050 (3)
C28	0.114 (3)	0.096 (3)	0.168 (4)	−0.025 (2)	0.035 (3)	−0.045 (3)
C29	0.124 (4)	0.068 (3)	0.238 (6)	0.010 (2)	0.057 (4)	0.006 (3)
N30	0.121 (3)	0.208 (3)	0.144 (3)	−0.054 (2)	0.036 (2)	−0.023 (2)
N31	0.130 (3)	0.182 (3)	0.122 (3)	−0.042 (2)	−0.013 (2)	0.045 (2)
N32	0.127 (2)	0.181 (3)	0.141 (3)	0.008 (2)	−0.020 (2)	−0.056 (3)
N33	0.111 (2)	0.191 (3)	0.123 (3)	0.007 (2)	0.0179 (19)	−0.017 (2)

Geometric parameters (Å, º)

O1—C4	1.344 (3)	C13—C23	1.440 (5)
O1—C10	1.437 (3)	C14—C17	1.377 (4)
N2—C3	1.378 (3)	C14—C21	1.393 (4)
N2—C9	1.443 (3)	C14—C26	1.433 (4)
N2—C22	1.445 (3)	C15—C16	1.386 (4)
C3—C18	1.393 (3)	C15—H15	0.9300
C3—C5	1.393 (3)	C16—H16	0.9300
C4—C16	1.385 (3)	C17—C20	1.380 (4)
C4—C11	1.394 (3)	C17—H17	0.9300
C5—C27	1.359 (4)	C18—C28	1.389 (4)
C5—H5	0.9300	C18—H18	0.9300
O6—C12	1.352 (3)	C19—C22	1.506 (4)
O6—C19	1.436 (3)	C19—H19A	0.9700
C7—C21	1.375 (3)	C19—H19B	0.9700
C7—C12	1.392 (4)	C20—H20	0.9300
C7—H7	0.9300	C21—C25	1.445 (5)
C8—C15	1.376 (4)	C22—H22A	0.9700
C8—C13	1.399 (4)	C22—H22B	0.9700
C8—C24	1.436 (4)	C23—N31	1.135 (4)
C9—C10	1.508 (3)	C24—N30	1.144 (4)
C9—H9A	0.9700	C25—N32	1.137 (4)
C9—H9B	0.9700	C26—N33	1.139 (4)
C10—H10A	0.9700	C27—C29	1.352 (5)
C10—H10B	0.9700	C27—H27	0.9300
C11—C13	1.378 (3)	C28—C29	1.367 (5)
C11—H11	0.9300	C28—H28	0.9300
C12—C20	1.377 (4)	C29—H29	0.9300
C4—O1—C10	118.2 (2)	C8—C15—C16	121.6 (3)
C3—N2—C9	121.2 (2)	C8—C15—H15	119.2
C3—N2—C22	121.7 (2)	C16—C15—H15	119.2
C9—N2—C22	117.1 (2)	C4—C16—C15	119.2 (3)
N2—C3—C18	121.6 (3)	C4—C16—H16	120.4
N2—C3—C5	120.7 (3)	C15—C16—H16	120.4
C18—C3—C5	117.6 (3)	C14—C17—C20	122.2 (3)
O1—C4—C16	124.1 (3)	C14—C17—H17	118.9
O1—C4—C11	115.9 (2)	C20—C17—H17	118.9
C16—C4—C11	120.0 (3)	C28—C18—C3	120.0 (3)
C27—C5—C3	120.9 (3)	C28—C18—H18	120.0
C27—C5—H5	119.5	C3—C18—H18	120.0
C3—C5—H5	119.5	O6—C19—C22	106.0 (3)
C12—O6—C19	119.6 (2)	O6—C19—H19A	110.5
C21—C7—C12	119.3 (3)	C22—C19—H19A	110.5
C21—C7—H7	120.3	O6—C19—H19B	110.5
C12—C7—H7	120.3	C22—C19—H19B	110.5
C15—C8—C13	118.8 (3)	H19A—C19—H19B	108.7
C15—C8—C24	120.6 (3)	C12—C20—C17	118.9 (3)
C13—C8—C24	120.6 (3)	C12—C20—H20	120.5
N2—C9—C10	113.0 (2)	C17—C20—H20	120.5
N2—C9—H9A	109.0	C7—C21—C14	121.3 (3)
C10—C9—H9A	109.0	C7—C21—C25	119.1 (3)
N2—C9—H9B	109.0	C14—C21—C25	119.6 (3)
C10—C9—H9B	109.0	N2—C22—C19	113.0 (2)
H9A—C9—H9B	107.8	N2—C22—H22A	109.0
O1—C10—C9	106.9 (2)	C19—C22—H22A	109.0
O1—C10—H10A	110.3	N2—C22—H22B	109.0
C9—C10—H10A	110.3	C19—C22—H22B	109.0
O1—C10—H10B	110.3	H22A—C22—H22B	107.8
C9—C10—H10B	110.3	N31—C23—C13	178.6 (4)
H10A—C10—H10B	108.6	N30—C24—C8	178.7 (5)
C13—C11—C4	120.0 (3)	N32—C25—C21	179.8 (5)
C13—C11—H11	120.0	N33—C26—C14	178.1 (4)
C4—C11—H11	120.0	C29—C27—C5	121.3 (4)
O6—C12—C20	124.7 (3)	C29—C27—H27	119.3
O6—C12—C7	114.8 (3)	C5—C27—H27	119.3
C20—C12—C7	120.4 (3)	C29—C28—C18	120.4 (4)
C11—C13—C8	120.4 (3)	C29—C28—H28	119.8
C11—C13—C23	120.2 (3)	C18—C28—H28	119.8
C8—C13—C23	119.5 (3)	C27—C29—C28	119.6 (4)
C17—C14—C21	117.8 (3)	C27—C29—H29	120.2
C17—C14—C26	120.7 (3)	C28—C29—H29	120.2
C21—C14—C26	121.5 (3)
C9—N2—C3—C18	−175.6 (2)	C24—C8—C15—C16	178.1 (3)
C22—N2—C3—C18	6.9 (4)	O1—C4—C16—C15	−179.6 (2)
C9—N2—C3—C5	3.8 (3)	C11—C4—C16—C15	−0.4 (4)
C22—N2—C3—C5	−173.8 (2)	C8—C15—C16—C4	1.2 (4)
C10—O1—C4—C16	6.1 (4)	C21—C14—C17—C20	−1.9 (4)
C10—O1—C4—C11	−173.1 (2)	C26—C14—C17—C20	177.1 (3)
N2—C3—C5—C27	−178.6 (2)	N2—C3—C18—C28	178.2 (3)
C18—C3—C5—C27	0.8 (4)	C5—C3—C18—C28	−1.2 (4)
C3—N2—C9—C10	79.7 (3)	C12—O6—C19—C22	175.4 (2)
C22—N2—C9—C10	−102.7 (3)	O6—C12—C20—C17	−177.8 (3)
C4—O1—C10—C9	177.4 (2)	C7—C12—C20—C17	1.6 (4)
N2—C9—C10—O1	66.2 (3)	C14—C17—C20—C12	0.5 (5)
O1—C4—C11—C13	178.8 (2)	C12—C7—C21—C14	0.9 (4)
C16—C4—C11—C13	−0.5 (4)	C12—C7—C21—C25	−179.3 (3)
C19—O6—C12—C20	−1.5 (4)	C17—C14—C21—C7	1.1 (4)
C19—O6—C12—C7	179.2 (2)	C26—C14—C21—C7	−177.8 (3)
C21—C7—C12—O6	177.1 (2)	C17—C14—C21—C25	−178.7 (3)
C21—C7—C12—C20	−2.3 (4)	C26—C14—C21—C25	2.3 (4)
C4—C11—C13—C8	0.5 (4)	C3—N2—C22—C19	82.7 (3)
C4—C11—C13—C23	−178.5 (3)	C9—N2—C22—C19	−94.9 (3)
C15—C8—C13—C11	0.4 (4)	O6—C19—C22—N2	62.0 (3)
C24—C8—C13—C11	−179.0 (3)	C3—C5—C27—C29	0.6 (5)
C15—C8—C13—C23	179.3 (3)	C3—C18—C28—C29	0.3 (5)
C24—C8—C13—C23	0.0 (4)	C5—C27—C29—C28	−1.5 (6)
C13—C8—C15—C16	−1.2 (4)	C18—C28—C29—C27	1.1 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···O6	0.97	2.59	3.086 (4)	112
C19—H19A···N31^i	0.97	2.59	3.546 (5)	170

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