Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805029053/ac6181sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805029053/ac6181Isup2.hkl |
CCDC reference: 287425
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.004 Å
- R factor = 0.053
- wR factor = 0.156
- Data-to-parameter ratio = 16.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low .... 47 Perc. PLAT230_ALERT_2_C Hirshfeld Test Diff for C9 - C14 .. 5.76 su PLAT230_ALERT_2_C Hirshfeld Test Diff for C11 - C12 .. 5.10 su PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C21 PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C5 - C8 ... 1.43 Ang. PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C6 - C7 ... 1.43 Ang. PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C22 PLAT480_ALERT_4_C Long H...A H-Bond Reported H15A .. N2 .. 2.71 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H17 .. N2 .. 2.79 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H22A .. O1 .. 2.90 Ang. PLAT482_ALERT_4_C Small D-H..A Angle Rep for C19 .. N3 .. 95.00 Deg. PLAT717_ALERT_1_C D...A Unknown or Inconsistent Label .......... G2
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 12 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 5 ALERT type 4 Improvement, methodology, query or suggestion
A mixture of 4-methylaniline (2.84 g, 26 mmol), water (50 ml) and concentrated hydrochloric acid (6.6 ml, 79 mmol) was stirred until a clear solution was obtained. This solution was cooled to 273–278 K and a solution of nitrite (2.5 g, 36.4 mmol) in water was added dropwise while the temperature was maintained below 278 K. The resulting mixture was stirred for 30 min in an ice bath. o-Cresol (3.9 g, 36.4 mmol) solution (pH 9) was added gradually to a cooled solution of 4-methylbenzenediazonium chloride, prepared as described above, and the resulting mixture was stirred at 273–278 K for 60 min in an ice bath. The product was recrystallized from ethanol to obtain solid 2-methyl-4- (4-methylphenylazo)phenol (yield 84%, m.p. 441–443 K). To a solution of the solid (3.74 g, 16.5 mmol) in dimethylformamide (DMF) was added potasium carbonate (3.43 g, 33 mmol). The mixture was stirred for 30 min under N2. 4-Nitrophtalonitrile solution in DMF was added. The mixture was stirred for 48 h at 323 K under N2 and poured into ice-water (150 g). The product was filtered off and washed with water. The product was recrystallized from ethanol to obtain solid (I). Crystals of (I) were obtained from an ethanol/CCl4 (1:2) mixture at room temparature via slow evaporation (yield 68%, m.p. 424–426 K).
The H atoms of atoms C19 and C22 were positioned geometrically at distances of 0.93 and 0.96 Å, respectively, from the parent C atoms; a riding model was used and Uiso(H) values were constrained to be 1.2 and 1.5 times Ueq(C), respectively. The other H atoms were located in a difference Fourier map and refined freely [CH C—H = 0.88 (3)–1.07 (3) Å, CH3 C—H = 0.94 (4)–0.97 (3) Å and Uiso(H) = 0.062 (6)–0.114 (12) Å2]. Please check changes to first sentence.
4-[2-Methyl-4-(4-methylphenyldiazenyl)phenoxy]phtalonitrile, (I), is a starting material in the synthesis of network polymeric phthalocyanines and high-performance aromatic polymers (McKeown, 1998; Takekoshi, 1987). In addition to their extensive use as dyes and pigments, phthalocyanines have found widespread applications in catalysis, optical recording, photoconductive materials, photodynamic theraphy and as chemical sensors (Leznoff & Lever, 1989–1996).
Polymeric phthalocyanines have been known for their use as dyes and industrial high-technology materials and are also of additional interest because of their high thermostability (Leznoff & Lever, 1989–1996). Azo compounds have been the most widely used class of dyes owing to their versatile applications in various fields, such as dyeing textile fibres, colouring different materials, plastics, biological medical studies, lasers, liquid crystalline displays, electrooptical devices and ink-jet printers in high-technology areas (Catino & Farris, 1985; Gregory, 1991). The azo compound class accounts for 60–70% of all dyes. The geometric isomerism of azo compounds is known to exist in two forms, viz. cis and trans. A change from trans to cis can be effected by exposure to UV radiation, which can lead to photochromism. Photochromic compounds are of great interest for the control and measurement of radiation intensity, optical computers and display systems (Dürr & Bouas-Laurent, 1990). Photochromic materials of this type are of interest for potential applications in molecular electronic devices (Martin et al., 1995), among others.
The molecular structure of (I) is shown in Fig. 1, with the atom-numbering scheme. Selected bond distances and angles are given in Table 1. The phenyl rings C9–C14 and C16–C21 adopt trans configurations about the azo funtional group, as observed in crystals of other azo compounds. The N3—C10 and N4—C18 bond lengths of 1.459 (3) and 1.449 (3) Å, respectively, indicate single-bond character, and the –N═N– bond length of 1.218 (3) Å is indicative of significant double-bond character. Similar values for corresponding bond distances and angles have been observed in related trans-azo compounds (Alder et al., 1999, 2001; Dimmock et al., 1997; Ersanlı et al., 2004; Koşar et al., 2004). The dihedral angles between the mean planes of the C9–C14 and C16–C21 phenyls rings and the C18—N4═N3—C10 azo bridge are 13.59 (9) and 33.3 (5)°, respectively. The C1—C2—O1—C13 and C10—N3—N4—C18 torsion angles are 145.4 (2) and -179.15 (18)°, respectively. The dihedral angles between rings A (C1–C6), B (C9–C14) and C (C16–C21) are A/B = 88.39 (6)°, A/C = 88.39 (6)° and B/C = 13.09 (14)°. The intramolecular C—H···N hydrogen bonds (Table 2) seem to affect the molecular conformation (Fig. 1). The molecules are linked by intermolecular C—H···N and C—H···O hydrogen bonds, and C—H···π interactions (Table 2), forming a three-dimensional network. In Table 2, Cg2 is the centroid of ring B. The C19—H19···N3 hydrogen-bonded ring is coplanar with the adjacent ring, with a C19—C18—N4—N3 torsion angle of 0.32 (34) Å.
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED (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).
C22H16N4O | F(000) = 736 |
Mr = 352.39 | Dx = 1.290 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -p 2ybc | Cell parameters from 13869 reflections |
a = 12.7084 (10) Å | θ = 1.8–27.9° |
b = 8.0446 (9) Å | µ = 0.08 mm−1 |
c = 20.2971 (16) Å | T = 296 K |
β = 119.050 (5)° | Prism., brown |
V = 1814.0 (3) Å3 | 0.43 × 0.30 × 0.14 mm |
Z = 4 |
Stoe IPDS-2 diffractometer | 4285 independent reflections |
Radiation source: sealed X-ray tube | 1998 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.059 |
Detector resolution: 6.67 pixels mm-1 | θmax = 27.8°, θmin = 1.8° |
rotation method scans | h = −16→16 |
Absorption correction: integration (X-RED; Stoe & Cie, 2002) | k = −10→10 |
Tmin = 0.964, Tmax = 0.990 | l = −24→26 |
17432 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.157 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.91 | w = 1/[σ2(Fo2) + (0.0805P)2] where P = (Fo2 + 2Fc2)/3 |
4285 reflections | (Δ/σ)max < 0.001 |
256 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C22H16N4O | V = 1814.0 (3) Å3 |
Mr = 352.39 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.7084 (10) Å | µ = 0.08 mm−1 |
b = 8.0446 (9) Å | T = 296 K |
c = 20.2971 (16) Å | 0.43 × 0.30 × 0.14 mm |
β = 119.050 (5)° |
Stoe IPDS-2 diffractometer | 4285 independent reflections |
Absorption correction: integration (X-RED; Stoe & Cie, 2002) | 1998 reflections with I > 2σ(I) |
Tmin = 0.964, Tmax = 0.990 | Rint = 0.059 |
17432 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.157 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.91 | Δρmax = 0.40 e Å−3 |
4285 reflections | Δρmin = −0.21 e Å−3 |
256 parameters |
Experimental. 215 frames, detector distance = 100 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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.3345 (2) | 0.3867 (3) | 0.23129 (13) | 0.0569 (6) | |
C2 | 0.22959 (19) | 0.4437 (3) | 0.22799 (12) | 0.0507 (5) | |
C3 | 0.1716 (2) | 0.5822 (3) | 0.18615 (13) | 0.0553 (6) | |
C4 | 0.2187 (2) | 0.6653 (3) | 0.14674 (13) | 0.0567 (6) | |
C5 | 0.32372 (19) | 0.6113 (3) | 0.14962 (12) | 0.0545 (4) | |
C6 | 0.38272 (19) | 0.4719 (3) | 0.19314 (11) | 0.0521 (5) | |
C7 | 0.4958 (2) | 0.4225 (3) | 0.19989 (14) | 0.0678 (7) | |
C8 | 0.3745 (2) | 0.6987 (3) | 0.11033 (12) | 0.0545 (4) | |
C9 | 0.1391 (2) | 0.6045 (3) | 0.39910 (15) | 0.0614 (3) | |
C10 | 0.0191 (2) | 0.5799 (3) | 0.37385 (13) | 0.0614 (3) | |
C11 | −0.0488 (2) | 0.4847 (3) | 0.31002 (13) | 0.0614 (3) | |
C12 | 0.0079 (2) | 0.4130 (3) | 0.27338 (15) | 0.0608 (6) | |
C13 | 0.1288 (2) | 0.4377 (3) | 0.30063 (12) | 0.0524 (5) | |
C14 | 0.1985 (2) | 0.5340 (3) | 0.36421 (12) | 0.0541 (5) | |
C15 | 0.3310 (2) | 0.5592 (5) | 0.39446 (18) | 0.0699 (7) | |
C16 | −0.3294 (2) | 0.7384 (4) | 0.47598 (15) | 0.0701 (7) | |
C17 | −0.2813 (2) | 0.6619 (3) | 0.43649 (15) | 0.0660 (3) | |
C18 | −0.1680 (2) | 0.7045 (3) | 0.45024 (14) | 0.0660 (3) | |
C19 | −0.1054 (2) | 0.8267 (3) | 0.50270 (14) | 0.0660 (3) | |
H19 | −0.0292 | 0.8583 | 0.5117 | 0.079* | |
C20 | −0.1564 (2) | 0.9020 (4) | 0.54192 (16) | 0.0716 (7) | |
C21 | −0.2688 (2) | 0.8579 (3) | 0.52950 (14) | 0.0608 (6) | |
C22 | −0.3226 (3) | 0.9391 (4) | 0.57321 (17) | 0.0913 (9) | |
H22A | −0.2717 | 0.9188 | 0.6261 | 0.137* | |
H22B | −0.4010 | 0.8934 | 0.5575 | 0.137* | |
H22C | −0.3292 | 1.0566 | 0.5639 | 0.137* | |
N1 | 0.5869 (2) | 0.3875 (4) | 0.20607 (14) | 0.0996 (9) | |
N2 | 0.4172 (2) | 0.7694 (3) | 0.08035 (13) | 0.0838 (7) | |
N3 | −0.02561 (18) | 0.6637 (2) | 0.41914 (11) | 0.0614 (3) | |
N4 | −0.12549 (18) | 0.6172 (3) | 0.40522 (11) | 0.0660 (3) | |
O1 | 0.18625 (14) | 0.35213 (18) | 0.26680 (9) | 0.0622 (4) | |
H1 | 0.374 (2) | 0.291 (3) | 0.2605 (14) | 0.077 (8)* | |
H3 | 0.101 (2) | 0.615 (3) | 0.1860 (13) | 0.066 (7)* | |
H4 | 0.1753 (19) | 0.762 (3) | 0.1166 (12) | 0.062 (6)* | |
H9 | 0.183 (2) | 0.675 (3) | 0.4420 (15) | 0.087 (8)* | |
H11 | −0.140 (2) | 0.467 (3) | 0.2877 (13) | 0.077 (7)* | |
H12 | −0.034 (2) | 0.355 (3) | 0.2301 (14) | 0.068 (7)* | |
H15A | 0.367 (2) | 0.606 (3) | 0.4437 (16) | 0.083 (8)* | |
H15B | 0.367 (3) | 0.462 (4) | 0.3897 (18) | 0.114 (12)* | |
H15C | 0.348 (2) | 0.640 (4) | 0.3650 (15) | 0.083 (8)* | |
H16 | −0.410 (3) | 0.707 (3) | 0.4649 (15) | 0.092 (9)* | |
H17 | −0.327 (3) | 0.567 (4) | 0.3954 (17) | 0.109 (10)* | |
H20 | −0.120 (3) | 0.980 (4) | 0.5761 (16) | 0.089 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0664 (15) | 0.0519 (13) | 0.0550 (13) | 0.0111 (11) | 0.0315 (12) | 0.0057 (11) |
C2 | 0.0605 (13) | 0.0474 (12) | 0.0490 (12) | −0.0029 (10) | 0.0304 (10) | −0.0055 (10) |
C3 | 0.0551 (14) | 0.0561 (14) | 0.0582 (13) | 0.0045 (11) | 0.0303 (11) | −0.0010 (11) |
C4 | 0.0565 (13) | 0.0579 (14) | 0.0553 (13) | 0.0100 (11) | 0.0269 (11) | 0.0083 (12) |
C5 | 0.0544 (9) | 0.0572 (9) | 0.0499 (9) | 0.0023 (7) | 0.0236 (7) | −0.0003 (7) |
C6 | 0.0536 (12) | 0.0576 (13) | 0.0455 (11) | 0.0041 (10) | 0.0244 (10) | −0.0045 (10) |
C7 | 0.0661 (16) | 0.0763 (17) | 0.0651 (15) | 0.0178 (13) | 0.0352 (13) | 0.0157 (13) |
C8 | 0.0544 (9) | 0.0572 (9) | 0.0499 (9) | 0.0023 (7) | 0.0236 (7) | −0.0003 (7) |
C9 | 0.0650 (7) | 0.0612 (7) | 0.0631 (7) | 0.0025 (5) | 0.0352 (6) | 0.0072 (5) |
C10 | 0.0650 (7) | 0.0612 (7) | 0.0631 (7) | 0.0025 (5) | 0.0352 (6) | 0.0072 (5) |
C11 | 0.0650 (7) | 0.0612 (7) | 0.0631 (7) | 0.0025 (5) | 0.0352 (6) | 0.0072 (5) |
C12 | 0.0673 (16) | 0.0566 (14) | 0.0576 (14) | −0.0113 (12) | 0.0296 (13) | −0.0030 (12) |
C13 | 0.0658 (14) | 0.0450 (12) | 0.0565 (13) | 0.0001 (10) | 0.0376 (11) | 0.0019 (10) |
C14 | 0.0610 (13) | 0.0521 (13) | 0.0534 (12) | 0.0024 (10) | 0.0311 (11) | 0.0041 (11) |
C15 | 0.0652 (17) | 0.081 (2) | 0.0655 (17) | −0.0109 (15) | 0.0337 (14) | −0.0101 (16) |
C16 | 0.0609 (16) | 0.0806 (18) | 0.0762 (17) | −0.0056 (14) | 0.0391 (14) | 0.0121 (15) |
C17 | 0.0628 (7) | 0.0707 (8) | 0.0676 (7) | 0.0009 (6) | 0.0340 (6) | 0.0070 (6) |
C18 | 0.0628 (7) | 0.0707 (8) | 0.0676 (7) | 0.0009 (6) | 0.0340 (6) | 0.0070 (6) |
C19 | 0.0628 (7) | 0.0707 (8) | 0.0676 (7) | 0.0009 (6) | 0.0340 (6) | 0.0070 (6) |
C20 | 0.0653 (16) | 0.0819 (19) | 0.0678 (16) | 0.0001 (14) | 0.0325 (14) | −0.0090 (15) |
C21 | 0.0603 (14) | 0.0690 (15) | 0.0625 (14) | 0.0119 (12) | 0.0371 (12) | 0.0143 (13) |
C22 | 0.094 (2) | 0.103 (2) | 0.100 (2) | 0.0238 (17) | 0.0651 (18) | 0.0107 (18) |
N1 | 0.0790 (16) | 0.131 (2) | 0.1020 (19) | 0.0390 (15) | 0.0541 (15) | 0.0358 (17) |
N2 | 0.0827 (15) | 0.0904 (17) | 0.0904 (16) | 0.0066 (13) | 0.0515 (14) | 0.0230 (14) |
N3 | 0.0650 (7) | 0.0612 (7) | 0.0631 (7) | 0.0025 (5) | 0.0352 (6) | 0.0072 (5) |
N4 | 0.0628 (7) | 0.0707 (8) | 0.0676 (7) | 0.0009 (6) | 0.0340 (6) | 0.0070 (6) |
O1 | 0.0824 (11) | 0.0494 (9) | 0.0731 (11) | −0.0022 (8) | 0.0522 (10) | −0.0036 (8) |
C1—C6 | 1.380 (3) | C13—C14 | 1.393 (3) |
C1—C2 | 1.380 (3) | C13—O1 | 1.402 (3) |
C1—H1 | 0.95 (3) | C14—C15 | 1.500 (3) |
C2—O1 | 1.374 (3) | C15—H15A | 0.95 (3) |
C2—C3 | 1.377 (3) | C15—H15B | 0.94 (4) |
C3—C4 | 1.382 (3) | C15—H15C | 0.97 (3) |
C3—H3 | 0.93 (2) | C16—C17 | 1.368 (4) |
C4—C5 | 1.378 (3) | C16—C21 | 1.373 (4) |
C4—H4 | 0.98 (2) | C16—H16 | 0.97 (3) |
C5—C6 | 1.399 (3) | C17—C18 | 1.370 (3) |
C5—C8 | 1.431 (3) | C17—H17 | 1.07 (3) |
C6—C7 | 1.432 (3) | C18—C19 | 1.382 (4) |
C7—N1 | 1.138 (3) | C18—N4 | 1.449 (3) |
C8—N2 | 1.144 (3) | C19—C20 | 1.386 (4) |
C9—C10 | 1.367 (3) | C19—H19 | 0.9300 |
C9—C14 | 1.383 (3) | C20—C21 | 1.372 (4) |
C9—H9 | 0.96 (3) | C20—H20 | 0.88 (3) |
C10—C11 | 1.387 (3) | C21—C22 | 1.506 (3) |
C10—N3 | 1.459 (3) | C22—H22A | 0.9600 |
C11—C12 | 1.388 (3) | C22—H22B | 0.9600 |
C11—H11 | 1.02 (2) | C22—H22C | 0.9600 |
C12—C13 | 1.371 (3) | N3—N4 | 1.218 (3) |
C12—H12 | 0.90 (2) | ||
C6—C1—C2 | 119.3 (2) | C9—C14—C15 | 121.2 (2) |
C6—C1—H1 | 120.7 (15) | C13—C14—C15 | 122.5 (2) |
C2—C1—H1 | 120.0 (15) | C14—C15—H15A | 110.7 (16) |
O1—C2—C3 | 122.9 (2) | C14—C15—H15B | 110 (2) |
O1—C2—C1 | 116.1 (2) | H15A—C15—H15B | 116 (3) |
C3—C2—C1 | 120.9 (2) | C14—C15—H15C | 111.9 (16) |
C2—C3—C4 | 119.7 (2) | H15A—C15—H15C | 104 (2) |
C2—C3—H3 | 117.2 (15) | H15B—C15—H15C | 104 (3) |
C4—C3—H3 | 123.1 (15) | C17—C16—C21 | 122.6 (2) |
C5—C4—C3 | 120.4 (2) | C17—C16—H16 | 117.9 (16) |
C5—C4—H4 | 121.1 (13) | C21—C16—H16 | 119.4 (16) |
C3—C4—H4 | 118.5 (13) | C16—C17—C18 | 119.6 (3) |
C4—C5—C6 | 119.4 (2) | C16—C17—H17 | 123.0 (16) |
C4—C5—C8 | 120.8 (2) | C18—C17—H17 | 117.4 (16) |
C6—C5—C8 | 119.8 (2) | C17—C18—C19 | 119.3 (2) |
C1—C6—C5 | 120.3 (2) | C17—C18—N4 | 115.3 (2) |
C1—C6—C7 | 120.5 (2) | C19—C18—N4 | 125.4 (2) |
C5—C6—C7 | 119.2 (2) | C18—C19—C20 | 119.9 (2) |
N1—C7—C6 | 178.1 (3) | C18—C19—H19 | 120.0 |
N2—C8—C5 | 178.6 (3) | C20—C19—H19 | 120.0 |
C10—C9—C14 | 122.4 (2) | C21—C20—C19 | 121.1 (3) |
C10—C9—H9 | 118.8 (16) | C21—C20—H20 | 115.8 (19) |
C14—C9—H9 | 118.8 (16) | C19—C20—H20 | 123.0 (19) |
C9—C10—C11 | 120.3 (2) | C20—C21—C16 | 117.4 (2) |
C9—C10—N3 | 113.7 (2) | C20—C21—C22 | 120.7 (3) |
C11—C10—N3 | 126.0 (2) | C16—C21—C22 | 121.9 (2) |
C10—C11—C12 | 118.7 (2) | C21—C22—H22A | 109.5 |
C10—C11—H11 | 123.2 (13) | C21—C22—H22B | 109.5 |
C12—C11—H11 | 118.1 (14) | H22A—C22—H22B | 109.5 |
C13—C12—C11 | 119.7 (2) | C21—C22—H22C | 109.5 |
C13—C12—H12 | 118.8 (15) | H22A—C22—H22C | 109.5 |
C11—C12—H12 | 121.4 (15) | H22B—C22—H22C | 109.5 |
C12—C13—C14 | 122.6 (2) | N4—N3—C10 | 113.1 (2) |
C12—C13—O1 | 118.6 (2) | N3—N4—C18 | 111.7 (2) |
C14—C13—O1 | 118.59 (19) | C2—O1—C13 | 117.82 (17) |
C9—C14—C13 | 116.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19···N3 | 0.93 | 2.46 | 2.701 (3) | 95 |
C15—H15A···N2i | 0.96 (3) | 2.71 (3) | 3.649 (4) | 166 (2) |
C17—H17···N2ii | 1.07 (3) | 2.79 (3) | 3.534 (4) | 127 (2) |
C22—H22A···O1iii | 0.96 | 2.90 | 3.684 (3) | 140 |
C12—H12···Cg2ii | 0.90 (2) | 3.03 (2) | 3.796 (3) | 144.2 (19) |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x, y−1/2, −z+1/2; (iii) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C22H16N4O |
Mr | 352.39 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 12.7084 (10), 8.0446 (9), 20.2971 (16) |
β (°) | 119.050 (5) |
V (Å3) | 1814.0 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.43 × 0.30 × 0.14 |
Data collection | |
Diffractometer | Stoe IPDS2 |
Absorption correction | Integration (X-RED; Stoe & Cie, 2002) |
Tmin, Tmax | 0.964, 0.990 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17432, 4285, 1998 |
Rint | 0.059 |
(sin θ/λ)max (Å−1) | 0.656 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.157, 0.91 |
No. of reflections | 4285 |
No. of parameters | 256 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.40, −0.21 |
Computer programs: X-AREA (Stoe & Cie, 2002), X-AREA, X-RED (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
C1—C6 | 1.380 (3) | C9—C14 | 1.383 (3) |
C1—C2 | 1.380 (3) | C10—C11 | 1.387 (3) |
C3—C4 | 1.382 (3) | C11—C12 | 1.388 (3) |
C5—C6 | 1.399 (3) | C13—C14 | 1.393 (3) |
C5—C8 | 1.431 (3) | C18—C19 | 1.382 (4) |
C6—C7 | 1.432 (3) | C19—C20 | 1.386 (4) |
C6—C1—C2 | 119.3 (2) | C17—C18—C19 | 119.3 (2) |
C3—C2—C1 | 120.9 (2) | C21—C20—C19 | 121.1 (3) |
C4—C5—C6 | 119.4 (2) | C20—C21—C16 | 117.4 (2) |
C10—C9—C14 | 122.4 (2) | N4—N3—C10 | 113.1 (2) |
C10—C11—C12 | 118.7 (2) | N3—N4—C18 | 111.7 (2) |
C12—C13—C14 | 122.6 (2) | C2—O1—C13 | 117.82 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19···N3 | 0.93 | 2.46 | 2.701 (3) | 95 |
C15—H15A···N2i | 0.96 (3) | 2.71 (3) | 3.649 (4) | 166 (2) |
C17—H17···N2ii | 1.07 (3) | 2.79 (3) | 3.534 (4) | 127 (2) |
C22—H22A···O1iii | 0.96 | 2.90 | 3.684 (3) | 140 |
C12—H12···Cg2ii | 0.90 (2) | 3.03 (2) | 3.796 (3) | 144.2 (19) |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x, y−1/2, −z+1/2; (iii) −x, −y+1, −z+1. |
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4-[2-Methyl-4-(4-methylphenyldiazenyl)phenoxy]phtalonitrile, (I), is a starting material in the synthesis of network polymeric phthalocyanines and high-performance aromatic polymers (McKeown, 1998; Takekoshi, 1987). In addition to their extensive use as dyes and pigments, phthalocyanines have found widespread applications in catalysis, optical recording, photoconductive materials, photodynamic theraphy and as chemical sensors (Leznoff & Lever, 1989–1996).
Polymeric phthalocyanines have been known for their use as dyes and industrial high-technology materials and are also of additional interest because of their high thermostability (Leznoff & Lever, 1989–1996). Azo compounds have been the most widely used class of dyes owing to their versatile applications in various fields, such as dyeing textile fibres, colouring different materials, plastics, biological medical studies, lasers, liquid crystalline displays, electrooptical devices and ink-jet printers in high-technology areas (Catino & Farris, 1985; Gregory, 1991). The azo compound class accounts for 60–70% of all dyes. The geometric isomerism of azo compounds is known to exist in two forms, viz. cis and trans. A change from trans to cis can be effected by exposure to UV radiation, which can lead to photochromism. Photochromic compounds are of great interest for the control and measurement of radiation intensity, optical computers and display systems (Dürr & Bouas-Laurent, 1990). Photochromic materials of this type are of interest for potential applications in molecular electronic devices (Martin et al., 1995), among others.
The molecular structure of (I) is shown in Fig. 1, with the atom-numbering scheme. Selected bond distances and angles are given in Table 1. The phenyl rings C9–C14 and C16–C21 adopt trans configurations about the azo funtional group, as observed in crystals of other azo compounds. The N3—C10 and N4—C18 bond lengths of 1.459 (3) and 1.449 (3) Å, respectively, indicate single-bond character, and the –N═N– bond length of 1.218 (3) Å is indicative of significant double-bond character. Similar values for corresponding bond distances and angles have been observed in related trans-azo compounds (Alder et al., 1999, 2001; Dimmock et al., 1997; Ersanlı et al., 2004; Koşar et al., 2004). The dihedral angles between the mean planes of the C9–C14 and C16–C21 phenyls rings and the C18—N4═N3—C10 azo bridge are 13.59 (9) and 33.3 (5)°, respectively. The C1—C2—O1—C13 and C10—N3—N4—C18 torsion angles are 145.4 (2) and -179.15 (18)°, respectively. The dihedral angles between rings A (C1–C6), B (C9–C14) and C (C16–C21) are A/B = 88.39 (6)°, A/C = 88.39 (6)° and B/C = 13.09 (14)°. The intramolecular C—H···N hydrogen bonds (Table 2) seem to affect the molecular conformation (Fig. 1). The molecules are linked by intermolecular C—H···N and C—H···O hydrogen bonds, and C—H···π interactions (Table 2), forming a three-dimensional network. In Table 2, Cg2 is the centroid of ring B. The C19—H19···N3 hydrogen-bonded ring is coplanar with the adjacent ring, with a C19—C18—N4—N3 torsion angle of 0.32 (34) Å.