supplementary materials
(E)-4-{2-[(4-Chlorophenyl)iminomethyl]phenoxy}phthalonitrile
To a solution of Salicylaldehyde (0.5 g, 4.09 mmol) in DMF was added potasium
carbonato (1.12 g, 8.18 mmol). The mixture was stirred for 30 min under N2.
4-Nitrophtalonitrile (0.71 g, 4.09 mmol) 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 2-(3,4-Dicyanophenoxy) benzaldehyde was filtered off and
washed with water. The title compound (I) was prepared by reflux a mixture of
a solution containing 2-(3,4-Dicyanophenoxy) benzaldehyde (0.5 g 2.016 mmol)
in 20 ml e thanol and a solution containing 2-Chloroaniline (0.257 g 2.016 mmol) in 20 ml e thanol. The reaction mixture was stirred for 1 h under
reflux. The crystals of the title compound were obtained from ethylalcohol
by slow evaporation (yield % 51; m.p.409–411 K).
The H atom bonded to C15 was refined freely. 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 Uiso(H) = 1.2 Ueq(C) or
1.5Ueq(methyl C).
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, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999).
(
E)-4-{2-[(4-Chlorophenyl)iminomethyl]phenoxy}phthalonitrile
top
Crystal data top
| C21H12ClN3O | Z = 2 |
| Mr = 357.79 | F(000) = 368 |
| Triclinic, P1 | Dx = 1.334 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 8.8342 (9) Å | Cell parameters from 6275 reflections |
| b = 10.2301 (8) Å | θ = 1.9–28.1° |
| c = 11.2401 (9) Å | µ = 0.23 mm−1 |
| α = 76.473 (6)° | T = 296 K |
| β = 84.912 (7)° | Block, colorless |
| γ = 64.419 (6)° | 0.78 × 0.66 × 0.51 mm |
| V = 890.74 (13) Å3 | |
Data collection top
Stoe IPDS-II
diffractometer | 3503 independent reflections |
| Radiation source: fine-focus sealed tube | 2825 reflections with I > 2σ(I) |
| graphite | Rint = 0.044 |
| Detector resolution: 6.67 pixels mm-1 | θmax = 26.0°, θmin = 1.9° |
| ω scans | h = −10→10 |
Absorption correction: integration
(X-RED32; Stoe & Cie, 2002) | k = −12→12 |
| Tmin = 0.870, Tmax = 0.904 | l = −13→13 |
| 8944 measured reflections | |
Refinement top
| 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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.04 | w = 1/[σ2(Fo2) + (0.0664P)2 + 0.1064P]
where P = (Fo2 + 2Fc2)/3 |
| 3503 reflections | (Δ/σ)max < 0.001 |
| 239 parameters | Δρmax = 0.17 e Å−3 |
| 0 restraints | Δρmin = −0.40 e Å−3 |
Crystal data top
| C21H12ClN3O | γ = 64.419 (6)° |
| Mr = 357.79 | V = 890.74 (13) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 8.8342 (9) Å | Mo Kα radiation |
| b = 10.2301 (8) Å | µ = 0.23 mm−1 |
| c = 11.2401 (9) Å | T = 296 K |
| α = 76.473 (6)° | 0.78 × 0.66 × 0.51 mm |
| β = 84.912 (7)° | |
Data collection top
Stoe IPDS-II
diffractometer | 3503 independent reflections |
Absorption correction: integration
(X-RED32; Stoe & Cie, 2002) | 2825 reflections with I > 2σ(I) |
| Tmin = 0.870, Tmax = 0.904 | Rint = 0.044 |
| 8944 measured reflections | θmax = 26.0° |
Refinement top
| R[F2 > 2σ(F2)] = 0.045 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.130 | Δρmax = 0.17 e Å−3 |
| S = 1.04 | Δρmin = −0.40 e Å−3 |
| 3503 reflections | Absolute structure: ? |
| 239 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Special details top
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) top| | x | y | z | Uiso*/Ueq | |
| C1 | 0.51280 (17) | 0.26143 (17) | 0.40778 (14) | 0.0464 (3) | |
| C2 | 0.66702 (18) | 0.26554 (19) | 0.40930 (14) | 0.0505 (4) | |
| H2 | 0.7379 | 0.2495 | 0.3427 | 0.061* | |
| C3 | 0.71421 (18) | 0.29367 (18) | 0.51070 (13) | 0.0475 (4) | |
| C4 | 0.6080 (2) | 0.31856 (18) | 0.61105 (14) | 0.0497 (4) | |
| C5 | 0.4538 (2) | 0.3153 (2) | 0.60666 (16) | 0.0602 (4) | |
| H5 | 0.3817 | 0.3324 | 0.6725 | 0.072* | |
| C6 | 0.4063 (2) | 0.2869 (2) | 0.50597 (16) | 0.0560 (4) | |
| H6 | 0.3024 | 0.2847 | 0.5039 | 0.067* | |
| C7 | 0.8749 (2) | 0.2967 (2) | 0.51519 (16) | 0.0661 (5) | |
| C8 | 0.6607 (3) | 0.3483 (2) | 0.71432 (17) | 0.0696 (5) | |
| C9 | 0.55995 (19) | 0.14409 (18) | 0.23769 (15) | 0.0497 (4) | |
| C10 | 0.6889 (2) | 0.0109 (2) | 0.28960 (17) | 0.0606 (4) | |
| H10 | 0.7120 | −0.0135 | 0.3731 | 0.073* | |
| C11 | 0.7829 (2) | −0.0855 (2) | 0.21644 (19) | 0.0678 (5) | |
| H11 | 0.8710 | −0.1751 | 0.2505 | 0.081* | |
| C12 | 0.7476 (2) | −0.0504 (2) | 0.09301 (19) | 0.0678 (5) | |
| H12 | 0.8110 | −0.1166 | 0.0442 | 0.081* | |
| C13 | 0.6185 (2) | 0.0823 (2) | 0.04203 (16) | 0.0583 (4) | |
| H13 | 0.5952 | 0.1051 | −0.0413 | 0.070* | |
| C14 | 0.52227 (18) | 0.18339 (18) | 0.11312 (15) | 0.0490 (4) | |
| C15 | 0.38617 (18) | 0.32668 (19) | 0.05899 (15) | 0.0486 (4) | |
| C16 | 0.20883 (18) | 0.49755 (18) | −0.09784 (13) | 0.0474 (4) | |
| C17 | 0.0858 (2) | 0.5086 (2) | −0.17321 (15) | 0.0550 (4) | |
| H17 | 0.0871 | 0.4229 | −0.1892 | 0.066* | |
| C18 | −0.0379 (2) | 0.6449 (2) | −0.22445 (15) | 0.0590 (4) | |
| H18 | −0.1210 | 0.6519 | −0.2742 | 0.071* | |
| C19 | −0.0371 (2) | 0.7704 (2) | −0.20116 (16) | 0.0576 (4) | |
| C20 | 0.0837 (2) | 0.7630 (2) | −0.12803 (16) | 0.0584 (4) | |
| H20 | 0.0827 | 0.8492 | −0.1134 | 0.070* | |
| C21 | 0.2069 (2) | 0.62566 (19) | −0.07630 (14) | 0.0529 (4) | |
| H21 | 0.2895 | 0.6194 | −0.0265 | 0.063* | |
| N1 | 1.0006 (2) | 0.2993 (3) | 0.52178 (18) | 0.1025 (8) | |
| N2 | 0.7057 (3) | 0.3728 (3) | 0.79419 (19) | 0.1125 (8) | |
| N3 | 0.33454 (16) | 0.35400 (16) | −0.04982 (12) | 0.0533 (3) | |
| O1 | 0.45285 (13) | 0.24132 (14) | 0.30878 (11) | 0.0594 (3) | |
| Cl1 | −0.19019 (7) | 0.94362 (6) | −0.26930 (6) | 0.0948 (2) | |
| H15 | 0.346 (2) | 0.3985 (19) | 0.1112 (15) | 0.048 (4)* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| C1 | 0.0430 (7) | 0.0486 (8) | 0.0424 (8) | −0.0151 (6) | −0.0058 (6) | −0.0067 (6) |
| C2 | 0.0435 (7) | 0.0656 (10) | 0.0384 (8) | −0.0198 (7) | −0.0002 (6) | −0.0099 (7) |
| C3 | 0.0451 (7) | 0.0522 (9) | 0.0407 (8) | −0.0187 (6) | −0.0062 (6) | −0.0033 (6) |
| C4 | 0.0576 (8) | 0.0479 (8) | 0.0400 (8) | −0.0190 (7) | −0.0022 (6) | −0.0088 (6) |
| C5 | 0.0592 (9) | 0.0692 (11) | 0.0505 (10) | −0.0254 (8) | 0.0144 (7) | −0.0188 (8) |
| C6 | 0.0461 (8) | 0.0651 (10) | 0.0565 (10) | −0.0247 (7) | 0.0036 (7) | −0.0116 (8) |
| C7 | 0.0583 (10) | 0.0966 (15) | 0.0460 (9) | −0.0378 (10) | −0.0084 (7) | −0.0072 (9) |
| C8 | 0.0874 (13) | 0.0719 (12) | 0.0501 (10) | −0.0316 (10) | 0.0007 (9) | −0.0187 (9) |
| C9 | 0.0487 (8) | 0.0539 (9) | 0.0496 (9) | −0.0237 (7) | −0.0056 (6) | −0.0109 (7) |
| C10 | 0.0683 (10) | 0.0553 (10) | 0.0557 (10) | −0.0246 (8) | −0.0160 (8) | −0.0046 (8) |
| C11 | 0.0736 (11) | 0.0454 (9) | 0.0765 (13) | −0.0160 (8) | −0.0191 (9) | −0.0097 (9) |
| C12 | 0.0722 (11) | 0.0550 (10) | 0.0739 (12) | −0.0190 (9) | −0.0057 (9) | −0.0229 (9) |
| C13 | 0.0639 (10) | 0.0570 (10) | 0.0555 (10) | −0.0246 (8) | −0.0062 (7) | −0.0143 (8) |
| C14 | 0.0488 (8) | 0.0511 (8) | 0.0500 (9) | −0.0244 (7) | −0.0059 (6) | −0.0077 (7) |
| C15 | 0.0470 (7) | 0.0531 (9) | 0.0474 (8) | −0.0224 (7) | −0.0034 (6) | −0.0102 (7) |
| C16 | 0.0469 (7) | 0.0539 (9) | 0.0399 (8) | −0.0203 (7) | 0.0010 (6) | −0.0099 (6) |
| C17 | 0.0555 (9) | 0.0580 (10) | 0.0520 (9) | −0.0216 (7) | −0.0064 (7) | −0.0152 (7) |
| C18 | 0.0483 (8) | 0.0714 (11) | 0.0515 (9) | −0.0208 (8) | −0.0065 (7) | −0.0094 (8) |
| C19 | 0.0483 (8) | 0.0565 (10) | 0.0532 (10) | −0.0138 (7) | 0.0053 (7) | −0.0035 (7) |
| C20 | 0.0651 (10) | 0.0535 (10) | 0.0574 (10) | −0.0268 (8) | 0.0075 (8) | −0.0131 (8) |
| C21 | 0.0557 (8) | 0.0621 (10) | 0.0438 (8) | −0.0277 (7) | −0.0014 (6) | −0.0109 (7) |
| N1 | 0.0731 (11) | 0.175 (2) | 0.0727 (12) | −0.0723 (14) | −0.0127 (9) | −0.0072 (13) |
| N2 | 0.160 (2) | 0.130 (2) | 0.0671 (13) | −0.0674 (17) | −0.0122 (13) | −0.0413 (13) |
| N3 | 0.0529 (7) | 0.0549 (8) | 0.0489 (7) | −0.0187 (6) | −0.0087 (6) | −0.0104 (6) |
| O1 | 0.0454 (6) | 0.0776 (8) | 0.0522 (6) | −0.0184 (5) | −0.0088 (5) | −0.0207 (6) |
| Cl1 | 0.0776 (4) | 0.0632 (3) | 0.1105 (5) | −0.0075 (3) | −0.0174 (3) | 0.0041 (3) |
Geometric parameters (Å, °) top
| C1—O1 | 1.3663 (19) | C11—H11 | 0.9300 |
| C1—C6 | 1.382 (2) | C12—C13 | 1.374 (2) |
| C1—C2 | 1.383 (2) | C12—H12 | 0.9300 |
| C2—C3 | 1.377 (2) | C13—C14 | 1.392 (2) |
| C2—H2 | 0.9300 | C13—H13 | 0.9300 |
| C3—C4 | 1.399 (2) | C14—C15 | 1.468 (2) |
| C3—C7 | 1.439 (2) | C15—N3 | 1.269 (2) |
| C4—C5 | 1.383 (2) | C15—H15 | 0.975 (17) |
| C4—C8 | 1.428 (2) | C16—C21 | 1.380 (2) |
| C5—C6 | 1.373 (2) | C16—C17 | 1.387 (2) |
| C5—H5 | 0.9300 | C16—N3 | 1.417 (2) |
| C6—H6 | 0.9300 | C17—C18 | 1.375 (2) |
| C7—N1 | 1.132 (2) | C17—H17 | 0.9300 |
| C8—N2 | 1.132 (3) | C18—C19 | 1.373 (3) |
| C9—C10 | 1.379 (2) | C18—H18 | 0.9300 |
| C9—C14 | 1.392 (2) | C19—C20 | 1.370 (3) |
| C9—O1 | 1.3958 (19) | C19—Cl1 | 1.7420 (17) |
| C10—C11 | 1.375 (3) | C20—C21 | 1.381 (2) |
| C10—H10 | 0.9300 | C20—H20 | 0.9300 |
| C11—C12 | 1.378 (3) | C21—H21 | 0.9300 |
| | | |
| O1—C1—C6 | 116.38 (14) | C11—C12—H12 | 120.0 |
| O1—C1—C2 | 122.92 (14) | C12—C13—C14 | 121.04 (17) |
| C6—C1—C2 | 120.58 (15) | C12—C13—H13 | 119.5 |
| C3—C2—C1 | 119.13 (14) | C14—C13—H13 | 119.5 |
| C3—C2—H2 | 120.4 | C9—C14—C13 | 117.61 (14) |
| C1—C2—H2 | 120.4 | C9—C14—C15 | 120.99 (15) |
| C2—C3—C4 | 120.84 (14) | C13—C14—C15 | 121.40 (15) |
| C2—C3—C7 | 120.21 (14) | N3—C15—C14 | 121.16 (15) |
| C4—C3—C7 | 118.95 (15) | N3—C15—H15 | 124.2 (10) |
| C5—C4—C3 | 118.85 (15) | C14—C15—H15 | 114.5 (10) |
| C5—C4—C8 | 121.86 (15) | C21—C16—C17 | 119.08 (15) |
| C3—C4—C8 | 119.28 (15) | C21—C16—N3 | 123.10 (14) |
| C6—C5—C4 | 120.58 (14) | C17—C16—N3 | 117.79 (15) |
| C6—C5—H5 | 119.7 | C18—C17—C16 | 120.62 (17) |
| C4—C5—H5 | 119.7 | C18—C17—H17 | 119.7 |
| C5—C6—C1 | 120.02 (15) | C16—C17—H17 | 119.7 |
| C5—C6—H6 | 120.0 | C19—C18—C17 | 119.06 (16) |
| C1—C6—H6 | 120.0 | C19—C18—H18 | 120.5 |
| N1—C7—C3 | 178.2 (2) | C17—C18—H18 | 120.5 |
| N2—C8—C4 | 178.1 (2) | C20—C19—C18 | 121.59 (16) |
| C10—C9—C14 | 121.69 (15) | C20—C19—Cl1 | 119.19 (15) |
| C10—C9—O1 | 121.60 (15) | C18—C19—Cl1 | 119.20 (14) |
| C14—C9—O1 | 116.54 (13) | C19—C20—C21 | 119.01 (17) |
| C11—C10—C9 | 119.18 (16) | C19—C20—H20 | 120.5 |
| C11—C10—H10 | 120.4 | C21—C20—H20 | 120.5 |
| C9—C10—H10 | 120.4 | C16—C21—C20 | 120.64 (15) |
| C10—C11—C12 | 120.48 (17) | C16—C21—H21 | 119.7 |
| C10—C11—H11 | 119.8 | C20—C21—H21 | 119.7 |
| C12—C11—H11 | 119.8 | C15—N3—C16 | 117.86 (14) |
| C13—C12—C11 | 119.99 (17) | C1—O1—C9 | 120.84 (11) |
| C13—C12—H12 | 120.0 | | |
| | | |
| O1—C1—C2—C3 | 176.80 (14) | C12—C13—C14—C9 | −0.9 (3) |
| C6—C1—C2—C3 | 0.7 (2) | C12—C13—C14—C15 | 178.86 (17) |
| C1—C2—C3—C4 | −0.3 (2) | C9—C14—C15—N3 | −169.24 (16) |
| C1—C2—C3—C7 | 179.22 (16) | C13—C14—C15—N3 | 11.0 (2) |
| C2—C3—C4—C5 | −0.3 (2) | C21—C16—C17—C18 | −1.0 (2) |
| C7—C3—C4—C5 | −179.85 (16) | N3—C16—C17—C18 | −178.84 (15) |
| C2—C3—C4—C8 | −179.60 (16) | C16—C17—C18—C19 | 0.8 (3) |
| C7—C3—C4—C8 | 0.9 (3) | C17—C18—C19—C20 | −0.2 (3) |
| C3—C4—C5—C6 | 0.5 (3) | C17—C18—C19—Cl1 | 178.23 (13) |
| C8—C4—C5—C6 | 179.76 (17) | C18—C19—C20—C21 | −0.2 (3) |
| C4—C5—C6—C1 | −0.1 (3) | Cl1—C19—C20—C21 | −178.63 (12) |
| O1—C1—C6—C5 | −176.87 (15) | C17—C16—C21—C20 | 0.6 (2) |
| C2—C1—C6—C5 | −0.6 (3) | N3—C16—C21—C20 | 178.31 (14) |
| C14—C9—C10—C11 | 0.1 (3) | C19—C20—C21—C16 | 0.0 (2) |
| O1—C9—C10—C11 | 175.30 (17) | C14—C15—N3—C16 | −176.75 (14) |
| C9—C10—C11—C12 | −0.8 (3) | C21—C16—N3—C15 | 39.8 (2) |
| C10—C11—C12—C13 | 0.6 (3) | C17—C16—N3—C15 | −142.39 (16) |
| C11—C12—C13—C14 | 0.3 (3) | C6—C1—O1—C9 | −145.81 (16) |
| C10—C9—C14—C13 | 0.7 (3) | C2—C1—O1—C9 | 38.0 (2) |
| O1—C9—C14—C13 | −174.69 (14) | C10—C9—O1—C1 | 38.3 (2) |
| C10—C9—C14—C15 | −179.06 (15) | C14—C9—O1—C1 | −146.30 (15) |
| O1—C9—C14—C15 | 5.6 (2) | | |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C6—H6···N1i | 0.93 | 2.60 | 3.521 (3) | 172 |
| C2—H2···Cg3ii | 0.93 | 2.89 | 3.7044 (18) | 148 |
| Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C6—H6···N1i | 0.93 | 2.60 | 3.521 (3) | 172 |
| C2—H2···Cg3ii | 0.93 | 2.89 | 3.7044 (18) | 148 |
| Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z. |
The authors 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).
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Janczak, J. & Kubiak, R. (1995). Acta Cryst. C51, 1399–1401.
Kartal, A., Ocak Ískeleli, N., Albayrak, C., Ağar, E. & Erdönmez, A. (2006). Acta Cryst. E62, o548–o549.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
Stoe & Cie (2002). X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany.
N and C-H![[pi]](/logos/entities/pi_rmgif.gif)
contacts, and ![[Figure 1]](./si2163fig1thm.gif)
![[Figure 2]](./si2163fig2thm.gif)
Substituted phthalonitriles are generally used for preparing symmetrically and unsymmetrically peripherally and non- peripherally substituted phthalocyanines and subphthalocyanines. In addition to their extensive use as dyes and pigments, phthalocyanines have found widespread application in catalysis, in optical recording, as photoconductive materials, in photodynamic therapy and as chemical sensors (Kartal et al. 2006 with literature cited therein).
The geometry of the phthalonitrile group in the title compound (Fig. 1), agrees with that of previously reported structures (Janczak & Kubiak, 1995; Kartal et al., 2006). The values of the two C—O bond lengths are consistent with those found in a similar compound (Kartal et al., 2006). Rings A (atoms C16 - C21) and B(C9 - C14) have a dihedral angle of 51.42 (5)°. The molecule is not planar, the dihedral angle between the phthalonitrile moiety and the ring B(C19 - C14) being 65.01 (6)°.
The unit cell of the structure of (I) (Fig. 2) shows an intermolecular π–π contact between the two symmetry related phthalonitrile rings of neighbouring molecules. The centre of gravity Cg1 of the ring C1–C6 has a perpendicular distance to Cg1i of 3.556Å [symmetry code (i): 1 - x, 1 - y, 1 - z]. The distance between the ring centroids is 3.9104 (11) Å, with a slippage between the rings of 1.626 Å. Furthermore, the molecules are linked through weak intermolecular C—H···N contacts to form chains along the a axis (Fig. 2). These chains are connected via inversion related π–π interactions given above, and together with C—H···π contacts (Table 1) a three-dimensional network is formed. Cg3 is the centroid of the chlorophenyl ring C16 - C21.