The syntheses of 4-[4-(4,4,5,5-tetramethyl-2-imidazoline-3-oxide-1-oxyl-2-yl)phenoxy]phthalonitrile (
3, C
21H
19N
4O
3) and 4-[4-(4,4,5,5-tetramethyl-2-imidazoline-1-oxyl-2-yl)phenoxy]phthalonitrile (
4) were carried out by microwave-assisted nucleophilic aromatic substitution of 4-nitrophthalonitrile (
2) by the pre-formed 2-(4-hydroxyphenyl)-4,4,5,5-tetramethyl-2-imidazoline-3-oxide-1-oxyl (
1). Compounds
3 and
4 were characterized unambiguously by a rich array of analyses, such as melting point, FT–IR, MALDI–TOF MS, elemental analysis, UV–Vis, CV, EPR, magnetic measurements and single-crystal X-ray diffraction. Structural studies demonstrate that the C—H
X and C—
Xπ (
X = O and N) interactions in the radical nitronyl nitroxide groups play an important role in the assembly of the crystal structures. Moreover, cyclic voltammetry analyses show that the phthalonitrile substituent retains the redox properties of the Ullman radicals.
Supporting information
CCDC reference: 1913919
Data collection: APEX2 (Bruker, 2014); cell refinement: APEX2 (Bruker, 2014); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009), PLATON (Spek, 2009,
2015) and Mercury (Macrae
et al., 2020).
4-[4-(4,4,5,5-Tetramethyl-2-imidazoline-3-oxide-1-oxyl-2-yl)phenoxy]benzene-1,2-dicarbonitrile
top
Crystal data top
C21H19N4O3 | F(000) = 788 |
Mr = 375.40 | Dx = 1.365 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.575 (3) Å | Cell parameters from 1457 reflections |
b = 17.149 (5) Å | θ = 2.3–21.9° |
c = 10.615 (3) Å | µ = 0.09 mm−1 |
β = 108.434 (14)° | T = 173 K |
V = 1826.3 (9) Å3 | Plate, blue |
Z = 4 | 0.24 × 0.15 × 0.08 mm |
Data collection top
Bruker APEXII CCD diffractometer | 3237 independent reflections |
Multilayer QUAZAR mirrors monochromator | 1988 reflections with I > 2σ(I) |
Detector resolution: 8.3333 pixels mm-1 | Rint = 0.084 |
φ and ω scans | θmax = 25.1°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | h = −12→12 |
Tmin = 0.983, Tmax = 0.992 | k = −20→20 |
12874 measured reflections | l = −12→12 |
Refinement top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.063 | H-atom parameters constrained |
wR(F2) = 0.177 | w = 1/[σ2(Fo2) + (0.0704P)2 + 1.145P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
3237 reflections | Δρmax = 0.30 e Å−3 |
257 parameters | Δρmin = −0.26 e Å−3 |
0 restraints | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. The data were obtained with Bruker APEX II QUAZAR three-circle
diffractometer. Indexing was performed using APEX2 (Bruker, 2014). Data
integration and reduction were carried out with SAINT (Bruker, 2013).
Absorption correction was performed by multi-scan method implemented in SADABS
(Bruker, 2014). The structure was solved using SHELXT
(Sheldrick, 2015) and
then refined by full-matrix least-squares refinements on F2 using the SHELXL
(Sheldrick, 2015) in OLEX2 (Dolomanov et al., 2009). All
non-hydrogen
atoms were refined anisotropically using all reflections with I > 2σ(I). Crystal structure validations
and geometrical calculations were performed using Platon software and Mercury
was used for visualization of the cif file (Spek, 2009; Spek
2015; Macrae
et al., 2006). Additional crystallographic data with CCDC
reference
number 1913919 have been deposited within the Cambridge Crystallographic Data
Center via www.ccdc.cam.ac.uk/deposit |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.8584 (2) | 0.07900 (15) | 0.5861 (2) | 0.0351 (7) | |
O2 | 0.2906 (2) | 0.04040 (15) | 0.6936 (2) | 0.0383 (7) | |
O3 | 0.5691 (2) | 0.21512 (15) | 0.9834 (2) | 0.0383 (7) | |
N5 | 1.2488 (4) | 0.0964 (2) | 0.3142 (3) | 0.0484 (9) | |
N6 | 0.9779 (3) | 0.2050 (2) | 0.0376 (3) | 0.0414 (9) | |
N7 | 0.3399 (3) | 0.08735 (17) | 0.7906 (3) | 0.0268 (7) | |
N8 | 0.4735 (3) | 0.16700 (17) | 0.9304 (3) | 0.0277 (7) | |
C101 | 1.1465 (4) | 0.1049 (2) | 0.3271 (3) | 0.0331 (9) | |
C102 | 0.9488 (3) | 0.1865 (2) | 0.1284 (3) | 0.0319 (9) | |
C103 | 1.0181 (3) | 0.1195 (2) | 0.3424 (3) | 0.0247 (8) | |
C104 | 0.9210 (3) | 0.1618 (2) | 0.2464 (3) | 0.0273 (8) | |
C105 | 0.8008 (3) | 0.1790 (2) | 0.2667 (3) | 0.0294 (9) | |
H105 | 0.735443 | 0.208496 | 0.202293 | 0.035* | |
C106 | 0.7755 (3) | 0.1538 (2) | 0.3796 (3) | 0.0312 (9) | |
H106 | 0.693805 | 0.166436 | 0.394219 | 0.037* | |
C107 | 0.8706 (3) | 0.1098 (2) | 0.4712 (3) | 0.0272 (8) | |
C108 | 0.9933 (3) | 0.0932 (2) | 0.4550 (3) | 0.0278 (8) | |
H108 | 1.058814 | 0.064359 | 0.520326 | 0.033* | |
C109 | 0.7512 (3) | 0.0952 (2) | 0.6318 (3) | 0.0285 (8) | |
C110 | 0.6201 (3) | 0.0815 (2) | 0.5589 (3) | 0.0306 (9) | |
H110 | 0.596564 | 0.065001 | 0.469015 | 0.037* | |
C111 | 0.5228 (3) | 0.0925 (2) | 0.6203 (3) | 0.0288 (8) | |
H111 | 0.431814 | 0.083932 | 0.571168 | 0.035* | |
C112 | 0.5568 (3) | 0.1159 (2) | 0.7518 (3) | 0.0243 (8) | |
C113 | 0.6913 (3) | 0.1287 (2) | 0.8226 (3) | 0.0324 (9) | |
H113 | 0.716074 | 0.144591 | 0.912874 | 0.039* | |
C114 | 0.7877 (3) | 0.1184 (2) | 0.7625 (3) | 0.0310 (9) | |
H114 | 0.878847 | 0.127216 | 0.810801 | 0.037* | |
C115 | 0.4587 (3) | 0.1242 (2) | 0.8200 (3) | 0.0242 (8) | |
C116 | 0.3731 (3) | 0.1465 (2) | 0.9981 (3) | 0.0273 (8) | |
C117 | 0.2598 (3) | 0.1142 (2) | 0.8778 (3) | 0.0285 (8) | |
C118 | 0.4389 (4) | 0.0853 (2) | 1.1017 (3) | 0.0407 (10) | |
H11A | 0.520580 | 0.106914 | 1.164184 | 0.061* | |
H11B | 0.461049 | 0.039459 | 1.057753 | 0.061* | |
H11C | 0.377570 | 0.070227 | 1.149917 | 0.061* | |
C119 | 0.3367 (4) | 0.2178 (2) | 1.0622 (4) | 0.0373 (9) | |
H11D | 0.311834 | 0.260221 | 0.997127 | 0.056* | |
H11E | 0.413254 | 0.233953 | 1.137429 | 0.056* | |
H11F | 0.261308 | 0.205667 | 1.093820 | 0.056* | |
C120 | 0.1838 (4) | 0.0463 (2) | 0.9080 (4) | 0.0402 (10) | |
H12A | 0.245343 | 0.003152 | 0.944094 | 0.060* | |
H12B | 0.115673 | 0.029329 | 0.826294 | 0.060* | |
H12C | 0.140785 | 0.062212 | 0.973286 | 0.060* | |
C121 | 0.1667 (3) | 0.1770 (2) | 0.8016 (3) | 0.0365 (9) | |
H12D | 0.106826 | 0.155151 | 0.718881 | 0.055* | |
H12E | 0.218831 | 0.219520 | 0.780791 | 0.055* | |
H12F | 0.114003 | 0.197222 | 0.855542 | 0.055* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0269 (14) | 0.0525 (18) | 0.0307 (14) | 0.0069 (11) | 0.0158 (11) | 0.0075 (12) |
O2 | 0.0316 (14) | 0.0453 (18) | 0.0381 (15) | −0.0086 (12) | 0.0112 (12) | −0.0186 (13) |
O3 | 0.0308 (14) | 0.0474 (18) | 0.0365 (14) | −0.0128 (12) | 0.0103 (11) | −0.0152 (13) |
N5 | 0.043 (2) | 0.058 (3) | 0.053 (2) | 0.0108 (17) | 0.0270 (18) | 0.0105 (18) |
N6 | 0.0362 (19) | 0.058 (2) | 0.0287 (18) | −0.0032 (16) | 0.0080 (14) | 0.0016 (16) |
N7 | 0.0245 (16) | 0.0310 (18) | 0.0253 (16) | −0.0012 (13) | 0.0084 (12) | −0.0044 (13) |
N8 | 0.0225 (15) | 0.0348 (19) | 0.0269 (16) | −0.0019 (13) | 0.0092 (12) | −0.0014 (14) |
C101 | 0.038 (2) | 0.035 (2) | 0.029 (2) | 0.0018 (17) | 0.0139 (17) | 0.0036 (17) |
C102 | 0.029 (2) | 0.039 (2) | 0.025 (2) | −0.0032 (16) | 0.0055 (16) | −0.0012 (17) |
C103 | 0.0274 (19) | 0.027 (2) | 0.0225 (18) | −0.0019 (15) | 0.0112 (14) | −0.0040 (15) |
C104 | 0.027 (2) | 0.034 (2) | 0.0204 (18) | −0.0034 (15) | 0.0065 (14) | −0.0061 (16) |
C105 | 0.027 (2) | 0.032 (2) | 0.0254 (19) | −0.0019 (15) | 0.0042 (15) | −0.0013 (16) |
C106 | 0.0210 (19) | 0.041 (2) | 0.030 (2) | −0.0022 (16) | 0.0069 (15) | −0.0059 (17) |
C107 | 0.028 (2) | 0.033 (2) | 0.0226 (18) | −0.0017 (16) | 0.0108 (15) | −0.0024 (16) |
C108 | 0.0236 (19) | 0.032 (2) | 0.0271 (19) | 0.0006 (15) | 0.0068 (15) | −0.0017 (16) |
C109 | 0.027 (2) | 0.035 (2) | 0.0282 (19) | 0.0039 (15) | 0.0158 (15) | 0.0034 (16) |
C110 | 0.030 (2) | 0.039 (2) | 0.0243 (18) | −0.0021 (16) | 0.0115 (15) | −0.0006 (16) |
C111 | 0.0225 (19) | 0.038 (2) | 0.0244 (19) | −0.0005 (15) | 0.0046 (15) | 0.0001 (16) |
C112 | 0.0240 (19) | 0.026 (2) | 0.0228 (18) | 0.0032 (14) | 0.0074 (14) | 0.0019 (15) |
C113 | 0.027 (2) | 0.045 (2) | 0.0236 (19) | −0.0022 (16) | 0.0054 (15) | 0.0018 (17) |
C114 | 0.0236 (19) | 0.041 (2) | 0.029 (2) | 0.0000 (16) | 0.0092 (15) | 0.0017 (17) |
C115 | 0.0227 (19) | 0.028 (2) | 0.0208 (18) | 0.0002 (15) | 0.0053 (14) | 0.0000 (15) |
C116 | 0.0229 (19) | 0.036 (2) | 0.0243 (18) | 0.0004 (15) | 0.0099 (14) | −0.0019 (16) |
C117 | 0.026 (2) | 0.034 (2) | 0.0281 (19) | 0.0021 (15) | 0.0127 (15) | −0.0002 (16) |
C118 | 0.040 (2) | 0.057 (3) | 0.027 (2) | 0.0090 (19) | 0.0138 (17) | 0.0057 (19) |
C119 | 0.035 (2) | 0.043 (3) | 0.038 (2) | −0.0020 (18) | 0.0181 (17) | −0.0100 (19) |
C120 | 0.038 (2) | 0.043 (3) | 0.045 (2) | −0.0122 (18) | 0.0224 (19) | −0.0040 (19) |
C121 | 0.027 (2) | 0.046 (3) | 0.037 (2) | 0.0072 (17) | 0.0100 (16) | 0.0035 (18) |
Geometric parameters (Å, º) top
O1—C107 | 1.372 (4) | C111—H111 | 0.9500 |
O1—C109 | 1.394 (4) | C111—C112 | 1.386 (4) |
O2—N7 | 1.281 (3) | C112—C113 | 1.400 (5) |
O3—N8 | 1.289 (3) | C112—C115 | 1.447 (4) |
N5—C101 | 1.142 (4) | C113—H113 | 0.9500 |
N6—C102 | 1.146 (4) | C113—C114 | 1.375 (5) |
N7—C115 | 1.352 (4) | C114—H114 | 0.9500 |
N7—C117 | 1.510 (4) | C116—C117 | 1.551 (5) |
N8—C115 | 1.350 (4) | C116—C118 | 1.519 (5) |
N8—C116 | 1.499 (4) | C116—C119 | 1.508 (5) |
C101—C103 | 1.440 (5) | C117—C120 | 1.506 (5) |
C102—C104 | 1.438 (5) | C117—C121 | 1.511 (5) |
C103—C104 | 1.399 (5) | C118—H11A | 0.9800 |
C103—C108 | 1.377 (4) | C118—H11B | 0.9800 |
C104—C105 | 1.387 (5) | C118—H11C | 0.9800 |
C105—H105 | 0.9500 | C119—H11D | 0.9800 |
C105—C106 | 1.378 (5) | C119—H11E | 0.9800 |
C106—H106 | 0.9500 | C119—H11F | 0.9800 |
C106—C107 | 1.381 (5) | C120—H12A | 0.9800 |
C107—C108 | 1.391 (5) | C120—H12B | 0.9800 |
C108—H108 | 0.9500 | C120—H12C | 0.9800 |
C109—C110 | 1.377 (5) | C121—H12D | 0.9800 |
C109—C114 | 1.376 (5) | C121—H12E | 0.9800 |
C110—H110 | 0.9500 | C121—H12F | 0.9800 |
C110—C111 | 1.393 (5) | | |
| | | |
C107—O1—C109 | 123.2 (3) | C109—C114—H114 | 120.3 |
O2—N7—C115 | 126.2 (3) | C113—C114—C109 | 119.5 (3) |
O2—N7—C117 | 121.3 (3) | C113—C114—H114 | 120.3 |
C115—N7—C117 | 112.2 (3) | N7—C115—C112 | 126.8 (3) |
O3—N8—C115 | 125.9 (3) | N8—C115—N7 | 107.3 (3) |
O3—N8—C116 | 121.2 (3) | N8—C115—C112 | 125.7 (3) |
C115—N8—C116 | 112.5 (3) | N8—C116—C117 | 99.7 (2) |
N5—C101—C103 | 177.3 (4) | N8—C116—C118 | 106.1 (3) |
N6—C102—C104 | 176.3 (4) | N8—C116—C119 | 110.3 (3) |
C104—C103—C101 | 120.6 (3) | C118—C116—C117 | 114.0 (3) |
C108—C103—C101 | 119.1 (3) | C119—C116—C117 | 114.8 (3) |
C108—C103—C104 | 120.3 (3) | C119—C116—C118 | 110.9 (3) |
C103—C104—C102 | 118.9 (3) | N7—C117—C116 | 100.1 (2) |
C105—C104—C102 | 121.5 (3) | C120—C117—N7 | 109.6 (3) |
C105—C104—C103 | 119.7 (3) | C120—C117—C116 | 115.2 (3) |
C104—C105—H105 | 119.7 | C120—C117—C121 | 111.4 (3) |
C106—C105—C104 | 120.5 (3) | C121—C117—N7 | 106.6 (3) |
C106—C105—H105 | 119.7 | C121—C117—C116 | 112.9 (3) |
C105—C106—H106 | 120.5 | C116—C118—H11A | 109.5 |
C105—C106—C107 | 119.0 (3) | C116—C118—H11B | 109.5 |
C107—C106—H106 | 120.5 | C116—C118—H11C | 109.5 |
O1—C107—C106 | 125.7 (3) | H11A—C118—H11B | 109.5 |
O1—C107—C108 | 112.7 (3) | H11A—C118—H11C | 109.5 |
C106—C107—C108 | 121.6 (3) | H11B—C118—H11C | 109.5 |
C103—C108—C107 | 118.8 (3) | C116—C119—H11D | 109.5 |
C103—C108—H108 | 120.6 | C116—C119—H11E | 109.5 |
C107—C108—H108 | 120.6 | C116—C119—H11F | 109.5 |
C110—C109—O1 | 123.7 (3) | H11D—C119—H11E | 109.5 |
C114—C109—O1 | 114.1 (3) | H11D—C119—H11F | 109.5 |
C114—C109—C110 | 121.8 (3) | H11E—C119—H11F | 109.5 |
C109—C110—H110 | 120.8 | C117—C120—H12A | 109.5 |
C109—C110—C111 | 118.4 (3) | C117—C120—H12B | 109.5 |
C111—C110—H110 | 120.8 | C117—C120—H12C | 109.5 |
C110—C111—H111 | 119.5 | H12A—C120—H12B | 109.5 |
C112—C111—C110 | 121.0 (3) | H12A—C120—H12C | 109.5 |
C112—C111—H111 | 119.5 | H12B—C120—H12C | 109.5 |
C111—C112—C113 | 118.8 (3) | C117—C121—H12D | 109.5 |
C111—C112—C115 | 122.3 (3) | C117—C121—H12E | 109.5 |
C113—C112—C115 | 118.9 (3) | C117—C121—H12F | 109.5 |
C112—C113—H113 | 119.8 | H12D—C121—H12E | 109.5 |
C114—C113—C112 | 120.5 (3) | H12D—C121—H12F | 109.5 |
C114—C113—H113 | 119.8 | H12E—C121—H12F | 109.5 |
| | | |
O1—C107—C108—C103 | 178.9 (3) | C109—O1—C107—C106 | −6.6 (5) |
O1—C109—C110—C111 | 173.5 (3) | C109—O1—C107—C108 | 172.4 (3) |
O1—C109—C114—C113 | −173.7 (3) | C109—C110—C111—C112 | −0.7 (5) |
O2—N7—C115—N8 | −179.0 (3) | C110—C109—C114—C113 | −0.3 (6) |
O2—N7—C115—C112 | −2.7 (5) | C110—C111—C112—C113 | 0.3 (5) |
O2—N7—C117—C116 | 163.6 (3) | C110—C111—C112—C115 | −177.0 (3) |
O2—N7—C117—C120 | 42.0 (4) | C111—C112—C113—C114 | 0.1 (5) |
O2—N7—C117—C121 | −78.7 (4) | C111—C112—C115—N7 | 25.1 (5) |
O3—N8—C115—N7 | −174.2 (3) | C111—C112—C115—N8 | −159.3 (3) |
O3—N8—C115—C112 | 9.5 (5) | C112—C113—C114—C109 | −0.1 (5) |
O3—N8—C116—C117 | 160.8 (3) | C113—C112—C115—N7 | −152.2 (3) |
O3—N8—C116—C118 | −80.6 (4) | C113—C112—C115—N8 | 23.5 (5) |
O3—N8—C116—C119 | 39.6 (4) | C114—C109—C110—C111 | 0.6 (5) |
N8—C116—C117—N7 | 26.2 (3) | C115—N7—C117—C116 | −22.4 (3) |
N8—C116—C117—C120 | 143.6 (3) | C115—N7—C117—C120 | −144.0 (3) |
N8—C116—C117—C121 | −86.8 (3) | C115—N7—C117—C121 | 95.4 (3) |
C101—C103—C104—C102 | 3.6 (5) | C115—N8—C116—C117 | −25.6 (3) |
C101—C103—C104—C105 | −176.3 (3) | C115—N8—C116—C118 | 93.1 (3) |
C101—C103—C108—C107 | 177.9 (3) | C115—N8—C116—C119 | −146.8 (3) |
C102—C104—C105—C106 | 179.1 (3) | C115—C112—C113—C114 | 177.5 (3) |
C103—C104—C105—C106 | −1.1 (5) | C116—N8—C115—N7 | 12.5 (4) |
C104—C103—C108—C107 | −0.2 (5) | C116—N8—C115—C112 | −163.9 (3) |
C104—C105—C106—C107 | −1.2 (5) | C117—N7—C115—N8 | 7.3 (4) |
C105—C106—C107—O1 | −178.3 (3) | C117—N7—C115—C112 | −176.4 (3) |
C105—C106—C107—C108 | 2.8 (5) | C118—C116—C117—N7 | −86.5 (3) |
C106—C107—C108—C103 | −2.1 (5) | C118—C116—C117—C120 | 31.0 (4) |
C107—O1—C109—C110 | 57.1 (5) | C118—C116—C117—C121 | 160.6 (3) |
C107—O1—C109—C114 | −129.5 (3) | C119—C116—C117—N7 | 144.0 (3) |
C108—C103—C104—C102 | −178.4 (3) | C119—C116—C117—C120 | −98.6 (4) |
C108—C103—C104—C105 | 1.8 (5) | C119—C116—C117—C121 | 31.0 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C118—H11C···N5i | 0.98 | 2.57 | 3.469 (6) | 153 |
C105—H105···O3ii | 0.95 | 2.43 | 3.282 (4) | 149 |
C108—H108···O2iii | 0.95 | 2.59 | 3.476 (4) | 155 |
C111—H111···O2 | 0.95 | 2.39 | 2.940 (4) | 117 |
C113—H113···O3 | 0.95 | 2.27 | 2.859 (4) | 119 |
Symmetry codes: (i) x−1, y, z+1; (ii) x, y, z−1; (iii) x+1, y, z. |
Selected bond lengths (Å) and bond angles (°) for compound 3 topBond lengths (Å) | | | |
Phthalonitrile moiety | | Nitronyl nitroxide moiety | |
O1—C107 | 1.372 (4) | O2—N7 | 1.281 (3) |
O1—C109 | 1.394 (4) | O3—N8 | 1.289 (3) |
N5—C101 | 1.142 (4) | N7– C115 | 1.352 (4) |
N6—C102 | 1.146 (4) | N8– C115 | 1.350 (4) |
C101—C103 | 1.440 (5) | N7—C117 | 1.510 (4) |
C102—C104 | 1.438 (5) | N8—C116 | 1.499 (4) |
| | | |
Bond angles (°) | | | |
Phthalonitrile moiety | | Nitronyl nitroxide moiety | |
C104—C103—C101 | 120.6 (3) | O2—N7—C115 | 126.2 (3) |
C103—C104—C102 | 118.9 (3) | O2—N7—C117 | 121.3 (3) |
C107—O1—C109 | 123.2 (3) | O3—N8—C115 | 125.9 (3) |
| | O8—N3—C116 | 121.2 (3) |
Intermolecular N—O···π and C—N···π interaction parameters (Å and °)
for compound 3 topCg1 and Cg2 are the centroids of the C103–C108 and C109–C114
rings, respectively. |
Y—X···π | X···π | Y—X···π | Y···π |
N7—O2···Cg1iv | 3.563 (3) | 136.66 (19) | 4.580 (4) |
N8—O3···Cg2v | 3.729 (3) | 142.93 (19) | 4.820 (4) |
C101—N5···Cg2vi | 3.612 (4) | 114.0 (3) | 4.208 (4) |
C102—N6···Cg1vii | 3.268 (4) | 128.6 (3) | 4.082 (4) |
Symmetry codes: (iv) -x+1, -y, -z+1;
(v) x, -y+1/2, z+1/2;
(vi) -x+2, -y, -z+1;
(vii) x, -y+1/2, z-1/2. |
UV–Vis data for the n→π* transitions of phthalonitriles
3 and 4 at room temperaturea top | Nitronyl nitroxide | | | | Imino nitroxide | | | |
Solvent | λmax 3 | ε 3 | λmax PhNNb | ε PhNNb | λmax 4 | ε 4 | λmax PhINc | ε PhINc |
Acetonitrile | 615 | 491 | 583 | 485 | 445 | 484 | 441 | 418 |
Dichloromethane | 621 | 555 | 608d | 731d | 447 | 512 | 443d | 484d |
Toluene | 637 | 454 | 631 | 481 | 449 | 479 | 445 | 442 |
Notes: (a) λmax in nm, ε in cm-1 M-1; (b) taken
from Fidan et al. (2017); (c) taken from Fidan et
al.
(2016); (d) spectrum recorded in CHCl3. |