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The synthesis and characterization of the conjugated macrocycle trioxazolo[23]metacyclophane, C27H15N3O3 (M), is reported. The macrocycle was synthesized in three steps by the multicomponent van Leusen reaction and consists of meta-linked phenylenes connected through positions 4 and 5 of an oxazole heterocyclic ring. The molecular structure was investigated by NMR spectroscopy, mass spectrometry, gel permeation chromatography (GPC), and single-crystal X-ray crystallography. X-ray diffraction (XRD) analysis shows that M possesses a twisted saddle-like shape and interacts with nearby molecules by various π–π interactions. Absorption and emission spectroscopy and density functional theory (DFT) calculations were further used to study the electronic properties of M.
Keywords: metacyclophane; conjugated macrocycle; van Leusen reaction; gel permeation chromatography; van Leusen MCRs; crystal structure.
Supporting information
 | Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229622000298/eq3005sup1.cif |
 | Structure factor file (CIF format) https://doi.org/10.1107/S2053229622000298/eq3005Isup2.hkl |
 | Portable Document Format (PDF) file https://doi.org/10.1107/S2053229622000298/eq3005sup3.pdf |
CCDC reference: 2133260
Computing details top
Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014), XPREP (Bruker, 2014) and SADABS (Krause et al., 2015); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXTL (Bruker, 2014) and CrystalMaker (Palmer, 2014); software used to prepare material for publication: XCIF (Bruker, 2014).
Trioxazolo[23]metacyclophane top
Crystal data top
| C27H15N3O3 | F(000) = 888 |
| Mr = 429.42 | Dx = 1.473 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 14.1863 (4) Å | Cell parameters from 14248 reflections |
| b = 7.4446 (2) Å | θ = 2.6–25.4° |
| c = 18.3380 (5) Å | µ = 0.10 mm−1 |
| β = 90.3606 (10)° | T = 100 K |
| V = 1936.66 (9) Å3 | Rod, colourless |
| Z = 4 | 0.35 × 0.10 × 0.09 mm |
Data collection top
| Bruker D8 Venture/Photon 100 diffractometer | 3543 independent reflections |
| Radiation source: microfocus sealed tube | 3059 reflections with I > 2σ(I) |
| Multilayer mirrors monochromator | Rint = 0.046 |
| profile data from φ and ω scans | θmax = 25.4°, θmin = 2.6° |
| Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −17→17 |
| Tmin = 0.976, Tmax = 0.995 | k = −8→8 |
| 29490 measured reflections | l = −22→22 |
Refinement top
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.037 | w = 1/[σ2(Fo2) + (0.0321P)2 + 1.4734P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.091 | (Δ/σ)max < 0.001 |
| S = 1.07 | Δρmax = 0.21 e Å−3 |
| 3543 reflections | Δρmin = −0.21 e Å−3 |
| 299 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 0 restraints | Extinction coefficient: 0.0238 (13) |
Special details top
Experimental. One distinct cell was identified using APEX3 (Bruker, 2016). Four frame series were integrated and filtered for statistical outliers using SAINT (Bruker, 2014) then corrected for absorption by multi-scan methods using SADABS v2014/7 (Krause et al., 2015). No decay correction was applied.?? |
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. Structure was phased by intrinsic phasing methods (Sheldrick, 2015). Systematic conditions suggested the unambiguous space group. The space group choice was confirmed by successful convergence of the full-matrix least-squares refinement on F2. The final difference Fourier map had no significant features. A final analysis of variance between observed and calculated structure factors showed little dependence on amplitude or resolution. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.25521 (9) | 1.17960 (17) | 0.55661 (7) | 0.0307 (3) | |
| O2 | 0.52062 (8) | 0.91417 (16) | 0.90810 (6) | 0.0226 (3) | |
| O3 | 0.14470 (8) | 0.22834 (16) | 0.75091 (6) | 0.0246 (3) | |
| N1 | 0.10693 (10) | 1.08426 (18) | 0.56060 (7) | 0.0203 (3) | |
| N2 | 0.59511 (9) | 0.94354 (18) | 0.80225 (7) | 0.0155 (3) | |
| N3 | 0.21600 (9) | 0.27953 (18) | 0.85737 (7) | 0.0178 (3) | |
| C1 | 0.16490 (13) | 1.2051 (2) | 0.53759 (10) | 0.0288 (4) | |
| H1 | 0.1449 | 1.3049 | 0.5092 | 0.035* | |
| C2 | 0.25443 (12) | 1.0216 (2) | 0.59694 (8) | 0.0197 (4) | |
| C3 | 0.34764 (11) | 0.9537 (2) | 0.61972 (8) | 0.0175 (3) | |
| C4 | 0.41099 (12) | 0.8996 (2) | 0.56582 (9) | 0.0203 (4) | |
| H4 | 0.3924 | 0.9022 | 0.5160 | 0.024* | |
| C5 | 0.50090 (12) | 0.8421 (2) | 0.58482 (9) | 0.0214 (4) | |
| H5 | 0.5432 | 0.8041 | 0.5480 | 0.026* | |
| C6 | 0.52924 (11) | 0.8398 (2) | 0.65725 (9) | 0.0185 (4) | |
| H6 | 0.5910 | 0.8006 | 0.6698 | 0.022* | |
| C7 | 0.46724 (11) | 0.8951 (2) | 0.71194 (8) | 0.0162 (3) | |
| C8 | 0.37659 (11) | 0.9524 (2) | 0.69260 (8) | 0.0167 (3) | |
| H8 | 0.3343 | 0.9908 | 0.7294 | 0.020* | |
| C9 | 0.50052 (11) | 0.9019 (2) | 0.78802 (9) | 0.0162 (3) | |
| C10 | 0.60120 (11) | 0.9496 (2) | 0.87279 (9) | 0.0206 (4) | |
| H10 | 0.6584 | 0.9770 | 0.8976 | 0.025* | |
| C11 | 0.45585 (11) | 0.8824 (2) | 0.85275 (8) | 0.0169 (3) | |
| C12 | 0.36130 (11) | 0.8241 (2) | 0.87417 (8) | 0.0159 (3) | |
| C13 | 0.31515 (11) | 0.8982 (2) | 0.93425 (8) | 0.0185 (4) | |
| H13 | 0.3428 | 0.9950 | 0.9604 | 0.022* | |
| C14 | 0.22854 (12) | 0.8292 (2) | 0.95536 (9) | 0.0205 (4) | |
| H14 | 0.1968 | 0.8809 | 0.9957 | 0.025* | |
| C15 | 0.18761 (11) | 0.6858 (2) | 0.91855 (9) | 0.0195 (4) | |
| H15 | 0.1287 | 0.6390 | 0.9340 | 0.023* | |
| C16 | 0.23344 (11) | 0.6107 (2) | 0.85856 (8) | 0.0165 (3) | |
| C17 | 0.31929 (11) | 0.6826 (2) | 0.83626 (8) | 0.0160 (3) | |
| H17 | 0.3496 | 0.6344 | 0.7946 | 0.019* | |
| C18 | 0.19925 (11) | 0.4443 (2) | 0.82283 (9) | 0.0178 (4) | |
| C19 | 0.18240 (11) | 0.1612 (2) | 0.81212 (9) | 0.0217 (4) | |
| H19 | 0.1845 | 0.0359 | 0.8218 | 0.026* | |
| C20 | 0.15639 (11) | 0.4127 (2) | 0.75790 (9) | 0.0184 (4) | |
| C21 | 0.11910 (11) | 0.5233 (2) | 0.69836 (9) | 0.0185 (4) | |
| C22 | 0.04212 (12) | 0.4601 (2) | 0.65821 (9) | 0.0223 (4) | |
| H22 | 0.0156 | 0.3462 | 0.6691 | 0.027* | |
| C23 | 0.00435 (12) | 0.5636 (2) | 0.60243 (9) | 0.0234 (4) | |
| H23 | −0.0479 | 0.5196 | 0.5752 | 0.028* | |
| C24 | 0.04187 (11) | 0.7301 (2) | 0.58595 (9) | 0.0207 (4) | |
| H24 | 0.0141 | 0.8015 | 0.5486 | 0.025* | |
| C25 | 0.12098 (11) | 0.7937 (2) | 0.62434 (8) | 0.0178 (3) | |
| C26 | 0.15890 (11) | 0.6899 (2) | 0.68061 (9) | 0.0180 (3) | |
| H26 | 0.2122 | 0.7324 | 0.7071 | 0.022* | |
| C27 | 0.16367 (12) | 0.9627 (2) | 0.59926 (8) | 0.0186 (4) |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0373 (8) | 0.0240 (7) | 0.0306 (7) | −0.0071 (6) | −0.0133 (6) | 0.0080 (6) |
| O2 | 0.0239 (6) | 0.0246 (7) | 0.0194 (6) | −0.0007 (5) | −0.0029 (5) | 0.0013 (5) |
| O3 | 0.0270 (6) | 0.0198 (6) | 0.0269 (7) | −0.0022 (5) | 0.0020 (5) | 0.0016 (5) |
| N1 | 0.0275 (8) | 0.0150 (7) | 0.0184 (7) | 0.0019 (6) | −0.0082 (6) | 0.0015 (6) |
| N2 | 0.0144 (7) | 0.0163 (7) | 0.0158 (7) | 0.0003 (5) | −0.0023 (5) | 0.0030 (5) |
| N3 | 0.0174 (7) | 0.0167 (7) | 0.0193 (7) | −0.0010 (6) | 0.0025 (5) | 0.0046 (6) |
| C1 | 0.0367 (10) | 0.0203 (9) | 0.0291 (10) | 0.0001 (8) | −0.0178 (8) | 0.0054 (8) |
| C2 | 0.0291 (9) | 0.0160 (8) | 0.0139 (8) | −0.0020 (7) | −0.0053 (7) | 0.0012 (6) |
| C3 | 0.0224 (8) | 0.0123 (8) | 0.0178 (8) | −0.0047 (6) | −0.0016 (6) | 0.0020 (6) |
| C4 | 0.0308 (9) | 0.0171 (8) | 0.0130 (8) | −0.0071 (7) | −0.0008 (7) | 0.0002 (6) |
| C5 | 0.0269 (9) | 0.0185 (9) | 0.0188 (8) | −0.0055 (7) | 0.0068 (7) | −0.0034 (7) |
| C6 | 0.0186 (8) | 0.0141 (8) | 0.0227 (8) | −0.0030 (6) | 0.0026 (7) | 0.0003 (7) |
| C7 | 0.0197 (8) | 0.0127 (8) | 0.0162 (8) | −0.0029 (6) | 0.0000 (6) | 0.0013 (6) |
| C8 | 0.0201 (8) | 0.0153 (8) | 0.0149 (8) | −0.0020 (6) | 0.0021 (6) | 0.0014 (6) |
| C9 | 0.0162 (8) | 0.0134 (8) | 0.0189 (8) | 0.0013 (6) | −0.0016 (6) | 0.0009 (6) |
| C10 | 0.0178 (8) | 0.0210 (9) | 0.0231 (9) | −0.0006 (7) | −0.0029 (7) | 0.0027 (7) |
| C11 | 0.0198 (8) | 0.0138 (8) | 0.0170 (8) | 0.0012 (6) | −0.0040 (6) | −0.0005 (6) |
| C12 | 0.0191 (8) | 0.0158 (8) | 0.0129 (7) | 0.0037 (6) | −0.0009 (6) | 0.0047 (6) |
| C13 | 0.0252 (9) | 0.0173 (8) | 0.0129 (8) | 0.0036 (7) | −0.0009 (6) | 0.0016 (6) |
| C14 | 0.0271 (9) | 0.0193 (9) | 0.0151 (8) | 0.0076 (7) | 0.0057 (7) | 0.0025 (7) |
| C15 | 0.0193 (8) | 0.0204 (9) | 0.0187 (8) | 0.0031 (7) | 0.0035 (6) | 0.0074 (7) |
| C16 | 0.0186 (8) | 0.0154 (8) | 0.0154 (8) | 0.0031 (6) | −0.0010 (6) | 0.0046 (6) |
| C17 | 0.0187 (8) | 0.0170 (8) | 0.0124 (7) | 0.0043 (6) | 0.0007 (6) | 0.0016 (6) |
| C18 | 0.0150 (8) | 0.0186 (9) | 0.0200 (8) | 0.0010 (6) | 0.0047 (6) | 0.0039 (7) |
| C19 | 0.0215 (8) | 0.0175 (9) | 0.0260 (9) | 0.0007 (7) | 0.0037 (7) | 0.0062 (7) |
| C20 | 0.0172 (8) | 0.0166 (8) | 0.0216 (8) | −0.0007 (6) | 0.0042 (6) | 0.0017 (7) |
| C21 | 0.0188 (8) | 0.0202 (9) | 0.0165 (8) | 0.0026 (7) | 0.0021 (6) | −0.0007 (7) |
| C22 | 0.0211 (9) | 0.0227 (9) | 0.0232 (9) | −0.0032 (7) | 0.0017 (7) | 0.0002 (7) |
| C23 | 0.0169 (8) | 0.0323 (10) | 0.0209 (8) | −0.0032 (7) | −0.0018 (7) | 0.0000 (7) |
| C24 | 0.0174 (8) | 0.0277 (9) | 0.0169 (8) | 0.0035 (7) | 0.0000 (6) | 0.0021 (7) |
| C25 | 0.0179 (8) | 0.0198 (9) | 0.0157 (8) | 0.0025 (7) | 0.0018 (6) | −0.0016 (7) |
| C26 | 0.0177 (8) | 0.0204 (9) | 0.0158 (8) | 0.0011 (7) | −0.0015 (6) | −0.0020 (7) |
| C27 | 0.0252 (9) | 0.0175 (8) | 0.0130 (7) | 0.0035 (7) | −0.0036 (6) | −0.0016 (6) |
Geometric parameters (Å, º) top
| O1—C1 | 1.339 (2) | C10—H10 | 0.9500 |
| O1—C2 | 1.389 (2) | C11—C12 | 1.466 (2) |
| O2—C10 | 1.343 (2) | C12—C17 | 1.394 (2) |
| O2—C11 | 1.3852 (19) | C12—C13 | 1.398 (2) |
| O3—C19 | 1.337 (2) | C13—C14 | 1.389 (2) |
| O3—C20 | 1.389 (2) | C13—H13 | 0.9500 |
| N1—C1 | 1.291 (2) | C14—C15 | 1.388 (2) |
| N1—C27 | 1.401 (2) | C14—H14 | 0.9500 |
| N2—C10 | 1.297 (2) | C15—C16 | 1.398 (2) |
| N2—C9 | 1.400 (2) | C15—H15 | 0.9500 |
| N3—C19 | 1.299 (2) | C16—C17 | 1.394 (2) |
| N3—C18 | 1.400 (2) | C16—C18 | 1.482 (2) |
| C1—H1 | 0.9500 | C17—H17 | 0.9500 |
| C2—C27 | 1.361 (2) | C18—C20 | 1.354 (2) |
| C2—C3 | 1.474 (2) | C19—H19 | 0.9500 |
| C3—C8 | 1.396 (2) | C20—C21 | 1.464 (2) |
| C3—C4 | 1.399 (2) | C21—C22 | 1.395 (2) |
| C4—C5 | 1.388 (2) | C21—C26 | 1.401 (2) |
| C4—H4 | 0.9500 | C22—C23 | 1.385 (2) |
| C5—C6 | 1.385 (2) | C22—H22 | 0.9500 |
| C5—H5 | 0.9500 | C23—C24 | 1.384 (3) |
| C6—C7 | 1.400 (2) | C23—H23 | 0.9500 |
| C6—H6 | 0.9500 | C24—C25 | 1.403 (2) |
| C7—C8 | 1.398 (2) | C24—H24 | 0.9500 |
| C7—C9 | 1.471 (2) | C25—C26 | 1.395 (2) |
| C8—H8 | 0.9500 | C25—C27 | 1.471 (2) |
| C9—C11 | 1.357 (2) | C26—H26 | 0.9500 |
| C1—O1—C2 | 104.33 (14) | C12—C13—H13 | 120.2 |
| C10—O2—C11 | 104.06 (12) | C15—C14—C13 | 121.13 (15) |
| C19—O3—C20 | 104.20 (13) | C15—C14—H14 | 119.4 |
| C1—N1—C27 | 104.48 (14) | C13—C14—H14 | 119.4 |
| C10—N2—C9 | 104.56 (13) | C14—C15—C16 | 119.65 (15) |
| C19—N3—C18 | 104.17 (13) | C14—C15—H15 | 120.2 |
| N1—C1—O1 | 115.25 (15) | C16—C15—H15 | 120.2 |
| N1—C1—H1 | 122.4 | C17—C16—C15 | 119.27 (15) |
| O1—C1—H1 | 122.4 | C17—C16—C18 | 118.39 (14) |
| C27—C2—O1 | 107.46 (14) | C15—C16—C18 | 121.98 (14) |
| C27—C2—C3 | 136.72 (15) | C12—C17—C16 | 121.02 (15) |
| O1—C2—C3 | 115.54 (14) | C12—C17—H17 | 119.5 |
| C8—C3—C4 | 119.20 (15) | C16—C17—H17 | 119.5 |
| C8—C3—C2 | 122.14 (15) | C20—C18—N3 | 108.64 (14) |
| C4—C3—C2 | 118.53 (14) | C20—C18—C16 | 132.68 (15) |
| C5—C4—C3 | 120.32 (15) | N3—C18—C16 | 118.58 (13) |
| C5—C4—H4 | 119.8 | N3—C19—O3 | 115.20 (15) |
| C3—C4—H4 | 119.8 | N3—C19—H19 | 122.4 |
| C6—C5—C4 | 120.35 (15) | O3—C19—H19 | 122.4 |
| C6—C5—H5 | 119.8 | C18—C20—O3 | 107.79 (14) |
| C4—C5—H5 | 119.8 | C18—C20—C21 | 135.76 (16) |
| C5—C6—C7 | 120.22 (15) | O3—C20—C21 | 116.41 (14) |
| C5—C6—H6 | 119.9 | C22—C21—C26 | 119.41 (15) |
| C7—C6—H6 | 119.9 | C22—C21—C20 | 118.82 (15) |
| C8—C7—C6 | 119.27 (14) | C26—C21—C20 | 121.77 (15) |
| C8—C7—C9 | 121.27 (14) | C23—C22—C21 | 120.00 (16) |
| C6—C7—C9 | 119.36 (14) | C23—C22—H22 | 120.0 |
| C3—C8—C7 | 120.63 (15) | C21—C22—H22 | 120.0 |
| C3—C8—H8 | 119.7 | C24—C23—C22 | 120.79 (16) |
| C7—C8—H8 | 119.7 | C24—C23—H23 | 119.6 |
| C11—C9—N2 | 108.24 (14) | C22—C23—H23 | 119.6 |
| C11—C9—C7 | 132.62 (15) | C23—C24—C25 | 120.02 (15) |
| N2—C9—C7 | 119.08 (14) | C23—C24—H24 | 120.0 |
| N2—C10—O2 | 114.99 (14) | C25—C24—H24 | 120.0 |
| N2—C10—H10 | 122.5 | C26—C25—C24 | 119.20 (15) |
| O2—C10—H10 | 122.5 | C26—C25—C27 | 123.21 (15) |
| C9—C11—O2 | 108.14 (14) | C24—C25—C27 | 117.46 (14) |
| C9—C11—C12 | 134.39 (15) | C25—C26—C21 | 120.53 (15) |
| O2—C11—C12 | 117.26 (13) | C25—C26—H26 | 119.7 |
| C17—C12—C13 | 119.35 (15) | C21—C26—H26 | 119.7 |
| C17—C12—C11 | 118.62 (14) | C2—C27—N1 | 108.48 (15) |
| C13—C12—C11 | 121.89 (15) | C2—C27—C25 | 132.57 (15) |
| C14—C13—C12 | 119.54 (16) | N1—C27—C25 | 118.31 (14) |
| C14—C13—H13 | 120.2 | ||
| C27—N1—C1—O1 | −0.3 (2) | C13—C12—C17—C16 | −1.8 (2) |
| C2—O1—C1—N1 | 0.1 (2) | C11—C12—C17—C16 | 173.98 (14) |
| C1—O1—C2—C27 | 0.13 (18) | C15—C16—C17—C12 | 2.0 (2) |
| C1—O1—C2—C3 | 175.03 (15) | C18—C16—C17—C12 | −171.26 (14) |
| C27—C2—C3—C8 | −75.4 (3) | C19—N3—C18—C20 | −0.30 (17) |
| O1—C2—C3—C8 | 111.75 (17) | C19—N3—C18—C16 | −177.14 (14) |
| C27—C2—C3—C4 | 108.7 (2) | C17—C16—C18—C20 | −78.8 (2) |
| O1—C2—C3—C4 | −64.2 (2) | C15—C16—C18—C20 | 108.1 (2) |
| C8—C3—C4—C5 | 1.2 (2) | C17—C16—C18—N3 | 97.09 (17) |
| C2—C3—C4—C5 | 177.23 (15) | C15—C16—C18—N3 | −76.0 (2) |
| C3—C4—C5—C6 | −0.8 (2) | C18—N3—C19—O3 | −0.11 (18) |
| C4—C5—C6—C7 | 0.2 (2) | C20—O3—C19—N3 | 0.46 (18) |
| C5—C6—C7—C8 | 0.0 (2) | N3—C18—C20—O3 | 0.58 (17) |
| C5—C6—C7—C9 | −176.38 (15) | C16—C18—C20—O3 | 176.80 (16) |
| C4—C3—C8—C7 | −1.0 (2) | N3—C18—C20—C21 | 178.11 (17) |
| C2—C3—C8—C7 | −176.88 (15) | C16—C18—C20—C21 | −5.7 (3) |
| C6—C7—C8—C3 | 0.4 (2) | C19—O3—C20—C18 | −0.62 (17) |
| C9—C7—C8—C3 | 176.72 (15) | C19—O3—C20—C21 | −178.70 (13) |
| C10—N2—C9—C11 | −1.09 (18) | C18—C20—C21—C22 | −148.82 (19) |
| C10—N2—C9—C7 | 176.37 (15) | O3—C20—C21—C22 | 28.6 (2) |
| C8—C7—C9—C11 | 32.5 (3) | C18—C20—C21—C26 | 31.5 (3) |
| C6—C7—C9—C11 | −151.20 (18) | O3—C20—C21—C26 | −151.16 (15) |
| C8—C7—C9—N2 | −144.26 (15) | C26—C21—C22—C23 | −1.5 (2) |
| C6—C7—C9—N2 | 32.1 (2) | C20—C21—C22—C23 | 178.83 (15) |
| C9—N2—C10—O2 | 0.76 (19) | C21—C22—C23—C24 | −0.2 (3) |
| C11—O2—C10—N2 | −0.14 (19) | C22—C23—C24—C25 | 2.1 (2) |
| N2—C9—C11—O2 | 1.04 (18) | C23—C24—C25—C26 | −2.2 (2) |
| C7—C9—C11—O2 | −175.93 (16) | C23—C24—C25—C27 | 173.70 (15) |
| N2—C9—C11—C12 | −173.36 (17) | C24—C25—C26—C21 | 0.5 (2) |
| C7—C9—C11—C12 | 9.7 (3) | C27—C25—C26—C21 | −175.12 (15) |
| C10—O2—C11—C9 | −0.57 (17) | C22—C21—C26—C25 | 1.3 (2) |
| C10—O2—C11—C12 | 174.92 (14) | C20—C21—C26—C25 | −178.98 (15) |
| C9—C11—C12—C17 | 38.7 (3) | O1—C2—C27—N1 | −0.29 (18) |
| O2—C11—C12—C17 | −135.32 (15) | C3—C2—C27—N1 | −173.57 (18) |
| C9—C11—C12—C13 | −145.62 (19) | O1—C2—C27—C25 | 170.06 (16) |
| O2—C11—C12—C13 | 40.4 (2) | C3—C2—C27—C25 | −3.2 (3) |
| C17—C12—C13—C14 | 0.3 (2) | C1—N1—C27—C2 | 0.33 (18) |
| C11—C12—C13—C14 | −175.36 (15) | C1—N1—C27—C25 | −171.61 (15) |
| C12—C13—C14—C15 | 1.0 (2) | C26—C25—C27—C2 | 30.8 (3) |
| C13—C14—C15—C16 | −0.9 (2) | C24—C25—C27—C2 | −144.92 (18) |
| C14—C15—C16—C17 | −0.6 (2) | C26—C25—C27—N1 | −159.64 (15) |
| C14—C15—C16—C18 | 172.37 (14) | C24—C25—C27—N1 | 24.7 (2) |
Dehydration of tosylmethylformamide top
| Entry | Solvent | Temperature (°C) | POCl3 (equiv) | Base | Base (equiv) | Concentration (M) | Separation yield |
| 1 | DME | 0 | 3 | Et3N | 5 | 0.2 | - |
| 2 | DME | -40 | 3 | DIPA | 5 | 0.2 | <5 |
| 3 | DME | -40 | 3 | DIPA | 5 | 0.2 | <5 |
| 4 | THF | 60 | 3 | Et3N | 5 | 0.2 | - |
| 5 | THF | -40 | 3 | DIPA | 10 | 0.2 | <5 |
| 6 | THF | -78 | 2 | Et3N | 4 | 0.2 | 20 |
| 7 | THF | -78 | 3 | Et3N | 5 | 0.05 | 80 |
| 8 | THF | -78 | 6 | Et3N | 12 | 0.2 | 30 |
Selected dihedral angles (°) in M top
| O1—C2—C3—C4 | -64.2 (2) |
| C6—C7—C9—N2 | 32.1 (2) |
| O2—C11—C12—C13 | 40.4 (2) |
| C15—C16—C18—N3 | -76.0 (2) |
| O3—C20—C21—C22 | 28.6 (2) |
| C24—C25—C27—N1 | 24.7 (2) |
Parameters for π–p interactions between O2/C10/N2/C9/C11 and C3–C8 rings
(Å, °) top
| No. | Intercentroid distance (Å) | Interplanar angle (°) | Centroid shift (Å) |
| 1 | 3.597 (9) | 8.56 (6) | O2/C10/N2/C9/C11i to C3–C8: 1.237 (3) C3–C8 to O2/C10/N2/C9/C11i: 1.550 (2) |
| 2 | 3.910 (9) | 8.56 (6) | O2/C10/N2/C9/C11i to C3–C8: 0.585 (3) C3–C8i to O2/C10/N2/C9/C11: 1.140 (3) |
| Symmetry code: (i) -x+1, y-1/2, -z+3/2. |
