Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102006868/fg1641sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102006868/fg1641Isup2.hkl |
CCDC reference: 188621
Compound (I) was synthesized as reported by Masci & Saccheo (1993) and was recrystallized from benzene.
The H atoms attached to atoms C17, C27 and C37 appeared as annular regions of electron density and were introduced in calculated positions (C—H = 0.95–0.97 Å) corresponding to two possible opposite conformations. One of these was such that one C—H bond was oriented normal to and the remaining C—H bonds below the aromatic ring. Only the occupancy was refined for these methyl H atoms. All other H atoms showed up clearly in a difference synthesis, with the exception of the two H atoms on C51, which were introduced in calculated positions. For all H atoms, a riding model was used in the final refinement and their displacement parameters were kept equal to those of the parent atom.
Data collection: XCS (Colapietro et al., 1992); cell refinement: XCS; data reduction: XCS; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: CAOS (Camalli & Spagna, 1994); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: CAOS and PARST97 (Nardelli, 1995).
C44H52O10 | F(000) = 3168 |
Mr = 740.89 | Dx = 1.240 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71069 Å |
a = 29.982 (5) Å | Cell parameters from 16 reflections |
b = 14.154 (3) Å | θ = 14.0–18.0° |
c = 27.612 (2) Å | µ = 0.09 mm−1 |
β = 137.36 (3)° | T = 293 K |
V = 7937 (5) Å3 | Prism, colourless |
Z = 8 | 0.3 × 0.2 × 0.2 mm |
Huber CS four-circle diffractometer | Rint = 0.022 |
Radiation source: X-ray tube | θmax = 28.0°, θmin = 2.2° |
Graphite monochromator | h = 0→39 |
ω scans | k = 0→18 |
11136 measured reflections | l = −35→24 |
9464 independent reflections | 3 standard reflections every 97 reflections |
4754 reflections with F > 3σ(F) | intensity decay: none |
Refinement on F | 496 parameters |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.052 | w = 1/(3.7038 + 0.0304F + 0.0009F2) |
wR(F2) = 0.067 | (Δ/σ)max < 0.001 |
S = 0.85 | Δρmax = 0.18 e Å−3 |
4754 reflections | Δρmin = −0.19 e Å−3 |
C44H52O10 | V = 7937 (5) Å3 |
Mr = 740.89 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 29.982 (5) Å | µ = 0.09 mm−1 |
b = 14.154 (3) Å | T = 293 K |
c = 27.612 (2) Å | 0.3 × 0.2 × 0.2 mm |
β = 137.36 (3)° |
Huber CS four-circle diffractometer | Rint = 0.022 |
11136 measured reflections | 3 standard reflections every 97 reflections |
9464 independent reflections | intensity decay: none |
4754 reflections with F > 3σ(F) |
R[F2 > 2σ(F2)] = 0.052 | 496 parameters |
wR(F2) = 0.067 | H-atom parameters constrained |
S = 0.85 | Δρmax = 0.18 e Å−3 |
4754 reflections | Δρmin = −0.19 e Å−3 |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O1 | 0.7651 (1) | 0.1921 (1) | 0.6194 (1) | 0.069 (2) | |
O2 | 0.5379 (1) | 0.5344 (1) | 0.4746 (1) | 0.069 (2) | |
O3 | 0.6584 (1) | 0.9746 (1) | 0.5516 (1) | 0.070 (2) | |
O4 | 0.8762 (1) | 0.6499 (1) | 0.6917 (1) | 0.069 (2) | |
O5 | 0.6384 (1) | 0.3699 (1) | 0.5916 (1) | 0.063 (2) | |
O6 | 0.6358 (1) | 0.7089 (2) | 0.4778 (1) | 0.065 (2) | |
O7 | 0.7419 (1) | 0.7388 (1) | 0.6641 (1) | 0.068 (2) | |
O8 | 0.8249 (1) | 0.4442 (1) | 0.6031 (1) | 0.059 (2) | |
O9 | 0.7360 (1) | 0.5645 (2) | 0.7163 (1) | 0.083 (3) | |
O10 | 0.6725 (1) | 0.5573 (1) | 0.4431 (1) | 0.062 (2) | |
C11 | 0.6181 (1) | 0.3357 (2) | 0.5303 (2) | 0.051 (3) | |
C12 | 0.6544 (1) | 0.2631 (2) | 0.5382 (2) | 0.054 (3) | |
C13 | 0.6319 (2) | 0.2259 (2) | 0.4765 (2) | 0.061 (3) | |
C14 | 0.5757 (2) | 0.2596 (2) | 0.4092 (2) | 0.062 (3) | |
C15 | 0.5406 (1) | 0.3310 (2) | 0.4042 (2) | 0.059 (3) | |
C16 | 0.5601 (1) | 0.3702 (2) | 0.4634 (2) | 0.053 (3) | |
C18 | 0.7149 (2) | 0.2222 (2) | 0.6113 (2) | 0.069 (3) | |
C19 | 0.5155 (2) | 0.4381 (2) | 0.4544 (2) | 0.069 (4) | |
C21 | 0.5832 (1) | 0.7475 (2) | 0.4608 (2) | 0.053 (3) | |
C22 | 0.5326 (2) | 0.6889 (2) | 0.4366 (2) | 0.056 (3) | |
C23 | 0.4818 (2) | 0.7279 (2) | 0.4229 (2) | 0.057 (3) | |
C24 | 0.4802 (1) | 0.8243 (2) | 0.4334 (2) | 0.053 (2) | |
C25 | 0.5317 (1) | 0.8803 (2) | 0.4579 (2) | 0.055 (2) | |
C26 | 0.5835 (1) | 0.8446 (2) | 0.4721 (1) | 0.053 (2) | |
C27 | 0.4241 (2) | 0.8657 (3) | 0.4170 (2) | 0.073 (3) | |
C28 | 0.5321 (2) | 0.5837 (2) | 0.4251 (2) | 0.071 (4) | |
C29 | 0.6388 (2) | 0.9085 (2) | 0.5000 (2) | 0.068 (3) | |
C31 | 0.7848 (2) | 0.8087 (2) | 0.6811 (2) | 0.055 (3) | |
C32 | 0.7620 (2) | 0.9021 (2) | 0.6585 (2) | 0.055 (2) | |
C33 | 0.8053 (2) | 0.9692 (2) | 0.6739 (2) | 0.055 (3) | |
C34 | 0.8680 (2) | 0.9469 (2) | 0.7090 (2) | 0.058 (3) | |
C35 | 0.8889 (2) | 0.8532 (2) | 0.7306 (2) | 0.063 (3) | |
C36 | 0.8476 (2) | 0.7834 (2) | 0.7165 (2) | 0.058 (3) | |
C38 | 0.6934 (2) | 0.9305 (2) | 0.6181 (2) | 0.067 (3) | |
C39 | 0.8717 (2) | 0.6821 (2) | 0.7372 (2) | 0.072 (4) | |
C41 | 0.8531 (1) | 0.4200 (2) | 0.6700 (2) | 0.051 (3) | |
C42 | 0.8978 (2) | 0.4810 (2) | 0.7276 (2) | 0.057 (3) | |
C43 | 0.9244 (2) | 0.4543 (2) | 0.7932 (2) | 0.063 (3) | |
C44 | 0.9083 (2) | 0.3686 (2) | 0.8025 (2) | 0.062 (3) | |
C45 | 0.8659 (2) | 0.3079 (2) | 0.7442 (2) | 0.060 (3) | |
C46 | 0.8378 (1) | 0.3321 (2) | 0.6774 (2) | 0.053 (3) | |
C47 | 0.9368 (2) | 0.3430 (3) | 0.8742 (2) | 0.086 (4) | |
C48 | 0.9201 (2) | 0.5718 (2) | 0.7212 (2) | 0.072 (4) | |
C49 | 0.7930 (2) | 0.2656 (2) | 0.6138 (2) | 0.067 (3) | |
C50 | 0.6795 (2) | 0.4539 (2) | 0.6215 (2) | 0.069 (3) | |
C52 | 0.6991 (2) | 0.6462 (2) | 0.6944 (2) | 0.076 (4) | |
C53 | 0.7415 (2) | 0.7308 (2) | 0.7156 (2) | 0.073 (4) | |
C60 | 0.6303 (2) | 0.7118 (2) | 0.4217 (2) | 0.064 (3) | |
C61 | 0.6867 (2) | 0.6549 (2) | 0.4470 (2) | 0.060 (3) | |
C62 | 0.7294 (2) | 0.4991 (2) | 0.4850 (2) | 0.063 (3) | |
C63 | 0.7646 (2) | 0.4971 (2) | 0.5606 (2) | 0.067 (3) | |
C17 | 0.5518 (2) | 0.2184 (5) | 0.3430 (2) | 0.094 (4) | |
C37 | 0.9125 (2) | 1.0212 (3) | 0.7224 (2) | 0.080 (3) | |
C51 | 0.6955 (3) | 0.4813 (2) | 0.6841 (2) | 0.097 (5) | |
H13 | 0.6583 | 0.1751 | 0.4824 | 0.061* | |
H15 | 0.5020 | 0.3553 | 0.3603 | 0.058* | |
H23 | 0.4468 | 0.6886 | 0.4054 | 0.054* | |
H25 | 0.5328 | 0.9455 | 0.4685 | 0.052* | |
H33 | 0.7889 | 1.0324 | 0.6579 | 0.054* | |
H35 | 0.9337 | 0.8356 | 0.7572 | 0.062* | |
H43 | 0.9551 | 0.4920 | 0.8328 | 0.062* | |
H45 | 0.8551 | 0.2477 | 0.7504 | 0.060* | |
H181 | 0.7348 | 0.2681 | 0.6498 | 0.07* | |
H182 | 0.7049 | 0.1711 | 0.6238 | 0.07* | |
H191 | 0.5099 | 0.4136 | 0.4847 | 0.07* | |
H192 | 0.4706 | 0.4404 | 0.4018 | 0.07* | |
H281 | 0.5692 | 0.5665 | 0.4328 | 0.07* | |
H282 | 0.4916 | 0.5630 | 0.3797 | 0.07* | |
H291 | 0.6778 | 0.8700 | 0.5195 | 0.067* | |
H292 | 0.6263 | 0.9438 | 0.4620 | 0.067* | |
H381 | 0.6703 | 0.8798 | 0.6116 | 0.066* | |
H382 | 0.6966 | 0.9805 | 0.6466 | 0.07* | |
H391 | 0.9170 | 0.6788 | 0.7855 | 0.07* | |
H392 | 0.8386 | 0.6426 | 0.7301 | 0.07* | |
H481 | 0.9243 | 0.5636 | 0.6896 | 0.07* | |
H482 | 0.9650 | 0.5901 | 0.7692 | 0.07* | |
H491 | 0.7543 | 0.3008 | 0.5660 | 0.07* | |
H492 | 0.8223 | 0.2325 | 0.6133 | 0.07* | |
H501 | 0.7220 | 0.4429 | 0.6371 | 0.07* | |
H502 | 0.6508 | 0.5026 | 0.5823 | 0.07* | |
H521 | 0.6595 | 0.6406 | 0.6405 | 0.07* | |
H522 | 0.6866 | 0.6500 | 0.7190 | 0.07* | |
H531 | 0.7891 | 0.7212 | 0.7630 | 0.07* | |
H532 | 0.7194 | 0.7895 | 0.7141 | 0.07* | |
H601 | 0.5861 | 0.6816 | 0.3771 | 0.06* | |
H602 | 0.6321 | 0.7786 | 0.4112 | 0.062* | |
H611 | 0.7311 | 0.6745 | 0.5008 | 0.060* | |
H612 | 0.6918 | 0.6673 | 0.4163 | 0.060* | |
H621 | 0.7616 | 0.5223 | 0.4854 | 0.062* | |
H622 | 0.7118 | 0.4348 | 0.4623 | 0.06* | |
H631 | 0.7735 | 0.5558 | 0.5795 | 0.067* | |
H632 | 0.7347 | 0.4680 | 0.5632 | 0.07* | |
H171 | 0.5719 | 0.2514 | 0.3324 | 0.098* | 0.578 |
H172 | 0.5647 | 0.1524 | 0.3516 | 0.098* | 0.634 |
H173 | 0.5053 | 0.2233 | 0.3041 | 0.098* | 0.615 |
H174 | 0.5227 | 0.1667 | 0.3262 | 0.098* | 0.422 |
H175 | 0.5300 | 0.2657 | 0.3072 | 0.098* | 0.366 |
H176 | 0.5893 | 0.1948 | 0.3547 | 0.098* | 0.385 |
H271 | 0.3901 | 0.8866 | 0.3681 | 0.07* | 0.666 |
H272 | 0.4062 | 0.8186 | 0.4242 | 0.07* | 0.552 |
H273 | 0.4395 | 0.9183 | 0.4481 | 0.07* | 0.671 |
H274 | 0.4338 | 0.8624 | 0.4588 | 0.07* | 0.334 |
H275 | 0.4177 | 0.9304 | 0.4028 | 0.07* | 0.448 |
H276 | 0.3843 | 0.8307 | 0.3789 | 0.07* | 0.329 |
H371 | 0.9067 | 1.0222 | 0.6830 | 0.079* | 0.731 |
H372 | 0.9024 | 1.0816 | 0.7274 | 0.079* | 0.640 |
H373 | 0.9580 | 1.0058 | 0.7656 | 0.079* | 0.735 |
H374 | 0.9381 | 1.0509 | 0.7676 | 0.079* | 0.269 |
H375 | 0.9423 | 0.9914 | 0.7233 | 0.079* | 0.360 |
H376 | 0.8867 | 1.0673 | 0.6851 | 0.079* | 0.265 |
H471 | 0.9202 | 0.3805 | 0.8870 | 0.09* | |
H472 | 0.9274 | 0.2789 | 0.8757 | 0.09* | |
H473 | 0.9835 | 0.3507 | 0.9102 | 0.09* | |
H511 | 0.6555 | 0.4940 | 0.6696 | 0.096* | |
H512 | 0.7188 | 0.4307 | 0.7183 | 0.096* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.061 (1) | 0.047 (1) | 0.091 (2) | 0.004 (1) | 0.053 (1) | 0.007 (1) |
O2 | 0.105 (2) | 0.047 (1) | 0.083 (2) | 0.016 (1) | 0.078 (2) | 0.013 (1) |
O3 | 0.068 (1) | 0.047 (1) | 0.069 (1) | −0.001 (1) | 0.042 (1) | 0.004 (1) |
O4 | 0.106 (2) | 0.044 (1) | 0.082 (2) | 0.003 (1) | 0.077 (2) | 0.001 (1) |
O5 | 0.088 (2) | 0.052 (1) | 0.073 (1) | −0.013 (1) | 0.067 (1) | −0.009 (1) |
O6 | 0.070 (1) | 0.080 (2) | 0.059 (1) | 0.025 (1) | 0.052 (1) | 0.019 (1) |
O7 | 0.096 (2) | 0.051 (1) | 0.071 (1) | −0.017 (1) | 0.066 (1) | −0.012 (1) |
O8 | 0.065 (1) | 0.058 (1) | 0.070 (1) | 0.011 (1) | 0.055 (1) | 0.010 (1) |
O9 | 0.115 (2) | 0.047 (1) | 0.085 (2) | −0.003 (1) | 0.072 (2) | −0.002 (1) |
O10 | 0.061 (1) | 0.055 (1) | 0.064 (1) | 0.001 (1) | 0.044 (1) | −0.001 (1) |
C11 | 0.066 (2) | 0.043 (2) | 0.063 (2) | −0.003 (1) | 0.053 (2) | −0.001 (1) |
C12 | 0.055 (2) | 0.045 (2) | 0.067 (2) | −0.000 (1) | 0.046 (2) | 0.002 (1) |
C13 | 0.061 (2) | 0.052 (2) | 0.080 (2) | 0.003 (1) | 0.055 (2) | −0.005 (2) |
C14 | 0.061 (2) | 0.071 (2) | 0.068 (2) | −0.005 (2) | 0.051 (2) | −0.011 (2) |
C15 | 0.057 (2) | 0.063 (2) | 0.063 (2) | 0.007 (1) | 0.045 (2) | 0.009 (2) |
C16 | 0.065 (2) | 0.042 (2) | 0.073 (2) | 0.004 (1) | 0.057 (2) | 0.006 (1) |
C18 | 0.064 (2) | 0.069 (2) | 0.075 (2) | 0.010 (2) | 0.052 (2) | 0.021 (2) |
C19 | 0.090 (2) | 0.046 (2) | 0.106 (3) | 0.013 (2) | 0.083 (2) | 0.013 (2) |
C21 | 0.061 (2) | 0.055 (2) | 0.053 (2) | 0.012 (1) | 0.045 (2) | 0.011 (1) |
C22 | 0.075 (2) | 0.046 (2) | 0.056 (2) | 0.008 (1) | 0.051 (2) | 0.007 (1) |
C23 | 0.064 (2) | 0.051 (2) | 0.059 (2) | −0.006 (1) | 0.046 (2) | −0.001 (1) |
C24 | 0.056 (2) | 0.052 (2) | 0.053 (2) | 0.002 (1) | 0.040 (2) | 0.002 (1) |
C25 | 0.059 (2) | 0.045 (2) | 0.054 (2) | 0.005 (1) | 0.040 (2) | 0.002 (1) |
C26 | 0.052 (2) | 0.053 (2) | 0.047 (2) | 0.001 (1) | 0.034 (1) | 0.005 (1) |
C27 | 0.070 (2) | 0.071 (2) | 0.087 (2) | 0.010 (2) | 0.060 (2) | 0.004 (2) |
C28 | 0.109 (3) | 0.048 (2) | 0.082 (2) | 0.006 (2) | 0.078 (2) | 0.004 (2) |
C29 | 0.062 (2) | 0.074 (2) | 0.061 (2) | −0.009 (2) | 0.043 (2) | 0.003 (2) |
C31 | 0.077 (2) | 0.042 (2) | 0.053 (2) | −0.009 (1) | 0.049 (2) | −0.007 (1) |
C32 | 0.066 (2) | 0.046 (2) | 0.047 (2) | 0.001 (1) | 0.040 (2) | −0.001 (1) |
C33 | 0.065 (2) | 0.038 (2) | 0.053 (2) | −0.000 (1) | 0.040 (2) | −0.001 (1) |
C34 | 0.066 (2) | 0.049 (2) | 0.049 (2) | −0.008 (1) | 0.038 (2) | −0.005 (1) |
C35 | 0.066 (2) | 0.057 (2) | 0.055 (2) | 0.007 (2) | 0.041 (2) | 0.003 (1) |
C36 | 0.081 (2) | 0.043 (2) | 0.054 (2) | 0.005 (2) | 0.051 (2) | 0.002 (1) |
C38 | 0.068 (2) | 0.063 (2) | 0.063 (2) | −0.003 (2) | 0.046 (2) | −0.006 (2) |
C39 | 0.109 (3) | 0.050 (2) | 0.076 (2) | 0.019 (2) | 0.074 (2) | 0.012 (2) |
C41 | 0.056 (2) | 0.046 (2) | 0.065 (2) | 0.009 (1) | 0.049 (2) | 0.007 (1) |
C42 | 0.064 (2) | 0.045 (2) | 0.076 (2) | 0.005 (1) | 0.057 (2) | 0.000 (1) |
C43 | 0.065 (2) | 0.052 (2) | 0.068 (2) | 0.005 (2) | 0.047 (2) | −0.004 (2) |
C44 | 0.062 (2) | 0.059 (2) | 0.063 (2) | 0.015 (2) | 0.046 (2) | 0.009 (2) |
C45 | 0.064 (2) | 0.052 (2) | 0.073 (2) | 0.008 (2) | 0.052 (2) | 0.012 (2) |
C46 | 0.050 (2) | 0.046 (2) | 0.066 (2) | 0.006 (1) | 0.044 (2) | 0.004 (1) |
C47 | 0.097 (3) | 0.090 (3) | 0.076 (2) | 0.018 (2) | 0.065 (2) | 0.015 (2) |
C48 | 0.087 (2) | 0.051 (2) | 0.102 (3) | −0.004 (2) | 0.077 (2) | −0.005 (2) |
C49 | 0.062 (2) | 0.059 (2) | 0.080 (2) | −0.010 (2) | 0.052 (2) | −0.006 (2) |
C50 | 0.089 (2) | 0.058 (2) | 0.075 (2) | −0.017 (2) | 0.065 (2) | −0.012 (2) |
C52 | 0.103 (3) | 0.053 (2) | 0.104 (3) | −0.007 (2) | 0.086 (3) | −0.007 (2) |
C53 | 0.108 (3) | 0.049 (2) | 0.091 (3) | −0.014 (2) | 0.082 (2) | −0.011 (2) |
C60 | 0.076 (2) | 0.069 (2) | 0.061 (2) | 0.016 (2) | 0.055 (2) | 0.016 (2) |
C61 | 0.070 (2) | 0.057 (2) | 0.068 (2) | 0.004 (2) | 0.056 (2) | 0.005 (2) |
C62 | 0.069 (2) | 0.058 (2) | 0.066 (2) | 0.005 (2) | 0.050 (2) | −0.002 (2) |
C63 | 0.076 (2) | 0.070 (2) | 0.070 (2) | 0.024 (2) | 0.059 (2) | 0.014 (2) |
C17 | 0.078 (3) | 0.130 (4) | 0.082 (3) | −0.011 (2) | 0.062 (2) | −0.033 (3) |
C37 | 0.076 (2) | 0.071 (2) | 0.074 (2) | −0.019 (2) | 0.049 (2) | −0.010 (2) |
C51 | 0.169 (4) | 0.051 (2) | 0.102 (3) | −0.028 (2) | 0.110 (3) | −0.019 (2) |
O1—C18 | 1.416 (6) | C39—H392 | 1.025 |
O1—C49 | 1.414 (5) | C41—C42 | 1.39 (1) |
O2—C19 | 1.438 (5) | C41—C46 | 1.392 (4) |
O2—C28 | 1.425 (6) | C42—C43 | 1.39 (1) |
O3—C29 | 1.421 (7) | C42—C48 | 1.519 (5) |
O3—C38 | 1.423 (4) | C43—C44 | 1.397 (5) |
O4—C39 | 1.431 (6) | C43—H43 | 0.920 |
O4—C48 | 1.429 (8) | C44—C45 | 1.39 (1) |
O5—C11 | 1.397 (7) | C44—C47 | 1.51 (1) |
O5—C50 | 1.455 (7) | C45—C46 | 1.40 (1) |
O6—C21 | 1.385 (7) | C45—H45 | 0.969 |
O6—C60 | 1.433 (6) | C46—C49 | 1.52 (1) |
O7—C31 | 1.402 (6) | C47—H471 | 0.957 |
O7—C53 | 1.437 (6) | C47—H472 | 0.960 |
O8—C41 | 1.396 (8) | C47—H473 | 0.954 |
O8—C63 | 1.445 (9) | C48—H481 | 0.975 |
O9—C52 | 1.393 (7) | C48—H482 | 1.005 |
O9—C51 | 1.436 (9) | C49—H491 | 1.040 |
O10—C61 | 1.426 (4) | C49—H492 | 1.003 |
O10—C62 | 1.423 (8) | C50—C51 | 1.47 (1) |
C11—C12 | 1.393 (6) | C50—H501 | 1.011 |
C11—C16 | 1.40 (1) | C50—H502 | 1.008 |
C12—C13 | 1.394 (9) | C52—C53 | 1.514 (9) |
C12—C18 | 1.52 (1) | C52—H521 | 1.015 |
C13—C14 | 1.38 (1) | C52—H522 | 0.992 |
C13—H13 | 0.990 | C53—H531 | 1.009 |
C14—C15 | 1.389 (6) | C53—H532 | 1.045 |
C14—C17 | 1.51 (1) | C60—C61 | 1.500 (9) |
C15—C16 | 1.386 (8) | C60—H601 | 1.027 |
C15—H15 | 0.929 | C60—H602 | 1.001 |
C16—C19 | 1.511 (7) | C61—H611 | 1.071 |
C18—H181 | 0.987 | C61—H612 | 0.984 |
C18—H182 | 0.938 | C62—C63 | 1.50 (1) |
C19—H191 | 1.026 | C62—H621 | 1.011 |
C19—H192 | 1.023 | C62—H622 | 1.006 |
C21—C22 | 1.395 (8) | C63—H631 | 0.910 |
C21—C26 | 1.409 (4) | C63—H632 | 1.036 |
C22—C23 | 1.386 (8) | C17—H171 | 0.962 |
C22—C28 | 1.520 (4) | C17—H172 | 0.971 |
C23—C24 | 1.403 (4) | C17—H173 | 0.948 |
C23—H23 | 0.948 | C17—H174 | 0.959 |
C24—C25 | 1.389 (8) | C17—H175 | 0.949 |
C24—C27 | 1.505 (9) | C17—H176 | 0.973 |
C25—C26 | 1.388 (7) | C37—H371 | 0.968 |
C25—H25 | 0.960 | C37—H372 | 0.950 |
C26—C29 | 1.512 (8) | C37—H373 | 0.968 |
C27—H271 | 0.962 | C37—H374 | 0.956 |
C27—H272 | 0.963 | C37—H375 | 0.974 |
C27—H273 | 0.959 | C37—H376 | 0.956 |
C27—H274 | 0.961 | C51—H511 | 0.960 |
C27—H275 | 0.959 | C51—H512 | 0.960 |
C27—H276 | 0.963 | H171—H175 | 0.905 |
C28—H281 | 0.999 | H171—H176 | 0.905 |
C28—H282 | 0.945 | H172—H174 | 0.905 |
C29—H291 | 1.014 | H172—H176 | 0.905 |
C29—H292 | 0.956 | H173—H174 | 0.905 |
C31—C32 | 1.406 (6) | H173—H175 | 0.905 |
C31—C36 | 1.39 (1) | H271—H275 | 0.905 |
C32—C33 | 1.398 (7) | H271—H276 | 0.905 |
C32—C38 | 1.50 (1) | H272—H274 | 0.905 |
C33—C34 | 1.38 (1) | H272—H276 | 0.905 |
C33—H33 | 0.958 | H273—H274 | 0.905 |
C34—C35 | 1.400 (6) | H273—H275 | 0.905 |
C34—C37 | 1.516 (8) | H371—H375 | 0.905 |
C35—C36 | 1.397 (7) | H371—H376 | 0.905 |
C35—H35 | 0.976 | H372—H374 | 0.905 |
C36—C39 | 1.515 (6) | H372—H376 | 0.905 |
C38—H381 | 0.920 | H373—H374 | 0.905 |
C38—H382 | 1.010 | H373—H375 | 0.905 |
C39—H391 | 0.980 | ||
C49—O1—C18 | 114.1 (3) | O1—C49—H492 | 104.6 |
C28—O2—C19 | 113.6 (5) | C46—C49—H492 | 105.6 |
C38—O3—C29 | 111.9 (3) | C46—C49—O1 | 114.7 (5) |
C48—O4—C39 | 112.9 (5) | H491—C49—H492 | 112.2 |
C11—O5—C50 | 113.7 (3) | H491—C49—O1 | 107.0 |
C60—O6—C21 | 115.3 (6) | H491—C49—C46 | 112.5 |
C53—O7—C31 | 113.5 (5) | H501—C50—C51 | 108.7 |
C63—O8—C41 | 112.3 (3) | H502—C50—C51 | 111.4 |
C51—O9—C52 | 111.9 (7) | H502—C50—H501 | 112.1 |
C62—O10—C61 | 112.8 (5) | O5—C50—C51 | 106.8 (4) |
C12—C11—O5 | 118.1 (3) | O5—C50—H501 | 113.1 |
C16—C11—O5 | 119.4 (4) | O5—C50—H502 | 104.6 |
C16—C11—C12 | 122.3 (6) | O9—C52—H522 | 109.0 |
C13—C12—C11 | 117.9 (7) | H521—C52—H522 | 112.4 |
C18—C12—C11 | 121.3 (6) | H521—C52—O9 | 105.8 |
C18—C12—C13 | 120.7 (4) | C53—C52—H522 | 109.0 |
C14—C13—C12 | 121.9 (4) | C53—C52—O9 | 108.5 (7) |
H13—C13—C12 | 117.6 | C53—C52—H521 | 112.0 |
H13—C13—C14 | 120.5 | O7—C53—H532 | 111.4 |
C17—C14—C15 | 120.8 (8) | C52—C53—H532 | 106.7 |
C13—C14—C15 | 117.9 (6) | C52—C53—O7 | 107.1 (6) |
C13—C14—C17 | 121.3 (5) | H531—C53—H532 | 114.1 |
C14—C15—C16 | 122.9 (8) | H531—C53—O7 | 105.1 |
H15—C15—C16 | 115.3 | H531—C53—C52 | 112.3 |
H15—C15—C14 | 121.8 | H601—C60—H602 | 110.1 |
C15—C16—C11 | 117.1 (4) | C61—C60—H602 | 111.2 |
C19—C16—C11 | 122.0 (5) | C61—C60—H601 | 110.7 |
C19—C16—C15 | 120.4 (3) | O6—C60—H602 | 110.5 |
H182—C18—C12 | 112.9 | O6—C60—H601 | 107.7 |
H181—C18—C12 | 111.4 | O6—C60—C61 | 106.6 (6) |
H181—C18—H182 | 102.5 | H612—C61—O10 | 109.5 |
O1—C18—C12 | 114.6 (5) | C60—C61—O10 | 108.4 (5) |
O1—C18—H182 | 107.4 | C60—C61—H612 | 109.8 |
O1—C18—H181 | 107.3 | H611—C61—O10 | 110.7 |
H191—C19—C16 | 107.8 | H611—C61—H612 | 109.0 |
O2—C19—C16 | 115.7 (6) | H611—C61—C60 | 109.4 |
O2—C19—H191 | 108.3 | O10—C62—H621 | 112.6 |
H192—C19—C16 | 109.5 | C63—C62—H621 | 107.7 |
H192—C19—H191 | 109.6 | C63—C62—O10 | 109.8 (4) |
H192—C19—O2 | 105.8 | H622—C62—H621 | 111.2 |
C26—C21—O6 | 119.4 (5) | H622—C62—O10 | 104.5 |
C22—C21—O6 | 119.7 (3) | H622—C62—C63 | 111.1 |
C22—C21—C26 | 120.8 (5) | O8—C63—H632 | 111.6 |
C21—C22—C28 | 121.5 (5) | H631—C63—H632 | 103.3 |
C23—C22—C28 | 119.5 (5) | H631—C63—O8 | 110.0 |
C23—C22—C21 | 119.0 (3) | C62—C63—H632 | 110.3 |
H23—C23—C24 | 118.9 | C62—C63—O8 | 108.6 (4) |
C22—C23—C24 | 121.8 (5) | C62—C63—H631 | 113.0 |
C22—C23—H23 | 119.2 | H171—C17—H172 | 108.4 |
C27—C24—C25 | 121.4 (3) | H175—C17—H172 | 141.0 |
C23—C24—C25 | 117.6 (4) | H175—C17—H171 | 56.5 |
C23—C24—C27 | 121.1 (5) | H173—C17—H172 | 109.6 |
H25—C25—C26 | 118.8 | H173—C17—H171 | 110.4 |
C24—C25—C26 | 122.7 (3) | H173—C17—H175 | 57.0 |
C24—C25—H25 | 118.4 | H174—C17—H172 | 55.9 |
C29—C26—C21 | 121.5 (5) | H174—C17—H171 | 140.9 |
C25—C26—C21 | 118.1 (5) | H174—C17—H175 | 110.5 |
C25—C26—C29 | 120.5 (3) | H174—C17—H173 | 56.7 |
H275—C27—H272 | 140.6 | C14—C17—H172 | 109.1 |
H276—C27—H272 | 56.0 | C14—C17—H171 | 109.6 |
H276—C27—H275 | 109.3 | C14—C17—H175 | 109.9 |
H273—C27—H272 | 109.3 | C14—C17—H173 | 109.7 |
H273—C27—H275 | 56.3 | C14—C17—H174 | 109.4 |
H273—C27—H276 | 140.6 | H176—C17—H172 | 55.5 |
C24—C27—H272 | 109.8 | H176—C17—H171 | 55.8 |
C24—C27—H275 | 109.6 | H176—C17—H175 | 109.3 |
C24—C27—H276 | 109.8 | H176—C17—H173 | 141.0 |
C24—C27—H273 | 109.6 | H176—C17—H174 | 108.5 |
H274—C27—H272 | 56.1 | H176—C17—C14 | 109.2 |
H274—C27—H275 | 109.4 | H374—C37—H372 | 56.7 |
H274—C27—H276 | 109.1 | H375—C37—H372 | 140.4 |
H274—C27—H273 | 56.2 | H375—C37—H374 | 108.6 |
H274—C27—C24 | 109.7 | H371—C37—H372 | 109.6 |
H271—C27—H272 | 109.1 | H371—C37—H374 | 140.3 |
H271—C27—H275 | 56.2 | H371—C37—H375 | 55.6 |
H271—C27—H276 | 56.1 | H376—C37—H372 | 56.7 |
H271—C27—H273 | 109.4 | H376—C37—H374 | 110.1 |
H271—C27—C24 | 109.7 | H376—C37—H375 | 108.7 |
H271—C27—H274 | 140.6 | H376—C37—H371 | 56.1 |
H282—C28—H281 | 110.3 | C34—C37—H372 | 110.1 |
C22—C28—H281 | 110.9 | C34—C37—H374 | 109.9 |
C22—C28—H282 | 112.7 | C34—C37—H375 | 109.5 |
O2—C28—H281 | 110.2 | C34—C37—H371 | 109.8 |
O2—C28—H282 | 104.7 | C34—C37—H376 | 110.0 |
O2—C28—C22 | 107.8 (4) | H373—C37—H372 | 109.6 |
O3—C29—H292 | 107.2 | H373—C37—H374 | 56.1 |
C26—C29—H292 | 110.9 | H373—C37—H375 | 55.5 |
C26—C29—O3 | 113.1 (3) | H373—C37—H371 | 108.1 |
H291—C29—H292 | 103.4 | H373—C37—H376 | 140.4 |
H291—C29—O3 | 111.0 | H373—C37—C34 | 109.6 |
H291—C29—C26 | 110.7 | H512—C51—O9 | 109.4 |
O7—C31—C36 | 119.3 (4) | H511—C51—O9 | 109.3 |
C32—C31—C36 | 121.3 (5) | H511—C51—H512 | 109.5 |
C32—C31—O7 | 119.3 (6) | C50—C51—O9 | 109.9 (4) |
C33—C32—C31 | 117.7 (6) | C50—C51—H512 | 109.4 |
C38—C32—C31 | 122.3 (5) | C50—C51—H511 | 109.4 |
C38—C32—C33 | 120.0 (4) | H176—H171—C17 | 62.7 |
C32—C33—H33 | 116.6 | H175—H171—C17 | 61.0 |
C34—C33—H33 | 120.7 | H175—H171—H176 | 120.0 |
C34—C33—C32 | 122.7 (4) | H174—H172—C17 | 61.3 |
C35—C34—C33 | 118.0 (5) | H176—H172—C17 | 62.3 |
C37—C34—C33 | 121.0 (4) | H176—H172—H174 | 120.0 |
C37—C34—C35 | 121.0 (7) | H174—H173—C17 | 62.3 |
C34—C35—H35 | 119.9 | H175—H173—C17 | 61.6 |
C36—C35—H35 | 118.5 | H175—H173—H174 | 120.0 |
C36—C35—C34 | 121.6 (7) | H172—H174—C17 | 62.7 |
C31—C36—C39 | 122.3 (5) | H173—H174—C17 | 61.0 |
C35—C36—C39 | 119.0 (6) | H173—H174—H172 | 120.0 |
C35—C36—C31 | 118.7 (4) | H173—H175—H171 | 120.0 |
H381—C38—O3 | 110.8 | C17—H175—H171 | 62.4 |
C32—C38—O3 | 112.6 (4) | C17—H175—H173 | 61.4 |
C32—C38—H381 | 111.1 | C17—H176—H172 | 62.2 |
H382—C38—O3 | 104.8 | H171—H176—H172 | 120.0 |
H382—C38—H381 | 108.9 | H171—H176—C17 | 61.5 |
H382—C38—C32 | 108.3 | C27—H271—H275 | 61.8 |
H391—C39—C36 | 111.0 | H276—H271—H275 | 120.0 |
H392—C39—C36 | 108.5 | H276—H271—C27 | 62.1 |
H392—C39—H391 | 114.2 | C27—H272—H276 | 62.0 |
O4—C39—C36 | 107.3 (4) | H274—H272—H276 | 120.0 |
O4—C39—H391 | 104.5 | H274—H272—C27 | 61.8 |
O4—C39—H392 | 111.2 | H275—H273—H274 | 120.0 |
O8—C41—C42 | 119.9 (3) | C27—H273—H274 | 62.0 |
C46—C41—C42 | 122.1 (6) | C27—H273—H275 | 61.9 |
C46—C41—O8 | 117.9 (5) | H273—H274—H272 | 120.0 |
C43—C42—C41 | 117.9 (4) | C27—H274—H272 | 62.1 |
C48—C42—C41 | 121.9 (6) | C27—H274—H273 | 61.8 |
C48—C42—C43 | 120.1 (3) | H271—H275—C27 | 62.0 |
H43—C43—C44 | 117.6 | H273—H275—C27 | 61.8 |
C42—C43—C44 | 122.0 (3) | H273—H275—H271 | 120.0 |
C42—C43—H43 | 120.4 | H271—H276—C27 | 61.8 |
C47—C44—C43 | 120.5 (3) | H272—H276—C27 | 62.0 |
C45—C44—C43 | 118.1 (6) | H272—H276—H271 | 120.0 |
C45—C44—C47 | 121.4 (4) | H375—H371—H376 | 120.0 |
C46—C45—C44 | 121.8 (4) | C37—H371—H376 | 61.3 |
H45—C45—C44 | 118.6 | C37—H371—H375 | 62.5 |
H45—C45—C46 | 119.6 | H374—H372—H376 | 120.0 |
C49—C46—C41 | 119.4 (6) | C37—H372—H376 | 62.0 |
C45—C46—C41 | 118.0 (6) | C37—H372—H374 | 62.0 |
C45—C46—C49 | 122.5 (3) | H375—H373—H374 | 120.0 |
C44—C47—H472 | 112.6 | C37—H373—H374 | 61.3 |
H473—C47—H472 | 108.4 | C37—H373—H375 | 62.6 |
H473—C47—C44 | 108.8 | C37—H374—H372 | 61.3 |
H471—C47—H472 | 104.9 | H373—H374—H372 | 120.0 |
H471—C47—C44 | 113.9 | H373—H374—C37 | 62.6 |
H471—C47—H473 | 108.2 | C37—H375—H371 | 61.9 |
C42—C48—O4 | 114.9 (5) | H373—H375—H371 | 120.0 |
H482—C48—O4 | 109.3 | H373—H375—C37 | 61.9 |
H482—C48—C42 | 109.9 | C37—H376—H372 | 61.3 |
H481—C48—O4 | 104.7 | H371—H376—H372 | 120.0 |
H481—C48—C42 | 111.2 | H371—H376—C37 | 62.6 |
H481—C48—H482 | 106.5 |
Experimental details
Crystal data | |
Chemical formula | C44H52O10 |
Mr | 740.89 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 29.982 (5), 14.154 (3), 27.612 (2) |
β (°) | 137.36 (3) |
V (Å3) | 7937 (5) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.3 × 0.2 × 0.2 |
Data collection | |
Diffractometer | Huber CS four-circle diffractometer |
Absorption correction | – |
No. of measured, independent and observed [F > 3σ(F)] reflections | 11136, 9464, 4754 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.660 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.067, 0.85 |
No. of reflections | 4754 |
No. of parameters | 496 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.19 |
Computer programs: XCS (Colapietro et al., 1992), XCS, SIR97 (Altomare et al., 1999), CAOS (Camalli & Spagna, 1994), ORTEP-3 (Farrugia, 1997), CAOS and PARST97 (Nardelli, 1995).
In octahomotetraoxacalix[4]arenes, the CH2 groups linking the aromatics in the typical calix[4]arene series are replaced by CH2OCH2 units (Masci, 2001). Although the same main conformations as in calix[4]arene can be considered, the size and flexibility of the ring are much increased (Masci et al., 1998) and lower rim substituents can be partly included in the cavity (Masci et al., 2001).
In the present study, the tricyclic derivative, (I), has distal aromatic rings bridged at the lower rim by dioxyethylene chains, thus forcing the compound to adopt a highly distorted 1,3-alternate conformation. Some bis-crown[n]ether (n = 5–7) compounds with the 1,3–2,4 bridging pattern have been investigated in the calix[4]erene series, and in all reported cases moderate deviations from a regular 1,3-alternate arrangement have been observed, the opposed aromatic units being almost parallel and the molecule having an elongated globular shape (Casnati et al., 2001; Thuéry et al., 2000). \sch
The enlarged calixarene ring and the shorter polyoxyethylene bridges account for the different shape of (I). The least-squares planes P1, P2, P3 and P4, defined by the four aromatic rings 1, 2, 3 and 4 containing atoms C11, C21, C31 and C41, respectively (Fig. 1), form dihedral angles between vicinal aromatics which are small in the case of rings P2 and P3 [24.6 (1)°] and large in the case of rings P1 and P2, P3 and P4, and P1 and P4 [74.4 (1), 74.9 (1) and 68.9 (1)°, respectively]. A reference least-squares plane defined by atoms O1, O2, O3 and O4 is intersected by planes P1, P2, P3 and P4 with dihedral angles of 68.0 (1), 21.8 (1), 14.3 (1) and 72.1 (1)°, respectively. On extending to homooxacalixarenes the notation of Kanamathareddy & Gutsche (1993), the conformation can be indicated as u, do, uo, d.
Apart from the orientation of the aromatic rings, the conformation of homooxacalixarenes relies on the arrangement of the ArCH2OCH2Ar units that are usually found to be in anti-anti or anti-gauche conformation. In the case of (I), opposite ArCH2OCH2Ar units are in the same gross conformation, namely almost anti-gauche around atoms O2 and O4, and gauche-gauche around atoms O1 and O3 [torsion angles 73.0 (5) and -63.4 (5)° around O1, 159.4 (4) and -73.6 (5)° around O2, 72.4 (4) and -73.3 (4)° around O3, and 158.0 (4) and -66.9 (5)° around O4.
The relatively short bridges at the lower rim are apparently responsible for the unusual conformation of the latter, which has only previously been observed in the related bicyclic compound, (II) (Masci et al., 2001). In the bicyclic compound, the methoxy-substituted aromatics are almost perpendicular to the plane defined by the ArCH2OCH2Ar O atoms [dihedral angles 79.7 (1) and 80.6 (1)°]. Another difference between the bicyclic and the tricyclic compounds lies in the conformation of the dioxyethylene bridges, which are anti, gauche, gauche, gauche, gauche, anti in the bicycle, (II), and almost anti, anti, gauche, anti, gauche, anti for both bridges of the present macrotricycle, (I). In fact, in (I), the torsion angles are 178.9 (4), 179.7 (4), -97.3 (5), -166.7 (4), 78.6 (5) and 173.9 (4)° from ring 1 to ring 3, and -166.2 (3), 175.1 (3), 84.4 (4), -162.2 (3), 74.6 (4) and 171.9 (3)° from ring 4 to ring 2.
The bridges in (I) partly fill the potential cavity formed by the two opposed aromatics and are not in close contact. The self-filled structure prevents the intermolecular inclusion noted in the related bicycle, (II); the closest intermolecular contact detected in (I), namely H33···O1i 2.37 Å, C33···O1i 3.317 (3) Å and C33—H33···O1i 168° [symmetry code: (i) x, 1 + y, z], corresponds to a weak C—H···O hydrogen bond (Desiraju & Steiner, 1999).