Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103005298/na1598sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103005298/na1598Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103005298/na1598IIsup3.hkl |
CCDC references: 211755; 211756
Derivatives of calixarenes (I) and (II) were synthesized by the reaction of calix[4]arene with ethylbromoacetate according to modified procedures (Guillon et al., 2000; Aoki et al., 1992; Iwamoto & Shinkai, 1992). (I): Calix[4]arene (1.00 g, 2.35 mmol), Cs2CO3 (0.77 g, 2.35 mmol) and ethylbromoacetate (5.23 ml, 47.2 mmol) were heated at reflux in acetone (70 ml) and stirred for 12 h under N2. The reaction mixture was left to cool, and a solid residue was separated by filtration and washed with acetone. The solvent was removed, water (200 ml) was added and the residue was extracted with two portions of CHCl3 (100 ml) and dried over Na2SO4. A brown oil was obtained after evaporation, which was dissolved in methanol (60 ml) on a steam bath. Water (25 ml) was added dropwise and the mixture was put aside at room temperature to form monocrystals, which were recrystallized from methanol/CHCl3 (7:1) to obtain crystals (990 mg, 66%; m.p. 443–445 K. (II): Calix[4]arene (2.00 g, 4.70 mmol), Cs2CO3 (30.12 g, 94 mmol) and ethylbromoacetate (10.42 ml, 94 mmol) were suspended in acetone (150 ml) and kept at reflux for 13 h under N2. The rest of the procedure followed that of (I) and yielded monocrystals (620 mg, 17.1%; m.p. 381–383 K).
Both sets of crystals without additional solvent proved to be stable in air. The diffraction data for (I) and (II) were collected for several crystals, both at room temperature (Ljubljana) and at 150 K (Vienna). The best low-temperature data were used, because the R values of the room temperature data were rather high [0.072 for (I) and 0.096 for (II)]. Neither the expected disorder in the ethoxycarbonylmethoxy moieties nor solvate formation were observed in either of the two determinations. The data were checked with option SQUEEZE of PLATON (Spek, 1998) and with the TWIN refinement.
All H atoms were found in the difference electron-density map and were placed at calculated position with isotropic displacement parameters taken from those of the adjacent atom multiplied by 1.2 (1.5 for methyl). The two phenolic H atoms of (I) were left to refine freely. There were no suitable anomalous scatterers for Mo Kα radiation, and therefore the determination of the absolute configuration was not possible from the X-ray data for (II) and the Friedel diffraction data were merged accordingly. There were only two peaks of residual electron density of 0.91 e Å−3 [1.08 Å away from O8] and 0.91 e Å−3 [1.43 Å away H35B] in (I). However, we were not able to resolve these effects, either as a disorder or as an additional solvent molecule in (I). The refinement with the TWIN instruction did not affect these values.
For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS86 (Sheldrick, 1986); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1971), PLUTON (Spek, 1991), PLATON (Spek, 2003; Farrugia, 2000), ORTEP-3 (Farrugia, 1997), Mercury (Bruno et al., 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997), PARST (Nardelli, 1983 and 1995), WinGX (Farrugia, 1999).
C36H36O8 | F(000) = 1264 |
Mr = 596.65 | Dx = 1.301 Mg m−3 Dm = 1.26 (5) Mg m−3 Dm measured by flotation |
Monoclinic, P21/c | Melting point = 170–172 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 10.1364 (5) Å | Cell parameters from 5652 reflections |
b = 10.9403 (5) Å | θ = 1.0–27.5° |
c = 27.7309 (10) Å | µ = 0.09 mm−1 |
β = 97.917 (3)° | T = 150 K |
V = 3045.9 (2) Å3 | Plate, colourless |
Z = 4 | 0.28 × 0.24 × 0.18 mm |
Nonius KappaCCD diffractometer | 5280 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.018 |
Graphite monochromator | θmax = 27.5°, θmin = 2.4° |
Detector resolution: 0.055 pixels mm-1 | h = −13→13 |
ϕ and ω scans | k = −14→14 |
13551 measured reflections | l = −36→35 |
6968 independent 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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.146 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0689P)2 + 1.324P] where P = (Fo2 + 2Fc2)/3 |
6968 reflections | (Δ/σ)max < 0.001 |
407 parameters | Δρmax = 0.91 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
C36H36O8 | V = 3045.9 (2) Å3 |
Mr = 596.65 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.1364 (5) Å | µ = 0.09 mm−1 |
b = 10.9403 (5) Å | T = 150 K |
c = 27.7309 (10) Å | 0.28 × 0.24 × 0.18 mm |
β = 97.917 (3)° |
Nonius KappaCCD diffractometer | 5280 reflections with I > 2σ(I) |
13551 measured reflections | Rint = 0.018 |
6968 independent reflections |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.146 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.91 e Å−3 |
6968 reflections | Δρmin = −0.33 e Å−3 |
407 parameters |
Experimental. KappaCCD Nonius diffractometer. 476 frames in 3 sets of ϕ and ω scans. Rotation/frame=1°. Crystal-detector distance=40.0 mm. Measuring time=300 s/°. |
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 | ||
O1 | 0.55518 (11) | 0.40004 (12) | 0.34327 (4) | 0.0357 (3) | |
O2 | 0.47010 (12) | 0.48737 (12) | 0.42382 (5) | 0.0372 (3) | |
H2 | 0.511 (3) | 0.451 (2) | 0.4020 (9) | 0.063 (7)* | |
O3 | 0.40695 (11) | 0.74115 (11) | 0.39941 (4) | 0.0347 (3) | |
O4 | 0.44742 (12) | 0.64100 (13) | 0.30877 (5) | 0.0416 (3) | |
H4 | 0.443 (2) | 0.688 (2) | 0.3335 (10) | 0.062 (7)* | |
O5 | 0.79333 (14) | 0.34387 (17) | 0.39910 (5) | 0.0592 (4) | |
O6 | 0.90209 (11) | 0.42250 (12) | 0.34111 (4) | 0.0368 (3) | |
O7 | 0.63881 (15) | 0.83154 (14) | 0.37722 (5) | 0.0556 (4) | |
O8 | 0.65365 (13) | 0.96094 (12) | 0.44053 (5) | 0.0422 (3) | |
C1 | 0.40375 (17) | 0.33973 (16) | 0.27145 (6) | 0.0342 (4) | |
C2 | 0.30902 (18) | 0.25408 (18) | 0.25145 (7) | 0.0408 (4) | |
H02 | 0.2736 | 0.2600 | 0.2180 | 0.049* | |
C3 | 0.2660 (2) | 0.16162 (17) | 0.27905 (8) | 0.0450 (5) | |
H03 | 0.2021 | 0.1043 | 0.2645 | 0.054* | |
C4 | 0.3155 (2) | 0.15205 (16) | 0.32773 (7) | 0.0422 (4) | |
H04 | 0.2822 | 0.0903 | 0.3469 | 0.051* | |
C5 | 0.41361 (17) | 0.23142 (15) | 0.34920 (6) | 0.0343 (4) | |
C6 | 0.45835 (16) | 0.32205 (15) | 0.31998 (6) | 0.0311 (4) | |
C7 | 0.46555 (18) | 0.22288 (16) | 0.40317 (6) | 0.0377 (4) | |
H7A | 0.4738 | 0.1356 | 0.4125 | 0.045* | |
H7B | 0.5557 | 0.2594 | 0.4090 | 0.045* | |
C8 | 0.37756 (17) | 0.28644 (16) | 0.43553 (6) | 0.0322 (4) | |
C9 | 0.28696 (19) | 0.22015 (17) | 0.45844 (7) | 0.0394 (4) | |
H9 | 0.2790 | 0.1346 | 0.4529 | 0.047* | |
C10 | 0.20798 (19) | 0.27538 (18) | 0.48918 (7) | 0.0428 (4) | |
H10 | 0.1469 | 0.2281 | 0.5045 | 0.051* | |
C11 | 0.21883 (18) | 0.39961 (18) | 0.49734 (6) | 0.0379 (4) | |
H11 | 0.1662 | 0.4372 | 0.5190 | 0.045* | |
C12 | 0.30545 (16) | 0.47088 (15) | 0.47443 (6) | 0.0306 (3) | |
C13 | 0.38489 (16) | 0.41310 (15) | 0.44379 (5) | 0.0293 (3) | |
C14 | 0.31347 (17) | 0.60817 (16) | 0.48115 (6) | 0.0329 (4) | |
H14A | 0.4067 | 0.6353 | 0.4812 | 0.040* | |
H14B | 0.2864 | 0.6300 | 0.5130 | 0.040* | |
C15 | 0.22394 (17) | 0.67361 (15) | 0.44086 (6) | 0.0315 (4) | |
C16 | 0.08619 (18) | 0.67156 (17) | 0.44102 (7) | 0.0389 (4) | |
H16 | 0.0515 | 0.6349 | 0.4677 | 0.047* | |
C17 | −0.00094 (19) | 0.72144 (19) | 0.40346 (8) | 0.0446 (5) | |
H17 | −0.0941 | 0.7200 | 0.4047 | 0.054* | |
C18 | 0.04821 (19) | 0.77344 (18) | 0.36405 (7) | 0.0433 (4) | |
H18 | −0.0119 | 0.8060 | 0.3379 | 0.052* | |
C19 | 0.18502 (18) | 0.77865 (15) | 0.36226 (7) | 0.0355 (4) | |
C20 | 0.27040 (16) | 0.73171 (15) | 0.40158 (6) | 0.0313 (4) | |
C21 | 0.2363 (2) | 0.82373 (16) | 0.31651 (7) | 0.0422 (4) | |
H21A | 0.3296 | 0.8515 | 0.3248 | 0.051* | |
H22B | 0.1822 | 0.8944 | 0.3031 | 0.051* | |
C22 | 0.22980 (18) | 0.72377 (16) | 0.27812 (6) | 0.0370 (4) | |
C23 | 0.1161 (2) | 0.7133 (2) | 0.24378 (7) | 0.0470 (5) | |
H23 | 0.0452 | 0.7697 | 0.2444 | 0.056* | |
C24 | 0.1048 (2) | 0.6219 (2) | 0.20871 (7) | 0.0503 (5) | |
H24 | 0.0267 | 0.6158 | 0.1856 | 0.060* | |
C25 | 0.20793 (19) | 0.5397 (2) | 0.20771 (6) | 0.0437 (5) | |
H25 | 0.2005 | 0.4779 | 0.1834 | 0.052* | |
C26 | 0.32230 (17) | 0.54583 (17) | 0.24158 (6) | 0.0356 (4) | |
C27 | 0.33195 (17) | 0.63876 (16) | 0.27678 (6) | 0.0338 (4) | |
C28 | 0.43074 (18) | 0.45075 (18) | 0.24121 (6) | 0.0376 (4) | |
H28A | 0.5177 | 0.4869 | 0.2545 | 0.045* | |
H28B | 0.4355 | 0.4250 | 0.2073 | 0.045* | |
C29 | 0.67486 (17) | 0.4171 (2) | 0.32306 (6) | 0.0402 (4) | |
H29A | 0.6801 | 0.5028 | 0.3119 | 0.048* | |
H29B | 0.6749 | 0.3631 | 0.2944 | 0.048* | |
C30 | 0.79399 (17) | 0.38900 (17) | 0.35979 (6) | 0.0343 (4) | |
C31 | 1.03113 (17) | 0.39529 (18) | 0.36862 (7) | 0.0381 (4) | |
H31A | 1.0425 | 0.3060 | 0.3732 | 0.046* | |
H31B | 1.0400 | 0.4348 | 0.4010 | 0.046* | |
C32 | 1.13250 (17) | 0.44482 (18) | 0.33940 (7) | 0.0402 (4) | |
H32A | 1.1272 | 0.4002 | 0.3086 | 0.060* | |
H32B | 1.2217 | 0.4350 | 0.3577 | 0.060* | |
H32C | 1.1151 | 0.5317 | 0.3328 | 0.060* | |
C33 | 0.4697 (2) | 0.8357 (2) | 0.43005 (8) | 0.0554 (6) | |
H33A | 0.4894 | 0.8057 | 0.4640 | 0.066* | |
H33B | 0.4094 | 0.9069 | 0.4297 | 0.066* | |
C34 | 0.59667 (18) | 0.87292 (16) | 0.41183 (6) | 0.0362 (4) | |
C35 | 0.7748 (2) | 1.01580 (19) | 0.42750 (8) | 0.0456 (5) | |
H35A | 0.7542 | 1.0680 | 0.3983 | 0.055* | |
H35B | 0.8386 | 0.9517 | 0.4206 | 0.055* | |
C36 | 0.8322 (3) | 1.0911 (2) | 0.47067 (10) | 0.0661 (7) | |
H36A | 0.7647 | 1.1488 | 0.4789 | 0.099* | |
H36B | 0.9097 | 1.1365 | 0.4627 | 0.099* | |
H36C | 0.8595 | 1.0373 | 0.4985 | 0.099* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0243 (6) | 0.0507 (7) | 0.0340 (6) | −0.0048 (5) | 0.0108 (5) | −0.0072 (5) |
O2 | 0.0408 (7) | 0.0351 (6) | 0.0396 (7) | −0.0030 (5) | 0.0189 (6) | −0.0007 (5) |
O3 | 0.0292 (6) | 0.0341 (6) | 0.0413 (6) | −0.0055 (5) | 0.0066 (5) | −0.0028 (5) |
O4 | 0.0317 (7) | 0.0536 (8) | 0.0380 (7) | −0.0013 (6) | −0.0001 (5) | −0.0067 (6) |
O5 | 0.0406 (8) | 0.0958 (12) | 0.0423 (8) | −0.0021 (8) | 0.0096 (6) | 0.0218 (8) |
O6 | 0.0240 (6) | 0.0506 (7) | 0.0359 (6) | −0.0040 (5) | 0.0048 (5) | 0.0036 (5) |
O7 | 0.0561 (9) | 0.0648 (10) | 0.0489 (8) | −0.0217 (7) | 0.0173 (7) | −0.0163 (7) |
O8 | 0.0384 (7) | 0.0377 (7) | 0.0501 (7) | −0.0084 (5) | 0.0052 (6) | −0.0046 (6) |
C1 | 0.0296 (8) | 0.0400 (9) | 0.0351 (9) | 0.0013 (7) | 0.0114 (7) | −0.0085 (7) |
C2 | 0.0377 (10) | 0.0459 (10) | 0.0397 (9) | 0.0000 (8) | 0.0079 (8) | −0.0139 (8) |
C3 | 0.0440 (11) | 0.0369 (10) | 0.0549 (12) | −0.0060 (8) | 0.0096 (9) | −0.0156 (9) |
C4 | 0.0474 (11) | 0.0283 (9) | 0.0535 (11) | −0.0021 (8) | 0.0159 (9) | −0.0065 (8) |
C5 | 0.0330 (9) | 0.0295 (8) | 0.0422 (9) | 0.0080 (7) | 0.0116 (7) | −0.0041 (7) |
C6 | 0.0246 (8) | 0.0345 (9) | 0.0359 (8) | 0.0014 (6) | 0.0102 (6) | −0.0077 (7) |
C7 | 0.0392 (10) | 0.0318 (9) | 0.0428 (10) | 0.0090 (7) | 0.0086 (8) | 0.0047 (7) |
C8 | 0.0331 (9) | 0.0336 (9) | 0.0295 (8) | 0.0047 (7) | 0.0031 (7) | 0.0055 (7) |
C9 | 0.0446 (10) | 0.0318 (9) | 0.0421 (10) | −0.0011 (8) | 0.0076 (8) | 0.0076 (7) |
C10 | 0.0429 (10) | 0.0448 (10) | 0.0434 (10) | −0.0061 (8) | 0.0149 (8) | 0.0097 (8) |
C11 | 0.0374 (9) | 0.0463 (10) | 0.0321 (9) | 0.0004 (8) | 0.0125 (7) | 0.0034 (7) |
C12 | 0.0313 (8) | 0.0368 (9) | 0.0235 (7) | −0.0005 (7) | 0.0030 (6) | 0.0009 (6) |
C13 | 0.0279 (8) | 0.0348 (8) | 0.0250 (7) | −0.0003 (6) | 0.0034 (6) | 0.0042 (6) |
C14 | 0.0359 (9) | 0.0374 (9) | 0.0263 (8) | −0.0008 (7) | 0.0068 (7) | −0.0043 (7) |
C15 | 0.0324 (9) | 0.0296 (8) | 0.0334 (8) | −0.0011 (7) | 0.0075 (7) | −0.0085 (7) |
C16 | 0.0338 (9) | 0.0419 (10) | 0.0433 (10) | 0.0001 (8) | 0.0136 (8) | −0.0068 (8) |
C17 | 0.0293 (9) | 0.0485 (11) | 0.0571 (12) | 0.0053 (8) | 0.0097 (8) | −0.0069 (9) |
C18 | 0.0369 (10) | 0.0397 (10) | 0.0515 (11) | 0.0095 (8) | 0.0000 (8) | −0.0013 (8) |
C19 | 0.0366 (9) | 0.0256 (8) | 0.0441 (10) | 0.0016 (7) | 0.0051 (7) | −0.0003 (7) |
C20 | 0.0287 (8) | 0.0264 (8) | 0.0390 (9) | −0.0015 (6) | 0.0054 (7) | −0.0044 (7) |
C21 | 0.0466 (11) | 0.0296 (9) | 0.0492 (11) | 0.0003 (8) | 0.0028 (8) | 0.0119 (8) |
C22 | 0.0400 (10) | 0.0366 (9) | 0.0340 (9) | −0.0028 (8) | 0.0038 (7) | 0.0143 (7) |
C23 | 0.0430 (11) | 0.0518 (12) | 0.0442 (10) | 0.0045 (9) | −0.0010 (8) | 0.0183 (9) |
C24 | 0.0452 (11) | 0.0650 (13) | 0.0367 (10) | −0.0021 (10) | −0.0086 (8) | 0.0109 (9) |
C25 | 0.0433 (10) | 0.0579 (12) | 0.0284 (8) | −0.0072 (9) | 0.0000 (8) | 0.0049 (8) |
C26 | 0.0339 (9) | 0.0469 (10) | 0.0264 (8) | −0.0075 (8) | 0.0060 (7) | 0.0070 (7) |
C27 | 0.0324 (9) | 0.0400 (9) | 0.0290 (8) | −0.0067 (7) | 0.0042 (7) | 0.0086 (7) |
C28 | 0.0332 (9) | 0.0541 (11) | 0.0269 (8) | −0.0049 (8) | 0.0096 (7) | −0.0034 (7) |
C29 | 0.0257 (8) | 0.0611 (12) | 0.0355 (9) | −0.0032 (8) | 0.0103 (7) | 0.0007 (8) |
C30 | 0.0297 (8) | 0.0401 (9) | 0.0342 (9) | −0.0027 (7) | 0.0083 (7) | −0.0035 (7) |
C31 | 0.0276 (9) | 0.0448 (10) | 0.0401 (9) | −0.0011 (7) | −0.0016 (7) | 0.0005 (8) |
C32 | 0.0261 (8) | 0.0454 (10) | 0.0491 (10) | −0.0013 (8) | 0.0048 (7) | −0.0036 (8) |
C33 | 0.0496 (12) | 0.0644 (14) | 0.0537 (12) | −0.0244 (10) | 0.0125 (10) | −0.0199 (11) |
C34 | 0.0392 (10) | 0.0353 (9) | 0.0325 (8) | −0.0012 (7) | −0.0007 (7) | 0.0022 (7) |
C35 | 0.0409 (10) | 0.0445 (11) | 0.0526 (11) | −0.0096 (8) | 0.0104 (9) | −0.0034 (9) |
C36 | 0.0653 (15) | 0.0475 (12) | 0.0786 (16) | −0.0220 (11) | −0.0146 (13) | −0.0051 (12) |
O1—C6 | 1.391 (2) | C15—C20 | 1.398 (2) |
O1—C29 | 1.4171 (19) | C16—C17 | 1.382 (3) |
O2—C13 | 1.3582 (19) | C16—H16 | 0.9500 |
O2—H2 | 0.88 (3) | C17—C18 | 1.384 (3) |
O3—C20 | 1.398 (2) | C17—H17 | 0.9500 |
O3—C33 | 1.431 (2) | C18—C19 | 1.396 (3) |
O4—C27 | 1.368 (2) | C18—H18 | 0.9500 |
O4—H4 | 0.86 (3) | C19—C20 | 1.393 (2) |
O5—C30 | 1.198 (2) | C19—C21 | 1.518 (3) |
O6—C30 | 1.326 (2) | C21—C22 | 1.521 (3) |
O6—C31 | 1.451 (2) | C21—H21A | 0.9900 |
O7—C34 | 1.192 (2) | C21—H22B | 0.9900 |
O8—C34 | 1.330 (2) | C22—C23 | 1.395 (3) |
O8—C35 | 1.457 (2) | C22—C27 | 1.396 (3) |
C1—C6 | 1.396 (2) | C23—C24 | 1.389 (3) |
C1—C2 | 1.400 (3) | C23—H23 | 0.9500 |
C1—C28 | 1.522 (3) | C24—C25 | 1.382 (3) |
C2—C3 | 1.375 (3) | C24—H24 | 0.9500 |
C2—H02 | 0.9500 | C25—C26 | 1.390 (2) |
C3—C4 | 1.378 (3) | C25—H25 | 0.9500 |
C3—H03 | 0.9500 | C26—C27 | 1.404 (3) |
C4—C5 | 1.391 (3) | C26—C28 | 1.514 (3) |
C4—H04 | 0.9500 | C28—H28A | 0.9900 |
C5—C6 | 1.395 (2) | C28—H28B | 0.9900 |
C5—C7 | 1.520 (3) | C29—C30 | 1.500 (2) |
C7—C8 | 1.518 (2) | C29—H29A | 0.9900 |
C7—H7A | 0.9900 | C29—H29B | 0.9900 |
C7—H7B | 0.9900 | C31—C32 | 1.495 (3) |
C8—C9 | 1.391 (2) | C31—H31A | 0.9900 |
C8—C13 | 1.405 (2) | C31—H31B | 0.9900 |
C9—C10 | 1.386 (3) | C32—H32A | 0.9800 |
C9—H9 | 0.9500 | C32—H32B | 0.9800 |
C10—C11 | 1.380 (3) | C32—H32C | 0.9800 |
C10—H10 | 0.9500 | C33—C34 | 1.502 (3) |
C11—C12 | 1.391 (2) | C33—H33A | 0.9900 |
C11—H11 | 0.9500 | C33—H33B | 0.9900 |
C12—C13 | 1.400 (2) | C35—C36 | 1.503 (3) |
C12—C14 | 1.514 (2) | C35—H35A | 0.9900 |
C14—C15 | 1.518 (2) | C35—H35B | 0.9900 |
C14—H14A | 0.9900 | C36—H36A | 0.9800 |
C14—H14B | 0.9900 | C36—H36B | 0.9800 |
C15—C16 | 1.397 (2) | C36—H36C | 0.9800 |
C6—O1—C29 | 119.02 (13) | C19—C21—C22 | 111.38 (14) |
C13—O2—H2 | 113.5 (16) | C19—C21—H21A | 109.4 |
C20—O3—C33 | 112.94 (14) | C22—C21—H21A | 109.4 |
C27—O4—H4 | 112.9 (17) | C19—C21—H22B | 109.4 |
C30—O6—C31 | 118.12 (14) | C22—C21—H22B | 109.4 |
C34—O8—C35 | 117.49 (15) | H21A—C21—H22B | 108.0 |
C6—C1—C2 | 116.63 (17) | C23—C22—C27 | 118.23 (18) |
C6—C1—C28 | 124.34 (15) | C23—C22—C21 | 119.27 (18) |
C2—C1—C28 | 118.77 (16) | C27—C22—C21 | 122.46 (16) |
C3—C2—C1 | 121.63 (18) | C24—C23—C22 | 121.22 (19) |
C3—C2—H02 | 119.2 | C24—C23—H23 | 119.4 |
C1—C2—H02 | 119.2 | C22—C23—H23 | 119.4 |
C2—C3—C4 | 120.02 (18) | C25—C24—C23 | 119.51 (18) |
C2—C3—H03 | 120.0 | C25—C24—H24 | 120.2 |
C4—C3—H03 | 120.0 | C23—C24—H24 | 120.2 |
C3—C4—C5 | 120.96 (18) | C24—C25—C26 | 121.21 (19) |
C3—C4—H04 | 119.5 | C24—C25—H25 | 119.4 |
C5—C4—H04 | 119.5 | C26—C25—H25 | 119.4 |
C4—C5—C6 | 117.75 (17) | C25—C26—C27 | 118.47 (18) |
C4—C5—C7 | 120.89 (16) | C25—C26—C28 | 120.07 (17) |
C6—C5—C7 | 121.30 (16) | C27—C26—C28 | 121.41 (15) |
O1—C6—C5 | 115.56 (15) | O4—C27—C22 | 122.85 (16) |
O1—C6—C1 | 121.56 (15) | O4—C27—C26 | 115.81 (16) |
C5—C6—C1 | 122.74 (16) | C22—C27—C26 | 121.34 (16) |
C8—C7—C5 | 113.70 (14) | C26—C28—C1 | 111.02 (14) |
C8—C7—H7A | 108.8 | C26—C28—H28A | 109.4 |
C5—C7—H7A | 108.8 | C1—C28—H28A | 109.4 |
C8—C7—H7B | 108.8 | C26—C28—H28B | 109.4 |
C5—C7—H7B | 108.8 | C1—C28—H28B | 109.4 |
H7A—C7—H7B | 107.7 | H28A—C28—H28B | 108.0 |
C9—C8—C13 | 117.61 (15) | O1—C29—C30 | 110.93 (14) |
C9—C8—C7 | 120.66 (16) | O1—C29—H29A | 109.5 |
C13—C8—C7 | 121.73 (15) | C30—C29—H29A | 109.5 |
C10—C9—C8 | 121.84 (17) | O1—C29—H29B | 109.5 |
C10—C9—H9 | 119.1 | C30—C29—H29B | 109.5 |
C8—C9—H9 | 119.1 | H29A—C29—H29B | 108.0 |
C11—C10—C9 | 119.37 (16) | O5—C30—O6 | 125.30 (17) |
C11—C10—H10 | 120.3 | O5—C30—C29 | 126.70 (16) |
C9—C10—H10 | 120.3 | O6—C30—C29 | 108.01 (14) |
C10—C11—C12 | 121.22 (16) | O6—C31—C32 | 106.13 (14) |
C10—C11—H11 | 119.4 | O6—C31—H31A | 110.5 |
C12—C11—H11 | 119.4 | C32—C31—H31A | 110.5 |
C11—C12—C13 | 118.43 (16) | O6—C31—H31B | 110.5 |
C11—C12—C14 | 121.75 (15) | C32—C31—H31B | 110.5 |
C13—C12—C14 | 119.81 (15) | H31A—C31—H31B | 108.7 |
O2—C13—C12 | 115.39 (15) | C31—C32—H32A | 109.5 |
O2—C13—C8 | 123.10 (15) | C31—C32—H32B | 109.5 |
C12—C13—C8 | 121.50 (15) | H32A—C32—H32B | 109.5 |
C12—C14—C15 | 111.14 (13) | C31—C32—H32C | 109.5 |
C12—C14—H14A | 109.4 | H32A—C32—H32C | 109.5 |
C15—C14—H14A | 109.4 | H32B—C32—H32C | 109.5 |
C12—C14—H14B | 109.4 | O3—C33—C34 | 109.13 (16) |
C15—C14—H14B | 109.4 | O3—C33—H33A | 109.9 |
H14A—C14—H14B | 108.0 | C34—C33—H33A | 109.9 |
C16—C15—C20 | 116.99 (16) | O3—C33—H33B | 109.9 |
C16—C15—C14 | 119.11 (15) | C34—C33—H33B | 109.9 |
C20—C15—C14 | 123.82 (15) | H33A—C33—H33B | 108.3 |
C17—C16—C15 | 121.78 (17) | O7—C34—O8 | 125.63 (17) |
C17—C16—H16 | 119.1 | O7—C34—C33 | 125.89 (17) |
C15—C16—H16 | 119.1 | O8—C34—C33 | 108.47 (15) |
C16—C17—C18 | 119.69 (17) | O8—C35—C36 | 105.97 (17) |
C16—C17—H17 | 120.2 | O8—C35—H35A | 110.5 |
C18—C17—H17 | 120.2 | C36—C35—H35A | 110.5 |
C17—C18—C19 | 120.82 (18) | O8—C35—H35B | 110.5 |
C17—C18—H18 | 119.6 | C36—C35—H35B | 110.5 |
C19—C18—H18 | 119.6 | H35A—C35—H35B | 108.7 |
C20—C19—C18 | 118.05 (17) | C35—C36—H36A | 109.5 |
C20—C19—C21 | 121.77 (16) | C35—C36—H36B | 109.5 |
C18—C19—C21 | 119.94 (17) | H36A—C36—H36B | 109.5 |
C19—C20—O3 | 116.82 (15) | C35—C36—H36C | 109.5 |
C19—C20—C15 | 122.54 (16) | H36A—C36—H36C | 109.5 |
O3—C20—C15 | 120.61 (15) | H36B—C36—H36C | 109.5 |
C6—C1—C2—C3 | 3.9 (3) | C18—C19—C20—O3 | −178.30 (15) |
C28—C1—C2—C3 | −170.49 (17) | C21—C19—C20—O3 | 7.3 (2) |
C1—C2—C3—C4 | 0.4 (3) | C18—C19—C20—C15 | 4.0 (3) |
C2—C3—C4—C5 | −3.0 (3) | C21—C19—C20—C15 | −170.43 (16) |
C3—C4—C5—C6 | 1.0 (3) | C33—O3—C20—C19 | 104.08 (19) |
C3—C4—C5—C7 | 178.39 (16) | C33—O3—C20—C15 | −78.2 (2) |
C29—O1—C6—C5 | 127.35 (16) | C16—C15—C20—C19 | −4.4 (2) |
C29—O1—C6—C1 | −57.0 (2) | C14—C15—C20—C19 | 172.33 (15) |
C4—C5—C6—O1 | 179.21 (14) | C16—C15—C20—O3 | 177.99 (15) |
C7—C5—C6—O1 | 1.9 (2) | C14—C15—C20—O3 | −5.3 (2) |
C4—C5—C6—C1 | 3.6 (2) | C20—C19—C21—C22 | 93.8 (2) |
C7—C5—C6—C1 | −173.76 (15) | C18—C19—C21—C22 | −80.5 (2) |
C2—C1—C6—O1 | 178.70 (14) | C19—C21—C22—C23 | 91.4 (2) |
C28—C1—C6—O1 | −7.3 (2) | C19—C21—C22—C27 | −86.4 (2) |
C2—C1—C6—C5 | −5.9 (2) | C27—C22—C23—C24 | −0.8 (3) |
C28—C1—C6—C5 | 168.07 (15) | C21—C22—C23—C24 | −178.66 (17) |
C4—C5—C7—C8 | −81.9 (2) | C22—C23—C24—C25 | −0.1 (3) |
C6—C5—C7—C8 | 95.38 (19) | C23—C24—C25—C26 | 0.9 (3) |
C5—C7—C8—C9 | 98.47 (19) | C24—C25—C26—C27 | −0.8 (3) |
C5—C7—C8—C13 | −82.0 (2) | C24—C25—C26—C28 | 176.89 (17) |
C13—C8—C9—C10 | −1.3 (3) | C23—C22—C27—O4 | 179.97 (16) |
C7—C8—C9—C10 | 178.26 (17) | C21—C22—C27—O4 | −2.2 (3) |
C8—C9—C10—C11 | 0.2 (3) | C23—C22—C27—C26 | 0.8 (2) |
C9—C10—C11—C12 | 1.4 (3) | C21—C22—C27—C26 | 178.65 (15) |
C10—C11—C12—C13 | −1.8 (3) | C25—C26—C27—O4 | −179.27 (15) |
C10—C11—C12—C14 | 176.99 (17) | C28—C26—C27—O4 | 3.1 (2) |
C11—C12—C13—O2 | −178.01 (15) | C25—C26—C27—C22 | −0.1 (2) |
C14—C12—C13—O2 | 3.1 (2) | C28—C26—C27—C22 | −177.72 (15) |
C11—C12—C13—C8 | 0.7 (2) | C25—C26—C28—C1 | −87.00 (19) |
C14—C12—C13—C8 | −178.18 (15) | C27—C26—C28—C1 | 90.62 (19) |
C9—C8—C13—O2 | 179.43 (15) | C6—C1—C28—C26 | −95.81 (19) |
C7—C8—C13—O2 | −0.1 (2) | C2—C1—C28—C26 | 78.08 (19) |
C9—C8—C13—C12 | 0.8 (2) | C6—O1—C29—C30 | −124.85 (17) |
C7—C8—C13—C12 | −178.70 (15) | C31—O6—C30—O5 | 4.5 (3) |
C11—C12—C14—C15 | −94.32 (18) | C31—O6—C30—C29 | −175.22 (15) |
C13—C12—C14—C15 | 84.51 (19) | O1—C29—C30—O5 | 8.7 (3) |
C12—C14—C15—C16 | 73.77 (19) | O1—C29—C30—O6 | −171.56 (15) |
C12—C14—C15—C20 | −102.86 (18) | C30—O6—C31—C32 | −179.11 (15) |
C20—C15—C16—C17 | 1.8 (3) | C20—O3—C33—C34 | −157.92 (16) |
C14—C15—C16—C17 | −175.05 (16) | C35—O8—C34—O7 | 3.0 (3) |
C15—C16—C17—C18 | 1.0 (3) | C35—O8—C34—C33 | −176.36 (17) |
C16—C17—C18—C19 | −1.5 (3) | O3—C33—C34—O7 | 0.5 (3) |
C17—C18—C19—C20 | −0.9 (3) | O3—C33—C34—O8 | 179.82 (16) |
C17—C18—C19—C21 | 173.55 (17) | C34—O8—C35—C36 | −168.42 (17) |
C44H48O12 | Dx = 1.148 Mg m−3 Dm = 1.10 (5) Mg m−3 Dm measured by flotation |
Mr = 768.82 | Melting point = 108–110 K |
Tetragonal, P4 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P -4 | Cell parameters from 5413 reflections |
a = 12.0173 (8) Å | θ = 1.0–29.1° |
c = 7.6972 (5) Å | µ = 0.08 mm−1 |
V = 1111.60 (13) Å3 | T = 150 K |
Z = 1 | Prism, colourless |
F(000) = 408 | 0.36 × 0.24 × 0.22 mm |
Nonius KappaCCD diffractometer | 1453 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.015 |
Graphite monochromator | θmax = 29.2°, θmin = 5.4° |
Detector resolution: 0.055 pixels mm-1 | h = 0→16 |
ω scans | k = −11→11 |
2991 measured reflections | l = −10→10 |
1604 independent 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)] = 0.065 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.192 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | w = 1/[σ2(Fo2) + (0.124P)2 + 0.2336P] where P = (Fo2 + 2Fc2)/3 |
1604 reflections | (Δ/σ)max < 0.001 |
128 parameters | Δρmax = 0.46 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C44H48O12 | Z = 1 |
Mr = 768.82 | Mo Kα radiation |
Tetragonal, P4 | µ = 0.08 mm−1 |
a = 12.0173 (8) Å | T = 150 K |
c = 7.6972 (5) Å | 0.36 × 0.24 × 0.22 mm |
V = 1111.60 (13) Å3 |
Nonius KappaCCD diffractometer | 1453 reflections with I > 2σ(I) |
2991 measured reflections | Rint = 0.015 |
1604 independent reflections |
R[F2 > 2σ(F2)] = 0.065 | 0 restraints |
wR(F2) = 0.192 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 0.46 e Å−3 |
1604 reflections | Δρmin = −0.23 e Å−3 |
128 parameters |
Experimental. KappaCCD Nonius diffractometer. 225 frames in 5 sets of ω scans. Rotation/frame=2°. Crystal-detector distance=30.4 mm. Measuring time=200 s/°. |
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 | 0.26396 (19) | 0.4626 (2) | 0.5988 (4) | 0.0348 (5) | |
C2 | 0.2820 (2) | 0.4593 (3) | 0.7781 (4) | 0.0418 (6) | |
H2 | 0.2700 | 0.3918 | 0.8394 | 0.050* | |
C3 | 0.3169 (3) | 0.5527 (3) | 0.8679 (4) | 0.0479 (7) | |
H3 | 0.3258 | 0.5502 | 0.9905 | 0.057* | |
C4 | 0.3386 (3) | 0.6496 (3) | 0.7780 (4) | 0.0421 (6) | |
H4 | 0.3658 | 0.7126 | 0.8393 | 0.050* | |
C5 | 0.3214 (2) | 0.6573 (2) | 0.5995 (4) | 0.0346 (5) | |
C6 | 0.27945 (19) | 0.5644 (2) | 0.5143 (3) | 0.0328 (5) | |
C7 | 0.2406 (2) | 0.3562 (2) | 0.5007 (4) | 0.0362 (5) | |
H7A | 0.2194 | 0.2967 | 0.5833 | 0.043* | |
H7B | 0.1778 | 0.3679 | 0.4195 | 0.043* | |
C8 | 0.1456 (3) | 0.5701 (3) | 0.2921 (5) | 0.0538 (9) | |
H8A | 0.0996 | 0.5697 | 0.3987 | 0.065* | |
H8B | 0.1300 | 0.5008 | 0.2271 | 0.065* | |
C9 | 0.1145 (3) | 0.6675 (3) | 0.1833 (6) | 0.0623 (11) | |
C10 | −0.0248 (5) | 0.7249 (7) | −0.0156 (14) | 0.121 (3) | |
H10A | 0.0019 | 0.8008 | 0.0124 | 0.145* | |
H10B | −0.1072 | 0.7263 | −0.0115 | 0.145* | |
C11 | 0.0099 (7) | 0.6973 (11) | −0.1919 (15) | 0.162 (5) | |
H11A | 0.0886 | 0.6760 | −0.1915 | 0.242* | |
H11B | −0.0005 | 0.7622 | −0.2673 | 0.242* | |
H11C | −0.0350 | 0.6352 | −0.2353 | 0.242* | |
O1 | 0.25834 (16) | 0.57292 (17) | 0.3381 (2) | 0.0388 (5) | |
O2 | 0.1708 (2) | 0.7465 (2) | 0.1525 (5) | 0.0836 (12) | |
O3 | 0.0146 (3) | 0.6500 (4) | 0.1151 (7) | 0.1039 (17) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0294 (10) | 0.0399 (12) | 0.0350 (13) | 0.0016 (9) | 0.0005 (9) | 0.0021 (11) |
C2 | 0.0458 (14) | 0.0459 (14) | 0.0336 (13) | 0.0027 (11) | 0.0016 (11) | 0.0067 (11) |
C3 | 0.0589 (17) | 0.0537 (16) | 0.0310 (12) | 0.0023 (13) | −0.0006 (12) | 0.0019 (12) |
C4 | 0.0471 (13) | 0.0436 (14) | 0.0355 (14) | 0.0005 (11) | −0.0007 (11) | −0.0034 (11) |
C5 | 0.0332 (11) | 0.0359 (12) | 0.0348 (12) | 0.0033 (9) | 0.0003 (10) | 0.0008 (10) |
C6 | 0.0306 (10) | 0.0380 (12) | 0.0300 (11) | 0.0019 (9) | −0.0023 (9) | 0.0020 (10) |
C7 | 0.0330 (11) | 0.0369 (11) | 0.0387 (12) | −0.0020 (8) | 0.0018 (10) | 0.0031 (10) |
C8 | 0.0443 (15) | 0.0575 (17) | 0.060 (2) | −0.0157 (12) | −0.0178 (14) | 0.0221 (16) |
C9 | 0.0428 (15) | 0.0622 (18) | 0.082 (3) | −0.0072 (13) | −0.0172 (17) | 0.032 (2) |
C10 | 0.068 (3) | 0.125 (5) | 0.170 (8) | −0.009 (3) | −0.049 (4) | 0.079 (5) |
C11 | 0.092 (5) | 0.262 (14) | 0.130 (7) | 0.008 (6) | −0.021 (5) | 0.099 (9) |
O1 | 0.0380 (9) | 0.0449 (10) | 0.0334 (9) | −0.0045 (7) | −0.0082 (7) | 0.0065 (8) |
O2 | 0.0630 (16) | 0.0655 (16) | 0.122 (3) | −0.0168 (12) | −0.0336 (19) | 0.0451 (19) |
O3 | 0.0547 (16) | 0.114 (3) | 0.143 (4) | −0.0211 (16) | −0.042 (2) | 0.069 (3) |
C1—C2 | 1.397 (4) | C7—H7B | 0.9900 |
C1—C6 | 1.398 (4) | C8—O1 | 1.400 (3) |
C1—C7 | 1.511 (4) | C8—C9 | 1.487 (5) |
C2—C3 | 1.383 (4) | C8—H8A | 0.9900 |
C2—H2 | 0.9500 | C8—H8B | 0.9900 |
C3—C4 | 1.379 (4) | C9—O2 | 1.190 (4) |
C3—H3 | 0.9500 | C9—O3 | 1.327 (4) |
C4—C5 | 1.393 (4) | C10—O3 | 1.431 (7) |
C4—H4 | 0.9500 | C10—C11 | 1.458 (16) |
C5—C6 | 1.389 (4) | C10—H10A | 0.9900 |
C5—C7i | 1.509 (4) | C10—H10B | 0.9900 |
C6—O1 | 1.384 (3) | C11—H11A | 0.9800 |
C7—C5ii | 1.509 (4) | C11—H11B | 0.9800 |
C7—H7A | 0.9900 | C11—H11C | 0.9800 |
C2—C1—C6 | 117.6 (3) | O1—C8—C9 | 111.5 (2) |
C2—C1—C7 | 119.9 (3) | O1—C8—H8A | 109.3 |
C6—C1—C7 | 122.2 (2) | C9—C8—H8A | 109.3 |
C3—C2—C1 | 121.2 (3) | O1—C8—H8B | 109.3 |
C3—C2—H2 | 119.4 | C9—C8—H8B | 109.3 |
C1—C2—H2 | 119.4 | H8A—C8—H8B | 108.0 |
C4—C3—C2 | 119.5 (3) | O2—C9—O3 | 124.2 (3) |
C4—C3—H3 | 120.3 | O2—C9—C8 | 126.7 (3) |
C2—C3—H3 | 120.3 | O3—C9—C8 | 109.0 (3) |
C3—C4—C5 | 121.5 (3) | O3—C10—C11 | 114.6 (8) |
C3—C4—H4 | 119.2 | O3—C10—H10A | 108.6 |
C5—C4—H4 | 119.2 | C11—C10—H10A | 108.6 |
C6—C5—C4 | 117.8 (3) | O3—C10—H10B | 108.6 |
C6—C5—C7i | 120.9 (2) | C11—C10—H10B | 108.6 |
C4—C5—C7i | 121.1 (3) | H10A—C10—H10B | 107.6 |
O1—C6—C5 | 118.0 (2) | C10—C11—H11A | 109.5 |
O1—C6—C1 | 119.8 (2) | C10—C11—H11B | 109.5 |
C5—C6—C1 | 122.1 (2) | H11A—C11—H11B | 109.5 |
C5ii—C7—C1 | 109.8 (2) | C10—C11—H11C | 109.5 |
C5ii—C7—H7A | 109.7 | H11A—C11—H11C | 109.5 |
C1—C7—H7A | 109.7 | H11B—C11—H11C | 109.5 |
C5ii—C7—H7B | 109.7 | C6—O1—C8 | 115.1 (2) |
C1—C7—H7B | 109.7 | C9—O3—C10 | 118.6 (4) |
H7A—C7—H7B | 108.2 | ||
C6—C1—C2—C3 | −1.8 (4) | C2—C1—C6—C5 | 6.1 (4) |
C7—C1—C2—C3 | 172.0 (3) | C7—C1—C6—C5 | −167.5 (2) |
C1—C2—C3—C4 | −2.6 (5) | C2—C1—C7—C5ii | −104.3 (3) |
C2—C3—C4—C5 | 2.9 (5) | C6—C1—C7—C5ii | 69.1 (3) |
C3—C4—C5—C6 | 1.2 (4) | O1—C8—C9—O2 | −8.5 (7) |
C3—C4—C5—C7i | −173.7 (3) | O1—C8—C9—O3 | 167.7 (4) |
C4—C5—C6—O1 | 177.6 (2) | C5—C6—O1—C8 | −111.3 (3) |
C7i—C5—C6—O1 | −7.4 (3) | C1—C6—O1—C8 | 72.1 (3) |
C4—C5—C6—C1 | −5.8 (4) | C9—C8—O1—C6 | 126.5 (4) |
C7i—C5—C6—C1 | 169.1 (2) | O2—C9—O3—C10 | 5.8 (10) |
C2—C1—C6—O1 | −177.4 (2) | C8—C9—O3—C10 | −170.5 (6) |
C7—C1—C6—O1 | 9.0 (3) | C11—C10—O3—C9 | 86.2 (9) |
Symmetry codes: (i) y, −x+1, −z+1; (ii) −y+1, x, −z+1. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C36H36O8 | C44H48O12 |
Mr | 596.65 | 768.82 |
Crystal system, space group | Monoclinic, P21/c | Tetragonal, P4 |
Temperature (K) | 150 | 150 |
a, b, c (Å) | 10.1364 (5), 10.9403 (5), 27.7309 (10) | 12.0173 (8), 12.0173 (8), 7.6972 (5) |
α, β, γ (°) | 90, 97.917 (3), 90 | 90, 90, 90 |
V (Å3) | 3045.9 (2) | 1111.60 (13) |
Z | 4 | 1 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.08 |
Crystal size (mm) | 0.28 × 0.24 × 0.18 | 0.36 × 0.24 × 0.22 |
Data collection | ||
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13551, 6968, 5280 | 2991, 1604, 1453 |
Rint | 0.018 | 0.015 |
(sin θ/λ)max (Å−1) | 0.649 | 0.686 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.146, 1.05 | 0.065, 0.192, 1.09 |
No. of reflections | 6968 | 1604 |
No. of parameters | 407 | 128 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.91, −0.33 | 0.46, −0.23 |
Computer programs: COLLECT (Nonius, 1999), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS86 (Sheldrick, 1986), ORTEPII (Johnson, 1971), PLUTON (Spek, 1991), PLATON (Spek, 2003; Farrugia, 2000), ORTEP-3 (Farrugia, 1997), Mercury (Bruno et al., 2002), SHELXL97 (Sheldrick, 1997), PARST (Nardelli, 1983 and 1995), WinGX (Farrugia, 1999).
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
Substituted calix[4]arenes, ?which are synthetic macrocycles due to their conformational flexibility compared with cyclodextrins, have attracted much interest in recent years owing to their ability to complex cations and small molecules ?and their usefulness? in the design of supramolecular structures (see Gutsche, 1998, for a survey).
Moreover, self-assembled nanotubes have recently been constructed using sodium cations to trigger the one-dimensional polymerization of four guanosine moieties attached to a calix[4]arene- 1,3-alternate scaffold (Sidorov et al., 2000) ?as well as secondary amides forming self-assembled channels in an anionic dependent process? (Sidorov et al., 2002). The conformation of bis-OH calix[4]arene possesses unique structural peculiarities, like two hard phenolic ?O atoms? and two soft π-basic benzene rings, forming two binding sets at the edges of the calix[4]arene cavity, which are linked together by a π-basic benzene tunnel. Since unequivocal evidence exists that metal cations can easily pass through the π-basic holes with the aid of the π-interactions, and thus play a crucial role in metal transport through ion channels, a nanotube with well defined inner diameters for the metal passage may be synthesized. The 1,3-alternate core thus orients two orthogonal pairs of self-complementary guanosines to form an artificial ion channel (Ikeda & Shinkai, 1994). When we searched for structural parameters to show that appropriate introduced substituents immobilize the calix[4]arene conformation, we found that the crystal structures of the title compounds, (I) and (II), have not yet been reported, although Brunink et al. (1992) reported the synthesis and preliminary structure of the 1,2-alternate isomer of (I), and a CHCl3 solvate of (I) was also recently reported (Coles et al., 2002). In the same paper a honeycomb supramolecular structure of columnar hexagonal tubes of the parent precursor 2,4-dihydroxy-1,3-bis(methoxycarbonylmethoxy) calix[4]arene was also found. These results prompted us to determine the crystal structure of the missing basic structures of the well established building blocks and scaffolds. A much simplified procedure to obtain the crystals of (I) and (II) was also used.
A search of the Cambridge Structural Database (release 5.2.1, April 2001; Allen et al., 1993) gave no results on structural work on (II). However, there was a general observation that there were problems with the disorder on the side chains and frequently solvates were formed. In all these cases the conventional R values of the known crystal structures were rather high.
The molecules of (I) and (II), with the atomic numbering scheme, are shown in Figs. 1 and 2, while the packing of the molecules (II) is depicted in Fig. 3. Hydrogen bonds O—H···O and C—H···O for (I) and C—H···O for (II) are presented in Tables 1 and 2.
We were able to prepare by a simplified procedure both solvent-free compounds, which were stable in air. The bond lengths and angles are normal and in agreement with the values for the related compounds, for example, with 1,3-bis(ethoxycarbonylmethoxy)-2,4-dihydroxycalix[4]arene chloroform solvate (Coles et al., 2002; International Tables for X-ray Crystallography, 1995, Vol. C, pp. 693–703).
The different conformation of (I), which exists as a cone, and the 1,3-alternate conformation of (II) are in agreement with the results of Grynszpan et al. (1991), who concluded that the presence of three phenolic OH groups are sufficient to stabilize the cone conformation, with a preference for OH-depleted or substituted calix[4]arenes to adopt the 1,3-alternate conformation. Furthermore, in our determination of (I) the two OH groups forced the molecule into the cone conformation. This has also been previously found in cases where either two vicinal (Brunink et al., 1992) or two opposite (Böhmer, 1995) phenolic groups are ?replaced? by ester groups. Special attention was therefore devoted to the structure of the 1,3-alternate conformer, (II). The most interesting feature of this structure is the packing of the molecules. 1,3-alternate molecules are packed along the c axis, forming a kind of a nanotubular array (Fig. 3). This is not the case with (I) [1,3-bis(ethoxycarbonylmethoxy) derivative], although the similar 1,3-bis(methoxycarbonylmethoxy) derivative (Coles et al., 2002) produced a supramolecular honeycomb structure.
The structures of (I) and (II) are similar to those reported by Coles et al., (2002). The separations between meso-C atoms C7, C14, C21 and C28 in (I) are 5.073 (3), 5.106 (3), 5.103 (2) and 5.102 (3) Å, with cross-ring distances between meso-C atoms of 7.270 (3) and 7.130 (2) Å, respectively. Because of the symmetry the corresponding distances in (II) are 5.041 (4) and 7.129 (5) Å. The dihedral angles between the aromatic rings and the mean plane of the macrocycle through the meso-C atoms are 64.58 (3), 48.61 (5), 67.54 (5) and 56.44 (5)° in (I), which differ from those of the chloroform solvate of (I). The appropriate dihedral angles (aromatic ring/mean plane of macrocycle) in (II) are 80.43 (7) and 99.57 (7)°, respectively. The dihedral angle between the vicinal aromatic rings is 88.41 (9)°, but the opposite aromatic rings are tilted to each other by 19.15 (8)° in (II).
It seems that the presence of CHCl3 has a significant influence on the conformation of the calix[4]arene skeleton in the solvate structure. The C31···C35 separation in (I) [7.528 (3) Å] is larger than that found in the solvate of (I) [7.141 (3) Å], probably because of the molecular packing of CHCl3. One of the main differences between (I) and the solvate of (I) is in the conformations of the ester groups attached to the calix[4]arene rim. The methoxycarbonylethoxy groups exist in the fully extended form, the corresponding torsion angles ranging from −168.4 (2) to 179.8 (2)°, but the torsion angles C6—O1—C29—C30 and C20—O3—C33—C34 are different [−124.9 (2) and −157.9 (2)°]. The dihedral angle between the extended, nearly planar, ester groups, using weighted least-squares planes through O1—C29—C30(O5)—O6—C31—C32 and O3—C33—C34(O7)—O8—C35—C36, is 63.03 (5)°. On the other hand, the overall conformation of the ester groups in (II) are completely different. The diversity of the torsion angles [C6—O1—C8—C9 126.5 (4), O1—C8—C9—O3 167.7 (4), C8—C9—O3—C10 − 170.5 (7) and C9—O3—C10—C11 86.2 (9)°] is the consequence of the specific molecular packing and C—H···O interactions.
The cone conformer in (I) is caused by two intramolecular O—H···O hydrogen bonds (see Table 1), which have a partial influence on the orientation of the ester groups. Two intramolecular hydrogen bonds [O4—H4···O3 = 2.823 (2) and O4—H4···O7 = 3.271 (2) Å] seem to be bifurcated and lock the ester group into the fixed position, while the ester group attached to atom C6 forms only one stronger intramolecular bond [O2—H2···O1 = 2.679 (2) Å], with the consequence that the O2···O5 distance is considerably longer [3.780 (2) Å]. However, this ester group is also held in position by the C7—H7B···O5 interaction [3.593 (2) Å].
Taking into account the general discussion on the C—H···O hydrogen bonding (Leban et al., 2002), with reference to the work of Taylor & Kennard (1982), Taylor & Kennard (1983), Steiner & Saenger (1992), Steiner (1997), Steiner & Desiraju (1998) and a review of Steiner (2002), explaining that the longer H···O distances up to 3.2 Å and an angular cut-off at angles greater than 90° could also give evidence of the electrostatic interaction of C—H···O bonds, we checked the values given for the C—H···O interactions (Tables 1 and 2) for directionality at the acceptor site. Namely, in the case of O═CR1R2 or R1C—O—CR2 as acceptors, the angles H···O—C at acceptor side are expected to be dispersed around the value of 120°. Normalized C—H values were used in these calculations using the program PARST (Nardelli, 1983 and 1995). While only intermolecular, presumably electrostatic, C—H···O interactions were found in (I), it appears that the C7—H7A···O2(1 − y,x,1 − z) hydrogen bond [3.481 (5) Å] is responsible for the specific arrangement of the ester groups in (II). There are also additional intermolecular C—H···O interactions (Table 2).
No significant solvent-accessible areas were found in (I), exhibiting that the cone molecules are relatively closely packed. However, the 1,3-alternate shape of (II) produces rather large calculated cavities of 157 Å3 in the crystal, 14.1% of the volume of the crystal unit cell being void; hence the difference in the crystal density was observed (PLATON; Spek, 1998). Channels extend along the entire crystal in the c direction in (II) (Fig. 3).