organic compounds
31-Benzyloxy-5,11,17,23,29-penta-tert-butylcalix[5]arene-32,33,34,35-tetraol
aDipartimento di Scienze Chimiche, Università di Messina, Viale F. Stagno d'Alcontres 31, 98166 Messina, Italy, and bDipartimento di Scienze Chimiche, Università di Catania, Viale A. Doria 6, 95125 Catania, Italy
*Correspondence e-mail: anotti@unime.it
The title compound, C62H76O5, known to be one of the most versatile synthetic precursors/intermediates of calix[5]arene derivatives, adopts an approximate Cs-symmetric cone-in conformation. The aryloxybenzyl ring is tilted in such a way that the p-tert-butyl group fills the macrocycle cavity, while the benzyl group moves away from the cavity axis. In the crystal, this conformational arrangement is secured by intra- and intermolecular O—H⋯O hydrogen bonds forming inversion dimers. Four tert-butyl groups are disordered over two orientations, with occupancy ratios of 0.745 (6):0.255 (6), 0.837 (5):0.163 (5), 0.850 (5):0.150 (5) and 0.845 (8):0.155 (8).
Related literature
For the synthesis of the title compound, see: Stewart et al. (1995). For calix[5]arene molecules derived from the title compound, see: Garozzo et al. (2005); Capici et al. (2011); Pappalardo et al. (2012). For the structures of calix[5]arene/alkylammonium complexes, see: Gattuso et al. (2012).
Experimental
Crystal data
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Data collection
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Refinement
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Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XPW (Siemens, 1996); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Supporting information
10.1107/S1600536812047435/is5208sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812047435/is5208Isup2.hkl
The title compound was prepared according to the procedure described by Stewart et al. (1995). p-tert-Butylcalix[5]arene (5.00 g, 6.17 mmol) and anhydrous KHCO3 (1.23 g, 12.32 mmol) were suspended in anhydrous MeCN (125 ml). The mixture was heated at reflux for 1 h under an inert atmosphere. Benzyl chloride (0.262 g, 2.09 mmol) was added, and heating was continued for 24 h. The mixture was then allowed to cool, and the solvent was removed under reduced pressure. The resulting residue was partitioned between CHCl3 (100 ml) and aqueous HCl (1 M, 75 ml). The organic layer was washed with H2O (2 × 100 ml) and dried over anhydrous MgSO4. The solvent was evaporated under reduced pressure, and the resulting residue was subjected to
(SiO2, toluene/n-hexane 1:1 v/v), to yield the title compound (68%, 1.15 g). Single crystals were obtained by slow evaporation from a CHCl3/MeOH solution. Spectral data are in full agreement with those reported in the literature (Stewart et al., 1995).H atoms were included in the
via the "riding model" method, with C—H = 0.93–0.97 Å and O—H = 0.82 Å, and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O, Cmethyl). Four of the five tert-butyl groups showed a rotational disorder. As a result, they were individually treated as an overlap of two rotated conformations and the occupancy factors of the methyl groups were then refined. Owing to the significant disorder, suitable bond and displacement restraints (DFIX and ISOR) were applied and the C atoms of minor components were refined isotropically.Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XPW (Siemens, 1996); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C62H76O5 | Z = 2 |
Mr = 901.23 | F(000) = 976 |
Triclinic, P1 | Dx = 1.090 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 14.1467 (8) Å | Cell parameters from 9983 reflections |
b = 14.3235 (9) Å | θ = 2.8–22.1° |
c = 15.2179 (9) Å | µ = 0.07 mm−1 |
α = 70.653 (3)° | T = 296 K |
β = 78.776 (3)° | Irregular, colourless |
γ = 71.573 (3)° | 0.38 × 0.18 × 0.10 mm |
V = 2746.3 (3) Å3 |
Bruker APEXII CCD diffractometer | 5343 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.044 |
Graphite monochromator | θmax = 26.0°, θmin = 2.0° |
ϕ and ω scans | h = −17→17 |
75089 measured reflections | k = −17→17 |
10532 independent reflections | l = −18→18 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.052 | H-atom parameters constrained |
wR(F2) = 0.161 | w = 1/[σ2(Fo2) + (0.0863P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.96 | (Δ/σ)max = 0.001 |
10532 reflections | Δρmax = 0.45 e Å−3 |
677 parameters | Δρmin = −0.16 e Å−3 |
120 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0062 (10) |
C62H76O5 | γ = 71.573 (3)° |
Mr = 901.23 | V = 2746.3 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 14.1467 (8) Å | Mo Kα radiation |
b = 14.3235 (9) Å | µ = 0.07 mm−1 |
c = 15.2179 (9) Å | T = 296 K |
α = 70.653 (3)° | 0.38 × 0.18 × 0.10 mm |
β = 78.776 (3)° |
Bruker APEXII CCD diffractometer | 5343 reflections with I > 2σ(I) |
75089 measured reflections | Rint = 0.044 |
10532 independent reflections |
R[F2 > 2σ(F2)] = 0.052 | 120 restraints |
wR(F2) = 0.161 | H-atom parameters constrained |
S = 0.96 | Δρmax = 0.45 e Å−3 |
10532 reflections | Δρmin = −0.16 e Å−3 |
677 parameters |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 | Occ. (<1) | |
O1 | 0.36078 (11) | 0.28637 (11) | 0.59304 (10) | 0.0549 (4) | |
O2 | 0.62075 (12) | 0.12493 (12) | 0.56199 (12) | 0.0650 (5) | |
H2 | 0.5669 | 0.1678 | 0.5506 | 0.098* | |
O3 | 0.71031 (12) | −0.05203 (12) | 0.43351 (10) | 0.0543 (4) | |
H3 | 0.6972 | −0.0509 | 0.4881 | 0.081* | |
O4 | 0.55263 (11) | −0.01224 (12) | 0.32381 (10) | 0.0575 (4) | |
H4 | 0.6024 | −0.0311 | 0.3519 | 0.086* | |
O5 | 0.37944 (11) | 0.11640 (11) | 0.39079 (9) | 0.0521 (4) | |
H5 | 0.4243 | 0.0749 | 0.3693 | 0.078* | |
C1 | 0.41318 (16) | 0.32444 (16) | 0.50767 (14) | 0.0458 (5) | |
C2 | 0.50301 (17) | 0.34459 (17) | 0.50671 (15) | 0.0520 (6) | |
C3 | 0.54754 (17) | 0.3264 (2) | 0.59638 (16) | 0.0641 (7) | |
H3A | 0.5417 | 0.3921 | 0.6051 | 0.077* | |
H3B | 0.5097 | 0.2896 | 0.6492 | 0.077* | |
C4 | 0.65643 (17) | 0.26538 (18) | 0.59418 (14) | 0.0513 (6) | |
C5 | 0.68675 (17) | 0.17104 (17) | 0.57534 (14) | 0.0477 (6) | |
C6 | 0.78683 (16) | 0.11664 (16) | 0.56911 (14) | 0.0448 (5) | |
C7 | 0.81837 (17) | 0.01950 (16) | 0.54016 (14) | 0.0481 (6) | |
H7A | 0.7693 | −0.0191 | 0.5685 | 0.058* | |
H7B | 0.8820 | −0.0225 | 0.5637 | 0.058* | |
C8 | 0.82882 (15) | 0.03977 (15) | 0.43458 (14) | 0.0415 (5) | |
C9 | 0.78124 (15) | 0.00094 (15) | 0.38942 (14) | 0.0416 (5) | |
C10 | 0.80587 (15) | 0.00926 (15) | 0.29388 (14) | 0.0430 (5) | |
C11 | 0.76412 (16) | −0.04627 (17) | 0.24796 (15) | 0.0495 (6) | |
H11A | 0.8178 | −0.0770 | 0.2073 | 0.059* | |
H11B | 0.7433 | −0.1019 | 0.2965 | 0.059* | |
C12 | 0.67691 (16) | 0.01793 (16) | 0.19121 (15) | 0.0455 (5) | |
C13 | 0.57818 (16) | 0.02790 (16) | 0.22883 (14) | 0.0443 (5) | |
C14 | 0.49976 (16) | 0.07443 (15) | 0.17293 (15) | 0.0450 (5) | |
C15 | 0.39230 (16) | 0.07875 (16) | 0.21118 (15) | 0.0488 (6) | |
H15A | 0.3911 | 0.0227 | 0.2683 | 0.059* | |
H15B | 0.3592 | 0.0686 | 0.1663 | 0.059* | |
C16 | 0.33380 (15) | 0.17948 (15) | 0.23208 (14) | 0.0412 (5) | |
C17 | 0.33033 (15) | 0.19305 (16) | 0.31852 (14) | 0.0414 (5) | |
C18 | 0.27617 (15) | 0.28567 (16) | 0.33713 (14) | 0.0430 (5) | |
C19 | 0.28254 (16) | 0.30445 (17) | 0.42731 (14) | 0.0482 (6) | |
H19A | 0.2801 | 0.2431 | 0.4788 | 0.058* | |
H19B | 0.2253 | 0.3598 | 0.4382 | 0.058* | |
C20 | 0.37805 (16) | 0.33231 (15) | 0.42491 (14) | 0.0448 (5) | |
C21 | 0.2932 (2) | 0.3616 (2) | 0.63292 (17) | 0.0727 (8) | |
H21A | 0.2359 | 0.3967 | 0.5971 | 0.087* | |
H21B | 0.3258 | 0.4122 | 0.6322 | 0.087* | |
C22 | 0.25972 (19) | 0.3090 (2) | 0.73196 (17) | 0.0613 (7) | |
C23 | 0.3257 (2) | 0.2356 (2) | 0.79098 (19) | 0.0747 (8) | |
H23 | 0.3933 | 0.2179 | 0.7694 | 0.090* | |
C24 | 0.2951 (3) | 0.1873 (2) | 0.8811 (2) | 0.0867 (9) | |
H24 | 0.3418 | 0.1378 | 0.9197 | 0.104* | |
C25 | 0.1978 (4) | 0.2110 (3) | 0.9140 (2) | 0.1052 (12) | |
H25 | 0.1775 | 0.1786 | 0.9754 | 0.126* | |
C26 | 0.1291 (3) | 0.2826 (3) | 0.8570 (3) | 0.1205 (13) | |
H26 | 0.0614 | 0.2979 | 0.8788 | 0.145* | |
C27 | 0.1609 (2) | 0.3329 (3) | 0.7654 (2) | 0.0993 (10) | |
H27 | 0.1144 | 0.3831 | 0.7270 | 0.119* | |
C28 | 0.73001 (18) | 0.30385 (18) | 0.60666 (15) | 0.0562 (6) | |
H28 | 0.7107 | 0.3675 | 0.6180 | 0.067* | |
C29 | 0.83081 (18) | 0.25165 (18) | 0.60289 (16) | 0.0550 (6) | |
C30 | 0.85644 (17) | 0.15751 (17) | 0.58484 (14) | 0.0514 (6) | |
H30 | 0.9234 | 0.1201 | 0.5832 | 0.062* | |
C31 | 0.91070 (19) | 0.29486 (19) | 0.61607 (19) | 0.0754 (8) | |
C32 | 0.9620 (4) | 0.2200 (4) | 0.7031 (4) | 0.162 (3) | 0.745 (6) |
H32A | 0.9891 | 0.1527 | 0.6946 | 0.243* | 0.745 (6) |
H32B | 0.9138 | 0.2170 | 0.7573 | 0.243* | 0.745 (6) |
H32C | 1.0150 | 0.2435 | 0.7118 | 0.243* | 0.745 (6) |
C33 | 0.8703 (3) | 0.3968 (3) | 0.6352 (5) | 0.126 (3) | 0.745 (6) |
H33A | 0.9237 | 0.4160 | 0.6489 | 0.189* | 0.745 (6) |
H33B | 0.8202 | 0.3922 | 0.6878 | 0.189* | 0.745 (6) |
H33C | 0.8411 | 0.4476 | 0.5812 | 0.189* | 0.745 (6) |
C34 | 0.9895 (5) | 0.2986 (7) | 0.5337 (5) | 0.200 (5) | 0.745 (6) |
H34A | 1.0450 | 0.3146 | 0.5474 | 0.300* | 0.745 (6) |
H34B | 0.9617 | 0.3506 | 0.4796 | 0.300* | 0.745 (6) |
H34C | 1.0122 | 0.2330 | 0.5215 | 0.300* | 0.745 (6) |
C32' | 0.8858 (11) | 0.3258 (13) | 0.7054 (7) | 0.116 (6)* | 0.255 (6) |
H32D | 0.8904 | 0.2655 | 0.7583 | 0.173* | 0.255 (6) |
H32E | 0.8190 | 0.3704 | 0.7070 | 0.173* | 0.255 (6) |
H32F | 0.9323 | 0.3611 | 0.7079 | 0.173* | 0.255 (6) |
C33' | 0.9007 (11) | 0.3965 (8) | 0.5359 (8) | 0.114 (6)* | 0.255 (6) |
H33D | 0.9500 | 0.4287 | 0.5381 | 0.172* | 0.255 (6) |
H33E | 0.8349 | 0.4417 | 0.5430 | 0.172* | 0.255 (6) |
H33F | 0.9109 | 0.3823 | 0.4769 | 0.172* | 0.255 (6) |
C34' | 1.0182 (5) | 0.2400 (10) | 0.5963 (9) | 0.085 (5)* | 0.255 (6) |
H34D | 1.0284 | 0.2303 | 0.5353 | 0.128* | 0.255 (6) |
H34E | 1.0347 | 0.1743 | 0.6425 | 0.128* | 0.255 (6) |
H34F | 1.0602 | 0.2802 | 0.5983 | 0.128* | 0.255 (6) |
C35 | 0.89385 (16) | 0.09669 (16) | 0.37994 (15) | 0.0483 (6) | |
H35 | 0.9242 | 0.1255 | 0.4094 | 0.058* | |
C36 | 0.91619 (16) | 0.11311 (17) | 0.28425 (15) | 0.0502 (6) | |
C37 | 0.87201 (16) | 0.06520 (17) | 0.24414 (15) | 0.0511 (6) | |
H37 | 0.8880 | 0.0713 | 0.1806 | 0.061* | |
C38 | 0.98979 (18) | 0.17462 (19) | 0.22501 (16) | 0.0619 (7) | |
C39 | 1.0147 (2) | 0.2362 (2) | 0.2786 (2) | 0.0927 (9) | |
H39A | 1.0445 | 0.1900 | 0.3341 | 0.139* | |
H39B | 0.9545 | 0.2837 | 0.2956 | 0.139* | |
H39C | 1.0609 | 0.2734 | 0.2396 | 0.139* | |
C40 | 1.0877 (2) | 0.1008 (2) | 0.1996 (2) | 0.0897 (9) | |
H40A | 1.0751 | 0.0624 | 0.1642 | 0.135* | |
H40B | 1.1160 | 0.0544 | 0.2558 | 0.135* | |
H40C | 1.1339 | 0.1392 | 0.1629 | 0.135* | |
C41 | 0.9457 (2) | 0.2485 (2) | 0.1357 (2) | 0.0993 (10) | |
H41A | 0.9912 | 0.2883 | 0.1002 | 0.149* | |
H41B | 0.8830 | 0.2938 | 0.1514 | 0.149* | |
H41C | 0.9352 | 0.2102 | 0.0990 | 0.149* | |
C42 | 0.69514 (17) | 0.06404 (17) | 0.09611 (15) | 0.0522 (6) | |
H42 | 0.7611 | 0.0605 | 0.0706 | 0.063* | |
C43 | 0.61966 (18) | 0.11512 (17) | 0.03748 (15) | 0.0512 (6) | |
C44 | 0.52328 (17) | 0.11696 (17) | 0.07761 (15) | 0.0509 (6) | |
H44 | 0.4714 | 0.1481 | 0.0393 | 0.061* | |
C45 | 0.64528 (17) | 0.16541 (18) | −0.06686 (15) | 0.0620 (7) | |
C46 | 0.7301 (3) | 0.0902 (3) | −0.1089 (2) | 0.0960 (15) | 0.837 (5) |
H46A | 0.7137 | 0.0262 | −0.0941 | 0.144* | 0.837 (5) |
H46B | 0.7912 | 0.0784 | −0.0833 | 0.144* | 0.837 (5) |
H46C | 0.7387 | 0.1188 | −0.1756 | 0.144* | 0.837 (5) |
C47 | 0.6761 (4) | 0.2596 (3) | −0.0760 (2) | 0.1068 (16) | 0.837 (5) |
H47A | 0.7349 | 0.2401 | −0.0443 | 0.160* | 0.837 (5) |
H47B | 0.6228 | 0.3055 | −0.0486 | 0.160* | 0.837 (5) |
H47C | 0.6905 | 0.2935 | −0.1410 | 0.160* | 0.837 (5) |
C48 | 0.5569 (3) | 0.1925 (4) | −0.1228 (2) | 0.1080 (17) | 0.837 (5) |
H48A | 0.5764 | 0.2199 | −0.1881 | 0.162* | 0.837 (5) |
H48B | 0.5022 | 0.2429 | −0.1021 | 0.162* | 0.837 (5) |
H48C | 0.5363 | 0.1318 | −0.1133 | 0.162* | 0.837 (5) |
C46' | 0.7528 (6) | 0.1730 (16) | −0.0891 (14) | 0.102 (7)* | 0.163 (5) |
H46D | 0.7610 | 0.2196 | −0.0600 | 0.153* | 0.163 (5) |
H46E | 0.7676 | 0.1978 | −0.1557 | 0.153* | 0.163 (5) |
H46F | 0.7977 | 0.1062 | −0.0658 | 0.153* | 0.163 (5) |
C47' | 0.5730 (12) | 0.2719 (8) | −0.0950 (13) | 0.099 (7)* | 0.163 (5) |
H47D | 0.5847 | 0.3026 | −0.1611 | 0.149* | 0.163 (5) |
H47E | 0.5832 | 0.3139 | −0.0618 | 0.149* | 0.163 (5) |
H47F | 0.5054 | 0.2665 | −0.0798 | 0.149* | 0.163 (5) |
C48' | 0.6344 (15) | 0.0990 (12) | −0.1214 (12) | 0.094 (7)* | 0.163 (5) |
H48D | 0.6556 | 0.1261 | −0.1864 | 0.141* | 0.163 (5) |
H48E | 0.5656 | 0.0986 | −0.1145 | 0.141* | 0.163 (5) |
H48F | 0.6752 | 0.0301 | −0.0979 | 0.141* | 0.163 (5) |
C49 | 0.28559 (15) | 0.26181 (17) | 0.16264 (14) | 0.0464 (5) | |
H49 | 0.2892 | 0.2532 | 0.1040 | 0.056* | |
C50 | 0.23254 (16) | 0.35584 (17) | 0.17608 (15) | 0.0467 (5) | |
C51 | 0.22843 (16) | 0.36418 (17) | 0.26557 (15) | 0.0487 (6) | |
H51 | 0.1916 | 0.4259 | 0.2776 | 0.058* | |
C52 | 0.18700 (18) | 0.44912 (17) | 0.09701 (15) | 0.0588 (6) | |
C53 | 0.0794 (3) | 0.4987 (3) | 0.1274 (3) | 0.1048 (16) | 0.850 (5) |
H53A | 0.0526 | 0.5586 | 0.0781 | 0.157* | 0.850 (5) |
H53B | 0.0769 | 0.5181 | 0.1826 | 0.157* | 0.850 (5) |
H53C | 0.0404 | 0.4507 | 0.1407 | 0.157* | 0.850 (5) |
C54 | 0.1829 (3) | 0.4194 (2) | 0.0103 (2) | 0.0907 (14) | 0.850 (5) |
H54A | 0.1498 | 0.3658 | 0.0281 | 0.136* | 0.850 (5) |
H54B | 0.2497 | 0.3954 | −0.0170 | 0.136* | 0.850 (5) |
H54C | 0.1465 | 0.4783 | −0.0344 | 0.136* | 0.850 (5) |
C55 | 0.2503 (4) | 0.5231 (3) | 0.0704 (3) | 0.125 (2) | 0.850 (5) |
H55A | 0.2262 | 0.5792 | 0.0171 | 0.187* | 0.850 (5) |
H55B | 0.3186 | 0.4883 | 0.0551 | 0.187* | 0.850 (5) |
H55C | 0.2465 | 0.5491 | 0.1220 | 0.187* | 0.850 (5) |
C53' | 0.0982 (12) | 0.4379 (19) | 0.0641 (17) | 0.122 (10)* | 0.150 (5) |
H53D | 0.0717 | 0.4989 | 0.0156 | 0.183* | 0.150 (5) |
H53E | 0.0475 | 0.4281 | 0.1157 | 0.183* | 0.150 (5) |
H53F | 0.1190 | 0.3796 | 0.0402 | 0.183* | 0.150 (5) |
C54' | 0.2703 (14) | 0.462 (2) | 0.0183 (14) | 0.142 (11)* | 0.150 (5) |
H54D | 0.3029 | 0.3975 | 0.0057 | 0.212* | 0.150 (5) |
H54E | 0.3181 | 0.4857 | 0.0363 | 0.212* | 0.150 (5) |
H54F | 0.2427 | 0.5118 | −0.0370 | 0.212* | 0.150 (5) |
C55' | 0.1526 (15) | 0.5447 (10) | 0.1309 (13) | 0.084 (7)* | 0.150 (5) |
H55D | 0.1199 | 0.6025 | 0.0828 | 0.126* | 0.150 (5) |
H55E | 0.2096 | 0.5581 | 0.1448 | 0.126* | 0.150 (5) |
H55F | 0.1066 | 0.5337 | 0.1862 | 0.126* | 0.150 (5) |
C56 | 0.43687 (17) | 0.36095 (16) | 0.34192 (15) | 0.0508 (6) | |
H56 | 0.4143 | 0.3671 | 0.2863 | 0.061* | |
C57 | 0.52754 (17) | 0.38087 (17) | 0.33753 (15) | 0.0519 (6) | |
C58 | 0.55820 (18) | 0.37356 (18) | 0.42081 (17) | 0.0573 (6) | |
H58 | 0.6179 | 0.3885 | 0.4195 | 0.069* | |
C59 | 0.59229 (18) | 0.40210 (19) | 0.24439 (16) | 0.0663 (7) | |
C60 | 0.6308 (5) | 0.3040 (3) | 0.2156 (4) | 0.134 (2) | 0.845 (8) |
H60A | 0.6693 | 0.3167 | 0.1556 | 0.202* | 0.845 (8) |
H60B | 0.5752 | 0.2812 | 0.2117 | 0.202* | 0.845 (8) |
H60C | 0.6723 | 0.2518 | 0.2612 | 0.202* | 0.845 (8) |
C61 | 0.6830 (4) | 0.4321 (6) | 0.2516 (3) | 0.145 (3) | 0.845 (8) |
H61A | 0.7216 | 0.4445 | 0.1916 | 0.218* | 0.845 (8) |
H61B | 0.7233 | 0.3775 | 0.2966 | 0.218* | 0.845 (8) |
H61C | 0.6618 | 0.4935 | 0.2710 | 0.218* | 0.845 (8) |
C62 | 0.5313 (3) | 0.4880 (6) | 0.1718 (3) | 0.189 (4) | 0.845 (8) |
H62A | 0.5049 | 0.5480 | 0.1933 | 0.284* | 0.845 (8) |
H62B | 0.4771 | 0.4670 | 0.1618 | 0.284* | 0.845 (8) |
H62C | 0.5731 | 0.5035 | 0.1141 | 0.284* | 0.845 (8) |
C60' | 0.6857 (12) | 0.3130 (14) | 0.2529 (16) | 0.113 (10)* | 0.155 (8) |
H60D | 0.7162 | 0.3093 | 0.1916 | 0.169* | 0.155 (8) |
H60E | 0.6683 | 0.2502 | 0.2873 | 0.169* | 0.155 (8) |
H60F | 0.7320 | 0.3229 | 0.2853 | 0.169* | 0.155 (8) |
C61' | 0.6164 (19) | 0.5021 (11) | 0.2300 (15) | 0.091 (8)* | 0.155 (8) |
H61D | 0.6569 | 0.4936 | 0.2774 | 0.136* | 0.155 (8) |
H61E | 0.5553 | 0.5550 | 0.2342 | 0.136* | 0.155 (8) |
H61F | 0.6522 | 0.5212 | 0.1694 | 0.136* | 0.155 (8) |
C62' | 0.5416 (13) | 0.4107 (16) | 0.1617 (9) | 0.065 (6)* | 0.155 (8) |
H62D | 0.4793 | 0.4634 | 0.1586 | 0.097* | 0.155 (8) |
H62E | 0.5293 | 0.3462 | 0.1692 | 0.097* | 0.155 (8) |
H62F | 0.5843 | 0.4281 | 0.1049 | 0.097* | 0.155 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0611 (10) | 0.0554 (10) | 0.0425 (9) | −0.0073 (8) | 0.0004 (7) | −0.0183 (7) |
O2 | 0.0566 (11) | 0.0627 (11) | 0.0809 (12) | −0.0222 (8) | −0.0185 (9) | −0.0150 (9) |
O3 | 0.0653 (11) | 0.0633 (10) | 0.0404 (9) | −0.0316 (8) | −0.0003 (8) | −0.0124 (8) |
O4 | 0.0513 (10) | 0.0703 (11) | 0.0436 (9) | −0.0118 (8) | −0.0040 (7) | −0.0119 (8) |
O5 | 0.0561 (10) | 0.0479 (9) | 0.0418 (9) | −0.0060 (7) | −0.0028 (7) | −0.0086 (7) |
C1 | 0.0486 (14) | 0.0435 (13) | 0.0394 (13) | −0.0040 (10) | −0.0044 (10) | −0.0126 (10) |
C2 | 0.0489 (14) | 0.0572 (14) | 0.0487 (15) | −0.0046 (11) | −0.0097 (11) | −0.0205 (11) |
C3 | 0.0549 (16) | 0.0833 (18) | 0.0576 (16) | −0.0056 (13) | −0.0125 (12) | −0.0336 (14) |
C4 | 0.0521 (15) | 0.0582 (15) | 0.0427 (13) | −0.0078 (12) | −0.0096 (10) | −0.0176 (11) |
C5 | 0.0495 (14) | 0.0564 (15) | 0.0392 (13) | −0.0180 (12) | −0.0099 (10) | −0.0099 (11) |
C6 | 0.0515 (14) | 0.0464 (13) | 0.0366 (12) | −0.0138 (11) | −0.0098 (10) | −0.0083 (10) |
C7 | 0.0578 (14) | 0.0451 (13) | 0.0407 (13) | −0.0147 (11) | −0.0118 (10) | −0.0071 (10) |
C8 | 0.0425 (12) | 0.0370 (12) | 0.0406 (12) | −0.0075 (10) | −0.0058 (10) | −0.0078 (10) |
C9 | 0.0408 (12) | 0.0368 (12) | 0.0411 (13) | −0.0097 (10) | −0.0027 (10) | −0.0053 (10) |
C10 | 0.0418 (13) | 0.0425 (13) | 0.0406 (13) | −0.0052 (10) | −0.0044 (10) | −0.0126 (10) |
C11 | 0.0483 (14) | 0.0520 (14) | 0.0460 (13) | −0.0054 (11) | −0.0017 (10) | −0.0209 (11) |
C12 | 0.0482 (14) | 0.0471 (13) | 0.0429 (13) | −0.0073 (10) | −0.0064 (10) | −0.0194 (11) |
C13 | 0.0496 (14) | 0.0447 (13) | 0.0363 (13) | −0.0090 (10) | −0.0014 (10) | −0.0139 (10) |
C14 | 0.0460 (13) | 0.0434 (13) | 0.0484 (14) | −0.0095 (10) | −0.0037 (11) | −0.0200 (11) |
C15 | 0.0499 (14) | 0.0511 (14) | 0.0505 (13) | −0.0159 (11) | −0.0070 (10) | −0.0182 (11) |
C16 | 0.0381 (12) | 0.0472 (13) | 0.0406 (13) | −0.0158 (10) | −0.0006 (9) | −0.0136 (11) |
C17 | 0.0388 (12) | 0.0452 (13) | 0.0373 (13) | −0.0141 (10) | −0.0053 (9) | −0.0048 (10) |
C18 | 0.0440 (13) | 0.0460 (13) | 0.0387 (12) | −0.0147 (10) | −0.0020 (10) | −0.0108 (10) |
C19 | 0.0515 (14) | 0.0486 (13) | 0.0428 (13) | −0.0111 (11) | −0.0036 (10) | −0.0140 (10) |
C20 | 0.0489 (14) | 0.0409 (13) | 0.0423 (13) | −0.0070 (10) | −0.0073 (10) | −0.0124 (10) |
C21 | 0.0689 (18) | 0.0747 (18) | 0.0664 (18) | −0.0004 (14) | 0.0017 (14) | −0.0332 (15) |
C22 | 0.0600 (17) | 0.0704 (17) | 0.0572 (16) | −0.0131 (14) | 0.0031 (13) | −0.0329 (14) |
C23 | 0.0705 (19) | 0.093 (2) | 0.0608 (18) | −0.0297 (16) | −0.0067 (15) | −0.0147 (16) |
C24 | 0.105 (3) | 0.103 (2) | 0.064 (2) | −0.044 (2) | −0.0059 (18) | −0.0268 (18) |
C25 | 0.144 (4) | 0.109 (3) | 0.067 (2) | −0.043 (3) | 0.026 (2) | −0.043 (2) |
C26 | 0.100 (3) | 0.134 (3) | 0.102 (3) | −0.012 (3) | 0.042 (2) | −0.049 (3) |
C27 | 0.081 (2) | 0.108 (2) | 0.087 (2) | 0.0032 (19) | 0.0102 (18) | −0.038 (2) |
C28 | 0.0598 (16) | 0.0561 (15) | 0.0588 (15) | −0.0097 (12) | −0.0154 (12) | −0.0247 (12) |
C29 | 0.0571 (16) | 0.0549 (15) | 0.0587 (15) | −0.0120 (12) | −0.0155 (12) | −0.0214 (12) |
C30 | 0.0473 (14) | 0.0562 (15) | 0.0513 (14) | −0.0101 (11) | −0.0111 (11) | −0.0168 (12) |
C31 | 0.0654 (18) | 0.0744 (19) | 0.104 (2) | −0.0210 (15) | −0.0191 (16) | −0.0402 (17) |
C32 | 0.151 (6) | 0.123 (5) | 0.249 (8) | −0.036 (4) | −0.144 (6) | −0.032 (4) |
C33 | 0.100 (4) | 0.087 (4) | 0.234 (7) | −0.020 (3) | −0.052 (4) | −0.088 (4) |
C34 | 0.172 (7) | 0.322 (12) | 0.228 (9) | −0.194 (8) | 0.091 (6) | −0.182 (9) |
C35 | 0.0466 (14) | 0.0514 (14) | 0.0469 (14) | −0.0146 (11) | −0.0096 (10) | −0.0104 (11) |
C36 | 0.0424 (13) | 0.0524 (14) | 0.0485 (14) | −0.0123 (11) | −0.0027 (10) | −0.0070 (11) |
C37 | 0.0452 (14) | 0.0609 (15) | 0.0382 (13) | −0.0087 (12) | 0.0001 (10) | −0.0107 (11) |
C38 | 0.0568 (16) | 0.0661 (16) | 0.0555 (15) | −0.0265 (13) | 0.0014 (12) | −0.0027 (13) |
C39 | 0.102 (2) | 0.096 (2) | 0.089 (2) | −0.0631 (19) | 0.0056 (17) | −0.0130 (18) |
C40 | 0.0609 (19) | 0.114 (2) | 0.082 (2) | −0.0322 (17) | 0.0139 (15) | −0.0171 (18) |
C41 | 0.098 (2) | 0.105 (2) | 0.078 (2) | −0.0536 (19) | −0.0187 (17) | 0.0263 (18) |
C42 | 0.0497 (14) | 0.0626 (15) | 0.0461 (14) | −0.0143 (12) | −0.0014 (11) | −0.0208 (12) |
C43 | 0.0562 (16) | 0.0551 (14) | 0.0434 (13) | −0.0122 (11) | −0.0039 (11) | −0.0192 (11) |
C44 | 0.0512 (15) | 0.0573 (14) | 0.0446 (14) | −0.0092 (11) | −0.0099 (11) | −0.0176 (11) |
C45 | 0.0644 (17) | 0.0718 (17) | 0.0448 (14) | −0.0175 (13) | −0.0060 (12) | −0.0113 (13) |
C46 | 0.105 (3) | 0.123 (3) | 0.052 (2) | −0.021 (2) | 0.0083 (19) | −0.033 (2) |
C47 | 0.162 (5) | 0.093 (3) | 0.066 (2) | −0.068 (3) | −0.006 (2) | 0.005 (2) |
C48 | 0.091 (3) | 0.173 (5) | 0.046 (2) | −0.043 (3) | −0.0165 (18) | −0.001 (2) |
C49 | 0.0450 (13) | 0.0565 (15) | 0.0404 (13) | −0.0173 (11) | −0.0035 (10) | −0.0144 (11) |
C50 | 0.0468 (13) | 0.0493 (14) | 0.0434 (13) | −0.0146 (11) | −0.0076 (10) | −0.0094 (11) |
C51 | 0.0472 (14) | 0.0454 (13) | 0.0511 (14) | −0.0087 (10) | −0.0066 (11) | −0.0138 (11) |
C52 | 0.0687 (17) | 0.0534 (15) | 0.0483 (14) | −0.0135 (13) | −0.0164 (12) | −0.0038 (12) |
C53 | 0.095 (3) | 0.089 (3) | 0.089 (3) | 0.025 (2) | −0.030 (2) | −0.008 (2) |
C54 | 0.126 (4) | 0.075 (2) | 0.063 (2) | −0.010 (2) | −0.048 (2) | −0.0056 (18) |
C55 | 0.180 (5) | 0.095 (3) | 0.105 (3) | −0.092 (3) | −0.070 (3) | 0.046 (3) |
C56 | 0.0562 (15) | 0.0547 (14) | 0.0409 (13) | −0.0146 (11) | −0.0096 (11) | −0.0108 (11) |
C57 | 0.0550 (15) | 0.0488 (14) | 0.0487 (14) | −0.0138 (11) | −0.0046 (11) | −0.0106 (11) |
C58 | 0.0504 (15) | 0.0621 (16) | 0.0617 (16) | −0.0155 (12) | −0.0092 (12) | −0.0189 (12) |
C59 | 0.0623 (17) | 0.0794 (19) | 0.0546 (16) | −0.0277 (14) | 0.0027 (13) | −0.0126 (14) |
C60 | 0.148 (5) | 0.153 (4) | 0.127 (4) | −0.080 (4) | 0.081 (4) | −0.089 (3) |
C61 | 0.138 (5) | 0.248 (8) | 0.103 (3) | −0.143 (6) | 0.052 (3) | −0.071 (4) |
C62 | 0.122 (4) | 0.198 (7) | 0.096 (4) | 0.010 (4) | 0.027 (3) | 0.081 (4) |
O1—C1 | 1.395 (2) | C38—C40 | 1.524 (4) |
O1—C21 | 1.414 (3) | C38—C39 | 1.534 (4) |
O2—C5 | 1.379 (3) | C39—H39A | 0.9600 |
O2—H2 | 0.8200 | C39—H39B | 0.9600 |
O3—C9 | 1.384 (2) | C39—H39C | 0.9600 |
O3—H3 | 0.8200 | C40—H40A | 0.9600 |
O4—C13 | 1.388 (2) | C40—H40B | 0.9600 |
O4—H4 | 0.8200 | C40—H40C | 0.9600 |
O5—C17 | 1.383 (2) | C41—H41A | 0.9600 |
O5—H5 | 0.8200 | C41—H41B | 0.9600 |
C1—C2 | 1.386 (3) | C41—H41C | 0.9600 |
C1—C20 | 1.400 (3) | C42—C43 | 1.384 (3) |
C2—C58 | 1.392 (3) | C42—H42 | 0.9300 |
C2—C3 | 1.524 (3) | C43—C44 | 1.377 (3) |
C3—C4 | 1.512 (3) | C43—C45 | 1.534 (3) |
C3—H3A | 0.9700 | C44—H44 | 0.9300 |
C3—H3B | 0.9700 | C45—C47 | 1.502 (3) |
C4—C28 | 1.390 (3) | C45—C48' | 1.511 (5) |
C4—C5 | 1.391 (3) | C45—C47' | 1.519 (5) |
C5—C6 | 1.386 (3) | C45—C48 | 1.526 (3) |
C6—C30 | 1.385 (3) | C45—C46' | 1.523 (5) |
C6—C7 | 1.505 (3) | C45—C46 | 1.533 (3) |
C7—C8 | 1.521 (3) | C46—H46A | 0.9600 |
C7—H7A | 0.9700 | C46—H46B | 0.9600 |
C7—H7B | 0.9700 | C46—H46C | 0.9600 |
C8—C9 | 1.380 (3) | C47—H47A | 0.9600 |
C8—C35 | 1.389 (3) | C47—H47B | 0.9600 |
C9—C10 | 1.401 (3) | C47—H47C | 0.9600 |
C10—C37 | 1.374 (3) | C48—H48A | 0.9600 |
C10—C11 | 1.515 (3) | C48—H48B | 0.9600 |
C11—C12 | 1.512 (3) | C48—H48C | 0.9600 |
C11—H11A | 0.9700 | C46'—H46D | 0.9600 |
C11—H11B | 0.9700 | C46'—H46E | 0.9600 |
C12—C13 | 1.384 (3) | C46'—H46F | 0.9600 |
C12—C42 | 1.388 (3) | C47'—H47D | 0.9600 |
C13—C14 | 1.387 (3) | C47'—H47E | 0.9600 |
C14—C44 | 1.393 (3) | C47'—H47F | 0.9600 |
C14—C15 | 1.508 (3) | C48'—H48D | 0.9600 |
C15—C16 | 1.521 (3) | C48'—H48E | 0.9600 |
C15—H15A | 0.9700 | C48'—H48F | 0.9600 |
C15—H15B | 0.9700 | C49—C50 | 1.379 (3) |
C16—C17 | 1.382 (3) | C49—H49 | 0.9300 |
C16—C49 | 1.385 (3) | C50—C51 | 1.395 (3) |
C17—C18 | 1.396 (3) | C50—C52 | 1.530 (3) |
C18—C51 | 1.379 (3) | C51—H51 | 0.9300 |
C18—C19 | 1.507 (3) | C52—C55 | 1.505 (3) |
C19—C20 | 1.516 (3) | C52—C53' | 1.510 (5) |
C19—H19A | 0.9700 | C52—C53 | 1.515 (3) |
C19—H19B | 0.9700 | C52—C54' | 1.517 (5) |
C20—C56 | 1.385 (3) | C52—C55' | 1.525 (5) |
C21—C22 | 1.503 (3) | C52—C54 | 1.531 (3) |
C21—H21A | 0.9700 | C53—H53A | 0.9600 |
C21—H21B | 0.9700 | C53—H53B | 0.9600 |
C22—C27 | 1.366 (4) | C53—H53C | 0.9600 |
C22—C23 | 1.365 (3) | C54—H54A | 0.9600 |
C23—C24 | 1.369 (4) | C54—H54B | 0.9600 |
C23—H23 | 0.9300 | C54—H54C | 0.9600 |
C24—C25 | 1.345 (4) | C55—H55A | 0.9600 |
C24—H24 | 0.9300 | C55—H55B | 0.9600 |
C25—C26 | 1.363 (5) | C55—H55C | 0.9600 |
C25—H25 | 0.9300 | C53'—H53D | 0.9600 |
C26—C27 | 1.400 (4) | C53'—H53E | 0.9600 |
C26—H26 | 0.9300 | C53'—H53F | 0.9600 |
C27—H27 | 0.9300 | C54'—H54D | 0.9600 |
C28—C29 | 1.385 (3) | C54'—H54E | 0.9600 |
C28—H28 | 0.9300 | C54'—H54F | 0.9600 |
C29—C30 | 1.387 (3) | C55'—H55D | 0.9600 |
C29—C31 | 1.521 (3) | C55'—H55E | 0.9600 |
C30—H30 | 0.9300 | C55'—H55F | 0.9600 |
C31—C34' | 1.498 (5) | C56—C57 | 1.384 (3) |
C31—C33 | 1.494 (4) | C56—H56 | 0.9300 |
C31—C34 | 1.506 (4) | C57—C58 | 1.379 (3) |
C31—C32' | 1.511 (5) | C57—C59 | 1.525 (3) |
C31—C32 | 1.541 (4) | C58—H58 | 0.9300 |
C31—C33' | 1.545 (5) | C59—C61' | 1.513 (5) |
C32—H32A | 0.9600 | C59—C60 | 1.515 (3) |
C32—H32B | 0.9600 | C59—C62 | 1.509 (4) |
C32—H32C | 0.9600 | C59—C60' | 1.511 (5) |
C33—H33A | 0.9600 | C59—C61 | 1.510 (4) |
C33—H33B | 0.9600 | C59—C62' | 1.518 (5) |
C33—H33C | 0.9600 | C60—H60A | 0.9600 |
C34—H34A | 0.9600 | C60—H60B | 0.9600 |
C34—H34B | 0.9600 | C60—H60C | 0.9600 |
C34—H34C | 0.9600 | C61—H61A | 0.9600 |
C32'—H32D | 0.9600 | C61—H61B | 0.9600 |
C32'—H32E | 0.9600 | C61—H61C | 0.9600 |
C32'—H32F | 0.9600 | C62—H62A | 0.9600 |
C33'—H33D | 0.9600 | C62—H62B | 0.9600 |
C33'—H33E | 0.9600 | C62—H62C | 0.9600 |
C33'—H33F | 0.9600 | C60'—H60D | 0.9600 |
C34'—H34D | 0.9600 | C60'—H60E | 0.9600 |
C34'—H34E | 0.9600 | C60'—H60F | 0.9600 |
C34'—H34F | 0.9600 | C61'—H61D | 0.9600 |
C35—C36 | 1.384 (3) | C61'—H61E | 0.9600 |
C35—H35 | 0.9300 | C61'—H61F | 0.9600 |
C36—C37 | 1.390 (3) | C62'—H62D | 0.9600 |
C36—C38 | 1.537 (3) | C62'—H62E | 0.9600 |
C37—H37 | 0.9300 | C62'—H62F | 0.9600 |
C38—C41 | 1.522 (3) | ||
C1—O1—C21 | 115.40 (17) | C39—C38—C36 | 111.8 (2) |
C5—O2—H2 | 109.5 | C38—C39—H39A | 109.5 |
C9—O3—H3 | 109.5 | C38—C39—H39B | 109.5 |
C13—O4—H4 | 109.5 | H39A—C39—H39B | 109.5 |
C17—O5—H5 | 109.5 | C38—C39—H39C | 109.5 |
C2—C1—O1 | 119.59 (19) | H39A—C39—H39C | 109.5 |
C2—C1—C20 | 121.4 (2) | H39B—C39—H39C | 109.5 |
O1—C1—C20 | 118.7 (2) | C38—C40—H40A | 109.5 |
C1—C2—C58 | 118.4 (2) | C38—C40—H40B | 109.5 |
C1—C2—C3 | 122.2 (2) | H40A—C40—H40B | 109.5 |
C58—C2—C3 | 119.2 (2) | C38—C40—H40C | 109.5 |
C4—C3—C2 | 112.05 (18) | H40A—C40—H40C | 109.5 |
C4—C3—H3A | 109.2 | H40B—C40—H40C | 109.5 |
C2—C3—H3A | 109.2 | C38—C41—H41A | 109.5 |
C4—C3—H3B | 109.2 | C38—C41—H41B | 109.5 |
C2—C3—H3B | 109.2 | H41A—C41—H41B | 109.5 |
H3A—C3—H3B | 107.9 | C38—C41—H41C | 109.5 |
C28—C4—C5 | 117.8 (2) | H41A—C41—H41C | 109.5 |
C28—C4—C3 | 121.1 (2) | H41B—C41—H41C | 109.5 |
C5—C4—C3 | 121.0 (2) | C43—C42—C12 | 123.0 (2) |
O2—C5—C6 | 115.4 (2) | C43—C42—H42 | 118.5 |
O2—C5—C4 | 123.1 (2) | C12—C42—H42 | 118.5 |
C6—C5—C4 | 121.5 (2) | C44—C43—C42 | 116.7 (2) |
C30—C6—C5 | 118.0 (2) | C44—C43—C45 | 123.2 (2) |
C30—C6—C7 | 121.5 (2) | C42—C43—C45 | 120.1 (2) |
C5—C6—C7 | 120.31 (19) | C43—C44—C14 | 123.1 (2) |
C6—C7—C8 | 112.92 (16) | C43—C44—H44 | 118.4 |
C6—C7—H7A | 109.0 | C14—C44—H44 | 118.4 |
C8—C7—H7A | 109.0 | C48'—C45—C47' | 110.7 (9) |
C6—C7—H7B | 109.0 | C47—C45—C48 | 111.0 (3) |
C8—C7—H7B | 109.0 | C48'—C45—C46' | 107.1 (9) |
H7A—C7—H7B | 107.8 | C47'—C45—C46' | 110.1 (9) |
C9—C8—C35 | 117.42 (19) | C48—C45—C46' | 136.0 (8) |
C9—C8—C7 | 124.07 (19) | C47—C45—C43 | 108.1 (2) |
C35—C8—C7 | 118.43 (19) | C48'—C45—C43 | 108.2 (7) |
C8—C9—O3 | 124.07 (18) | C47'—C45—C43 | 108.3 (8) |
C8—C9—C10 | 121.02 (19) | C48—C45—C43 | 111.5 (2) |
O3—C9—C10 | 114.86 (18) | C46'—C45—C43 | 112.5 (8) |
C37—C10—C9 | 118.3 (2) | C47—C45—C46 | 110.4 (3) |
C37—C10—C11 | 121.01 (19) | C48—C45—C46 | 105.5 (3) |
C9—C10—C11 | 120.61 (19) | C43—C45—C46 | 110.5 (2) |
C12—C11—C10 | 116.47 (17) | C45—C46—H46A | 109.5 |
C12—C11—H11A | 108.2 | C45—C46—H46B | 109.5 |
C10—C11—H11A | 108.2 | C45—C46—H46C | 109.5 |
C12—C11—H11B | 108.2 | C45—C47—H47A | 109.5 |
C10—C11—H11B | 108.2 | C45—C47—H47B | 109.5 |
H11A—C11—H11B | 107.3 | C45—C47—H47C | 109.5 |
C13—C12—C42 | 117.8 (2) | C45—C48—H48A | 109.5 |
C13—C12—C11 | 122.67 (19) | C45—C48—H48B | 109.5 |
C42—C12—C11 | 119.4 (2) | C45—C48—H48C | 109.5 |
C12—C13—C14 | 121.65 (19) | C45—C46'—H46D | 109.5 |
C12—C13—O4 | 121.84 (19) | C45—C46'—H46E | 109.5 |
C14—C13—O4 | 116.45 (19) | H46D—C46'—H46E | 109.5 |
C13—C14—C44 | 117.6 (2) | C45—C46'—H46F | 109.5 |
C13—C14—C15 | 122.64 (19) | H46D—C46'—H46F | 109.5 |
C44—C14—C15 | 119.80 (19) | H46E—C46'—H46F | 109.5 |
C14—C15—C16 | 113.64 (17) | C45—C47'—H47D | 109.5 |
C14—C15—H15A | 108.8 | C45—C47'—H47E | 109.5 |
C16—C15—H15A | 108.8 | H47D—C47'—H47E | 109.5 |
C14—C15—H15B | 108.8 | C45—C47'—H47F | 109.5 |
C16—C15—H15B | 108.8 | H47D—C47'—H47F | 109.5 |
H15A—C15—H15B | 107.7 | H47E—C47'—H47F | 109.5 |
C17—C16—C49 | 118.26 (19) | C45—C48'—H48D | 109.5 |
C17—C16—C15 | 121.58 (18) | C45—C48'—H48E | 109.5 |
C49—C16—C15 | 120.11 (18) | H48D—C48'—H48E | 109.5 |
C16—C17—O5 | 122.21 (19) | C45—C48'—H48F | 109.5 |
C16—C17—C18 | 121.16 (18) | H48D—C48'—H48F | 109.5 |
O5—C17—C18 | 116.63 (18) | H48E—C48'—H48F | 109.5 |
C51—C18—C17 | 117.78 (19) | C50—C49—C16 | 123.32 (19) |
C51—C18—C19 | 120.78 (19) | C50—C49—H49 | 118.3 |
C17—C18—C19 | 120.81 (18) | C16—C49—H49 | 118.3 |
C18—C19—C20 | 111.67 (17) | C49—C50—C51 | 116.04 (19) |
C18—C19—H19A | 109.3 | C49—C50—C52 | 123.01 (19) |
C20—C19—H19A | 109.3 | C51—C50—C52 | 120.8 (2) |
C18—C19—H19B | 109.3 | C18—C51—C50 | 123.4 (2) |
C20—C19—H19B | 109.3 | C18—C51—H51 | 118.3 |
H19A—C19—H19B | 107.9 | C50—C51—H51 | 118.3 |
C56—C20—C1 | 117.3 (2) | C55—C52—C53 | 111.6 (3) |
C56—C20—C19 | 121.72 (19) | C53'—C52—C54' | 111.4 (11) |
C1—C20—C19 | 120.92 (19) | C55—C52—C50 | 108.4 (2) |
O1—C21—C22 | 108.4 (2) | C53'—C52—C50 | 112.9 (10) |
O1—C21—H21A | 110.0 | C53—C52—C50 | 110.3 (2) |
C22—C21—H21A | 110.0 | C54'—C52—C50 | 106.6 (11) |
O1—C21—H21B | 110.0 | C53'—C52—C55' | 108.2 (10) |
C22—C21—H21B | 110.0 | C54'—C52—C55' | 108.5 (10) |
H21A—C21—H21B | 108.4 | C50—C52—C55' | 109.3 (7) |
C27—C22—C23 | 117.8 (3) | C55—C52—C54 | 108.8 (3) |
C27—C22—C21 | 120.5 (3) | C53—C52—C54 | 105.5 (2) |
C23—C22—C21 | 121.8 (2) | C50—C52—C54 | 112.1 (2) |
C22—C23—C24 | 121.7 (3) | C55'—C52—C54 | 138.4 (7) |
C22—C23—H23 | 119.1 | C52—C53—H53A | 109.5 |
C24—C23—H23 | 119.1 | C52—C53—H53B | 109.5 |
C25—C24—C23 | 120.4 (3) | C52—C53—H53C | 109.5 |
C25—C24—H24 | 119.8 | C52—C54—H54A | 109.5 |
C23—C24—H24 | 119.8 | C52—C54—H54B | 109.5 |
C24—C25—C26 | 119.8 (3) | C52—C54—H54C | 109.5 |
C24—C25—H25 | 120.1 | C52—C55—H55A | 109.5 |
C26—C25—H25 | 120.1 | C52—C55—H55B | 109.5 |
C25—C26—C27 | 119.5 (3) | C52—C55—H55C | 109.5 |
C25—C26—H26 | 120.2 | C52—C53'—H53D | 109.5 |
C27—C26—H26 | 120.2 | C52—C53'—H53E | 109.5 |
C22—C27—C26 | 120.7 (3) | H53D—C53'—H53E | 109.5 |
C22—C27—H27 | 119.7 | C52—C53'—H53F | 109.5 |
C26—C27—H27 | 119.7 | H53D—C53'—H53F | 109.5 |
C29—C28—C4 | 123.0 (2) | H53E—C53'—H53F | 109.5 |
C29—C28—H28 | 118.5 | C52—C54'—H54D | 109.5 |
C4—C28—H28 | 118.5 | C52—C54'—H54E | 109.5 |
C30—C29—C28 | 116.6 (2) | H54D—C54'—H54E | 109.5 |
C30—C29—C31 | 120.9 (2) | C52—C54'—H54F | 109.5 |
C28—C29—C31 | 122.5 (2) | H54D—C54'—H54F | 109.5 |
C29—C30—C6 | 123.0 (2) | H54E—C54'—H54F | 109.5 |
C29—C30—H30 | 118.5 | C52—C55'—H55D | 109.5 |
C6—C30—H30 | 118.5 | C52—C55'—H55E | 109.5 |
C33—C31—C34 | 111.3 (4) | H55D—C55'—H55E | 109.5 |
C34'—C31—C32' | 115.3 (7) | C52—C55'—H55F | 109.5 |
C34'—C31—C29 | 117.9 (6) | H55D—C55'—H55F | 109.5 |
C33—C31—C29 | 114.0 (3) | H55E—C55'—H55F | 109.5 |
C34—C31—C29 | 110.3 (3) | C57—C56—C20 | 123.4 (2) |
C32'—C31—C29 | 111.2 (6) | C57—C56—H56 | 118.3 |
C33—C31—C32 | 106.0 (3) | C20—C56—H56 | 118.3 |
C34—C31—C32 | 107.5 (5) | C58—C57—C56 | 117.2 (2) |
C29—C31—C32 | 107.4 (2) | C58—C57—C59 | 122.7 (2) |
C34'—C31—C33' | 100.9 (7) | C56—C57—C59 | 120.0 (2) |
C32'—C31—C33' | 105.5 (8) | C57—C58—C2 | 122.4 (2) |
C29—C31—C33' | 103.8 (6) | C57—C58—H58 | 118.8 |
C31—C32—H32A | 109.5 | C2—C58—H58 | 118.8 |
C31—C32—H32B | 109.5 | C60—C59—C62 | 111.2 (4) |
C31—C32—H32C | 109.5 | C61'—C59—C60' | 111.6 (10) |
C31—C33—H33A | 109.5 | C61'—C59—C57 | 107.1 (9) |
C31—C33—H33B | 109.5 | C60—C59—C57 | 108.3 (2) |
C31—C33—H33C | 109.5 | C62—C59—C57 | 109.7 (2) |
C31—C34—H34A | 109.5 | C60'—C59—C57 | 106.8 (9) |
C31—C34—H34B | 109.5 | C60—C59—C61 | 106.8 (3) |
C31—C34—H34C | 109.5 | C62—C59—C61 | 108.6 (4) |
C31—C32'—H32D | 109.5 | C57—C59—C61 | 112.3 (2) |
C31—C32'—H32E | 109.5 | C61'—C59—C62' | 109.4 (9) |
H32D—C32'—H32E | 109.5 | C60'—C59—C62' | 108.6 (9) |
C31—C32'—H32F | 109.5 | C57—C59—C62' | 113.4 (7) |
H32D—C32'—H32F | 109.5 | C59—C60—H60A | 109.5 |
H32E—C32'—H32F | 109.5 | C59—C60—H60B | 109.5 |
C31—C33'—H33D | 109.5 | C59—C60—H60C | 109.5 |
C31—C33'—H33E | 109.5 | C59—C61—H61A | 109.5 |
H33D—C33'—H33E | 109.5 | C59—C61—H61B | 109.5 |
C31—C33'—H33F | 109.5 | C59—C61—H61C | 109.5 |
H33D—C33'—H33F | 109.5 | C59—C62—H62A | 109.5 |
H33E—C33'—H33F | 109.5 | C59—C62—H62B | 109.5 |
C31—C34'—H34D | 109.5 | C59—C62—H62C | 109.5 |
C31—C34'—H34E | 109.5 | C59—C60'—H60D | 109.5 |
H34D—C34'—H34E | 109.5 | C59—C60'—H60E | 109.5 |
C31—C34'—H34F | 109.5 | H60D—C60'—H60E | 109.5 |
H34D—C34'—H34F | 109.5 | C59—C60'—H60F | 109.5 |
H34E—C34'—H34F | 109.5 | H60D—C60'—H60F | 109.5 |
C36—C35—C8 | 123.9 (2) | H60E—C60'—H60F | 109.5 |
C36—C35—H35 | 118.0 | C59—C61'—H61D | 109.5 |
C8—C35—H35 | 118.0 | C59—C61'—H61E | 109.5 |
C35—C36—C37 | 115.8 (2) | H61D—C61'—H61E | 109.5 |
C35—C36—C38 | 123.3 (2) | C59—C61'—H61F | 109.5 |
C37—C36—C38 | 120.8 (2) | H61D—C61'—H61F | 109.5 |
C10—C37—C36 | 123.1 (2) | H61E—C61'—H61F | 109.5 |
C10—C37—H37 | 118.4 | C59—C62'—H62D | 109.5 |
C36—C37—H37 | 118.4 | C59—C62'—H62E | 109.5 |
C41—C38—C40 | 109.3 (2) | H62D—C62'—H62E | 109.5 |
C41—C38—C39 | 108.8 (2) | C59—C62'—H62F | 109.5 |
C40—C38—C39 | 107.3 (2) | H62D—C62'—H62F | 109.5 |
C41—C38—C36 | 110.1 (2) | H62E—C62'—H62F | 109.5 |
C40—C38—C36 | 109.4 (2) | ||
C21—O1—C1—C2 | 88.0 (2) | C28—C29—C31—C33 | 1.2 (4) |
C21—O1—C1—C20 | −97.9 (2) | C30—C29—C31—C34 | 54.1 (5) |
O1—C1—C2—C58 | 174.25 (18) | C28—C29—C31—C34 | −124.9 (5) |
C20—C1—C2—C58 | 0.2 (3) | C30—C29—C31—C32' | −128.4 (7) |
O1—C1—C2—C3 | 0.1 (3) | C28—C29—C31—C32' | 52.6 (8) |
C20—C1—C2—C3 | −173.9 (2) | C30—C29—C31—C32 | −62.7 (4) |
C1—C2—C3—C4 | 130.4 (2) | C28—C29—C31—C32 | 118.3 (4) |
C58—C2—C3—C4 | −43.7 (3) | C30—C29—C31—C33' | 118.6 (6) |
C2—C3—C4—C28 | 123.0 (2) | C28—C29—C31—C33' | −60.3 (7) |
C2—C3—C4—C5 | −54.0 (3) | C9—C8—C35—C36 | −2.5 (3) |
C28—C4—C5—O2 | 179.8 (2) | C7—C8—C35—C36 | 174.43 (19) |
C3—C4—C5—O2 | −3.1 (3) | C8—C35—C36—C37 | −2.4 (3) |
C28—C4—C5—C6 | 0.0 (3) | C8—C35—C36—C38 | −178.8 (2) |
C3—C4—C5—C6 | 177.1 (2) | C9—C10—C37—C36 | 0.6 (3) |
O2—C5—C6—C30 | −177.98 (18) | C11—C10—C37—C36 | −176.65 (19) |
C4—C5—C6—C30 | 1.8 (3) | C35—C36—C37—C10 | 3.4 (3) |
O2—C5—C6—C7 | 5.7 (3) | C38—C36—C37—C10 | 179.9 (2) |
C4—C5—C6—C7 | −174.50 (18) | C35—C36—C38—C41 | −135.0 (3) |
C30—C6—C7—C8 | −93.9 (2) | C37—C36—C38—C41 | 48.7 (3) |
C5—C6—C7—C8 | 82.3 (2) | C35—C36—C38—C40 | 104.9 (3) |
C6—C7—C8—C9 | −126.2 (2) | C37—C36—C38—C40 | −71.4 (3) |
C6—C7—C8—C35 | 57.0 (3) | C35—C36—C38—C39 | −13.9 (3) |
C35—C8—C9—O3 | −176.16 (18) | C37—C36—C38—C39 | 169.9 (2) |
C7—C8—C9—O3 | 7.1 (3) | C13—C12—C42—C43 | −2.8 (3) |
C35—C8—C9—C10 | 6.7 (3) | C11—C12—C42—C43 | 173.2 (2) |
C7—C8—C9—C10 | −170.06 (18) | C12—C42—C43—C44 | −1.2 (3) |
C8—C9—C10—C37 | −5.8 (3) | C12—C42—C43—C45 | 179.3 (2) |
O3—C9—C10—C37 | 176.79 (18) | C42—C43—C44—C14 | 2.9 (3) |
C8—C9—C10—C11 | 171.38 (18) | C45—C43—C44—C14 | −177.67 (19) |
O3—C9—C10—C11 | −6.0 (3) | C13—C14—C44—C43 | −0.3 (3) |
C37—C10—C11—C12 | −81.4 (3) | C15—C14—C44—C43 | −179.39 (19) |
C9—C10—C11—C12 | 101.4 (2) | C44—C43—C45—C47 | 108.0 (3) |
C10—C11—C12—C13 | −92.6 (3) | C42—C43—C45—C47 | −72.5 (3) |
C10—C11—C12—C42 | 91.6 (2) | C44—C43—C45—C48' | −74.4 (8) |
C42—C12—C13—C14 | 5.5 (3) | C42—C43—C45—C48' | 105.0 (8) |
C11—C12—C13—C14 | −170.40 (19) | C44—C43—C45—C47' | 45.6 (9) |
C42—C12—C13—O4 | −177.51 (18) | C42—C43—C45—C47' | −134.9 (9) |
C11—C12—C13—O4 | 6.6 (3) | C44—C43—C45—C48 | −14.2 (4) |
C12—C13—C14—C44 | −4.0 (3) | C42—C43—C45—C48 | 165.3 (3) |
O4—C13—C14—C44 | 178.87 (17) | C44—C43—C45—C46' | 167.5 (9) |
C12—C13—C14—C15 | 175.02 (19) | C42—C43—C45—C46' | −13.1 (9) |
O4—C13—C14—C15 | −2.1 (3) | C44—C43—C45—C46 | −131.1 (3) |
C13—C14—C15—C16 | 97.2 (2) | C42—C43—C45—C46 | 48.4 (3) |
C44—C14—C15—C16 | −83.8 (2) | C17—C16—C49—C50 | −1.5 (3) |
C14—C15—C16—C17 | −89.7 (2) | C15—C16—C49—C50 | −179.0 (2) |
C14—C15—C16—C49 | 87.8 (2) | C16—C49—C50—C51 | −0.8 (3) |
C49—C16—C17—O5 | −177.51 (18) | C16—C49—C50—C52 | 174.7 (2) |
C15—C16—C17—O5 | 0.0 (3) | C17—C18—C51—C50 | −0.7 (3) |
C49—C16—C17—C18 | 2.7 (3) | C19—C18—C51—C50 | 170.31 (19) |
C15—C16—C17—C18 | −179.79 (19) | C49—C50—C51—C18 | 1.9 (3) |
C16—C17—C18—C51 | −1.7 (3) | C52—C50—C51—C18 | −173.7 (2) |
O5—C17—C18—C51 | 178.52 (18) | C49—C50—C52—C55 | −105.1 (3) |
C16—C17—C18—C19 | −172.71 (18) | C51—C50—C52—C55 | 70.1 (3) |
O5—C17—C18—C19 | 7.5 (3) | C49—C50—C52—C53' | 70.9 (11) |
C51—C18—C19—C20 | −92.5 (2) | C51—C50—C52—C53' | −113.8 (11) |
C17—C18—C19—C20 | 78.2 (2) | C49—C50—C52—C53 | 132.3 (3) |
C2—C1—C20—C56 | 0.1 (3) | C51—C50—C52—C53 | −52.4 (3) |
O1—C1—C20—C56 | −173.96 (17) | C49—C50—C52—C54' | −51.6 (11) |
C2—C1—C20—C19 | 176.6 (2) | C51—C50—C52—C54' | 123.6 (11) |
O1—C1—C20—C19 | 2.6 (3) | C49—C50—C52—C55' | −168.6 (9) |
C18—C19—C20—C56 | 14.7 (3) | C51—C50—C52—C55' | 6.6 (9) |
C18—C19—C20—C1 | −161.70 (19) | C49—C50—C52—C54 | 15.0 (3) |
C1—O1—C21—C22 | −168.44 (19) | C51—C50—C52—C54 | −169.7 (2) |
O1—C21—C22—C27 | −134.9 (3) | C1—C20—C56—C57 | 0.6 (3) |
O1—C21—C22—C23 | 44.4 (3) | C19—C20—C56—C57 | −175.9 (2) |
C27—C22—C23—C24 | −0.4 (4) | C20—C56—C57—C58 | −1.5 (3) |
C21—C22—C23—C24 | −179.7 (2) | C20—C56—C57—C59 | 174.23 (19) |
C22—C23—C24—C25 | 0.3 (4) | C56—C57—C58—C2 | 1.8 (3) |
C23—C24—C25—C26 | 0.8 (5) | C59—C57—C58—C2 | −173.8 (2) |
C24—C25—C26—C27 | −1.8 (6) | C1—C2—C58—C57 | −1.3 (3) |
C23—C22—C27—C26 | −0.6 (5) | C3—C2—C58—C57 | 173.0 (2) |
C21—C22—C27—C26 | 178.7 (3) | C58—C57—C59—C61' | −57.1 (10) |
C25—C26—C27—C22 | 1.7 (5) | C56—C57—C59—C61' | 127.4 (10) |
C5—C4—C28—C29 | −1.3 (3) | C58—C57—C59—C60 | 107.6 (4) |
C3—C4—C28—C29 | −178.4 (2) | C56—C57—C59—C60 | −67.9 (4) |
C4—C28—C29—C30 | 0.6 (3) | C58—C57—C59—C62 | −130.8 (5) |
C4—C28—C29—C31 | 179.6 (2) | C56—C57—C59—C62 | 53.7 (5) |
C28—C29—C30—C6 | 1.3 (3) | C58—C57—C59—C60' | 62.5 (11) |
C31—C29—C30—C6 | −177.7 (2) | C56—C57—C59—C60' | −113.0 (11) |
C5—C6—C30—C29 | −2.5 (3) | C58—C57—C59—C61 | −10.1 (5) |
C7—C6—C30—C29 | 173.72 (19) | C56—C57—C59—C61 | 174.5 (4) |
C30—C29—C31—C34' | 8.1 (7) | C58—C57—C59—C62' | −177.9 (9) |
C28—C29—C31—C34' | −170.9 (6) | C56—C57—C59—C62' | 6.6 (9) |
C30—C29—C31—C33 | −179.8 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O5i | 0.82 | 2.04 | 2.7197 (19) | 140 |
O4—H4···O3 | 0.82 | 2.04 | 2.847 (2) | 168 |
O5—H5···O4 | 0.82 | 2.00 | 2.803 (2) | 168 |
Symmetry code: (i) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C62H76O5 |
Mr | 901.23 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 14.1467 (8), 14.3235 (9), 15.2179 (9) |
α, β, γ (°) | 70.653 (3), 78.776 (3), 71.573 (3) |
V (Å3) | 2746.3 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.38 × 0.18 × 0.10 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 75089, 10532, 5343 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.161, 0.96 |
No. of reflections | 10532 |
No. of parameters | 677 |
No. of restraints | 120 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.45, −0.16 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XPW (Siemens, 1996), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O5i | 0.82 | 2.04 | 2.7197 (19) | 140 |
O4—H4···O3 | 0.82 | 2.04 | 2.847 (2) | 168 |
O5—H5···O4 | 0.82 | 2.00 | 2.803 (2) | 168 |
Symmetry code: (i) −x+1, −y, −z+1. |
Acknowledgements
MIUR (PRIN-2009 A5Y3N9 project) is gratefully acknowledged for financial support.
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In the solid state the title compound adopts an approximate Cs-symmetric cone-in conformation, best described by (i) the leaning of the p-tert-butyl group of the benzylated ring inside the macrocycle cavity (defined by the four remaining p-tert-butylphenolic rings) and (ii) the concomitant tilting of the benzyl pendant group away from the cavity axis. The crystal packing shows the presence of pairs of centrosymmetric cone-shaped calix[5]arene molecules glued together –via their narrow rims– by several intra- and intermolecular hydrogen-bonding interactions involving the four hydroxyl groups present on each molecule. In addition, the benzyl (C22–C27) moiety and the p-tert-butylphenolic ring (C12–C14/C44/C43/C42) of each pair of centrosymmetric molecules lie on roughly parallel planes and their edges (C23/C24 and C12/C14, respectively) are seen at a spatial proximity of 3.5 Å (centroid-centroid = 4.47 (2) Å). In analogy with previously reported calixarene structures, collected at low temperature, four tert-butyl groups are disordered over two rotated orientations with refined occupancy factors.