Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807050106/hg2300sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807050106/hg2300Isup2.hkl |
CCDC reference: 662146
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.006 Å
- H-atom completeness 99%
- Disorder in main residue
- R factor = 0.052
- wR factor = 0.187
- Data-to-parameter ratio = 16.5
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT220_ALERT_2_A Large Non-Solvent C Ueq(max)/Ueq(min) ... 6.05 Ratio
Author Response: Explained in the text of the _publ_section_exptl_refinement section. |
PLAT222_ALERT_3_A Large Non-Solvent H Ueq(max)/Ueq(min) ... 6.78 Ratio
Author Response: Explained in the text of the _publ_section_exptl_refinement section. |
Alert level B PLAT201_ALERT_2_B Isotropic non-H Atoms in Main Residue(s) ....... 4
Alert level C CHEMW01_ALERT_1_C The difference between the given and expected weight for compound is greater 1 mass unit. Check that all hydrogen atoms have been taken into account. PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ? PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 100 Deg. PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 3 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C54 PLAT301_ALERT_3_C Main Residue Disorder ......................... 9.00 Perc. PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 42.00 Perc. PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) ..... <O1W PLAT413_ALERT_2_C Short Inter XH3 .. XHn H46C .. H56D .. 2.13 Ang.
Alert level G FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C56 H68.83 Br4 O8.41 Atom count from the _atom_site data: C56 H68 Br4 O8.415 CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected. CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional? From the CIF: _cell_formula_units_Z 2 From the CIF: _chemical_formula_sum C56 H68.83 Br4 O8.41 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 112.00 112.00 0.00 H 137.66 136.00 1.66 Br 8.00 8.00 0.00 O 16.82 16.83 -0.01 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 102
2 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 11 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 7 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 6 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related literature, see: Boerrigter et al. (1997); Cram et al. (1988); Sorrell & Pigge (1993); Tunstad et al. (1989).
Methyl cavitand (I) (1.00 g, 1.15 mmol) and N-bromosuccinimide (0.90 g, 5.04 mmol) were added to CCl4 (100 ml). A catalytic amount of benzoyl peroxide was added to the solution, and the solution allowed to reflux overnight under irradiation of white light. The orange solution accompanied by a succinimide precipitate was then allowed to cool to room temperature. The precipitate was filtered off, and the orange filtrate concentrated on a rotary evaporator. The resulting solid was chromatographed on silica gel using a chloroform mobile phase. The fractions that were collected were concentrated on a rotary evaporator, and the orange solid product stirred in methanol overnight. The solution was then filtered, and the purified product dried overnight to yield the title compound as a dark orange powder. (1.03 g, 76%), mp 553–555 K. 1H NMR [CDCl3, 300 MHz]: δ = 0.89 (t, 12 H, CH3), 1.28 - 1.50 (m, 24 H, (CH2)3), 2.15 - 2.22 (m, 8 H, CH2), 4.40 (s, 8 H, CH2Br), 4.55 (d, 4 H, inner of OCH2O), 4.76 (t, 4 H, CH(CH2)4CH3), 6.02 (d, 4 H, outer of OCH2O), 7.11 (s, 4 H, Ar H). 13C NMR [CDCl3, 75 MHz]: δ = 153.55, 138.13, 124.55, 121.18, 98.17, 36.87, 32.68, 31.98, 30.08, 27.55, 22.67, 14.10.
Crystals suitable for X-ray crystallography were grown by slow liquid diffusion of methanol into a solution of the title compound in 1:1 e thyl acetate:hexane.
Hydrogen atoms, first located in the difference map, were positioned geometrically and allowed to ride on their respective parent atoms, with C—H bond lengths of 1.00 (CH), 0.99 (CH2), or 0.98 (CH3). They were then refined with a riding model with Uiso(H) = 1.5Ueq(CH3) and Uiso(H) = 1.2Ueq(X) for X = CH or CH2. Two of the four pentyl groups are disordered. These were refined over two positions using SIMU, SADI and DELU restraints with the final occupancies being 0.681 (5) for atoms C49—C51, C53—C56 and 0.319 (5) for atoms C49A—C51A, C53A—C56A. In addition, atoms C53—C56 and C53A—C56A were refined isotropically as they did not refine well when refined anisotropically. This is likely due to the presence of further structural disorder which is not fully accounted for by the current disorder model. The atom O1W was introduced into the structural model to account for an electron density feature of approximately 1.4 e/Å3. Its coordinates and sof were refined with its Uiso fixed. This feature is interpreted as the O atom of a water molecule but its low occupancy factor [0.415] has prevented discovery of the associated H atoms which are, therefore, absent from the structural model.
The title compound, (II, Scheme 1), has been previously prepared by Boerrigter et al. (1997), as the result of a free radical bromination of (I) using N-bromosuccinimide and the radical initiator, AIBN. The synthesis of (II) in this study, however, followed the synthetic conditions as set out by Sorrell & Pigge (1993), which used benzoyl peroxide as the radical initiator. Interestingly, this is despite observations by Boerrigter et al. that this protocol did not afford the desired product. Indeed, the conditions of Sorrell & Pigge, in conjunction with the use of white light, yielded 76% of pure (II).
In the title compound the [4]arene moiety is a cyclic tetramer. The labelling scheme for one of the monomers, shown in Fig.1, extends over the whole molecule.
The asymmetric unit of (II) is shown in Fig. 2. The bond lengths and bond angles all fall within the normal ranges and are not discussed further. The four bromine atoms which appear at the upper rim of the molecule are orientated such that all four face inwards towards the molecular cavity. Interestingly, (II) appears with a water molecule of partial (0.42) occupancy inside the molecular cavity. This is despite the hydrophobic nature of the cavity. Such partial occupancy has been reported in related structures; for examples see Tunstad et al., (1989) and Cram et al.,(1988).
The bromine atoms give rise to interesting packing arrangements in the crystal structure of (II). As shown in Fig. 3, the individual resorcin[4]arene cavitand molecules pack such that the bromine atoms are in close contact with the corresponding bromine atoms of a neighbouring molecule. This results in alternate layers of bromine atoms, in between the cavities and the 'feet' (pentyl groups) representing the remainder of the cavitand molecules.
In Fig. 4, the feet of (II) are such that two adjacent pentyl groups are linear, while the remaining two are bent. This is due to the interdigitation of a pair of linear chains from one cavitand molecule, with the corresponding chains of a neighbouring cavitand molecule. This results in insufficient space for the remaining pairs of alkyl groups to extend in a linear fashion.
For related literature, see: Boerrigter et al. (1997); Cram et al. (1988); Sorrell & Pigge (1993); Tunstad et al. (1989).
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-NT (Bruker, 2005); data reduction: SAINT-NT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Bruker, 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Version 1.4.2; Bruno et al., 2002); software used to prepare material for publication: SHELXTL (Bruker, 1999).
C56H68Br4O8·0.415H2O | Z = 2 |
Mr = 1197.75 | F(000) = 1224.3 |
Triclinic, P1 | Dx = 1.457 Mg m−3 Dm = 1.454 Mg m−3 Dm measured by not measured |
Hall symbol: -P 1 | Melting point: 553 K |
a = 11.5151 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.9323 (2) Å | Cell parameters from 7203 reflections |
c = 22.7986 (5) Å | θ = 2.3–28.2° |
α = 93.655 (1)° | µ = 3.00 mm−1 |
β = 92.921 (1)° | T = 173 K |
γ = 118.676 (1)° | Block, colourless |
V = 2730.83 (9) Å3 | 0.41 × 0.30 × 0.29 mm |
Bruker APEXII CCD area-detector diffractometer | 10730 independent reflections |
Radiation source: fine-focus sealed tube | 7721 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
φ and ω scans | θmax = 26.0°, θmin = 0.9° |
Absorption correction: integration [face-indexed absorption corrections carried out with XPREP (Bruker, 2005)] | h = −14→14 |
Tmin = 0.373, Tmax = 0.477 | k = −14→14 |
42983 measured reflections | l = −28→28 |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.187 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.113P)2 + 1.1716P] where P = (Fo2 + 2Fc2)/3 |
10730 reflections | (Δ/σ)max = 0.001 |
649 parameters | Δρmax = 1.41 e Å−3 |
102 restraints | Δρmin = −1.41 e Å−3 |
C56H68Br4O8·0.415H2O | γ = 118.676 (1)° |
Mr = 1197.75 | V = 2730.83 (9) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.5151 (2) Å | Mo Kα radiation |
b = 11.9323 (2) Å | µ = 3.00 mm−1 |
c = 22.7986 (5) Å | T = 173 K |
α = 93.655 (1)° | 0.41 × 0.30 × 0.29 mm |
β = 92.921 (1)° |
Bruker APEXII CCD area-detector diffractometer | 10730 independent reflections |
Absorption correction: integration [face-indexed absorption corrections carried out with XPREP (Bruker, 2005)] | 7721 reflections with I > 2σ(I) |
Tmin = 0.373, Tmax = 0.477 | Rint = 0.044 |
42983 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 102 restraints |
wR(F2) = 0.187 | H-atom parameters constrained |
S = 1.12 | Δρmax = 1.41 e Å−3 |
10730 reflections | Δρmin = −1.41 e Å−3 |
649 parameters |
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 | Occ. (<1) | |
C1 | 0.2648 (4) | 0.3135 (4) | 0.83103 (19) | 0.0297 (10) | |
C2 | 0.3949 (4) | 0.4079 (4) | 0.82396 (18) | 0.0280 (9) | |
C3 | 0.4596 (4) | 0.4022 (4) | 0.77546 (18) | 0.0271 (9) | |
C4 | 0.3927 (4) | 0.2972 (4) | 0.73324 (18) | 0.0284 (9) | |
H4 | 0.4370 | 0.2907 | 0.7002 | 0.034* | |
C5 | 0.2636 (4) | 0.2017 (4) | 0.73754 (18) | 0.0285 (9) | |
C6 | 0.2009 (4) | 0.2118 (4) | 0.78623 (19) | 0.0294 (9) | |
C7 | 0.1982 (4) | 0.3215 (5) | 0.88375 (19) | 0.0354 (10) | |
H7A | 0.1008 | 0.2781 | 0.8736 | 0.042* | |
H7B | 0.2286 | 0.4126 | 0.8972 | 0.042* | |
C8 | 0.0440 (4) | 0.0068 (4) | 0.8155 (2) | 0.0342 (10) | |
H8A | −0.0346 | −0.0220 | 0.8383 | 0.041* | |
H8B | 0.1211 | 0.0234 | 0.8430 | 0.041* | |
C9 | 0.1912 (4) | 0.0826 (4) | 0.69345 (18) | 0.0294 (9) | |
H9 | 0.0940 | 0.0537 | 0.6933 | 0.035* | |
C10 | 0.1518 (4) | −0.1964 (4) | 0.77947 (17) | 0.0253 (9) | |
C11 | 0.1310 (4) | −0.1024 (4) | 0.75608 (18) | 0.0270 (9) | |
C12 | 0.2135 (4) | −0.0228 (4) | 0.71655 (17) | 0.0256 (9) | |
C13 | 0.3202 (4) | −0.0405 (4) | 0.70139 (17) | 0.0239 (8) | |
H13 | 0.3787 | 0.0140 | 0.6753 | 0.029* | |
C14 | 0.3437 (4) | −0.1343 (4) | 0.72296 (17) | 0.0223 (8) | |
C15 | 0.2598 (4) | −0.2102 (4) | 0.76253 (17) | 0.0251 (9) | |
C16 | 0.0631 (4) | −0.2791 (4) | 0.82210 (19) | 0.0335 (10) | |
H16A | 0.0617 | −0.3629 | 0.8190 | 0.040* | |
H16B | −0.0286 | −0.2951 | 0.8121 | 0.040* | |
C17 | 0.3759 (4) | −0.2732 (4) | 0.83114 (19) | 0.0299 (9) | |
H17A | 0.3872 | −0.1954 | 0.8547 | 0.036* | |
H17B | 0.3467 | −0.3432 | 0.8573 | 0.036* | |
C18 | 0.4623 (4) | −0.1500 (4) | 0.70673 (17) | 0.0235 (8) | |
H18 | 0.4376 | −0.2418 | 0.7099 | 0.028* | |
C19 | 0.6874 (4) | −0.0514 (4) | 0.85005 (18) | 0.0248 (9) | |
C20 | 0.5878 (4) | −0.1207 (4) | 0.80484 (19) | 0.0254 (9) | |
C21 | 0.5767 (4) | −0.0697 (4) | 0.75303 (17) | 0.0208 (8) | |
C22 | 0.6708 (4) | 0.0567 (4) | 0.74812 (17) | 0.0227 (8) | |
H22 | 0.6656 | 0.0938 | 0.7131 | 0.027* | |
C23 | 0.7723 (4) | 0.1315 (4) | 0.79198 (17) | 0.0217 (8) | |
C24 | 0.7765 (4) | 0.0762 (4) | 0.84305 (17) | 0.0231 (8) | |
C25 | 0.6987 (5) | −0.1108 (4) | 0.9045 (2) | 0.0357 (10) | |
H25A | 0.7936 | −0.0742 | 0.9190 | 0.043* | |
H25B | 0.6614 | −0.2044 | 0.8949 | 0.043* | |
C26 | 0.8615 (4) | 0.2342 (4) | 0.92645 (18) | 0.0301 (10) | |
H26A | 0.8973 | 0.2351 | 0.9670 | 0.036* | |
H26B | 0.7656 | 0.2061 | 0.9272 | 0.036* | |
C27 | 0.8734 (4) | 0.2700 (4) | 0.78705 (17) | 0.0232 (8) | |
H27 | 0.9546 | 0.2880 | 0.8128 | 0.028* | |
C28 | 0.8035 (4) | 0.4716 (4) | 0.90174 (17) | 0.0238 (9) | |
C29 | 0.8498 (4) | 0.3950 (4) | 0.87391 (17) | 0.0228 (8) | |
C30 | 0.8234 (4) | 0.3565 (4) | 0.81336 (17) | 0.0220 (8) | |
C31 | 0.7456 (4) | 0.3949 (4) | 0.78090 (17) | 0.0236 (8) | |
H31 | 0.7265 | 0.3694 | 0.7397 | 0.028* | |
C32 | 0.6944 (4) | 0.4697 (4) | 0.80646 (18) | 0.0250 (9) | |
C33 | 0.7244 (4) | 0.5066 (4) | 0.86678 (17) | 0.0240 (8) | |
C34 | 0.8352 (4) | 0.5136 (4) | 0.96568 (18) | 0.0286 (9) | |
H34A | 0.8344 | 0.5957 | 0.9740 | 0.034* | |
H34B | 0.9251 | 0.5277 | 0.9783 | 0.034* | |
C35 | 0.5449 (4) | 0.5140 (4) | 0.91094 (18) | 0.0279 (9) | |
H35A | 0.5229 | 0.4250 | 0.9174 | 0.034* | |
H35B | 0.5383 | 0.5562 | 0.9485 | 0.034* | |
C36 | 0.6030 (4) | 0.5056 (4) | 0.77138 (19) | 0.0305 (10) | |
H36 | 0.6134 | 0.5865 | 0.7924 | 0.037* | |
C37 | 0.2275 (5) | 0.1072 (5) | 0.62994 (18) | 0.0360 (11) | |
H37A | 0.3228 | 0.1331 | 0.6284 | 0.043* | |
H37B | 0.2144 | 0.1793 | 0.6185 | 0.043* | |
C38 | 0.1437 (5) | −0.0115 (5) | 0.58520 (18) | 0.0424 (12) | |
H38A | 0.1488 | −0.0861 | 0.5991 | 0.051* | |
H38B | 0.0496 | −0.0315 | 0.5835 | 0.051* | |
C39 | 0.1889 (5) | 0.0076 (5) | 0.52436 (18) | 0.0475 (13) | |
H39A | 0.1933 | 0.0878 | 0.5125 | 0.057* | |
H39B | 0.2800 | 0.0187 | 0.5255 | 0.057* | |
C40 | 0.1015 (6) | −0.1002 (6) | 0.47847 (19) | 0.0566 (15) | |
H40A | 0.0102 | −0.1120 | 0.4773 | 0.068* | |
H40B | 0.0978 | −0.1805 | 0.4899 | 0.068* | |
C41 | 0.1496 (7) | −0.0772 (7) | 0.4167 (2) | 0.080 (2) | |
H41A | 0.1602 | 0.0055 | 0.4064 | 0.120* | |
H41B | 0.0842 | −0.1462 | 0.3879 | 0.120* | |
H41C | 0.2352 | −0.0762 | 0.4163 | 0.120* | |
C42 | 0.4991 (4) | −0.1216 (4) | 0.64416 (17) | 0.0279 (9) | |
H42A | 0.5816 | −0.1262 | 0.6389 | 0.033* | |
H42B | 0.5183 | −0.0327 | 0.6391 | 0.033* | |
C43 | 0.3914 (4) | −0.2131 (5) | 0.59580 (19) | 0.0372 (11) | |
H43A | 0.3669 | −0.3026 | 0.6025 | 0.045* | |
H43B | 0.3112 | −0.2033 | 0.5988 | 0.045* | |
C44 | 0.4348 (5) | −0.1893 (5) | 0.5340 (2) | 0.0407 (11) | |
H44A | 0.4597 | −0.0994 | 0.5279 | 0.049* | |
H44B | 0.5157 | −0.1981 | 0.5316 | 0.049* | |
C45 | 0.3352 (6) | −0.2749 (6) | 0.4848 (2) | 0.0535 (14) | |
H45A | 0.2546 | −0.2653 | 0.4863 | 0.064* | |
H45B | 0.3094 | −0.3651 | 0.4906 | 0.064* | |
C46 | 0.3868 (6) | −0.2465 (6) | 0.4223 (2) | 0.0617 (16) | |
H46A | 0.4129 | −0.1573 | 0.4162 | 0.093* | |
H46B | 0.3160 | −0.3042 | 0.3920 | 0.093* | |
H46C | 0.4637 | −0.2604 | 0.4197 | 0.093* | |
C47 | 0.9170 (4) | 0.2961 (4) | 0.72461 (18) | 0.0292 (9) | |
H47A | 0.9383 | 0.2294 | 0.7090 | 0.035* | |
H47B | 0.8425 | 0.2901 | 0.6985 | 0.035* | |
C48 | 1.0383 (5) | 0.4283 (5) | 0.7235 (2) | 0.0488 (14) | |
H48A | 1.0107 | 0.4941 | 0.7320 | 0.059* | |
H48B | 1.1050 | 0.4400 | 0.7559 | 0.059* | |
C49 | 1.1046 (14) | 0.4535 (19) | 0.6669 (4) | 0.064 (2) | 0.681 (5) |
H49A | 1.1883 | 0.5363 | 0.6735 | 0.077* | 0.681 (5) |
H49B | 1.1283 | 0.3854 | 0.6572 | 0.077* | 0.681 (5) |
C50 | 1.0233 (9) | 0.4583 (9) | 0.6152 (4) | 0.076 (2) | 0.681 (5) |
H50A | 1.0735 | 0.4733 | 0.5800 | 0.091* | 0.681 (5) |
H50B | 0.9405 | 0.3750 | 0.6071 | 0.091* | 0.681 (5) |
C51 | 0.9896 (11) | 0.5626 (10) | 0.6269 (5) | 0.090 (3) | 0.681 (5) |
H51A | 0.9374 | 0.5655 | 0.5923 | 0.135* | 0.681 (5) |
H51B | 1.0716 | 0.6450 | 0.6351 | 0.135* | 0.681 (5) |
H51C | 0.9375 | 0.5462 | 0.6611 | 0.135* | 0.681 (5) |
C49A | 1.081 (4) | 0.462 (4) | 0.6627 (9) | 0.068 (3) | 0.319 (5) |
H49C | 1.0012 | 0.4284 | 0.6340 | 0.082* | 0.319 (5) |
H49D | 1.1307 | 0.5565 | 0.6626 | 0.082* | 0.319 (5) |
C50A | 1.167 (2) | 0.4054 (19) | 0.6450 (8) | 0.070 (3) | 0.319 (5) |
H50C | 1.2477 | 0.4468 | 0.6730 | 0.084* | 0.319 (5) |
H50D | 1.1187 | 0.3137 | 0.6521 | 0.084* | 0.319 (5) |
C51A | 1.211 (2) | 0.411 (2) | 0.5848 (8) | 0.088 (5) | 0.319 (5) |
H51D | 1.1986 | 0.3260 | 0.5702 | 0.132* | 0.319 (5) |
H51E | 1.3055 | 0.4743 | 0.5862 | 0.132* | 0.319 (5) |
H51F | 1.1589 | 0.4346 | 0.5583 | 0.132* | 0.319 (5) |
C52 | 0.6385 (5) | 0.5344 (5) | 0.7090 (2) | 0.0457 (12) | |
H52A | 0.7363 | 0.5879 | 0.7101 | 0.055* | 0.681 (5) |
H52B | 0.6133 | 0.4524 | 0.6851 | 0.055* | 0.681 (5) |
H52C | 0.6598 | 0.4683 | 0.6924 | 0.055* | 0.319 (5) |
H52D | 0.5580 | 0.5222 | 0.6854 | 0.055* | 0.319 (5) |
C53 | 0.5770 (9) | 0.5997 (9) | 0.6787 (3) | 0.067 (2)* | 0.681 (5) |
H53A | 0.6236 | 0.6910 | 0.6951 | 0.080* | 0.681 (5) |
H53B | 0.4839 | 0.5625 | 0.6888 | 0.080* | 0.681 (5) |
C54 | 0.5754 (8) | 0.5953 (13) | 0.6128 (4) | 0.115 (3)* | 0.681 (5) |
H54A | 0.5335 | 0.5044 | 0.5961 | 0.138* | 0.681 (5) |
H54B | 0.5193 | 0.6314 | 0.5980 | 0.138* | 0.681 (5) |
C55 | 0.7097 (9) | 0.6669 (14) | 0.5908 (4) | 0.124 (3)* | 0.681 (5) |
H55A | 0.7701 | 0.6400 | 0.6102 | 0.149* | 0.681 (5) |
H55B | 0.7462 | 0.7599 | 0.6023 | 0.149* | 0.681 (5) |
C56 | 0.7070 (13) | 0.6444 (14) | 0.5237 (4) | 0.122 (4)* | 0.681 (5) |
H56A | 0.7972 | 0.6936 | 0.5118 | 0.183* | 0.681 (5) |
H56B | 0.6489 | 0.6724 | 0.5043 | 0.183* | 0.681 (5) |
H56C | 0.6733 | 0.5528 | 0.5122 | 0.183* | 0.681 (5) |
C53A | 0.7517 (16) | 0.6654 (12) | 0.7093 (7) | 0.072 (5)* | 0.319 (5) |
H53C | 0.8321 | 0.6666 | 0.7277 | 0.086* | 0.319 (5) |
H53D | 0.7339 | 0.7248 | 0.7347 | 0.086* | 0.319 (5) |
C54A | 0.781 (2) | 0.7159 (16) | 0.6503 (7) | 0.103 (4)* | 0.319 (5) |
H54C | 0.7186 | 0.7469 | 0.6387 | 0.123* | 0.319 (5) |
H54D | 0.8722 | 0.7903 | 0.6539 | 0.123* | 0.319 (5) |
C55A | 0.772 (2) | 0.620 (3) | 0.6022 (8) | 0.120 (4)* | 0.319 (5) |
H55C | 0.7929 | 0.5568 | 0.6197 | 0.144* | 0.319 (5) |
H55D | 0.8397 | 0.6643 | 0.5746 | 0.144* | 0.319 (5) |
C56A | 0.635 (2) | 0.548 (3) | 0.5675 (11) | 0.116 (5)* | 0.319 (5) |
H56D | 0.6049 | 0.4553 | 0.5637 | 0.174* | 0.319 (5) |
H56E | 0.6400 | 0.5774 | 0.5282 | 0.174* | 0.319 (5) |
H56F | 0.5714 | 0.5639 | 0.5886 | 0.174* | 0.319 (5) |
O1 | 0.0691 (3) | 0.1223 (3) | 0.79143 (14) | 0.0344 (7) | |
O2 | 0.0211 (3) | −0.0925 (3) | 0.77090 (13) | 0.0326 (7) | |
O3 | 0.2756 (3) | −0.3082 (3) | 0.78403 (13) | 0.0279 (6) | |
O4 | 0.4997 (3) | −0.2486 (3) | 0.81165 (13) | 0.0291 (7) | |
O5 | 0.8766 (3) | 0.1446 (3) | 0.88846 (12) | 0.0265 (6) | |
O6 | 0.9272 (3) | 0.3609 (3) | 0.90898 (12) | 0.0256 (6) | |
O7 | 0.6788 (3) | 0.5819 (3) | 0.89468 (12) | 0.0278 (6) | |
O8 | 0.4525 (3) | 0.5112 (3) | 0.86706 (13) | 0.0312 (7) | |
Br1 | 0.24027 (5) | 0.23895 (5) | 0.94766 (2) | 0.04566 (17) | |
Br2 | 0.12420 (6) | −0.19738 (6) | 0.90338 (2) | 0.05765 (19) | |
Br3 | 0.60254 (6) | −0.07854 (7) | 0.96640 (3) | 0.0609 (2) | |
Br4 | 0.70324 (6) | 0.38183 (5) | 1.00981 (2) | 0.04434 (17) | |
O1W | 0.467 (2) | 0.126 (2) | 0.8609 (10) | 0.157 (11) | 0.415 (19) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.034 (2) | 0.039 (3) | 0.029 (2) | 0.029 (2) | −0.0028 (18) | −0.0017 (19) |
C2 | 0.036 (2) | 0.030 (2) | 0.029 (2) | 0.026 (2) | −0.0053 (18) | −0.0003 (18) |
C3 | 0.039 (2) | 0.027 (2) | 0.025 (2) | 0.024 (2) | −0.0018 (17) | 0.0045 (17) |
C4 | 0.038 (2) | 0.033 (2) | 0.022 (2) | 0.024 (2) | −0.0010 (17) | 0.0034 (18) |
C5 | 0.037 (2) | 0.036 (2) | 0.022 (2) | 0.028 (2) | −0.0070 (17) | −0.0017 (18) |
C6 | 0.029 (2) | 0.035 (2) | 0.031 (2) | 0.023 (2) | −0.0047 (17) | −0.0026 (19) |
C7 | 0.035 (2) | 0.046 (3) | 0.034 (2) | 0.029 (2) | −0.0023 (19) | −0.007 (2) |
C8 | 0.034 (2) | 0.039 (3) | 0.031 (2) | 0.020 (2) | 0.0049 (19) | −0.005 (2) |
C9 | 0.031 (2) | 0.036 (2) | 0.024 (2) | 0.020 (2) | −0.0050 (17) | −0.0038 (18) |
C10 | 0.0234 (19) | 0.024 (2) | 0.020 (2) | 0.0056 (17) | 0.0008 (15) | −0.0059 (17) |
C11 | 0.0211 (19) | 0.033 (2) | 0.022 (2) | 0.0108 (18) | −0.0010 (16) | −0.0082 (18) |
C12 | 0.027 (2) | 0.029 (2) | 0.0187 (19) | 0.0136 (18) | −0.0043 (16) | −0.0073 (17) |
C13 | 0.026 (2) | 0.023 (2) | 0.0174 (19) | 0.0080 (17) | −0.0008 (15) | −0.0043 (16) |
C14 | 0.0183 (18) | 0.020 (2) | 0.0205 (19) | 0.0045 (16) | −0.0036 (15) | −0.0089 (16) |
C15 | 0.0236 (19) | 0.019 (2) | 0.025 (2) | 0.0059 (17) | −0.0020 (16) | −0.0062 (17) |
C16 | 0.032 (2) | 0.034 (3) | 0.028 (2) | 0.010 (2) | 0.0076 (18) | −0.0020 (19) |
C17 | 0.032 (2) | 0.026 (2) | 0.031 (2) | 0.0128 (19) | 0.0072 (18) | 0.0066 (19) |
C18 | 0.0242 (19) | 0.018 (2) | 0.026 (2) | 0.0094 (17) | 0.0041 (16) | −0.0031 (16) |
C19 | 0.029 (2) | 0.028 (2) | 0.025 (2) | 0.0196 (19) | 0.0029 (16) | 0.0027 (17) |
C20 | 0.028 (2) | 0.017 (2) | 0.034 (2) | 0.0124 (17) | 0.0074 (17) | 0.0008 (17) |
C21 | 0.0228 (19) | 0.019 (2) | 0.023 (2) | 0.0127 (17) | 0.0060 (15) | −0.0006 (16) |
C22 | 0.0224 (19) | 0.023 (2) | 0.023 (2) | 0.0109 (17) | 0.0065 (15) | −0.0002 (16) |
C23 | 0.0213 (18) | 0.024 (2) | 0.024 (2) | 0.0138 (17) | 0.0053 (15) | −0.0037 (16) |
C24 | 0.0196 (18) | 0.026 (2) | 0.026 (2) | 0.0137 (17) | 0.0015 (15) | −0.0038 (17) |
C25 | 0.042 (3) | 0.033 (3) | 0.038 (3) | 0.023 (2) | 0.001 (2) | 0.005 (2) |
C26 | 0.036 (2) | 0.034 (2) | 0.024 (2) | 0.021 (2) | −0.0018 (17) | −0.0047 (18) |
C27 | 0.0205 (18) | 0.022 (2) | 0.0209 (19) | 0.0058 (17) | 0.0032 (15) | −0.0032 (16) |
C28 | 0.0202 (18) | 0.018 (2) | 0.027 (2) | 0.0042 (16) | 0.0033 (16) | −0.0030 (16) |
C29 | 0.0177 (18) | 0.020 (2) | 0.024 (2) | 0.0035 (16) | 0.0043 (15) | −0.0008 (16) |
C30 | 0.0192 (18) | 0.0158 (19) | 0.0221 (19) | 0.0015 (16) | 0.0059 (15) | −0.0021 (16) |
C31 | 0.026 (2) | 0.0158 (19) | 0.0201 (19) | 0.0031 (16) | 0.0049 (15) | −0.0005 (16) |
C32 | 0.026 (2) | 0.0154 (19) | 0.028 (2) | 0.0050 (17) | 0.0048 (16) | 0.0051 (17) |
C33 | 0.027 (2) | 0.0145 (19) | 0.025 (2) | 0.0058 (17) | 0.0052 (16) | 0.0010 (16) |
C34 | 0.031 (2) | 0.023 (2) | 0.027 (2) | 0.0111 (18) | 0.0013 (17) | −0.0060 (18) |
C35 | 0.034 (2) | 0.031 (2) | 0.024 (2) | 0.022 (2) | −0.0033 (17) | −0.0066 (18) |
C36 | 0.043 (2) | 0.022 (2) | 0.029 (2) | 0.018 (2) | 0.0030 (19) | 0.0043 (18) |
C37 | 0.044 (3) | 0.044 (3) | 0.025 (2) | 0.026 (2) | −0.0048 (19) | −0.001 (2) |
C38 | 0.049 (3) | 0.050 (3) | 0.030 (2) | 0.028 (3) | −0.004 (2) | −0.003 (2) |
C39 | 0.048 (3) | 0.060 (4) | 0.035 (3) | 0.028 (3) | −0.003 (2) | −0.004 (2) |
C40 | 0.062 (4) | 0.069 (4) | 0.039 (3) | 0.034 (3) | 0.001 (3) | −0.011 (3) |
C41 | 0.097 (5) | 0.090 (5) | 0.045 (4) | 0.041 (4) | 0.013 (3) | −0.012 (3) |
C42 | 0.026 (2) | 0.026 (2) | 0.026 (2) | 0.0086 (18) | 0.0065 (16) | −0.0047 (18) |
C43 | 0.036 (2) | 0.035 (3) | 0.029 (2) | 0.010 (2) | 0.0023 (19) | −0.010 (2) |
C44 | 0.043 (3) | 0.038 (3) | 0.034 (3) | 0.015 (2) | 0.005 (2) | −0.007 (2) |
C45 | 0.062 (3) | 0.062 (4) | 0.030 (3) | 0.028 (3) | −0.001 (2) | −0.008 (3) |
C46 | 0.067 (4) | 0.072 (4) | 0.038 (3) | 0.031 (3) | −0.007 (3) | −0.017 (3) |
C47 | 0.027 (2) | 0.026 (2) | 0.025 (2) | 0.0059 (18) | 0.0076 (17) | −0.0041 (18) |
C48 | 0.049 (3) | 0.037 (3) | 0.036 (3) | 0.001 (2) | 0.015 (2) | −0.001 (2) |
C49 | 0.066 (5) | 0.051 (4) | 0.053 (3) | 0.009 (3) | 0.028 (3) | 0.007 (3) |
C50 | 0.078 (5) | 0.060 (4) | 0.053 (3) | 0.003 (3) | 0.019 (3) | 0.011 (3) |
C51 | 0.083 (6) | 0.079 (6) | 0.083 (6) | 0.020 (5) | −0.007 (5) | 0.008 (5) |
C49A | 0.070 (5) | 0.052 (4) | 0.056 (4) | 0.007 (4) | 0.027 (4) | 0.008 (4) |
C50A | 0.073 (5) | 0.052 (5) | 0.062 (4) | 0.009 (4) | 0.029 (4) | 0.008 (4) |
C51A | 0.098 (9) | 0.064 (9) | 0.073 (7) | 0.013 (7) | 0.044 (7) | 0.002 (8) |
C52 | 0.065 (3) | 0.036 (3) | 0.035 (3) | 0.023 (3) | 0.007 (2) | 0.008 (2) |
O1 | 0.0295 (15) | 0.0422 (19) | 0.0380 (17) | 0.0238 (15) | 0.0001 (13) | −0.0039 (15) |
O2 | 0.0227 (14) | 0.0355 (17) | 0.0377 (17) | 0.0140 (13) | 0.0029 (12) | −0.0073 (14) |
O3 | 0.0290 (15) | 0.0151 (14) | 0.0335 (16) | 0.0062 (12) | 0.0019 (12) | 0.0001 (12) |
O4 | 0.0298 (15) | 0.0166 (14) | 0.0405 (17) | 0.0103 (12) | 0.0067 (13) | 0.0052 (13) |
O5 | 0.0255 (14) | 0.0285 (16) | 0.0263 (15) | 0.0156 (13) | −0.0057 (11) | −0.0060 (12) |
O6 | 0.0222 (13) | 0.0242 (15) | 0.0250 (14) | 0.0081 (12) | −0.0030 (11) | −0.0049 (12) |
O7 | 0.0321 (15) | 0.0197 (15) | 0.0307 (16) | 0.0127 (13) | 0.0029 (12) | −0.0051 (12) |
O8 | 0.0400 (16) | 0.0283 (16) | 0.0332 (16) | 0.0245 (14) | −0.0036 (13) | −0.0063 (13) |
Br1 | 0.0529 (3) | 0.0517 (3) | 0.0312 (3) | 0.0251 (3) | 0.0032 (2) | −0.0019 (2) |
Br2 | 0.0725 (4) | 0.0600 (4) | 0.0348 (3) | 0.0269 (3) | 0.0122 (3) | 0.0052 (3) |
Br3 | 0.0680 (4) | 0.0706 (4) | 0.0414 (3) | 0.0293 (3) | 0.0125 (3) | 0.0181 (3) |
Br4 | 0.0657 (3) | 0.0457 (3) | 0.0279 (3) | 0.0309 (3) | 0.0146 (2) | 0.0047 (2) |
O1W | 0.149 (17) | 0.17 (2) | 0.19 (2) | 0.095 (15) | 0.071 (14) | 0.038 (15) |
C1—C6 | 1.402 (6) | C37—H37A | 0.9900 |
C1—C2 | 1.403 (6) | C37—H37B | 0.9900 |
C1—C7 | 1.480 (6) | C38—C39 | 1.499 (5) |
C2—C3 | 1.381 (6) | C38—H38A | 0.9900 |
C2—O8 | 1.386 (5) | C38—H38B | 0.9900 |
C3—C4 | 1.391 (6) | C39—C40 | 1.497 (5) |
C3—C36 | 1.527 (6) | C39—H39A | 0.9900 |
C4—C5 | 1.386 (6) | C39—H39B | 0.9900 |
C4—H4 | 0.9500 | C40—C41 | 1.532 (6) |
C5—C6 | 1.384 (6) | C40—H40A | 0.9900 |
C5—C9 | 1.523 (6) | C40—H40B | 0.9900 |
C6—O1 | 1.392 (5) | C41—H41A | 0.9800 |
C7—Br1 | 1.974 (5) | C41—H41B | 0.9800 |
C7—H7A | 0.9900 | C41—H41C | 0.9800 |
C7—H7B | 0.9900 | C42—C43 | 1.534 (6) |
C8—O1 | 1.420 (6) | C42—H42A | 0.9900 |
C8—O2 | 1.423 (5) | C42—H42B | 0.9900 |
C8—H8A | 0.9900 | C43—C44 | 1.517 (6) |
C8—H8B | 0.9900 | C43—H43A | 0.9900 |
C9—C12 | 1.519 (6) | C43—H43B | 0.9900 |
C9—C37 | 1.535 (6) | C44—C45 | 1.488 (6) |
C9—H9 | 1.0000 | C44—H44A | 0.9900 |
C10—C11 | 1.385 (6) | C44—H44B | 0.9900 |
C10—C15 | 1.400 (6) | C45—C46 | 1.566 (8) |
C10—C16 | 1.489 (6) | C45—H45A | 0.9900 |
C11—O2 | 1.383 (5) | C45—H45B | 0.9900 |
C11—C12 | 1.396 (6) | C46—H46A | 0.9800 |
C12—C13 | 1.398 (6) | C46—H46B | 0.9800 |
C13—C14 | 1.385 (6) | C46—H46C | 0.9800 |
C13—H13 | 0.9500 | C47—C48 | 1.528 (6) |
C14—C15 | 1.386 (6) | C47—H47A | 0.9900 |
C14—C18 | 1.524 (5) | C47—H47B | 0.9900 |
C15—O3 | 1.382 (5) | C48—C49 | 1.506 (7) |
C16—Br2 | 1.964 (4) | C48—C49A | 1.508 (9) |
C16—H16A | 0.9900 | C48—H48A | 0.9900 |
C16—H16B | 0.9900 | C48—H48B | 0.9900 |
C17—O4 | 1.412 (5) | C49—C50 | 1.488 (9) |
C17—O3 | 1.420 (5) | C49—H49A | 0.9900 |
C17—H17A | 0.9900 | C49—H49B | 0.9900 |
C17—H17B | 0.9900 | C50—C51 | 1.484 (9) |
C18—C21 | 1.512 (5) | C50—H50A | 0.9900 |
C18—C42 | 1.521 (5) | C50—H50B | 0.9900 |
C18—H18 | 1.0000 | C51—H51A | 0.9800 |
C19—C20 | 1.387 (6) | C51—H51B | 0.9800 |
C19—C24 | 1.395 (6) | C51—H51C | 0.9800 |
C19—C25 | 1.497 (6) | C49A—C50A | 1.498 (10) |
C20—C21 | 1.390 (6) | C49A—H49C | 0.9900 |
C20—O4 | 1.394 (5) | C49A—H49D | 0.9900 |
C21—C22 | 1.389 (6) | C50A—C51A | 1.484 (10) |
C22—C23 | 1.388 (5) | C50A—H50C | 0.9900 |
C22—H22 | 0.9500 | C50A—H50D | 0.9900 |
C23—C24 | 1.384 (6) | C51A—H51D | 0.9800 |
C23—C27 | 1.514 (5) | C51A—H51E | 0.9800 |
C24—O5 | 1.391 (4) | C51A—H51F | 0.9800 |
C25—Br3 | 1.966 (5) | C52—C53 | 1.461 (7) |
C25—H25A | 0.9900 | C52—C53A | 1.478 (8) |
C25—H25B | 0.9900 | C52—H52A | 0.9900 |
C26—O5 | 1.414 (5) | C52—H52B | 0.9900 |
C26—O6 | 1.424 (5) | C52—H52C | 0.9900 |
C26—H26A | 0.9900 | C52—H52D | 0.9900 |
C26—H26B | 0.9900 | C53—C54 | 1.499 (5) |
C27—C30 | 1.512 (5) | C53—H52D | 0.8681 |
C27—C47 | 1.534 (5) | C53—H53A | 0.9900 |
C27—H27 | 1.0000 | C53—H53B | 0.9900 |
C28—C29 | 1.397 (6) | C54—C55 | 1.497 (5) |
C28—C33 | 1.404 (6) | C54—H54A | 0.9900 |
C28—C34 | 1.479 (5) | C54—H54B | 0.9900 |
C29—O6 | 1.384 (5) | C55—C56 | 1.533 (6) |
C29—C30 | 1.397 (5) | C55—H55A | 0.9900 |
C30—C31 | 1.388 (6) | C55—H55B | 0.9900 |
C31—C32 | 1.399 (6) | C56—H56A | 0.9800 |
C31—H31 | 0.9500 | C56—H56B | 0.9800 |
C32—C33 | 1.390 (6) | C56—H56C | 0.9800 |
C32—C36 | 1.523 (6) | C53A—C54A | 1.499 (5) |
C33—O7 | 1.379 (5) | C53A—H53C | 0.9900 |
C34—Br4 | 1.964 (4) | C53A—H53D | 0.9900 |
C34—H34A | 0.9900 | C54A—C55A | 1.497 (5) |
C34—H34B | 0.9900 | C54A—H54C | 0.9900 |
C35—O8 | 1.410 (5) | C54A—H54D | 0.9900 |
C35—O7 | 1.438 (5) | C55A—C56A | 1.532 (6) |
C35—H35A | 0.9900 | C55A—H55C | 0.9900 |
C35—H35B | 0.9900 | C55A—H55D | 0.9900 |
C36—C52 | 1.516 (6) | C56A—H56D | 0.9800 |
C36—H36 | 1.0000 | C56A—H56E | 0.9800 |
C37—C38 | 1.544 (6) | C56A—H56F | 0.9800 |
C6—C1—C2 | 117.3 (4) | C41—C40—H40B | 109.0 |
C6—C1—C7 | 121.6 (4) | H40A—C40—H40B | 107.8 |
C2—C1—C7 | 121.1 (4) | C40—C41—H41A | 109.5 |
C3—C2—O8 | 121.7 (4) | C40—C41—H41B | 109.5 |
C3—C2—C1 | 122.2 (4) | H41A—C41—H41B | 109.5 |
O8—C2—C1 | 116.0 (4) | C40—C41—H41C | 109.5 |
C2—C3—C4 | 117.9 (4) | H41A—C41—H41C | 109.5 |
C2—C3—C36 | 119.7 (4) | H41B—C41—H41C | 109.5 |
C4—C3—C36 | 122.3 (4) | C18—C42—C43 | 114.3 (3) |
C5—C4—C3 | 122.4 (4) | C18—C42—H42A | 108.7 |
C5—C4—H4 | 118.8 | C43—C42—H42A | 108.7 |
C3—C4—H4 | 118.8 | C18—C42—H42B | 108.7 |
C6—C5—C4 | 118.1 (4) | C43—C42—H42B | 108.7 |
C6—C5—C9 | 118.7 (4) | H42A—C42—H42B | 107.6 |
C4—C5—C9 | 123.2 (4) | C44—C43—C42 | 113.2 (4) |
C5—C6—O1 | 120.6 (4) | C44—C43—H43A | 108.9 |
C5—C6—C1 | 122.0 (4) | C42—C43—H43A | 108.9 |
O1—C6—C1 | 117.3 (4) | C44—C43—H43B | 108.9 |
C1—C7—Br1 | 109.9 (3) | C42—C43—H43B | 108.9 |
C1—C7—H7A | 109.7 | H43A—C43—H43B | 107.8 |
Br1—C7—H7A | 109.7 | C45—C44—C43 | 116.1 (4) |
C1—C7—H7B | 109.7 | C45—C44—H44A | 108.3 |
Br1—C7—H7B | 109.7 | C43—C44—H44A | 108.3 |
H7A—C7—H7B | 108.2 | C45—C44—H44B | 108.3 |
O1—C8—O2 | 112.0 (4) | C43—C44—H44B | 108.3 |
O1—C8—H8A | 109.2 | H44A—C44—H44B | 107.4 |
O2—C8—H8A | 109.2 | C44—C45—C46 | 113.5 (5) |
O1—C8—H8B | 109.2 | C44—C45—H45A | 108.9 |
O2—C8—H8B | 109.2 | C46—C45—H45A | 108.9 |
H8A—C8—H8B | 107.9 | C44—C45—H45B | 108.9 |
C12—C9—C5 | 108.1 (3) | C46—C45—H45B | 108.9 |
C12—C9—C37 | 113.4 (4) | H45A—C45—H45B | 107.7 |
C5—C9—C37 | 113.7 (4) | C45—C46—H46A | 109.5 |
C12—C9—H9 | 107.1 | C45—C46—H46B | 109.5 |
C5—C9—H9 | 107.1 | H46A—C46—H46B | 109.5 |
C37—C9—H9 | 107.1 | C45—C46—H46C | 109.5 |
C11—C10—C15 | 118.1 (4) | H46A—C46—H46C | 109.5 |
C11—C10—C16 | 121.0 (4) | H46B—C46—H46C | 109.5 |
C15—C10—C16 | 120.9 (4) | C48—C47—C27 | 112.2 (3) |
O2—C11—C10 | 118.0 (4) | C48—C47—H47A | 109.2 |
O2—C11—C12 | 119.8 (4) | C27—C47—H47A | 109.2 |
C10—C11—C12 | 122.1 (4) | C48—C47—H47B | 109.2 |
C11—C12—C13 | 117.3 (4) | C27—C47—H47B | 109.2 |
C11—C12—C9 | 120.9 (4) | H47A—C47—H47B | 107.9 |
C13—C12—C9 | 121.8 (4) | C49—C48—C47 | 116.2 (8) |
C14—C13—C12 | 122.6 (4) | C49A—C48—C47 | 114.4 (18) |
C14—C13—H13 | 118.7 | C49—C48—H48A | 108.2 |
C12—C13—H13 | 118.7 | C49A—C48—H48A | 97.5 |
C13—C14—C15 | 117.9 (4) | C47—C48—H48A | 108.2 |
C13—C14—C18 | 121.6 (4) | C49—C48—H48B | 108.2 |
C15—C14—C18 | 120.4 (4) | C49A—C48—H48B | 119.9 |
O3—C15—C14 | 120.5 (4) | C47—C48—H48B | 108.2 |
O3—C15—C10 | 117.4 (4) | H48A—C48—H48B | 107.4 |
C14—C15—C10 | 121.9 (4) | C50—C49—C48 | 115.0 (8) |
C10—C16—Br2 | 111.0 (3) | C50—C49—H49A | 108.5 |
C10—C16—H16A | 109.4 | C48—C49—H49A | 108.5 |
Br2—C16—H16A | 109.4 | C50—C49—H49B | 108.5 |
C10—C16—H16B | 109.4 | C48—C49—H49B | 108.5 |
Br2—C16—H16B | 109.4 | H49A—C49—H49B | 107.5 |
H16A—C16—H16B | 108.0 | C51—C50—C49 | 110.5 (10) |
O4—C17—O3 | 113.0 (3) | C51—C50—H50A | 109.6 |
O4—C17—H17A | 109.0 | C49—C50—H50A | 109.6 |
O3—C17—H17A | 109.0 | C51—C50—H50B | 109.6 |
O4—C17—H17B | 109.0 | C49—C50—H50B | 109.6 |
O3—C17—H17B | 109.0 | H50A—C50—H50B | 108.1 |
H17A—C17—H17B | 107.8 | C50—C51—H51A | 109.5 |
C21—C18—C42 | 112.9 (3) | C50—C51—H51B | 109.5 |
C21—C18—C14 | 107.8 (3) | H51A—C51—H51B | 109.5 |
C42—C18—C14 | 114.4 (3) | C50—C51—H51C | 109.5 |
C21—C18—H18 | 107.1 | H51A—C51—H51C | 109.5 |
C42—C18—H18 | 107.1 | H51B—C51—H51C | 109.5 |
C14—C18—H18 | 107.1 | C50A—C49A—C48 | 109.9 (14) |
C20—C19—C24 | 117.4 (4) | C50A—C49A—H49C | 109.7 |
C20—C19—C25 | 121.4 (4) | C48—C49A—H49C | 109.7 |
C24—C19—C25 | 121.2 (4) | C50A—C49A—H49D | 109.7 |
C19—C20—C21 | 122.9 (4) | C48—C49A—H49D | 109.7 |
C19—C20—O4 | 117.3 (4) | H49C—C49A—H49D | 108.2 |
C21—C20—O4 | 119.7 (4) | C51A—C50A—C49A | 122.1 (18) |
C22—C21—C20 | 116.8 (4) | C51A—C50A—H50C | 106.8 |
C22—C21—C18 | 123.5 (4) | C49A—C50A—H50C | 106.8 |
C20—C21—C18 | 119.7 (3) | C51A—C50A—H50D | 106.8 |
C23—C22—C21 | 123.1 (4) | C49A—C50A—H50D | 106.8 |
C23—C22—H22 | 118.5 | H50C—C50A—H50D | 106.7 |
C21—C22—H22 | 118.5 | C50A—C51A—H51D | 109.5 |
C24—C23—C22 | 117.5 (4) | C50A—C51A—H51E | 109.5 |
C24—C23—C27 | 119.5 (3) | H51D—C51A—H51E | 109.5 |
C22—C23—C27 | 123.0 (4) | C50A—C51A—H51F | 109.5 |
C23—C24—O5 | 120.7 (4) | H51D—C51A—H51F | 109.5 |
C23—C24—C19 | 122.3 (4) | H51E—C51A—H51F | 109.5 |
O5—C24—C19 | 116.9 (3) | C53—C52—C53A | 78.0 (9) |
C19—C25—Br3 | 110.5 (3) | C53—C52—C36 | 116.0 (5) |
C19—C25—H25A | 109.6 | C53A—C52—C36 | 110.2 (7) |
Br3—C25—H25A | 109.6 | C53—C52—H52A | 108.3 |
C19—C25—H25B | 109.6 | C36—C52—H52A | 108.3 |
Br3—C25—H25B | 109.6 | C53—C52—H52B | 108.3 |
H25A—C25—H25B | 108.1 | C53A—C52—H52B | 132.7 |
O5—C26—O6 | 112.9 (3) | C36—C52—H52B | 108.3 |
O5—C26—H26A | 109.0 | H52A—C52—H52B | 107.4 |
O6—C26—H26A | 109.0 | C53—C52—H52C | 128.9 |
O5—C26—H26B | 109.0 | C53A—C52—H52C | 111.8 |
O6—C26—H26B | 109.0 | C36—C52—H52C | 107.2 |
H26A—C26—H26B | 107.8 | H52A—C52—H52C | 81.1 |
C30—C27—C23 | 109.2 (3) | C53A—C52—H52D | 112.7 |
C30—C27—C47 | 114.4 (3) | C36—C52—H52D | 107.8 |
C23—C27—C47 | 113.5 (3) | H52A—C52—H52D | 138.5 |
C30—C27—H27 | 106.3 | H52B—C52—H52D | 79.7 |
C23—C27—H27 | 106.3 | H52C—C52—H52D | 107.0 |
C47—C27—H27 | 106.3 | C52—C53—C54 | 117.6 (8) |
C29—C28—C33 | 117.5 (4) | C54—C53—H52D | 103.1 |
C29—C28—C34 | 121.5 (4) | C52—C53—H53A | 107.9 |
C33—C28—C34 | 121.0 (4) | C54—C53—H53A | 107.9 |
O6—C29—C30 | 120.8 (3) | H52D—C53—H53A | 145.1 |
O6—C29—C28 | 116.8 (3) | C52—C53—H53B | 107.9 |
C30—C29—C28 | 122.4 (4) | C54—C53—H53B | 107.9 |
C31—C30—C29 | 117.6 (4) | H52D—C53—H53B | 77.4 |
C31—C30—C27 | 123.3 (3) | H53A—C53—H53B | 107.2 |
C29—C30—C27 | 119.1 (4) | C55—C54—C53 | 114.3 (4) |
C30—C31—C32 | 122.6 (4) | C55—C54—H54A | 108.7 |
C30—C31—H31 | 118.7 | C53—C54—H54A | 108.7 |
C32—C31—H31 | 118.7 | C55—C54—H54B | 108.7 |
C33—C32—C31 | 117.7 (4) | C53—C54—H54B | 108.7 |
C33—C32—C36 | 119.8 (4) | H54A—C54—H54B | 107.6 |
C31—C32—C36 | 122.5 (4) | C54—C55—C56 | 113.0 (5) |
O7—C33—C32 | 120.7 (4) | C54—C55—H55A | 109.0 |
O7—C33—C28 | 117.1 (3) | C56—C55—H55A | 109.0 |
C32—C33—C28 | 122.2 (4) | C54—C55—H55B | 109.0 |
C28—C34—Br4 | 109.6 (3) | C56—C55—H55B | 109.0 |
C28—C34—H34A | 109.8 | H55A—C55—H55B | 107.8 |
Br4—C34—H34A | 109.8 | C55—C56—H56A | 109.5 |
C28—C34—H34B | 109.8 | C55—C56—H56B | 109.5 |
Br4—C34—H34B | 109.8 | H56A—C56—H56B | 109.5 |
H34A—C34—H34B | 108.2 | C55—C56—H56C | 109.5 |
O8—C35—O7 | 111.7 (3) | H56A—C56—H56C | 109.5 |
O8—C35—H35A | 109.3 | H56B—C56—H56C | 109.5 |
O7—C35—H35A | 109.3 | C52—C53A—C54A | 115.9 (12) |
O8—C35—H35B | 109.3 | C52—C53A—H53C | 108.3 |
O7—C35—H35B | 109.3 | C54A—C53A—H53C | 108.3 |
H35A—C35—H35B | 107.9 | C52—C53A—H53D | 108.3 |
C52—C36—C32 | 114.1 (4) | C54A—C53A—H53D | 108.3 |
C52—C36—C3 | 114.3 (4) | H53C—C53A—H53D | 107.4 |
C32—C36—C3 | 108.1 (3) | C55A—C54A—C53A | 114.3 (4) |
C52—C36—H36 | 106.6 | C55A—C54A—H54C | 108.7 |
C32—C36—H36 | 106.6 | C53A—C54A—H54C | 108.7 |
C3—C36—H36 | 106.6 | C55A—C54A—H54D | 108.7 |
C9—C37—C38 | 112.8 (4) | C53A—C54A—H54D | 108.7 |
C9—C37—H37A | 109.0 | H54C—C54A—H54D | 107.6 |
C38—C37—H37A | 109.0 | C54A—C55A—C56A | 113.0 (5) |
C9—C37—H37B | 109.0 | C54A—C55A—H55C | 109.0 |
C38—C37—H37B | 109.0 | C56A—C55A—H55C | 109.0 |
H37A—C37—H37B | 107.8 | C54A—C55A—H55D | 109.0 |
C39—C38—C37 | 112.8 (4) | C56A—C55A—H55D | 109.0 |
C39—C38—H38A | 109.0 | H55C—C55A—H55D | 107.8 |
C37—C38—H38A | 109.0 | C55A—C56A—H56D | 109.5 |
C39—C38—H38B | 109.0 | C55A—C56A—H56E | 109.5 |
C37—C38—H38B | 109.0 | H56D—C56A—H56E | 109.5 |
H38A—C38—H38B | 107.8 | C55A—C56A—H56F | 109.5 |
C40—C39—C38 | 114.3 (4) | H56D—C56A—H56F | 109.5 |
C40—C39—H39A | 108.7 | H56E—C56A—H56F | 109.5 |
C38—C39—H39A | 108.7 | C6—O1—C8 | 117.5 (3) |
C40—C39—H39B | 108.7 | C11—O2—C8 | 116.6 (3) |
C38—C39—H39B | 108.7 | C15—O3—C17 | 116.9 (3) |
H39A—C39—H39B | 107.6 | C20—O4—C17 | 115.8 (3) |
C39—C40—C41 | 113.0 (5) | C24—O5—C26 | 116.8 (3) |
C39—C40—H40A | 109.0 | C29—O6—C26 | 115.8 (3) |
C41—C40—H40A | 109.0 | C33—O7—C35 | 115.4 (3) |
C39—C40—H40B | 109.0 | C2—O8—C35 | 118.2 (3) |
C6—C1—C2—C3 | −0.6 (6) | C33—C28—C29—C30 | 2.0 (6) |
C7—C1—C2—C3 | 179.5 (4) | C34—C28—C29—C30 | −178.6 (4) |
C6—C1—C2—O8 | 176.2 (3) | O6—C29—C30—C31 | −179.6 (3) |
C7—C1—C2—O8 | −3.8 (6) | C28—C29—C30—C31 | −1.4 (6) |
O8—C2—C3—C4 | −177.7 (3) | O6—C29—C30—C27 | 3.8 (5) |
C1—C2—C3—C4 | −1.2 (6) | C28—C29—C30—C27 | −178.0 (3) |
O8—C2—C3—C36 | 5.6 (6) | C23—C27—C30—C31 | −89.7 (4) |
C1—C2—C3—C36 | −177.9 (4) | C47—C27—C30—C31 | 38.8 (5) |
C2—C3—C4—C5 | 1.9 (6) | C23—C27—C30—C29 | 86.7 (4) |
C36—C3—C4—C5 | 178.5 (4) | C47—C27—C30—C29 | −144.8 (4) |
C3—C4—C5—C6 | −0.7 (6) | C29—C30—C31—C32 | 0.2 (6) |
C3—C4—C5—C9 | −176.8 (4) | C27—C30—C31—C32 | 176.7 (4) |
C4—C5—C6—O1 | 176.7 (4) | C30—C31—C32—C33 | 0.4 (6) |
C9—C5—C6—O1 | −7.1 (6) | C30—C31—C32—C36 | −176.6 (4) |
C4—C5—C6—C1 | −1.2 (6) | C31—C32—C33—O7 | 179.1 (3) |
C9—C5—C6—C1 | 175.1 (4) | C36—C32—C33—O7 | −3.9 (6) |
C2—C1—C6—C5 | 1.8 (6) | C31—C32—C33—C28 | 0.2 (6) |
C7—C1—C6—C5 | −178.2 (4) | C36—C32—C33—C28 | 177.2 (4) |
C2—C1—C6—O1 | −176.1 (3) | C29—C28—C33—O7 | 179.8 (3) |
C7—C1—C6—O1 | 3.8 (6) | C34—C28—C33—O7 | 0.3 (5) |
C6—C1—C7—Br1 | 92.4 (4) | C29—C28—C33—C32 | −1.3 (6) |
C2—C1—C7—Br1 | −87.6 (4) | C34—C28—C33—C32 | 179.2 (4) |
C6—C5—C9—C12 | −83.5 (4) | C29—C28—C34—Br4 | −86.8 (4) |
C4—C5—C9—C12 | 92.5 (5) | C33—C28—C34—Br4 | 92.7 (4) |
C6—C5—C9—C37 | 149.7 (4) | C33—C32—C36—C52 | 145.4 (4) |
C4—C5—C9—C37 | −34.3 (5) | C31—C32—C36—C52 | −37.7 (5) |
C15—C10—C11—O2 | 177.3 (3) | C33—C32—C36—C3 | −86.2 (4) |
C16—C10—C11—O2 | −3.5 (6) | C31—C32—C36—C3 | 90.7 (5) |
C15—C10—C11—C12 | 0.2 (6) | C2—C3—C36—C52 | −148.6 (4) |
C16—C10—C11—C12 | 179.3 (4) | C4—C3—C36—C52 | 34.9 (6) |
O2—C11—C12—C13 | −177.6 (3) | C2—C3—C36—C32 | 83.2 (5) |
C10—C11—C12—C13 | −0.5 (6) | C4—C3—C36—C32 | −93.3 (4) |
O2—C11—C12—C9 | 5.2 (5) | C12—C9—C37—C38 | 61.2 (5) |
C10—C11—C12—C9 | −177.7 (4) | C5—C9—C37—C38 | −174.7 (4) |
C5—C9—C12—C11 | 86.0 (4) | C9—C37—C38—C39 | −173.7 (4) |
C37—C9—C12—C11 | −146.9 (4) | C37—C38—C39—C40 | −174.0 (5) |
C5—C9—C12—C13 | −91.1 (4) | C38—C39—C40—C41 | 179.5 (5) |
C37—C9—C12—C13 | 36.0 (5) | C21—C18—C42—C43 | 172.5 (4) |
C11—C12—C13—C14 | 1.4 (6) | C14—C18—C42—C43 | −63.7 (5) |
C9—C12—C13—C14 | 178.6 (3) | C18—C42—C43—C44 | −175.5 (4) |
C12—C13—C14—C15 | −2.0 (5) | C42—C43—C44—C45 | 179.8 (5) |
C12—C13—C14—C18 | −178.8 (3) | C43—C44—C45—C46 | −179.3 (5) |
C13—C14—C15—O3 | 177.8 (3) | C30—C27—C47—C48 | 65.3 (5) |
C18—C14—C15—O3 | −5.4 (5) | C23—C27—C47—C48 | −168.4 (4) |
C13—C14—C15—C10 | 1.7 (5) | C27—C47—C48—C49 | 168.8 (6) |
C18—C14—C15—C10 | 178.5 (3) | C27—C47—C48—C49A | −176.7 (11) |
C11—C10—C15—O3 | −177.0 (3) | C49A—C48—C49—C50 | −19 (9) |
C16—C10—C15—O3 | 3.8 (5) | C47—C48—C49—C50 | 66.4 (14) |
C11—C10—C15—C14 | −0.8 (6) | C48—C49—C50—C51 | 60.5 (15) |
C16—C10—C15—C14 | −180.0 (4) | C49—C48—C49A—C50A | 17 (8) |
C11—C10—C16—Br2 | −87.0 (4) | C47—C48—C49A—C50A | −83 (3) |
C15—C10—C16—Br2 | 92.2 (4) | C48—C49A—C50A—C51A | 173 (2) |
C13—C14—C18—C21 | 91.7 (4) | C32—C36—C52—C53 | −165.1 (5) |
C15—C14—C18—C21 | −85.0 (4) | C3—C36—C52—C53 | 69.8 (6) |
C13—C14—C18—C42 | −34.8 (5) | C32—C36—C52—C53A | −78.9 (10) |
C15—C14—C18—C42 | 148.5 (4) | C3—C36—C52—C53A | 156.0 (10) |
C24—C19—C20—C21 | 2.2 (6) | C53A—C52—C53—C54 | 91.1 (9) |
C25—C19—C20—C21 | −178.1 (4) | C36—C52—C53—C54 | −162.2 (6) |
C24—C19—C20—O4 | 179.3 (3) | C52—C53—C54—C55 | −67.0 (15) |
C25—C19—C20—O4 | −1.0 (6) | C53—C54—C55—C56 | 171.6 (12) |
C19—C20—C21—C22 | −0.4 (6) | C53—C52—C53A—C54A | −55.5 (16) |
O4—C20—C21—C22 | −177.5 (3) | C36—C52—C53A—C54A | −169.1 (14) |
C19—C20—C21—C18 | −177.8 (4) | C52—C53A—C54A—C55A | −42 (2) |
O4—C20—C21—C18 | 5.1 (5) | C53A—C54A—C55A—C56A | 93 (2) |
C42—C18—C21—C22 | 35.5 (5) | C5—C6—O1—C8 | 84.5 (5) |
C14—C18—C21—C22 | −91.8 (4) | C1—C6—O1—C8 | −97.6 (4) |
C42—C18—C21—C20 | −147.2 (4) | O2—C8—O1—C6 | −92.3 (4) |
C14—C18—C21—C20 | 85.4 (4) | C10—C11—O2—C8 | 100.7 (4) |
C20—C21—C22—C23 | −0.1 (6) | C12—C11—O2—C8 | −82.1 (5) |
C18—C21—C22—C23 | 177.2 (4) | O1—C8—O2—C11 | 91.4 (4) |
C21—C22—C23—C24 | −1.2 (6) | C14—C15—O3—C17 | 80.7 (5) |
C21—C22—C23—C27 | −178.9 (3) | C10—C15—O3—C17 | −103.1 (4) |
C22—C23—C24—O5 | 178.9 (3) | O4—C17—O3—C15 | −92.0 (4) |
C27—C23—C24—O5 | −3.3 (5) | C19—C20—O4—C17 | 99.4 (4) |
C22—C23—C24—C19 | 3.1 (6) | C21—C20—O4—C17 | −83.4 (5) |
C27—C23—C24—C19 | −179.1 (3) | O3—C17—O4—C20 | 93.9 (4) |
C20—C19—C24—C23 | −3.6 (6) | C23—C24—O5—C26 | 79.7 (5) |
C25—C19—C24—C23 | 176.7 (4) | C19—C24—O5—C26 | −104.3 (4) |
C20—C19—C24—O5 | −179.6 (3) | O6—C26—O5—C24 | −94.1 (4) |
C25—C19—C24—O5 | 0.8 (6) | C30—C29—O6—C26 | −80.2 (4) |
C20—C19—C25—Br3 | −92.9 (4) | C28—C29—O6—C26 | 101.5 (4) |
C24—C19—C25—Br3 | 86.8 (4) | O5—C26—O6—C29 | 94.3 (4) |
C24—C23—C27—C30 | −86.5 (4) | C32—C33—O7—C35 | 82.8 (4) |
C22—C23—C27—C30 | 91.1 (4) | C28—C33—O7—C35 | −98.3 (4) |
C24—C23—C27—C47 | 144.4 (4) | O8—C35—O7—C33 | −93.6 (4) |
C22—C23—C27—C47 | −37.9 (5) | C3—C2—O8—C35 | −81.4 (5) |
C33—C28—C29—O6 | −179.8 (3) | C1—C2—O8—C35 | 101.9 (4) |
C34—C28—C29—O6 | −0.3 (5) | O7—C35—O8—C2 | 91.9 (4) |
Experimental details
Crystal data | |
Chemical formula | C56H68Br4O8·0.415H2O |
Mr | 1197.75 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 11.5151 (2), 11.9323 (2), 22.7986 (5) |
α, β, γ (°) | 93.655 (1), 92.921 (1), 118.676 (1) |
V (Å3) | 2730.83 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.00 |
Crystal size (mm) | 0.41 × 0.30 × 0.29 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector |
Absorption correction | Integration [face-indexed absorption corrections carried out with XPREP (Bruker, 2005)] |
Tmin, Tmax | 0.373, 0.477 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 42983, 10730, 7721 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.187, 1.12 |
No. of reflections | 10730 |
No. of parameters | 649 |
No. of restraints | 102 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.41, −1.41 |
Computer programs: APEX2 (Bruker, 2005), SAINT-NT (Bruker, 2005), SHELXTL (Bruker, 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Version 1.4.2; Bruno et al., 2002).
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
The title compound, (II, Scheme 1), has been previously prepared by Boerrigter et al. (1997), as the result of a free radical bromination of (I) using N-bromosuccinimide and the radical initiator, AIBN. The synthesis of (II) in this study, however, followed the synthetic conditions as set out by Sorrell & Pigge (1993), which used benzoyl peroxide as the radical initiator. Interestingly, this is despite observations by Boerrigter et al. that this protocol did not afford the desired product. Indeed, the conditions of Sorrell & Pigge, in conjunction with the use of white light, yielded 76% of pure (II).
In the title compound the [4]arene moiety is a cyclic tetramer. The labelling scheme for one of the monomers, shown in Fig.1, extends over the whole molecule.
The asymmetric unit of (II) is shown in Fig. 2. The bond lengths and bond angles all fall within the normal ranges and are not discussed further. The four bromine atoms which appear at the upper rim of the molecule are orientated such that all four face inwards towards the molecular cavity. Interestingly, (II) appears with a water molecule of partial (0.42) occupancy inside the molecular cavity. This is despite the hydrophobic nature of the cavity. Such partial occupancy has been reported in related structures; for examples see Tunstad et al., (1989) and Cram et al.,(1988).
The bromine atoms give rise to interesting packing arrangements in the crystal structure of (II). As shown in Fig. 3, the individual resorcin[4]arene cavitand molecules pack such that the bromine atoms are in close contact with the corresponding bromine atoms of a neighbouring molecule. This results in alternate layers of bromine atoms, in between the cavities and the 'feet' (pentyl groups) representing the remainder of the cavitand molecules.
In Fig. 4, the feet of (II) are such that two adjacent pentyl groups are linear, while the remaining two are bent. This is due to the interdigitation of a pair of linear chains from one cavitand molecule, with the corresponding chains of a neighbouring cavitand molecule. This results in insufficient space for the remaining pairs of alkyl groups to extend in a linear fashion.