organic compounds
Calixarene-based molecular capsule from olefin metathesis
aDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
*Correspondence e-mail: rbutcher99@yahoo.com
The reaction of tetrakis(allyloxy)calix[4]arene with the first-generation Grubbs catalyst, followed by catalytic hydrogenation, gave the novel bis-calixarene 15,20,46,51,64,69,74,79-octaoxatridecacyclo[32.28.8.83,28.113,53.122,44.09,14.021,26.038,70.040,45.052,57.059,63.07,80.032,73]octaconta-1(63),3,5,7(80),9(14),10,12,21,23,25,28(73),29,31,34,36,38(70),40,42,44,52,54,56,59,61-tetracosaene benzene monosolvate, C72H72O8·C6H6. The structure consists of two calix[4]arene units connected by four-carbon chains at each of the four O atoms on their narrow rims, to form a cage. Each of the calix[4]arene units has a flattened cone conformation in which two of the opposite are closer together and nearly parallel [dihedral angle between planes = 7.35 (16)°], and the other two are splayed outward [dihedral angle between planes = 72.20 (8)°]. While the cavity contains no solvent or other guest molecule, there is benzene solvent molecule in the lattice. Two of the alkyl linking arms were disordered over two conformations with occupancies of 0.582 (3)/0.418 (3) and 0.33 (4)/0.467 (4). They were constrained to have similar metrical and thermal parameters.
Related literature
For literature related to the use of et al. (2001); Gutsche (2008). For literature related to the preparation of bridged see: Yang & Swager (2007); Hailu et al. (2012). For literature related to the conformation of see: Arduini et al. (1995, 1996); Drew et al. (1997). For literature related to starting material and catalyst used, see: Ho et al. (1996); Vougioukalakis & Grubbs (2010).
as easily isolable reaction products, see: AsfariExperimental
Crystal data
|
Data collection: CrysAlis PRO (Agilent, 2012); cell CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S1600536813014438/hg5315sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813014438/hg5315Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536813014438/hg5315Isup3.cml
A 20-mg (0.024 mmol) sample of first-generation Grubbs catalyst measured under nitrogen atmosphere in a glove bag was placed in a 100-ml three-necked flask on a nitrogen line. To this 92 mg (0.157 mmol) of tetrakis(allyloxy)calix[4]arene (Ho et al., 1996) and 40 ml of dichloromethane (distilled from CaH2) was added. The mixture was then stirred under reflux in a N2 atmosphere at 45 °C (oil bath temperature) for 2 h. Solvent was removed by rotary evaporator to give 92 mg of black solid residue. The residue was then dissolved in 3 ml of dichloromethane and chromatographed (34 g of silica gel, 2.5 x 22.5 cm,
with hexane/dichloromethane). A black residue (presumably catalyst) remained on top of the column, and the fractions were all combined. After removal of solvent by rotary evaporator, a white powder was obtained.The product was suspended in 7 ml of ethyl acetate and placed on a nitrogen line. Then 20 mg of Pd on powdered
(10%) and 33 ml of ethyl acetate were added while flushing nitrogen through the flask. The flask was then fitted with a stopcock adapter attached to a hydrogen-filled balloon. The connection to the N2 line was closed, the stopcock to the hydrogen-filled balloon was opened, and a small amount of hydrogen was allowed to sweep through the flask for few s by slightly opening the glass stopper on one of the necks. The reaction mixture was stirred at room temperature for 6 h. The mixture was then filtered on Celite and solvent removed by rotary evaporator to give 68 mg of white solid product. The product was then chromatographed (8.56 g of silica gel, 1.2 x 18 cm, with hexane/dichloromethane). Attempted recrystallization of an 8-mg fraction (which showed only one spot on TLC) using CH2Cl2 and MeOH, and finally benzene gave white crystals suitable for X-ray diffraction analysis.H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with a C—H distance of 0.95 and 0.99 Å Uiso(H) = 1.2Ueq(C).
Calixarenes are macrocyclic molecules made up of phenol and methylene units. The ease of their preparation and chemical modification coupled with the easily isolable reaction products makes them ideal starting materials for the construction of host molecules with different properties (Asfari et al., 2001, Gutsche, 2008). Unsubstituted
have flexible conformations at higher temperatures, and controlling the conformations of is an important subject to pursue for better knowledge of the complexing ability of these molecules for various guest ions and molecules. An olefin metathesis reaction (Vougioukalakis & Grubbs, 2010) has been used to prepare bridged (Yang & Swager, 2007). In our first attempt to prepare a bridged calixarene by olefin metathesis, the reaction of tetrakis(allyloxy)calix[4]arene with the first generation Grubbs catalyst gave a novel dimeric calixarene with a complex chiral structure (Hailu et al., 2012). In our further investigation of this approach, catalytic hydrogenation of the initial metathesis product gave a small amount of a novel bis-calixarene. In contrast to the chiral structure prepared earlier, the present compound has a very symmetric structure. The two calix[4]arene units which are joined by covalent bonds of (CH2)4 groups have flattened cone conformations. The degree of flattening of a cone calix[4]arene has been characterized (Arduini et al., 1995; Arduini et al., 1996; Drew et al., 1997) using the dihedral angles between the plane of the four methylene linkers with the phenolic rings. These angles are 83.02 (8)° and 89.67 (8)° for rings B and D, respectively, which are almost parallel to each other, and 145.47 (8)° and 142.32 (7)° for rings A and C, respectively, which are inclined outwards.Figure 2 shows the molecular packing for the bis-calix[4]arene, C72H72O8. The recrystallization solvent, benzene, used in this experiment is shown in the lattice but outside the calixarene cavity.
For literature related to the use of
as easily isolable reaction products, see: Asfari et al. (2001); Gutsche (2008). For literature related to the preparation of bridged see: Yang & Swager (2007); Hailu et al. (2012). For literature related to the conformation of see: Arduini et al. (1995, 1996); Drew et al. (1997). For literature related to starting material and catalyst used, see: Ho et al. (1996); Vougioukalakis & Grubbs (2010).Data collection: CrysAlis PRO (Agilent, 2012); cell
CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C72H72O8·C6H6 | F(000) = 1220 |
Mr = 1143.40 | Dx = 1.247 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2ybc | Cell parameters from 1980 reflections |
a = 14.8804 (10) Å | θ = 3.1–75.5° |
b = 17.3004 (11) Å | µ = 0.62 mm−1 |
c = 12.1888 (8) Å | T = 123 K |
β = 103.929 (7)° | Plate, colorless |
V = 3045.6 (3) Å3 | 0.87 × 0.35 × 0.03 mm |
Z = 2 |
Agilent Xcalibur (Ruby, Gemini) diffractometer | 9972 independent reflections |
Radiation source: Enhance (Cu) X-ray Source | 5548 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.000 |
Detector resolution: 10.5081 pixels mm-1 | θmax = 75.9°, θmin = 3.1° |
ω scans | h = −18→18 |
Absorption correction: analytical (CrysAlis PRO; Agilent, 2012; Clark & Reid, 1995) | k = −21→21 |
Tmin = 0.795, Tmax = 0.982 | l = −15→14 |
9972 measured 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)] = 0.078 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.249 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.1443P)2] where P = (Fo2 + 2Fc2)/3 |
9972 reflections | (Δ/σ)max < 0.001 |
415 parameters | Δρmax = 1.03 e Å−3 |
10 restraints | Δρmin = −0.24 e Å−3 |
C72H72O8·C6H6 | V = 3045.6 (3) Å3 |
Mr = 1143.40 | Z = 2 |
Monoclinic, P21/c | Cu Kα radiation |
a = 14.8804 (10) Å | µ = 0.62 mm−1 |
b = 17.3004 (11) Å | T = 123 K |
c = 12.1888 (8) Å | 0.87 × 0.35 × 0.03 mm |
β = 103.929 (7)° |
Agilent Xcalibur (Ruby, Gemini) diffractometer | 9972 independent reflections |
Absorption correction: analytical (CrysAlis PRO; Agilent, 2012; Clark & Reid, 1995) | 5548 reflections with I > 2σ(I) |
Tmin = 0.795, Tmax = 0.982 | Rint = 0.000 |
9972 measured reflections |
R[F2 > 2σ(F2)] = 0.078 | 10 restraints |
wR(F2) = 0.249 | H-atom parameters constrained |
S = 1.00 | Δρmax = 1.03 e Å−3 |
9972 reflections | Δρmin = −0.24 e Å−3 |
415 parameters |
Experimental. Absorption correction: CrysAlis PRO (Agilent, 2012, Clark & Reid, 1995) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. |
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) | |
O1 | 0.30199 (13) | 0.55520 (14) | 0.31841 (19) | 0.0602 (6) | |
O2 | 0.69820 (13) | 0.54928 (11) | 0.45949 (17) | 0.0472 (5) | |
O3 | 0.66583 (12) | 0.35803 (11) | 0.43693 (17) | 0.0492 (5) | |
O4 | 0.33639 (13) | 0.36946 (12) | 0.32522 (19) | 0.0568 (6) | |
C1 | 0.74710 (18) | 0.58325 (17) | 0.3899 (3) | 0.0485 (7) | |
C2 | 0.77581 (19) | 0.66002 (18) | 0.4122 (3) | 0.0573 (8) | |
C3 | 0.8277 (2) | 0.6930 (2) | 0.3425 (3) | 0.0691 (11) | |
H3A | 0.8489 | 0.7447 | 0.3558 | 0.083* | |
C4 | 0.8488 (2) | 0.6516 (3) | 0.2543 (3) | 0.0747 (11) | |
H4A | 0.8815 | 0.6757 | 0.2057 | 0.090* | |
C5 | 0.8222 (2) | 0.5757 (3) | 0.2378 (3) | 0.0691 (10) | |
H5A | 0.8391 | 0.5472 | 0.1793 | 0.083* | |
C6 | 0.77098 (19) | 0.5396 (2) | 0.3047 (3) | 0.0557 (8) | |
C7 | 0.7496 (2) | 0.4546 (2) | 0.2948 (3) | 0.0567 (8) | |
H7A | 0.7658 | 0.4337 | 0.2265 | 0.068* | |
H7B | 0.6824 | 0.4466 | 0.2868 | 0.068* | |
C8 | 0.80383 (19) | 0.41190 (17) | 0.3989 (3) | 0.0493 (7) | |
C9 | 0.8995 (2) | 0.42163 (18) | 0.4304 (3) | 0.0531 (7) | |
H9A | 0.9292 | 0.4513 | 0.3837 | 0.064* | |
C10 | 0.95165 (19) | 0.38909 (18) | 0.5278 (3) | 0.0564 (8) | |
H10A | 1.0170 | 0.3956 | 0.5481 | 0.068* | |
C11 | 0.90806 (19) | 0.34675 (18) | 0.5961 (3) | 0.0555 (8) | |
H11A | 0.9442 | 0.3245 | 0.6636 | 0.067* | |
C12 | 0.8129 (2) | 0.33586 (16) | 0.5687 (3) | 0.0516 (7) | |
C13 | 0.76157 (18) | 0.36740 (16) | 0.4673 (3) | 0.0459 (6) | |
C14 | 0.7682 (2) | 0.29599 (19) | 0.6526 (3) | 0.0672 (10) | |
H14A | 0.7002 | 0.2949 | 0.6225 | 0.081* | |
H14B | 0.7905 | 0.2420 | 0.6636 | 0.081* | |
C15 | 0.6360 (3) | 0.2828 (3) | 0.3918 (5) | 0.0497 (11) | 0.582 (3) |
H15A | 0.6652 | 0.2422 | 0.4459 | 0.060* | 0.582 (3) |
H15B | 0.6549 | 0.2746 | 0.3201 | 0.060* | 0.582 (3) |
C16 | 0.5311 (4) | 0.2779 (3) | 0.3707 (4) | 0.0532 (10) | 0.582 (3) |
H16A | 0.5128 | 0.2229 | 0.3587 | 0.064* | 0.582 (3) |
H16B | 0.5133 | 0.2954 | 0.4398 | 0.064* | 0.582 (3) |
C17 | 0.4767 (4) | 0.3238 (3) | 0.2723 (5) | 0.0580 (11) | 0.582 (3) |
H17A | 0.4944 | 0.3789 | 0.2850 | 0.070* | 0.582 (3) |
H17D | 0.4955 | 0.3069 | 0.2035 | 0.070* | 0.582 (3) |
C18 | 0.3738 (4) | 0.3183 (4) | 0.2498 (6) | 0.0591 (14) | 0.582 (3) |
H18A | 0.3462 | 0.3325 | 0.1702 | 0.071* | 0.582 (3) |
H18B | 0.3562 | 0.2642 | 0.2609 | 0.071* | 0.582 (3) |
C15B | 0.6356 (4) | 0.3113 (4) | 0.3308 (7) | 0.0497 (11) | 0.418 (3) |
H15C | 0.6513 | 0.2562 | 0.3466 | 0.060* | 0.418 (3) |
H15D | 0.6675 | 0.3297 | 0.2731 | 0.060* | 0.418 (3) |
C16B | 0.5309 (5) | 0.3207 (4) | 0.2876 (6) | 0.0532 (10) | 0.418 (3) |
H16C | 0.5172 | 0.3767 | 0.2784 | 0.064* | 0.418 (3) |
H16D | 0.5124 | 0.2970 | 0.2116 | 0.064* | 0.418 (3) |
C17B | 0.4721 (5) | 0.2880 (5) | 0.3568 (7) | 0.0580 (11) | 0.418 (3) |
H17B | 0.4868 | 0.3150 | 0.4306 | 0.070* | 0.418 (3) |
H17C | 0.4895 | 0.2331 | 0.3715 | 0.070* | 0.418 (3) |
C18B | 0.3699 (5) | 0.2917 (5) | 0.3101 (8) | 0.0591 (14) | 0.418 (3) |
H18C | 0.3548 | 0.2785 | 0.2287 | 0.071* | 0.418 (3) |
H18D | 0.3389 | 0.2538 | 0.3494 | 0.071* | 0.418 (3) |
C19 | 0.23955 (18) | 0.37101 (16) | 0.3028 (3) | 0.0508 (7) | |
C20 | 0.1945 (2) | 0.33526 (16) | 0.3766 (3) | 0.0513 (7) | |
C21 | 0.0987 (2) | 0.33485 (18) | 0.3495 (3) | 0.0564 (8) | |
H21A | 0.0670 | 0.3099 | 0.3985 | 0.068* | |
C22 | 0.0481 (2) | 0.3706 (2) | 0.2514 (3) | 0.0613 (9) | |
H22A | −0.0177 | 0.3685 | 0.2324 | 0.074* | |
C23 | 0.0938 (2) | 0.4086 (2) | 0.1829 (3) | 0.0617 (9) | |
H23A | 0.0589 | 0.4341 | 0.1174 | 0.074* | |
C24 | 0.1900 (2) | 0.4110 (2) | 0.2062 (3) | 0.0555 (8) | |
C25 | 0.2460 (2) | 0.29988 (17) | 0.4875 (3) | 0.0621 (9) | |
H25A | 0.2293 | 0.2446 | 0.4886 | 0.075* | |
H25B | 0.3135 | 0.3031 | 0.4933 | 0.075* | |
C26 | 0.2364 (2) | 0.4584 (2) | 0.1310 (3) | 0.0735 (11) | |
H26A | 0.3044 | 0.4535 | 0.1581 | 0.088* | |
H26B | 0.2185 | 0.4378 | 0.0529 | 0.088* | |
C27 | 0.2098 (2) | 0.5424 (2) | 0.1301 (3) | 0.0646 (9) | |
C28 | 0.1481 (2) | 0.5766 (3) | 0.0381 (3) | 0.0770 (12) | |
H28A | 0.1263 | 0.5476 | −0.0293 | 0.092* | |
C29 | 0.1186 (2) | 0.6510 (3) | 0.0433 (3) | 0.0811 (13) | |
H29A | 0.0780 | 0.6736 | −0.0209 | 0.097* | |
C30 | 0.1469 (2) | 0.6929 (2) | 0.1395 (3) | 0.0738 (12) | |
H30A | 0.1245 | 0.7441 | 0.1422 | 0.089* | |
C31 | 0.2087 (2) | 0.6620 (2) | 0.2352 (3) | 0.0618 (9) | |
C32 | 0.24148 (19) | 0.5878 (2) | 0.2264 (3) | 0.0616 (9) | |
C33 | 0.3978 (4) | 0.5395 (3) | 0.2990 (5) | 0.0500 (9) | 0.533 (4) |
H33A | 0.4286 | 0.4970 | 0.3485 | 0.060* | 0.533 (4) |
H33B | 0.3931 | 0.5248 | 0.2193 | 0.060* | 0.533 (4) |
C34 | 0.4508 (4) | 0.6121 (3) | 0.3265 (5) | 0.0540 (10) | 0.533 (4) |
H34A | 0.4408 | 0.6322 | 0.3986 | 0.065* | 0.533 (4) |
H34D | 0.4251 | 0.6506 | 0.2670 | 0.065* | 0.533 (4) |
C35 | 0.5543 (6) | 0.6059 (6) | 0.3371 (13) | 0.055 (2) | 0.533 (4) |
H35A | 0.5834 | 0.6561 | 0.3638 | 0.066* | 0.533 (4) |
H35B | 0.5650 | 0.5960 | 0.2613 | 0.066* | 0.533 (4) |
C36 | 0.6019 (19) | 0.5425 (19) | 0.418 (2) | 0.061 (3) | 0.533 (4) |
H36A | 0.5731 | 0.5410 | 0.4830 | 0.073* | 0.533 (4) |
H36B | 0.5890 | 0.4923 | 0.3782 | 0.073* | 0.533 (4) |
C33B | 0.3947 (4) | 0.5932 (4) | 0.3494 (5) | 0.0500 (9) | 0.467 (4) |
H33C | 0.3877 | 0.6499 | 0.3401 | 0.060* | 0.467 (4) |
H33D | 0.4254 | 0.5821 | 0.4293 | 0.060* | 0.467 (4) |
C34B | 0.4506 (4) | 0.5629 (4) | 0.2750 (6) | 0.0540 (10) | 0.467 (4) |
H34B | 0.4271 | 0.5849 | 0.1984 | 0.065* | 0.467 (4) |
H34C | 0.4423 | 0.5061 | 0.2690 | 0.065* | 0.467 (4) |
C35B | 0.5533 (7) | 0.5807 (8) | 0.3147 (15) | 0.055 (2) | 0.467 (4) |
H35C | 0.5616 | 0.6375 | 0.3171 | 0.066* | 0.467 (4) |
H35D | 0.5852 | 0.5600 | 0.2584 | 0.066* | 0.467 (4) |
C36B | 0.600 (2) | 0.547 (2) | 0.431 (3) | 0.061 (3) | 0.467 (4) |
H36C | 0.5775 | 0.5766 | 0.4890 | 0.073* | 0.467 (4) |
H36D | 0.5796 | 0.4931 | 0.4338 | 0.073* | 0.467 (4) |
C2B | 0.5952 (3) | 0.5016 (3) | 0.0310 (3) | 0.0789 (11) | |
H2BA | 0.6609 | 0.5034 | 0.0528 | 0.095* | |
C3B | 0.5466 (3) | 0.5696 (3) | 0.0090 (3) | 0.0832 (12) | |
H3BA | 0.5787 | 0.6174 | 0.0148 | 0.100* | |
C1B | 0.5521 (3) | 0.4318 (3) | 0.0225 (3) | 0.0842 (12) | |
H1BA | 0.5868 | 0.3852 | 0.0371 | 0.101* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0406 (10) | 0.0834 (16) | 0.0504 (12) | 0.0035 (10) | −0.0015 (9) | 0.0210 (11) |
O2 | 0.0453 (10) | 0.0508 (11) | 0.0466 (11) | 0.0008 (8) | 0.0132 (8) | 0.0061 (9) |
O3 | 0.0388 (9) | 0.0511 (11) | 0.0523 (12) | −0.0009 (8) | 0.0003 (8) | −0.0101 (9) |
O4 | 0.0406 (10) | 0.0584 (12) | 0.0637 (14) | 0.0027 (9) | −0.0025 (9) | −0.0163 (10) |
C1 | 0.0362 (13) | 0.0587 (17) | 0.0468 (16) | 0.0026 (11) | 0.0023 (11) | 0.0181 (13) |
C2 | 0.0413 (14) | 0.0564 (18) | 0.066 (2) | 0.0024 (12) | −0.0041 (13) | 0.0259 (15) |
C3 | 0.0461 (16) | 0.069 (2) | 0.082 (3) | −0.0011 (15) | −0.0058 (16) | 0.042 (2) |
C4 | 0.0524 (18) | 0.108 (3) | 0.060 (2) | 0.0006 (19) | 0.0060 (16) | 0.046 (2) |
C5 | 0.0526 (17) | 0.110 (3) | 0.0413 (17) | 0.0066 (18) | 0.0043 (14) | 0.0273 (18) |
C6 | 0.0400 (14) | 0.085 (2) | 0.0373 (15) | 0.0043 (14) | 0.0010 (11) | 0.0198 (15) |
C7 | 0.0507 (16) | 0.079 (2) | 0.0385 (15) | −0.0010 (15) | 0.0070 (12) | −0.0100 (15) |
C8 | 0.0463 (14) | 0.0545 (16) | 0.0438 (16) | 0.0046 (12) | 0.0046 (12) | −0.0125 (13) |
C9 | 0.0446 (14) | 0.0636 (18) | 0.0504 (17) | 0.0008 (13) | 0.0102 (13) | −0.0051 (14) |
C10 | 0.0358 (14) | 0.0645 (19) | 0.064 (2) | 0.0009 (13) | 0.0032 (13) | −0.0028 (16) |
C11 | 0.0440 (14) | 0.0493 (16) | 0.065 (2) | 0.0010 (13) | −0.0035 (14) | 0.0053 (14) |
C12 | 0.0454 (14) | 0.0413 (14) | 0.0619 (19) | −0.0020 (11) | 0.0009 (13) | 0.0011 (13) |
C13 | 0.0386 (13) | 0.0436 (14) | 0.0505 (16) | −0.0002 (11) | 0.0008 (11) | −0.0098 (12) |
C14 | 0.0467 (16) | 0.0586 (19) | 0.085 (3) | −0.0114 (14) | −0.0074 (16) | 0.0227 (18) |
C15 | 0.0473 (19) | 0.036 (2) | 0.058 (3) | −0.0012 (18) | −0.002 (2) | −0.0046 (18) |
C16 | 0.054 (2) | 0.050 (2) | 0.048 (2) | −0.006 (2) | −0.001 (2) | −0.0067 (17) |
C17 | 0.049 (2) | 0.061 (3) | 0.059 (3) | 0.004 (2) | 0.003 (2) | −0.003 (2) |
C18 | 0.048 (2) | 0.059 (4) | 0.067 (4) | 0.011 (2) | 0.009 (3) | −0.014 (3) |
C15B | 0.0473 (19) | 0.036 (2) | 0.058 (3) | −0.0012 (18) | −0.002 (2) | −0.0046 (18) |
C16B | 0.054 (2) | 0.050 (2) | 0.048 (2) | −0.006 (2) | −0.001 (2) | −0.0067 (17) |
C17B | 0.049 (2) | 0.061 (3) | 0.059 (3) | 0.004 (2) | 0.003 (2) | −0.003 (2) |
C18B | 0.048 (2) | 0.059 (4) | 0.067 (4) | 0.011 (2) | 0.009 (3) | −0.014 (3) |
C19 | 0.0403 (14) | 0.0467 (15) | 0.0576 (18) | 0.0043 (11) | −0.0032 (13) | −0.0185 (13) |
C20 | 0.0488 (15) | 0.0410 (15) | 0.0584 (18) | 0.0012 (12) | 0.0018 (13) | −0.0105 (13) |
C21 | 0.0490 (15) | 0.0551 (18) | 0.0598 (19) | 0.0039 (13) | 0.0030 (14) | −0.0102 (15) |
C22 | 0.0389 (14) | 0.085 (2) | 0.0549 (19) | 0.0049 (14) | 0.0009 (13) | −0.0135 (17) |
C23 | 0.0460 (16) | 0.086 (2) | 0.0461 (17) | 0.0164 (15) | −0.0026 (14) | −0.0141 (16) |
C24 | 0.0485 (16) | 0.070 (2) | 0.0447 (17) | 0.0037 (14) | 0.0043 (13) | −0.0140 (14) |
C25 | 0.0463 (15) | 0.0436 (16) | 0.088 (3) | 0.0006 (12) | −0.0001 (16) | 0.0109 (16) |
C26 | 0.0520 (18) | 0.126 (3) | 0.0403 (17) | 0.0173 (19) | 0.0073 (14) | −0.0030 (19) |
C27 | 0.0454 (16) | 0.104 (3) | 0.0426 (17) | 0.0038 (16) | 0.0069 (13) | 0.0215 (18) |
C28 | 0.0524 (18) | 0.130 (4) | 0.0441 (18) | 0.002 (2) | 0.0025 (15) | 0.026 (2) |
C29 | 0.0578 (19) | 0.111 (3) | 0.062 (2) | −0.010 (2) | −0.0089 (17) | 0.047 (2) |
C30 | 0.0516 (17) | 0.083 (2) | 0.078 (3) | −0.0124 (16) | −0.0023 (17) | 0.048 (2) |
C31 | 0.0421 (14) | 0.071 (2) | 0.064 (2) | −0.0143 (14) | −0.0024 (13) | 0.0342 (17) |
C32 | 0.0358 (14) | 0.092 (3) | 0.0531 (19) | −0.0039 (14) | 0.0035 (13) | 0.0313 (18) |
C33 | 0.049 (2) | 0.053 (2) | 0.045 (2) | 0.003 (2) | 0.0049 (19) | −0.0055 (17) |
C34 | 0.052 (2) | 0.061 (3) | 0.050 (3) | −0.003 (2) | 0.013 (2) | 0.0011 (19) |
C35 | 0.0464 (17) | 0.060 (7) | 0.055 (6) | 0.000 (3) | 0.007 (2) | 0.010 (5) |
C36 | 0.0468 (18) | 0.076 (4) | 0.060 (5) | −0.0029 (19) | 0.013 (3) | 0.014 (4) |
C33B | 0.049 (2) | 0.053 (2) | 0.045 (2) | 0.003 (2) | 0.0049 (19) | −0.0055 (17) |
C34B | 0.052 (2) | 0.061 (3) | 0.050 (3) | −0.003 (2) | 0.013 (2) | 0.0011 (19) |
C35B | 0.0464 (17) | 0.060 (7) | 0.055 (6) | 0.000 (3) | 0.007 (2) | 0.010 (5) |
C36B | 0.0468 (18) | 0.076 (4) | 0.060 (5) | −0.0029 (19) | 0.013 (3) | 0.014 (4) |
C2B | 0.064 (2) | 0.123 (3) | 0.0475 (19) | −0.002 (2) | 0.0073 (17) | 0.005 (2) |
C3B | 0.082 (3) | 0.124 (4) | 0.0413 (18) | −0.001 (2) | 0.0098 (17) | −0.001 (2) |
C1B | 0.083 (3) | 0.117 (4) | 0.048 (2) | −0.001 (2) | 0.0080 (19) | −0.004 (2) |
O1—C32 | 1.379 (3) | C18B—H18C | 0.9900 |
O1—C33B | 1.492 (7) | C18B—H18D | 0.9900 |
O1—C33 | 1.525 (6) | C19—C20 | 1.390 (5) |
O2—C1 | 1.375 (3) | C19—C24 | 1.411 (4) |
O2—C36 | 1.41 (3) | C20—C21 | 1.383 (4) |
O2—C36B | 1.42 (3) | C20—C25 | 1.513 (4) |
O3—C13 | 1.393 (3) | C21—C22 | 1.395 (5) |
O3—C15 | 1.440 (5) | C21—H21A | 0.9500 |
O3—C15B | 1.500 (7) | C22—C23 | 1.366 (5) |
O4—C19 | 1.401 (3) | C22—H22A | 0.9500 |
O4—C18B | 1.461 (8) | C23—C24 | 1.391 (4) |
O4—C18 | 1.478 (6) | C23—H23A | 0.9500 |
C1—C6 | 1.398 (5) | C24—C26 | 1.516 (5) |
C1—C2 | 1.402 (4) | C25—C2i | 1.508 (5) |
C2—C3 | 1.400 (5) | C25—H25A | 0.9900 |
C2—C25i | 1.508 (5) | C25—H25B | 0.9900 |
C3—C4 | 1.389 (6) | C26—C27 | 1.505 (5) |
C3—H3A | 0.9500 | C26—H26A | 0.9900 |
C4—C5 | 1.372 (6) | C26—H26B | 0.9900 |
C4—H4A | 0.9500 | C27—C32 | 1.397 (5) |
C5—C6 | 1.391 (5) | C27—C28 | 1.399 (4) |
C5—H5A | 0.9500 | C28—C29 | 1.366 (6) |
C6—C7 | 1.502 (5) | C28—H28A | 0.9500 |
C7—C8 | 1.522 (4) | C29—C30 | 1.356 (6) |
C7—H7A | 0.9900 | C29—H29A | 0.9500 |
C7—H7B | 0.9900 | C30—C31 | 1.406 (4) |
C8—C13 | 1.392 (4) | C30—H30A | 0.9500 |
C8—C9 | 1.392 (4) | C31—C32 | 1.386 (5) |
C9—C10 | 1.374 (5) | C31—C14i | 1.513 (5) |
C9—H9A | 0.9500 | C33—C34 | 1.478 (7) |
C10—C11 | 1.382 (5) | C33—H33A | 0.9900 |
C10—H10A | 0.9500 | C33—H33B | 0.9900 |
C11—C12 | 1.387 (4) | C34—C35 | 1.518 (10) |
C11—H11A | 0.9500 | C34—H34A | 0.9900 |
C12—C13 | 1.398 (4) | C34—H34D | 0.9900 |
C12—C14 | 1.514 (5) | C35—C36 | 1.528 (13) |
C14—C31i | 1.513 (5) | C35—H35A | 0.9900 |
C14—H14A | 0.9900 | C35—H35B | 0.9900 |
C14—H14B | 0.9900 | C36—H36A | 0.9900 |
C15—C16 | 1.521 (7) | C36—H36B | 0.9900 |
C15—H15A | 0.9900 | C33B—C34B | 1.467 (8) |
C15—H15B | 0.9900 | C33B—H33C | 0.9900 |
C16—C17 | 1.503 (7) | C33B—H33D | 0.9900 |
C16—H16A | 0.9900 | C34B—C35B | 1.519 (11) |
C16—H16B | 0.9900 | C34B—H34B | 0.9900 |
C17—C18 | 1.492 (7) | C34B—H34C | 0.9900 |
C17—H17A | 0.9900 | C35B—C36B | 1.531 (15) |
C17—H17D | 0.9900 | C35B—H35C | 0.9900 |
C18—H18A | 0.9900 | C35B—H35D | 0.9900 |
C18—H18B | 0.9900 | C36B—H36C | 0.9900 |
C15B—C16B | 1.529 (9) | C36B—H36D | 0.9900 |
C15B—H15C | 0.9900 | C2B—C1B | 1.361 (6) |
C15B—H15D | 0.9900 | C2B—C3B | 1.372 (6) |
C16B—C17B | 1.466 (10) | C2B—H2BA | 0.9500 |
C16B—H16C | 0.9900 | C3B—C1Bii | 1.426 (6) |
C16B—H16D | 0.9900 | C3B—H3BA | 0.9500 |
C17B—C18B | 1.492 (9) | C1B—C3Bii | 1.426 (6) |
C17B—H17B | 0.9900 | C1B—H1BA | 0.9500 |
C17B—H17C | 0.9900 | ||
C32—O1—C33B | 114.1 (3) | C20—C19—C24 | 121.4 (3) |
C32—O1—C33 | 113.5 (3) | O4—C19—C24 | 118.6 (3) |
C1—O2—C36 | 117.2 (12) | C21—C20—C19 | 118.5 (3) |
C1—O2—C36B | 121.7 (12) | C21—C20—C25 | 118.9 (3) |
C13—O3—C15 | 114.1 (3) | C19—C20—C25 | 122.6 (3) |
C13—O3—C15B | 111.6 (3) | C20—C21—C22 | 121.0 (3) |
C19—O4—C18B | 111.0 (4) | C20—C21—H21A | 119.5 |
C19—O4—C18 | 114.5 (3) | C22—C21—H21A | 119.5 |
O2—C1—C6 | 119.6 (3) | C23—C22—C21 | 119.4 (3) |
O2—C1—C2 | 117.9 (3) | C23—C22—H22A | 120.3 |
C6—C1—C2 | 122.4 (3) | C21—C22—H22A | 120.3 |
C3—C2—C1 | 117.1 (4) | C22—C23—C24 | 121.9 (3) |
C3—C2—C25i | 124.2 (3) | C22—C23—H23A | 119.0 |
C1—C2—C25i | 118.5 (3) | C24—C23—H23A | 119.0 |
C4—C3—C2 | 121.3 (4) | C23—C24—C19 | 117.5 (3) |
C4—C3—H3A | 119.3 | C23—C24—C26 | 119.3 (3) |
C2—C3—H3A | 119.3 | C19—C24—C26 | 123.2 (3) |
C5—C4—C3 | 119.7 (3) | C2i—C25—C20 | 112.1 (2) |
C5—C4—H4A | 120.1 | C2i—C25—H25A | 109.2 |
C3—C4—H4A | 120.1 | C20—C25—H25A | 109.2 |
C4—C5—C6 | 121.6 (4) | C2i—C25—H25B | 109.2 |
C4—C5—H5A | 119.2 | C20—C25—H25B | 109.2 |
C6—C5—H5A | 119.2 | H25A—C25—H25B | 107.9 |
C5—C6—C1 | 117.7 (3) | C27—C26—C24 | 111.6 (3) |
C5—C6—C7 | 121.9 (3) | C27—C26—H26A | 109.3 |
C1—C6—C7 | 120.1 (3) | C24—C26—H26A | 109.3 |
C6—C7—C8 | 110.4 (2) | C27—C26—H26B | 109.3 |
C6—C7—H7A | 109.6 | C24—C26—H26B | 109.3 |
C8—C7—H7A | 109.6 | H26A—C26—H26B | 108.0 |
C6—C7—H7B | 109.6 | C32—C27—C28 | 117.3 (4) |
C8—C7—H7B | 109.6 | C32—C27—C26 | 120.2 (3) |
H7A—C7—H7B | 108.1 | C28—C27—C26 | 122.4 (4) |
C13—C8—C9 | 118.8 (3) | C29—C28—C27 | 121.2 (4) |
C13—C8—C7 | 122.9 (3) | C29—C28—H28A | 119.4 |
C9—C8—C7 | 118.2 (3) | C27—C28—H28A | 119.4 |
C10—C9—C8 | 121.1 (3) | C30—C29—C28 | 120.5 (3) |
C10—C9—H9A | 119.5 | C30—C29—H29A | 119.8 |
C8—C9—H9A | 119.5 | C28—C29—H29A | 119.8 |
C9—C10—C11 | 119.3 (3) | C29—C30—C31 | 121.3 (4) |
C9—C10—H10A | 120.4 | C29—C30—H30A | 119.3 |
C11—C10—H10A | 120.4 | C31—C30—H30A | 119.3 |
C10—C11—C12 | 121.8 (3) | C32—C31—C30 | 117.3 (4) |
C10—C11—H11A | 119.1 | C32—C31—C14i | 120.5 (3) |
C12—C11—H11A | 119.1 | C30—C31—C14i | 122.0 (4) |
C11—C12—C13 | 118.0 (3) | O1—C32—C31 | 119.3 (3) |
C11—C12—C14 | 119.2 (3) | O1—C32—C27 | 118.3 (3) |
C13—C12—C14 | 122.6 (3) | C31—C32—C27 | 122.2 (3) |
C8—C13—O3 | 119.1 (2) | C34—C33—O1 | 106.3 (4) |
C8—C13—C12 | 121.1 (2) | C34—C33—H33A | 110.5 |
O3—C13—C12 | 119.8 (3) | O1—C33—H33A | 110.5 |
C31i—C14—C12 | 110.5 (2) | C34—C33—H33B | 110.5 |
C31i—C14—H14A | 109.6 | O1—C33—H33B | 110.5 |
C12—C14—H14A | 109.6 | H33A—C33—H33B | 108.7 |
C31i—C14—H14B | 109.6 | C33—C34—C35 | 115.7 (6) |
C12—C14—H14B | 109.6 | C33—C34—H34A | 108.3 |
H14A—C14—H14B | 108.1 | C35—C34—H34A | 108.3 |
O3—C15—C16 | 109.0 (4) | C33—C34—H34D | 108.3 |
O3—C15—H15A | 109.9 | C35—C34—H34D | 108.3 |
C16—C15—H15A | 109.9 | H34A—C34—H34D | 107.4 |
O3—C15—H15B | 109.9 | C34—C35—C36 | 114.2 (13) |
C16—C15—H15B | 109.9 | C34—C35—H35A | 108.7 |
H15A—C15—H15B | 108.3 | C36—C35—H35A | 108.7 |
C17—C16—C15 | 116.0 (5) | C34—C35—H35B | 108.7 |
C17—C16—H16A | 108.3 | C36—C35—H35B | 108.7 |
C15—C16—H16A | 108.3 | H35A—C35—H35B | 107.6 |
C17—C16—H16B | 108.3 | O2—C36—C35 | 117 (2) |
C15—C16—H16B | 108.3 | O2—C36—H36A | 108.1 |
H16A—C16—H16B | 107.4 | C35—C36—H36A | 108.1 |
C18—C17—C16 | 116.4 (5) | O2—C36—H36B | 108.1 |
C18—C17—H17A | 108.2 | C35—C36—H36B | 108.1 |
C16—C17—H17A | 108.2 | H36A—C36—H36B | 107.3 |
C18—C17—H17D | 108.2 | C34B—C33B—O1 | 108.2 (5) |
C16—C17—H17D | 108.2 | C34B—C33B—H33C | 110.1 |
H17A—C17—H17D | 107.3 | O1—C33B—H33C | 110.1 |
O4—C18—C17 | 111.8 (5) | C34B—C33B—H33D | 110.1 |
O4—C18—H18A | 109.3 | O1—C33B—H33D | 110.1 |
C17—C18—H18A | 109.3 | H33C—C33B—H33D | 108.4 |
O4—C18—H18B | 109.3 | C33B—C34B—C35B | 114.0 (7) |
C17—C18—H18B | 109.3 | C33B—C34B—H34B | 108.7 |
H18A—C18—H18B | 107.9 | C35B—C34B—H34B | 108.7 |
O3—C15B—C16B | 108.0 (5) | C33B—C34B—H34C | 108.7 |
O3—C15B—H15C | 110.1 | C35B—C34B—H34C | 108.7 |
C16B—C15B—H15C | 110.1 | H34B—C34B—H34C | 107.6 |
O3—C15B—H15D | 110.1 | C34B—C35B—C36B | 114.5 (15) |
C16B—C15B—H15D | 110.1 | C34B—C35B—H35C | 108.6 |
H15C—C15B—H15D | 108.4 | C36B—C35B—H35C | 108.6 |
C17B—C16B—C15B | 117.4 (7) | C34B—C35B—H35D | 108.6 |
C17B—C16B—H16C | 108.0 | C36B—C35B—H35D | 108.6 |
C15B—C16B—H16C | 108.0 | H35C—C35B—H35D | 107.6 |
C17B—C16B—H16D | 108.0 | O2—C36B—C35B | 115 (2) |
C15B—C16B—H16D | 108.0 | O2—C36B—H36C | 108.4 |
H16C—C16B—H16D | 107.2 | C35B—C36B—H36C | 108.4 |
C16B—C17B—C18B | 117.3 (7) | O2—C36B—H36D | 108.4 |
C16B—C17B—H17B | 108.0 | C35B—C36B—H36D | 108.4 |
C18B—C17B—H17B | 108.0 | H36C—C36B—H36D | 107.5 |
C16B—C17B—H17C | 108.0 | C1B—C2B—C3B | 122.0 (4) |
C18B—C17B—H17C | 108.0 | C1B—C2B—H2BA | 119.0 |
H17B—C17B—H17C | 107.2 | C3B—C2B—H2BA | 119.0 |
O4—C18B—C17B | 109.8 (6) | C2B—C3B—C1Bii | 119.9 (5) |
O4—C18B—H18C | 109.7 | C2B—C3B—H3BA | 120.0 |
C17B—C18B—H18C | 109.7 | C1Bii—C3B—H3BA | 120.0 |
O4—C18B—H18D | 109.7 | C2B—C1B—C3Bii | 118.1 (5) |
C17B—C18B—H18D | 109.7 | C2B—C1B—H1BA | 121.0 |
H18C—C18B—H18D | 108.2 | C3Bii—C1B—H1BA | 121.0 |
C20—C19—O4 | 119.9 (3) | ||
C36—O2—C1—C6 | −81.0 (18) | C18—O4—C19—C20 | 107.8 (4) |
C36B—O2—C1—C6 | −88 (2) | C18B—O4—C19—C24 | −111.5 (5) |
C36—O2—C1—C2 | 102.7 (17) | C18—O4—C19—C24 | −73.8 (4) |
C36B—O2—C1—C2 | 95 (2) | O4—C19—C20—C21 | −177.2 (2) |
O2—C1—C2—C3 | 178.3 (2) | C24—C19—C20—C21 | 4.5 (4) |
C6—C1—C2—C3 | 2.0 (4) | O4—C19—C20—C25 | 5.5 (4) |
O2—C1—C2—C25i | 1.7 (4) | C24—C19—C20—C25 | −172.8 (3) |
C6—C1—C2—C25i | −174.6 (2) | C19—C20—C21—C22 | −1.1 (5) |
C1—C2—C3—C4 | 0.7 (4) | C25—C20—C21—C22 | 176.3 (3) |
C25i—C2—C3—C4 | 177.1 (3) | C20—C21—C22—C23 | −2.0 (5) |
C2—C3—C4—C5 | −3.0 (5) | C21—C22—C23—C24 | 1.9 (5) |
C3—C4—C5—C6 | 2.6 (5) | C22—C23—C24—C19 | 1.4 (5) |
C4—C5—C6—C1 | 0.1 (4) | C22—C23—C24—C26 | −176.2 (3) |
C4—C5—C6—C7 | −173.9 (3) | C20—C19—C24—C23 | −4.6 (4) |
O2—C1—C6—C5 | −178.6 (2) | O4—C19—C24—C23 | 177.0 (3) |
C2—C1—C6—C5 | −2.5 (4) | C20—C19—C24—C26 | 172.8 (3) |
O2—C1—C6—C7 | −4.6 (4) | O4—C19—C24—C26 | −5.5 (4) |
C2—C1—C6—C7 | 171.6 (3) | C21—C20—C25—C2i | −60.7 (4) |
C5—C6—C7—C8 | 109.6 (3) | C19—C20—C25—C2i | 116.6 (3) |
C1—C6—C7—C8 | −64.2 (3) | C23—C24—C26—C27 | 59.7 (4) |
C6—C7—C8—C13 | 122.4 (3) | C19—C24—C26—C27 | −117.7 (3) |
C6—C7—C8—C9 | −53.7 (4) | C24—C26—C27—C32 | 69.7 (4) |
C13—C8—C9—C10 | −0.9 (5) | C24—C26—C27—C28 | −105.5 (4) |
C7—C8—C9—C10 | 175.3 (3) | C32—C27—C28—C29 | −1.4 (5) |
C8—C9—C10—C11 | −0.7 (5) | C26—C27—C28—C29 | 174.0 (3) |
C9—C10—C11—C12 | 0.3 (5) | C27—C28—C29—C30 | −1.7 (6) |
C10—C11—C12—C13 | 1.7 (5) | C28—C29—C30—C31 | 1.5 (6) |
C10—C11—C12—C14 | −173.8 (3) | C29—C30—C31—C32 | 1.8 (5) |
C9—C8—C13—O3 | 179.4 (3) | C29—C30—C31—C14i | −172.4 (3) |
C7—C8—C13—O3 | 3.3 (4) | C33B—O1—C32—C31 | −67.4 (4) |
C9—C8—C13—C12 | 3.0 (4) | C33—O1—C32—C31 | −115.3 (4) |
C7—C8—C13—C12 | −173.1 (3) | C33B—O1—C32—C27 | 117.5 (4) |
C15—O3—C13—C8 | 105.6 (4) | C33—O1—C32—C27 | 69.6 (4) |
C15B—O3—C13—C8 | 67.4 (4) | C30—C31—C32—O1 | −179.8 (3) |
C15—O3—C13—C12 | −78.0 (4) | C14i—C31—C32—O1 | −5.6 (4) |
C15B—O3—C13—C12 | −116.2 (4) | C30—C31—C32—C27 | −5.0 (5) |
C11—C12—C13—C8 | −3.4 (4) | C14i—C31—C32—C27 | 169.3 (3) |
C14—C12—C13—C8 | 171.9 (3) | C28—C27—C32—O1 | 179.7 (3) |
C11—C12—C13—O3 | −179.7 (3) | C26—C27—C32—O1 | 4.2 (5) |
C14—C12—C13—O3 | −4.4 (4) | C28—C27—C32—C31 | 4.8 (5) |
C11—C12—C14—C31i | 56.5 (4) | C26—C27—C32—C31 | −170.7 (3) |
C13—C12—C14—C31i | −118.8 (3) | C32—O1—C33—C34 | 85.6 (5) |
C13—O3—C15—C16 | 175.6 (4) | C33B—O1—C33—C34 | −15.3 (5) |
C15B—O3—C15—C16 | −90.7 (7) | O1—C33—C34—C35 | 167.7 (8) |
O3—C15—C16—C17 | 72.4 (6) | C33—C34—C35—C36 | −52.3 (18) |
C15—C16—C17—C18 | 179.0 (5) | C1—O2—C36—C35 | −32 (3) |
C19—O4—C18—C17 | 175.6 (4) | C36B—O2—C36—C35 | 95 (19) |
C18B—O4—C18—C17 | −92.3 (8) | C34—C35—C36—O2 | −160 (2) |
C16—C17—C18—O4 | 80.8 (6) | C32—O1—C33B—C34B | −81.5 (6) |
C13—O3—C15B—C16B | −166.0 (5) | C33—O1—C33B—C34B | 17.9 (5) |
C15—O3—C15B—C16B | 92.3 (8) | O1—C33B—C34B—C35B | −165.5 (8) |
O3—C15B—C16B—C17B | −66.8 (8) | C33B—C34B—C35B—C36B | 60 (2) |
C15B—C16B—C17B—C18B | −175.3 (7) | C1—O2—C36B—C35B | 4 (4) |
C19—O4—C18B—C17B | −168.4 (6) | C36—O2—C36B—C35B | −53 (16) |
C18—O4—C18B—C17B | 88.7 (9) | C34B—C35B—C36B—O2 | 168 (2) |
C16B—C17B—C18B—O4 | −78.3 (9) | C1B—C2B—C3B—C1Bii | 0.8 (7) |
C18B—O4—C19—C20 | 70.1 (5) | C3B—C2B—C1B—C3Bii | −0.7 (7) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C72H72O8·C6H6 |
Mr | 1143.40 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 123 |
a, b, c (Å) | 14.8804 (10), 17.3004 (11), 12.1888 (8) |
β (°) | 103.929 (7) |
V (Å3) | 3045.6 (3) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 0.62 |
Crystal size (mm) | 0.87 × 0.35 × 0.03 |
Data collection | |
Diffractometer | Agilent Xcalibur (Ruby, Gemini) |
Absorption correction | Analytical (CrysAlis PRO; Agilent, 2012; Clark & Reid, 1995) |
Tmin, Tmax | 0.795, 0.982 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9972, 9972, 5548 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.629 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.078, 0.249, 1.00 |
No. of reflections | 9972 |
No. of parameters | 415 |
No. of restraints | 10 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.03, −0.24 |
Computer programs: CrysAlis PRO (Agilent, 2012), CrysAlis RED (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
RJB wishes to acknowledge the NSF–MRI program (grant CHE-0619278) for funds to purchase the diffractometer. STH wishes to acknowledge the Howard University Graduate School for a Teaching Assistantship.
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Calixarenes are macrocyclic molecules made up of phenol and methylene units. The ease of their preparation and chemical modification coupled with the easily isolable reaction products makes them ideal starting materials for the construction of host molecules with different properties (Asfari et al., 2001, Gutsche, 2008). Unsubstituted calixarenes have flexible conformations at higher temperatures, and controlling the conformations of calixarenes is an important subject to pursue for better knowledge of the complexing ability of these molecules for various guest ions and molecules. An olefin metathesis reaction (Vougioukalakis & Grubbs, 2010) has been used to prepare bridged calixarenes (Yang & Swager, 2007). In our first attempt to prepare a bridged calixarene by olefin metathesis, the reaction of tetrakis(allyloxy)calix[4]arene with the first generation Grubbs catalyst gave a novel dimeric calixarene with a complex chiral structure (Hailu et al., 2012). In our further investigation of this approach, catalytic hydrogenation of the initial metathesis product gave a small amount of a novel bis-calixarene. In contrast to the chiral structure prepared earlier, the present compound has a very symmetric structure. The two calix[4]arene units which are joined by covalent bonds of (CH2)4 groups have flattened cone conformations. The degree of flattening of a cone calix[4]arene has been characterized (Arduini et al., 1995; Arduini et al., 1996; Drew et al., 1997) using the dihedral angles between the plane of the four methylene linkers with the phenolic rings. These angles are 83.02 (8)° and 89.67 (8)° for rings B and D, respectively, which are almost parallel to each other, and 145.47 (8)° and 142.32 (7)° for rings A and C, respectively, which are inclined outwards.
Figure 2 shows the molecular packing for the bis-calix[4]arene, C72H72O8. The recrystallization solvent, benzene, used in this experiment is shown in the lattice but outside the calixarene cavity.