1,3-Bridged p-methyloctahomotetraoxacalix[4]arene-bis-crown-3

The title compound, 13,21,35,43-tetra­methyl-3,6,9,17,25,28,31,39,46,49-decaoxahepta­cyclo­[21.21.3.3^11,33.0^2,41.0^10,15.0^19,24.0^32,37]pentaconta-1,10,12,14,19,21,23,32,34,36,41,43-dodecaene, C₄₄H₅₂O₁₀, differs from previously reported 1,3-bridged calix­[4]­arene-bis-crown compounds in having an enlarged calixarene ring and shorter polyoxy­ethyl­ene bridges. The cavity is partly filled by the bridges.

S1. Comment

In octahomotetraoxacalix[4]arenes, the CH₂ groups linking the aromatics in the typical calix[4]arene series are replaced by CH₂OCH₂ units (Masci, 2001). Although the same main conformations as in calix[4]arene can be considered, the size and flexibility of the ring are much increased (Masci et al., 1998) and lower rim substituents can be partly included in the cavity (Masci et al., 2001).

In the present study, the tricyclic derivative, (I), has distal aromatic rings bridged at the lower rim by dioxyethylene chains, thus forcing the compound to adopt a highly distorted 1,3-alternate conformation. Some bis-crown[n]ether (n = 5–7) compounds with the 1,3–2,4 bridging pattern have been investigated in the calix[4]erene series, and in all reported cases moderate deviations from a regular 1,3-alternate arrangement have been observed, the opposed aromatic units being almost parallel and the molecule having an elongated globular shape (Casnati et al., 2001; Thuéry et al., 2000). \sch

The enlarged calixarene ring and the shorter polyoxyethylene bridges account for the different shape of (I). The least-squares planes P1, P2, P3 and P4, defined by the four aromatic rings 1, 2, 3 and 4 containing atoms C11, C21, C31 and C41, respectively (Fig. 1), form dihedral angles between vicinal aromatics which are small in the case of rings P2 and P3 [24.6 (1)°] and large in the case of rings P1 and P2, P3 and P4, and P1 and P4 [74.4 (1), 74.9 (1) and 68.9 (1)°, respectively]. A reference least-squares plane defined by atoms O1, O2, O3 and O4 is intersected by planes P1, P2, P3 and P4 with dihedral angles of 68.0 (1), 21.8 (1), 14.3 (1) and 72.1 (1)°, respectively. On extending to homooxacalixarenes the notation of Kanamathareddy & Gutsche (1993), the conformation can be indicated as u, do, uo, d.

Apart from the orientation of the aromatic rings, the conformation of homooxacalixarenes relies on the arrangement of the ArCH₂OCH₂Ar units that are usually found to be in anti-anti or anti-gauche conformation. In the case of (I), opposite ArCH₂OCH₂Ar units are in the same gross conformation, namely almost anti-gauche around atoms O2 and O4, and gauche-gauche around atoms O1 and O3 [torsion angles 73.0 (5) and -63.4 (5)° around O1, 159.4 (4) and -73.6 (5)° around O2, 72.4 (4) and -73.3 (4)° around O3, and 158.0 (4) and -66.9 (5)° around O4.

The relatively short bridges at the lower rim are apparently responsible for the unusual conformation of the latter, which has only previously been observed in the related bicyclic compound, (II) (Masci et al., 2001). In the bicyclic compound, the methoxy-substituted aromatics are almost perpendicular to the plane defined by the ArCH₂OCH₂Ar O atoms [dihedral angles 79.7 (1) and 80.6 (1)°]. Another difference between the bicyclic and the tricyclic compounds lies in the conformation of the dioxyethylene bridges, which are anti, gauche, gauche, gauche, gauche, anti in the bicycle, (II), and almost anti, anti, gauche, anti, gauche, anti for both bridges of the present macrotricycle, (I). In fact, in (I), the torsion angles are 178.9 (4), 179.7 (4), -97.3 (5), -166.7 (4), 78.6 (5) and 173.9 (4)° from ring 1 to ring 3, and -166.2 (3), 175.1 (3), 84.4 (4), -162.2 (3), 74.6 (4) and 171.9 (3)° from ring 4 to ring 2.

The bridges in (I) partly fill the potential cavity formed by the two opposed aromatics and are not in close contact. The self-filled structure prevents the intermolecular inclusion noted in the related bicycle, (II); the closest intermolecular contact detected in (I), namely H33···O1ⁱ 2.37 Å, C33···O1ⁱ 3.317 (3) Å and C33—H33···O1ⁱ 168° [symmetry code: (i) x, 1 + y, z], corresponds to a weak C—H···O hydrogen bond (Desiraju & Steiner, 1999).

S2. Experimental

Compound (I) was synthesized as reported by Masci & Saccheo (1993) and was recrystallized from benzene.

S3. Refinement

The H atoms attached to atoms C17, C27 and C37 appeared as annular regions of electron density and were introduced in calculated positions (C—H = 0.95–0.97 Å) corresponding to two possible opposite conformations. One of these was such that one C—H bond was oriented normal to and the remaining C—H bonds below the aromatic ring. Only the occupancy was refined for these methyl H atoms. All other H atoms showed up clearly in a difference synthesis, with the exception of the two H atoms on C51, which were introduced in calculated positions. For all H atoms, a riding model was used in the final refinement and their displacement parameters were kept equal to those of the parent atom.

Computing details

Data collection: XCS (Colapietro et al., 1992); cell refinement: XCS; data reduction: XCS; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: CAOS (Camalli & Spagna, 1994); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: CAOS and PARST97 (Nardelli, 1995).

Figures

Fig. 1. A view of the molecule of (I) in the crystal with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The methyl groups at C17, C27 and C37 are shown in the most populated conformation.

13,21,35,43-tetramethyl-3,6,9,17,25,28,31,39,46,49- decaoxaheptacyclo[21.21.3^1,23.3^11,33.0^2,41.0^10,15.0^19,24.0^32,37] pentaconta-1,10,12,14,19,21,23,32,34,36,41,43-dodecaene

Crystal data

C44H52O10	F(000) = 3168
Mr = 740.89	Dx = 1.240 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71069 Å
a = 29.982 (5) Å	Cell parameters from 16 reflections
b = 14.154 (3) Å	θ = 14.0–18.0°
c = 27.612 (2) Å	µ = 0.09 mm^−1
β = 137.36 (3)°	T = 293 K
V = 7937 (5) Å^3	Prism, colourless
Z = 8	0.3 × 0.2 × 0.2 mm

Data collection

Huber CS four-circle diffractometer	Rint = 0.022
Radiation source: X-ray tube	θmax = 28.0°, θmin = 2.2°
Graphite monochromator	h = 0→39
ω scans	k = 0→18
11136 measured reflections	l = −35→24
9464 independent reflections	3 standard reflections every 97 reflections
4754 reflections with F > 3σ(F)	intensity decay: none

Refinement

Refinement on F	496 parameters
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.052	w = 1/(3.7038 + 0.0304F + 0.0009F^2)
wR(F^2) = 0.067	(Δ/σ)max < 0.001
S = 0.85	Δρmax = 0.18 e Å^−3
4754 reflections	Δρmin = −0.19 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.7651 (1)	0.1921 (1)	0.6194 (1)	0.069 (2)
O2	0.5379 (1)	0.5344 (1)	0.4746 (1)	0.069 (2)
O3	0.6584 (1)	0.9746 (1)	0.5516 (1)	0.070 (2)
O4	0.8762 (1)	0.6499 (1)	0.6917 (1)	0.069 (2)
O5	0.6384 (1)	0.3699 (1)	0.5916 (1)	0.063 (2)
O6	0.6358 (1)	0.7089 (2)	0.4778 (1)	0.065 (2)
O7	0.7419 (1)	0.7388 (1)	0.6641 (1)	0.068 (2)
O8	0.8249 (1)	0.4442 (1)	0.6031 (1)	0.059 (2)
O9	0.7360 (1)	0.5645 (2)	0.7163 (1)	0.083 (3)
O10	0.6725 (1)	0.5573 (1)	0.4431 (1)	0.062 (2)
C11	0.6181 (1)	0.3357 (2)	0.5303 (2)	0.051 (3)
C12	0.6544 (1)	0.2631 (2)	0.5382 (2)	0.054 (3)
C13	0.6319 (2)	0.2259 (2)	0.4765 (2)	0.061 (3)
C14	0.5757 (2)	0.2596 (2)	0.4092 (2)	0.062 (3)
C15	0.5406 (1)	0.3310 (2)	0.4042 (2)	0.059 (3)
C16	0.5601 (1)	0.3702 (2)	0.4634 (2)	0.053 (3)
C18	0.7149 (2)	0.2222 (2)	0.6113 (2)	0.069 (3)
C19	0.5155 (2)	0.4381 (2)	0.4544 (2)	0.069 (4)
C21	0.5832 (1)	0.7475 (2)	0.4608 (2)	0.053 (3)
C22	0.5326 (2)	0.6889 (2)	0.4366 (2)	0.056 (3)
C23	0.4818 (2)	0.7279 (2)	0.4229 (2)	0.057 (3)
C24	0.4802 (1)	0.8243 (2)	0.4334 (2)	0.053 (2)
C25	0.5317 (1)	0.8803 (2)	0.4579 (2)	0.055 (2)
C26	0.5835 (1)	0.8446 (2)	0.4721 (1)	0.053 (2)
C27	0.4241 (2)	0.8657 (3)	0.4170 (2)	0.073 (3)
C28	0.5321 (2)	0.5837 (2)	0.4251 (2)	0.071 (4)
C29	0.6388 (2)	0.9085 (2)	0.5000 (2)	0.068 (3)
C31	0.7848 (2)	0.8087 (2)	0.6811 (2)	0.055 (3)
C32	0.7620 (2)	0.9021 (2)	0.6585 (2)	0.055 (2)
C33	0.8053 (2)	0.9692 (2)	0.6739 (2)	0.055 (3)
C34	0.8680 (2)	0.9469 (2)	0.7090 (2)	0.058 (3)
C35	0.8889 (2)	0.8532 (2)	0.7306 (2)	0.063 (3)
C36	0.8476 (2)	0.7834 (2)	0.7165 (2)	0.058 (3)
C38	0.6934 (2)	0.9305 (2)	0.6181 (2)	0.067 (3)
C39	0.8717 (2)	0.6821 (2)	0.7372 (2)	0.072 (4)
C41	0.8531 (1)	0.4200 (2)	0.6700 (2)	0.051 (3)
C42	0.8978 (2)	0.4810 (2)	0.7276 (2)	0.057 (3)
C43	0.9244 (2)	0.4543 (2)	0.7932 (2)	0.063 (3)
C44	0.9083 (2)	0.3686 (2)	0.8025 (2)	0.062 (3)
C45	0.8659 (2)	0.3079 (2)	0.7442 (2)	0.060 (3)
C46	0.8378 (1)	0.3321 (2)	0.6774 (2)	0.053 (3)
C47	0.9368 (2)	0.3430 (3)	0.8742 (2)	0.086 (4)
C48	0.9201 (2)	0.5718 (2)	0.7212 (2)	0.072 (4)
C49	0.7930 (2)	0.2656 (2)	0.6138 (2)	0.067 (3)
C50	0.6795 (2)	0.4539 (2)	0.6215 (2)	0.069 (3)
C52	0.6991 (2)	0.6462 (2)	0.6944 (2)	0.076 (4)
C53	0.7415 (2)	0.7308 (2)	0.7156 (2)	0.073 (4)
C60	0.6303 (2)	0.7118 (2)	0.4217 (2)	0.064 (3)
C61	0.6867 (2)	0.6549 (2)	0.4470 (2)	0.060 (3)
C62	0.7294 (2)	0.4991 (2)	0.4850 (2)	0.063 (3)
C63	0.7646 (2)	0.4971 (2)	0.5606 (2)	0.067 (3)
C17	0.5518 (2)	0.2184 (5)	0.3430 (2)	0.094 (4)
C37	0.9125 (2)	1.0212 (3)	0.7224 (2)	0.080 (3)
C51	0.6955 (3)	0.4813 (2)	0.6841 (2)	0.097 (5)
H13	0.6583	0.1751	0.4824	0.061*
H15	0.5020	0.3553	0.3603	0.058*
H23	0.4468	0.6886	0.4054	0.054*
H25	0.5328	0.9455	0.4685	0.052*
H33	0.7889	1.0324	0.6579	0.054*
H35	0.9337	0.8356	0.7572	0.062*
H43	0.9551	0.4920	0.8328	0.062*
H45	0.8551	0.2477	0.7504	0.060*
H181	0.7348	0.2681	0.6498	0.07*
H182	0.7049	0.1711	0.6238	0.07*
H191	0.5099	0.4136	0.4847	0.07*
H192	0.4706	0.4404	0.4018	0.07*
H281	0.5692	0.5665	0.4328	0.07*
H282	0.4916	0.5630	0.3797	0.07*
H291	0.6778	0.8700	0.5195	0.067*
H292	0.6263	0.9438	0.4620	0.067*
H381	0.6703	0.8798	0.6116	0.066*
H382	0.6966	0.9805	0.6466	0.07*
H391	0.9170	0.6788	0.7855	0.07*
H392	0.8386	0.6426	0.7301	0.07*
H481	0.9243	0.5636	0.6896	0.07*
H482	0.9650	0.5901	0.7692	0.07*
H491	0.7543	0.3008	0.5660	0.07*
H492	0.8223	0.2325	0.6133	0.07*
H501	0.7220	0.4429	0.6371	0.07*
H502	0.6508	0.5026	0.5823	0.07*
H521	0.6595	0.6406	0.6405	0.07*
H522	0.6866	0.6500	0.7190	0.07*
H531	0.7891	0.7212	0.7630	0.07*
H532	0.7194	0.7895	0.7141	0.07*
H601	0.5861	0.6816	0.3771	0.06*
H602	0.6321	0.7786	0.4112	0.062*
H611	0.7311	0.6745	0.5008	0.060*
H612	0.6918	0.6673	0.4163	0.060*
H621	0.7616	0.5223	0.4854	0.062*
H622	0.7118	0.4348	0.4623	0.06*
H631	0.7735	0.5558	0.5795	0.067*
H632	0.7347	0.4680	0.5632	0.07*
H171	0.5719	0.2514	0.3324	0.098*	0.578
H172	0.5647	0.1524	0.3516	0.098*	0.634
H173	0.5053	0.2233	0.3041	0.098*	0.615
H174	0.5227	0.1667	0.3262	0.098*	0.422
H175	0.5300	0.2657	0.3072	0.098*	0.366
H176	0.5893	0.1948	0.3547	0.098*	0.385
H271	0.3901	0.8866	0.3681	0.07*	0.666
H272	0.4062	0.8186	0.4242	0.07*	0.552
H273	0.4395	0.9183	0.4481	0.07*	0.671
H274	0.4338	0.8624	0.4588	0.07*	0.334
H275	0.4177	0.9304	0.4028	0.07*	0.448
H276	0.3843	0.8307	0.3789	0.07*	0.329
H371	0.9067	1.0222	0.6830	0.079*	0.731
H372	0.9024	1.0816	0.7274	0.079*	0.640
H373	0.9580	1.0058	0.7656	0.079*	0.735
H374	0.9381	1.0509	0.7676	0.079*	0.269
H375	0.9423	0.9914	0.7233	0.079*	0.360
H376	0.8867	1.0673	0.6851	0.079*	0.265
H471	0.9202	0.3805	0.8870	0.09*
H472	0.9274	0.2789	0.8757	0.09*
H473	0.9835	0.3507	0.9102	0.09*
H511	0.6555	0.4940	0.6696	0.096*
H512	0.7188	0.4307	0.7183	0.096*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.061 (1)	0.047 (1)	0.091 (2)	0.004 (1)	0.053 (1)	0.007 (1)
O2	0.105 (2)	0.047 (1)	0.083 (2)	0.016 (1)	0.078 (2)	0.013 (1)
O3	0.068 (1)	0.047 (1)	0.069 (1)	−0.001 (1)	0.042 (1)	0.004 (1)
O4	0.106 (2)	0.044 (1)	0.082 (2)	0.003 (1)	0.077 (2)	0.001 (1)
O5	0.088 (2)	0.052 (1)	0.073 (1)	−0.013 (1)	0.067 (1)	−0.009 (1)
O6	0.070 (1)	0.080 (2)	0.059 (1)	0.025 (1)	0.052 (1)	0.019 (1)
O7	0.096 (2)	0.051 (1)	0.071 (1)	−0.017 (1)	0.066 (1)	−0.012 (1)
O8	0.065 (1)	0.058 (1)	0.070 (1)	0.011 (1)	0.055 (1)	0.010 (1)
O9	0.115 (2)	0.047 (1)	0.085 (2)	−0.003 (1)	0.072 (2)	−0.002 (1)
O10	0.061 (1)	0.055 (1)	0.064 (1)	0.001 (1)	0.044 (1)	−0.001 (1)
C11	0.066 (2)	0.043 (2)	0.063 (2)	−0.003 (1)	0.053 (2)	−0.001 (1)
C12	0.055 (2)	0.045 (2)	0.067 (2)	−0.000 (1)	0.046 (2)	0.002 (1)
C13	0.061 (2)	0.052 (2)	0.080 (2)	0.003 (1)	0.055 (2)	−0.005 (2)
C14	0.061 (2)	0.071 (2)	0.068 (2)	−0.005 (2)	0.051 (2)	−0.011 (2)
C15	0.057 (2)	0.063 (2)	0.063 (2)	0.007 (1)	0.045 (2)	0.009 (2)
C16	0.065 (2)	0.042 (2)	0.073 (2)	0.004 (1)	0.057 (2)	0.006 (1)
C18	0.064 (2)	0.069 (2)	0.075 (2)	0.010 (2)	0.052 (2)	0.021 (2)
C19	0.090 (2)	0.046 (2)	0.106 (3)	0.013 (2)	0.083 (2)	0.013 (2)
C21	0.061 (2)	0.055 (2)	0.053 (2)	0.012 (1)	0.045 (2)	0.011 (1)
C22	0.075 (2)	0.046 (2)	0.056 (2)	0.008 (1)	0.051 (2)	0.007 (1)
C23	0.064 (2)	0.051 (2)	0.059 (2)	−0.006 (1)	0.046 (2)	−0.001 (1)
C24	0.056 (2)	0.052 (2)	0.053 (2)	0.002 (1)	0.040 (2)	0.002 (1)
C25	0.059 (2)	0.045 (2)	0.054 (2)	0.005 (1)	0.040 (2)	0.002 (1)
C26	0.052 (2)	0.053 (2)	0.047 (2)	0.001 (1)	0.034 (1)	0.005 (1)
C27	0.070 (2)	0.071 (2)	0.087 (2)	0.010 (2)	0.060 (2)	0.004 (2)
C28	0.109 (3)	0.048 (2)	0.082 (2)	0.006 (2)	0.078 (2)	0.004 (2)
C29	0.062 (2)	0.074 (2)	0.061 (2)	−0.009 (2)	0.043 (2)	0.003 (2)
C31	0.077 (2)	0.042 (2)	0.053 (2)	−0.009 (1)	0.049 (2)	−0.007 (1)
C32	0.066 (2)	0.046 (2)	0.047 (2)	0.001 (1)	0.040 (2)	−0.001 (1)
C33	0.065 (2)	0.038 (2)	0.053 (2)	−0.000 (1)	0.040 (2)	−0.001 (1)
C34	0.066 (2)	0.049 (2)	0.049 (2)	−0.008 (1)	0.038 (2)	−0.005 (1)
C35	0.066 (2)	0.057 (2)	0.055 (2)	0.007 (2)	0.041 (2)	0.003 (1)
C36	0.081 (2)	0.043 (2)	0.054 (2)	0.005 (2)	0.051 (2)	0.002 (1)
C38	0.068 (2)	0.063 (2)	0.063 (2)	−0.003 (2)	0.046 (2)	−0.006 (2)
C39	0.109 (3)	0.050 (2)	0.076 (2)	0.019 (2)	0.074 (2)	0.012 (2)
C41	0.056 (2)	0.046 (2)	0.065 (2)	0.009 (1)	0.049 (2)	0.007 (1)
C42	0.064 (2)	0.045 (2)	0.076 (2)	0.005 (1)	0.057 (2)	0.000 (1)
C43	0.065 (2)	0.052 (2)	0.068 (2)	0.005 (2)	0.047 (2)	−0.004 (2)
C44	0.062 (2)	0.059 (2)	0.063 (2)	0.015 (2)	0.046 (2)	0.009 (2)
C45	0.064 (2)	0.052 (2)	0.073 (2)	0.008 (2)	0.052 (2)	0.012 (2)
C46	0.050 (2)	0.046 (2)	0.066 (2)	0.006 (1)	0.044 (2)	0.004 (1)
C47	0.097 (3)	0.090 (3)	0.076 (2)	0.018 (2)	0.065 (2)	0.015 (2)
C48	0.087 (2)	0.051 (2)	0.102 (3)	−0.004 (2)	0.077 (2)	−0.005 (2)
C49	0.062 (2)	0.059 (2)	0.080 (2)	−0.010 (2)	0.052 (2)	−0.006 (2)
C50	0.089 (2)	0.058 (2)	0.075 (2)	−0.017 (2)	0.065 (2)	−0.012 (2)
C52	0.103 (3)	0.053 (2)	0.104 (3)	−0.007 (2)	0.086 (3)	−0.007 (2)
C53	0.108 (3)	0.049 (2)	0.091 (3)	−0.014 (2)	0.082 (2)	−0.011 (2)
C60	0.076 (2)	0.069 (2)	0.061 (2)	0.016 (2)	0.055 (2)	0.016 (2)
C61	0.070 (2)	0.057 (2)	0.068 (2)	0.004 (2)	0.056 (2)	0.005 (2)
C62	0.069 (2)	0.058 (2)	0.066 (2)	0.005 (2)	0.050 (2)	−0.002 (2)
C63	0.076 (2)	0.070 (2)	0.070 (2)	0.024 (2)	0.059 (2)	0.014 (2)
C17	0.078 (3)	0.130 (4)	0.082 (3)	−0.011 (2)	0.062 (2)	−0.033 (3)
C37	0.076 (2)	0.071 (2)	0.074 (2)	−0.019 (2)	0.049 (2)	−0.010 (2)
C51	0.169 (4)	0.051 (2)	0.102 (3)	−0.028 (2)	0.110 (3)	−0.019 (2)

Geometric parameters (Å, º)

O1—C18	1.416 (6)	C39—H392	1.025
O1—C49	1.414 (5)	C41—C42	1.39 (1)
O2—C19	1.438 (5)	C41—C46	1.392 (4)
O2—C28	1.425 (6)	C42—C43	1.39 (1)
O3—C29	1.421 (7)	C42—C48	1.519 (5)
O3—C38	1.423 (4)	C43—C44	1.397 (5)
O4—C39	1.431 (6)	C43—H43	0.920
O4—C48	1.429 (8)	C44—C45	1.39 (1)
O5—C11	1.397 (7)	C44—C47	1.51 (1)
O5—C50	1.455 (7)	C45—C46	1.40 (1)
O6—C21	1.385 (7)	C45—H45	0.969
O6—C60	1.433 (6)	C46—C49	1.52 (1)
O7—C31	1.402 (6)	C47—H471	0.957
O7—C53	1.437 (6)	C47—H472	0.960
O8—C41	1.396 (8)	C47—H473	0.954
O8—C63	1.445 (9)	C48—H481	0.975
O9—C52	1.393 (7)	C48—H482	1.005
O9—C51	1.436 (9)	C49—H491	1.040
O10—C61	1.426 (4)	C49—H492	1.003
O10—C62	1.423 (8)	C50—C51	1.47 (1)
C11—C12	1.393 (6)	C50—H501	1.011
C11—C16	1.40 (1)	C50—H502	1.008
C12—C13	1.394 (9)	C52—C53	1.514 (9)
C12—C18	1.52 (1)	C52—H521	1.015
C13—C14	1.38 (1)	C52—H522	0.992
C13—H13	0.990	C53—H531	1.009
C14—C15	1.389 (6)	C53—H532	1.045
C14—C17	1.51 (1)	C60—C61	1.500 (9)
C15—C16	1.386 (8)	C60—H601	1.027
C15—H15	0.929	C60—H602	1.001
C16—C19	1.511 (7)	C61—H611	1.071
C18—H181	0.987	C61—H612	0.984
C18—H182	0.938	C62—C63	1.50 (1)
C19—H191	1.026	C62—H621	1.011
C19—H192	1.023	C62—H622	1.006
C21—C22	1.395 (8)	C63—H631	0.910
C21—C26	1.409 (4)	C63—H632	1.036
C22—C23	1.386 (8)	C17—H171	0.962
C22—C28	1.520 (4)	C17—H172	0.971
C23—C24	1.403 (4)	C17—H173	0.948
C23—H23	0.948	C17—H174	0.959
C24—C25	1.389 (8)	C17—H175	0.949
C24—C27	1.505 (9)	C17—H176	0.973
C25—C26	1.388 (7)	C37—H371	0.968
C25—H25	0.960	C37—H372	0.950
C26—C29	1.512 (8)	C37—H373	0.968
C27—H271	0.962	C37—H374	0.956
C27—H272	0.963	C37—H375	0.974
C27—H273	0.959	C37—H376	0.956
C27—H274	0.961	C51—H511	0.960
C27—H275	0.959	C51—H512	0.960
C27—H276	0.963	H171—H175	0.905
C28—H281	0.999	H171—H176	0.905
C28—H282	0.945	H172—H174	0.905
C29—H291	1.014	H172—H176	0.905
C29—H292	0.956	H173—H174	0.905
C31—C32	1.406 (6)	H173—H175	0.905
C31—C36	1.39 (1)	H271—H275	0.905
C32—C33	1.398 (7)	H271—H276	0.905
C32—C38	1.50 (1)	H272—H274	0.905
C33—C34	1.38 (1)	H272—H276	0.905
C33—H33	0.958	H273—H274	0.905
C34—C35	1.400 (6)	H273—H275	0.905
C34—C37	1.516 (8)	H371—H375	0.905
C35—C36	1.397 (7)	H371—H376	0.905
C35—H35	0.976	H372—H374	0.905
C36—C39	1.515 (6)	H372—H376	0.905
C38—H381	0.920	H373—H374	0.905
C38—H382	1.010	H373—H375	0.905
C39—H391	0.980
C49—O1—C18	114.1 (3)	O1—C49—H492	104.6
C28—O2—C19	113.6 (5)	C46—C49—H492	105.6
C38—O3—C29	111.9 (3)	C46—C49—O1	114.7 (5)
C48—O4—C39	112.9 (5)	H491—C49—H492	112.2
C11—O5—C50	113.7 (3)	H491—C49—O1	107.0
C60—O6—C21	115.3 (6)	H491—C49—C46	112.5
C53—O7—C31	113.5 (5)	H501—C50—C51	108.7
C63—O8—C41	112.3 (3)	H502—C50—C51	111.4
C51—O9—C52	111.9 (7)	H502—C50—H501	112.1
C62—O10—C61	112.8 (5)	O5—C50—C51	106.8 (4)
C12—C11—O5	118.1 (3)	O5—C50—H501	113.1
C16—C11—O5	119.4 (4)	O5—C50—H502	104.6
C16—C11—C12	122.3 (6)	O9—C52—H522	109.0
C13—C12—C11	117.9 (7)	H521—C52—H522	112.4
C18—C12—C11	121.3 (6)	H521—C52—O9	105.8
C18—C12—C13	120.7 (4)	C53—C52—H522	109.0
C14—C13—C12	121.9 (4)	C53—C52—O9	108.5 (7)
H13—C13—C12	117.6	C53—C52—H521	112.0
H13—C13—C14	120.5	O7—C53—H532	111.4
C17—C14—C15	120.8 (8)	C52—C53—H532	106.7
C13—C14—C15	117.9 (6)	C52—C53—O7	107.1 (6)
C13—C14—C17	121.3 (5)	H531—C53—H532	114.1
C14—C15—C16	122.9 (8)	H531—C53—O7	105.1
H15—C15—C16	115.3	H531—C53—C52	112.3
H15—C15—C14	121.8	H601—C60—H602	110.1
C15—C16—C11	117.1 (4)	C61—C60—H602	111.2
C19—C16—C11	122.0 (5)	C61—C60—H601	110.7
C19—C16—C15	120.4 (3)	O6—C60—H602	110.5
H182—C18—C12	112.9	O6—C60—H601	107.7
H181—C18—C12	111.4	O6—C60—C61	106.6 (6)
H181—C18—H182	102.5	H612—C61—O10	109.5
O1—C18—C12	114.6 (5)	C60—C61—O10	108.4 (5)
O1—C18—H182	107.4	C60—C61—H612	109.8
O1—C18—H181	107.3	H611—C61—O10	110.7
H191—C19—C16	107.8	H611—C61—H612	109.0
O2—C19—C16	115.7 (6)	H611—C61—C60	109.4
O2—C19—H191	108.3	O10—C62—H621	112.6
H192—C19—C16	109.5	C63—C62—H621	107.7
H192—C19—H191	109.6	C63—C62—O10	109.8 (4)
H192—C19—O2	105.8	H622—C62—H621	111.2
C26—C21—O6	119.4 (5)	H622—C62—O10	104.5
C22—C21—O6	119.7 (3)	H622—C62—C63	111.1
C22—C21—C26	120.8 (5)	O8—C63—H632	111.6
C21—C22—C28	121.5 (5)	H631—C63—H632	103.3
C23—C22—C28	119.5 (5)	H631—C63—O8	110.0
C23—C22—C21	119.0 (3)	C62—C63—H632	110.3
H23—C23—C24	118.9	C62—C63—O8	108.6 (4)
C22—C23—C24	121.8 (5)	C62—C63—H631	113.0
C22—C23—H23	119.2	H171—C17—H172	108.4
C27—C24—C25	121.4 (3)	H175—C17—H172	141.0
C23—C24—C25	117.6 (4)	H175—C17—H171	56.5
C23—C24—C27	121.1 (5)	H173—C17—H172	109.6
H25—C25—C26	118.8	H173—C17—H171	110.4
C24—C25—C26	122.7 (3)	H173—C17—H175	57.0
C24—C25—H25	118.4	H174—C17—H172	55.9
C29—C26—C21	121.5 (5)	H174—C17—H171	140.9
C25—C26—C21	118.1 (5)	H174—C17—H175	110.5
C25—C26—C29	120.5 (3)	H174—C17—H173	56.7
H275—C27—H272	140.6	C14—C17—H172	109.1
H276—C27—H272	56.0	C14—C17—H171	109.6
H276—C27—H275	109.3	C14—C17—H175	109.9
H273—C27—H272	109.3	C14—C17—H173	109.7
H273—C27—H275	56.3	C14—C17—H174	109.4
H273—C27—H276	140.6	H176—C17—H172	55.5
C24—C27—H272	109.8	H176—C17—H171	55.8
C24—C27—H275	109.6	H176—C17—H175	109.3
C24—C27—H276	109.8	H176—C17—H173	141.0
C24—C27—H273	109.6	H176—C17—H174	108.5
H274—C27—H272	56.1	H176—C17—C14	109.2
H274—C27—H275	109.4	H374—C37—H372	56.7
H274—C27—H276	109.1	H375—C37—H372	140.4
H274—C27—H273	56.2	H375—C37—H374	108.6
H274—C27—C24	109.7	H371—C37—H372	109.6
H271—C27—H272	109.1	H371—C37—H374	140.3
H271—C27—H275	56.2	H371—C37—H375	55.6
H271—C27—H276	56.1	H376—C37—H372	56.7
H271—C27—H273	109.4	H376—C37—H374	110.1
H271—C27—C24	109.7	H376—C37—H375	108.7
H271—C27—H274	140.6	H376—C37—H371	56.1
H282—C28—H281	110.3	C34—C37—H372	110.1
C22—C28—H281	110.9	C34—C37—H374	109.9
C22—C28—H282	112.7	C34—C37—H375	109.5
O2—C28—H281	110.2	C34—C37—H371	109.8
O2—C28—H282	104.7	C34—C37—H376	110.0
O2—C28—C22	107.8 (4)	H373—C37—H372	109.6
O3—C29—H292	107.2	H373—C37—H374	56.1
C26—C29—H292	110.9	H373—C37—H375	55.5
C26—C29—O3	113.1 (3)	H373—C37—H371	108.1
H291—C29—H292	103.4	H373—C37—H376	140.4
H291—C29—O3	111.0	H373—C37—C34	109.6
H291—C29—C26	110.7	H512—C51—O9	109.4
O7—C31—C36	119.3 (4)	H511—C51—O9	109.3
C32—C31—C36	121.3 (5)	H511—C51—H512	109.5
C32—C31—O7	119.3 (6)	C50—C51—O9	109.9 (4)
C33—C32—C31	117.7 (6)	C50—C51—H512	109.4
C38—C32—C31	122.3 (5)	C50—C51—H511	109.4
C38—C32—C33	120.0 (4)	H176—H171—C17	62.7
C32—C33—H33	116.6	H175—H171—C17	61.0
C34—C33—H33	120.7	H175—H171—H176	120.0
C34—C33—C32	122.7 (4)	H174—H172—C17	61.3
C35—C34—C33	118.0 (5)	H176—H172—C17	62.3
C37—C34—C33	121.0 (4)	H176—H172—H174	120.0
C37—C34—C35	121.0 (7)	H174—H173—C17	62.3
C34—C35—H35	119.9	H175—H173—C17	61.6
C36—C35—H35	118.5	H175—H173—H174	120.0
C36—C35—C34	121.6 (7)	H172—H174—C17	62.7
C31—C36—C39	122.3 (5)	H173—H174—C17	61.0
C35—C36—C39	119.0 (6)	H173—H174—H172	120.0
C35—C36—C31	118.7 (4)	H173—H175—H171	120.0
H381—C38—O3	110.8	C17—H175—H171	62.4
C32—C38—O3	112.6 (4)	C17—H175—H173	61.4
C32—C38—H381	111.1	C17—H176—H172	62.2
H382—C38—O3	104.8	H171—H176—H172	120.0
H382—C38—H381	108.9	H171—H176—C17	61.5
H382—C38—C32	108.3	C27—H271—H275	61.8
H391—C39—C36	111.0	H276—H271—H275	120.0
H392—C39—C36	108.5	H276—H271—C27	62.1
H392—C39—H391	114.2	C27—H272—H276	62.0
O4—C39—C36	107.3 (4)	H274—H272—H276	120.0
O4—C39—H391	104.5	H274—H272—C27	61.8
O4—C39—H392	111.2	H275—H273—H274	120.0
O8—C41—C42	119.9 (3)	C27—H273—H274	62.0
C46—C41—C42	122.1 (6)	C27—H273—H275	61.9
C46—C41—O8	117.9 (5)	H273—H274—H272	120.0
C43—C42—C41	117.9 (4)	C27—H274—H272	62.1
C48—C42—C41	121.9 (6)	C27—H274—H273	61.8
C48—C42—C43	120.1 (3)	H271—H275—C27	62.0
H43—C43—C44	117.6	H273—H275—C27	61.8
C42—C43—C44	122.0 (3)	H273—H275—H271	120.0
C42—C43—H43	120.4	H271—H276—C27	61.8
C47—C44—C43	120.5 (3)	H272—H276—C27	62.0
C45—C44—C43	118.1 (6)	H272—H276—H271	120.0
C45—C44—C47	121.4 (4)	H375—H371—H376	120.0
C46—C45—C44	121.8 (4)	C37—H371—H376	61.3
H45—C45—C44	118.6	C37—H371—H375	62.5
H45—C45—C46	119.6	H374—H372—H376	120.0
C49—C46—C41	119.4 (6)	C37—H372—H376	62.0
C45—C46—C41	118.0 (6)	C37—H372—H374	62.0
C45—C46—C49	122.5 (3)	H375—H373—H374	120.0
C44—C47—H472	112.6	C37—H373—H374	61.3
H473—C47—H472	108.4	C37—H373—H375	62.6
H473—C47—C44	108.8	C37—H374—H372	61.3
H471—C47—H472	104.9	H373—H374—H372	120.0
H471—C47—C44	113.9	H373—H374—C37	62.6
H471—C47—H473	108.2	C37—H375—H371	61.9
C42—C48—O4	114.9 (5)	H373—H375—H371	120.0
H482—C48—O4	109.3	H373—H375—C37	61.9
H482—C48—C42	109.9	C37—H376—H372	61.3
H481—C48—O4	104.7	H371—H376—H372	120.0
H481—C48—C42	111.2	H371—H376—C37	62.6
H481—C48—H482	106.5