Cone and 1,3-alternate conformers of 1,3-bis­(ethoxy­carbonyl­methoxy)-2,4-di­hydroxy­calix­[4]­arene and 1,2,3,4-tetrakis­(ethoxy­carbonyl­methoxy)­calix­[4]­arene

The two title ethoxy­carbonyl­methoxy derivatives of calix­[4]­arene, namely diethyl 2,4-di­hydroxy­calix­[4]­arene-1,3-diyldi(oxy­ace­tate), C₃₆H₃₆O₈, (I), and tetraethyl ­calix­[4]­arene-1,2,3,4-tetra­yltetra­(oxy­acetate), C₄₄H₄₈O₁₂, (II), form two different conformations, viz. a cone in (I), where intramol­ecular hydrogen bonds are formed through OH groups in a partially substituted calix­[4]­arene, and a 1,3-alternate form of a completely substituted calix­[4]­arene in (II). A unique three-dimensional array of mol­ecules exists in (II), with the channels extended along the entire crystal.

S1. Comment

Substituted calix[4]arenes, ?which are synthetic macrocycles due to their conformational flexibility compared with cyclodextrins, have attracted much interest in recent years owing to their ability to complex cations and small molecules ?and their usefulness? in the design of supramolecular structures (see Gutsche, 1998, for a survey).

Moreover, self-assembled nanotubes have recently been constructed using sodium cations to trigger the one-dimensional polymerization of four guanosine moieties attached to a calix[4]arene- 1,3-alternate scaffold (Sidorov et al., 2000) ?as well as secondary amides forming self-assembled channels in an anionic dependent process? (Sidorov et al., 2002). The conformation of bis-OH calix[4]arene possesses unique structural peculiarities, like two hard phenolic ?O atoms? and two soft π-basic benzene rings, forming two binding sets at the edges of the calix[4]arene cavity, which are linked together by a π-basic benzene tunnel. Since unequivocal evidence exists that metal cations can easily pass through the π-basic holes with the aid of the π-interactions, and thus play a crucial role in metal transport through ion channels, a nanotube with well defined inner diameters for the metal passage may be synthesized. The 1,3-alternate core thus orients two orthogonal pairs of self-complementary guanosines to form an artificial ion channel (Ikeda & Shinkai, 1994). When we searched for structural parameters to show that appropriate introduced substituents immobilize the calix[4]arene conformation, we found that the crystal structures of the title compounds, (I) and (II), have not yet been reported, although Brunink et al. (1992) reported the synthesis and preliminary structure of the 1,2-alternate isomer of (I), and a CHCl₃ solvate of (I) was also recently reported (Coles et al., 2002). In the same paper a honeycomb supramolecular structure of columnar hexagonal tubes of the parent precursor 2,4-dihydroxy-1,3-bis(methoxycarbonylmethoxy) calix[4]arene was also found. These results prompted us to determine the crystal structure of the missing basic structures of the well established building blocks and scaffolds. A much simplified procedure to obtain the crystals of (I) and (II) was also used.

A search of the Cambridge Structural Database (release 5.2.1, April 2001; Allen et al., 1993) gave no results on structural work on (II). However, there was a general observation that there were problems with the disorder on the side chains and frequently solvates were formed. In all these cases the conventional R values of the known crystal structures were rather high.

The molecules of (I) and (II), with the atomic numbering scheme, are shown in Figs. 1 and 2, while the packing of the molecules (II) is depicted in Fig. 3. Hydrogen bonds O—H···O and C—H···O for (I) and C—H···O for (II) are presented in Tables 1 and 2.

We were able to prepare by a simplified procedure both solvent-free compounds, which were stable in air. The bond lengths and angles are normal and in agreement with the values for the related compounds, for example, with 1,3-bis(ethoxycarbonylmethoxy)-2,4-dihydroxycalix[4]arene chloroform solvate (Coles et al., 2002; International Tables for X-ray Crystallography, 1995, Vol. C, pp. 693–703).

The different conformation of (I), which exists as a cone, and the 1,3-alternate conformation of (II) are in agreement with the results of Grynszpan et al. (1991), who concluded that the presence of three phenolic OH groups are sufficient to stabilize the cone conformation, with a preference for OH-depleted or substituted calix[4]arenes to adopt the 1,3-alternate conformation. Furthermore, in our determination of (I) the two OH groups forced the molecule into the cone conformation. This has also been previously found in cases where either two vicinal (Brunink et al., 1992) or two opposite (Böhmer, 1995) phenolic groups are ?replaced? by ester groups. Special attention was therefore devoted to the structure of the 1,3-alternate conformer, (II). The most interesting feature of this structure is the packing of the molecules. 1,3-alternate molecules are packed along the c axis, forming a kind of a nanotubular array (Fig. 3). This is not the case with (I) [1,3-bis(ethoxycarbonylmethoxy) derivative], although the similar 1,3-bis(methoxycarbonylmethoxy) derivative (Coles et al., 2002) produced a supramolecular honeycomb structure.

The structures of (I) and (II) are similar to those reported by Coles et al., (2002). The separations between meso-C atoms C7, C14, C21 and C28 in (I) are 5.073 (3), 5.106 (3), 5.103 (2) and 5.102 (3) Å, with cross-ring distances between meso-C atoms of 7.270 (3) and 7.130 (2) Å, respectively. Because of the symmetry the corresponding distances in (II) are 5.041 (4) and 7.129 (5) Å. The dihedral angles between the aromatic rings and the mean plane of the macrocycle through the meso-C atoms are 64.58 (3), 48.61 (5), 67.54 (5) and 56.44 (5)° in (I), which differ from those of the chloroform solvate of (I). The appropriate dihedral angles (aromatic ring/mean plane of macrocycle) in (II) are 80.43 (7) and 99.57 (7)°, respectively. The dihedral angle between the vicinal aromatic rings is 88.41 (9)°, but the opposite aromatic rings are tilted to each other by 19.15 (8)° in (II).

It seems that the presence of CHCl₃ has a significant influence on the conformation of the calix[4]arene skeleton in the solvate structure. The C31···C35 separation in (I) [7.528 (3) Å] is larger than that found in the solvate of (I) [7.141 (3) Å], probably because of the molecular packing of CHCl₃. One of the main differences between (I) and the solvate of (I) is in the conformations of the ester groups attached to the calix[4]arene rim. The methoxycarbonylethoxy groups exist in the fully extended form, the corresponding torsion angles ranging from −168.4 (2) to 179.8 (2)°, but the torsion angles C6—O1—C29—C30 and C20—O3—C33—C34 are different [−124.9 (2) and −157.9 (2)°]. The dihedral angle between the extended, nearly planar, ester groups, using weighted least-squares planes through O1—C29—C30(O5)—O6—C31—C32 and O3—C33—C34(O7)—O8—C35—C36, is 63.03 (5)°. On the other hand, the overall conformation of the ester groups in (II) are completely different. The diversity of the torsion angles [C6—O1—C8—C9 126.5 (4), O1—C8—C9—O3 167.7 (4), C8—C9—O3—C10 − 170.5 (7) and C9—O3—C10—C11 86.2 (9)°] is the consequence of the specific molecular packing and C—H···O interactions.

The cone conformer in (I) is caused by two intramolecular O—H···O hydrogen bonds (see Table 1), which have a partial influence on the orientation of the ester groups. Two intramolecular hydrogen bonds [O4—H4···O3 = 2.823 (2) and O4—H4···O7 = 3.271 (2) Å] seem to be bifurcated and lock the ester group into the fixed position, while the ester group attached to atom C6 forms only one stronger intramolecular bond [O2—H2···O1 = 2.679 (2) Å], with the consequence that the O2···O5 distance is considerably longer [3.780 (2) Å]. However, this ester group is also held in position by the C7—H7B···O5 interaction [3.593 (2) Å].

Taking into account the general discussion on the C—H···O hydrogen bonding (Leban et al., 2002), with reference to the work of Taylor & Kennard (1982), Taylor & Kennard (1983), Steiner & Saenger (1992), Steiner (1997), Steiner & Desiraju (1998) and a review of Steiner (2002), explaining that the longer H···O distances up to 3.2 Å and an angular cut-off at angles greater than 90° could also give evidence of the electrostatic interaction of C—H···O bonds, we checked the values given for the C—H···O interactions (Tables 1 and 2) for directionality at the acceptor site. Namely, in the case of O═CR₁R₂ or R₁C—O—CR₂ as acceptors, the angles H···O—C at acceptor side are expected to be dispersed around the value of 120°. Normalized C—H values were used in these calculations using the program PARST (Nardelli, 1983 and 1995). While only intermolecular, presumably electrostatic, C—H···O interactions were found in (I), it appears that the C7—H7A···O2(1 − y,x,1 − z) hydrogen bond [3.481 (5) Å] is responsible for the specific arrangement of the ester groups in (II). There are also additional intermolecular C—H···O interactions (Table 2).

No significant solvent-accessible areas were found in (I), exhibiting that the cone molecules are relatively closely packed. However, the 1,3-alternate shape of (II) produces rather large calculated cavities of 157 ų in the crystal, 14.1% of the volume of the crystal unit cell being void; hence the difference in the crystal density was observed (PLATON; Spek, 1998). Channels extend along the entire crystal in the c direction in (II) (Fig. 3).

S2. Experimental

Derivatives of calixarenes (I) and (II) were synthesized by the reaction of calix[4]arene with ethylbromoacetate according to modified procedures (Guillon et al., 2000; Aoki et al., 1992; Iwamoto & Shinkai, 1992). (I): Calix[4]arene (1.00 g, 2.35 mmol), Cs₂CO₃ (0.77 g, 2.35 mmol) and ethylbromoacetate (5.23 ml, 47.2 mmol) were heated at reflux in acetone (70 ml) and stirred for 12 h under N₂. The reaction mixture was left to cool, and a solid residue was separated by filtration and washed with acetone. The solvent was removed, water (200 ml) was added and the residue was extracted with two portions of CHCl₃ (100 ml) and dried over Na₂SO₄. A brown oil was obtained after evaporation, which was dissolved in methanol (60 ml) on a steam bath. Water (25 ml) was added dropwise and the mixture was put aside at room temperature to form monocrystals, which were recrystallized from methanol/CHCl₃ (7:1) to obtain crystals (990 mg, 66%; m.p. 443–445 K. (II): Calix[4]arene (2.00 g, 4.70 mmol), Cs₂CO₃ (30.12 g, 94 mmol) and ethylbromoacetate (10.42 ml, 94 mmol) were suspended in acetone (150 ml) and kept at reflux for 13 h under N₂. The rest of the procedure followed that of (I) and yielded monocrystals (620 mg, 17.1%; m.p. 381–383 K).

Both sets of crystals without additional solvent proved to be stable in air. The diffraction data for (I) and (II) were collected for several crystals, both at room temperature (Ljubljana) and at 150 K (Vienna). The best low-temperature data were used, because the R values of the room temperature data were rather high [0.072 for (I) and 0.096 for (II)]. Neither the expected disorder in the ethoxycarbonylmethoxy moieties nor solvate formation were observed in either of the two determinations. The data were checked with option SQUEEZE of PLATON (Spek, 1998) and with the TWIN refinement.

S3. Refinement

All H atoms were found in the difference electron-density map and were placed at calculated position with isotropic displacement parameters taken from those of the adjacent atom multiplied by 1.2 (1.5 for methyl). The two phenolic H atoms of (I) were left to refine freely. There were no suitable anomalous scatterers for Mo Kα radiation, and therefore the determination of the absolute configuration was not possible from the X-ray data for (II) and the Friedel diffraction data were merged accordingly. There were only two peaks of residual electron density of 0.91 e Å⁻³ [1.08 Å away from O8] and 0.91 e Å⁻³ [1.43 Å away H35B] in (I). However, we were not able to resolve these effects, either as a disorder or as an additional solvent molecule in (I). The refinement with the TWIN instruction did not affect these values.

Computing details

For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS86 (Sheldrick, 1986); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1971), PLUTON (Spek, 1991), PLATON (Spek, 2003; Farrugia, 2000), ORTEP-3 (Farrugia, 1997), Mercury (Bruno et al., 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997), PARST (Nardelli, 1983 and 1995), WinGX (Farrugia, 1999).

Figures

Fig. 1. View of (I), with displacement ellipsoids show at the 30% probability level. H atoms (except phenolic) have been omitted for clarity. Fig. 2. View of (II), with displacement ellipsoids shown at the 30% probability level. H atoms have been omitted for clarity. Fig. 3. Packing of (II) perpendicular to [001], showing the pattern of channels along the c axis.

(I) diethyl 2,4-dihydroxycalix[4]arene-1,3-diyldi(oxyacetate)

Crystal data

C36H36O8	F(000) = 1264
Mr = 596.65	Dx = 1.301 Mg m^−3 Dm = 1.26 (5) Mg m^−3 Dm measured by flotation
Monoclinic, P21/c	Melting point = 170–172 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 10.1364 (5) Å	Cell parameters from 5652 reflections
b = 10.9403 (5) Å	θ = 1.0–27.5°
c = 27.7309 (10) Å	µ = 0.09 mm^−1
β = 97.917 (3)°	T = 150 K
V = 3045.9 (2) Å^3	Plate, colourless
Z = 4	0.28 × 0.24 × 0.18 mm

Data collection

Nonius KappaCCD diffractometer	5280 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.018
Graphite monochromator	θmax = 27.5°, θmin = 2.4°
Detector resolution: 0.055 pixels mm^-1	h = −13→13
ϕ and ω scans	k = −14→14
13551 measured reflections	l = −36→35
6968 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0689P)^2 + 1.324P] where P = (Fo^2 + 2Fc^2)/3
6968 reflections	(Δ/σ)max < 0.001
407 parameters	Δρmax = 0.91 e Å^−3
0 restraints	Δρmin = −0.33 e Å^−3

Special details

Experimental. KappaCCD Nonius diffractometer. 476 frames in 3 sets of ϕ and ω scans. Rotation/frame=1°. Crystal-detector distance=40.0 mm. Measuring time=300 s/°.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
O1	0.55518 (11)	0.40004 (12)	0.34327 (4)	0.0357 (3)
O2	0.47010 (12)	0.48737 (12)	0.42382 (5)	0.0372 (3)
H2	0.511 (3)	0.451 (2)	0.4020 (9)	0.063 (7)*
O3	0.40695 (11)	0.74115 (11)	0.39941 (4)	0.0347 (3)
O4	0.44742 (12)	0.64100 (13)	0.30877 (5)	0.0416 (3)
H4	0.443 (2)	0.688 (2)	0.3335 (10)	0.062 (7)*
O5	0.79333 (14)	0.34387 (17)	0.39910 (5)	0.0592 (4)
O6	0.90209 (11)	0.42250 (12)	0.34111 (4)	0.0368 (3)
O7	0.63881 (15)	0.83154 (14)	0.37722 (5)	0.0556 (4)
O8	0.65365 (13)	0.96094 (12)	0.44053 (5)	0.0422 (3)
C1	0.40375 (17)	0.33973 (16)	0.27145 (6)	0.0342 (4)
C2	0.30902 (18)	0.25408 (18)	0.25145 (7)	0.0408 (4)
H02	0.2736	0.2600	0.2180	0.049*
C3	0.2660 (2)	0.16162 (17)	0.27905 (8)	0.0450 (5)
H03	0.2021	0.1043	0.2645	0.054*
C4	0.3155 (2)	0.15205 (16)	0.32773 (7)	0.0422 (4)
H04	0.2822	0.0903	0.3469	0.051*
C5	0.41361 (17)	0.23142 (15)	0.34920 (6)	0.0343 (4)
C6	0.45835 (16)	0.32205 (15)	0.31998 (6)	0.0311 (4)
C7	0.46555 (18)	0.22288 (16)	0.40317 (6)	0.0377 (4)
H7A	0.4738	0.1356	0.4125	0.045*
H7B	0.5557	0.2594	0.4090	0.045*
C8	0.37756 (17)	0.28644 (16)	0.43553 (6)	0.0322 (4)
C9	0.28696 (19)	0.22015 (17)	0.45844 (7)	0.0394 (4)
H9	0.2790	0.1346	0.4529	0.047*
C10	0.20798 (19)	0.27538 (18)	0.48918 (7)	0.0428 (4)
H10	0.1469	0.2281	0.5045	0.051*
C11	0.21883 (18)	0.39961 (18)	0.49734 (6)	0.0379 (4)
H11	0.1662	0.4372	0.5190	0.045*
C12	0.30545 (16)	0.47088 (15)	0.47443 (6)	0.0306 (3)
C13	0.38489 (16)	0.41310 (15)	0.44379 (5)	0.0293 (3)
C14	0.31347 (17)	0.60817 (16)	0.48115 (6)	0.0329 (4)
H14A	0.4067	0.6353	0.4812	0.040*
H14B	0.2864	0.6300	0.5130	0.040*
C15	0.22394 (17)	0.67361 (15)	0.44086 (6)	0.0315 (4)
C16	0.08619 (18)	0.67156 (17)	0.44102 (7)	0.0389 (4)
H16	0.0515	0.6349	0.4677	0.047*
C17	−0.00094 (19)	0.72144 (19)	0.40346 (8)	0.0446 (5)
H17	−0.0941	0.7200	0.4047	0.054*
C18	0.04821 (19)	0.77344 (18)	0.36405 (7)	0.0433 (4)
H18	−0.0119	0.8060	0.3379	0.052*
C19	0.18502 (18)	0.77865 (15)	0.36226 (7)	0.0355 (4)
C20	0.27040 (16)	0.73171 (15)	0.40158 (6)	0.0313 (4)
C21	0.2363 (2)	0.82373 (16)	0.31651 (7)	0.0422 (4)
H21A	0.3296	0.8515	0.3248	0.051*
H22B	0.1822	0.8944	0.3031	0.051*
C22	0.22980 (18)	0.72377 (16)	0.27812 (6)	0.0370 (4)
C23	0.1161 (2)	0.7133 (2)	0.24378 (7)	0.0470 (5)
H23	0.0452	0.7697	0.2444	0.056*
C24	0.1048 (2)	0.6219 (2)	0.20871 (7)	0.0503 (5)
H24	0.0267	0.6158	0.1856	0.060*
C25	0.20793 (19)	0.5397 (2)	0.20771 (6)	0.0437 (5)
H25	0.2005	0.4779	0.1834	0.052*
C26	0.32230 (17)	0.54583 (17)	0.24158 (6)	0.0356 (4)
C27	0.33195 (17)	0.63876 (16)	0.27678 (6)	0.0338 (4)
C28	0.43074 (18)	0.45075 (18)	0.24121 (6)	0.0376 (4)
H28A	0.5177	0.4869	0.2545	0.045*
H28B	0.4355	0.4250	0.2073	0.045*
C29	0.67486 (17)	0.4171 (2)	0.32306 (6)	0.0402 (4)
H29A	0.6801	0.5028	0.3119	0.048*
H29B	0.6749	0.3631	0.2944	0.048*
C30	0.79399 (17)	0.38900 (17)	0.35979 (6)	0.0343 (4)
C31	1.03113 (17)	0.39529 (18)	0.36862 (7)	0.0381 (4)
H31A	1.0425	0.3060	0.3732	0.046*
H31B	1.0400	0.4348	0.4010	0.046*
C32	1.13250 (17)	0.44482 (18)	0.33940 (7)	0.0402 (4)
H32A	1.1272	0.4002	0.3086	0.060*
H32B	1.2217	0.4350	0.3577	0.060*
H32C	1.1151	0.5317	0.3328	0.060*
C33	0.4697 (2)	0.8357 (2)	0.43005 (8)	0.0554 (6)
H33A	0.4894	0.8057	0.4640	0.066*
H33B	0.4094	0.9069	0.4297	0.066*
C34	0.59667 (18)	0.87292 (16)	0.41183 (6)	0.0362 (4)
C35	0.7748 (2)	1.01580 (19)	0.42750 (8)	0.0456 (5)
H35A	0.7542	1.0680	0.3983	0.055*
H35B	0.8386	0.9517	0.4206	0.055*
C36	0.8322 (3)	1.0911 (2)	0.47067 (10)	0.0661 (7)
H36A	0.7647	1.1488	0.4789	0.099*
H36B	0.9097	1.1365	0.4627	0.099*
H36C	0.8595	1.0373	0.4985	0.099*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0243 (6)	0.0507 (7)	0.0340 (6)	−0.0048 (5)	0.0108 (5)	−0.0072 (5)
O2	0.0408 (7)	0.0351 (6)	0.0396 (7)	−0.0030 (5)	0.0189 (6)	−0.0007 (5)
O3	0.0292 (6)	0.0341 (6)	0.0413 (6)	−0.0055 (5)	0.0066 (5)	−0.0028 (5)
O4	0.0317 (7)	0.0536 (8)	0.0380 (7)	−0.0013 (6)	−0.0001 (5)	−0.0067 (6)
O5	0.0406 (8)	0.0958 (12)	0.0423 (8)	−0.0021 (8)	0.0096 (6)	0.0218 (8)
O6	0.0240 (6)	0.0506 (7)	0.0359 (6)	−0.0040 (5)	0.0048 (5)	0.0036 (5)
O7	0.0561 (9)	0.0648 (10)	0.0489 (8)	−0.0217 (7)	0.0173 (7)	−0.0163 (7)
O8	0.0384 (7)	0.0377 (7)	0.0501 (7)	−0.0084 (5)	0.0052 (6)	−0.0046 (6)
C1	0.0296 (8)	0.0400 (9)	0.0351 (9)	0.0013 (7)	0.0114 (7)	−0.0085 (7)
C2	0.0377 (10)	0.0459 (10)	0.0397 (9)	0.0000 (8)	0.0079 (8)	−0.0139 (8)
C3	0.0440 (11)	0.0369 (10)	0.0549 (12)	−0.0060 (8)	0.0096 (9)	−0.0156 (9)
C4	0.0474 (11)	0.0283 (9)	0.0535 (11)	−0.0021 (8)	0.0159 (9)	−0.0065 (8)
C5	0.0330 (9)	0.0295 (8)	0.0422 (9)	0.0080 (7)	0.0116 (7)	−0.0041 (7)
C6	0.0246 (8)	0.0345 (9)	0.0359 (8)	0.0014 (6)	0.0102 (6)	−0.0077 (7)
C7	0.0392 (10)	0.0318 (9)	0.0428 (10)	0.0090 (7)	0.0086 (8)	0.0047 (7)
C8	0.0331 (9)	0.0336 (9)	0.0295 (8)	0.0047 (7)	0.0031 (7)	0.0055 (7)
C9	0.0446 (10)	0.0318 (9)	0.0421 (10)	−0.0011 (8)	0.0076 (8)	0.0076 (7)
C10	0.0429 (10)	0.0448 (10)	0.0434 (10)	−0.0061 (8)	0.0149 (8)	0.0097 (8)
C11	0.0374 (9)	0.0463 (10)	0.0321 (9)	0.0004 (8)	0.0125 (7)	0.0034 (7)
C12	0.0313 (8)	0.0368 (9)	0.0235 (7)	−0.0005 (7)	0.0030 (6)	0.0009 (6)
C13	0.0279 (8)	0.0348 (8)	0.0250 (7)	−0.0003 (6)	0.0034 (6)	0.0042 (6)
C14	0.0359 (9)	0.0374 (9)	0.0263 (8)	−0.0008 (7)	0.0068 (7)	−0.0043 (7)
C15	0.0324 (9)	0.0296 (8)	0.0334 (8)	−0.0011 (7)	0.0075 (7)	−0.0085 (7)
C16	0.0338 (9)	0.0419 (10)	0.0433 (10)	0.0001 (8)	0.0136 (8)	−0.0068 (8)
C17	0.0293 (9)	0.0485 (11)	0.0571 (12)	0.0053 (8)	0.0097 (8)	−0.0069 (9)
C18	0.0369 (10)	0.0397 (10)	0.0515 (11)	0.0095 (8)	0.0000 (8)	−0.0013 (8)
C19	0.0366 (9)	0.0256 (8)	0.0441 (10)	0.0016 (7)	0.0051 (7)	−0.0003 (7)
C20	0.0287 (8)	0.0264 (8)	0.0390 (9)	−0.0015 (6)	0.0054 (7)	−0.0044 (7)
C21	0.0466 (11)	0.0296 (9)	0.0492 (11)	0.0003 (8)	0.0028 (8)	0.0119 (8)
C22	0.0400 (10)	0.0366 (9)	0.0340 (9)	−0.0028 (8)	0.0038 (7)	0.0143 (7)
C23	0.0430 (11)	0.0518 (12)	0.0442 (10)	0.0045 (9)	−0.0010 (8)	0.0183 (9)
C24	0.0452 (11)	0.0650 (13)	0.0367 (10)	−0.0021 (10)	−0.0086 (8)	0.0109 (9)
C25	0.0433 (10)	0.0579 (12)	0.0284 (8)	−0.0072 (9)	0.0000 (8)	0.0049 (8)
C26	0.0339 (9)	0.0469 (10)	0.0264 (8)	−0.0075 (8)	0.0060 (7)	0.0070 (7)
C27	0.0324 (9)	0.0400 (9)	0.0290 (8)	−0.0067 (7)	0.0042 (7)	0.0086 (7)
C28	0.0332 (9)	0.0541 (11)	0.0269 (8)	−0.0049 (8)	0.0096 (7)	−0.0034 (7)
C29	0.0257 (8)	0.0611 (12)	0.0355 (9)	−0.0032 (8)	0.0103 (7)	0.0007 (8)
C30	0.0297 (8)	0.0401 (9)	0.0342 (9)	−0.0027 (7)	0.0083 (7)	−0.0035 (7)
C31	0.0276 (9)	0.0448 (10)	0.0401 (9)	−0.0011 (7)	−0.0016 (7)	0.0005 (8)
C32	0.0261 (8)	0.0454 (10)	0.0491 (10)	−0.0013 (8)	0.0048 (7)	−0.0036 (8)
C33	0.0496 (12)	0.0644 (14)	0.0537 (12)	−0.0244 (10)	0.0125 (10)	−0.0199 (11)
C34	0.0392 (10)	0.0353 (9)	0.0325 (8)	−0.0012 (7)	−0.0007 (7)	0.0022 (7)
C35	0.0409 (10)	0.0445 (11)	0.0526 (11)	−0.0096 (8)	0.0104 (9)	−0.0034 (9)
C36	0.0653 (15)	0.0475 (12)	0.0786 (16)	−0.0220 (11)	−0.0146 (13)	−0.0051 (12)

Geometric parameters (Å, º)

O1—C6	1.391 (2)	C15—C20	1.398 (2)
O1—C29	1.4171 (19)	C16—C17	1.382 (3)
O2—C13	1.3582 (19)	C16—H16	0.9500
O2—H2	0.88 (3)	C17—C18	1.384 (3)
O3—C20	1.398 (2)	C17—H17	0.9500
O3—C33	1.431 (2)	C18—C19	1.396 (3)
O4—C27	1.368 (2)	C18—H18	0.9500
O4—H4	0.86 (3)	C19—C20	1.393 (2)
O5—C30	1.198 (2)	C19—C21	1.518 (3)
O6—C30	1.326 (2)	C21—C22	1.521 (3)
O6—C31	1.451 (2)	C21—H21A	0.9900
O7—C34	1.192 (2)	C21—H22B	0.9900
O8—C34	1.330 (2)	C22—C23	1.395 (3)
O8—C35	1.457 (2)	C22—C27	1.396 (3)
C1—C6	1.396 (2)	C23—C24	1.389 (3)
C1—C2	1.400 (3)	C23—H23	0.9500
C1—C28	1.522 (3)	C24—C25	1.382 (3)
C2—C3	1.375 (3)	C24—H24	0.9500
C2—H02	0.9500	C25—C26	1.390 (2)
C3—C4	1.378 (3)	C25—H25	0.9500
C3—H03	0.9500	C26—C27	1.404 (3)
C4—C5	1.391 (3)	C26—C28	1.514 (3)
C4—H04	0.9500	C28—H28A	0.9900
C5—C6	1.395 (2)	C28—H28B	0.9900
C5—C7	1.520 (3)	C29—C30	1.500 (2)
C7—C8	1.518 (2)	C29—H29A	0.9900
C7—H7A	0.9900	C29—H29B	0.9900
C7—H7B	0.9900	C31—C32	1.495 (3)
C8—C9	1.391 (2)	C31—H31A	0.9900
C8—C13	1.405 (2)	C31—H31B	0.9900
C9—C10	1.386 (3)	C32—H32A	0.9800
C9—H9	0.9500	C32—H32B	0.9800
C10—C11	1.380 (3)	C32—H32C	0.9800
C10—H10	0.9500	C33—C34	1.502 (3)
C11—C12	1.391 (2)	C33—H33A	0.9900
C11—H11	0.9500	C33—H33B	0.9900
C12—C13	1.400 (2)	C35—C36	1.503 (3)
C12—C14	1.514 (2)	C35—H35A	0.9900
C14—C15	1.518 (2)	C35—H35B	0.9900
C14—H14A	0.9900	C36—H36A	0.9800
C14—H14B	0.9900	C36—H36B	0.9800
C15—C16	1.397 (2)	C36—H36C	0.9800
C6—O1—C29	119.02 (13)	C19—C21—C22	111.38 (14)
C13—O2—H2	113.5 (16)	C19—C21—H21A	109.4
C20—O3—C33	112.94 (14)	C22—C21—H21A	109.4
C27—O4—H4	112.9 (17)	C19—C21—H22B	109.4
C30—O6—C31	118.12 (14)	C22—C21—H22B	109.4
C34—O8—C35	117.49 (15)	H21A—C21—H22B	108.0
C6—C1—C2	116.63 (17)	C23—C22—C27	118.23 (18)
C6—C1—C28	124.34 (15)	C23—C22—C21	119.27 (18)
C2—C1—C28	118.77 (16)	C27—C22—C21	122.46 (16)
C3—C2—C1	121.63 (18)	C24—C23—C22	121.22 (19)
C3—C2—H02	119.2	C24—C23—H23	119.4
C1—C2—H02	119.2	C22—C23—H23	119.4
C2—C3—C4	120.02 (18)	C25—C24—C23	119.51 (18)
C2—C3—H03	120.0	C25—C24—H24	120.2
C4—C3—H03	120.0	C23—C24—H24	120.2
C3—C4—C5	120.96 (18)	C24—C25—C26	121.21 (19)
C3—C4—H04	119.5	C24—C25—H25	119.4
C5—C4—H04	119.5	C26—C25—H25	119.4
C4—C5—C6	117.75 (17)	C25—C26—C27	118.47 (18)
C4—C5—C7	120.89 (16)	C25—C26—C28	120.07 (17)
C6—C5—C7	121.30 (16)	C27—C26—C28	121.41 (15)
O1—C6—C5	115.56 (15)	O4—C27—C22	122.85 (16)
O1—C6—C1	121.56 (15)	O4—C27—C26	115.81 (16)
C5—C6—C1	122.74 (16)	C22—C27—C26	121.34 (16)
C8—C7—C5	113.70 (14)	C26—C28—C1	111.02 (14)
C8—C7—H7A	108.8	C26—C28—H28A	109.4
C5—C7—H7A	108.8	C1—C28—H28A	109.4
C8—C7—H7B	108.8	C26—C28—H28B	109.4
C5—C7—H7B	108.8	C1—C28—H28B	109.4
H7A—C7—H7B	107.7	H28A—C28—H28B	108.0
C9—C8—C13	117.61 (15)	O1—C29—C30	110.93 (14)
C9—C8—C7	120.66 (16)	O1—C29—H29A	109.5
C13—C8—C7	121.73 (15)	C30—C29—H29A	109.5
C10—C9—C8	121.84 (17)	O1—C29—H29B	109.5
C10—C9—H9	119.1	C30—C29—H29B	109.5
C8—C9—H9	119.1	H29A—C29—H29B	108.0
C11—C10—C9	119.37 (16)	O5—C30—O6	125.30 (17)
C11—C10—H10	120.3	O5—C30—C29	126.70 (16)
C9—C10—H10	120.3	O6—C30—C29	108.01 (14)
C10—C11—C12	121.22 (16)	O6—C31—C32	106.13 (14)
C10—C11—H11	119.4	O6—C31—H31A	110.5
C12—C11—H11	119.4	C32—C31—H31A	110.5
C11—C12—C13	118.43 (16)	O6—C31—H31B	110.5
C11—C12—C14	121.75 (15)	C32—C31—H31B	110.5
C13—C12—C14	119.81 (15)	H31A—C31—H31B	108.7
O2—C13—C12	115.39 (15)	C31—C32—H32A	109.5
O2—C13—C8	123.10 (15)	C31—C32—H32B	109.5
C12—C13—C8	121.50 (15)	H32A—C32—H32B	109.5
C12—C14—C15	111.14 (13)	C31—C32—H32C	109.5
C12—C14—H14A	109.4	H32A—C32—H32C	109.5
C15—C14—H14A	109.4	H32B—C32—H32C	109.5
C12—C14—H14B	109.4	O3—C33—C34	109.13 (16)
C15—C14—H14B	109.4	O3—C33—H33A	109.9
H14A—C14—H14B	108.0	C34—C33—H33A	109.9
C16—C15—C20	116.99 (16)	O3—C33—H33B	109.9
C16—C15—C14	119.11 (15)	C34—C33—H33B	109.9
C20—C15—C14	123.82 (15)	H33A—C33—H33B	108.3
C17—C16—C15	121.78 (17)	O7—C34—O8	125.63 (17)
C17—C16—H16	119.1	O7—C34—C33	125.89 (17)
C15—C16—H16	119.1	O8—C34—C33	108.47 (15)
C16—C17—C18	119.69 (17)	O8—C35—C36	105.97 (17)
C16—C17—H17	120.2	O8—C35—H35A	110.5
C18—C17—H17	120.2	C36—C35—H35A	110.5
C17—C18—C19	120.82 (18)	O8—C35—H35B	110.5
C17—C18—H18	119.6	C36—C35—H35B	110.5
C19—C18—H18	119.6	H35A—C35—H35B	108.7
C20—C19—C18	118.05 (17)	C35—C36—H36A	109.5
C20—C19—C21	121.77 (16)	C35—C36—H36B	109.5
C18—C19—C21	119.94 (17)	H36A—C36—H36B	109.5
C19—C20—O3	116.82 (15)	C35—C36—H36C	109.5
C19—C20—C15	122.54 (16)	H36A—C36—H36C	109.5
O3—C20—C15	120.61 (15)	H36B—C36—H36C	109.5
C6—C1—C2—C3	3.9 (3)	C18—C19—C20—O3	−178.30 (15)
C28—C1—C2—C3	−170.49 (17)	C21—C19—C20—O3	7.3 (2)
C1—C2—C3—C4	0.4 (3)	C18—C19—C20—C15	4.0 (3)
C2—C3—C4—C5	−3.0 (3)	C21—C19—C20—C15	−170.43 (16)
C3—C4—C5—C6	1.0 (3)	C33—O3—C20—C19	104.08 (19)
C3—C4—C5—C7	178.39 (16)	C33—O3—C20—C15	−78.2 (2)
C29—O1—C6—C5	127.35 (16)	C16—C15—C20—C19	−4.4 (2)
C29—O1—C6—C1	−57.0 (2)	C14—C15—C20—C19	172.33 (15)
C4—C5—C6—O1	179.21 (14)	C16—C15—C20—O3	177.99 (15)
C7—C5—C6—O1	1.9 (2)	C14—C15—C20—O3	−5.3 (2)
C4—C5—C6—C1	3.6 (2)	C20—C19—C21—C22	93.8 (2)
C7—C5—C6—C1	−173.76 (15)	C18—C19—C21—C22	−80.5 (2)
C2—C1—C6—O1	178.70 (14)	C19—C21—C22—C23	91.4 (2)
C28—C1—C6—O1	−7.3 (2)	C19—C21—C22—C27	−86.4 (2)
C2—C1—C6—C5	−5.9 (2)	C27—C22—C23—C24	−0.8 (3)
C28—C1—C6—C5	168.07 (15)	C21—C22—C23—C24	−178.66 (17)
C4—C5—C7—C8	−81.9 (2)	C22—C23—C24—C25	−0.1 (3)
C6—C5—C7—C8	95.38 (19)	C23—C24—C25—C26	0.9 (3)
C5—C7—C8—C9	98.47 (19)	C24—C25—C26—C27	−0.8 (3)
C5—C7—C8—C13	−82.0 (2)	C24—C25—C26—C28	176.89 (17)
C13—C8—C9—C10	−1.3 (3)	C23—C22—C27—O4	179.97 (16)
C7—C8—C9—C10	178.26 (17)	C21—C22—C27—O4	−2.2 (3)
C8—C9—C10—C11	0.2 (3)	C23—C22—C27—C26	0.8 (2)
C9—C10—C11—C12	1.4 (3)	C21—C22—C27—C26	178.65 (15)
C10—C11—C12—C13	−1.8 (3)	C25—C26—C27—O4	−179.27 (15)
C10—C11—C12—C14	176.99 (17)	C28—C26—C27—O4	3.1 (2)
C11—C12—C13—O2	−178.01 (15)	C25—C26—C27—C22	−0.1 (2)
C14—C12—C13—O2	3.1 (2)	C28—C26—C27—C22	−177.72 (15)
C11—C12—C13—C8	0.7 (2)	C25—C26—C28—C1	−87.00 (19)
C14—C12—C13—C8	−178.18 (15)	C27—C26—C28—C1	90.62 (19)
C9—C8—C13—O2	179.43 (15)	C6—C1—C28—C26	−95.81 (19)
C7—C8—C13—O2	−0.1 (2)	C2—C1—C28—C26	78.08 (19)
C9—C8—C13—C12	0.8 (2)	C6—O1—C29—C30	−124.85 (17)
C7—C8—C13—C12	−178.70 (15)	C31—O6—C30—O5	4.5 (3)
C11—C12—C14—C15	−94.32 (18)	C31—O6—C30—C29	−175.22 (15)
C13—C12—C14—C15	84.51 (19)	O1—C29—C30—O5	8.7 (3)
C12—C14—C15—C16	73.77 (19)	O1—C29—C30—O6	−171.56 (15)
C12—C14—C15—C20	−102.86 (18)	C30—O6—C31—C32	−179.11 (15)
C20—C15—C16—C17	1.8 (3)	C20—O3—C33—C34	−157.92 (16)
C14—C15—C16—C17	−175.05 (16)	C35—O8—C34—O7	3.0 (3)
C15—C16—C17—C18	1.0 (3)	C35—O8—C34—C33	−176.36 (17)
C16—C17—C18—C19	−1.5 (3)	O3—C33—C34—O7	0.5 (3)
C17—C18—C19—C20	−0.9 (3)	O3—C33—C34—O8	179.82 (16)
C17—C18—C19—C21	173.55 (17)	C34—O8—C35—C36	−168.42 (17)

(II) tetraethyl calix[4]arene-1,2,3,4-tetrayltetra(oxyacetate)

Crystal data

C44H48O12	Dx = 1.148 Mg m^−3 Dm = 1.10 (5) Mg m^−3 Dm measured by flotation
Mr = 768.82	Melting point = 108–110 K
Tetragonal, P4	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -4	Cell parameters from 5413 reflections
a = 12.0173 (8) Å	θ = 1.0–29.1°
c = 7.6972 (5) Å	µ = 0.08 mm^−1
V = 1111.60 (13) Å^3	T = 150 K
Z = 1	Prism, colourless
F(000) = 408	0.36 × 0.24 × 0.22 mm

Data collection

Nonius KappaCCD diffractometer	1453 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.015
Graphite monochromator	θmax = 29.2°, θmin = 5.4°
Detector resolution: 0.055 pixels mm^-1	h = 0→16
ω scans	k = −11→11
2991 measured reflections	l = −10→10
1604 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.192	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.124P)^2 + 0.2336P] where P = (Fo^2 + 2Fc^2)/3
1604 reflections	(Δ/σ)max < 0.001
128 parameters	Δρmax = 0.46 e Å^−3
0 restraints	Δρmin = −0.23 e Å^−3

Special details

Experimental. KappaCCD Nonius diffractometer. 225 frames in 5 sets of ω scans. Rotation/frame=2°. Crystal-detector distance=30.4 mm. Measuring time=200 s/°.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
C1	0.26396 (19)	0.4626 (2)	0.5988 (4)	0.0348 (5)
C2	0.2820 (2)	0.4593 (3)	0.7781 (4)	0.0418 (6)
H2	0.2700	0.3918	0.8394	0.050*
C3	0.3169 (3)	0.5527 (3)	0.8679 (4)	0.0479 (7)
H3	0.3258	0.5502	0.9905	0.057*
C4	0.3386 (3)	0.6496 (3)	0.7780 (4)	0.0421 (6)
H4	0.3658	0.7126	0.8393	0.050*
C5	0.3214 (2)	0.6573 (2)	0.5995 (4)	0.0346 (5)
C6	0.27945 (19)	0.5644 (2)	0.5143 (3)	0.0328 (5)
C7	0.2406 (2)	0.3562 (2)	0.5007 (4)	0.0362 (5)
H7A	0.2194	0.2967	0.5833	0.043*
H7B	0.1778	0.3679	0.4195	0.043*
C8	0.1456 (3)	0.5701 (3)	0.2921 (5)	0.0538 (9)
H8A	0.0996	0.5697	0.3987	0.065*
H8B	0.1300	0.5008	0.2271	0.065*
C9	0.1145 (3)	0.6675 (3)	0.1833 (6)	0.0623 (11)
C10	−0.0248 (5)	0.7249 (7)	−0.0156 (14)	0.121 (3)
H10A	0.0019	0.8008	0.0124	0.145*
H10B	−0.1072	0.7263	−0.0115	0.145*
C11	0.0099 (7)	0.6973 (11)	−0.1919 (15)	0.162 (5)
H11A	0.0886	0.6760	−0.1915	0.242*
H11B	−0.0005	0.7622	−0.2673	0.242*
H11C	−0.0350	0.6352	−0.2353	0.242*
O1	0.25834 (16)	0.57292 (17)	0.3381 (2)	0.0388 (5)
O2	0.1708 (2)	0.7465 (2)	0.1525 (5)	0.0836 (12)
O3	0.0146 (3)	0.6500 (4)	0.1151 (7)	0.1039 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0294 (10)	0.0399 (12)	0.0350 (13)	0.0016 (9)	0.0005 (9)	0.0021 (11)
C2	0.0458 (14)	0.0459 (14)	0.0336 (13)	0.0027 (11)	0.0016 (11)	0.0067 (11)
C3	0.0589 (17)	0.0537 (16)	0.0310 (12)	0.0023 (13)	−0.0006 (12)	0.0019 (12)
C4	0.0471 (13)	0.0436 (14)	0.0355 (14)	0.0005 (11)	−0.0007 (11)	−0.0034 (11)
C5	0.0332 (11)	0.0359 (12)	0.0348 (12)	0.0033 (9)	0.0003 (10)	0.0008 (10)
C6	0.0306 (10)	0.0380 (12)	0.0300 (11)	0.0019 (9)	−0.0023 (9)	0.0020 (10)
C7	0.0330 (11)	0.0369 (11)	0.0387 (12)	−0.0020 (8)	0.0018 (10)	0.0031 (10)
C8	0.0443 (15)	0.0575 (17)	0.060 (2)	−0.0157 (12)	−0.0178 (14)	0.0221 (16)
C9	0.0428 (15)	0.0622 (18)	0.082 (3)	−0.0072 (13)	−0.0172 (17)	0.032 (2)
C10	0.068 (3)	0.125 (5)	0.170 (8)	−0.009 (3)	−0.049 (4)	0.079 (5)
C11	0.092 (5)	0.262 (14)	0.130 (7)	0.008 (6)	−0.021 (5)	0.099 (9)
O1	0.0380 (9)	0.0449 (10)	0.0334 (9)	−0.0045 (7)	−0.0082 (7)	0.0065 (8)
O2	0.0630 (16)	0.0655 (16)	0.122 (3)	−0.0168 (12)	−0.0336 (19)	0.0451 (19)
O3	0.0547 (16)	0.114 (3)	0.143 (4)	−0.0211 (16)	−0.042 (2)	0.069 (3)

Geometric parameters (Å, º)

C1—C2	1.397 (4)	C7—H7B	0.9900
C1—C6	1.398 (4)	C8—O1	1.400 (3)
C1—C7	1.511 (4)	C8—C9	1.487 (5)
C2—C3	1.383 (4)	C8—H8A	0.9900
C2—H2	0.9500	C8—H8B	0.9900
C3—C4	1.379 (4)	C9—O2	1.190 (4)
C3—H3	0.9500	C9—O3	1.327 (4)
C4—C5	1.393 (4)	C10—O3	1.431 (7)
C4—H4	0.9500	C10—C11	1.458 (16)
C5—C6	1.389 (4)	C10—H10A	0.9900
C5—C7^i	1.509 (4)	C10—H10B	0.9900
C6—O1	1.384 (3)	C11—H11A	0.9800
C7—C5^ii	1.509 (4)	C11—H11B	0.9800
C7—H7A	0.9900	C11—H11C	0.9800
C2—C1—C6	117.6 (3)	O1—C8—C9	111.5 (2)
C2—C1—C7	119.9 (3)	O1—C8—H8A	109.3
C6—C1—C7	122.2 (2)	C9—C8—H8A	109.3
C3—C2—C1	121.2 (3)	O1—C8—H8B	109.3
C3—C2—H2	119.4	C9—C8—H8B	109.3
C1—C2—H2	119.4	H8A—C8—H8B	108.0
C4—C3—C2	119.5 (3)	O2—C9—O3	124.2 (3)
C4—C3—H3	120.3	O2—C9—C8	126.7 (3)
C2—C3—H3	120.3	O3—C9—C8	109.0 (3)
C3—C4—C5	121.5 (3)	O3—C10—C11	114.6 (8)
C3—C4—H4	119.2	O3—C10—H10A	108.6
C5—C4—H4	119.2	C11—C10—H10A	108.6
C6—C5—C4	117.8 (3)	O3—C10—H10B	108.6
C6—C5—C7^i	120.9 (2)	C11—C10—H10B	108.6
C4—C5—C7^i	121.1 (3)	H10A—C10—H10B	107.6
O1—C6—C5	118.0 (2)	C10—C11—H11A	109.5
O1—C6—C1	119.8 (2)	C10—C11—H11B	109.5
C5—C6—C1	122.1 (2)	H11A—C11—H11B	109.5
C5^ii—C7—C1	109.8 (2)	C10—C11—H11C	109.5
C5^ii—C7—H7A	109.7	H11A—C11—H11C	109.5
C1—C7—H7A	109.7	H11B—C11—H11C	109.5
C5^ii—C7—H7B	109.7	C6—O1—C8	115.1 (2)
C1—C7—H7B	109.7	C9—O3—C10	118.6 (4)
H7A—C7—H7B	108.2
C6—C1—C2—C3	−1.8 (4)	C2—C1—C6—C5	6.1 (4)
C7—C1—C2—C3	172.0 (3)	C7—C1—C6—C5	−167.5 (2)
C1—C2—C3—C4	−2.6 (5)	C2—C1—C7—C5^ii	−104.3 (3)
C2—C3—C4—C5	2.9 (5)	C6—C1—C7—C5^ii	69.1 (3)
C3—C4—C5—C6	1.2 (4)	O1—C8—C9—O2	−8.5 (7)
C3—C4—C5—C7^i	−173.7 (3)	O1—C8—C9—O3	167.7 (4)
C4—C5—C6—O1	177.6 (2)	C5—C6—O1—C8	−111.3 (3)
C7^i—C5—C6—O1	−7.4 (3)	C1—C6—O1—C8	72.1 (3)
C4—C5—C6—C1	−5.8 (4)	C9—C8—O1—C6	126.5 (4)
C7^i—C5—C6—C1	169.1 (2)	O2—C9—O3—C10	5.8 (10)
C2—C1—C6—O1	−177.4 (2)	C8—C9—O3—C10	−170.5 (6)
C7—C1—C6—O1	9.0 (3)	C11—C10—O3—C9	86.2 (9)

Symmetry codes: (i) y, −x+1, −z+1; (ii) −y+1, x, −z+1.