The rubidium salt of an ω-hydroxy­carboxyl­ic acid with six ethereal O atoms

The title compound, aqua­[2-({2-[2-(2-{2-[2-(2-hydroxy­ethoxy)­phenoxy]­ethoxy}phenoxy)­ethoxy]­phenoxy}­methyl)­ben­zoato]­rubidium monohydrate, [Rb(C₃₂H₃₃O₁₀)]·H₂O, shows a monomeric structure. The polyether chain encloses Rb⁺ and adopts an S-like conformation. The Rb⁺ centre is ninefold coordinated by one O atom of the carboxyl­ate group, the O atom of the terminal hydroxy group, six ethereal O atoms and one water mol­ecule. An intermolecular hydrogen bond was observed between the terminal hydroxy group and the hydrate water mol­ecule.

Key indicators

• Single-crystal X-ray study
• T = 123 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.040
• wR factor = 0.115
• Data-to-parameter ratio = 16.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

Naturally occurring acid ionophores are known to mediate active ion transport through lipophilic membranes by formation of hydrophobic complexes with ions (Taylor et al., 1982, and references therein) and their structures were studied to provide information on their function (Duesler & Paul, 1983, and references therein). We have synthesized a series of relatively simple ω-hydroxycarboxylic acids as model compounds for the naturally occurring ionophores to investigate the relationship between the primary molecular structures and ion-transport properties (Kuboniwa et al., 1982, 1985; Yamazaki et al., 1978, 1979; Yamaguchi et al., 1988, 1989).

The model compounds, (1)–(3), transport K⁺ over Na⁺ through the ClCH₂CH₂Cl membrane using the pH gradient of outer aqueous phases. The competitive ion-transport experiments show that the amount of transported ions, as well as K⁺ selectivity over Na⁺, increases in the order of (1) → (2) → (3) (Kuboniwa et al., 1985; Yamaguchi et al., 1988). The model compound, (1), having five ethereal O atoms, forms a 2:2 dimer with K⁺. The polyether chain of (1) encloses K⁺ and adopts an S-like conformation. One hydroxy group, six ethereal O atoms including one from the polyether chain of the dimer, and two water molecules coordinate to K⁺ and the cation is a ninefold coordination. Two O atoms of the carboxylate group do not coordinate to the cation. Solvent water molecules are located between the K salt molecules (Kasuga et al., 1995). Compound (3), having eight ethereal O atoms, forms 1:1 salts with K⁺, Rb⁺ and Cs⁺. The conformation of three alkali metal salts of (3) are very similar to each other. The backbone of three salts of (3) forms a pseudocyclic ring by head-to-tail hydrogen bonding between the terminal carboxylate and hydroxy groups. The main chain of (3) is bent at O12 and O39 and wraps the cation like the seam of a tennis ball to give a complex with a lipophilic exterior. One hydroxy group, eight ethereal O atoms of the main chain and one O atom of the carboxylate group participate in the coordination and K⁺ is tenfold coordinated. The chloroform molecules, used as the recrystallization solvent, fill the space between the salt molecules in the crystals (Kuboniwa et al., 1988; Kasuga et al., 1991). Slow evaporation of a chloroform solution of the Rb salt of (2), which has six ethereal O atoms and shows ion-transport properties intermediate between those of (1) and (3), afforded single crystals. This paper reports the structure of the Rb salt of (2), i.e. (I).

The molecular structure of (I) (Fig. 1) reveals that the salt forms a 1:1 monomeric structure. The Rb—O distances [2.877 (3)–3.147 (3) Å] indicate that one O atom of the carboxylate group, six ethereal O atoms, the terminal hydroxy group and a water molecule coordinate to Rb⁺. As a result, Rb⁺ is ninefold coordinated. Water coordination to the cation is observed in the structure of the K salt of (1), but not in the structure of the K salt of (3). In (I), another water molecule (O44) lies near the coordinating water molecule (O43), with an O43···O44 distance of 3.151 (4) Å. The O42···O44 distance of 2.724 (4) Å shows that intermolecular hydrogen bonding is formed between the terminal hydroxy group and the solvent water molecule. The head-to-tail hydrogen bonding seen in the structure of the K salt of (3) is not observed in (I). Generally, Csp³—Csp³—O—Csp²(quaternary) torsion angles are near 180°, Csp²—Csp²(quaternary)—O—Csp³ are 0° and O—Csp³—Csp³—O are gauche. In (I), this rule also holds except four torsion angles, C10—C11—O12—C13 [-65.0 (4)°], C14—C13—O12—C11 [-22.4 (5)°], C20—C21—O22—C23 [70.4 (4)°] and C24—C23—O22—C21 [69.8 (4)°]. Consequently, the backbone bend of (2) in (I) occurs in a shorter period (O12 and O22) compared with that in the alkali metal salts of (3) (O12 and O39).

In conclusion, the three-dimensional structure of the Rb salt of (2) is intermediate between that of the K salt of (1) and that of the alkali metal salts of (3).

S2. Experimental

Model compound (2) was synthesized using successive Williamson's method (Kuboniwa et al., 1985). Ion-transport experiment using (2) through a ClCH₂CH₂Cl liquid membrane was carried out in a U-tube apparatus as described previously (Yamaguchi et al., 1988), however, transported ions were analyzed by atomic absorption spectrometry instead of flame analysis. The analysis showed that 22% of Na⁺ and 73% of K⁺ were transported by (2) with errors of about 5% in 5 d. A solution of RbOH in MeOH (0.54 ml, 3.74 mM) was added to the solution of (2) (11.3 mg) in 20 ml MeOH and the mixture was stirred overnight. After removal of the solvent, the solid was dried in vacuo. Compound (2) and its Rb salt were characterized by EA, IR, ¹H and ¹³C NMR. A chloroform solution of the Rb salt of (2) was slowly evaporated to give single crystals of (I). Crystals of the K salt of (2) were also obtained from chloroform solution, however, the quality of the reflection data was not good.

S3. Refinement

H atoms attached to C atoms were included in idealized positions and refined using a riding model (C—H = 0.93 Å). H atoms attached to O atoms were found in the difference Fourier maps and their positional parameters were refined with restraints on the O—H distances. The O—H distances were 0.803 (18)–1.00 (4) Å.

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Molecular Structure Corporation and Rigaku, 2001); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. An ORTEP-3 drawing (Farrugia, 1997) of (I) with 50% probability displacement ellipsoids.

2-[[2-[2-[2-[2-[2-(2-Hydroxyethoxy)phenoxy]ethoxy]phenoxy]ethoxy] phenoxy]methyl]benzoato-aquarubidium monohydrate

Crystal data

[Rb(C32H33O10)]·H2O	F(000) = 704
Mr = 681.07	Dx = 1.50 Mg m^−3
Triclinic, P1	Melting point: not measured K
a = 10.0948 (10) Å	Mo Kα radiation, λ = 0.71069 Å
b = 11.2408 (10) Å	Cell parameters from 1053 reflections
c = 14.055 (3) Å	θ = 2.3–13.7°
α = 85.524 (11)°	µ = 1.70 mm^−1
β = 71.679 (11)°	T = 123 K
γ = 89.852 (14)°	Platelet, colorless
V = 1509.0 (4) Å^3	0.30 × 0.10 × 0.05 mm
Z = 2

Data collection

Rigaku RAXIS-RAPID Imaging Plate diffractometer	6684 independent reflections
Radiation source: rotor	4520 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
Detector resolution: 10.0 pixels mm^-1	θmax = 27.3°, θmin = 1.5°
ω scans	h = −13→13
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −14→14
Tmin = 0.616, Tmax = 0.919	l = −18→18
12683 measured 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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 0.94	w = 1/[σ^2(Fo^2) + (0.0549P)^2] where P = (Fo^2 + 2Fc^2)/3
6684 reflections	(Δ/σ)max < 0.001
413 parameters	Δρmax = 0.53 e Å^−3
4 restraints	Δρmin = −0.52 e Å^−3

Special details

Experimental. Compound 2. Anal. Calcd. for C₃₂H₃₂O₉ 0.5H₂O. C 67.47, H 5.84. Found. C 67.53, H 5.69. ¹H NMR (500 MHz, CDCl₃) δ 3.85(2H, t, J=4.1 Hz), 4.04(2H, t, J=4.1 Hz), 4.33–4.37(8H,m), 5.39(2H, s), 6.85–6.96(12H, m), 7.31(1H, t, J=7.7 Hz), 7.44(1H, t, J=7.7 Hz), 7.59(1H, d, J=7.7 Hz), 7.82(1H, d, J=7.7 Hz). ¹³C NMR (125 MHz, CDCl₃) δ 61.09, 67.98, 68.05(2 C), 68.30, 70.19, 71.77, 114.60, 114.88, 115.12, 115.54, 115.64, 115.93, 121.83(2 C), 121.87, 122.02, 122.25(2 C), 127.56, 128.45, 128.79, 130.95, 132.31, 139.00, 148.57, 148.74, 148.88, 149.01, 149.10(2 C), 169.60. IR (KBr) ν _C=O 1684 cm^-1.

Rb salt of 2. Anal. Calcd. for C₃₂H₃₁O₉Rb 0.25H₂O. C, 59.17 H, 4.89 O, 22.78 Rb, 13.16. Found (E. Pascher, Remagen, Germany) C 59.05, H 5.03, O 22.4, Cl < 0.1, Rb, 13.2. IR (KBr) ν _C=O 1637 cm^{-1. 1}H NMR (500 MHz, CDCl₃) δ 3.85(2H, m), 3.96 (2H, m), 4.07(2H, m), 4.15(2H, m), 4.26(2H, m), 4.34(2H, m), 5.30(2H, s), 6.63(1H, d, J=8.1 Hz), 6.76–7.02 (11H, m), 7.09–7.18 (3H, m), 7.62(1H, d, J=7.3 Hz). ¹³C NMR (125 MHz, CDCl₃) δ 59.78, 66.72, 67.31, 67.42, 68.07, 70.07, 70.65, 112.80, 113.07, 113.67, 114.25, 114.59, 114.78, 120.86, 120.91, 122.17, 122.21, 122.32, 122.75, 127.13, 128.38, 128.89, 130.05, 132.88, 142.59, 147.04, 147.37, 147.57, 147.98, 148.23, 148.92, 174.72.

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
C4	0.7051 (4)	0.4217 (3)	0.3119 (3)	0.0181 (8)
C5	0.8510 (3)	0.4029 (3)	0.3179 (2)	0.0161 (7)
C6	0.9029 (4)	0.2873 (4)	0.3098 (3)	0.0220 (8)
H6	0.8519	0.2274	0.2940	0.026*
C7	1.0295 (4)	0.2609 (4)	0.3251 (3)	0.0270 (9)
H7	1.0634	0.1840	0.3186	0.032*
C8	1.1049 (4)	0.3490 (4)	0.3499 (3)	0.0316 (10)
H8	1.1875	0.3308	0.3635	0.038*
C9	1.0568 (4)	0.4646 (4)	0.3545 (3)	0.0239 (9)
H9	1.1093	0.5238	0.3697	0.029*
C10	0.9324 (4)	0.4948 (3)	0.3372 (3)	0.0176 (8)
C11	0.8946 (4)	0.6252 (3)	0.3314 (3)	0.0181 (8)
H11A	0.8071	0.6372	0.3833	0.022*
H11B	0.9662	0.6738	0.3432	0.022*
C13	1.0020 (3)	0.6608 (3)	0.1519 (3)	0.0149 (7)
C14	1.1362 (3)	0.6664 (3)	0.1586 (3)	0.0173 (8)
H14	1.1490	0.6706	0.2209	0.021*
C15	1.2521 (3)	0.6656 (3)	0.0721 (3)	0.0193 (8)
H15	1.3418	0.6675	0.0772	0.023*
C16	1.2332 (4)	0.6622 (3)	−0.0211 (3)	0.0206 (8)
H16	1.3102	0.6632	−0.0788	0.025*
C17	1.0989 (3)	0.6571 (3)	−0.0285 (3)	0.0174 (8)
H17	1.0868	0.6554	−0.0913	0.021*
C18	0.9827 (3)	0.6547 (3)	0.0575 (3)	0.0150 (7)
C20	0.8282 (3)	0.6411 (3)	−0.0405 (3)	0.0169 (8)
H20A	0.8775	0.5741	−0.0738	0.020*
H20B	0.8652	0.7138	−0.0822	0.020*
C21	0.6742 (4)	0.6276 (3)	−0.0251 (3)	0.0183 (8)
H21A	0.6603	0.6151	−0.0889	0.022*
H21B	0.6371	0.5579	0.0208	0.022*
C23	0.6229 (3)	0.8331 (3)	−0.0510 (3)	0.0168 (8)
C24	0.5756 (4)	0.8421 (4)	−0.1333 (3)	0.0222 (8)
H24	0.5329	0.7763	−0.1486	0.027*
C25	0.5913 (4)	0.9488 (4)	−0.1937 (3)	0.0281 (9)
H25	0.5583	0.9551	−0.2486	0.034*
C26	0.6566 (4)	1.0448 (4)	−0.1706 (3)	0.0313 (10)
H26	0.6679	1.1162	−0.2107	0.038*
C27	0.7058 (4)	1.0368 (4)	−0.0887 (3)	0.0264 (9)
H27	0.7495	1.1026	−0.0743	0.032*
C28	0.6899 (4)	0.9308 (3)	−0.0283 (3)	0.0193 (8)
C30	0.7926 (4)	1.0163 (3)	0.0827 (3)	0.0208 (8)
H30A	0.7226	1.0770	0.1000	0.025*
H30B	0.8713	1.0494	0.0274	0.025*
C31	0.8388 (4)	0.9786 (3)	0.1713 (3)	0.0220 (8)
H31A	0.9035	0.9137	0.1557	0.026*
H31B	0.8852	1.0448	0.1891	0.026*
C33	0.7335 (4)	0.9188 (3)	0.3464 (3)	0.0194 (8)
C34	0.8582 (4)	0.9322 (3)	0.3667 (3)	0.0241 (9)
H34	0.9394	0.9559	0.3152	0.029*
C35	0.8607 (4)	0.9099 (4)	0.4645 (3)	0.0285 (9)
H35	0.9443	0.9176	0.4784	0.034*
C36	0.7414 (4)	0.8767 (4)	0.5407 (3)	0.0278 (9)
H36	0.7438	0.8652	0.6064	0.033*
C37	0.6160 (4)	0.8600 (4)	0.5209 (3)	0.0237 (8)
H37	0.5357	0.8356	0.5730	0.028*
C38	0.6112 (4)	0.8799 (3)	0.4235 (3)	0.0187 (8)
C40	0.3705 (4)	0.8165 (3)	0.4715 (3)	0.0200 (8)
H40A	0.3376	0.8730	0.5221	0.024*
H40B	0.3903	0.7424	0.5040	0.024*
C41	0.2611 (4)	0.7952 (4)	0.4225 (3)	0.0218 (8)
H41A	0.1749	0.7691	0.4740	0.026*
H41B	0.2438	0.8699	0.3894	0.026*
O2	0.6344 (2)	0.5027 (2)	0.36233 (18)	0.0200 (6)
O3	0.6603 (3)	0.3542 (3)	0.2613 (2)	0.0271 (6)
O12	0.8813 (2)	0.6621 (2)	0.23368 (17)	0.0152 (5)
O19	0.8465 (2)	0.6454 (2)	0.05654 (17)	0.0157 (5)
O22	0.5985 (2)	0.7317 (2)	0.01520 (17)	0.0165 (5)
O29	0.7355 (3)	0.9132 (2)	0.05368 (18)	0.0209 (6)
O32	0.7169 (2)	0.9406 (2)	0.25301 (18)	0.0207 (6)
O39	0.4953 (2)	0.8634 (2)	0.39466 (17)	0.0183 (5)
O42	0.3000 (3)	0.7082 (3)	0.35054 (19)	0.0216 (6)
O44	0.3517 (3)	0.4964 (3)	0.4390 (2)	0.0233 (6)
O43	0.4577 (3)	0.4757 (3)	0.2049 (2)	0.0256 (6)
Rb1	0.59851 (3)	0.70710 (3)	0.22048 (3)	0.01660 (10)
H42	0.309 (4)	0.648 (2)	0.383 (3)	0.018 (11)*
H43A	0.518 (4)	0.420 (4)	0.231 (3)	0.025*
H43B	0.384 (3)	0.470 (4)	0.251 (2)	0.025*
H44A	0.436 (2)	0.493 (3)	0.415 (3)	0.019*
H44B	0.336 (4)	0.490 (4)	0.4988 (15)	0.019*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C4	0.0182 (17)	0.022 (2)	0.0129 (17)	0.0008 (15)	−0.0038 (14)	0.0022 (15)
C5	0.0190 (17)	0.019 (2)	0.0083 (15)	−0.0007 (14)	−0.0021 (14)	0.0040 (14)
C6	0.0219 (19)	0.025 (2)	0.0180 (18)	−0.0029 (15)	−0.0056 (16)	0.0014 (16)
C7	0.024 (2)	0.019 (2)	0.036 (2)	0.0033 (16)	−0.0078 (18)	0.0060 (18)
C8	0.0167 (19)	0.034 (3)	0.043 (3)	0.0007 (17)	−0.0123 (18)	0.014 (2)
C9	0.0195 (18)	0.024 (2)	0.029 (2)	−0.0042 (15)	−0.0114 (17)	0.0070 (17)
C10	0.0175 (17)	0.021 (2)	0.0138 (17)	−0.0011 (14)	−0.0060 (14)	0.0042 (15)
C11	0.0168 (17)	0.024 (2)	0.0146 (17)	−0.0027 (14)	−0.0066 (14)	−0.0012 (15)
C13	0.0152 (17)	0.0082 (17)	0.0182 (17)	−0.0026 (13)	−0.0012 (14)	0.0004 (14)
C14	0.0197 (18)	0.0108 (18)	0.0224 (18)	−0.0030 (13)	−0.0086 (15)	0.0011 (15)
C15	0.0113 (16)	0.0152 (19)	0.032 (2)	−0.0011 (13)	−0.0073 (15)	−0.0011 (16)
C16	0.0168 (17)	0.0138 (19)	0.026 (2)	−0.0024 (14)	0.0001 (15)	−0.0015 (16)
C17	0.0187 (17)	0.0143 (19)	0.0167 (17)	−0.0002 (14)	−0.0020 (15)	−0.0009 (15)
C18	0.0145 (16)	0.0107 (18)	0.0194 (18)	−0.0002 (13)	−0.0046 (15)	−0.0006 (14)
C20	0.0203 (17)	0.016 (2)	0.0139 (17)	0.0023 (14)	−0.0048 (15)	−0.0024 (14)
C21	0.0215 (18)	0.0144 (19)	0.0203 (18)	0.0005 (14)	−0.0084 (15)	−0.0021 (15)
C23	0.0159 (17)	0.017 (2)	0.0155 (17)	0.0047 (14)	−0.0032 (14)	0.0010 (15)
C24	0.0180 (18)	0.030 (2)	0.0187 (18)	0.0051 (15)	−0.0057 (15)	−0.0036 (17)
C25	0.034 (2)	0.034 (3)	0.0150 (18)	0.0106 (18)	−0.0075 (17)	0.0043 (17)
C26	0.043 (2)	0.027 (2)	0.020 (2)	0.0109 (19)	−0.0054 (18)	0.0059 (17)
C27	0.038 (2)	0.015 (2)	0.022 (2)	0.0010 (17)	−0.0041 (18)	0.0014 (16)
C28	0.0214 (18)	0.017 (2)	0.0164 (18)	0.0033 (14)	−0.0026 (15)	0.0006 (15)
C30	0.0233 (18)	0.014 (2)	0.0223 (19)	−0.0065 (15)	−0.0031 (16)	−0.0001 (15)
C31	0.0175 (18)	0.019 (2)	0.026 (2)	−0.0048 (15)	−0.0016 (16)	−0.0046 (16)
C33	0.0258 (19)	0.0140 (19)	0.0224 (19)	0.0016 (15)	−0.0119 (16)	−0.0069 (15)
C34	0.024 (2)	0.018 (2)	0.034 (2)	−0.0001 (15)	−0.0130 (18)	−0.0073 (17)
C35	0.034 (2)	0.021 (2)	0.042 (2)	0.0084 (17)	−0.027 (2)	−0.0128 (19)
C36	0.040 (2)	0.023 (2)	0.029 (2)	0.0100 (18)	−0.022 (2)	−0.0063 (18)
C37	0.034 (2)	0.020 (2)	0.0207 (19)	0.0070 (16)	−0.0129 (17)	−0.0039 (16)
C38	0.0236 (19)	0.0128 (19)	0.0215 (19)	0.0032 (14)	−0.0093 (16)	−0.0035 (15)
C40	0.0232 (19)	0.020 (2)	0.0144 (17)	−0.0012 (15)	−0.0016 (15)	−0.0014 (15)
C41	0.0193 (18)	0.025 (2)	0.0187 (18)	0.0017 (15)	−0.0026 (15)	−0.0021 (16)
O2	0.0156 (12)	0.0259 (15)	0.0179 (13)	0.0009 (10)	−0.0044 (10)	−0.0014 (11)
O3	0.0264 (14)	0.0303 (17)	0.0303 (15)	0.0028 (12)	−0.0148 (12)	−0.0120 (13)
O12	0.0144 (11)	0.0176 (14)	0.0122 (12)	0.0004 (9)	−0.0027 (10)	0.0012 (10)
O19	0.0117 (11)	0.0199 (14)	0.0157 (12)	−0.0008 (9)	−0.0049 (10)	−0.0009 (10)
O22	0.0170 (12)	0.0146 (13)	0.0174 (12)	0.0012 (10)	−0.0051 (10)	0.0011 (10)
O29	0.0308 (14)	0.0134 (14)	0.0206 (13)	−0.0031 (11)	−0.0117 (11)	0.0011 (11)
O32	0.0200 (13)	0.0245 (15)	0.0169 (13)	−0.0053 (11)	−0.0053 (11)	0.0016 (11)
O39	0.0190 (12)	0.0231 (15)	0.0133 (12)	−0.0014 (10)	−0.0064 (10)	0.0010 (11)
O42	0.0254 (14)	0.0226 (16)	0.0172 (13)	−0.0020 (12)	−0.0080 (11)	0.0012 (12)
O44	0.0169 (13)	0.0328 (17)	0.0185 (13)	−0.0003 (12)	−0.0035 (12)	−0.0007 (13)
O43	0.0221 (14)	0.0348 (18)	0.0211 (14)	−0.0015 (13)	−0.0079 (12)	−0.0052 (13)
Rb1	0.01534 (16)	0.01794 (19)	0.01532 (17)	−0.00006 (12)	−0.00305 (13)	−0.00152 (13)

Geometric parameters (Å, º)

C4—O3	1.253 (4)	C27—H27	0.9300
C4—O2	1.273 (4)	C28—O29	1.370 (4)
C4—C5	1.515 (5)	C30—O29	1.438 (4)
C5—C6	1.399 (5)	C30—C31	1.492 (5)
C5—C10	1.415 (5)	C30—H30A	0.9700
C6—C7	1.389 (5)	C30—H30B	0.9700
C6—H6	0.9300	C31—O32	1.433 (4)
C7—C8	1.381 (6)	C31—H31A	0.9700
C7—H7	0.9300	C31—H31B	0.9700
C8—C9	1.385 (6)	C33—O32	1.378 (4)
C8—H8	0.9300	C33—C34	1.386 (5)
C9—C10	1.388 (5)	C33—C38	1.406 (5)
C9—H9	0.9300	C34—C35	1.386 (6)
C10—C11	1.516 (5)	C34—H34	0.9300
C11—O12	1.450 (4)	C35—C36	1.366 (6)
C11—H11A	0.9700	C35—H35	0.9300
C11—H11B	0.9700	C36—C37	1.395 (5)
C13—O12	1.389 (4)	C36—H36	0.9300
C13—C14	1.389 (5)	C37—C38	1.385 (5)
C13—C18	1.407 (5)	C37—H37	0.9300
C14—C15	1.398 (5)	C38—O39	1.371 (4)
C14—H14	0.9300	C40—O39	1.445 (4)
C15—C16	1.386 (5)	C40—C41	1.502 (5)
C15—H15	0.9300	C40—H40A	0.9700
C16—C17	1.393 (5)	C40—H40B	0.9700
C16—H16	0.9300	C41—O42	1.427 (4)
C17—C18	1.393 (5)	C41—H41A	0.9700
C17—H17	0.9300	C41—H41B	0.9700
C18—O19	1.383 (4)	O2—Rb1	3.020 (3)
C20—O19	1.437 (4)	O12—Rb1	2.958 (2)
C20—C21	1.507 (5)	O19—Rb1	2.945 (2)
C20—H20A	0.9700	O22—Rb1	2.877 (3)
C20—H20B	0.9700	O29—Rb1	3.147 (3)
C21—O22	1.449 (4)	O32—Rb1	3.012 (3)
C21—H21A	0.9700	O39—Rb1	3.037 (2)
C21—H21B	0.9700	O42—Rb1	2.994 (3)
C23—C24	1.380 (5)	O43—Rb1	3.023 (3)
C23—O22	1.385 (4)	O42—O43	3.510 (4)
C23—C28	1.399 (5)	O42—H42	0.807 (19)
C24—C25	1.394 (6)	O42—O44	2.724 (4)
C24—H24	0.9300	O43—O44	3.151 (4)
C25—C26	1.377 (6)	O44—H44A	0.816 (18)
C25—H25	0.9300	O44—H44B	0.803 (18)
C26—C27	1.386 (6)	O43—H43A	1.00 (4)
C26—H26	0.9300	O43—H43B	0.819 (18)
C27—C28	1.387 (5)
O3—C4—O2	124.6 (3)	C31—C30—H30B	110.1
O3—C4—C5	118.4 (3)	H30A—C30—H30B	108.4
O2—C4—C5	117.0 (3)	O32—C31—C30	107.6 (3)
C6—C5—C10	119.1 (3)	O32—C31—H31A	110.2
C6—C5—C4	117.7 (3)	C30—C31—H31A	110.2
C10—C5—C4	123.1 (3)	O32—C31—H31B	110.2
C7—C6—C5	120.9 (4)	C30—C31—H31B	110.2
C7—C6—H6	119.6	H31A—C31—H31B	108.5
C5—C6—H6	119.6	O32—C33—C34	124.9 (3)
C8—C7—C6	120.0 (4)	O32—C33—C38	114.5 (3)
C8—C7—H7	120.0	C34—C33—C38	120.6 (4)
C6—C7—H7	120.0	C33—C34—C35	119.4 (4)
C7—C8—C9	119.5 (4)	C33—C34—H34	120.3
C7—C8—H8	120.2	C35—C34—H34	120.3
C9—C8—H8	120.2	C36—C35—C34	120.6 (4)
C8—C9—C10	122.0 (4)	C36—C35—H35	119.7
C8—C9—H9	119.0	C34—C35—H35	119.7
C10—C9—H9	119.0	C35—C36—C37	120.6 (4)
C9—C10—C5	118.4 (3)	C35—C36—H36	119.7
C9—C10—C11	119.1 (3)	C37—C36—H36	119.7
C5—C10—C11	122.4 (3)	C38—C37—C36	119.9 (4)
O12—C11—C10	110.7 (3)	C38—C37—H37	120.1
O12—C11—H11A	109.5	C36—C37—H37	120.1
C10—C11—H11A	109.5	O39—C38—C37	125.0 (3)
O12—C11—H11B	109.5	O39—C38—C33	116.0 (3)
C10—C11—H11B	109.5	C37—C38—C33	118.9 (3)
H11A—C11—H11B	108.1	O39—C40—C41	108.3 (3)
O12—C13—C14	124.1 (3)	O39—C40—H40A	110.0
O12—C13—C18	116.1 (3)	C41—C40—H40A	110.0
C14—C13—C18	119.8 (3)	O39—C40—H40B	110.0
C13—C14—C15	120.4 (3)	C41—C40—H40B	110.0
C13—C14—H14	119.8	H40A—C40—H40B	108.4
C15—C14—H14	119.8	O42—C41—C40	113.0 (3)
C16—C15—C14	119.9 (3)	O42—C41—H41A	109.0
C16—C15—H15	120.1	C40—C41—H41A	109.0
C14—C15—H15	120.1	O42—C41—H41B	109.0
C15—C16—C17	120.1 (3)	C40—C41—H41B	109.0
C15—C16—H16	120.0	H41A—C41—H41B	107.8
C17—C16—H16	120.0	C13—O12—C11	116.5 (3)
C18—C17—C16	120.5 (3)	C18—O19—C20	116.2 (2)
C18—C17—H17	119.7	C23—O22—C21	115.1 (3)
C16—C17—H17	119.7	C28—O29—C30	116.3 (3)
O19—C18—C17	123.8 (3)	C33—O32—C31	116.9 (3)
O19—C18—C13	116.8 (3)	C38—O39—C40	117.1 (3)
C17—C18—C13	119.3 (3)	C41—O42—H42	104 (3)
O19—C20—C21	108.0 (3)	H44A—O44—H44B	105 (4)
O19—C20—H20A	110.1	H43A—O43—H43B	102 (4)
C21—C20—H20A	110.1	O22—Rb1—O19	59.55 (7)
O19—C20—H20B	110.1	O22—Rb1—O12	111.69 (6)
C21—C20—H20B	110.1	O19—Rb1—O12	53.18 (6)
H20A—C20—H20B	108.4	O22—Rb1—O42	106.89 (7)
O22—C21—C20	111.9 (3)	O19—Rb1—O42	159.16 (7)
O22—C21—Rb1	53.94 (16)	O12—Rb1—O42	140.90 (7)
C20—C21—Rb1	90.3 (2)	O22—Rb1—O32	105.10 (7)
O22—C21—H21A	109.2	O19—Rb1—O32	95.62 (7)
C20—C21—H21A	109.2	O12—Rb1—O32	72.46 (7)
Rb1—C21—H21A	158.9	O42—Rb1—O32	103.64 (7)
O22—C21—H21B	109.2	O22—Rb1—O2	135.12 (7)
C20—C21—H21B	109.2	O19—Rb1—O2	93.21 (7)
Rb1—C21—H21B	71.3	O12—Rb1—O2	61.61 (6)
H21A—C21—H21B	107.9	O42—Rb1—O2	86.59 (7)
C24—C23—O22	122.0 (3)	O32—Rb1—O2	113.06 (7)
C24—C23—C28	120.2 (3)	O22—Rb1—O43	78.18 (7)
O22—C23—C28	117.7 (3)	O19—Rb1—O43	89.54 (7)
C23—C24—C25	120.7 (4)	O12—Rb1—O43	110.32 (7)
C23—C24—H24	119.7	O42—Rb1—O43	71.37 (7)
C25—C24—H24	119.7	O32—Rb1—O43	174.79 (7)
C26—C25—C24	118.8 (4)	O2—Rb1—O43	65.74 (7)
C26—C25—H25	120.6	O22—Rb1—O39	133.16 (7)
C24—C25—H25	120.6	O19—Rb1—O39	143.85 (6)
C25—C26—C27	121.2 (4)	O12—Rb1—O39	98.52 (6)
C25—C26—H26	119.4	O42—Rb1—O39	56.96 (7)
C27—C26—H26	119.4	O32—Rb1—O39	50.51 (6)
C26—C27—C28	120.1 (4)	O2—Rb1—O39	90.40 (7)
C26—C27—H27	120.0	O43—Rb1—O39	124.30 (7)
C28—C27—H27	120.0	O22—Rb1—O29	51.97 (7)
O29—C28—C27	124.7 (4)	O19—Rb1—O29	63.52 (7)
O29—C28—C23	116.2 (3)	O12—Rb1—O29	87.19 (7)
C27—C28—C23	119.0 (4)	O42—Rb1—O29	122.75 (7)
O29—C30—C31	108.2 (3)	O32—Rb1—O29	53.81 (7)
O29—C30—H30A	110.1	O2—Rb1—O29	148.71 (6)
C31—C30—H30A	110.1	O43—Rb1—O29	129.94 (7)
O29—C30—H30B	110.1	O39—Rb1—O29	96.95 (7)
C10—C11—O12—C13	−65.0 (4)	C24—C23—O22—C21	69.8 (4)
C21—C20—O19—C18	178.4 (3)	C27—C28—O29—C30	5.6 (5)
C20—C21—O22—C23	70.4 (4)	C34—C33—O32—C31	0.7 (5)
C31—C30—O29—C28	−178.8 (3)	C37—C38—O39—C40	−2.9 (5)
C30—C31—O32—C33	−170.6 (3)	O19—C20—C21—O22	65.6 (4)
C41—C40—O39—C38	−175.0 (3)	O29—C30—C31—O32	−64.8 (4)
C14—C13—O12—C11	−22.4 (5)	O39—C40—C41—O42	62.6 (4)
C17—C18—O19—C20	−1.5 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O42—H42···O44	0.81 (2)	1.93 (2)	2.724 (4)	169 (4)