Hydrogen-bond network in cyclodecaamylose hydrate at 20 K; neutron diffraction study of novel structural motifs band-flip and kink in α-(1→4)-D-glucoside oligosaccharides

A single-crystal neutron diffraction study of cyclodecaamylose (CA10) was carried out at 20 K. CA10 crystallizes with 27.18 water molecules [(C₆H₁₀O₅)₁₀·27.18H₂O] in space group C2 with unit-cell constants a = 29.31 (5), b = 9.976 (10), c = 19.34 (2) Å, β = 121.07 (2)°. The asymmetric unit contains a half molecule of CA10 and 13.59 water molecules, the other half being related by a crystallographic twofold rotation axis. All H atoms except two water H atoms could be located from difference neutron-density maps; structure refinement converged at R = 0.635. Two of the five CH₂—O6 groups and one of the 15 O2, O3 hydroxyl groups of CA10 are twofold orientationally disordered. A total of 13.59 water molecules in the asymmetric unit are distributed over 23 positions; 20 of which are in the CA10 cavity, and the other three occupy intermolecular interstices. Of the 123 symmetry-independent hydrogen bonds, 25 (= 20%) are three-centered and 7 (= 6%) are four-centered. Water molecules and O—H groups of CA10 form an extended network with cooperative O—H...O—H...O—H hydrogen bonds. They are arranged in 11 polygons with three, four, five, six and eight O—H bonds and in homodromic, antidromic and heterodromic arrangements. Nine polygons are located within the cavity and the others are outside.

Computing details

Data collection: ILL programs Hklgen and Mad; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: MOLSCRIPT, Xtal View; software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

[Cyclodecaamylose].27.18 H2 O

Crystal data

(C60H100O50)·27.18(H2O)	Dx = 1.446 Mg m^−3
Mr = 2108.30	Melting point: not measured K
Monoclinic, C2	Neutron radiation, λ = 1.53200 Å
a = 29.31 (5) Å	Cell parameters from 2193 reflections
b = 9.976 (10) Å	θ = 3.6–50.9°
c = 19.34 (2) Å	µ = 2.31 mm^−1
β = 121.07 (2)°	T = 20 K
V = 4843 (11) Å^3	Plate, colorless
Z = 2	1.0 × 0.6 × 0.2 mm
F(000) = 546

Data collection

D19 diffractometer	2355 reflections with I > 2σ(I)
Radiation source: neutron reactor at ILL	Rint = 0.048
Cu(220) monochromateor	θmax = 50.8°, θmin = 2.7°
4x64 deg. position–sensitive detector (Thomas et. al., 1983) scans	h = −29→29
Absorption correction: analytical ?	k = −4→10
Tmin = 0.816, Tmax = 0.948	l = −19→19
3929 measured reflections	3 standard reflections every 50 reflections
2494 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.064	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.148	w = 1/[σ^2(Fo^2) + (0.054P)^2 + 409.4507P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.073
2494 reflections	Δρmax = 1.04 e Å^−3
736 parameters	Δρmin = −1.08 e Å^−3
393 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0 (10)

Special details

Experimental. atomic scattering factors were taken from Sears (1992).

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	Occ. (<1)
C11	0.2610 (3)	−0.0239 (9)	−0.2546 (5)	0.0069 (18)*
H11	0.2751 (6)	−0.0462 (17)	−0.2933 (9)	0.019 (4)*
C21	0.2251 (3)	−0.1351 (9)	−0.2551 (4)	0.0075 (18)*
H21	0.2459 (6)	−0.2301 (18)	−0.2474 (9)	0.020 (4)*
C31	0.2145 (3)	−0.1201 (9)	−0.1857 (4)	0.0058 (17)*
H31	0.1922 (6)	−0.0267 (19)	−0.1957 (10)	0.022 (4)*
C41	0.2676 (3)	−0.1117 (8)	−0.1061 (4)	0.0030 (17)*
H41	0.2916 (6)	−0.206 (2)	−0.0931 (10)	0.027 (4)*
C51	0.2993 (3)	0.0090 (9)	−0.1116 (5)	0.0076 (18)*
H51	0.2750 (6)	0.0943 (19)	−0.1240 (9)	0.023 (4)*
C61A	0.3539 (5)	0.0400 (11)	−0.0338 (7)	0.004 (3)*	0.77
H611	0.3817 (10)	−0.051 (3)	−0.0172 (15)	0.021*	0.77
H621	0.3472 (8)	0.061 (2)	0.0160 (13)	0.020 (5)*	0.77
C61B	0.3548 (17)	0.006 (3)	−0.040 (2)	0.007*	0.23
H631	0.3749	0.0916	−0.0488	0.024*	0.23
H641	0.3506	0.0322	0.0116	0.024*	0.23
O21	0.1753 (4)	−0.1336 (11)	−0.3328 (5)	0.010 (2)*
HO21	0.1558 (6)	−0.218 (2)	−0.3416 (10)	0.026 (4)*
O31	0.1832 (3)	−0.2332 (10)	−0.1875 (5)	0.005 (2)*
HO31	0.1492 (7)	−0.1995 (19)	−0.1982 (10)	0.027 (4)*
O41	0.2605 (3)	−0.0779 (10)	−0.0403 (5)	0.009 (2)*
O51	0.3085 (3)	−0.0159 (11)	−0.1762 (6)	0.011 (2)*
O61A	0.3773 (5)	0.1505 (14)	−0.0470 (8)	0.011 (3)*	0.77
HO61	0.3998 (17)	0.199 (5)	0.001 (3)	0.083 (11)*	0.77
O61B	0.3933 (14)	−0.100 (5)	−0.011 (2)	0.005*	0.23
HB61	0.4288	−0.0627	0.0193	0.18 (5)*	0.23
C12	0.2476 (3)	−0.1844 (8)	−0.0061 (5)	0.0037 (17)*
H12	0.2182 (7)	−0.2521 (19)	−0.0540 (10)	0.026 (4)*
C22	0.2253 (3)	−0.1196 (8)	0.0411 (4)	0.0020 (17)*
H22	0.2078 (6)	−0.1984 (18)	0.0597 (9)	0.018 (4)*
C32	0.2695 (3)	−0.0466 (7)	0.1165 (4)	0.0069 (18)*
H32	0.2837	0.0378	0.0959	0.024 (4)*
C42	0.3175 (3)	−0.1441 (9)	0.1663 (4)	0.0065 (18)*
H42	0.3063 (6)	−0.2221 (18)	0.1915 (9)	0.018 (4)*
C52	0.3373 (2)	−0.1983 (7)	0.1123 (4)	0.0057 (18)*
H52	0.3493	−0.1136	0.0888	0.025 (4)*
C62	0.3844 (2)	−0.2930 (7)	0.1577 (4)	0.0070 (18)*
H612	0.3936	−0.3395	0.1147	0.028 (4)*
H622	0.4195	−0.2352	0.2016	0.031 (4)*
O22	0.1814 (3)	−0.0306 (11)	−0.0122 (5)	0.009 (2)*
HO22	0.1956 (7)	0.035 (2)	−0.0281 (10)	0.026 (4)*
O32	0.2508 (4)	0.0050 (10)	0.1647 (5)	0.009 (2)*
HO32	0.2301 (7)	−0.061 (2)	0.1711 (10)	0.026 (4)*
O42	0.3598 (3)	−0.0627 (10)	0.2287 (5)	0.011 (2)*
O52	0.2934 (4)	−0.2670 (10)	0.0456 (5)	0.012 (2)*
O62	0.3738 (4)	−0.3956 (12)	0.1991 (5)	0.014 (2)*
HB62	0.3917 (12)	−0.362 (3)	0.2587 (9)	0.014 (9)*	0.40
HO62	0.3891 (13)	−0.480 (4)	0.200 (2)	0.036 (8)*	0.60
C13	0.3834 (2)	−0.1035 (8)	0.3102 (4)	0.0080 (18)*
H13	0.3568	−0.1742	0.3160	0.017 (4)*
C23	0.3881 (3)	0.0258 (9)	0.3565 (5)	0.010 (2)*
H23	0.4052 (7)	0.0027 (19)	0.4212 (10)	0.027 (4)*
C33	0.4243 (3)	0.1221 (8)	0.3461 (4)	0.0053 (18)*
H33	0.4078 (7)	0.138 (2)	0.2808 (10)	0.030 (4)*
C43	0.4795 (3)	0.0542 (8)	0.3811 (3)	0.0095 (18)*
H43	0.4968	0.0382	0.4463	0.022 (4)*
C53	0.4742 (3)	−0.0808 (10)	0.3407 (5)	0.024 (2)*
H53	0.4617 (8)	−0.062 (2)	0.2767 (7)	0.042 (5)*
C63A	0.5267 (5)	−0.1482 (18)	0.3697 (13)	0.030 (6)*	0.57 (3)
H613	0.5537 (12)	−0.091 (3)	0.362 (2)	0.042 (9)*	0.57 (3)
H623	0.5197 (15)	−0.243 (3)	0.341 (2)	0.042 (12)*	0.57 (3)
C63B	0.5228 (6)	−0.1701 (19)	0.3954 (12)	0.006 (6)*	0.43 (3)
H633	0.561 (2)	−0.115 (5)	0.412 (4)	0.046 (14)*	0.43 (3)
H643	0.5288 (17)	−0.202 (4)	0.4552 (18)	0.014 (12)*	0.43 (3)
O23	0.3353 (3)	0.0819 (10)	0.3274 (6)	0.007 (2)*
HO23	0.3133 (6)	0.0730 (19)	0.2687 (10)	0.027 (4)*
O33	0.4294 (3)	0.2439 (10)	0.3873 (5)	0.008 (2)*
HO33	0.4486 (7)	0.308 (2)	0.3749 (10)	0.030 (4)*
O43	0.5135 (4)	0.1403 (11)	0.3693 (6)	0.015 (2)*
O53	0.4344 (4)	−0.1631 (11)	0.3418 (5)	0.015 (2)*
O63A	0.5436 (8)	−0.171 (2)	0.4479 (12)	0.008 (6)*	0.57 (3)
HO63	0.5820 (9)	−0.211 (3)	0.4792 (16)	0.035 (9)*	0.57 (3)
O63B	0.5289 (10)	−0.295 (3)	0.3636 (16)	0.019 (8)*	0.43 (3)
HB63	0.573 (2)	−0.320 (5)	0.405 (3)	0.060 (17)*	0.43 (3)
C14	0.5506 (3)	0.2137 (9)	0.4389 (5)	0.014 (2)*
H14	0.5367 (6)	0.2228 (16)	0.4798 (10)	0.027 (4)*
C24	0.5574 (3)	0.3560 (9)	0.4131 (5)	0.015 (2)*
H24	0.5833 (6)	0.4122 (18)	0.4658 (10)	0.023 (4)*
C34	0.5846 (3)	0.3455 (9)	0.3647 (5)	0.014 (2)*
H34	0.5597 (6)	0.2839 (18)	0.3098 (8)	0.032 (4)*
C44	0.6380 (3)	0.2687 (9)	0.4162 (5)	0.0076 (18)*
H44	0.6660 (6)	0.3259 (17)	0.4696 (9)	0.018 (4)*
C54	0.6287 (3)	0.1325 (8)	0.4413 (4)	0.0106 (18)*
H54	0.6045	0.0709	0.3872	0.024 (4)*
C64	0.6802 (2)	0.0558 (7)	0.5003 (4)	0.0087 (18)*
H614	0.6695	−0.0450	0.5104	0.022 (4)*
H624	0.7045	0.0440	0.4725	0.026 (4)*
O24	0.5055 (4)	0.4158 (12)	0.3672 (6)	0.013 (2)*
HO24	0.5048 (9)	0.479 (4)	0.400 (2)	0.031 (8)*	0.60
HB24	0.5078 (14)	0.529 (4)	0.362 (2)	0.009 (9)*	0.40
O34	0.5935 (4)	0.4747 (11)	0.3459 (6)	0.016 (2)*
HO34	0.6075 (6)	0.4663 (19)	0.3131 (10)	0.027 (4)*
O44	0.6620 (3)	0.2467 (10)	0.3687 (5)	0.009 (2)*
O54	0.6013 (3)	0.1480 (10)	0.4838 (5)	0.010 (2)*
O64	0.7117 (3)	0.1225 (10)	0.5777 (5)	0.009 (2)*
HO64	0.6929 (6)	0.1125 (18)	0.6057 (9)	0.018 (4)*
C15	0.7032 (3)	0.3388 (7)	0.3807 (4)	0.0046 (17)*
H15	0.7010	0.4282	0.4122	0.029 (4)*
C25	0.6924 (3)	0.3791 (9)	0.2986 (4)	0.0068 (18)*
H25	0.7215 (6)	0.4527 (18)	0.3072 (9)	0.019 (4)*
C35	0.6978 (3)	0.2608 (9)	0.2533 (4)	0.0077 (18)*
H35	0.6658 (6)	0.1830 (17)	0.2408 (9)	0.018 (4)*
C45	0.7549 (3)	0.2024 (8)	0.3099 (4)	0.0038 (17)*
H45	0.7830 (6)	0.2798 (18)	0.3215 (9)	0.020 (4)*
C55	0.7632 (3)	0.1632 (8)	0.3927 (4)	0.0044 (18)*
H55	0.7341 (5)	0.0838 (15)	0.3848 (8)	0.007 (3)*
C65	0.8200 (3)	0.1139 (9)	0.4519 (5)	0.0101 (19)*
H615	0.8241 (12)	0.009 (3)	0.4355 (18)	0.012 (10)*	0.75 (2)
H625	0.8268 (12)	0.099 (4)	0.5149 (19)	0.037 (12)*	0.75 (2)
H635	0.842 (4)	0.193 (8)	0.447 (6)	0.044*	0.25 (2)
H645	0.825 (5)	0.029 (9)	0.425 (7)	0.04 (4)*	0.25 (2)
O25	0.6383 (4)	0.4363 (11)	0.2507 (6)	0.015 (2)*
HO25	0.6426 (6)	0.5206 (19)	0.2258 (10)	0.023 (4)*
O35	0.6909 (4)	0.3053 (10)	0.1795 (6)	0.010 (2)*
HO35	0.6648 (8)	0.259 (2)	0.1360 (12)	0.036 (5)*
O45	0.7687 (3)	0.0965 (10)	0.2754 (5)	0.006 (2)*
O55	0.7541 (3)	0.2802 (10)	0.4273 (5)	0.010 (2)*
O65A	0.8611 (7)	0.195 (2)	0.4557 (11)	0.032 (6)*	0.75 (2)
HO65	0.8733 (8)	0.157 (2)	0.4249 (12)	0.024 (6)*	0.75 (2)
O65B	0.8267 (19)	0.121 (6)	0.534 (3)	0.012*	0.25 (2)
HB65	0.859 (3)	0.082 (10)	0.579 (6)	0.06 (3)*	0.25 (2)
OW8A	0.5483 (6)	0.2909 (13)	0.1440 (8)	0.021 (3)*	0.76
H1W8	0.5781 (11)	0.338 (3)	0.1806 (16)	0.036 (6)*	0.76
H2W8	0.5549 (17)	0.201 (2)	0.134 (3)	0.086 (11)*	0.76
OW8B	0.5224 (13)	0.443 (4)	0.142 (2)	0.016 (10)*	0.24
H3W8	0.5593 (16)	0.418 (11)	0.174 (5)	0.05 (2)*	0.24
OW17	0.4731 (7)	−0.542 (2)	−0.0192 (10)	0.018 (5)*	0.50
H117	0.467 (3)	−0.615 (4)	−0.055 (3)	0.11 (2)*	0.50
H217	0.4360 (15)	−0.515 (6)	−0.027 (5)	0.06 (2)*	0.25
H317	0.4807 (17)	−0.593 (5)	0.033 (2)	0.10 (4)*	0.25
OW0A	0.5771 (5)	0.0344 (15)	0.1350 (8)	0.032 (4)*	0.76
H101	0.5909 (15)	−0.047 (2)	0.1683 (18)	0.139 (19)*	0.76
H102	0.598 (2)	0.061 (4)	0.111 (4)	0.06 (2)*	0.26
H103	0.584 (2)	0.113 (3)	0.1697 (17)	0.13 (3)*	0.50
OW0B	0.5336 (16)	0.171 (4)	0.083 (3)	0.028 (11)*	0.24
H104	0.5035 (18)	0.124 (9)	0.0789 (19)	0.060*	0.24
H105	0.5393 (7)	0.111 (6)	0.0474 (16)	0.024 (16)*	0.24
OW6	0.5801 (16)	0.096 (5)	0.237 (2)	0.028 (11)*	0.24
H1W6	0.605 (2)	0.146 (8)	0.284 (3)	0.034 (18)*	0.24
H2W6	0.567 (6)	0.122 (17)	0.183 (4)	0.10 (4)*	0.24
O11A	0.4435 (8)	0.238 (4)	0.1084 (15)	0.017 (6)*	0.60
H111	0.4815 (12)	0.267 (4)	0.1243 (17)	0.025 (9)*	0.60
H112	0.4304 (17)	0.295 (6)	0.139 (3)	0.069 (11)*	0.60
O11B	0.4392 (9)	0.294 (4)	0.0966 (16)	0.009 (9)*	0.40
H113	0.4765 (11)	0.316 (7)	0.1260 (19)	0.06 (2)*	0.40
H114	0.437 (3)	0.197 (4)	0.095 (7)	0.09 (3)*	0.40
OW1	0.4159 (4)	0.3596 (9)	0.2106 (5)	0.010 (2)*
H1W1	0.4508 (7)	0.362 (2)	0.2616 (11)	0.033 (5)*
H2W1	0.4029 (11)	0.4497 (14)	0.203 (3)	0.056 (11)*	0.60
H3W1	0.4250 (15)	0.334 (5)	0.1714 (18)	0.024 (10)*	0.40
O18A	0.5306 (6)	−0.3281 (18)	0.2257 (8)	0.016 (4)*	0.65
H181	0.5394 (16)	−0.398 (3)	0.2643 (19)	0.073 (11)*	0.65
H182	0.5140 (11)	−0.249 (2)	0.230 (2)	0.17 (3)*	0.65
O18B	0.5243 (9)	−0.255 (3)	0.2229 (17)	0.013 (7)*	0.35
H183	0.5614 (10)	−0.272 (4)	0.246 (2)	0.013 (10)*	0.35
H184	0.516 (2)	−0.170 (4)	0.196 (4)	0.09 (2)*	0.35
OW12	0.4649 (14)	−0.024 (3)	0.1570 (19)	0.069 (9)*	0.50
H121	0.462 (3)	−0.085 (7)	0.116 (4)	0.12 (2)*	0.50
H122	0.460 (4)	0.069 (4)	0.140 (6)	0.08 (2)*	0.30
H123	0.501 (3)	0.035 (4)	0.175 (3)	0.12 (5)*	0.20
O13A	0.4562 (8)	−0.219 (3)	0.0760 (13)	0.027 (6)*	0.45
H131	0.4809 (13)	−0.289 (3)	0.1074 (17)	0.13 (3)*	0.45
H132	0.4645 (18)	−0.167 (5)	0.042 (3)	0.058 (14)*	0.45
O13B	0.4816 (11)	−0.335 (3)	0.0687 (18)	0.016 (7)*	0.32
H133	0.503 (2)	−0.391 (5)	0.0563 (15)	0.045 (16)*	0.32
H134	0.493 (4)	−0.350 (8)	0.131 (5)	0.08 (2)*	0.32
O13C	0.471 (2)	−0.444 (6)	0.086 (3)	0.037*	0.23
H135	0.488 (3)	−0.458 (10)	0.055 (4)	0.031 (18)*	0.23
OW5	0.3790 (4)	−0.3910 (13)	−0.0376 (6)	0.037 (3)*
H1W5	0.3561 (6)	−0.437 (2)	−0.0243 (11)	0.039 (5)*
H2W5	0.4090 (8)	−0.344 (3)	0.0035 (14)	0.095 (10)*
OW19	0.5000	−0.0981 (19)	0.0000	0.060 (6)*
H119	0.4979 (16)	−0.170 (3)	0.0309 (17)	0.054 (12)*	0.50
H219	0.5258 (14)	−0.033 (3)	0.0522 (14)	0.049 (11)*	0.50
OW14	0.403 (2)	−0.673 (5)	−0.043 (4)	0.057*	0.25
H141	0.413 (2)	−0.703 (8)	0.012 (4)	0.021 (15)*	0.25
H142	0.401 (4)	−0.567 (5)	−0.051 (7)	0.07 (3)*	0.25
OW9	0.6200 (4)	−0.1557 (13)	0.2598 (7)	0.048 (4)*
H1W9	0.6513 (5)	−0.165 (2)	0.3110 (9)	0.050 (6)*
H2W9	0.5887 (7)	−0.204 (4)	0.2454 (17)	0.037 (9)*	0.50
H3W9	0.6053 (17)	−0.068 (2)	0.249 (3)	0.054 (12)*	0.50
OW2	0.7165 (4)	−0.1803 (11)	0.4056 (6)	0.016 (2)*
H1W2	0.7390 (7)	−0.242 (2)	0.4029 (10)	0.031 (4)*
H2W2	0.7159 (7)	−0.198 (2)	0.4533 (12)	0.038 (5)*
OW4	0.5056 (6)	−0.404 (2)	0.4708 (10)	0.019 (4)*	0.60
H1W4	0.5152 (10)	−0.316 (3)	0.4616 (14)	0.038 (8)*	0.60
H2W4	0.5411 (4)	−0.435 (4)	0.5310 (19)	0.056 (10)*	0.60
OW7	0.6578 (4)	−0.3440 (13)	0.1967 (6)	0.020 (2)*
H1W7	0.6464 (8)	−0.353 (2)	0.1412 (12)	0.039 (5)*
H2W7	0.6423 (8)	−0.269 (3)	0.2072 (13)	0.046 (5)*
OW3	0.3958 (4)	−0.4242 (11)	0.3652 (6)	0.033 (3)*
H1W3	0.3724 (5)	−0.4978 (13)	0.3515 (8)	0.020 (4)*
H3W3	0.4313 (4)	−0.429 (2)	0.4067 (14)	0.026 (9)*	0.45
H2W3	0.4046 (12)	−0.398 (3)	0.3254 (15)	0.039 (9)*	0.55

Geometric parameters (Å, º)

C11—O45^i	1.414 (13)	C44—H44	1.091 (19)
C11—O51	1.437 (13)	C54—O54	1.424 (12)
C11—C21	1.525 (12)	C54—C64	1.544 (10)
C11—H11	1.051 (19)	C54—H54	1.1000
C21—O21	1.458 (12)	C64—O64	1.451 (12)
C21—C31	1.533 (11)	C64—H614	1.1000
C21—H21	1.10 (2)	C64—H624	1.1000
C31—O31	1.443 (13)	O24—HO24	0.90 (5)
C31—C41	1.524 (11)	O24—HB24	1.14 (4)
C31—H31	1.10 (2)	O34—HO34	0.92 (3)
C41—O41	1.432 (12)	O44—C15	1.437 (12)
C41—C51	1.557 (11)	O64—HO64	0.96 (2)
C41—H41	1.12 (2)	C15—O55	1.411 (12)
C51—O51	1.431 (13)	C15—C25	1.506 (10)
C51—C61B	1.49 (4)	C15—H15	1.1000
C51—C61A	1.560 (14)	C25—O25	1.477 (13)
C51—H51	1.05 (2)	C25—C35	1.526 (12)
C61A—O61A	1.39 (2)	C25—H25	1.07 (2)
C61A—H611	1.15 (3)	C35—O35	1.407 (13)
C61A—H621	1.10 (2)	C35—C45	1.565 (11)
C61B—O61B	1.43 (6)	C35—H35	1.142 (19)
C61B—H631	1.1000	C45—O45	1.416 (13)
C61B—H641	1.1000	C45—C55	1.541 (11)
O21—HO21	0.98 (3)	C45—H45	1.07 (2)
O31—HO31	0.97 (2)	C55—O55	1.437 (14)
O41—C12	1.402 (13)	C55—C65	1.536 (11)
O61A—HO61	0.95 (6)	C55—H55	1.114 (17)
O61B—HB61	0.9700	C65—O65A	1.42 (2)
C12—O52	1.447 (13)	C65—O65B	1.50 (5)
C12—C22	1.515 (11)	C65—H615	1.12 (3)
C12—H12	1.11 (2)	C65—H625	1.14 (3)
C22—O22	1.462 (13)	C65—H635	1.051 (11)
C22—C32	1.544 (10)	C65—H645	1.049 (11)
C22—H22	1.10 (2)	O25—HO25	1.01 (3)
C32—O32	1.400 (12)	O35—HO35	0.92 (3)
C32—C42	1.567 (11)	O45—C11^i	1.414 (13)
C32—H32	1.1000	O65A—HO65	0.92 (3)
C42—O42	1.452 (13)	O65B—HB65	0.97 (13)
C42—C52	1.531 (10)	OW8A—H1W8	0.92 (4)
C42—H42	1.06 (2)	OW8A—H2W8	0.956 (11)
C52—O52	1.441 (12)	OW8B—H3W8	0.959 (11)
C52—C62	1.522 (10)	OW17—H117	0.958 (11)
C52—H52	1.1000	OW17—H217	1.048 (11)
C62—O62	1.428 (13)	OW17—H317	1.046 (11)
C62—H612	1.1000	OW0A—H101	0.988 (10)
C62—H622	1.1000	OW0A—H102	0.971 (11)
O22—HO22	0.91 (3)	OW0A—H103	0.985 (11)
O32—HO32	0.95 (3)	OW0B—H104	0.96 (3)
O42—C13	1.414 (12)	OW0B—H105	1.00 (3)
O62—HB62	1.047 (11)	OW6—H1W6	0.959 (11)
O62—HO62	0.95 (5)	OW6—H2W6	0.960 (11)
C13—O53	1.419 (13)	O11A—H111	1.03 (4)
C13—C23	1.537 (12)	O11A—H112	1.02 (7)
C13—H13	1.1000	O11B—H113	0.960 (11)
C23—O23	1.458 (13)	O11B—H114	0.964 (11)
C23—C33	1.521 (12)	OW1—H1W1	0.99 (2)
C23—H23	1.10 (2)	OW1—H2W1	0.958 (11)
C33—O33	1.418 (13)	OW1—H3W1	0.958 (11)
C33—C43	1.551 (11)	O18A—H181	0.957 (11)
C33—H33	1.11 (2)	O18A—H182	0.951 (11)
C43—O43	1.420 (13)	O18B—H183	0.952 (11)
C43—C53	1.525 (13)	O18B—H184	0.954 (11)
C43—H43	1.1000	OW12—H121	0.958 (11)
C53—O53	1.437 (14)	OW12—H122	0.961 (11)
C53—C63A	1.497 (10)	OW12—H123	1.09 (8)
C53—C63B	1.545 (10)	O13A—H131	0.962 (11)
C53—H53	1.109 (10)	O13A—H132	0.958 (11)
C63A—O63A	1.35 (3)	O13B—H133	0.960 (11)
C63A—H613	1.04 (3)	O13B—H134	1.07 (9)
C63A—H623	1.06 (3)	O13C—H135	0.961 (11)
C63B—O63B	1.44 (4)	OW5—H1W5	0.951 (10)
C63B—H633	1.12 (6)	OW5—H2W5	0.950 (10)
C63B—H643	1.12 (3)	OW19—H119	0.958 (11)
O23—HO23	0.98 (2)	OW19—H219	1.106 (11)
O33—HO33	0.96 (3)	OW14—H141	0.98 (12)
O43—C14	1.421 (14)	OW14—H142	1.06 (3)
O63A—HO63	1.04 (4)	OW9—H1W9	0.946 (10)
O63B—HB63	1.14 (6)	OW9—H2W9	0.945 (11)
C14—O54	1.437 (13)	OW9—H3W9	0.953 (11)
C14—C24	1.551 (14)	OW2—H1W2	0.92 (3)
C14—H14	1.06 (2)	OW2—H2W2	0.94 (3)
C24—O24	1.437 (14)	OW4—H1W4	0.96 (4)
C24—C34	1.513 (12)	OW4—H2W4	1.13 (3)
C24—H24	1.06 (2)	OW7—H1W7	0.95 (3)
C34—O34	1.400 (15)	OW7—H2W7	0.95 (3)
C34—C44	1.554 (12)	OW3—H1W3	0.944 (10)
C34—H34	1.113 (10)	OW3—H3W3	0.931 (10)
C44—O44	1.434 (12)	OW3—H2W3	0.966 (10)
C44—C54	1.514 (12)
O45^i—C11—O51	111.9 (8)	O63B—C63B—H633	103 (3)
O45^i—C11—C21	107.1 (6)	C53—C63B—H633	110 (3)
O51—C11—C21	109.7 (7)	H613—C63B—H633	35 (3)
O45^i—C11—H11	112.8 (11)	H623—C63B—H633	99 (3)
O51—C11—H11	103.8 (10)	O63B—C63B—H643	102 (3)
C21—C11—H11	111.5 (11)	C53—C63B—H643	118 (2)
O21—C21—C11	108.7 (7)	H613—C63B—H643	138 (3)
O21—C21—C31	110.7 (7)	H623—C63B—H643	128 (3)
C11—C21—C31	112.0 (6)	H633—C63B—H643	103 (4)
O21—C21—H21	109.9 (11)	C23—O23—HO23	110.3 (12)
C11—C21—H21	107.1 (11)	C33—O33—HO33	109.6 (14)
C31—C21—H21	108.4 (10)	C43—O43—C14	114.6 (8)
O31—C31—C41	111.9 (6)	C13—O53—C53	115.9 (8)
O31—C31—C21	108.4 (7)	C63A—O63A—H633	44 (3)
C41—C31—C21	109.0 (6)	C63A—O63A—H643	117 (3)
O31—C31—H31	110.3 (11)	H633—O63A—H643	161 (4)
C41—C31—H31	109.7 (11)	C63A—O63A—HO63	112 (2)
C21—C31—H31	107.4 (10)	H633—O63A—HO63	82 (3)
O41—C41—C31	111.6 (6)	H643—O63A—HO63	111 (4)
O41—C41—C51	104.1 (6)	C63B—O63B—H623	60 (3)
C31—C41—C51	107.9 (6)	C63B—O63B—HB63	104 (3)
O41—C41—H41	111.1 (11)	H623—O63B—HB63	125 (5)
C31—C41—H41	112.1 (11)	O43—C14—O54	112.6 (8)
C51—C41—H41	109.7 (11)	O43—C14—C24	109.2 (7)
O51—C51—C61B	101.3 (16)	O54—C14—C24	110.3 (7)
O51—C51—C41	108.2 (7)	O43—C14—H14	110.4 (11)
C61B—C51—C41	108.9 (10)	O54—C14—H14	105.3 (12)
O51—C51—C61A	108.3 (8)	C24—C14—H14	108.9 (11)
C61B—C51—C61A	13.6 (16)	O24—C24—C34	112.1 (8)
C41—C51—C61A	116.0 (7)	O24—C24—C14	107.9 (7)
O51—C51—H51	110.5 (11)	C34—C24—C14	109.4 (7)
C61B—C51—H51	120.9 (19)	O24—C24—H24	112.1 (12)
C41—C51—H51	106.5 (12)	C34—C24—H24	106.6 (11)
C61A—C51—H51	107.2 (11)	C14—C24—H24	108.7 (12)
O61A—C61A—C51	109.8 (10)	O34—C34—C24	109.0 (8)
O61A—C61A—H611	109.4 (17)	O34—C34—C44	111.0 (7)
C51—C61A—H611	109.8 (15)	C24—C34—C44	108.4 (7)
O61A—C61A—H621	109.6 (16)	O34—C34—H34	112.2 (13)
C51—C61A—H621	109.0 (13)	C24—C34—H34	109.4 (11)
H611—C61A—H621	109.2 (19)	C44—C34—H34	106.7 (12)
O61B—C61B—C51	130 (3)	O44—C44—C54	107.2 (7)
C51—C61B—H611	138 (4)	O44—C44—C34	109.3 (7)
C51—C61B—H631	104.9	C54—C44—C34	111.1 (6)
H611—C61B—H631	99.6	O44—C44—H44	108.0 (11)
H621—C61B—H631	97.4	C54—C44—H44	109.7 (11)
O61B—C61B—H641	104.9	C34—C44—H44	111.4 (11)
C51—C61B—H641	104.9	O54—C54—C44	109.6 (7)
H611—C61B—H641	100.7	O54—C54—C64	104.7 (6)
H621—C61B—H641	11.1	C44—C54—C64	114.4 (6)
H631—C61B—H641	105.8	O54—C54—H54	109.3
C21—O21—HO21	110.7 (13)	C44—C54—H54	109.3
C31—O31—HO31	107.8 (14)	C64—C54—H54	109.3
C12—O41—C41	116.1 (8)	O64—C64—C54	113.2 (6)
C51—O51—C11	114.4 (7)	O64—C64—H614	108.9
C61A—O61A—HO61	112 (3)	C54—C64—H614	108.9
C61B—O61B—HB61	109.5	O64—C64—H624	108.9
O41—C12—O52	112.2 (8)	C54—C64—H624	108.9
O41—C12—C22	105.5 (7)	H614—C64—H624	107.8
O52—C12—C22	111.1 (7)	C24—O24—HO24	104.8 (16)
O41—C12—H12	110.5 (11)	C24—O24—HB24	112.0 (19)
O52—C12—H12	105.8 (12)	HO24—O24—HB24	53 (2)
C22—C12—H12	111.8 (11)	C34—O34—HO34	107.8 (15)
O22—C22—C12	109.3 (7)	C44—O44—C15	116.5 (7)
O22—C22—C32	112.5 (7)	C54—O54—C14	114.6 (7)
C12—C22—C32	110.9 (6)	C64—O64—HO64	106.9 (12)
O22—C22—H22	106.1 (11)	O55—C15—O44	111.2 (7)
C12—C22—H22	108.2 (12)	O55—C15—C25	111.2 (6)
C32—C22—H22	109.6 (10)	O44—C15—C25	107.3 (6)
O32—C32—C22	112.1 (6)	O55—C15—H15	109.0
O32—C32—C42	110.7 (6)	O44—C15—H15	109.0
C22—C32—C42	109.7 (6)	C25—C15—H15	109.0
O32—C32—H32	108.1	O25—C25—C15	109.7 (7)
C22—C32—H32	108.1	O25—C25—C35	109.6 (7)
C42—C32—H32	108.1	C15—C25—C35	111.8 (7)
O42—C42—C52	107.7 (7)	O25—C25—H25	110.2 (12)
O42—C42—C32	105.9 (7)	C15—C25—H25	107.5 (10)
C52—C42—C32	109.6 (6)	C35—C25—H25	108.0 (11)
O42—C42—H42	111.2 (11)	O35—C35—C25	109.6 (7)
C52—C42—H42	111.9 (12)	O35—C35—C45	111.6 (7)
C32—C42—H42	110.2 (11)	C25—C35—C45	106.1 (6)
O52—C52—C62	110.3 (6)	O35—C35—H35	109.2 (10)
O52—C52—C42	107.5 (6)	C25—C35—H35	109.3 (10)
C62—C52—C42	112.0 (5)	C45—C35—H35	111.1 (10)
O52—C52—H52	109.0	O45—C45—C55	111.7 (7)
C62—C52—H52	109.0	O45—C45—C35	114.3 (6)
C42—C52—H52	109.0	C55—C45—C35	111.0 (6)
O62—C62—C52	112.0 (6)	O45—C45—H45	105.2 (11)
O62—C62—H612	109.2	C55—C45—H45	105.9 (10)
C52—C62—H612	109.2	C35—C45—H45	108.0 (11)
O62—C62—H622	109.2	O55—C55—C65	107.7 (6)
C52—C62—H622	109.2	O55—C55—C45	108.1 (7)
H612—C62—H622	107.9	C65—C55—C45	112.6 (6)
C22—O22—HO22	106.5 (13)	O55—C55—H55	109.2 (10)
C32—O32—HO32	109.3 (14)	C65—C55—H55	109.4 (10)
C13—O42—C42	118.9 (8)	C45—C55—H55	109.8 (9)
C52—O52—C12	115.4 (8)	O65A—C65—C55	114.8 (9)
C62—O62—HB62	104.9 (15)	O65B—C65—C55	106 (2)
C62—O62—HO62	114 (2)	O65A—C65—H615	109.6 (19)
HB62—O62—HO62	108 (3)	C55—C65—H615	108.9 (16)
O42—C13—O53	113.8 (7)	O65A—C65—H625	110.0 (19)
O42—C13—C23	104.6 (7)	C55—C65—H625	111.3 (17)
O53—C13—C23	110.1 (7)	H615—C65—H625	101 (2)
O42—C13—H13	109.4	O65B—C65—H635	108 (6)
O53—C13—H13	109.4	C55—C65—H635	100 (6)
C23—C13—H13	109.4	O65B—C65—H645	126 (8)
O23—C23—C33	112.4 (7)	C55—C65—H645	106 (7)
O23—C23—C13	109.9 (7)	H635—C65—H645	108 (10)
C33—C23—C13	108.1 (6)	C25—O25—HO25	105.2 (12)
O23—C23—H23	106.8 (11)	C35—O35—HO35	112.8 (15)
C33—C23—H23	110.0 (11)	C11^i—O45—C45	118.9 (7)
C13—C23—H23	109.7 (12)	C15—O55—C55	115.3 (7)
O33—C33—C23	110.2 (7)	C65—O65A—HO65	109 (2)
O33—C33—C43	110.2 (6)	C65—O65B—HB65	117 (7)
C23—C33—C43	108.0 (7)	H1W8—OW8A—H2W8	115 (3)
O33—C33—H33	111.9 (13)	H117—OW17—H217	107 (6)
C23—C33—H33	108.7 (11)	H117—OW17—H317	100.7 (14)
C43—C33—H33	107.7 (11)	H101—OW0A—H102	112.6 (16)
O43—C43—C53	110.3 (7)	H101—OW0A—H103	110.2 (15)
O43—C43—C33	109.0 (7)	H104—OW0B—H105	97 (7)
C53—C43—C33	110.8 (6)	H1W6—OW6—H2W6	126 (10)
O43—C43—H43	108.9	H111—O11A—H112	110 (4)
C53—C43—H43	108.9	H113—O11B—H114	106.0 (16)
C33—C43—H43	108.9	H1W1—OW1—H2W1	104 (3)
O53—C53—C63A	115.0 (11)	H1W1—OW1—H3W1	103 (3)
O53—C53—C43	111.4 (7)	H181—O18A—H182	119.1 (18)
C63A—C53—C43	113.0 (9)	H183—O18B—H184	108.5 (17)
O53—C53—C63B	97.4 (10)	H121—OW12—H122	113 (8)
C43—C53—C63B	110.1 (10)	H121—OW12—H123	106 (6)
O53—C53—H53	108.0 (13)	H131—O13A—H132	117.0 (19)
C63A—C53—H53	100.2 (15)	H133—O13B—H134	109 (6)
C43—C53—H53	108.2 (13)	H1W5—OW5—H2W5	119.3 (16)
C63B—C53—H53	121.1 (15)	H119—OW19—H219	96.0 (12)
O63A—C63A—C53	102.0 (15)	H141—OW14—H142	116 (8)
O63A—C63A—H613	112 (3)	H1W9—OW9—H2W9	121.9 (18)
C53—C63A—H613	114 (2)	H1W9—OW9—H3W9	114 (3)
O63A—C63A—H623	107 (3)	H1W2—OW2—H2W2	107.8 (19)
C53—C63A—H623	109 (2)	H1W4—OW4—H2W4	104 (3)
H613—C63A—H623	111 (3)	H1W7—OW7—H2W7	113 (2)
O63A—C63A—H633	58 (4)	H1W3—OW3—H3W3	122.0 (14)
O63B—C63B—C53	118.7 (18)	H1W3—OW3—H2W3	116.4 (16)
O45^i—C11—C21—O21	53.5 (9)	C33—C43—C53—O53	−51.1 (8)
O51—C11—C21—O21	175.2 (8)	O43—C43—C53—C63A	56.7 (12)
O45^i—C11—C21—C31	−69.1 (8)	C33—C43—C53—C63A	177.5 (11)
O51—C11—C21—C31	52.6 (9)	O43—C43—C53—C63B	81.2 (12)
O21—C21—C31—O31	62.1 (9)	C33—C43—C53—C63B	−158.1 (11)
C11—C21—C31—O31	−176.5 (6)	O53—C53—C63A—O63A	−65.3 (17)
O21—C21—C31—C41	−175.9 (8)	C43—C53—C63A—O63A	64.2 (17)
C11—C21—C31—C41	−54.5 (8)	O53—C53—C63B—O63B	72 (2)
O31—C31—C41—O41	−68.7 (9)	C43—C53—C63B—O63B	−171.9 (17)
C21—C31—C41—O41	171.4 (7)	C53—C43—O43—C14	−136.9 (8)
O31—C31—C41—C51	177.6 (6)	C33—C43—O43—C14	101.3 (8)
C21—C31—C41—C51	57.7 (8)	O42—C13—O53—C53	59.2 (10)
O41—C41—C51—O51	179.9 (7)	C23—C13—O53—C53	−58.0 (9)
C31—C41—C51—O51	−61.5 (8)	C63A—C53—O53—C13	−176.5 (11)
O41—C41—C51—C61B	70.5 (19)	C43—C53—O53—C13	53.2 (9)
C31—C41—C51—C61B	−170.8 (18)	C63B—C53—O53—C13	168.3 (11)
O41—C41—C51—C61A	58.0 (9)	C43—O43—C14—O54	94.1 (10)
C31—C41—C51—C61A	176.7 (7)	C43—O43—C14—C24	−143.0 (8)
O51—C51—C61A—O61A	58.8 (11)	O43—C14—C24—O24	54.7 (10)
C41—C51—C61A—O61A	−179.3 (9)	O54—C14—C24—O24	178.9 (8)
O51—C51—C61B—O61B	−60 (3)	O43—C14—C24—C34	−67.5 (9)
C41—C51—C61B—O61B	54 (4)	O54—C14—C24—C34	56.8 (9)
C31—C41—O41—C12	82.4 (9)	O24—C24—C34—O34	63.9 (10)
C51—C41—O41—C12	−161.5 (7)	C14—C24—C34—O34	−176.4 (7)
C61B—C51—O51—C11	177.8 (13)	O24—C24—C34—C44	−175.1 (8)
C41—C51—O51—C11	63.4 (10)	C14—C24—C34—C44	−55.4 (8)
C61A—C51—O51—C11	−170.1 (8)	O34—C34—C44—O44	−65.6 (9)
O45^i—C11—O51—C51	60.3 (11)	C24—C34—C44—O44	174.6 (7)
C21—C11—O51—C51	−58.5 (10)	O34—C34—C44—C54	176.2 (7)
C41—O41—C12—O52	76.5 (9)	C24—C34—C44—C54	56.5 (8)
C41—O41—C12—C22	−162.4 (6)	O44—C44—C54—O54	−175.8 (6)
O41—C12—C22—O22	54.6 (9)	C34—C44—C54—O54	−56.4 (8)
O52—C12—C22—O22	176.5 (8)	O44—C44—C54—C64	67.0 (8)
O41—C12—C22—C32	−70.1 (8)	C34—C44—C54—C64	−173.7 (6)
O52—C12—C22—C32	51.8 (9)	O54—C54—C64—O64	−56.1 (8)
O22—C22—C32—O32	62.0 (9)	C44—C54—C64—O64	64.0 (8)
C12—C22—C32—O32	−175.2 (7)	C54—C44—O44—C15	−141.0 (7)
O22—C22—C32—C42	−174.6 (7)	C34—C44—O44—C15	98.5 (8)
C12—C22—C32—C42	−51.7 (8)	C44—C54—O54—C14	58.8 (9)
O32—C32—C42—O42	−63.7 (9)	C64—C54—O54—C14	−178.0 (7)
C22—C32—C42—O42	172.0 (6)	O43—C14—O54—C54	63.1 (11)
O32—C32—C42—C52	−179.7 (7)	C24—C14—O54—C54	−59.2 (10)
C22—C32—C42—C52	56.1 (8)	C44—O44—C15—O55	103.9 (8)
O42—C42—C52—O52	−174.0 (7)	C44—O44—C15—C25	−134.3 (7)
C32—C42—C52—O52	−59.2 (8)	O55—C15—C25—O25	178.4 (8)
O42—C42—C52—C62	64.7 (8)	O44—C15—C25—O25	56.5 (9)
C32—C42—C52—C62	179.5 (6)	O55—C15—C25—C35	56.6 (8)
O52—C52—C62—O62	−68.3 (8)	O44—C15—C25—C35	−65.2 (8)
C42—C52—C62—O62	51.3 (8)	O25—C25—C35—O35	62.2 (9)
C52—C42—O42—C13	−116.3 (8)	C15—C25—C35—O35	−176.0 (7)
C32—C42—O42—C13	126.4 (8)	O25—C25—C35—C45	−177.3 (7)
C62—C52—O52—C12	−175.3 (7)	C15—C25—C35—C45	−55.4 (8)
C42—C52—O52—C12	62.3 (9)	O35—C35—C45—O45	−56.5 (10)
O41—C12—O52—C52	58.7 (10)	C25—C35—C45—O45	−175.7 (7)
C22—C12—O52—C52	−59.1 (10)	O35—C35—C45—C55	176.0 (7)
C42—O42—C13—O53	103.4 (9)	C25—C35—C45—C55	56.7 (8)
C42—O42—C13—C23	−136.4 (8)	O45—C45—C55—O55	173.5 (7)
O42—C13—C23—O23	61.0 (8)	C35—C45—C55—O55	−57.5 (8)
O53—C13—C23—O23	−176.3 (8)	O45—C45—C55—C65	54.8 (9)
O42—C13—C23—C33	−61.9 (7)	C35—C45—C55—C65	−176.3 (7)
O53—C13—C23—C33	60.8 (8)	O55—C55—C65—O65A	−72.6 (12)
O23—C23—C33—O33	58.0 (9)	C45—C55—C65—O65A	46.4 (13)
C13—C23—C33—O33	179.4 (6)	O55—C55—C65—O65B	44 (2)
O23—C23—C33—C43	178.4 (7)	C45—C55—C65—O65B	163 (2)
C13—C23—C33—C43	−60.2 (7)	C55—C45—O45—C11^i	64.2 (9)
O33—C33—C43—O43	−61.7 (8)	C35—C45—O45—C11^i	−63.0 (10)
C23—C33—C43—O43	177.8 (7)	O44—C15—O55—C55	61.1 (9)
O33—C33—C43—C53	176.8 (7)	C25—C15—O55—C55	−58.5 (9)
C23—C33—C43—C53	56.3 (7)	C65—C55—O55—C15	−179.6 (7)
O43—C43—C53—O53	−171.9 (7)	C45—C55—O55—C15	58.5 (9)

Symmetry code: (i) −x+1, y, −z.