Cocrystallization and configurations of myo-inositol-1,2-L-camphor acetals in two crystal structures

The inositol rings in (1S,2R,3R,4S,5S,6R,7S,8S,11S)-myo-inositol-1,2-camphor acetal {systematic name: (1R,2S,3S,4R,5S,6R)-5,6-[(1S,2S,4S)-1,7,7-trimethyl­bicyclo­[2.2.1]heptane-2,2-diyldi­oxy]cyclohexane-1,2,3,4-tetrol}, C₁₆H₂₆O₆, and (1R,2S,3S,4R,5R,6S,7R/S,8S,11S)-myo-inositol-1,2-camphor acetal trihydrate {systematic name: (1S,2R,3R,4S,5R,6S)-5,6-[(1S,4S,6R/S)-1,7,7-trimethyl­bicyclo­[2.2.1]heptane-2,2-diyldi­oxy]cyclohexane-1,2,3,4-tetrol trihydrate}, C₁₆H₂₆O₆·3H₂O, adopt flattened chair conformations with the latter crystal containing two stereoisomers in a 0.684 (2):0.316 (2) ratio, similar to that found both in solution and by calculation. Both mol­ecules pack in the crystals in similar two-dimensional layers, utilizing strong O—H...O hydrogen bonds, with the trihydrate cell expanded to incorporate the additional hydrogen-bonded water mol­ecules.

S1. Comment

The title compounds were studied as part of a programme to prepare chiral inositol derivatives (Baars & Hoberg, 2006; Cousins et al., 2004). The structure of (I) (see scheme) was noted (Pietrusiewicz et al., 1992) but no structural parameters have been reported. Previous studies of myo-inositol derivatives as listed in the Cambridge Structural Database [Allen, 2002; CSD Version 5.27 (updated August 2006); refcodes are given in capitals] indicate that these molecules frequently show novel conformational/packing effects, e.g. molecular dynamics simulation confirming two stable conformations (XADWII; Dillen et al., 2000) and `thermosalient behaviour' (HADKIG; Steiner et al., 1993). The camphor unit (bicyclo[2.2.1]heptane) has been found to be invariant (Clegg et al., 1995). Along with the structure of (I) (crystal A), we report a novel structure containing cocrystallized (II) and (III) (crystal B) in a ratio corresponding approximately to their relative concentrations in solution as determined by NMR. In both cases, the L-camphor used in the synthesis determined the absolute configuration assigned here, since anomalous dispersion affects, as expected, were insufficient [e.g. the Flack parameter for crystal B was -0.2 (7)]. Friedel pairs in the data have been retained for future reference purposes.

The asymmetric unit in each crystal contains one independent myo-inositol-1,2-camphor acetal unit (Figs. 1–3); in crystal B, there are also three water molecules. For crystal A (I) the inositol fragment absolute configuration of C1(S), C2(R), C3(R), C4(S), C5(S), C6(R), and for crystal B the opposite [C1(R), C2(S), C3(S), C4(R), C5(R), C6(S)], was determined from the chemical synthesis based on L-camphor. In both crystals, the acetal linkages to the myo-inositol unit are similar to those observed previously [TEKPUU (Spiers et al., 1996), NOZCIO (Spiers et al., 1997), PINMEE and PINMII (Chung et al., 1994)]. For (I) the five-membered link stereochemistry (O1/C1/C2/O2/C7) to the L-camphor unit is simlar to that reported for the dihydroxybutanedioic acid dimethyl ester (NAFWEW; Mikolajczyk et al., 1996).

The L-camphor unit is present in crystal B in two sites corresponding to the two alternative configurations of attachment at the C7 atoms [(II) and (III) in the scheme]; the two are distinguished by primed and unprimed labels (Figs. 2 and 3). An initial refinement of the primed and unprimed atoms with one common isotropic U factor and freely refined occupancies indicated unambiguously that only these two related stereoisomers were present; the two sets were then grouped and refined to a final stereoisomer ratio of 0.685 (2):0.315 (2). The four C7,C7'—O1,O2 distances were refined to a common dimension, giving the results in Table 3 (see Experimental). The observed ratio in solution from NMR was 75:25 in DMSO-d₆. We determined the relative electronic energies (gas phase) using the Amsterdam Density Functional program system (SCM, 2006) [with VWN local density approximation (Vosko et al., 1980)] optimizing the structures and starting from the X-ray coordinate positions. The difference between the stereoisomers (II) and (III) was 0.45 kcal mol^-1, in good agreement with both solid state and solution observations. Compound (I) was estimated to be less stable than (II) by 11 kcal mol^-1, somewhat larger than expected.

In all structures, the inositol ring adopts a slightly flattened chair conformation, as shown by the Cremer & Pople (1975) parameters (Table 5). In (I), the best `arms' of the chair are atoms C1, C6, C3 and C4 [the mean out-of-plane distance is 0.014 (2) Å], with atoms C2 and C5 lying 0.528 (4) and -0.727 (5) Å from the plane; for crystal B [(II) and (III)], the corresponding best parameters are C2, C3, C5 and C6 [0.0193 (8) Å], with C1 and C4 at 0.513 (2) and -0.696 (2) Å. The five-membered rings O1/C1/C2/O2/C7(C7') (rings 2A and 2B; Table 5) adopt twist conformations (Evans & Boeyens, 1989). The L-camphor fused rings adopt envelope or boat configurations for the five- and six-membered rings, respectively, as expected (Clegg et al., 1995).

The cystal packing (Tables 2 and 4) can be described as similar two-dimensional layers normal to the c axis (Figs. 4 and 5). These layers are formed from strong O—H···O hydrogen interactions involving all inositol O atoms in A, and both inositol and water O atoms in crystal B as acceptors. The L-camphor rings pack `head-to-head' separating the layers. The close C—H···O interactions in crystal B (not listed in Table 4) are regarded as fortuitous [even though they fulfil the normal criteria (Desiraju & Steiner, 1999)], because of their location and the availability of the acceptor O atoms (Fig. 5). There is also a fortuitous short contact (O—H4···H6O 1.99 Å) in (I) between two H atoms involved in strong hydrogen bonds (Table 2).

Related literature

For related literature, see: Allen (2002); Baars & Hoberg (2006); Chung et al. (1994); Clegg et al. (1995); Cousins et al. (2004); Cremer & Pople (1975); Desiraju & Steiner (1999); Dillen et al. (2000); Evans & Boeyens (1989); Flack (1983); Flack & Bernardinelli (2000); Lindberg et al. (2002); Mikolajczyk et al. (1996); Pietrusiewicz et al. (1992); SCM (2006); Sheldrick (1997); Spiers et al. (1996, 1997); Steiner et al. (1993); Vosko et al. (1980).

S2. Experimental

The mixed acetals were prepared by the method of Lindberg et al.(2002).

S3. Refinement

All the L-camphor atoms in (II) and (III) (C7, C8–C16 and their H atoms) were freely refined in two sets, each with one common occupancy factor restrained so that the sum of the two was unity. The final occupancies were 0.685 (2)/0.315 (2). The final difference maps showed no significant discrepancies, justifying this choice of disorder modelling. The four C7,C7'—O1,O2 distances were restrained to a common dimension (with an su of 0.01, using the SHEXL97 SADI option; Sheldrick, 1997).

All H atoms bound to carbon were constrained to their expected geometries (C—H = 0.98–1.00 Å). H atoms on inositol O atoms were restrained to tetrahedral positions with O—H distances of 0.84 (s.u.?) Å (AFIX 87). Positions of water H atoms were restrained to O—H distances of 0.84 Å (DFIX). All methyl, tertiary and hydroxyl H atoms were refined with U_iso(H) values of, respectively, 1.5, 1.2 and 1.5 times U_eq of the parent atom. In the absence of significant anomalous scattering, the values of the Flack (1983) parameter were indeterminate (Flack & Bernardinelli, 2000).

Computing details

For both compounds, data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT and SADABS (Sheldrick, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLUTON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

Figures

	Fig. 1. Molecular structure of (I) (Farrugia, 1997); displacement ellipsoids are shown at the 30% probability level.
	Fig. 2. Molecular structure of (II) (Farrugia, 1997); displacement ellipsoids are shown at the 30% probability level.
	Fig. 3. Molecular structure of (III) (Farrugia, 1997); displacement ellipsoids are shown at the 30% probability level.
	Fig. 4. The packing of crystal A, viewed down the b axis. Only H atoms involved in selected hydrogen bonds (dashed lines) are shown. For symmetry designations see Table 2.
	Fig. 5. The packing of crystal B, viewed down the b axis. Only the major stereoisomer (II) and H atoms involved in selected hydrogen bonds (dashed lines) are shown for clarity. For symmetry designations see Table 4.

(A) 5,6-(1,7,7-trimethylbicyclo[2.2.1]heptane-2,2-diyldioxy)benzene-1,2,3,4-tetrol

Crystal data

C16H26O6	F(000) = 680
Mr = 314.37	Dx = 1.341 Mg m^−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 2866 reflections
a = 12.700 (3) Å	θ = 2.3–24.2°
b = 6.9721 (17) Å	µ = 0.10 mm^−1
c = 18.422 (5) Å	T = 169 K
β = 107.275 (3)°	Hexagonal, colourless
V = 1557.7 (7) Å^3	0.47 × 0.33 × 0.03 mm
Z = 4

Data collection

Bruker-Nonius APEX2 CCD area-detector diffractometer	2953 independent reflections
Radiation source: fine-focus sealed tube	2026 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
Detector resolution: 8.192 pixels mm^-1	θmax = 26.5°, θmin = 2.3°
ϕ and ω scans	h = −11→15
Absorption correction: multi-scan (Blessing, 1995)	k = −8→8
Tmin = 0.796, Tmax = 0.997	l = −22→22
8809 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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.113	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0452P)^2 + 0.8396P] where P = (Fo^2 + 2Fc^2)/3
2953 reflections	(Δ/σ)max = 0.009
206 parameters	Δρmax = 0.27 e Å^−3
1 restraint	Δρmin = −0.26 e Å^−3

Special details

Experimental. Crystal decay was monitored by repeating the initial 10 frames at the end of the data collection and analyzing duplicate reflections. The standard 0.8 mm diameter collimator was used.

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	0.34056 (17)	0.3160 (3)	0.23347 (11)	0.0229 (5)
O2	0.19305 (17)	0.5175 (4)	0.18530 (11)	0.0237 (6)
O3	0.2618 (2)	0.7930 (3)	0.08317 (17)	0.0461 (8)
H3O	0.2995	0.8923	0.0980	0.069*
O4	0.4747 (2)	0.7149 (4)	0.06925 (15)	0.0388 (7)
H4O	0.4670	0.8072	0.0965	0.058*
O5	0.54279 (19)	0.3208 (4)	0.07593 (12)	0.0300 (6)
H5O	0.6078	0.3453	0.1020	0.045*
O6	0.44603 (19)	0.0562 (3)	0.15623 (13)	0.0295 (6)
H6O	0.5100	0.0528	0.1520	0.044*
C1	0.2974 (3)	0.2772 (5)	0.15264 (17)	0.0208 (8)
H1	0.2414	0.1721	0.1435	0.025*
C2	0.2408 (3)	0.4688 (5)	0.12480 (18)	0.0215 (8)
H2	0.1820	0.4527	0.0752	0.026*
C3	0.3228 (3)	0.6276 (5)	0.11944 (19)	0.0269 (9)
H3	0.3675	0.6640	0.1721	0.032*
C4	0.4016 (3)	0.5614 (5)	0.0750 (2)	0.0257 (9)
H4	0.3571	0.5223	0.0226	0.031*
C5	0.4670 (3)	0.3877 (5)	0.11557 (19)	0.0247 (8)
H5	0.5092	0.4242	0.1687	0.030*
C6	0.3889 (3)	0.2242 (5)	0.11751 (18)	0.0198 (8)
H6	0.3520	0.1861	0.0636	0.024*
C7	0.2503 (3)	0.4057 (5)	0.25293 (17)	0.0211 (8)
C8	0.2928 (3)	0.5323 (5)	0.32573 (17)	0.0243 (8)
C9	0.1908 (3)	0.6561 (5)	0.32850 (19)	0.0262 (8)
H9A	0.2132	0.7581	0.3674	0.031*
H9B	0.1551	0.7160	0.2785	0.031*
C10	0.1116 (3)	0.5099 (6)	0.3496 (2)	0.0311 (9)
H10A	0.0987	0.5442	0.3984	0.037*
H10B	0.0399	0.5033	0.3094	0.037*
C11	0.1755 (3)	0.3176 (6)	0.35615 (17)	0.0245 (8)
H11	0.1508	0.2160	0.3858	0.029*
C12	0.1712 (3)	0.2572 (5)	0.27395 (17)	0.0235 (9)
H12A	0.0954	0.2672	0.2389	0.028*
H12B	0.1982	0.1243	0.2728	0.028*
C13	0.3966 (3)	0.6486 (6)	0.3315 (2)	0.0341 (10)
H13A	0.4553	0.5626	0.3269	0.051*
H13B	0.4202	0.7141	0.3808	0.051*
H13C	0.3809	0.7438	0.2906	0.051*
C14	0.2977 (3)	0.3814 (5)	0.39083 (17)	0.0231 (8)
C15	0.3820 (3)	0.2177 (5)	0.39846 (18)	0.0282 (9)
H15A	0.4564	0.2717	0.4100	0.042*
H15B	0.3649	0.1460	0.3506	0.042*
H15C	0.3782	0.1313	0.4396	0.042*
C16	0.3210 (3)	0.4756 (6)	0.47065 (18)	0.0316 (9)
H16A	0.3142	0.3788	0.5075	0.047*
H16B	0.2677	0.5788	0.4683	0.047*
H16C	0.3959	0.5286	0.4863	0.047*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0165 (12)	0.0351 (14)	0.0170 (11)	0.0003 (12)	0.0050 (9)	−0.0001 (11)
O2	0.0170 (13)	0.0387 (14)	0.0178 (12)	0.0029 (12)	0.0087 (10)	0.0028 (11)
O3	0.0566 (18)	0.0216 (15)	0.078 (2)	0.0085 (15)	0.0469 (16)	0.0085 (16)
O4	0.0503 (17)	0.0269 (15)	0.0533 (19)	−0.0105 (14)	0.0370 (15)	−0.0104 (13)
O5	0.0118 (12)	0.0505 (16)	0.0291 (13)	0.0041 (14)	0.0082 (10)	0.0096 (13)
O6	0.0219 (14)	0.0330 (15)	0.0316 (14)	0.0029 (13)	0.0050 (12)	0.0075 (12)
C1	0.0173 (18)	0.030 (2)	0.0147 (17)	−0.0046 (17)	0.0048 (14)	0.0011 (15)
C2	0.021 (2)	0.027 (2)	0.0182 (17)	0.0049 (17)	0.0090 (15)	0.0003 (15)
C3	0.034 (2)	0.028 (2)	0.025 (2)	0.0021 (19)	0.0175 (17)	0.0031 (16)
C4	0.032 (2)	0.024 (2)	0.0259 (18)	−0.0060 (18)	0.0156 (16)	−0.0006 (17)
C5	0.022 (2)	0.033 (2)	0.0199 (18)	−0.0008 (17)	0.0083 (15)	−0.0015 (16)
C6	0.0153 (18)	0.0243 (19)	0.0196 (18)	0.0023 (17)	0.0049 (14)	0.0035 (15)
C7	0.0150 (18)	0.0302 (19)	0.0180 (17)	0.0057 (16)	0.0045 (14)	0.0053 (15)
C8	0.021 (2)	0.032 (2)	0.0205 (17)	−0.0065 (18)	0.0076 (15)	−0.0026 (17)
C9	0.024 (2)	0.035 (2)	0.0201 (18)	0.0011 (19)	0.0064 (15)	−0.0008 (17)
C10	0.021 (2)	0.050 (2)	0.0225 (18)	0.004 (2)	0.0073 (15)	0.0023 (18)
C11	0.0182 (18)	0.038 (2)	0.0205 (17)	−0.0042 (19)	0.0105 (14)	0.0015 (17)
C12	0.0199 (19)	0.029 (2)	0.0199 (18)	−0.0019 (17)	0.0031 (15)	0.0032 (15)
C13	0.031 (2)	0.045 (2)	0.029 (2)	−0.014 (2)	0.0129 (17)	−0.0080 (19)
C14	0.0114 (18)	0.039 (2)	0.0183 (17)	−0.0019 (17)	0.0031 (14)	−0.0010 (15)
C15	0.021 (2)	0.042 (2)	0.0212 (19)	0.0016 (19)	0.0068 (15)	0.0024 (17)
C16	0.024 (2)	0.048 (3)	0.0245 (19)	−0.002 (2)	0.0084 (16)	−0.0013 (17)

Geometric parameters (Å, º)

O1—C7	1.441 (4)	C8—C13	1.524 (5)
O1—C1	1.451 (4)	C8—C9	1.570 (5)
O2—C2	1.458 (4)	C8—C14	1.582 (5)
O2—C7	1.466 (4)	C9—C10	1.560 (5)
O3—C3	1.438 (4)	C9—H9A	0.9900
O3—H3O	0.8400	C9—H9B	0.9900
O4—C4	1.441 (4)	C10—C11	1.553 (5)
O4—H4O	0.8400	C10—H10A	0.9900
O5—C5	1.447 (4)	C10—H10B	0.9900
O5—H5O	0.8400	C11—C12	1.557 (4)
O6—C6	1.449 (4)	C11—C14	1.558 (5)
O6—H6O	0.8400	C11—H11	1.0000
C1—C2	1.531 (5)	C12—H12A	0.9900
C1—C6	1.534 (4)	C12—H12B	0.9900
C1—H1	1.0000	C13—H13A	0.9800
C2—C3	1.543 (5)	C13—H13B	0.9800
C2—H2	1.0000	C13—H13C	0.9800
C3—C4	1.541 (5)	C14—C15	1.542 (5)
C3—H3	1.0000	C14—C16	1.557 (4)
C4—C5	1.532 (5)	C15—H15A	0.9800
C4—H4	1.0000	C15—H15B	0.9800
C5—C6	1.518 (5)	C15—H15C	0.9800
C5—H5	1.0000	C16—H16A	0.9800
C6—H6	1.0000	C16—H16B	0.9800
C7—C8	1.562 (5)	C16—H16C	0.9800
C7—C12	1.569 (4)
C7—O1—C1	104.5 (2)	C13—C8—C14	117.5 (3)
C2—O2—C7	108.2 (2)	C7—C8—C14	101.6 (3)
C3—O3—H3O	109.5	C9—C8—C14	100.9 (3)
C4—O4—H4O	109.5	C10—C9—C8	104.4 (3)
C5—O5—H5O	109.5	C10—C9—H9A	110.9
C6—O6—H6O	109.5	C8—C9—H9A	110.9
O1—C1—C2	100.2 (2)	C10—C9—H9B	110.9
O1—C1—C6	112.0 (2)	C8—C9—H9B	110.9
C2—C1—C6	114.1 (3)	H9A—C9—H9B	108.9
O1—C1—H1	110.0	C11—C10—C9	102.9 (3)
C2—C1—H1	110.0	C11—C10—H10A	111.2
C6—C1—H1	110.0	C9—C10—H10A	111.2
O2—C2—C1	102.0 (2)	C11—C10—H10B	111.2
O2—C2—C3	108.9 (3)	C9—C10—H10B	111.2
C1—C2—C3	112.9 (3)	H10A—C10—H10B	109.1
O2—C2—H2	110.9	C10—C11—C12	107.0 (3)
C1—C2—H2	110.9	C10—C11—C14	102.7 (3)
C3—C2—H2	110.9	C12—C11—C14	102.6 (2)
O3—C3—C4	109.8 (3)	C10—C11—H11	114.4
O3—C3—C2	109.0 (3)	C12—C11—H11	114.4
C4—C3—C2	112.1 (3)	C14—C11—H11	114.4
O3—C3—H3	108.6	C11—C12—C7	102.8 (2)
C4—C3—H3	108.6	C11—C12—H12A	111.2
C2—C3—H3	108.6	C7—C12—H12A	111.2
O4—C4—C5	110.8 (3)	C11—C12—H12B	111.2
O4—C4—C3	110.5 (3)	C7—C12—H12B	111.2
C5—C4—C3	108.7 (3)	H12A—C12—H12B	109.1
O4—C4—H4	108.9	C8—C13—H13A	109.5
C5—C4—H4	108.9	C8—C13—H13B	109.5
C3—C4—H4	108.9	H13A—C13—H13B	109.5
O5—C5—C6	107.9 (3)	C8—C13—H13C	109.5
O5—C5—C4	110.7 (3)	H13A—C13—H13C	109.5
C6—C5—C4	110.0 (3)	H13B—C13—H13C	109.5
O5—C5—H5	109.4	C15—C14—C16	107.1 (3)
C6—C5—H5	109.4	C15—C14—C11	114.0 (3)
C4—C5—H5	109.4	C16—C14—C11	113.2 (3)
O6—C6—C5	112.6 (3)	C15—C14—C8	115.6 (3)
O6—C6—C1	108.6 (2)	C16—C14—C8	112.9 (3)
C5—C6—C1	114.3 (3)	C11—C14—C8	93.9 (2)
O6—C6—H6	107.0	C14—C15—H15A	109.5
C5—C6—H6	107.0	C14—C15—H15B	109.5
C1—C6—H6	107.0	H15A—C15—H15B	109.5
O1—C7—O2	104.4 (2)	C14—C15—H15C	109.5
O1—C7—C8	111.2 (3)	H15A—C15—H15C	109.5
O2—C7—C8	112.8 (3)	H15B—C15—H15C	109.5
O1—C7—C12	113.0 (3)	C14—C16—H16A	109.5
O2—C7—C12	111.6 (3)	C14—C16—H16B	109.5
C8—C7—C12	104.1 (2)	H16A—C16—H16B	109.5
C13—C8—C7	115.6 (3)	C14—C16—H16C	109.5
C13—C8—C9	114.2 (3)	H16A—C16—H16C	109.5
C7—C8—C9	105.1 (3)	H16B—C16—H16C	109.5
C7—O1—C1—C2	45.5 (3)	O2—C7—C8—C13	−76.8 (4)
C7—O1—C1—C6	166.8 (3)	C12—C7—C8—C13	162.0 (3)
C7—O2—C2—C1	19.2 (3)	O1—C7—C8—C9	167.0 (3)
C7—O2—C2—C3	−100.3 (3)	O2—C7—C8—C9	50.1 (3)
O1—C1—C2—O2	−39.0 (3)	C12—C7—C8—C9	−71.1 (3)
C6—C1—C2—O2	−158.9 (3)	O1—C7—C8—C14	−88.3 (3)
O1—C1—C2—C3	77.7 (3)	O2—C7—C8—C14	154.8 (2)
C6—C1—C2—C3	−42.2 (4)	C12—C7—C8—C14	33.7 (3)
O2—C2—C3—O3	−75.4 (3)	C13—C8—C9—C10	−161.2 (3)
C1—C2—C3—O3	172.1 (3)	C7—C8—C9—C10	71.0 (3)
O2—C2—C3—C4	162.9 (3)	C14—C8—C9—C10	−34.3 (3)
C1—C2—C3—C4	50.4 (4)	C8—C9—C10—C11	−0.4 (3)
O3—C3—C4—O4	57.1 (4)	C9—C10—C11—C12	−71.8 (3)
C2—C3—C4—O4	178.4 (3)	C9—C10—C11—C14	35.8 (3)
O3—C3—C4—C5	178.9 (3)	C10—C11—C12—C7	71.5 (3)
C2—C3—C4—C5	−59.8 (4)	C14—C11—C12—C7	−36.1 (3)
O4—C4—C5—O5	−58.1 (4)	O1—C7—C12—C11	121.7 (3)
C3—C4—C5—O5	−179.7 (3)	O2—C7—C12—C11	−120.9 (3)
O4—C4—C5—C6	−177.2 (2)	C8—C7—C12—C11	1.0 (3)
C3—C4—C5—C6	61.2 (4)	C10—C11—C14—C15	−175.8 (3)
O5—C5—C6—O6	59.9 (3)	C12—C11—C14—C15	−64.9 (3)
C4—C5—C6—O6	−179.2 (2)	C10—C11—C14—C16	61.4 (3)
O5—C5—C6—C1	−175.7 (2)	C12—C11—C14—C16	172.3 (3)
C4—C5—C6—C1	−54.8 (4)	C10—C11—C14—C8	−55.6 (3)
O1—C1—C6—O6	58.8 (3)	C12—C11—C14—C8	55.3 (3)
C2—C1—C6—O6	171.8 (2)	C13—C8—C14—C15	−62.1 (4)
O1—C1—C6—C5	−67.7 (3)	C7—C8—C14—C15	65.0 (3)
C2—C1—C6—C5	45.3 (4)	C9—C8—C14—C15	173.1 (3)
C1—O1—C7—O2	−34.2 (3)	C13—C8—C14—C16	61.6 (4)
C1—O1—C7—C8	−156.0 (3)	C7—C8—C14—C16	−171.2 (3)
C1—O1—C7—C12	87.3 (3)	C9—C8—C14—C16	−63.1 (3)
C2—O2—C7—O1	8.2 (3)	C13—C8—C14—C11	178.9 (3)
C2—O2—C7—C8	129.0 (3)	C7—C8—C14—C11	−53.9 (3)
C2—O2—C7—C12	−114.2 (3)	C9—C8—C14—C11	54.1 (3)
O1—C7—C8—C13	40.1 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H60···O2^i	0.84	2.23	3.034 (3)	159
O5—H5O···O3^i	0.84	2.12	2.752 (4)	132
O4—H4O···O6^ii	0.84	2.11	2.951 (4)	175
O3—H3O···O6^ii	0.84	2.18	2.964 (4)	156

Symmetry codes: (i) x+1/2, y−1/2, z; (ii) x, y+1, z.

(B) 5,6-(1,7,7-trimethylbicyclo[2.2.1]heptane-2,2-diyldioxy)benzene-1,2,3,4-tetrol

Crystal data

C16H26O6·3(H2O)	F(000) = 800
Mr = 368.42	Dx = 1.301 Mg m^−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 4457 reflections
a = 13.1708 (17) Å	θ = 3.0–26.3°
b = 6.9513 (9) Å	µ = 0.11 mm^−1
c = 20.737 (3) Å	T = 163 K
β = 97.899 (2)°	Plate, colourless
V = 1880.5 (4) Å^3	0.73 × 0.40 × 0.12 mm
Z = 4

Data collection

Bruker P4 CCD area-detector diffractometer	3205 independent reflections
Radiation source: fine-focus sealed tube	2697 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
Detector resolution: 8.192 pixels mm^-1	θmax = 26.4°, θmin = 2.0°
ϕ and ω scans	h = −16→16
Absorption correction: multi-scan (Blessing, 1995)	k = −8→4
Tmin = 0.795, Tmax = 0.987	l = −25→25
11666 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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.059	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0383P)^2] where P = (Fo^2 + 2Fc^2)/3
3205 reflections	(Δ/σ)max = 0.001
345 parameters	Δρmax = 0.15 e Å^−3
13 restraints	Δρmin = −0.14 e Å^−3

Special details

Experimental. Crystal decay was monitored by repeating the initial 10 frames at the end of the data collection and analyzing duplicate reflections. The standard 0.8 mm diameter collimator was used.

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)
O1	0.54094 (8)	0.23695 (17)	0.70402 (5)	0.0285 (3)
O2	0.54811 (8)	0.53515 (16)	0.75079 (5)	0.0303 (3)
O3	0.71153 (8)	0.70282 (16)	0.84148 (5)	0.0295 (3)
H3O	0.6573	0.7650	0.8304	0.044*
O4	0.67077 (8)	0.48980 (16)	0.95355 (5)	0.0272 (3)
H4O	0.6594	0.6064	0.9605	0.041*
O5	0.55353 (8)	0.15423 (17)	0.93618 (5)	0.0271 (3)
H5O	0.4956	0.2068	0.9319	0.041*
O6	0.55170 (8)	−0.04662 (17)	0.81492 (5)	0.0295 (3)
H6O	0.5052	−0.0880	0.8352	0.044*
O7	0.63963 (8)	0.84532 (17)	0.99827 (5)	0.0296 (3)
H7A	0.6964 (9)	0.901 (3)	1.0114 (9)	0.044*
H7B	0.6048 (13)	0.933 (2)	0.9767 (8)	0.044*
O8	0.37384 (8)	0.35812 (18)	0.91942 (5)	0.0288 (3)
H8A	0.3232 (10)	0.303 (3)	0.8995 (8)	0.043*
H8B	0.3628 (14)	0.368 (3)	0.9577 (5)	0.043*
O9	0.41424 (9)	0.75506 (18)	0.88054 (6)	0.0368 (3)
H9OA	0.4117 (15)	0.782 (3)	0.9196 (5)	0.055*
H9OB	0.4040 (15)	0.6344 (15)	0.8791 (9)	0.055*
C1	0.61071 (11)	0.2303 (2)	0.76358 (7)	0.0243 (3)
H1	0.6707	0.1465	0.7583	0.029*
C2	0.64377 (11)	0.4384 (2)	0.77078 (7)	0.0255 (4)
H2	0.6927	0.4679	0.7393	0.031*
C3	0.68969 (11)	0.5021 (2)	0.83842 (7)	0.0245 (4)
H3	0.7568	0.4338	0.8487	0.029*
C4	0.62357 (10)	0.4388 (2)	0.88919 (7)	0.0218 (3)
H4A	0.5550	0.5024	0.8801	0.026*
C5	0.60975 (10)	0.2223 (2)	0.88655 (7)	0.0223 (3)
H5	0.6793	0.1620	0.8938	0.027*
C6	0.55645 (11)	0.1571 (2)	0.81982 (7)	0.0228 (3)
H6	0.4848	0.2084	0.8137	0.027*
C7	0.4845 (2)	0.4129 (5)	0.70284 (15)	0.0259 (8)	0.685 (2)
C8	0.47401 (17)	0.4977 (4)	0.63322 (10)	0.0258 (6)	0.685 (2)
C9	0.4309 (3)	0.3324 (6)	0.58610 (19)	0.0322 (9)	0.685 (2)
H9A	0.4333	0.3684	0.5401	0.039*	0.685 (2)
H9B	0.4701	0.2119	0.5959	0.039*	0.685 (2)
C10	0.31869 (19)	0.3094 (4)	0.59976 (12)	0.0359 (7)	0.685 (2)
H10A	0.2695	0.3348	0.5601	0.043*	0.685 (2)
H10B	0.3064	0.1787	0.6159	0.043*	0.685 (2)
C11	0.30961 (17)	0.4628 (4)	0.65262 (11)	0.0315 (6)	0.685 (2)
H11	0.2376	0.5014	0.6566	0.038*	0.685 (2)
C12	0.3703 (5)	0.3898 (12)	0.7158 (5)	0.0294 (12)	0.685 (2)
H12A	0.3539	0.2537	0.7238	0.035*	0.685 (2)
H12B	0.3565	0.4685	0.7534	0.035*	0.685 (2)
C13	0.5711 (4)	0.5890 (8)	0.6159 (3)	0.0374 (12)	0.685 (2)
H13A	0.5945	0.6890	0.6478	0.056*	0.685 (2)
H13B	0.5573	0.6467	0.5724	0.056*	0.685 (2)
H13C	0.6244	0.4905	0.6161	0.056*	0.685 (2)
C14	0.37751 (18)	0.6291 (4)	0.63260 (11)	0.0308 (6)	0.685 (2)
C15	0.3888 (4)	0.7969 (6)	0.6808 (3)	0.0369 (11)	0.685 (2)
H15A	0.4433	0.8830	0.6706	0.055*	0.685 (2)
H15B	0.4063	0.7472	0.7251	0.055*	0.685 (2)
H15C	0.3241	0.8680	0.6775	0.055*	0.685 (2)
C16	0.3384 (2)	0.7162 (5)	0.56494 (12)	0.0435 (7)	0.685 (2)
H16A	0.2702	0.7717	0.5655	0.065*	0.685 (2)
H16B	0.3347	0.6151	0.5318	0.065*	0.685 (2)
H16C	0.3857	0.8170	0.5547	0.065*	0.685 (2)
C7'	0.5189 (5)	0.4433 (9)	0.6893 (3)	0.029 (2)	0.315 (2)
C8'	0.4036 (4)	0.4928 (8)	0.6737 (2)	0.0281 (14)	0.315 (2)
C9'	0.3924 (10)	0.7122 (13)	0.6795 (7)	0.043 (3)	0.315 (2)
H91	0.4289	0.7588	0.7215	0.052*	0.315 (2)
H92	0.3193	0.7487	0.6765	0.052*	0.315 (2)
C10'	0.4409 (5)	0.7981 (9)	0.6216 (3)	0.054 (2)	0.315 (2)
H101	0.5010	0.8796	0.6369	0.065*	0.315 (2)
H102	0.3904	0.8740	0.5922	0.065*	0.315 (2)
C11'	0.4726 (5)	0.6114 (9)	0.5882 (3)	0.0425 (17)	0.315 (2)
H111	0.4826	0.6292	0.5417	0.051*	0.315 (2)
C12'	0.5639 (11)	0.5294 (17)	0.6303 (5)	0.038 (3)	0.315 (2)
H121	0.6148	0.6311	0.6444	0.046*	0.315 (2)
H122	0.5972	0.4285	0.6068	0.046*	0.315 (2)
C13'	0.3375 (11)	0.374 (3)	0.7124 (12)	0.054 (5)	0.315 (2)
H131	0.3507	0.2373	0.7060	0.081*	0.315 (2)
H132	0.2652	0.4023	0.6977	0.081*	0.315 (2)
H133	0.3538	0.4060	0.7587	0.081*	0.315 (2)
C14'	0.3861 (5)	0.4695 (10)	0.5982 (2)	0.0375 (15)	0.315 (2)
C15'	0.4012 (8)	0.2650 (14)	0.5748 (5)	0.046 (3)	0.315 (2)
H151	0.3473	0.1818	0.5876	0.069*	0.315 (2)
H152	0.4684	0.2173	0.5945	0.069*	0.315 (2)
H153	0.3977	0.2644	0.5273	0.069*	0.315 (2)
C16'	0.2782 (5)	0.5321 (10)	0.5663 (3)	0.0512 (18)	0.315 (2)
H161	0.2762	0.5358	0.5189	0.077*	0.315 (2)
H162	0.2629	0.6603	0.5822	0.077*	0.315 (2)
H163	0.2272	0.4400	0.5777	0.077*	0.315 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0331 (6)	0.0281 (7)	0.0229 (5)	0.0047 (5)	−0.0009 (4)	−0.0038 (5)
O2	0.0378 (6)	0.0273 (7)	0.0229 (5)	0.0084 (5)	−0.0059 (4)	−0.0041 (5)
O3	0.0259 (5)	0.0234 (7)	0.0377 (6)	−0.0035 (5)	−0.0013 (4)	0.0010 (5)
O4	0.0327 (6)	0.0228 (7)	0.0242 (5)	0.0021 (5)	−0.0026 (4)	−0.0029 (5)
O5	0.0256 (5)	0.0286 (7)	0.0279 (5)	0.0034 (5)	0.0060 (4)	0.0046 (5)
O6	0.0318 (6)	0.0230 (7)	0.0341 (6)	−0.0027 (5)	0.0061 (4)	−0.0023 (5)
O7	0.0279 (6)	0.0248 (7)	0.0347 (6)	0.0009 (5)	−0.0013 (5)	0.0022 (5)
O8	0.0237 (6)	0.0346 (8)	0.0281 (6)	−0.0026 (5)	0.0035 (5)	−0.0049 (5)
O9	0.0383 (6)	0.0298 (8)	0.0441 (7)	0.0039 (6)	0.0126 (5)	−0.0012 (6)
C1	0.0232 (7)	0.0253 (10)	0.0237 (8)	0.0040 (7)	0.0013 (6)	−0.0020 (7)
C2	0.0256 (8)	0.0272 (10)	0.0244 (8)	0.0023 (7)	0.0065 (6)	0.0012 (7)
C3	0.0202 (7)	0.0225 (10)	0.0301 (8)	0.0025 (6)	0.0010 (6)	0.0017 (7)
C4	0.0197 (7)	0.0243 (9)	0.0205 (7)	0.0020 (6)	−0.0010 (6)	−0.0017 (6)
C5	0.0195 (7)	0.0234 (9)	0.0238 (7)	0.0036 (7)	0.0025 (5)	0.0018 (6)
C6	0.0214 (7)	0.0187 (9)	0.0280 (8)	0.0021 (7)	0.0018 (6)	−0.0012 (7)
C7	0.0258 (18)	0.0316 (18)	0.0210 (16)	0.0061 (13)	0.0060 (12)	−0.0075 (12)
C8	0.0245 (12)	0.0299 (16)	0.0223 (12)	−0.0039 (11)	0.0015 (9)	−0.0009 (11)
C9	0.039 (2)	0.035 (3)	0.0218 (17)	−0.0014 (18)	0.0013 (15)	0.0016 (16)
C10	0.0344 (14)	0.0357 (18)	0.0344 (13)	−0.0042 (12)	−0.0070 (11)	−0.0036 (12)
C11	0.0247 (12)	0.0390 (17)	0.0293 (12)	0.0000 (11)	−0.0014 (9)	−0.0010 (11)
C12	0.036 (3)	0.027 (2)	0.0256 (19)	−0.002 (2)	0.005 (2)	0.0023 (14)
C13	0.0357 (18)	0.048 (3)	0.029 (3)	−0.006 (2)	0.0091 (16)	0.0106 (17)
C14	0.0326 (13)	0.0321 (17)	0.0260 (13)	0.0019 (11)	−0.0024 (10)	0.0000 (13)
C15	0.042 (2)	0.035 (3)	0.0316 (17)	0.012 (2)	−0.0031 (13)	−0.002 (3)
C16	0.0512 (16)	0.0413 (19)	0.0348 (14)	0.0068 (14)	−0.0056 (11)	0.0037 (12)
C7'	0.027 (4)	0.045 (5)	0.017 (3)	0.012 (3)	0.012 (3)	−0.009 (3)
C8'	0.038 (3)	0.020 (3)	0.022 (2)	0.005 (2)	−0.011 (2)	−0.005 (2)
C9'	0.045 (4)	0.032 (7)	0.046 (5)	0.011 (5)	−0.017 (3)	−0.010 (6)
C10'	0.070 (4)	0.030 (4)	0.053 (4)	−0.009 (3)	−0.026 (3)	0.006 (3)
C11'	0.062 (4)	0.033 (4)	0.030 (3)	−0.008 (3)	−0.002 (3)	0.008 (3)
C12'	0.066 (6)	0.035 (7)	0.014 (4)	−0.020 (5)	0.005 (4)	0.003 (4)
C13'	0.059 (10)	0.063 (8)	0.041 (6)	0.002 (8)	0.012 (8)	−0.013 (5)
C14'	0.054 (4)	0.029 (4)	0.026 (3)	−0.002 (3)	−0.005 (2)	0.002 (3)
C15'	0.058 (6)	0.036 (6)	0.040 (4)	−0.010 (4)	−0.011 (4)	0.002 (4)
C16'	0.056 (4)	0.046 (5)	0.041 (3)	0.011 (3)	−0.030 (3)	−0.004 (3)

Geometric parameters (Å, º)

O1—C7	1.430 (3)	C11—C12	1.524 (8)
O1—C1	1.4352 (16)	C11—C14	1.553 (4)
O1—C7'	1.487 (6)	C11—H11	1.0000
O2—C7'	1.431 (6)	C12—H12A	0.9900
O2—C2	1.4380 (18)	C12—H12B	0.9900
O2—C7	1.477 (3)	C13—H13A	0.9800
O3—C3	1.425 (2)	C13—H13B	0.9800
O3—H3O	0.8400	C13—H13C	0.9800
O4—C4	1.4370 (16)	C14—C15	1.530 (5)
O4—H4O	0.8400	C14—C16	1.550 (3)
O5—C5	1.4286 (17)	C15—H15A	0.9800
O5—H5O	0.8400	C15—H15B	0.9800
O6—C6	1.420 (2)	C15—H15C	0.9800
O6—H6O	0.8400	C16—H16A	0.9800
O7—H7A	0.852 (10)	C16—H16B	0.9800
O7—H7B	0.852 (10)	C16—H16C	0.9800
O8—H8A	0.827 (9)	C7'—C8'	1.547 (8)
O8—H8B	0.830 (9)	C7'—C12'	1.552 (11)
O9—H9OA	0.837 (9)	C8'—C13'	1.51 (2)
O9—H9OB	0.849 (10)	C8'—C9'	1.538 (10)
C1—C2	1.512 (2)	C8'—C14'	1.560 (7)
C1—C6	1.536 (2)	C9'—C10'	1.553 (15)
C1—H1	1.0000	C9'—H91	0.9900
C2—C3	1.515 (2)	C9'—H92	0.9900
C2—H2	1.0000	C10'—C11'	1.555 (9)
C3—C4	1.5204 (19)	C10'—H101	0.9900
C3—H3	1.0000	C10'—H102	0.9900
C4—C5	1.516 (2)	C11'—C12'	1.498 (15)
C4—H4A	1.0000	C11'—C14'	1.542 (9)
C5—C6	1.532 (2)	C11'—H111	1.0000
C5—H5	1.0000	C12'—H121	0.9900
C6—H6	1.0000	C12'—H122	0.9900
C7—C8	1.548 (4)	C13'—H131	0.9800
C7—C12	1.572 (7)	C13'—H132	0.9800
C8—C13	1.515 (5)	C13'—H133	0.9800
C8—C14	1.564 (3)	C14'—C15'	1.523 (11)
C8—C9	1.564 (4)	C14'—C16'	1.544 (8)
C9—C10	1.550 (5)	C15'—H151	0.9800
C9—H9A	0.9900	C15'—H152	0.9800
C9—H9B	0.9900	C15'—H153	0.9800
C10—C11	1.545 (4)	C16'—H161	0.9800
C10—H10A	0.9900	C16'—H162	0.9800
C10—H10B	0.9900	C16'—H163	0.9800
C7—O1—C1	108.18 (15)	C10—C11—H11	114.2
C1—O1—C7'	106.9 (3)	C14—C11—H11	114.2
C7'—O2—C2	99.5 (3)	C11—C12—C7	102.7 (5)
C2—O2—C7	108.57 (16)	C11—C12—H12A	111.2
C3—O3—H3O	109.5	C7—C12—H12A	111.2
C4—O4—H4O	109.5	C11—C12—H12B	111.2
C5—O5—H5O	109.5	C7—C12—H12B	111.2
C6—O6—H6O	109.5	H12A—C12—H12B	109.1
H7A—O7—H7B	103.2 (19)	C15—C14—C16	106.5 (3)
H8A—O8—H8B	106.4 (18)	C15—C14—C11	113.7 (3)
H9OA—O9—H9OB	103 (2)	C16—C14—C11	113.7 (2)
O1—C1—C2	101.29 (12)	C15—C14—C8	115.7 (3)
O1—C1—C6	110.76 (11)	C16—C14—C8	113.8 (2)
C2—C1—C6	113.56 (13)	C11—C14—C8	93.5 (2)
O1—C1—H1	110.3	O2—C7'—O1	103.1 (4)
C2—C1—H1	110.3	O2—C7'—C8'	102.8 (4)
C6—C1—H1	110.3	O1—C7'—C8'	114.6 (5)
O2—C2—C1	100.94 (12)	O2—C7'—C12'	116.5 (6)
O2—C2—C3	110.66 (12)	O1—C7'—C12'	116.7 (6)
C1—C2—C3	116.33 (13)	C8'—C7'—C12'	102.7 (7)
O2—C2—H2	109.5	C13'—C8'—C9'	115.6 (11)
C1—C2—H2	109.5	C13'—C8'—C7'	112.9 (8)
C3—C2—H2	109.5	C9'—C8'—C7'	107.9 (6)
O3—C3—C2	112.31 (12)	C13'—C8'—C14'	117.4 (10)
O3—C3—C4	112.57 (12)	C9'—C8'—C14'	100.3 (6)
C2—C3—C4	111.28 (12)	C7'—C8'—C14'	101.1 (4)
O3—C3—H3	106.7	C8'—C9'—C10'	105.5 (8)
C2—C3—H3	106.7	C8'—C9'—H91	110.6
C4—C3—H3	106.7	C10'—C9'—H91	110.6
O4—C4—C5	108.22 (12)	C8'—C9'—H92	110.6
O4—C4—C3	110.85 (11)	C10'—C9'—H92	110.6
C5—C4—C3	109.84 (12)	H91—C9'—H92	108.8
O4—C4—H4A	109.3	C9'—C10'—C11'	100.8 (5)
C5—C4—H4A	109.3	C9'—C10'—H101	111.6
C3—C4—H4A	109.3	C11'—C10'—H101	111.6
O5—C5—C4	111.99 (12)	C9'—C10'—H102	111.6
O5—C5—C6	109.52 (12)	C11'—C10'—H102	111.6
C4—C5—C6	111.37 (12)	H101—C10'—H102	109.4
O5—C5—H5	107.9	C12'—C11'—C14'	103.2 (6)
C4—C5—H5	107.9	C12'—C11'—C10'	107.5 (7)
C6—C5—H5	107.9	C14'—C11'—C10'	103.0 (5)
O6—C6—C5	111.72 (12)	C12'—C11'—H111	114.0
O6—C6—C1	107.25 (12)	C14'—C11'—H111	114.0
C5—C6—C1	112.62 (12)	C10'—C11'—H111	114.0
O6—C6—H6	108.4	C11'—C12'—C7'	104.0 (9)
C5—C6—H6	108.4	C11'—C12'—H121	110.9
C1—C6—H6	108.4	C7'—C12'—H121	110.9
O1—C7—O2	103.6 (2)	C11'—C12'—H122	110.9
O1—C7—C8	108.7 (2)	C7'—C12'—H122	110.9
O2—C7—C8	112.3 (2)	H121—C12'—H122	109.0
O1—C7—C12	114.6 (4)	C8'—C13'—H131	109.5
O2—C7—C12	114.3 (4)	C8'—C13'—H132	109.5
C8—C7—C12	103.5 (4)	H131—C13'—H132	109.5
C13—C8—C7	114.3 (3)	C8'—C13'—H133	109.5
C13—C8—C14	117.7 (3)	H131—C13'—H133	109.5
C7—C8—C14	101.43 (18)	H132—C13'—H133	109.5
C13—C8—C9	113.9 (3)	C15'—C14'—C11'	115.0 (7)
C7—C8—C9	106.3 (2)	C15'—C14'—C16'	106.3 (6)
C14—C8—C9	101.5 (2)	C11'—C14'—C16'	114.5 (5)
C10—C9—C8	103.6 (3)	C15'—C14'—C8'	114.1 (6)
C10—C9—H9A	111.0	C11'—C14'—C8'	93.3 (4)
C8—C9—H9A	111.0	C16'—C14'—C8'	113.6 (5)
C10—C9—H9B	111.0	C14'—C15'—H151	109.5
C8—C9—H9B	111.0	C14'—C15'—H152	109.5
H9A—C9—H9B	109.0	H151—C15'—H152	109.5
C11—C10—C9	103.1 (2)	C14'—C15'—H153	109.5
C11—C10—H10A	111.1	H151—C15'—H153	109.5
C9—C10—H10A	111.1	H152—C15'—H153	109.5
C11—C10—H10B	111.1	C14'—C16'—H161	109.5
C9—C10—H10B	111.1	C14'—C16'—H162	109.5
H10A—C10—H10B	109.1	H161—C16'—H162	109.5
C12—C11—C10	107.3 (4)	C14'—C16'—H163	109.5
C12—C11—C14	102.9 (3)	H161—C16'—H163	109.5
C10—C11—C14	102.73 (19)	H162—C16'—H163	109.5
C12—C11—H11	114.2
C7—O1—C1—C2	−37.82 (18)	C8—C7—C12—C11	0.2 (6)
C7'—O1—C1—C2	−12.9 (3)	C12—C11—C14—C15	−64.1 (5)
C7—O1—C1—C6	82.95 (19)	C10—C11—C14—C15	−175.5 (3)
C7'—O1—C1—C6	107.9 (3)	C12—C11—C14—C16	173.9 (4)
C7'—O2—C2—C1	−52.8 (3)	C10—C11—C14—C16	62.5 (3)
C7—O2—C2—C1	−30.02 (18)	C12—C11—C14—C8	56.0 (4)
C7'—O2—C2—C3	−176.6 (3)	C10—C11—C14—C8	−55.4 (2)
C7—O2—C2—C3	−153.79 (17)	C13—C8—C14—C15	−61.9 (4)
O1—C1—C2—O2	40.49 (13)	C7—C8—C14—C15	63.6 (3)
C6—C1—C2—O2	−78.29 (14)	C9—C8—C14—C15	173.1 (3)
O1—C1—C2—C3	160.26 (11)	C13—C8—C14—C16	61.9 (4)
C6—C1—C2—C3	41.49 (17)	C7—C8—C14—C16	−172.6 (2)
O2—C2—C3—O3	−61.31 (16)	C9—C8—C14—C16	−63.1 (3)
C1—C2—C3—O3	−175.70 (12)	C13—C8—C14—C11	179.7 (3)
O2—C2—C3—C4	65.91 (17)	C7—C8—C14—C11	−54.8 (2)
C1—C2—C3—C4	−48.48 (17)	C9—C8—C14—C11	54.7 (2)
O3—C3—C4—O4	−56.34 (15)	C2—O2—C7'—O1	44.4 (4)
C2—C3—C4—O4	176.58 (13)	C7—O2—C7'—O1	−70.3 (7)
O3—C3—C4—C5	−175.89 (11)	C2—O2—C7'—C8'	163.8 (3)
C2—C3—C4—C5	57.03 (15)	C7—O2—C7'—C8'	49.1 (7)
O4—C4—C5—O5	55.12 (14)	C2—O2—C7'—C12'	−84.8 (7)
C3—C4—C5—O5	176.26 (10)	C7—O2—C7'—C12'	160.5 (13)
O4—C4—C5—C6	178.15 (11)	C7—O1—C7'—O2	77.7 (7)
C3—C4—C5—C6	−60.71 (14)	C1—O1—C7'—O2	−19.1 (4)
O5—C5—C6—O6	−61.00 (15)	C7—O1—C7'—C8'	−33.3 (6)
C4—C5—C6—O6	174.57 (11)	C1—O1—C7'—C8'	−130.0 (4)
O5—C5—C6—C1	178.22 (12)	C7—O1—C7'—C12'	−153.3 (13)
C4—C5—C6—C1	53.78 (16)	C1—O1—C7'—C12'	109.9 (7)
O1—C1—C6—O6	80.25 (15)	O2—C7'—C8'—C13'	−76.3 (12)
C2—C1—C6—O6	−166.57 (11)	O1—C7'—C8'—C13'	34.8 (12)
O1—C1—C6—C5	−156.44 (12)	C12'—C7'—C8'—C13'	162.3 (12)
C2—C1—C6—C5	−43.26 (17)	O2—C7'—C8'—C9'	52.7 (7)
C1—O1—C7—O2	19.5 (2)	O1—C7'—C8'—C9'	163.7 (6)
C7'—O1—C7—O2	−71.4 (8)	C12'—C7'—C8'—C9'	−68.7 (8)
C1—O1—C7—C8	139.02 (18)	O2—C7'—C8'—C14'	157.4 (4)
C7'—O1—C7—C8	48.1 (7)	O1—C7'—C8'—C14'	−91.5 (5)
C1—O1—C7—C12	−105.7 (4)	C12'—C7'—C8'—C14'	36.1 (7)
C7'—O1—C7—C12	163.4 (10)	C13'—C8'—C9'—C10'	−163.7 (10)
C7'—O2—C7—O1	78.8 (8)	C7'—C8'—C9'—C10'	68.9 (8)
C2—O2—C7—O1	7.9 (2)	C14'—C8'—C9'—C10'	−36.4 (8)
C7'—O2—C7—C8	−38.3 (8)	C8'—C9'—C10'—C11'	1.2 (9)
C2—O2—C7—C8	−109.2 (2)	C9'—C10'—C11'—C12'	−73.3 (8)
C7'—O2—C7—C12	−155.8 (10)	C9'—C10'—C11'—C14'	35.3 (7)
C2—O2—C7—C12	133.4 (4)	C14'—C11'—C12'—C7'	−34.7 (9)
O1—C7—C8—C13	−75.0 (4)	C10'—C11'—C12'—C7'	73.8 (8)
O2—C7—C8—C13	39.0 (4)	O2—C7'—C12'—C11'	−112.8 (7)
C12—C7—C8—C13	162.7 (5)	O1—C7'—C12'—C11'	124.9 (8)
O1—C7—C8—C14	157.3 (2)	C8'—C7'—C12'—C11'	−1.3 (9)
O2—C7—C8—C14	−88.7 (2)	C12'—C11'—C14'—C15'	−63.3 (8)
C12—C7—C8—C14	35.0 (4)	C10'—C11'—C14'—C15'	−175.2 (6)
O1—C7—C8—C9	51.6 (3)	C12'—C11'—C14'—C16'	173.1 (7)
O2—C7—C8—C9	165.6 (2)	C10'—C11'—C14'—C16'	61.3 (6)
C12—C7—C8—C9	−70.7 (4)	C12'—C11'—C14'—C8'	55.2 (8)
C13—C8—C9—C10	−162.7 (3)	C10'—C11'—C14'—C8'	−56.6 (5)
C7—C8—C9—C10	70.6 (3)	C13'—C8'—C14'—C15'	−58.9 (12)
C14—C8—C9—C10	−35.1 (3)	C9'—C8'—C14'—C15'	175.0 (8)
C8—C9—C10—C11	0.1 (3)	C7'—C8'—C14'—C15'	64.4 (7)
C9—C10—C11—C12	−72.7 (4)	C13'—C8'—C14'—C11'	−178.2 (10)
C9—C10—C11—C14	35.4 (3)	C9'—C8'—C14'—C11'	55.7 (7)
C10—C11—C12—C7	72.2 (5)	C7'—C8'—C14'—C11'	−55.0 (5)
C14—C11—C12—C7	−35.8 (6)	C13'—C8'—C14'—C16'	63.2 (11)
O1—C7—C12—C11	−118.1 (4)	C9'—C8'—C14'—C16'	−62.9 (8)
O2—C7—C12—C11	122.5 (5)	C7'—C8'—C14'—C16'	−173.6 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O6^i	0.84	1.91	2.7294 (16)	167
O4—H4O···O7	0.84	1.87	2.6908 (16)	165
O5—H5O···O8	0.84	1.91	2.7394 (16)	172
O6—H6O···O9^ii	0.84	1.95	2.7762 (17)	166
O7—H7A···O4^iii	0.85 (2)	1.90 (1)	2.7490 (16)	172 (2)
O7—H7B···O5^i	0.85 (2)	1.84 (2)	2.6746 (16)	168 (2)
O8—H8A···O3^iv	0.83 (2)	1.90 (2)	2.7199 (16)	170 (2)
O8—H8B···O4^v	0.83 (1)	2.13 (1)	2.9236 (15)	161 (2)
O9—H9OA···O7^v	0.84 (1)	1.97 (1)	2.7754 (17)	162 (2)
O9—H9OB···O8	0.85 (1)	2.15 (1)	2.9436 (18)	155 (2)

Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z; (iii) −x+3/2, y+1/2, −z+2; (iv) x−1/2, y−1/2, z; (v) −x+1, y, −z+2.