Correlation of the solid-state reactivities of racemic 2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-orthoformate and its 4,4′-bi­pyridine cocrystal with their crystal structures

Racemic 2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-ortho­form­ate, C₂₁H₁₈O₈, (1), shows a very efficient inter­molecular benzoyl-group migration reaction in its crystals. However, the presence of 4,4′-bi­pyridine mol­ecules in its cocrystal, C₂₁H₁₈O₈·C₁₀H₈N₂, (1)·BP, inhibits the inter­molecular benzoyl-group transfer reaction. In (1), molecules are assembled around the crystallographic twofold screw axis (b axis) to form a helical self-assembly through conventional O—H...O hydrogen-bonding inter­actions. This helical association places the reactive C6-O-benzoyl group (electrophile, El) and the C4-hy­droxy group (nucleophile, Nu) in proximity, with a preorganized El...Nu geometry favourable for the acyl transfer reaction. In the cocrystal (1)·BP, the dibenzoate and bi­pyridine mol­ecules are arranged alternately through O—H...N inter­actions. The presence of the bi­pyridine mol­ecules perturbs the regular helical assembly of the dibenzoate mol­ecules and thus restricts the solid-state reactivity. Hence, unlike the parent dibenzoate crystals, the cocrystals do not exhibit benzoyl-transfer reactions. This approach is useful for increasing the stability of small mol­ecules in the crystalline state and could find application in the design of functional solids.

S1. Introduction

There has been an upsurge in inter­est in the study of the cocrystals, due to their potential applications in the resolution of racemates (Gonnade et al., 2011; Iwama et al., 2014), for improving the solubility of pharmaceutical ingredients (Stevens et al., 2010; Tiago et al., 2013; Song et al., 2014), for the construction of reactive supra­molecular assemblies (Desiraju, 1995; Cheney et al., 2007; Kole et al., 2010), and for gaining insight into crystal-lattice inter­actions with the hope of engineering other crystals with required properties (Bhatt & Desiraju, 2008; Schulthesiss & Newman, 2009). Molecular cocrystals provide a good platform for carrying out heteromolecular reactions (A + B → products) in the crystalline state, often with selectivity and conversion rates not attainable in solution or in single-component crystals (MacGillivray et al., 2008; Tamboli et al., 2013). In contrast, if crystals of single molecular entities do facilitate chemical reactions in them, the presence of other small molecules, yielding cocrystals with the former, can enhance the chemical stability of such molecules in the crystalline state by preventing the molecules from reacting. This could be of significance pertaining to the stability issues of small molecules, especially active pharmaceutical ingredients (APIs) in their formulations (Chen et al., 2013; Geng et al., 2013). We report herein a curious case of complete inhibition of the solid-state acyl transfer reaction in crystals of racemic 2,4-di-O-benzoyl-myo-inositol 1,3,5-orthoformate, (1), by cocrystal formation with 4,4'-bipridine. Crystals of dibenzoate (1) facilitate an inter­molecular benzoyl-group transfer reaction between their constituent molecules in the presence of a base (Praveen et al., 1998). However, cocrystals [denoted (1).BP] of the racemic dibenzoate (1) with 4,4'-bi­pyridine are completely devoid of any ability to undergo an inter­molecular benzoyl-transfer reaction in the solid state.

S2. Experimental

S2.1. Synthesis and crystallization

The racemic dibenzoate (1) (Das & Shashidhar, 1998) (0.400 g, 1 mmol) and 4,4'-bi­pyridine (0.156 g, 1 mmol) were dissolved in warm ethyl acetate (20 ml). The solution was stored (open to atmosphere) at room temperature for 3–4 d, after which 1:1 cocrystals of (1).BP (yield 0.450–0.500 g) were obtained. The cocrystals were characterized by single-crystal X-ray diffraction analysis, powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC), and NMR and IR spectroscopy. We also attempted cocrystallization of (1) with other nitro­genous bases (adenine, guanine, cytosine, thymine and uracil) in different solvents (ethanol, methanol, acetone, iso­propanol and aceto­nitrile, and mixtures of these solvents), but no cocrystals were obtained Analysis for (1).BP ??: m.p. 403–404 K; IR (Nujol, ν, cm^-1): 3200–3450, 1721; ¹H NMR (400 MHz, CDCl₃, δ, p.p.m.): 4.01–4.15 (m, 1H, D₂O Ex.), 4.51 (m, 1H), 4.60–4.65 (m, 2H), 4.76 (m, 1H), 5.66 (d, J = 1.2 Hz, 1H), 5.73 (s, 1H), 5.81–5.85 (m, 1H), 7.42–7.50 (m, 4H), 7.50–7.54 (m, 4H), 7.55–7.63 (m, 2H), 8.05–8.10 (m, 2H), 8.14–8.19 (m, 2H), 8.67–8.75 (m, 4H); ¹³C NMR (101 MHz, CDCl₃, δ, p.p.m.): 63.9, 67.2, 68.5, 68.8, 69.7, 72.0, 103.0, 121.5, 128.5, 128.6, 129.0, 129.5, 129.9, 133.4, 133.6, 145.6, 150.5, 165.2, 166.1 (see Supporting information for NMR spectra; Figs. S1–S3).

S2.2. DSC analysis

DSC analyses of both (1) and cocrystal (1).BP were carried out on a Waters DSC instrument. Crystals (~3–4 mg) were placed on an aluminium pan (40 µl) and were analysed using an empty pan as the reference. The heating rate was 10 K min^-1 and nitro­gen gas was used for purging. The DSC thermograms of (1) and (1).BP revealed a single endotherm each, at 453 and 406 K, respectively, corresponding to their melting (see Supporting information for DSC plots; Fig. S4).

S2.3. PXRD analysis

Experimental powder X-ray diffraction (PXRD) patterns were recorded on a Rigaku Micromax-007HF instrument (high-intensity microfocous rotating anode X-ray generator) with an R-AXIS detector IV++ at a continuous scanning rate of 2° 2θ min^-1 using Cu Kα radiation (40 kV, 30 mA), with the intensity of the diffracted X-rays being collected at inter­vals of 0.1° 2θ. A nickel filter was used to remove Cu Kβ radiation. The PXRD patterns of (1) and (1).BP are different (see Supporting information for PXRD patterns; Fig S5).

S2.4. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were placed in geometrically idealized positions for both compounds. For (1), C—H = 0.98 Å for the inositol ring H atoms and the orthoformate H atom, C—H = 0.93 Å for the phenyl H atoms and O—H = 0.82 Å for the hy­droxy H atom. For cocrystal (1).BP, C—H = 1.00 Å for the inositol ring H atoms and the orthoformate H atom, C—H = 0.95 Å for the phenyl H atoms and O—H = 0.84 Å for the hy­droxy H atom. H atoms were constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(O). The anisotropic displacement parameters for atoms C20 and C21 of the C16–C21 phenyl ring were unusually large, indicating orientational disorder. A reasonable model was obtained by splitting these two atoms into two components, viz. C20—C21 and C20'—C21', with fixed equal occupancies (0.50), thereby summing the site-occupancy factors for both disordered atoms to unity.

S3. Results and discussion

Investigation of the crystal structure of dibenzoate (1) revealed that the facile reaction in the crystalline state was due to preorganization of the electrophile (C═O) and nucleophile (–OH) with the required geometry for nucleophilic addition (Bürgi & Dunitz, 1983) and the helical assembly of the molecules which allowed a domino type of reaction (Sarmah et al., 2005; Murali et al., 2009). We were curious to see whether the inclusion of a base in the crystal structure of the racemic dibenzoate would augment or hinder the benzoyl-transfer reactivity of the molecules. We chose symmetrical 4,4'-bi­pyridine (BP) as the cocrystal builder. A survey of the Cambridge Structural Database (CSD, Version 5.35; Allen, 2002) revealed several cocrystals of symmetrical BP with molecules having –OH or –COOH functional groups through O—H···N hydrogen bonding [Citations of these needed?].

Cocrystal (1).BP consists of equimolar amounts of dibenzoate (1) and 4,4'-bi­pyridine (BP), as revealed by ¹H NMR spectroscopy and single-crystal X-ray diffraction analysis. Crystal of (1).BP were stable under ambient conditions for several months, as revealed by their melting point and X-ray powder diffraction studies. The DSC profile of (1).BP revealed that it was stable up to the melting point and that there was no phase change prior to melting of the cocrystals. When heated, in either the presence or absence of sodium carbonate, (1).BP failed to undergo a benzoyl-transfer reaction, in contrast with the crystals of racemic dibenzoate (1) alone (Fig. 1).

Although the crystal structure of racemic dibenzoate (1) had been reported previously (Praveen et al., 1998; Sarmah et al., 2005), it was redetermined here (Fig. 2) for the sake of comparison with the cocrystal (1).BP. Both molecules in the asymmetric unit of (1) have a similar conformation, except for minute differences in the torsion angles of the two benzoyl groups. The molecular overlap of (1) in the crystal structures of (1) and (1).BP (Fig. 3) reveals major conformational differences in the orientation of the two benzoyl groups. The difference in the torsion angles of the C2-O-benzoyl group (C2—O2—C8—C9) is ca 48°, whereas the C4-O-benzoyl group (C4—O4—C15—C16) shows a difference of ca 59° (Fig. 4). The conformations of the hy­droxy group in both structures were found to be similar. These conformational changes in the benzoyl groups have a profound influence on the molecular association.

A comparison of the crystal structures of dibenzoate (1) and cocrystal (1).BP reveals distinctly different arrangements of the molecules. From similar views of the molecular packing in the two crystal structures, the difference is evident. Both symmetry-independent molecules (unprimed and primed labels) in (1) are arranged helically across the crystallographic twofold screw axis through conventional O—H···O hydrogen-bonding inter­actions, each molecule along the helix being twisted by 180° (Fig. 5). The –OH group at the C4 or C6 position donates its H atom to carbonyl atom O7 or O7' of the C2-equatorial benzoate group to generate O4—H4A···O7ⁱ or O6'—H6'A···O7'ⁱⁱ inter­actions [symmetry codes: (i) -x + 1, y - 1/2, -z + 1/2; (ii) -x, y + 1/2, -z + 1/2]. This arrangement brings the reactive functional groups, i.e. nucleophile (Nu) –OH (O4 or O6') and electrophile (El) C═O (C15═O8 or C15'═O8') of the C4-axial benzoate group into proximity with the proper orientation for the initiation and propagation of the inter­molecular benzoyl transfer reaction (Sarmah et al., 2005).

The presence of bi­pyridine molecules in cocrystal (1).BP breaks this O—H···O-linked helical assembly of dibenzoate (1) molecules by inter­acting with their –OH group through O—H···N hydrogen-bonding inter­actions. The –OH group of dibenzoate (1) forms a hydrogen bond with one of the N atoms (N2) of bi­pyridine [O6—H6A···N2ⁱ; symmetry code: (i) -x + 1, -y, -z + 1] while the other N atom (N1) is involved in C—H···N inter­actions with an aromatic C—H of the axial benzoyl group of (1) [C20—H20···N1ⁱⁱ; symmetry code: (ii) -x + 2, -y, -z], revealing an alternating arangement of dibenzoate (1) and bi­pyridine molecules to form a flat chain along the c axis (Fig. 6). The bi­pyridine molecule occupies the position of dibenzoate (1) between the two unit-translated molecules and disrupts the helical chain. This inter­vention precludes the juxtaposition of El (C═O) and Nu (–OH) groups along the helical chain.

Views of the molecular packing of (1) and its cocrystal (1).BP are displayed in Figs. 7 and 8. In crystals of dibenzoate (1), adjacent helices of two symmetry-independent molecules are packed much more discretely approximately along the ac diagonal through C—H···O [C21—H21···O2'ⁱⁱⁱ and C21'—H21'···O2^iv; symmetry codes: (iii) x, y - 1, z; (iv) x, y + 1, z] and off-centred C—H···π inter­actions to provide channels throughout the crystal structure for the efficient inter­molecular transfer of the benzoyl group (Fig. 7). This juxtaposition of the molecules of (1) is perturbed in cocrystal (1).BP due to the presence of the bi­pyridine molecules, resulting in the prevention of the inter­molecular benzoyl-group transfer between the molecules of (1). The unit-translated neighbouring chains comprising molecules of (1) and bi­pyridine are loosely connected along the b axis via van der Waals forces, to generate a two-dimensional sheet structure in the bc plane (Fig. 8).

A crystal structure that augments chemical reactions destabilizes both the crystal structure and the constituent molecules (Pathigoola et al., 2012). This destabilization could lead to a reduced shelf-life for crystalline solids and their mixtures (as in some pharmaceutical formulations) (Troup & Mitchner, 1964; Jacobs et al., 1966; Koshy et al., 1967). The results presented here show that cocrystallization can be a method to decrease the ease of chemical reactions between molecules in a crystal structure and thereby increase the stability of molecular solids.

Related literature

For related literature, see: Allen (2002); Bürgi & Dunitz (1983); Bhatt & Desiraju (2008); Chen et al. (2013); Cheney et al. (2007); Das & Shashidhar (1998); Desiraju (1995); Geng et al. (2013); Gonnade et al. (2011); Iwama et al. (2014); Jacobs et al. (1966); Kole et al. (2010); Koshy et al. (1967); MacGillivray et al. (2008); Murali et al. (2009); Praveen et al. (1998); Sarmah et al. (2005); Song et al. (2014); Stevens et al. (2010); Tamboli et al. (2013); Tiago et al. (2013); Troup & Mitchner (1964).

Computing details

For both compounds, data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXS97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures

	Fig. 1. The favourable El···Nu (El is electrophile and Nu is nucleophile) geometry in crystals of (1), which exhibit a benzoyl-group transfer reaction on heating in the presence of solid sodium carbonate.
	Fig. 2. The components of (1), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. The components of (1).BP, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Dashed bonds indicate the minor disorder component?]
	Fig. 4. The molecular overlap of the dibenzoate molecules in the crystal structures of (1) and (1).BP.
	Fig. 5. The helical assembly of molecules of (1) through O4—H4A···O7^i interactions (dashed lines?), bringing the nucleophile (O4—H4A) and electrophile (C15═O8) into close proximity with the proper orientation. [Symmetry code: (i) -x + 1, y - 1/2, -z + 1/2.]
	Fig. 6. The alternating arrangement of dibenzoate and bipyridine molecules in cocrystal (1).BP, generating a chain structure through O6—H6A···N2^i and C20—H20···N1^ii interactions (dashed lines?). [Symmetry codes: (i) -x + 1, -y, -z + 1; (ii) -x + 2, -y, -z.]
	Fig. 7. The molecular packing of (1), showing the discrete assembly of neighbouring helices linked through C21—H21···O2'^iii and C21'—H21'···O2^iv interactions (dashed lines? C—H..π also shown?). [Symmetry codes: (iii) x, y - 1, z; (iv) x, y + 1, z.]
	Fig. 8. The molecular packing of (1).BP, showing the two-dimensional sheet structure generated by the weak association (dashed lines?) of molecular chains constituted by dibenzoate and bipyridine molecules.

(1) 2,4(6)-Di-O-benzoyl-myo-inositol 1,3,5-orthoformate

Crystal data

C21H18O8	F(000) = 1664
Mr = 398.35	Dx = 1.436 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5959 reflections
a = 16.6753 (7) Å	θ = 2.4–27.5°
b = 9.8281 (5) Å	µ = 0.11 mm^−1
c = 22.4931 (10) Å	T = 296 K
β = 90.747 (2)°	Hexagonal plate, colourless
V = 3686.0 (3) Å^3	0.43 × 0.26 × 0.07 mm
Z = 8

Data collection

Bruker APEXII CCD area-detector diffractometer	7237 independent reflections
Radiation source: fine-focus sealed tube	4901 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
ϕ and ω scans	θmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −20→20
Tmin = 0.954, Tmax = 0.992	k = −11→12
29254 measured reflections	l = −27→27

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.133	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0466P)^2 + 1.5296P] where P = (Fo^2 + 2Fc^2)/3
7237 reflections	(Δ/σ)max < 0.001
525 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3

Special details

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	0.36121 (8)	0.07503 (16)	0.41260 (6)	0.0389 (4)
O2	0.35622 (9)	0.34860 (15)	0.36536 (7)	0.0387 (4)
O3	0.47307 (9)	0.20214 (17)	0.43738 (7)	0.0434 (4)
O4	0.56185 (9)	0.18261 (17)	0.29149 (7)	0.0465 (4)
H4A	0.5832	0.1205	0.2732	0.070*
O5	0.48688 (10)	−0.02664 (17)	0.41485 (7)	0.0467 (4)
O6	0.42891 (8)	0.01888 (16)	0.26004 (6)	0.0378 (4)
O7	0.37421 (10)	0.47472 (18)	0.28405 (8)	0.0549 (5)
O8	0.30596 (9)	−0.06473 (19)	0.23979 (7)	0.0492 (4)
O1'	0.02683 (9)	0.95791 (17)	0.06782 (7)	0.0436 (4)
O2'	0.14979 (9)	0.81694 (15)	0.13563 (6)	0.0376 (4)
O3'	0.13901 (9)	1.08875 (16)	0.08744 (7)	0.0410 (4)
O4'	0.08017 (8)	1.14458 (16)	0.24212 (7)	0.0397 (4)
O5'	0.01266 (10)	1.18779 (17)	0.08970 (8)	0.0491 (4)
O6'	−0.05244 (9)	0.97916 (17)	0.21647 (7)	0.0474 (4)
H6'A	−0.0795	1.0365	0.2335	0.071*
O7'	0.12888 (11)	0.68389 (18)	0.21450 (8)	0.0550 (5)
O8'	0.20093 (9)	1.23723 (19)	0.26190 (7)	0.0502 (5)
C1	0.36715 (12)	0.1070 (2)	0.35047 (9)	0.0309 (5)
H1	0.3137	0.1081	0.3318	0.037*
C2	0.40792 (12)	0.2433 (2)	0.34215 (10)	0.0328 (5)
H2	0.4178	0.2593	0.2999	0.039*
C3	0.48647 (12)	0.2423 (2)	0.37656 (10)	0.0372 (5)
H3	0.5110	0.3328	0.3755	0.045*
C4	0.54296 (12)	0.1378 (2)	0.34940 (10)	0.0365 (5)
H4	0.5924	0.1340	0.3734	0.044*
C5	0.50079 (13)	−0.0003 (2)	0.35269 (10)	0.0366 (5)
H5	0.5351	−0.0713	0.3361	0.044*
C6	0.41854 (12)	−0.0037 (2)	0.32251 (9)	0.0332 (5)
H6	0.3936	−0.0928	0.3288	0.040*
C7	0.43727 (14)	0.0741 (3)	0.43976 (10)	0.0435 (6)
H7	0.4301	0.0513	0.4818	0.052*
C8	0.34438 (12)	0.4600 (2)	0.33182 (10)	0.0344 (5)
C9	0.29067 (12)	0.5588 (2)	0.36120 (11)	0.0373 (5)
C10	0.27131 (15)	0.6780 (2)	0.33103 (13)	0.0514 (7)
H10	0.2915	0.6939	0.2933	0.062*
C11	0.22195 (16)	0.7728 (3)	0.35739 (16)	0.0640 (8)
H11	0.2094	0.8532	0.3375	0.077*
C12	0.19137 (16)	0.7490 (3)	0.41268 (15)	0.0645 (9)
H12	0.1584	0.8137	0.4301	0.077*
C13	0.20915 (15)	0.6291 (3)	0.44306 (12)	0.0558 (7)
H13	0.1876	0.6127	0.4803	0.067*
C14	0.25915 (14)	0.5351 (3)	0.41708 (11)	0.0437 (6)
H14	0.2719	0.4551	0.4372	0.052*
C15	0.36783 (13)	−0.0148 (2)	0.22331 (10)	0.0357 (5)
C16	0.38685 (12)	0.0187 (2)	0.16087 (10)	0.0357 (5)
C17	0.44790 (15)	0.1082 (3)	0.14654 (12)	0.0486 (6)
H17	0.4780	0.1503	0.1764	0.058*
C18	0.46352 (19)	0.1344 (3)	0.08734 (14)	0.0630 (8)
H18	0.5036	0.1958	0.0773	0.076*
C19	0.4199 (2)	0.0699 (3)	0.04333 (13)	0.0665 (9)
H19	0.4307	0.0875	0.0036	0.080*
C20	0.36078 (17)	−0.0200 (4)	0.05779 (12)	0.0657 (9)
H20	0.3324	−0.0649	0.0278	0.079*
C21	0.34295 (14)	−0.0447 (3)	0.11633 (11)	0.0482 (6)
H21	0.3015	−0.1039	0.1259	0.058*
C1'	0.01777 (12)	0.9201 (2)	0.12908 (10)	0.0351 (5)
H1'	−0.0059	0.8290	0.1315	0.042*
C2'	0.09888 (12)	0.9209 (2)	0.16044 (10)	0.0325 (5)
H2'	0.0923	0.9056	0.2032	0.039*
C3'	0.13794 (12)	1.0582 (2)	0.14978 (9)	0.0337 (5)
H3'	0.1926	1.0589	0.1663	0.040*
C4'	0.08729 (12)	1.1684 (2)	0.17952 (10)	0.0359 (5)
H4'	0.1110	1.2582	0.1726	0.043*
C5'	0.00330 (13)	1.1626 (2)	0.15236 (11)	0.0405 (6)
H5'	−0.0305	1.2332	0.1699	0.049*
C6'	−0.03748 (12)	1.0226 (2)	0.15787 (11)	0.0389 (6)
H6'	−0.0884	1.0246	0.1356	0.047*
C7'	0.06100 (14)	1.0874 (3)	0.06318 (11)	0.0444 (6)
H7'	0.0649	1.1092	0.0208	0.053*
C8'	0.15819 (12)	0.7009 (2)	0.16663 (10)	0.0342 (5)
C9'	0.20687 (12)	0.5992 (2)	0.13448 (10)	0.0344 (5)
C10'	0.23302 (14)	0.4845 (2)	0.16503 (12)	0.0462 (6)
H10'	0.2212	0.4736	0.2050	0.055*
C11'	0.27641 (15)	0.3872 (3)	0.13580 (15)	0.0601 (8)
H11'	0.2941	0.3104	0.1562	0.072*
C12'	0.29404 (16)	0.4020 (3)	0.07680 (15)	0.0622 (8)
H12'	0.3232	0.3351	0.0574	0.075*
C13'	0.26869 (16)	0.5158 (3)	0.04622 (13)	0.0593 (8)
H13'	0.2806	0.5257	0.0062	0.071*
C14'	0.22555 (14)	0.6150 (3)	0.07521 (11)	0.0476 (6)
H14'	0.2090	0.6926	0.0548	0.057*
C15'	0.14052 (12)	1.1836 (2)	0.27854 (10)	0.0350 (5)
C16'	0.12122 (12)	1.1504 (2)	0.34097 (10)	0.0360 (5)
C17'	0.05873 (15)	1.0631 (3)	0.35494 (12)	0.0509 (7)
H17'	0.0289	1.0217	0.3248	0.061*
C18'	0.0413 (2)	1.0383 (3)	0.41294 (15)	0.0758 (10)
H18'	−0.0002	0.9792	0.4224	0.091*
C19'	0.0853 (2)	1.1009 (4)	0.45770 (14)	0.0793 (10)
H19'	0.0726	1.0848	0.4972	0.095*
C20'	0.14744 (17)	1.1864 (3)	0.44433 (12)	0.0631 (8)
H20'	0.1771	1.2277	0.4746	0.076*
C21'	0.16570 (14)	1.2108 (3)	0.38587 (11)	0.0451 (6)
H21'	0.2081	1.2681	0.3766	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0408 (8)	0.0441 (10)	0.0321 (8)	−0.0005 (7)	0.0083 (6)	0.0076 (8)
O2	0.0473 (9)	0.0304 (9)	0.0386 (9)	0.0146 (7)	0.0107 (7)	0.0056 (8)
O3	0.0453 (9)	0.0484 (11)	0.0364 (9)	0.0020 (8)	0.0009 (7)	−0.0097 (8)
O4	0.0447 (9)	0.0415 (10)	0.0537 (10)	−0.0045 (8)	0.0195 (8)	−0.0074 (9)
O5	0.0552 (10)	0.0443 (10)	0.0406 (9)	0.0161 (8)	0.0003 (7)	0.0098 (8)
O6	0.0381 (8)	0.0407 (9)	0.0348 (9)	−0.0061 (7)	0.0039 (6)	−0.0060 (8)
O7	0.0674 (11)	0.0441 (11)	0.0536 (11)	0.0104 (9)	0.0198 (9)	0.0205 (9)
O8	0.0388 (9)	0.0624 (12)	0.0465 (10)	−0.0083 (8)	0.0033 (7)	0.0023 (9)
O1'	0.0500 (9)	0.0426 (10)	0.0380 (9)	−0.0078 (8)	−0.0030 (7)	−0.0033 (8)
O2'	0.0468 (9)	0.0309 (9)	0.0354 (8)	0.0096 (7)	0.0133 (7)	0.0065 (7)
O3'	0.0436 (9)	0.0429 (10)	0.0366 (9)	−0.0069 (8)	0.0048 (7)	0.0044 (8)
O4'	0.0393 (8)	0.0392 (9)	0.0408 (9)	−0.0085 (7)	0.0043 (7)	−0.0081 (8)
O5'	0.0560 (10)	0.0401 (10)	0.0509 (11)	0.0075 (8)	−0.0072 (8)	0.0087 (9)
O6'	0.0424 (9)	0.0433 (10)	0.0568 (11)	−0.0040 (8)	0.0179 (8)	−0.0076 (9)
O7'	0.0726 (12)	0.0430 (11)	0.0500 (11)	0.0098 (9)	0.0256 (9)	0.0143 (9)
O8'	0.0381 (9)	0.0635 (12)	0.0491 (10)	−0.0131 (9)	0.0024 (7)	0.0049 (9)
C1	0.0299 (10)	0.0334 (12)	0.0294 (11)	0.0014 (9)	0.0023 (8)	0.0024 (10)
C2	0.0389 (11)	0.0277 (12)	0.0320 (11)	0.0075 (10)	0.0105 (9)	0.0021 (10)
C3	0.0360 (11)	0.0307 (12)	0.0450 (14)	−0.0037 (10)	0.0065 (10)	−0.0077 (11)
C4	0.0302 (11)	0.0391 (14)	0.0404 (13)	0.0016 (10)	0.0036 (9)	−0.0054 (11)
C5	0.0391 (12)	0.0305 (12)	0.0403 (13)	0.0098 (10)	0.0057 (10)	−0.0020 (11)
C6	0.0381 (11)	0.0276 (12)	0.0341 (12)	−0.0026 (10)	0.0034 (9)	−0.0017 (10)
C7	0.0472 (13)	0.0501 (16)	0.0332 (13)	0.0079 (12)	0.0017 (10)	0.0061 (12)
C8	0.0343 (11)	0.0279 (12)	0.0408 (13)	−0.0014 (10)	−0.0028 (10)	0.0067 (11)
C9	0.0342 (11)	0.0280 (12)	0.0495 (14)	0.0014 (10)	−0.0089 (10)	−0.0020 (11)
C10	0.0499 (14)	0.0323 (14)	0.0718 (18)	0.0056 (12)	−0.0038 (13)	0.0088 (14)
C11	0.0595 (17)	0.0310 (15)	0.101 (3)	0.0115 (13)	−0.0084 (17)	0.0020 (16)
C12	0.0523 (16)	0.0482 (18)	0.092 (2)	0.0191 (14)	−0.0136 (16)	−0.0298 (18)
C13	0.0556 (15)	0.0568 (18)	0.0548 (16)	0.0115 (14)	−0.0063 (12)	−0.0204 (15)
C14	0.0470 (13)	0.0383 (14)	0.0455 (14)	0.0091 (11)	−0.0100 (11)	−0.0083 (12)
C15	0.0352 (11)	0.0310 (12)	0.0410 (13)	0.0048 (10)	0.0029 (10)	−0.0039 (11)
C16	0.0352 (11)	0.0328 (12)	0.0392 (13)	0.0104 (10)	0.0030 (9)	0.0014 (11)
C17	0.0603 (15)	0.0322 (13)	0.0534 (16)	0.0013 (12)	0.0107 (12)	0.0009 (12)
C18	0.083 (2)	0.0389 (16)	0.068 (2)	0.0015 (15)	0.0288 (16)	0.0149 (15)
C19	0.088 (2)	0.070 (2)	0.0427 (16)	0.0242 (18)	0.0119 (15)	0.0170 (17)
C20	0.0617 (17)	0.095 (3)	0.0400 (15)	0.0085 (17)	−0.0106 (13)	0.0089 (17)
C21	0.0364 (12)	0.0655 (18)	0.0425 (14)	0.0062 (12)	−0.0043 (10)	0.0031 (14)
C1'	0.0351 (11)	0.0291 (12)	0.0412 (13)	−0.0062 (10)	0.0037 (9)	−0.0017 (11)
C2'	0.0361 (11)	0.0274 (12)	0.0344 (12)	0.0058 (9)	0.0090 (9)	−0.0006 (10)
C3'	0.0310 (10)	0.0367 (13)	0.0335 (12)	−0.0022 (10)	0.0007 (9)	0.0002 (11)
C4'	0.0400 (12)	0.0275 (12)	0.0402 (13)	−0.0065 (10)	0.0010 (10)	−0.0013 (11)
C5'	0.0401 (12)	0.0301 (12)	0.0512 (15)	0.0048 (10)	−0.0006 (10)	−0.0013 (12)
C6'	0.0294 (11)	0.0383 (14)	0.0491 (14)	0.0003 (10)	0.0002 (10)	−0.0037 (12)
C7'	0.0530 (14)	0.0429 (15)	0.0374 (13)	−0.0036 (12)	−0.0016 (11)	0.0057 (12)
C8'	0.0339 (11)	0.0308 (13)	0.0378 (13)	−0.0011 (10)	0.0031 (9)	0.0053 (11)
C9'	0.0332 (11)	0.0265 (12)	0.0435 (13)	0.0001 (9)	−0.0004 (9)	0.0024 (11)
C10'	0.0460 (13)	0.0355 (14)	0.0573 (16)	0.0026 (11)	0.0054 (11)	0.0097 (13)
C11'	0.0540 (16)	0.0331 (15)	0.093 (2)	0.0090 (13)	0.0051 (15)	0.0090 (16)
C12'	0.0502 (15)	0.0417 (16)	0.095 (2)	0.0123 (13)	0.0090 (15)	−0.0196 (17)
C13'	0.0649 (17)	0.0610 (19)	0.0523 (16)	0.0165 (15)	0.0075 (13)	−0.0128 (15)
C14'	0.0547 (14)	0.0433 (15)	0.0449 (14)	0.0130 (12)	0.0033 (11)	0.0006 (13)
C15'	0.0328 (11)	0.0283 (12)	0.0441 (13)	0.0031 (10)	0.0035 (10)	−0.0025 (11)
C16'	0.0346 (11)	0.0300 (12)	0.0436 (13)	0.0090 (10)	0.0069 (10)	0.0004 (11)
C17'	0.0596 (15)	0.0333 (14)	0.0602 (17)	−0.0032 (12)	0.0148 (13)	0.0001 (13)
C18'	0.098 (2)	0.058 (2)	0.072 (2)	−0.0165 (19)	0.0306 (19)	0.0102 (18)
C19'	0.105 (3)	0.082 (3)	0.0512 (19)	0.004 (2)	0.0295 (18)	0.0157 (19)
C20'	0.0682 (18)	0.075 (2)	0.0461 (16)	0.0122 (17)	0.0023 (13)	−0.0052 (16)
C21'	0.0386 (12)	0.0514 (16)	0.0455 (15)	0.0054 (11)	0.0054 (11)	−0.0032 (13)

Geometric parameters (Å, º)

O1—C7	1.401 (3)	C13—H13	0.9300
O1—C1	1.437 (2)	C14—H14	0.9300
O2—C8	1.342 (3)	C15—C16	1.481 (3)
O2—C2	1.449 (2)	C16—C21	1.382 (3)
O3—C7	1.394 (3)	C16—C17	1.387 (3)
O3—C3	1.444 (3)	C17—C18	1.384 (4)
O4—C4	1.415 (3)	C17—H17	0.9300
O4—H4A	0.8200	C18—C19	1.376 (4)
O5—C7	1.411 (3)	C18—H18	0.9300
O5—C5	1.444 (3)	C19—C20	1.366 (4)
O6—C15	1.344 (3)	C19—H19	0.9300
O6—C6	1.435 (2)	C20—C21	1.375 (3)
O7—C8	1.199 (3)	C20—H20	0.9300
O8—C15	1.205 (2)	C21—H21	0.9300
O1'—C7'	1.399 (3)	C1'—C6'	1.516 (3)
O1'—C1'	1.437 (3)	C1'—C2'	1.517 (3)
O2'—C8'	1.344 (3)	C1'—H1'	0.9800
O2'—C2'	1.445 (2)	C2'—C3'	1.519 (3)
O3'—C7'	1.404 (3)	C2'—H2'	0.9800
O3'—C3'	1.434 (2)	C3'—C4'	1.533 (3)
O4'—C15'	1.345 (3)	C3'—H3'	0.9800
O4'—C4'	1.434 (3)	C4'—C5'	1.522 (3)
O5'—C7'	1.411 (3)	C4'—H4'	0.9800
O5'—C5'	1.442 (3)	C5'—C6'	1.540 (3)
O6'—C6'	1.411 (3)	C5'—H5'	0.9800
O6'—H6'A	0.8200	C6'—H6'	0.9800
O7'—C8'	1.200 (2)	C7'—H7'	0.9800
O8'—C15'	1.201 (2)	C8'—C9'	1.482 (3)
C1—C2	1.515 (3)	C9'—C14'	1.382 (3)
C1—C6	1.525 (3)	C9'—C10'	1.388 (3)
C1—H1	0.9800	C10'—C11'	1.372 (4)
C2—C3	1.513 (3)	C10'—H10'	0.9300
C2—H2	0.9800	C11'—C12'	1.371 (4)
C3—C4	1.526 (3)	C11'—H11'	0.9300
C3—H3	0.9800	C12'—C13'	1.376 (4)
C4—C5	1.530 (3)	C12'—H12'	0.9300
C4—H4	0.9800	C13'—C14'	1.381 (3)
C5—C6	1.523 (3)	C13'—H13'	0.9300
C5—H5	0.9800	C14'—H14'	0.9300
C6—H6	0.9800	C15'—C16'	1.481 (3)
C7—H7	0.9800	C16'—C21'	1.379 (3)
C8—C9	1.482 (3)	C16'—C17'	1.389 (3)
C9—C14	1.388 (3)	C17'—C18'	1.362 (4)
C9—C10	1.390 (3)	C17'—H17'	0.9300
C10—C11	1.382 (4)	C18'—C19'	1.382 (5)
C10—H10	0.9300	C18'—H18'	0.9300
C11—C12	1.370 (4)	C19'—C20'	1.371 (4)
C11—H11	0.9300	C19'—H19'	0.9300
C12—C13	1.392 (4)	C20'—C21'	1.375 (3)
C12—H12	0.9300	C20'—H20'	0.9300
C13—C14	1.379 (3)	C21'—H21'	0.9300
C7—O1—C1	110.61 (16)	C19—C20—C21	120.5 (3)
C8—O2—C2	117.64 (16)	C19—C20—H20	119.7
C7—O3—C3	110.76 (17)	C21—C20—H20	119.7
C4—O4—H4A	109.5	C20—C21—C16	119.7 (3)
C7—O5—C5	111.15 (16)	C20—C21—H21	120.2
C15—O6—C6	117.62 (16)	C16—C21—H21	120.2
C7'—O1'—C1'	110.79 (17)	O1'—C1'—C6'	108.03 (18)
C8'—O2'—C2'	117.24 (16)	O1'—C1'—C2'	109.90 (16)
C7'—O3'—C3'	110.78 (16)	C6'—C1'—C2'	109.93 (18)
C15'—O4'—C4'	118.71 (16)	O1'—C1'—H1'	109.7
C7'—O5'—C5'	111.28 (17)	C6'—C1'—H1'	109.7
C6'—O6'—H6'A	109.5	C2'—C1'—H1'	109.7
O1—C1—C2	110.50 (17)	O2'—C2'—C1'	109.96 (17)
O1—C1—C6	106.94 (17)	O2'—C2'—C3'	108.18 (16)
C2—C1—C6	108.91 (16)	C1'—C2'—C3'	108.22 (18)
O1—C1—H1	110.1	O2'—C2'—H2'	110.1
C2—C1—H1	110.1	C1'—C2'—H2'	110.1
C6—C1—H1	110.1	C3'—C2'—H2'	110.1
O2—C2—C3	109.60 (18)	O3'—C3'—C2'	110.55 (17)
O2—C2—C1	108.50 (16)	O3'—C3'—C4'	107.03 (17)
C3—C2—C1	108.54 (18)	C2'—C3'—C4'	108.62 (16)
O2—C2—H2	110.1	O3'—C3'—H3'	110.2
C3—C2—H2	110.1	C2'—C3'—H3'	110.2
C1—C2—H2	110.1	C4'—C3'—H3'	110.2
O3—C3—C2	110.05 (16)	O4'—C4'—C5'	107.48 (17)
O3—C3—C4	107.43 (18)	O4'—C4'—C3'	111.48 (18)
C2—C3—C4	109.53 (18)	C5'—C4'—C3'	107.92 (18)
O3—C3—H3	109.9	O4'—C4'—H4'	110.0
C2—C3—H3	109.9	C5'—C4'—H4'	110.0
C4—C3—H3	109.9	C3'—C4'—H4'	110.0
O4—C4—C3	107.77 (18)	O5'—C5'—C4'	105.97 (17)
O4—C4—C5	115.36 (18)	O5'—C5'—C6'	106.59 (19)
C3—C4—C5	106.89 (16)	C4'—C5'—C6'	113.97 (19)
O4—C4—H4	108.9	O5'—C5'—H5'	110.0
C3—C4—H4	108.9	C4'—C5'—H5'	110.0
C5—C4—H4	108.9	C6'—C5'—H5'	110.0
O5—C5—C6	105.82 (17)	O6'—C6'—C1'	108.28 (19)
O5—C5—C4	106.60 (18)	O6'—C6'—C5'	115.42 (19)
C6—C5—C4	114.20 (18)	C1'—C6'—C5'	106.73 (17)
O5—C5—H5	110.0	O6'—C6'—H6'	108.7
C6—C5—H5	110.0	C1'—C6'—H6'	108.7
C4—C5—H5	110.0	C5'—C6'—H6'	108.7
O6—C6—C5	108.28 (16)	O1'—C7'—O3'	110.8 (2)
O6—C6—C1	111.65 (17)	O1'—C7'—O5'	111.65 (18)
C5—C6—C1	107.94 (17)	O3'—C7'—O5'	111.13 (19)
O6—C6—H6	109.6	O1'—C7'—H7'	107.7
C5—C6—H6	109.6	O3'—C7'—H7'	107.7
C1—C6—H6	109.6	O5'—C7'—H7'	107.7
O3—C7—O1	111.31 (19)	O7'—C8'—O2'	122.9 (2)
O3—C7—O5	111.39 (18)	O7'—C8'—C9'	125.2 (2)
O1—C7—O5	111.3 (2)	O2'—C8'—C9'	111.93 (18)
O3—C7—H7	107.5	C14'—C9'—C10'	119.7 (2)
O1—C7—H7	107.5	C14'—C9'—C8'	121.8 (2)
O5—C7—H7	107.5	C10'—C9'—C8'	118.5 (2)
O7—C8—O2	122.9 (2)	C11'—C10'—C9'	119.5 (2)
O7—C8—C9	125.5 (2)	C11'—C10'—H10'	120.2
O2—C8—C9	111.65 (19)	C9'—C10'—H10'	120.2
C14—C9—C10	119.7 (2)	C12'—C11'—C10'	120.7 (3)
C14—C9—C8	122.1 (2)	C12'—C11'—H11'	119.6
C10—C9—C8	118.2 (2)	C10'—C11'—H11'	119.6
C11—C10—C9	119.7 (3)	C11'—C12'—C13'	120.1 (3)
C11—C10—H10	120.2	C11'—C12'—H12'	119.9
C9—C10—H10	120.2	C13'—C12'—H12'	119.9
C12—C11—C10	120.3 (3)	C12'—C13'—C14'	119.8 (3)
C12—C11—H11	119.8	C12'—C13'—H13'	120.1
C10—C11—H11	119.8	C14'—C13'—H13'	120.1
C11—C12—C13	120.7 (3)	C9'—C14'—C13'	120.1 (2)
C11—C12—H12	119.7	C9'—C14'—H14'	120.0
C13—C12—H12	119.7	C13'—C14'—H14'	120.0
C14—C13—C12	119.0 (3)	O8'—C15'—O4'	124.0 (2)
C14—C13—H13	120.5	O8'—C15'—C16'	125.9 (2)
C12—C13—H13	120.5	O4'—C15'—C16'	110.14 (18)
C13—C14—C9	120.6 (2)	C21'—C16'—C17'	119.9 (2)
C13—C14—H14	119.7	C21'—C16'—C15'	118.5 (2)
C9—C14—H14	119.7	C17'—C16'—C15'	121.6 (2)
O8—C15—O6	123.8 (2)	C18'—C17'—C16'	119.8 (3)
O8—C15—C16	125.2 (2)	C18'—C17'—H17'	120.1
O6—C15—C16	110.99 (18)	C16'—C17'—H17'	120.1
C21—C16—C17	120.1 (2)	C17'—C18'—C19'	120.0 (3)
C21—C16—C15	118.0 (2)	C17'—C18'—H18'	120.0
C17—C16—C15	121.9 (2)	C19'—C18'—H18'	120.0
C18—C17—C16	119.3 (3)	C20'—C19'—C18'	120.6 (3)
C18—C17—H17	120.4	C20'—C19'—H19'	119.7
C16—C17—H17	120.4	C18'—C19'—H19'	119.7
C19—C18—C17	120.1 (3)	C19'—C20'—C21'	119.6 (3)
C19—C18—H18	119.9	C19'—C20'—H20'	120.2
C17—C18—H18	119.9	C21'—C20'—H20'	120.2
C20—C19—C18	120.2 (3)	C20'—C21'—C16'	120.1 (2)
C20—C19—H19	119.9	C20'—C21'—H21'	119.9
C18—C19—H19	119.9	C16'—C21'—H21'	119.9
C7—O1—C1—C2	−57.7 (2)	C7'—O1'—C1'—C6'	60.9 (2)
C7—O1—C1—C6	60.7 (2)	C7'—O1'—C1'—C2'	−59.0 (2)
C8—O2—C2—C3	108.0 (2)	C8'—O2'—C2'—C1'	−101.5 (2)
C8—O2—C2—C1	−133.68 (19)	C8'—O2'—C2'—C3'	140.49 (19)
O1—C1—C2—O2	−66.5 (2)	O1'—C1'—C2'—O2'	−65.0 (2)
C6—C1—C2—O2	176.32 (17)	C6'—C1'—C2'—O2'	176.20 (17)
O1—C1—C2—C3	52.5 (2)	O1'—C1'—C2'—C3'	52.9 (2)
C6—C1—C2—C3	−64.6 (2)	C6'—C1'—C2'—C3'	−65.8 (2)
C7—O3—C3—C2	58.1 (2)	C7'—O3'—C3'—C2'	57.7 (2)
C7—O3—C3—C4	−61.1 (2)	C7'—O3'—C3'—C4'	−60.5 (2)
O2—C2—C3—O3	65.9 (2)	O2'—C2'—C3'—O3'	66.5 (2)
C1—C2—C3—O3	−52.4 (2)	C1'—C2'—C3'—O3'	−52.6 (2)
O2—C2—C3—C4	−176.22 (17)	O2'—C2'—C3'—C4'	−176.30 (17)
C1—C2—C3—C4	65.4 (2)	C1'—C2'—C3'—C4'	64.6 (2)
O3—C3—C4—O4	−175.08 (16)	C15'—O4'—C4'—C5'	−160.43 (18)
C2—C3—C4—O4	65.4 (2)	C15'—O4'—C4'—C3'	81.5 (2)
O3—C3—C4—C5	60.3 (2)	O3'—C3'—C4'—O4'	178.06 (15)
C2—C3—C4—C5	−59.2 (2)	C2'—C3'—C4'—O4'	58.7 (2)
C7—O5—C5—C6	−61.0 (2)	O3'—C3'—C4'—C5'	60.2 (2)
C7—O5—C5—C4	60.9 (2)	C2'—C3'—C4'—C5'	−59.1 (2)
O4—C4—C5—O5	−179.87 (16)	C7'—O5'—C5'—C4'	61.2 (2)
C3—C4—C5—O5	−60.1 (2)	C7'—O5'—C5'—C6'	−60.6 (2)
O4—C4—C5—C6	−63.4 (2)	O4'—C4'—C5'—O5'	179.65 (17)
C3—C4—C5—C6	56.4 (2)	C3'—C4'—C5'—O5'	−60.0 (2)
C15—O6—C6—C5	163.04 (18)	O4'—C4'—C5'—C6'	−63.5 (2)
C15—O6—C6—C1	−78.3 (2)	C3'—C4'—C5'—C6'	56.9 (2)
O5—C5—C6—O6	−178.66 (16)	O1'—C1'—C6'—O6'	174.73 (16)
C4—C5—C6—O6	64.4 (2)	C2'—C1'—C6'—O6'	−65.4 (2)
O5—C5—C6—C1	60.3 (2)	O1'—C1'—C6'—C5'	−60.4 (2)
C4—C5—C6—C1	−56.6 (2)	C2'—C1'—C6'—C5'	59.5 (2)
O1—C1—C6—O6	−179.61 (15)	O5'—C5'—C6'—O6'	−179.71 (17)
C2—C1—C6—O6	−60.2 (2)	C4'—C5'—C6'—O6'	63.8 (2)
O1—C1—C6—C5	−60.7 (2)	O5'—C5'—C6'—C1'	59.9 (2)
C2—C1—C6—C5	58.7 (2)	C4'—C5'—C6'—C1'	−56.6 (3)
C3—O3—C7—O1	−63.2 (2)	C1'—O1'—C7'—O3'	63.6 (2)
C3—O3—C7—O5	61.7 (2)	C1'—O1'—C7'—O5'	−60.9 (2)
C1—O1—C7—O3	62.9 (2)	C3'—O3'—C7'—O1'	−62.8 (2)
C1—O1—C7—O5	−62.0 (2)	C3'—O3'—C7'—O5'	62.0 (2)
C5—O5—C7—O3	−62.2 (2)	C5'—O5'—C7'—O1'	61.6 (2)
C5—O5—C7—O1	62.7 (2)	C5'—O5'—C7'—O3'	−62.8 (2)
C2—O2—C8—O7	0.4 (3)	C2'—O2'—C8'—O7'	−3.9 (3)
C2—O2—C8—C9	−179.79 (17)	C2'—O2'—C8'—C9'	175.85 (17)
O7—C8—C9—C14	−179.2 (2)	O7'—C8'—C9'—C14'	167.2 (2)
O2—C8—C9—C14	1.0 (3)	O2'—C8'—C9'—C14'	−12.5 (3)
O7—C8—C9—C10	1.3 (3)	O7'—C8'—C9'—C10'	−11.8 (3)
O2—C8—C9—C10	−178.5 (2)	O2'—C8'—C9'—C10'	168.44 (19)
C14—C9—C10—C11	1.1 (4)	C14'—C9'—C10'—C11'	−0.7 (3)
C8—C9—C10—C11	−179.4 (2)	C8'—C9'—C10'—C11'	178.3 (2)
C9—C10—C11—C12	−0.8 (4)	C9'—C10'—C11'—C12'	−0.1 (4)
C10—C11—C12—C13	−0.3 (4)	C10'—C11'—C12'—C13'	0.4 (4)
C11—C12—C13—C14	1.0 (4)	C11'—C12'—C13'—C14'	0.1 (4)
C12—C13—C14—C9	−0.7 (4)	C10'—C9'—C14'—C13'	1.3 (4)
C10—C9—C14—C13	−0.3 (3)	C8'—C9'—C14'—C13'	−177.8 (2)
C8—C9—C14—C13	−179.8 (2)	C12'—C13'—C14'—C9'	−1.0 (4)
C6—O6—C15—O8	−1.4 (3)	C4'—O4'—C15'—O8'	−0.4 (3)
C6—O6—C15—C16	178.17 (17)	C4'—O4'—C15'—C16'	179.80 (17)
O8—C15—C16—C21	−19.7 (3)	O8'—C15'—C16'—C21'	15.7 (3)
O6—C15—C16—C21	160.8 (2)	O4'—C15'—C16'—C21'	−164.54 (19)
O8—C15—C16—C17	161.9 (2)	O8'—C15'—C16'—C17'	−165.9 (2)
O6—C15—C16—C17	−17.7 (3)	O4'—C15'—C16'—C17'	13.9 (3)
C21—C16—C17—C18	0.8 (4)	C21'—C16'—C17'—C18'	0.5 (4)
C15—C16—C17—C18	179.3 (2)	C15'—C16'—C17'—C18'	−178.0 (2)
C16—C17—C18—C19	−1.3 (4)	C16'—C17'—C18'—C19'	0.6 (5)
C17—C18—C19—C20	0.2 (4)	C17'—C18'—C19'—C20'	−1.1 (5)
C18—C19—C20—C21	1.5 (5)	C18'—C19'—C20'—C21'	0.5 (5)
C19—C20—C21—C16	−2.0 (4)	C19'—C20'—C21'—C16'	0.6 (4)
C17—C16—C21—C20	0.9 (4)	C17'—C16'—C21'—C20'	−1.1 (4)
C15—C16—C21—C20	−177.7 (2)	C15'—C16'—C21'—C20'	177.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O7^i	0.82	2.06	2.871 (2)	171
O6′—H6′A···O7′^ii	0.82	2.04	2.852 (2)	170
C21—H21···O2′^iii	0.93	2.66	3.528 (3)	156
C21′—H21′···O2^iv	0.93	2.61	3.490 (3)	158

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

(1.BP) Racemic 2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-orthoformate–4,4'-bipyridine (1/1)

Crystal data

C21H18O8·C10H8N2	Z = 2
Mr = 554.54	F(000) = 580
Triclinic, P1	Dx = 1.418 Mg m^−3
Hall symbol: -1 P1	Mo Kα radiation, λ = 0.71073 Å
a = 10.7434 (3) Å	Cell parameters from 7512 reflections
b = 11.4077 (4) Å	θ = 2.4–28.3°
c = 11.7341 (4) Å	µ = 0.10 mm^−1
α = 82.246 (2)°	T = 100 K
β = 65.849 (2)°	Plate-like, colourless
γ = 89.549 (2)°	0.44 × 0.31 × 0.20 mm
V = 1298.44 (7) Å^3

Data collection

Bruker APEXII CCD area-detector diffractometer	4576 independent reflections
Radiation source: fine-focus sealed tube	3805 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
ϕ and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −12→12
Tmin = 0.956, Tmax = 0.980	k = −13→13
19394 measured reflections	l = −13→13

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.124	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0567P)^2 + 1.0414P] where P = (Fo^2 + 2Fc^2)/3
4576 reflections	(Δ/σ)max < 0.001
389 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

Special details

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	0.71927 (14)	0.50740 (11)	0.40497 (12)	0.0298 (3)
O2	0.97057 (14)	0.39474 (11)	0.30145 (11)	0.0268 (3)
O3	0.85038 (15)	0.49945 (11)	0.52086 (12)	0.0295 (3)
O4	0.75723 (16)	0.18966 (11)	0.64892 (12)	0.0369 (4)
O5	0.61436 (15)	0.48218 (11)	0.62435 (12)	0.0344 (4)
O6	0.59348 (16)	0.20033 (12)	0.50863 (13)	0.0397 (4)
H6A	0.5230	0.1669	0.5680	0.059*
O7	0.95080 (16)	0.27038 (13)	0.17523 (13)	0.0403 (4)
O8	0.61021 (15)	0.16521 (11)	0.85401 (12)	0.0326 (3)
N1	1.0817 (2)	0.21365 (16)	−0.32537 (18)	0.0505 (6)
N2	0.6214 (2)	−0.07757 (16)	0.27810 (18)	0.0481 (5)
C1	0.7217 (2)	0.38124 (16)	0.40181 (18)	0.0289 (4)
H1	0.7170	0.3641	0.3222	0.035*
C2	0.8524 (2)	0.33694 (16)	0.40749 (17)	0.0271 (4)
H2	0.8542	0.2490	0.4102	0.033*
C3	0.8628 (2)	0.37274 (16)	0.52387 (17)	0.0288 (4)
H3	0.9516	0.3496	0.5267	0.035*
C4	0.7429 (2)	0.31538 (16)	0.64317 (18)	0.0326 (5)
H4	0.7477	0.3422	0.7190	0.039*
C5	0.6109 (2)	0.35360 (16)	0.63387 (18)	0.0338 (5)
H5	0.5307	0.3183	0.7117	0.041*
C6	0.5964 (2)	0.32273 (17)	0.51624 (18)	0.0331 (5)
H6	0.5118	0.3569	0.5128	0.040*
C7	0.7272 (2)	0.53372 (17)	0.51543 (17)	0.0301 (5)
H7	0.7247	0.6216	0.5132	0.036*
C8	1.0091 (2)	0.35244 (16)	0.19072 (17)	0.0272 (4)
C9	1.13309 (19)	0.41934 (15)	0.09220 (16)	0.0229 (4)
C10	1.1735 (2)	0.40215 (17)	−0.03280 (17)	0.0284 (4)
H10	1.1202	0.3505	−0.0543	0.034*
C11	1.2911 (2)	0.46006 (17)	−0.12604 (18)	0.0298 (4)
H11	1.3184	0.4479	−0.2113	0.036*
C12	1.3684 (2)	0.53529 (17)	−0.09525 (19)	0.0315 (5)
H12	1.4494	0.5745	−0.1592	0.038*
C13	1.3283 (2)	0.55376 (18)	0.0285 (2)	0.0344 (5)
H13	1.3812	0.6065	0.0493	0.041*
C14	1.2113 (2)	0.49580 (17)	0.12243 (18)	0.0275 (4)
H14	1.1844	0.5083	0.2075	0.033*
C15	0.6796 (2)	0.12299 (17)	0.76066 (18)	0.0315 (5)
C16	0.6896 (3)	−0.00561 (17)	0.75060 (19)	0.0378 (5)
C17	0.6303 (2)	−0.08645 (17)	0.85805 (18)	0.0291 (4)
H17	0.5855	−0.0598	0.9376	0.035*
C18	0.6354 (2)	−0.20658 (18)	0.8509 (2)	0.0354 (5)
H18	0.5956	−0.2620	0.9258	0.042*
C19	0.6972 (3)	−0.24587 (19)	0.7370 (2)	0.0506 (7)
H19	0.6798	−0.3255	0.7300	0.061*
C20	0.7858 (11)	−0.1706 (10)	0.6301 (11)	0.055 (3)	0.50
H20	0.8440	−0.2011	0.5559	0.065*	0.50
C21	0.7855 (8)	−0.0498 (8)	0.6364 (8)	0.047 (2)	0.50
H21	0.8470	0.0038	0.5672	0.057*	0.50
C20'	0.7226 (10)	−0.1597 (9)	0.6278 (10)	0.060 (3)	0.50
H20'	0.7419	−0.1856	0.5489	0.072*	0.50
C21'	0.7195 (8)	−0.0395 (7)	0.6351 (7)	0.047 (2)	0.50
H21'	0.7375	0.0174	0.5625	0.057*	0.50
C22	1.0118 (2)	0.27367 (17)	−0.23144 (19)	0.0320 (5)
H22	1.0245	0.3576	−0.2469	0.038*
C23	0.9218 (2)	0.22186 (17)	−0.11288 (19)	0.0291 (4)
H23	0.8757	0.2699	−0.0496	0.035*
C24	0.8986 (2)	0.09926 (17)	−0.08591 (18)	0.0289 (4)
C25	0.8025 (2)	0.03906 (17)	0.04012 (18)	0.0283 (4)
C26	0.7264 (2)	0.10034 (18)	0.1389 (2)	0.0357 (5)
H26	0.7346	0.1844	0.1269	0.043*
C27	0.6389 (2)	0.03968 (18)	0.2547 (2)	0.0375 (5)
H27	0.5889	0.0841	0.3204	0.045*
C28	0.6970 (3)	−0.1365 (2)	0.1841 (2)	0.0574 (8)
H28	0.6889	−0.2206	0.1998	0.069*
C29	0.7859 (2)	−0.08374 (19)	0.0659 (2)	0.0433 (6)
H29	0.8355	−0.1308	0.0026	0.052*
C30	0.9715 (3)	0.0364 (2)	−0.1835 (2)	0.0493 (6)
H30	0.9609	−0.0476	−0.1713	0.059*
C31	1.0594 (3)	0.0962 (2)	−0.2981 (2)	0.0678 (9)
H31	1.1080	0.0504	−0.3630	0.081*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0411 (8)	0.0210 (7)	0.0217 (7)	−0.0067 (6)	−0.0075 (6)	−0.0014 (5)
O2	0.0353 (8)	0.0208 (6)	0.0148 (6)	−0.0073 (6)	−0.0003 (6)	−0.0033 (5)
O3	0.0431 (9)	0.0183 (6)	0.0211 (7)	−0.0082 (6)	−0.0071 (6)	−0.0027 (5)
O4	0.0624 (10)	0.0170 (7)	0.0172 (7)	−0.0065 (6)	−0.0028 (7)	−0.0008 (5)
O5	0.0465 (9)	0.0186 (7)	0.0231 (7)	−0.0060 (6)	0.0015 (6)	−0.0046 (5)
O6	0.0479 (10)	0.0248 (7)	0.0279 (8)	−0.0166 (7)	0.0038 (7)	−0.0057 (6)
O7	0.0479 (9)	0.0360 (8)	0.0267 (8)	−0.0180 (7)	−0.0023 (7)	−0.0116 (6)
O8	0.0460 (9)	0.0247 (7)	0.0184 (7)	−0.0049 (6)	−0.0049 (6)	−0.0015 (6)
N1	0.0676 (14)	0.0289 (10)	0.0330 (11)	0.0011 (9)	0.0002 (10)	−0.0007 (8)
N2	0.0531 (13)	0.0333 (10)	0.0365 (11)	−0.0161 (9)	0.0042 (9)	−0.0079 (8)
C1	0.0392 (12)	0.0208 (9)	0.0200 (9)	−0.0096 (8)	−0.0050 (9)	−0.0036 (7)
C2	0.0370 (11)	0.0176 (9)	0.0162 (9)	−0.0095 (8)	−0.0008 (8)	−0.0003 (7)
C3	0.0438 (12)	0.0165 (9)	0.0191 (9)	−0.0053 (8)	−0.0059 (9)	−0.0021 (7)
C4	0.0540 (14)	0.0175 (9)	0.0170 (9)	−0.0071 (9)	−0.0047 (9)	−0.0034 (7)
C5	0.0451 (13)	0.0182 (9)	0.0212 (10)	−0.0094 (9)	0.0034 (9)	−0.0027 (8)
C6	0.0382 (12)	0.0238 (10)	0.0258 (10)	−0.0097 (9)	−0.0008 (9)	−0.0055 (8)
C7	0.0408 (12)	0.0206 (9)	0.0203 (10)	−0.0063 (9)	−0.0038 (9)	−0.0024 (8)
C8	0.0363 (11)	0.0219 (9)	0.0174 (9)	−0.0015 (8)	−0.0045 (8)	−0.0049 (7)
C9	0.0280 (10)	0.0178 (8)	0.0188 (9)	0.0026 (7)	−0.0055 (8)	−0.0030 (7)
C10	0.0350 (11)	0.0265 (10)	0.0216 (10)	−0.0025 (8)	−0.0093 (9)	−0.0041 (8)
C11	0.0364 (11)	0.0297 (10)	0.0163 (9)	0.0030 (9)	−0.0048 (8)	−0.0002 (8)
C12	0.0268 (11)	0.0270 (10)	0.0272 (10)	0.0012 (8)	0.0019 (8)	−0.0020 (8)
C13	0.0262 (11)	0.0360 (11)	0.0345 (11)	−0.0037 (9)	−0.0030 (9)	−0.0145 (9)
C14	0.0282 (10)	0.0285 (10)	0.0218 (10)	0.0029 (8)	−0.0043 (8)	−0.0102 (8)
C15	0.0486 (13)	0.0237 (10)	0.0165 (9)	−0.0082 (9)	−0.0087 (9)	0.0011 (8)
C16	0.0637 (15)	0.0224 (10)	0.0207 (10)	−0.0058 (10)	−0.0109 (10)	−0.0018 (8)
C17	0.0336 (11)	0.0263 (10)	0.0228 (10)	0.0004 (8)	−0.0078 (9)	−0.0001 (8)
C18	0.0448 (13)	0.0243 (10)	0.0286 (11)	−0.0016 (9)	−0.0093 (10)	0.0055 (8)
C19	0.087 (2)	0.0220 (10)	0.0334 (13)	−0.0087 (11)	−0.0168 (13)	−0.0003 (9)
C20	0.098 (8)	0.025 (3)	0.031 (3)	0.013 (5)	−0.015 (5)	−0.009 (2)
C21	0.073 (5)	0.030 (3)	0.022 (3)	0.012 (4)	−0.004 (4)	0.001 (2)
C20'	0.111 (8)	0.022 (3)	0.023 (3)	−0.005 (5)	−0.003 (5)	−0.002 (2)
C21'	0.087 (6)	0.017 (3)	0.020 (3)	−0.003 (4)	−0.004 (4)	0.0004 (19)
C22	0.0344 (11)	0.0234 (10)	0.0319 (11)	0.0012 (9)	−0.0082 (9)	−0.0017 (8)
C23	0.0279 (11)	0.0260 (10)	0.0319 (11)	0.0010 (8)	−0.0105 (9)	−0.0048 (8)
C24	0.0265 (10)	0.0284 (10)	0.0296 (11)	0.0005 (8)	−0.0098 (9)	−0.0028 (8)
C25	0.0249 (10)	0.0286 (10)	0.0295 (10)	−0.0049 (8)	−0.0093 (9)	−0.0037 (8)
C26	0.0355 (12)	0.0257 (10)	0.0353 (12)	−0.0032 (9)	−0.0040 (10)	−0.0043 (9)
C27	0.0381 (12)	0.0293 (11)	0.0332 (11)	−0.0066 (9)	−0.0012 (10)	−0.0088 (9)
C28	0.0722 (19)	0.0278 (12)	0.0430 (14)	−0.0185 (12)	0.0069 (13)	−0.0081 (10)
C29	0.0484 (14)	0.0298 (11)	0.0353 (12)	−0.0122 (10)	0.0010 (10)	−0.0095 (9)
C30	0.0625 (16)	0.0252 (11)	0.0361 (13)	−0.0006 (11)	0.0044 (11)	−0.0052 (9)
C31	0.097 (2)	0.0308 (13)	0.0343 (14)	0.0039 (13)	0.0149 (14)	−0.0057 (10)

Geometric parameters (Å, º)

O1—C7	1.405 (2)	C12—H12	0.9500
O1—C1	1.444 (2)	C13—C14	1.384 (3)
O2—C8	1.348 (2)	C13—H13	0.9500
O2—C2	1.447 (2)	C14—H14	0.9500
O3—C7	1.401 (3)	C15—C16	1.487 (3)
O3—C3	1.448 (2)	C16—C21'	1.368 (8)
O4—C15	1.356 (2)	C16—C17	1.373 (3)
O4—C4	1.437 (2)	C16—C21	1.469 (8)
O5—C7	1.411 (2)	C17—C18	1.384 (3)
O5—C5	1.455 (2)	C17—H17	0.9500
O6—C6	1.413 (2)	C18—C19	1.363 (3)
O6—H6A	0.8400	C18—H18	0.9500
O7—C8	1.204 (2)	C19—C20	1.400 (12)
O8—C15	1.207 (2)	C19—C20'	1.436 (10)
N1—C22	1.329 (3)	C19—H19	0.9500
N1—C31	1.335 (3)	C20—C21	1.390 (15)
N2—C27	1.328 (3)	C20—H20	0.9500
N2—C28	1.337 (3)	C21—H21	0.9500
C1—C2	1.513 (3)	C20'—C21'	1.384 (13)
C1—C6	1.534 (3)	C20'—H20'	0.9500
C1—H1	1.0000	C21'—H21'	0.9500
C2—C3	1.523 (3)	C22—C23	1.380 (3)
C2—H2	1.0000	C22—H22	0.9500
C3—C4	1.529 (3)	C23—C24	1.393 (3)
C3—H3	1.0000	C23—H23	0.9500
C4—C5	1.522 (3)	C24—C30	1.385 (3)
C4—H4	1.0000	C24—C25	1.488 (3)
C5—C6	1.537 (3)	C25—C29	1.390 (3)
C5—H5	1.0000	C25—C26	1.391 (3)
C6—H6	1.0000	C26—C27	1.386 (3)
C7—H7	1.0000	C26—H26	0.9500
C8—C9	1.487 (3)	C27—H27	0.9500
C9—C14	1.390 (3)	C28—C29	1.378 (3)
C9—C10	1.391 (3)	C28—H28	0.9500
C10—C11	1.384 (3)	C29—H29	0.9500
C10—H10	0.9500	C30—C31	1.375 (3)
C11—C12	1.378 (3)	C30—H30	0.9500
C11—H11	0.9500	C31—H31	0.9500
C12—C13	1.382 (3)
C7—O1—C1	110.77 (14)	C14—C13—H13	119.9
C8—O2—C2	117.51 (14)	C13—C14—C9	119.97 (18)
C7—O3—C3	111.31 (14)	C13—C14—H14	120.0
C15—O4—C4	116.13 (15)	C9—C14—H14	120.0
C7—O5—C5	110.77 (14)	O8—C15—O4	123.03 (17)
C6—O6—H6A	109.5	O8—C15—C16	125.71 (17)
C22—N1—C31	115.18 (19)	O4—C15—C16	111.25 (16)
C27—N2—C28	116.31 (19)	C21'—C16—C17	119.8 (4)
O1—C1—C2	109.06 (15)	C21'—C16—C21	29.3 (4)
O1—C1—C6	107.57 (15)	C17—C16—C21	117.3 (4)
C2—C1—C6	110.89 (16)	C21'—C16—C15	118.1 (3)
O1—C1—H1	109.8	C17—C16—C15	119.12 (18)
C2—C1—H1	109.8	C21—C16—C15	122.1 (4)
C6—C1—H1	109.8	C16—C17—C18	120.24 (19)
O2—C2—C1	110.85 (15)	C16—C17—H17	119.9
O2—C2—C3	105.22 (15)	C18—C17—H17	119.9
C1—C2—C3	108.83 (16)	C19—C18—C17	120.43 (19)
O2—C2—H2	110.6	C19—C18—H18	119.8
C1—C2—H2	110.6	C17—C18—H18	119.8
C3—C2—H2	110.6	C18—C19—C20	121.0 (5)
O3—C3—C2	108.96 (15)	C18—C19—C20'	116.1 (4)
O3—C3—C4	106.24 (15)	C20—C19—C20'	28.6 (5)
C2—C3—C4	110.00 (16)	C18—C19—H19	119.5
O3—C3—H3	110.5	C20—C19—H19	119.5
C2—C3—H3	110.5	C20'—C19—H19	116.5
C4—C3—H3	110.5	C21—C20—C19	117.7 (8)
O4—C4—C5	113.04 (16)	C21—C20—H20	121.2
O4—C4—C3	106.49 (15)	C19—C20—H20	121.2
C5—C4—C3	108.26 (16)	C20—C21—C16	119.5 (8)
O4—C4—H4	109.7	C20—C21—H21	120.2
C5—C4—H4	109.7	C16—C21—H21	120.2
C3—C4—H4	109.7	C21'—C20'—C19	121.3 (8)
O5—C5—C4	106.19 (16)	C21'—C20'—H20'	119.4
O5—C5—C6	106.94 (16)	C19—C20'—H20'	119.4
C4—C5—C6	114.04 (17)	C16—C21'—C20'	117.7 (7)
O5—C5—H5	109.8	C16—C21'—H21'	121.2
C4—C5—H5	109.8	C20'—C21'—H21'	121.2
C6—C5—H5	109.8	N1—C22—C23	124.16 (18)
O6—C6—C1	107.64 (15)	N1—C22—H22	117.9
O6—C6—C5	114.78 (17)	C23—C22—H22	117.9
C1—C6—C5	106.51 (16)	C22—C23—C24	120.12 (19)
O6—C6—H6	109.3	C22—C23—H23	119.9
C1—C6—H6	109.3	C24—C23—H23	119.9
C5—C6—H6	109.3	C30—C24—C23	115.88 (19)
O3—C7—O1	111.44 (15)	C30—C24—C25	121.86 (18)
O3—C7—O5	110.98 (15)	C23—C24—C25	122.26 (18)
O1—C7—O5	111.43 (16)	C29—C25—C26	116.13 (18)
O3—C7—H7	107.6	C29—C25—C24	120.94 (18)
O1—C7—H7	107.6	C26—C25—C24	122.92 (18)
O5—C7—H7	107.6	C27—C26—C25	120.51 (19)
O7—C8—O2	123.92 (17)	C27—C26—H26	119.7
O7—C8—C9	125.02 (17)	C25—C26—H26	119.7
O2—C8—C9	111.05 (15)	N2—C27—C26	123.1 (2)
C14—C9—C10	119.40 (17)	N2—C27—H27	118.4
C14—C9—C8	121.67 (16)	C26—C27—H27	118.4
C10—C9—C8	118.90 (17)	N2—C28—C29	124.5 (2)
C11—C10—C9	120.23 (18)	N2—C28—H28	117.7
C11—C10—H10	119.9	C29—C28—H28	117.7
C9—C10—H10	119.9	C28—C29—C25	119.4 (2)
C12—C11—C10	120.03 (18)	C28—C29—H29	120.3
C12—C11—H11	120.0	C25—C29—H29	120.3
C10—C11—H11	120.0	C31—C30—C24	119.6 (2)
C11—C12—C13	120.10 (18)	C31—C30—H30	120.2
C11—C12—H12	120.0	C24—C30—H30	120.2
C13—C12—H12	120.0	N1—C31—C30	125.1 (2)
C12—C13—C14	120.27 (19)	N1—C31—H31	117.5
C12—C13—H13	119.9	C30—C31—H31	117.5
C7—O1—C1—C2	−59.07 (19)	C11—C12—C13—C14	0.8 (3)
C7—O1—C1—C6	61.3 (2)	C12—C13—C14—C9	−0.5 (3)
C8—O2—C2—C1	−81.33 (19)	C10—C9—C14—C13	−0.2 (3)
C8—O2—C2—C3	161.18 (16)	C8—C9—C14—C13	178.05 (18)
O1—C1—C2—O2	−60.05 (18)	C4—O4—C15—O8	−5.8 (3)
C6—C1—C2—O2	−178.33 (14)	C4—O4—C15—C16	172.77 (18)
O1—C1—C2—C3	55.21 (18)	O8—C15—C16—C21'	151.6 (4)
C6—C1—C2—C3	−63.07 (19)	O4—C15—C16—C21'	−26.9 (5)
C7—O3—C3—C2	57.71 (19)	O8—C15—C16—C17	−8.9 (4)
C7—O3—C3—C4	−60.76 (19)	O4—C15—C16—C17	172.6 (2)
O2—C2—C3—O3	64.46 (19)	O8—C15—C16—C21	−174.7 (4)
C1—C2—C3—O3	−54.39 (19)	O4—C15—C16—C21	6.7 (5)
O2—C2—C3—C4	−179.45 (15)	C21'—C16—C17—C18	18.3 (5)
C1—C2—C3—C4	61.70 (19)	C21—C16—C17—C18	−15.0 (5)
C15—O4—C4—C5	−75.3 (2)	C15—C16—C17—C18	178.5 (2)
C15—O4—C4—C3	165.99 (17)	C16—C17—C18—C19	−1.2 (3)
O3—C3—C4—O4	−178.10 (15)	C17—C18—C19—C20	16.5 (6)
C2—C3—C4—O4	64.1 (2)	C17—C18—C19—C20'	−15.6 (6)
O3—C3—C4—C5	60.05 (19)	C18—C19—C20—C21	−14.0 (9)
C2—C3—C4—C5	−57.7 (2)	C20'—C19—C20—C21	74.2 (16)
C7—O5—C5—C4	61.01 (19)	C19—C20—C21—C16	−2.8 (11)
C7—O5—C5—C6	−61.1 (2)	C21'—C16—C21—C20	−86.0 (15)
O4—C4—C5—O5	−178.00 (14)	C17—C16—C21—C20	17.0 (9)
C3—C4—C5—O5	−60.27 (18)	C15—C16—C21—C20	−176.9 (6)
O4—C4—C5—C6	−60.5 (2)	C18—C19—C20'—C21'	16.9 (11)
C3—C4—C5—C6	57.2 (2)	C20—C19—C20'—C21'	−91 (2)
O1—C1—C6—O6	176.08 (16)	C17—C16—C21'—C20'	−16.8 (9)
C2—C1—C6—O6	−64.7 (2)	C21—C16—C21'—C20'	76.5 (13)
O1—C1—C6—C5	−60.3 (2)	C15—C16—C21'—C20'	−177.2 (6)
C2—C1—C6—C5	58.8 (2)	C19—C20'—C21'—C16	−0.8 (12)
O5—C5—C6—O6	179.07 (16)	C31—N1—C22—C23	0.1 (4)
C4—C5—C6—O6	62.0 (2)	N1—C22—C23—C24	−0.6 (3)
O5—C5—C6—C1	60.1 (2)	C22—C23—C24—C30	0.7 (3)
C4—C5—C6—C1	−57.0 (2)	C22—C23—C24—C25	−179.82 (18)
C3—O3—C7—O1	−62.04 (18)	C30—C24—C25—C29	2.3 (3)
C3—O3—C7—O5	62.78 (18)	C23—C24—C25—C29	−177.2 (2)
C1—O1—C7—O3	62.55 (19)	C30—C24—C25—C26	−178.9 (2)
C1—O1—C7—O5	−62.0 (2)	C23—C24—C25—C26	1.7 (3)
C5—O5—C7—O3	−62.7 (2)	C29—C25—C26—C27	−0.8 (3)
C5—O5—C7—O1	62.1 (2)	C24—C25—C26—C27	−179.65 (19)
C2—O2—C8—O7	0.4 (3)	C28—N2—C27—C26	2.0 (4)
C2—O2—C8—C9	−178.88 (15)	C25—C26—C27—N2	−0.5 (4)
O7—C8—C9—C14	−166.3 (2)	C27—N2—C28—C29	−2.4 (4)
O2—C8—C9—C14	13.0 (3)	N2—C28—C29—C25	1.2 (4)
O7—C8—C9—C10	11.9 (3)	C26—C25—C29—C28	0.4 (3)
O2—C8—C9—C10	−168.83 (16)	C24—C25—C29—C28	179.4 (2)
C14—C9—C10—C11	0.5 (3)	C23—C24—C30—C31	−0.3 (4)
C8—C9—C10—C11	−177.77 (17)	C25—C24—C30—C31	−179.8 (2)
C9—C10—C11—C12	−0.2 (3)	C22—N1—C31—C30	0.3 (5)
C10—C11—C12—C13	−0.5 (3)	C24—C30—C31—N1	−0.1 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6A···N2^i	0.84	1.99	2.816 (2)	170
C20—H20···N1^ii	0.95	2.51	3.369 (11)	150
C20′—H20′···N1^ii	0.95	2.59	3.443 (10)	149

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