Chiral crystals from an achiral mol­ecule: 4,6-di-O-benzyl-1,3-O-benzyl­idene-2-O-(4-meth­oxy­benzyl)-myo-5-inosose

The title achiral compound, C₃₅H₃₄O₇, crystallizes in the chiral monoclinic space group P2₁. The mol­ecules are densely packed to form a helical assembly along the crystallographic twofold screw axis via C-H...O and C-H...[pi] inter­actions. Inter­estingly, the unit-translated helical chains are loosely connected via a rather un­common edge-to-edge Ph-H...H-Ph short contact (H...H = 2.33 Å).

S1. Comment

Among the various noncovalent interactions (Desiraju, 1989) which govern the molecular arrangement in crystals, those involving the less acidic C—H group, e.g. C—H···O, C—H···π, C—H···N, C—H···X (X = F, Cl, Br), have been scrutinized intensely over the past 20–30 years (Desiraju & Steiner, 1999; Hobza & Havlas, 2000; Scheiner, 2005). Their role in molecular recognition, crystal packing and polymorphic modifications is well established in either the presence (Gonnade et al., 2008; Krishnaswamy et al., 2009) or absence (Gonnade et al., 2010) of relatively strong conventional hydrogen-bonding interactions. O-Protected myo-inositol derivatives (Sureshan et al., 2003) are important intermediates for the preparation of biologically relevant phosphoinositols. These molecules, which lack functional groups capable of forming conventional hydrogen bonds, provide opportunities to study the role of weaker noncovalent interactions of similar energies in molecular aggregation. Encouraged by the frequent polymorphic (Gonnade et al., 2004, 2005, 2008, 2010; Bhosekar et al., 2005; Manoj et al., 2009) and solvatomorphic (Sureshan et al., 2001; Gonnade et al., 2004; Manoj et al., 2006, 2012; Krishnaswamy et al., 2010) behaviour exhibited by myo-inositol derivatives; the title compound, (I), was also screened for the same property. We reported previously the role of C—H···O interactions in directing the molecular aggregation of a meso molecule, leading to the formation of chiral crystals under kinetic crystallization conditions (Gonnade et al., 2004). We report here another such occurrence, where crystallization of the meso-ketone (I) under a variety of conditions and solvents yielded chiral crystals belonging to the monoclinic space group P2₁ with one molecule in the asymmetric unit. Molecules of (I) form a helical chain along the b axis, linked via C—H···O and C—H···π interactions comprising polar groups clustering along the helical axis, whereas the nonpolar groups protrude perpendicular to the helical axis. Surprisingly, these neighbouring chains are loosely held along the c axis via relatively uncommon C—H···H—C short contacts (Bhosekar et al., 2005).

The conformation of the molecule of (I) as observed in the crystal structure reveals a slight deviation of the inositol ring from a chair conformation, perhaps due to the presence of a planar carbonyl group at the C5 position. However, the C1–C3/O3/C7/O1 acetal ring adopts a regular chair conformation (Fig. 1). All the benzyl groups adopt an extended conformation, pointing in the same direction but away from the fourth phenyl ring. This results in sandwiching of the hydrophilic inositol ring between hydrophobic benzene rings and facilitates the formation of a short intramolecular C2—H2···O6 hydrogen bond [H2···O6 = 2.43 Å, C2···O6 = 2.835 (7) Å and C2—H2···O6 = 104°].

Molecules of (I) form a helical assembly across the crystallographic twofold screw axis via one C—H···π and two C—H···O interactions exclusively involving the 4-methoxybenzyl (PMB) group (Fig. 2). Methylene atom C8 and phenyl atom C14 of the PMB group are involved in C—H···O contacts with atoms O1 and O3, respectively (Table 1). The latter contact is shorter than the former, whereas the angles of approach in both cases are similar. This arrangement also brings the phenyl C10—H10 group of the PMB closer to the edge atoms C31, C32 and C33 of the acetal phenyl ring, rather than pointing towards the centre of the π-cloud, generating an off-centred C—H···π contact [C10—H10···.Cg2ⁱ; Cg2 is the centroid of the C30–C35 ring [Please check added text]; Table 1; symmetry code: (ii) -x + 2, y + 1/2, -z + 2]. This helical arrangement brings polar segments of neighbouring molecules into close association, creating a hydrophilic layer between the hydrophobic layers formed by the phenyl rings (see Supplementary materials for a space-filling model).

Neighbouring helices diagonal to the ac plane are held together via another relatively long but linear C—H···O contact involving carbonyl atom O5 and the methylene C16 group of the benzyl group [C16—H16A···O5ⁱⁱⁱ; Table 1; symmetry code: (iii) -x + 1, y + 1/2, -z + 2], thus generating a discrete packing of the helices throughout the crystal structure (Fig. 3). Viewed down the c axis, the molecular packing reveals the association of neighbouring unit-translated helices via hydrophobic forces; a somewhat uncommon edge-to-edge C—H···H—C contact [C33—H33···H26—C26^iv, with H···H = 2.31 Å, C33···H26 = 3.254 Å and C16—H16A···O5 = 171° [not in this contact]; symmetry code: (iv) x + 1, y, z + 1] joins adjacent helical chains (Fig. 4). Therefore, the cohesion of two-dimensional layers in the bc plane seems to be only via short H···H contacts (although just at the boundary of the sum of the van der Waals radii of two H atoms, 2.35 Å; [Standard reference?]), termed `dihydrogen bonds' or `dihydrogen interactions' (Echeverría et al., 2011; Crabtree et al., 1996; Crabtree, 1998; Custelcean & Jackson, 2001; Wang et al., 2004). It is noteworthy that there are no significant aromatic π–π or C—H···π contacts between phenyl rings of adjacent helical chains, although they are clustered together.

The computation of lattice energies (using the Oprop module of the OPIX program suite; Gavezzotti, 2007) by summation of atom–atom pair-wise potential energies described by the UNI force field (Filippini & Gavezzotti, 1993; Gavezzotti & Filippini, 1994) gave a value of -263.1 kJ mol^-1. The intermolecular interaction energies for C10—H10···O1 and H···H contacts were also estimated, giving values of -17.4 and 6.0 kJ mol^-1, respectively, suggesting that the former contact is attractive and the latter repulsive. However, an estimation of the intermolecular potentials [the sum of Coulombic, polarization, dispersion and repulsion terms, as defined in the PIXEL method and implemented in the program Mercury (Macrae et al., 2008)], gives the overall contribution from all the intermolecular forces (including van der Waals interactions) at the interface of the two helical chains (linked by H···H contact) in the bc plane enveloped by hydrophobic groups of -3.8 kJ mol^-1. This suggests that, although the H···H contact is repulsive, the other forces contribute to this bridging and thence to the overall stability of the structure. The energies of the other weak interactions such as C—H···π could not be computed separately. However, using UNI force-field calculations, approximate energies for the intermolecular potentials were estimated. The intermolecular potential associated with two neighbouring molecules involved in helical chain formation is -85.1 kJ mol^-1, with major contributions from C—H···O (C14—H14···O3 and C6—H8B···O1) and C—H···π (C10—H10···π) interactions and other van der Waals forces.

The intermolecular contacts in the crystal structure of (I) were quantified via Hirshfeld surface analysis (McKinnon et al., 2004; Spackman & McKinnon, 2002) using CrystalExplorer (Wolff et al.., 2007). Hirshfeld surfaces are a novel tool for the visualization and understanding of intermolecular interactions (McKinnon et al., 2007; Munshi et al., 2008; Hathwar et al., 2010). In the present study, the contacts responsible for the chiral crystal packing in (I) [C—H···O, C—H···π, H···H and others (O···O, C···C)] were evaluated with respect to their contribution to the overall stability of the crystal structure. The percentage contributions of these interactions to the relative Hirshfeld surface areas reveal noticeable involvement of C—H···π (24.8%) and C—H···O (17.7%), whereas a significant contribution comes from H···H contacts (56%), because of the considerable engagement of the hydrophobic groups in the molecular aggregation (see Supplementary materials for figures). However, it must be noted that these percentage contributions do not differentiate between close and distant contacts. The major C—H···O, C—H···π and H···H contacts are highlighted by conventional mapping of d_norm on molecular Hirshfeld surfaces (Fig. 5). The dark spots (red in the electronic version of the paper) on the left and right surfaces of the plot are due to C—H···O and C—H···π interactions, while that on the top is from an H···H contact.

In conclusion, the spontaneous generation of chirality of an achiral molecule solely by topology of weak interactions, as observed in the present case, is an enigmatic phenomenon which continues to fascinate crystal engineers and supramolecular chemists. Deeper insight into this phenomenon, especially in crystals formed from complex molecules, could be of value in designing unconventional methods for asymmetric synthesis.

Related literature

For related literature, see: Bhosekar et al. (2005); Crabtree (1998); Crabtree et al. (1996); Custelcean & Jackson (2001); Desiraju (1989); Desiraju & Steiner (1999); Echeverría et al. (2011); Filippini & Gavezzotti (1993); Gavezzotti (2007); Gavezzotti & Filippini (1994); Gonnade et al. (2004, 2005, 2008, 2010); Gurale et al. (2011); Hathwar et al. (2010); Hobza & Havlas (2000); Krishnaswamy et al. (2009, 2010); Macrae et al. (2008); Manoj et al. (2006, 2009, 2012); McKinnon et al. (2004, 2007); Munshi et al. (2008); Scheiner (2005); Spackman & McKinnon (2002); Sureshan et al. (2001, 2003); Wang et al. (2004); Wolff et al. (2007).

S2. Experimental

To a solution of 4,6-di-O-benzyl-1,3-O-benzylidene-2-O-(4-methoxybenzyl)-myo-inositol (Gurale et al., 2011; 1.80 g, 3.16 mmol) in ethyl acetate (20 ml) was added 2-iodoxybenzoic acid (IBX; 1.77 g, 6.32 mmol) and the resulting solution refluxed for 3 h. The reaction mixture was filtered through a sintered glass funnel and the residue was washed with ethyl acetate (3 × 50 ml). The combined filtrate and washings were evaporated under reduced pressure, and the residue was dissolved in hot methanol and stored at ambient temperature. Colourless prismatic crystals of (I) were spontaneously obtained within 1 h (yield 1.70 g, 95%). Analyses: thin-layer chromatography: R_F = 0.5 in 20% ethyl acetate/light petroleum; m.p. 348.8–350.5 K; IR (CHCl₃, ν, cm^-1): 1716; ¹H NMR (CDCl₃, 400 MHz, δ, p.p.m.): 7.41–7.49 (m, 2H, Ar H), 7.20–7.40 (m, 15H, Ar H), 6.83–6.88 (m, 2H, Ar H), 5.66 (s, 1H, HCO₂), 4.67 (s, 2H, CH₂), 4.63 (q, 4H, J = 11.8 Hz, 2 × CH₂), 4.49 (m, 2H, Ins H), 4.23 (t, 1H, J = 2.0 Hz, Ins H), 4.17 (d, 2H, J = 2.5 Hz, Ins H), 3.79 (s, 3H, CH₃); ¹³C NMR (CDCl₃, 100.6 MHz, δ, p.p.m.): 201.0 (C═O), 159.3 (C_arom), 137.7 (C_arom), 136.6 (C_arom), 129.9 (C_arom), 129.7 (C_arom), 129.4 (C_arom), 128.4 (C_arom), 128.3 (C_arom), 128.1 (C_arom), 127.9 (C_arom), 126.2 (C_arom), 113.8 (C_arom), 93.9 (HCO₂), 79.4 (Ins C), 73.7 (Ins C), 71.9 (CH₂), 70.7 (CH₂), 66.0 (Ins C), 55.2 (CH₃); analysis calculated for C₃₅H₃₄O₇: C 74.19, H 6.05%; found: C 74.36, H 6.04%. Crystallization from other common organic solvents like ethyl acetate, chloroform, dichloromethane and acetonitrile, as well as from the melt, also yielded chiral crystals spontaneously.

S3. Refinement

All H atoms were placed in geometrically idealized positions (C—H = 1.00 Å for inositol ring H atoms and atom H7, C—H = 0.95 Å for phenyl H atoms, C—H = 0.99 Å for methylene H atoms and C—H = 0.98 Å for methyl H atoms) and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C). In the absence of any significant anomalous scatterers in the molecule, the 1083 Friedel pairs were merged before the final refinement. The anisotropic displacement parameters (ADPs) for benzyl group C16–C22 were large, indicating orientational disorder. However, a reasonable model was obtained by splitting the benzyl group into two components (C16–C22 and C16'–C22') each with equal (0.5) occupancies, thus making the sum of the site-occupancy factors for the disordered atoms to unity. Furthermore, the ADPs of these group atoms were restrained to be similar using SIMU instruction. In addition, the bond length of O4—C16 and O4—C16' groups were restrained to be similar using the SADI instruction.

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SMART (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The dashed line indicates the intramolecular C—H···O interaction.
	Fig. 2. The molecular packing of (I), viewed down the a axis, showing the helical assembly of molecules along the crystallographic twofold screw axis (b axis). Dashed lines indicate intermolecular C—H···O and C—H···π interactions. [Symmetry codes: (i) -x + 2, y + 1/2, -z + 2; (ii) -x + 2, y - 1/2, -z + 2.]
	Fig. 3. The molecular packing of (I), viewed diagonal to the ac plane, revealing the association of discrete helices via C23—H23···O5 interactions. [Symmetry code: (iii) -x + 1, y + 1/2, -z + 2.]
	Fig. 4. The molecular packing of (I), viewed down the a axis, showing the cohesion of the helical chains along the c axis via edge-to-edge C33—H33···H26—C26 short contacts. [Symmetry code: (iv) x + 1, y, z + 1.]
	Fig. 5. The Hirshfeld surface of (I) mapped with dnorm; a molecule of (I) with a similar orientation has been added on the left-hand side for clarity. Selective atom labels on the left-hand side image indicate involvement of these atoms in intermolecular interactions. The dark spots indicated by arrows in the right-hand side image are attributed to the contribution of dnorm map to the Hershfield surface by intermolecular interactions such as C10—H10···π^i, C14—H14···O3^ii, H···H^iv, π···C10^Vi—H10^vi, O1···H8B^vi—C8^vi and O5···H16A^vii—C16^vii. [Symmetry code: (i) -x+2, y+1/2, -z+2; (ii) -x+2, y-1/2, -z+2; (iv) x+1, y, z+1; (vi) -x+2, y-1/2, -z+2; (vii) -x+1, y-1/2, -z+2.]

4,6-di-O-benzyl-1,3-O-benzylidene-2-O-(4-methoxybenzyl)- myo-5-inosose

Crystal data

C35H34O7	F(000) = 600
Mr = 566.62	Dx = 1.284 Mg m^−3
Monoclinic, P21	Melting point: 350 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 9.492 (8) Å	Cell parameters from 2778 reflections
b = 9.735 (8) Å	θ = 2.2–26.8°
c = 16.289 (13) Å	µ = 0.09 mm^−1
β = 103.206 (12)°	T = 133 K
V = 1465 (2) Å^3	Prism, colourless
Z = 2	0.18 × 0.13 × 0.09 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2741 independent reflections
Radiation source: fine-focus sealed tube	2503 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
ω and ϕ scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −11→11
Tmin = 0.984, Tmax = 0.992	k = −11→11
7169 measured reflections	l = −10→19

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)] = 0.073	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.138	H-atom parameters constrained
S = 1.26	w = 1/[σ^2(Fo^2) + (0.0251P)^2 + 1.6618P] where P = (Fo^2 + 2Fc^2)/3
2741 reflections	(Δ/σ)max < 0.001
443 parameters	Δρmax = 0.29 e Å^−3
188 restraints	Δρmin = −0.28 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.8474 (4)	−0.1715 (4)	1.0546 (2)	0.0189 (8)
O2	1.0289 (4)	−0.0858 (4)	0.9434 (2)	0.0193 (8)
O3	0.9249 (4)	0.0588 (4)	1.0729 (2)	0.0195 (9)
O4	0.6848 (4)	0.2010 (4)	0.8861 (2)	0.0228 (9)
O5	0.4902 (5)	0.0514 (4)	0.9894 (3)	0.0318 (10)
O6	0.6008 (4)	−0.1214 (4)	0.8509 (2)	0.0204 (8)
O7	0.8701 (5)	−0.1668 (4)	0.5423 (2)	0.0319 (10)
C1	0.7975 (6)	−0.1528 (5)	0.9652 (3)	0.0181 (12)
H1	0.8132	−0.2408	0.9368	0.022*
C2	0.8842 (5)	−0.0409 (6)	0.9339 (3)	0.0168 (12)
H2	0.8411	−0.0228	0.8729	0.020*
C3	0.8713 (6)	0.0888 (5)	0.9849 (3)	0.0171 (12)
H3	0.9329	0.1624	0.9684	0.021*
C4	0.7156 (6)	0.1404 (6)	0.9686 (3)	0.0210 (12)
H4	0.7077	0.2121	1.0113	0.025*
C5	0.6040 (6)	0.0271 (6)	0.9697 (3)	0.0217 (13)
C6	0.6362 (5)	−0.1192 (6)	0.9406 (3)	0.0200 (12)
H6	0.5789	−0.1897	0.9636	0.024*
C7	0.8465 (6)	−0.0499 (6)	1.1021 (3)	0.0211 (13)
H7	0.7446	−0.0203	1.0990	0.025*
C8	1.1005 (6)	−0.0236 (5)	0.8843 (3)	0.0209 (13)
H8A	1.2041	−0.0493	0.8994	0.025*
H8B	1.0945	0.0775	0.8891	0.025*
C9	1.0380 (6)	−0.0646 (6)	0.7938 (3)	0.0198 (12)
C10	1.0336 (6)	0.0288 (6)	0.7281 (3)	0.0231 (13)
H10	1.0705	0.1191	0.7403	0.028*
C11	0.9762 (7)	−0.0092 (6)	0.6463 (4)	0.0297 (15)
H11	0.9735	0.0557	0.6024	0.036*
C12	0.9219 (6)	−0.1405 (6)	0.6260 (3)	0.0201 (12)
C13	0.9261 (6)	−0.2345 (6)	0.6903 (4)	0.0238 (13)
H13	0.8897	−0.3248	0.6778	0.029*
C14	0.9840 (6)	−0.1954 (6)	0.7732 (3)	0.0236 (13)
H14	0.9866	−0.2604	0.8170	0.028*
C15	0.8230 (8)	−0.3025 (7)	0.5190 (4)	0.0386 (17)
H15A	0.7385	−0.3240	0.5418	0.058*
H15B	0.9011	−0.3673	0.5418	0.058*
H15C	0.7968	−0.3099	0.4574	0.058*
C16	0.5726 (14)	0.3062 (14)	0.8804 (10)	0.031 (3)	0.50
H16A	0.6019	0.3739	0.9265	0.037*	0.50
H16B	0.4805	0.2633	0.8857	0.037*	0.50
C17	0.553 (4)	0.376 (3)	0.796 (2)	0.023 (2)	0.50
C18	0.600 (3)	0.509 (2)	0.7918 (14)	0.026 (3)	0.50
H18	0.6435	0.5561	0.8423	0.031*	0.50
C19	0.5858 (18)	0.576 (2)	0.7147 (10)	0.025 (3)	0.50
H19	0.6253	0.6655	0.7123	0.030*	0.50
C20	0.515 (2)	0.5128 (19)	0.6437 (11)	0.028 (3)	0.50
H20	0.4961	0.5617	0.5918	0.034*	0.50
C21	0.469 (2)	0.3763 (16)	0.6446 (14)	0.025 (3)	0.50
H21	0.4245	0.3299	0.5940	0.030*	0.50
C22	0.492 (2)	0.309 (3)	0.7251 (11)	0.023 (3)	0.50
H22	0.4626	0.2165	0.7280	0.028*	0.50
C16'	0.5385 (11)	0.2576 (14)	0.8590 (9)	0.025 (3)	0.50
H16C	0.5099	0.3047	0.9066	0.030*	0.50
H16D	0.4680	0.1835	0.8383	0.030*	0.50
C17'	0.543 (4)	0.358 (3)	0.790 (3)	0.024 (2)	0.50
C18'	0.610 (3)	0.484 (2)	0.8077 (14)	0.024 (3)	0.50
H18'	0.6555	0.5054	0.8644	0.028*	0.50
C19'	0.6131 (18)	0.577 (2)	0.7464 (9)	0.026 (3)	0.50
H19'	0.6638	0.6612	0.7600	0.031*	0.50
C20'	0.5413 (19)	0.5493 (17)	0.6628 (13)	0.027 (3)	0.50
H20'	0.5424	0.6160	0.6204	0.033*	0.50
C21'	0.468 (2)	0.4245 (17)	0.6406 (13)	0.025 (3)	0.50
H21'	0.4177	0.4084	0.5839	0.030*	0.50
C22'	0.468 (2)	0.320 (3)	0.7046 (12)	0.026 (3)	0.50
H22'	0.4227	0.2333	0.6916	0.031*	0.50
C23	0.4499 (6)	−0.1230 (8)	0.8143 (3)	0.0315 (15)
H23A	0.4032	−0.0414	0.8328	0.038*
H23B	0.4053	−0.2063	0.8324	0.038*
C24	0.4288 (6)	−0.1221 (6)	0.7195 (3)	0.0246 (13)
C25	0.3052 (6)	−0.1812 (7)	0.6716 (3)	0.0294 (14)
H25	0.2361	−0.2211	0.6984	0.035*
C26	0.2813 (6)	−0.1827 (8)	0.5848 (4)	0.0383 (17)
H26	0.1956	−0.2232	0.5521	0.046*
C27	0.3822 (6)	−0.1253 (8)	0.5451 (4)	0.0365 (16)
H27	0.3662	−0.1267	0.4854	0.044*
C28	0.5062 (7)	−0.0661 (8)	0.5936 (4)	0.0375 (17)
H28	0.5760	−0.0267	0.5671	0.045*
C29	0.5285 (6)	−0.0644 (7)	0.6804 (4)	0.0288 (14)
H29	0.6134	−0.0230	0.7134	0.035*
C30	0.9215 (6)	−0.0793 (6)	1.1925 (3)	0.0218 (13)
C31	1.0589 (6)	−0.1286 (6)	1.2139 (4)	0.0270 (13)
H31	1.1097	−0.1469	1.1712	0.032*
C32	1.1240 (6)	−0.1521 (7)	1.2960 (4)	0.0346 (15)
H32	1.2206	−0.1854	1.3104	0.041*
C33	1.0506 (7)	−0.1279 (6)	1.3587 (4)	0.0324 (15)
H33	1.0967	−0.1451	1.4160	0.039*
C34	0.9112 (7)	−0.0790 (6)	1.3384 (4)	0.0314 (15)
H34	0.8601	−0.0629	1.3812	0.038*
C35	0.8457 (6)	−0.0533 (6)	1.2544 (4)	0.0265 (13)
H35	0.7498	−0.0182	1.2394	0.032*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.024 (2)	0.0161 (19)	0.0174 (18)	−0.0030 (17)	0.0063 (16)	0.0016 (16)
O2	0.0183 (19)	0.024 (2)	0.0169 (19)	0.0019 (16)	0.0065 (15)	0.0032 (16)
O3	0.030 (2)	0.0148 (19)	0.0162 (19)	0.0012 (17)	0.0093 (16)	0.0045 (16)
O4	0.028 (2)	0.026 (2)	0.020 (2)	0.0110 (18)	0.0185 (17)	0.0073 (18)
O5	0.027 (2)	0.044 (3)	0.031 (2)	0.007 (2)	0.0183 (18)	0.005 (2)
O6	0.0188 (19)	0.030 (2)	0.0140 (18)	−0.0001 (18)	0.0065 (15)	−0.0016 (17)
O7	0.050 (3)	0.031 (2)	0.0147 (19)	−0.003 (2)	0.0064 (18)	−0.0003 (19)
C1	0.029 (3)	0.013 (3)	0.013 (3)	−0.003 (2)	0.005 (2)	−0.003 (2)
C2	0.011 (3)	0.025 (3)	0.013 (2)	0.009 (2)	0.000 (2)	0.002 (2)
C3	0.028 (3)	0.016 (3)	0.007 (2)	−0.002 (2)	0.005 (2)	0.002 (2)
C4	0.031 (3)	0.021 (3)	0.014 (3)	0.001 (3)	0.011 (2)	0.002 (2)
C5	0.026 (3)	0.034 (3)	0.008 (2)	0.008 (3)	0.009 (2)	0.000 (2)
C6	0.020 (3)	0.026 (3)	0.017 (3)	−0.005 (3)	0.008 (2)	−0.004 (2)
C7	0.030 (3)	0.022 (3)	0.013 (3)	0.003 (3)	0.010 (2)	0.003 (2)
C8	0.015 (3)	0.016 (3)	0.034 (3)	0.007 (2)	0.011 (2)	0.002 (2)
C9	0.016 (3)	0.018 (3)	0.027 (3)	0.000 (2)	0.008 (2)	−0.008 (3)
C10	0.032 (3)	0.015 (3)	0.026 (3)	−0.001 (3)	0.014 (3)	−0.002 (2)
C11	0.038 (4)	0.029 (4)	0.022 (3)	0.001 (3)	0.007 (3)	0.014 (3)
C12	0.019 (3)	0.023 (3)	0.019 (3)	0.007 (3)	0.006 (2)	0.007 (2)
C13	0.033 (3)	0.014 (3)	0.028 (3)	−0.006 (3)	0.013 (3)	−0.004 (2)
C14	0.028 (3)	0.033 (3)	0.017 (3)	0.006 (3)	0.018 (2)	0.008 (3)
C15	0.062 (5)	0.034 (4)	0.019 (3)	−0.009 (4)	0.007 (3)	−0.008 (3)
C16	0.031 (5)	0.029 (6)	0.035 (6)	0.008 (5)	0.012 (5)	0.003 (5)
C17	0.022 (4)	0.023 (5)	0.028 (5)	0.013 (4)	0.010 (4)	0.002 (4)
C18	0.029 (4)	0.021 (5)	0.027 (6)	0.008 (4)	0.006 (5)	0.000 (4)
C19	0.029 (5)	0.019 (4)	0.028 (6)	0.006 (4)	0.011 (5)	0.000 (6)
C20	0.034 (5)	0.021 (6)	0.029 (5)	0.009 (5)	0.006 (4)	0.005 (5)
C21	0.024 (4)	0.023 (6)	0.030 (5)	0.007 (5)	0.012 (4)	0.006 (6)
C22	0.020 (5)	0.022 (5)	0.030 (6)	0.009 (4)	0.014 (5)	0.005 (5)
C16'	0.029 (5)	0.025 (6)	0.026 (6)	0.008 (5)	0.015 (4)	0.007 (5)
C17'	0.023 (4)	0.023 (5)	0.029 (5)	0.012 (4)	0.012 (4)	0.004 (4)
C18'	0.026 (5)	0.022 (6)	0.026 (6)	0.013 (5)	0.011 (5)	−0.002 (5)
C19'	0.026 (5)	0.024 (5)	0.027 (6)	0.008 (4)	0.003 (5)	0.002 (5)
C20'	0.029 (5)	0.023 (6)	0.029 (6)	0.007 (5)	0.003 (5)	0.004 (5)
C21'	0.026 (4)	0.025 (6)	0.026 (4)	0.007 (6)	0.011 (4)	−0.003 (6)
C22'	0.025 (5)	0.025 (5)	0.027 (5)	0.007 (4)	0.006 (4)	0.006 (5)
C23	0.015 (3)	0.051 (4)	0.029 (3)	−0.001 (3)	0.006 (2)	−0.008 (3)
C24	0.024 (3)	0.029 (3)	0.023 (3)	0.007 (3)	0.009 (2)	−0.002 (3)
C25	0.015 (3)	0.051 (4)	0.023 (3)	−0.001 (3)	0.006 (2)	0.003 (3)
C26	0.015 (3)	0.075 (5)	0.022 (3)	0.006 (3)	−0.003 (2)	0.000 (3)
C27	0.033 (3)	0.063 (5)	0.014 (3)	0.007 (4)	0.007 (2)	0.004 (3)
C28	0.035 (4)	0.054 (4)	0.028 (3)	0.006 (4)	0.016 (3)	0.008 (3)
C29	0.026 (3)	0.033 (3)	0.027 (3)	−0.005 (3)	0.006 (3)	0.004 (3)
C30	0.031 (3)	0.017 (3)	0.015 (3)	−0.005 (3)	−0.001 (2)	0.008 (2)
C31	0.025 (3)	0.029 (3)	0.030 (3)	−0.006 (3)	0.013 (3)	0.004 (3)
C32	0.020 (3)	0.033 (4)	0.046 (4)	0.001 (3)	−0.002 (3)	0.011 (3)
C33	0.037 (4)	0.031 (3)	0.021 (3)	−0.009 (3)	−0.010 (3)	0.016 (3)
C34	0.046 (4)	0.032 (4)	0.020 (3)	−0.021 (3)	0.016 (3)	−0.007 (3)
C35	0.019 (3)	0.024 (3)	0.038 (3)	0.000 (3)	0.008 (3)	−0.002 (3)

Geometric parameters (Å, º)

O1—C7	1.416 (7)	C18—C19	1.40 (2)
O1—C1	1.437 (6)	C18—H18	0.9500
O2—C2	1.416 (6)	C19—C20	1.35 (2)
O2—C8	1.434 (6)	C19—H19	0.9500
O3—C7	1.436 (6)	C20—C21	1.40 (2)
O3—C3	1.437 (6)	C20—H20	0.9500
O4—C4	1.436 (6)	C21—C22	1.44 (2)
O4—C16	1.465 (9)	C21—H21	0.9500
O4—C16'	1.465 (9)	C22—H22	0.9500
O5—C5	1.218 (6)	C16'—C17'	1.50 (4)
O6—C23	1.420 (6)	C16'—H16C	0.9900
O6—C6	1.424 (6)	C16'—H16D	0.9900
O7—C12	1.364 (7)	C17'—C18'	1.39 (3)
O7—C15	1.418 (8)	C17'—C22'	1.45 (4)
C1—C2	1.521 (7)	C18'—C19'	1.35 (2)
C1—C6	1.527 (7)	C18'—H18'	0.9500
C1—H1	1.0000	C19'—C20'	1.40 (2)
C2—C3	1.532 (7)	C19'—H19'	0.9500
C2—H2	1.0000	C20'—C21'	1.41 (2)
C3—C4	1.525 (8)	C20'—H20'	0.9500
C3—H3	1.0000	C21'—C22'	1.46 (3)
C4—C5	1.532 (8)	C21'—H21'	0.9500
C4—H4	1.0000	C22'—H22'	0.9500
C5—C6	1.553 (8)	C23—C24	1.511 (7)
C6—H6	1.0000	C23—H23A	0.9900
C7—C30	1.508 (7)	C23—H23B	0.9900
C7—H7	1.0000	C24—C29	1.376 (8)
C8—C9	1.512 (8)	C24—C25	1.378 (8)
C8—H8A	0.9900	C25—C26	1.379 (8)
C8—H8B	0.9900	C25—H25	0.9500
C9—C14	1.385 (8)	C26—C27	1.389 (8)
C9—C10	1.397 (8)	C26—H26	0.9500
C10—C11	1.371 (8)	C27—C28	1.384 (9)
C10—H10	0.9500	C27—H27	0.9500
C11—C12	1.389 (8)	C28—C29	1.381 (8)
C11—H11	0.9500	C28—H28	0.9500
C12—C13	1.384 (8)	C29—H29	0.9500
C13—C14	1.390 (8)	C30—C31	1.359 (8)
C13—H13	0.9500	C30—C35	1.389 (8)
C14—H14	0.9500	C31—C32	1.358 (8)
C15—H15A	0.9800	C31—H31	0.9500
C15—H15B	0.9800	C32—C33	1.382 (9)
C15—H15C	0.9800	C32—H32	0.9500
C16—C17	1.50 (4)	C33—C34	1.374 (9)
C16—H16A	0.9900	C33—H33	0.9500
C16—H16B	0.9900	C34—C35	1.390 (8)
C17—C22	1.34 (3)	C34—H34	0.9500
C17—C18	1.37 (3)	C35—H35	0.9500
C7—O1—C1	114.0 (4)	C22—C17—C16	120 (2)
C2—O2—C8	113.2 (4)	C18—C17—C16	120 (3)
C7—O3—C3	112.9 (4)	C17—C18—C19	122 (3)
C4—O4—C16	109.6 (7)	C17—C18—H18	119.2
C4—O4—C16'	114.4 (7)	C19—C18—H18	119.2
C23—O6—C6	114.2 (4)	C20—C19—C18	119.0 (18)
C12—O7—C15	117.5 (4)	C20—C19—H19	120.5
O1—C1—C2	110.6 (4)	C18—C19—H19	120.5
O1—C1—C6	111.8 (4)	C19—C20—C21	121.4 (18)
C2—C1—C6	110.2 (4)	C19—C20—H20	119.3
O1—C1—H1	108.0	C21—C20—H20	119.3
C2—C1—H1	108.0	C20—C21—C22	117 (2)
C6—C1—H1	108.0	C20—C21—H21	121.4
O2—C2—C1	109.1 (4)	C22—C21—H21	121.4
O2—C2—C3	113.0 (4)	C17—C22—C21	121 (3)
C1—C2—C3	107.0 (4)	C17—C22—H22	119.5
O2—C2—H2	109.2	C21—C22—H22	119.5
C1—C2—H2	109.2	O4—C16'—C17'	106.5 (16)
C3—C2—H2	109.2	O4—C16'—H16C	110.4
O3—C3—C4	110.4 (4)	C17'—C16'—H16C	110.4
O3—C3—C2	108.7 (4)	O4—C16'—H16D	110.4
C4—C3—C2	111.8 (4)	C17'—C16'—H16D	110.4
O3—C3—H3	108.6	H16C—C16'—H16D	108.6
C4—C3—H3	108.6	C18'—C17'—C22'	122 (3)
C2—C3—H3	108.6	C18'—C17'—C16'	120 (3)
O4—C4—C3	106.3 (4)	C22'—C17'—C16'	118 (2)
O4—C4—C5	108.3 (4)	C19'—C18'—C17'	122 (3)
C3—C4—C5	114.0 (4)	C19'—C18'—H18'	119.2
O4—C4—H4	109.4	C17'—C18'—H18'	119.2
C3—C4—H4	109.4	C18'—C19'—C20'	119.9 (19)
C5—C4—H4	109.4	C18'—C19'—H19'	120.0
O5—C5—C4	121.4 (5)	C20'—C19'—H19'	120.0
O5—C5—C6	120.4 (5)	C19'—C20'—C21'	121.2 (18)
C4—C5—C6	118.1 (4)	C19'—C20'—H20'	119.4
O6—C6—C1	104.6 (4)	C21'—C20'—H20'	119.4
O6—C6—C5	108.1 (4)	C20'—C21'—C22'	120 (2)
C1—C6—C5	111.9 (4)	C20'—C21'—H21'	120.0
O6—C6—H6	110.7	C22'—C21'—H21'	120.0
C1—C6—H6	110.7	C17'—C22'—C21'	115 (3)
C5—C6—H6	110.7	C17'—C22'—H22'	122.3
O1—C7—O3	111.5 (4)	C21'—C22'—H22'	122.3
O1—C7—C30	108.3 (4)	O6—C23—C24	108.3 (4)
O3—C7—C30	107.4 (4)	O6—C23—H23A	110.0
O1—C7—H7	109.8	C24—C23—H23A	110.0
O3—C7—H7	109.8	O6—C23—H23B	110.0
C30—C7—H7	109.8	C24—C23—H23B	110.0
O2—C8—C9	113.8 (4)	H23A—C23—H23B	108.4
O2—C8—H8A	108.8	C29—C24—C25	119.7 (5)
C9—C8—H8A	108.8	C29—C24—C23	122.0 (5)
O2—C8—H8B	108.8	C25—C24—C23	118.3 (5)
C9—C8—H8B	108.8	C24—C25—C26	120.3 (5)
H8A—C8—H8B	107.7	C24—C25—H25	119.9
C14—C9—C10	117.9 (5)	C26—C25—H25	119.9
C14—C9—C8	121.4 (5)	C25—C26—C27	120.2 (6)
C10—C9—C8	120.7 (5)	C25—C26—H26	119.9
C11—C10—C9	120.3 (5)	C27—C26—H26	119.9
C11—C10—H10	119.8	C28—C27—C26	119.3 (5)
C9—C10—H10	119.8	C28—C27—H27	120.4
C10—C11—C12	121.5 (5)	C26—C27—H27	120.4
C10—C11—H11	119.2	C29—C28—C27	120.0 (6)
C12—C11—H11	119.2	C29—C28—H28	120.0
O7—C12—C13	125.0 (5)	C27—C28—H28	120.0
O7—C12—C11	116.1 (5)	C24—C29—C28	120.5 (6)
C13—C12—C11	118.9 (5)	C24—C29—H29	119.7
C12—C13—C14	119.4 (5)	C28—C29—H29	119.7
C12—C13—H13	120.3	C31—C30—C35	120.3 (5)
C14—C13—H13	120.3	C31—C30—C7	121.9 (5)
C9—C14—C13	122.0 (5)	C35—C30—C7	117.8 (5)
C9—C14—H14	119.0	C32—C31—C30	120.5 (5)
C13—C14—H14	119.0	C32—C31—H31	119.8
O7—C15—H15A	109.5	C30—C31—H31	119.8
O7—C15—H15B	109.5	C31—C32—C33	120.4 (6)
H15A—C15—H15B	109.5	C31—C32—H32	119.8
O7—C15—H15C	109.5	C33—C32—H32	119.8
H15A—C15—H15C	109.5	C34—C33—C32	120.1 (5)
H15B—C15—H15C	109.5	C34—C33—H33	119.9
O4—C16—C17	108.1 (15)	C32—C33—H33	119.9
O4—C16—H16A	110.1	C33—C34—C35	119.3 (5)
C17—C16—H16A	110.1	C33—C34—H34	120.3
O4—C16—H16B	110.1	C35—C34—H34	120.3
C17—C16—H16B	110.1	C30—C35—C34	119.5 (5)
H16A—C16—H16B	108.4	C30—C35—H35	120.3
C22—C17—C18	119 (4)	C34—C35—H35	120.3
C7—O1—C1—C2	55.2 (5)	C11—C12—C13—C14	0.1 (8)
C7—O1—C1—C6	−68.0 (5)	C10—C9—C14—C13	−0.3 (8)
C8—O2—C2—C1	153.0 (4)	C8—C9—C14—C13	179.9 (5)
C8—O2—C2—C3	−88.1 (5)	C12—C13—C14—C9	0.0 (8)
O1—C1—C2—O2	66.5 (5)	C4—O4—C16—C17	174.8 (13)
C6—C1—C2—O2	−169.4 (4)	C16'—O4—C16—C17	−79 (3)
O1—C1—C2—C3	−56.0 (5)	O4—C16—C17—C22	70 (3)
C6—C1—C2—C3	68.1 (5)	O4—C16—C17—C18	−109 (3)
C7—O3—C3—C4	63.2 (5)	C22—C17—C18—C19	0 (4)
C7—O3—C3—C2	−59.7 (5)	C16—C17—C18—C19	179 (2)
O2—C2—C3—O3	−61.9 (5)	C17—C18—C19—C20	5 (3)
C1—C2—C3—O3	58.2 (5)	C18—C19—C20—C21	−7 (3)
O2—C2—C3—C4	176.0 (4)	C19—C20—C21—C22	4 (3)
C1—C2—C3—C4	−63.9 (5)	C18—C17—C22—C21	−3 (4)
C16—O4—C4—C3	−153.4 (7)	C16—C17—C22—C21	178 (2)
C16'—O4—C4—C3	−179.7 (7)	C20—C21—C22—C17	1 (3)
C16—O4—C4—C5	83.8 (8)	C4—O4—C16'—C17'	160.0 (12)
C16'—O4—C4—C5	57.4 (8)	C16—O4—C16'—C17'	76 (3)
O3—C3—C4—O4	165.1 (4)	O4—C16'—C17'—C18'	−74 (3)
C2—C3—C4—O4	−73.8 (5)	O4—C16'—C17'—C22'	109 (3)
O3—C3—C4—C5	−75.7 (5)	C22'—C17'—C18'—C19'	−2 (4)
C2—C3—C4—C5	45.4 (6)	C16'—C17'—C18'—C19'	−179 (2)
O4—C4—C5—O5	−90.0 (6)	C17'—C18'—C19'—C20'	3 (3)
C3—C4—C5—O5	151.9 (5)	C18'—C19'—C20'—C21'	−1 (3)
O4—C4—C5—C6	87.0 (5)	C19'—C20'—C21'—C22'	−2 (3)
C3—C4—C5—C6	−31.1 (6)	C18'—C17'—C22'—C21'	−1 (4)
C23—O6—C6—C1	166.7 (5)	C16'—C17'—C22'—C21'	176 (2)
C23—O6—C6—C5	−74.0 (6)	C20'—C21'—C22'—C17'	2 (3)
O1—C1—C6—O6	−172.8 (4)	C6—O6—C23—C24	178.8 (5)
C2—C1—C6—O6	63.8 (5)	O6—C23—C24—C29	−27.8 (8)
O1—C1—C6—C5	70.4 (5)	O6—C23—C24—C25	152.3 (6)
C2—C1—C6—C5	−53.0 (5)	C29—C24—C25—C26	0.0 (10)
O5—C5—C6—O6	97.0 (5)	C23—C24—C25—C26	179.9 (6)
C4—C5—C6—O6	−80.0 (6)	C24—C25—C26—C27	0.4 (11)
O5—C5—C6—C1	−148.3 (5)	C25—C26—C27—C28	−0.3 (11)
C4—C5—C6—C1	34.7 (6)	C26—C27—C28—C29	−0.1 (10)
C1—O1—C7—O3	−53.7 (6)	C25—C24—C29—C28	−0.5 (10)
C1—O1—C7—C30	−171.7 (4)	C23—C24—C29—C28	179.6 (6)
C3—O3—C7—O1	56.5 (5)	C27—C28—C29—C24	0.5 (10)
C3—O3—C7—C30	175.1 (4)	O1—C7—C30—C31	56.3 (7)
C2—O2—C8—C9	−66.3 (5)	O3—C7—C30—C31	−64.3 (6)
O2—C8—C9—C14	−34.9 (7)	O1—C7—C30—C35	−124.1 (5)
O2—C8—C9—C10	145.3 (5)	O3—C7—C30—C35	115.3 (5)
C14—C9—C10—C11	0.5 (8)	C35—C30—C31—C32	−0.5 (9)
C8—C9—C10—C11	−179.8 (5)	C7—C30—C31—C32	179.0 (6)
C9—C10—C11—C12	−0.4 (9)	C30—C31—C32—C33	0.9 (10)
C15—O7—C12—C13	−3.0 (8)	C31—C32—C33—C34	−0.4 (10)
C15—O7—C12—C11	175.8 (5)	C32—C33—C34—C35	−0.5 (9)
C10—C11—C12—O7	−178.8 (5)	C31—C30—C35—C34	−0.4 (8)
C10—C11—C12—C13	0.1 (8)	C7—C30—C35—C34	−180.0 (5)
O7—C12—C13—C14	178.9 (5)	C33—C34—C35—C30	0.9 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···O1^i	0.99	2.62	3.572 (7)	160
C10—H10···Cg2^i	0.95	2.76	3.588 (7)	146
C14—H14···O3^ii	0.95	2.52	3.430 (7)	161
C16—H16A···O5^iii	0.99	2.49	3.336 (14)	144

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