Resolution of (S,S)-4-(2,2,4-tri­methyl­chroman-4-yl)­phenyl camphanate and its 4-chromanyl epimer by crystallization

Dianin's compound (4-p-hydroxy­phenyl-2,2,4-tri­methyl­chroman) has been resolved by crystallization of the (S)-(-)-camphanic esters (S,S)- and (R,S)-4-(2,2,4-tri­methyl­chroman-4-yl)­phenyl 4,7,7-tri­methyl-3-oxo-2-oxabi­cyclo[2.2.1]heptane-1-carboxyl­ate, both C₂₈H₃₂O₅, from 2-methoxy­ethanol, yielding the pure S,S diastereomer. The relative stereochemistry of both diastereomers has been determined by X-ray crystallography, from which the absolute stereochemistry could be deduced from the known configuration of the camphanate moiety. The crystallographic conformations have been analysed, including the 1:1 disorder of the R,S diastereomer.

S1. Comment

Dianin's compound is well known for its ability to form clathrates (Finocchiaro & Failla, 1996). Racemates of the compound are required because the twelve-membered ring formed by the hydrogen bonding of six phenol OH moieties is comprised of three R-enantiomers presenting their hydroxy groups from one face of the ring interspersed by three S-enantiomers doing the same from the opposite face. The ring therefore lies on the plane of symmetry of an S₆ point group. Resolution of Dianin's compound and its derivatives allows for the formation of clathrates composed of complementing enantiomers of different species, thus forming quasi-racemic structures (Brienne & Jacques, 1975; Collet & Jacques, 1977). In principle, this can produce a chiral cavity that may show preference for one enantiomer of a guest molecule.

(1S)-Camphanic chloride was chosen as chiral adjuvant (Brienne & Jacques, 1975) because of its propensity to produce diastereomeric esters from alcohols which may be separated either by fractional crystallization or chromatography. The diastereomeric mixture obtained from treating Dianin's compound with (1S)-camphanic chloride was crystallized from ethanol, yielding a crystalline mixture of both diastereomers. This mixture was further crystallized from 2-methoxyethanol, yielding crystals of the resolved (S,S)-camphanate, (I), of Dianin's compound. X-ray crystallography of the resolved compound was necessary to deduce the absolute stereochemistry of the Dianin's compound moiety of the ester, as may be obtained from the known stereochemistry of the camphanate moiety. To complement the crystallography of the resolved compound, a suitable crystal of the (R,S)-isomer, (Ia), was obtained from the crystalline diastereomeric mixture before resolution, indicating that these diastereomers crystallize separately from methanol. \sch

The (S,S)-isomer of the title compound, (I), along with the numbering scheme, is shown in Fig. 1. The structure of the (R,S)-isomer, (Ia), is similar, although exhibiting disorder of the phenyl camphanate moiety, (Ia') and (Ia''), as shown in Fig. 2. The numbering scheme for (Ia) is identical to that of (I), except that the atoms in the two disordered parts are indicated by the suffixes A and B, respectively. Despite the disorder, the rigid bicyclic structure of the camphanate moiety ensures that it is almost identical in (I) and both conformations of (Ia), with comparable bond lengths and angles.

The orientation of the carboxyl group (atoms O2, C19 and O3) relative to the bicyclic structure of the camphanic moiety is, however, different in (I) and the two conformations of (Ia). In (I), the plane through atoms O2, C19 and O3 is only slightly twisted with respect to the plane through atoms O4, C21 and O5 [dihedral angle 17.6 (2)°], with the O4—C20—C19—O2 torsion angle being −177.7 (2)°. One of the conformations in (Ia) [(Ia')] is similarly only slightly twisted [dihedral angle 16.0 (7)° and O4—C20—C19—O2 torsion angle −167.5 (6)], whereas in the other conformation, (Ia''), it is substantially twisted away from the plane through atoms O4, C21 and O5 [dihedral angle 55.9 (3)° and O4—C20—C19—O2 torsion angle −47 (1)°]. The phenyl ring is twisted away from the O2/C19/O3 plane by 75.6 (1)° for (I), and by 54.4 (4) and 55.9 (3)° for conformations (Ia') and (Ia''), respectively. The phenyl ring in turn is twisted away from the plane through atoms C13, C7 and C8 in the trimethylchroman moiety by 61.8 (1)° for (I), and by 55.2 (4) and 57.1 (4)° for (Ia') and (Ia''), respectively, such that for (I) and (Ia'), atoms O1, C7, C8, C13, C16, O2, O3, C19, C20, O4, O5 and C21 are almost coplanar. In the case of (Ia''), these same atoms form an anti-clockwise spiral rather than a plane.

The packing of the stereoisomers is also different. In (I), face-to-edge π–π interactions between neighbouring trimethylchroman moieties in a herringbone pattern lead to broad flat bands of interacting molecules (Fig. 3). In (Ia), the orientations of the 0.50:0.50 disordered molecules require alternation of (Ia') and (Ia''), leading to off-set stepwise stacks (Fig. 4). The reason for the twisting of (Ia'') relative to (Ia') or (I) is clear from Fig. 4; the twisted orientation of the camphanic moiety allows C—H···O interactions between methyl groups and carbonyls on neighbouring molecules.

S2. Experimental

The benzene clathrate of Dianin's compound (1:6) (Baker et al., 1956) (1.00 g, 3.34 mmol), DMAP Please define (48 mg, 393 µmol) and triethylamine (1.08 g, 10.7 mmol) were dissolved/suspended in dichloromethane (15 ml) and the camphanic chloride (932 mg, 4.30 mmol)was then added. The mixture was stirred at ambient temperature for 30 h and ice (ca 20 ml) was then added to quench the reaction. The aqueous phase was extracted with dichloromethane (15 ml) and the combined organic phases washed with water (25 ml), dried over anhydrous magnesium sulfate, and the solvents removed under reduced pressure. On exposing the residue to a minimum of ethanol, white crystals formed, which were filtered off and washed with cold ethanol and dried under vacuum, yielding 1.367 g (91%). The compound was pure by NMR. The only indication of the presence of diastereomers in both ¹H and ¹³C NMR was the doubling of the signal at δ_C 127.63 and 127.66 (CDCl₃, 75 MHz; Varian VXR 300). In an unoptimized effort at resolving the diastereomers, a quantity (1.15 g, 2.56 mmol) was dissolved in a minimum of 2-methoxyethanol (Brienne & Jacques, 1975) at 333 K and allowed to crystallize on cooling to ambient temperature. Pure (S,S)-4-p-camphanyloxyphenyl-2,2,4-trimethylchroman (276 mg, 615 µmol) was obtained, m.p. 451 K (literature value 450 K; Brienne & Jacques, 1975). Spectroscopic analysis: ¹H NMR (300 MHz, CDCl₃, CHCl₃ used as reference at δ = 7.24, δ, p.p.m.): 0.87 (3H, s), 1.03 (3H, s), 1.08 (3H, s), 1.10 (3H, s), 1.30 (3H, s), 1.66 (3H, s), 1.70 (1H, ddd, J = 13.4, 9.3 and 4.3 Hz), 1.93 (1H, ddd, J = 13.2, 10.8 and 4.5 Hz), 2.05 (1H, d, J = 14.2 Hz), 2.13 (1H, ddd, J = 13.5, 9.5 and 4.7 Hz), 2.32 (1H, d, J = 14.2 Hz), 2.50 (1H, ddd, J = 13.6, 10.7 and 4.3 Hz), 6.86 (1H, d, J = 8.3 Hz), 6.91 (1H, t, J = 7.5 Hz), 6.99 (2H, d, J = 8.8 Hz), 7.14–7.19 (2H, m), 7.21 (2H, d, J = 8.8 Hz); ¹³C NMR (75 MHz, CDCl₃ used as reference at δ = 77.00, δ, p.p.m.): 9.48, 16.62, 27.28, 28.78, 29.76, 30.56, 32.27, 39.04, 50.19, 54.55, 54.78, 74.48, 90.85, 118.32, 120.33, 120.81, 127.63, 128.09, 128.28, 129.50, 148.05, 148.58, 153.81, 166.38 and 178.12.

S3. Refinement

The positions of the disordered atoms in (Ia) were identified from a difference Fourier map. Atoms from the different disorder groups were refined anisotropically [with appropriate restraints using SIMU and ISOR in SHELXL97 (Sheldrick, 1997)] with common site occupancies; refinement showed the disorder to be exactly 50:50%. H atoms were positioned geometrically and constrained to ride on the atoms they were attached to, with U_iso(H) = 1.2 or 1.5 (for methyl groups) times U_eq(C)

Computing details

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: X-SEED.

Figures

	Fig. 1. The molecular conformation of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The molecular conformation of (Ia), showing the disorder. The numbering scheme is identical to that for (I), except that the atoms in the two disordered parts are indicated by the suffixes A and B. H atoms have been omitted for clarity.
	Fig. 3. The packing of (I), showing the herringbone pattern of face-to-edge π–π interactions.
	Fig. 4. The packing of (Ia), showing the alternating pattern of (Ia)' and (Ia)'' connected by C—H···O interactions.

(I) (S,S)-4-(2,2,4-trimethylchroman-4-yl)phenyl 4,7,7-trimethyl-3-oxo-2-oxobicyclo[2.2.1]heptane-1-carboxylate

Crystal data

C28H32O5	Dx = 1.239 Mg m^−3
Mr = 448.54	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 4712 reflections
a = 7.398 (2) Å	θ = 2.5–26°
b = 8.413 (2) Å	µ = 0.08 mm^−1
c = 38.628 (11) Å	T = 100 K
V = 2404.3 (12) Å^3	Prism, colourless
Z = 4	0.27 × 0.24 × 0.19 mm
F(000) = 960

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2743 independent reflections
Radiation source: fine-focus sealed tube	2258 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
ω scans	θmax = 26.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −9→8
Tmin = 0.97, Tmax = 0.98	k = −10→7
13603 measured reflections	l = −47→43

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.082	w = 1/[σ^2(Fo^2) + (0.0356P)^2 + 0.0289P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max = 0.001
2743 reflections	Δρmax = 0.20 e Å^−3
304 parameters	Δρmin = −0.20 e Å^−3
0 restraints	Absolute structure: Flack (1983) with how many Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0 (10)

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	0.7461 (2)	−0.0724 (2)	0.54149 (4)	0.0314 (4)
O2	0.7800 (2)	0.1499 (2)	0.73014 (4)	0.0245 (4)
O3	0.6943 (2)	0.4046 (2)	0.73977 (4)	0.0280 (4)
O4	0.8157 (2)	0.39592 (18)	0.80588 (4)	0.0195 (4)
O5	0.8294 (2)	0.4380 (2)	0.86334 (4)	0.0255 (4)
C1	0.8362 (3)	0.0690 (3)	0.54357 (6)	0.0235 (6)
C2	0.9931 (4)	0.0783 (4)	0.52341 (6)	0.0320 (7)
H25	1.0324	−0.0105	0.5112	0.038*
C3	1.0890 (4)	0.2172 (4)	0.52148 (6)	0.0332 (7)
H27	1.1925	0.2223	0.5079	0.040*
C4	1.0330 (3)	0.3501 (3)	0.53965 (6)	0.0302 (6)
H32	1.0972	0.4449	0.5382	0.036*
C5	0.8793 (3)	0.3389 (3)	0.55998 (6)	0.0261 (6)
H29	0.8417	0.4282	0.5722	0.031*
C6	0.7788 (3)	0.2001 (3)	0.56290 (6)	0.0195 (6)
C7	0.6093 (3)	0.1908 (3)	0.58540 (6)	0.0194 (5)
C8	0.4951 (3)	0.3425 (3)	0.58104 (6)	0.0253 (6)
H26A	0.4793	0.3645	0.5568	0.038*
H26B	0.5558	0.4303	0.5919	0.038*
H26C	0.3791	0.3274	0.5917	0.038*
C9	0.4954 (3)	0.0511 (3)	0.57215 (6)	0.0215 (6)
H28A	0.4014	0.0294	0.5890	0.026*
H28B	0.4364	0.0836	0.5509	0.026*
C10	0.5978 (3)	−0.1027 (3)	0.56523 (6)	0.0258 (6)
C11	0.6760 (4)	−0.1793 (3)	0.59765 (7)	0.0348 (7)
H30A	0.7703	−0.1131	0.6068	0.052*
H30B	0.7247	−0.2818	0.5919	0.052*
H30C	0.5824	−0.1913	0.6147	0.052*
C12	0.4780 (4)	−0.2198 (3)	0.54623 (7)	0.0382 (7)
H33A	0.5459	−0.3141	0.5410	0.057*
H33B	0.4357	−0.1726	0.5251	0.057*
H33C	0.3766	−0.2470	0.5605	0.057*
C13	0.6576 (3)	0.1758 (3)	0.62422 (6)	0.0179 (5)
C14	0.8353 (3)	0.1798 (3)	0.63627 (6)	0.0202 (5)
H15	0.9299	0.1880	0.6205	0.024*
C15	0.8730 (3)	0.1719 (3)	0.67134 (6)	0.0208 (5)
H16	0.9921	0.1738	0.6790	0.025*
C16	0.7344 (3)	0.1612 (3)	0.69456 (6)	0.0206 (5)
C17	0.5573 (3)	0.1521 (3)	0.68394 (6)	0.0246 (6)
H22	0.4644	0.1403	0.7000	0.030*
C18	0.5202 (3)	0.1609 (3)	0.64872 (6)	0.0234 (6)
H12	0.4007	0.1567	0.6413	0.028*
C19	0.7613 (3)	0.2839 (3)	0.74965 (6)	0.0203 (5)
C20	0.8431 (3)	0.2538 (3)	0.78465 (6)	0.0179 (5)
C21	0.8393 (3)	0.3476 (3)	0.83958 (6)	0.0203 (5)
C22	0.8803 (3)	0.1715 (3)	0.83888 (6)	0.0204 (5)
C23	0.8562 (3)	0.0898 (3)	0.87344 (6)	0.0267 (6)
H1A	0.7321	0.0970	0.8805	0.040*
H1B	0.9315	0.1404	0.8904	0.040*
H1C	0.8899	−0.0200	0.8714	0.040*
C24	1.0734 (3)	0.1642 (3)	0.82325 (6)	0.0216 (6)
H13A	1.1553	0.2337	0.8357	0.026*
H13B	1.1206	0.0566	0.8239	0.026*
C25	1.0473 (3)	0.2214 (3)	0.78539 (6)	0.0207 (6)
H21A	1.1163	0.3171	0.7807	0.025*
H21B	1.0810	0.1397	0.7689	0.025*
C26	0.7596 (3)	0.1213 (3)	0.80769 (6)	0.0189 (5)
C27	0.5563 (3)	0.1452 (3)	0.81403 (6)	0.0237 (6)
H20A	0.5152	0.0706	0.8311	0.036*
H20B	0.4915	0.1285	0.7928	0.036*
H20C	0.5351	0.2515	0.8221	0.036*
C28	0.7910 (3)	−0.0487 (3)	0.79516 (6)	0.0230 (6)
H17A	0.7655	−0.1216	0.8136	0.035*
H17B	0.9145	−0.0606	0.7880	0.035*
H17C	0.7126	−0.0706	0.7759	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0431 (11)	0.0225 (10)	0.0285 (10)	0.0013 (9)	0.0088 (9)	−0.0054 (8)
O2	0.0379 (10)	0.0196 (9)	0.0159 (8)	0.0049 (8)	−0.0035 (8)	−0.0026 (7)
O3	0.0398 (11)	0.0211 (10)	0.0232 (9)	0.0058 (9)	−0.0072 (8)	−0.0006 (8)
O4	0.0242 (9)	0.0175 (9)	0.0167 (8)	0.0006 (8)	−0.0013 (7)	−0.0024 (7)
O5	0.0269 (9)	0.0280 (10)	0.0217 (9)	−0.0013 (9)	−0.0003 (8)	−0.0101 (8)
C1	0.0311 (14)	0.0251 (15)	0.0144 (12)	0.0045 (13)	−0.0048 (11)	0.0011 (11)
C2	0.0342 (16)	0.0424 (18)	0.0193 (13)	0.0083 (15)	0.0020 (12)	−0.0021 (13)
C3	0.0249 (15)	0.055 (2)	0.0192 (14)	0.0014 (14)	−0.0008 (12)	0.0097 (13)
C4	0.0289 (14)	0.0354 (17)	0.0263 (15)	−0.0097 (13)	−0.0061 (12)	0.0096 (13)
C5	0.0275 (13)	0.0282 (15)	0.0226 (13)	−0.0020 (13)	−0.0012 (11)	0.0044 (12)
C6	0.0219 (12)	0.0235 (14)	0.0131 (12)	0.0031 (11)	−0.0035 (10)	0.0006 (10)
C7	0.0224 (12)	0.0183 (13)	0.0174 (12)	0.0004 (11)	−0.0020 (10)	−0.0001 (10)
C8	0.0288 (13)	0.0259 (14)	0.0213 (13)	0.0039 (13)	−0.0011 (11)	−0.0002 (11)
C9	0.0237 (13)	0.0254 (15)	0.0152 (12)	−0.0030 (12)	−0.0027 (11)	0.0012 (10)
C10	0.0382 (15)	0.0199 (14)	0.0192 (13)	−0.0033 (12)	−0.0016 (12)	−0.0019 (11)
C11	0.0539 (18)	0.0213 (15)	0.0293 (14)	0.0020 (15)	−0.0082 (14)	0.0022 (12)
C12	0.0601 (19)	0.0258 (16)	0.0286 (15)	−0.0107 (15)	−0.0091 (15)	−0.0025 (12)
C13	0.0234 (12)	0.0133 (12)	0.0169 (12)	0.0002 (11)	0.0011 (10)	−0.0017 (10)
C14	0.0232 (12)	0.0180 (13)	0.0194 (12)	−0.0002 (11)	0.0018 (11)	−0.0002 (11)
C15	0.0222 (13)	0.0184 (13)	0.0218 (13)	0.0012 (12)	−0.0043 (10)	−0.0016 (10)
C16	0.0319 (14)	0.0156 (12)	0.0142 (12)	0.0022 (12)	−0.0037 (11)	−0.0018 (10)
C17	0.0296 (14)	0.0234 (15)	0.0209 (13)	0.0032 (12)	0.0025 (11)	−0.0005 (11)
C18	0.0217 (13)	0.0241 (14)	0.0243 (14)	0.0008 (12)	−0.0023 (11)	−0.0024 (11)
C19	0.0208 (12)	0.0189 (13)	0.0213 (13)	−0.0001 (11)	0.0034 (11)	−0.0014 (10)
C20	0.0222 (12)	0.0157 (13)	0.0157 (12)	0.0017 (11)	−0.0006 (11)	−0.0034 (10)
C21	0.0138 (11)	0.0288 (14)	0.0184 (13)	−0.0024 (12)	0.0007 (10)	−0.0008 (11)
C22	0.0207 (12)	0.0245 (14)	0.0159 (12)	−0.0005 (11)	−0.0005 (10)	0.0018 (11)
C23	0.0301 (14)	0.0306 (15)	0.0194 (13)	0.0008 (13)	0.0018 (11)	0.0023 (11)
C24	0.0183 (12)	0.0266 (14)	0.0200 (13)	0.0027 (12)	0.0000 (10)	−0.0014 (11)
C25	0.0211 (13)	0.0228 (14)	0.0181 (13)	−0.0013 (11)	0.0017 (10)	−0.0002 (10)
C26	0.0188 (12)	0.0225 (14)	0.0154 (12)	0.0022 (10)	−0.0002 (10)	0.0003 (10)
C27	0.0196 (12)	0.0247 (15)	0.0268 (14)	−0.0009 (11)	0.0009 (11)	−0.0047 (11)
C28	0.0294 (14)	0.0201 (13)	0.0196 (13)	−0.0011 (11)	0.0004 (11)	0.0000 (10)

Geometric parameters (Å, º)

O1—C1	1.366 (3)	C12—H33C	0.9600
O1—C10	1.453 (3)	C13—C18	1.395 (3)
O2—C19	1.363 (3)	C13—C14	1.396 (3)
O2—C16	1.419 (3)	C14—C15	1.384 (3)
O3—C19	1.193 (3)	C14—H15	0.9300
O4—C21	1.375 (3)	C15—C16	1.366 (3)
O4—C20	1.464 (3)	C15—H16	0.9300
O5—C21	1.194 (3)	C16—C17	1.375 (3)
C1—C2	1.400 (4)	C17—C18	1.390 (3)
C1—C6	1.398 (3)	C17—H22	0.9300
C2—C3	1.369 (4)	C18—H12	0.9300
C2—H25	0.9300	C19—C20	1.503 (3)
C3—C4	1.383 (4)	C20—C25	1.535 (3)
C3—H27	0.9300	C20—C26	1.554 (3)
C4—C5	1.385 (3)	C21—C22	1.513 (4)
C4—H32	0.9300	C22—C23	1.512 (3)
C5—C6	1.388 (3)	C22—C24	1.553 (3)
C5—H29	0.9300	C22—C26	1.557 (3)
C6—C7	1.528 (3)	C23—H1A	0.9600
C7—C9	1.534 (3)	C23—H1B	0.9600
C7—C8	1.540 (3)	C23—H1C	0.9600
C7—C13	1.547 (3)	C24—C25	1.552 (3)
C8—H26A	0.9600	C24—H13A	0.9700
C8—H26B	0.9600	C24—H13B	0.9700
C8—H26C	0.9600	C25—H21A	0.9700
C9—C10	1.523 (4)	C25—H21B	0.9700
C9—H28A	0.9700	C26—C28	1.528 (3)
C9—H28B	0.9700	C26—C27	1.538 (3)
C10—C12	1.514 (4)	C27—H20A	0.9600
C10—C11	1.523 (3)	C27—H20B	0.9600
C11—H30A	0.9600	C27—H20C	0.9600
C11—H30B	0.9600	C28—H17A	0.9600
C11—H30C	0.9600	C28—H17B	0.9600
C12—H33A	0.9600	C28—H17C	0.9600
C12—H33B	0.9600
C1—O1—C10	118.97 (18)	C14—C15—H16	120.2
C19—O2—C16	117.12 (18)	C15—C16—C17	121.6 (2)
C21—O4—C20	105.76 (17)	C15—C16—O2	117.5 (2)
O1—C1—C2	114.9 (2)	C17—C16—O2	120.8 (2)
O1—C1—C6	124.8 (2)	C16—C17—C18	118.5 (2)
C2—C1—C6	120.3 (2)	C16—C17—H22	120.7
C3—C2—C1	120.5 (3)	C18—C17—H22	120.7
C3—C2—H25	119.7	C17—C18—C13	121.7 (2)
C1—C2—H25	119.7	C17—C18—H12	119.2
C2—C3—C4	120.4 (2)	C13—C18—H12	119.2
C2—C3—H27	119.8	O3—C19—O2	124.7 (2)
C4—C3—H27	119.8	O3—C19—C20	126.8 (2)
C3—C4—C5	118.6 (3)	O2—C19—C20	108.50 (19)
C3—C4—H32	120.7	O4—C20—C19	108.12 (18)
C5—C4—H32	120.7	O4—C20—C25	105.71 (19)
C4—C5—C6	122.9 (3)	C19—C20—C25	116.3 (2)
C4—C5—H29	118.6	O4—C20—C26	102.11 (17)
C6—C5—H29	118.6	C19—C20—C26	118.4 (2)
C5—C6—C1	117.2 (2)	C25—C20—C26	104.66 (19)
C5—C6—C7	121.9 (2)	O5—C21—O4	122.1 (2)
C1—C6—C7	120.8 (2)	O5—C21—C22	130.5 (2)
C6—C7—C9	107.49 (19)	O4—C21—C22	107.33 (19)
C6—C7—C8	110.21 (19)	C23—C22—C21	113.9 (2)
C9—C7—C8	107.30 (18)	C23—C22—C24	115.7 (2)
C6—C7—C13	111.47 (18)	C21—C22—C24	103.3 (2)
C9—C7—C13	112.83 (19)	C23—C22—C26	119.5 (2)
C8—C7—C13	107.48 (18)	C21—C22—C26	99.45 (19)
C7—C8—H26A	109.5	C24—C22—C26	102.48 (18)
C7—C8—H26B	109.5	C22—C23—H1A	109.5
H26A—C8—H26B	109.5	C22—C23—H1B	109.5
C7—C8—H26C	109.5	H1A—C23—H1B	109.5
H26A—C8—H26C	109.5	C22—C23—H1C	109.5
H26B—C8—H26C	109.5	H1A—C23—H1C	109.5
C10—C9—C7	115.89 (19)	H1B—C23—H1C	109.5
C10—C9—H28A	108.3	C25—C24—C22	103.85 (18)
C7—C9—H28A	108.3	C25—C24—H13A	111.0
C10—C9—H28B	108.3	C22—C24—H13A	111.0
C7—C9—H28B	108.3	C25—C24—H13B	111.0
H28A—C9—H28B	107.4	C22—C24—H13B	111.0
O1—C10—C12	104.5 (2)	H13A—C24—H13B	109.0
O1—C10—C11	107.8 (2)	C20—C25—C24	101.26 (18)
C12—C10—C11	110.2 (2)	C20—C25—H21A	111.5
O1—C10—C9	109.7 (2)	C24—C25—H21A	111.5
C12—C10—C9	110.3 (2)	C20—C25—H21B	111.5
C11—C10—C9	113.8 (2)	C24—C25—H21B	111.5
C10—C11—H30A	109.5	H21A—C25—H21B	109.3
C10—C11—H30B	109.5	C28—C26—C27	108.8 (2)
H30A—C11—H30B	109.5	C28—C26—C20	115.44 (19)
C10—C11—H30C	109.5	C27—C26—C20	112.7 (2)
H30A—C11—H30C	109.5	C28—C26—C22	114.3 (2)
H30B—C11—H30C	109.5	C27—C26—C22	113.7 (2)
C10—C12—H33A	109.5	C20—C26—C22	91.20 (18)
C10—C12—H33B	109.5	C26—C27—H20A	109.5
H33A—C12—H33B	109.5	C26—C27—H20B	109.5
C10—C12—H33C	109.5	H20A—C27—H20B	109.5
H33A—C12—H33C	109.5	C26—C27—H20C	109.5
H33B—C12—H33C	109.5	H20A—C27—H20C	109.5
C18—C13—C14	117.6 (2)	H20B—C27—H20C	109.5
C18—C13—C7	119.8 (2)	C26—C28—H17A	109.5
C14—C13—C7	122.6 (2)	C26—C28—H17B	109.5
C15—C14—C13	121.0 (2)	H17A—C28—H17B	109.5
C15—C14—H15	119.5	C26—C28—H17C	109.5
C13—C14—H15	119.5	H17A—C28—H17C	109.5
C16—C15—C14	119.7 (2)	H17B—C28—H17C	109.5
C16—C15—H16	120.2
O4—C20—C19—O2	−177.68 (17)	C13—C7—C6—C5	−77.6 (3)
C20—C19—O2—C16	−171.26 (19)	C13—C7—C9—C10	−77.2 (3)
C14—C13—C7—C6	3.3 (3)

(Ia) (R,S)-4-(2,2,4-trimethylchroman-4-yl)phenyl 4,7,7-trimethyl-3-oxo-2-oxobicyclo[2.2.1]heptane-1-carboxylate

Crystal data

C28H32O5	Dx = 1.263 Mg m^−3
Mr = 448.54	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 5449 reflections
a = 7.0710 (5) Å	θ = 2.5–28°
b = 6.8500 (4) Å	µ = 0.09 mm^−1
c = 48.717 (4) Å	T = 100 K
V = 2359.7 (3) Å^3	Prism, colourless
Z = 4	0.22 × 0.21 × 0.17 mm
F(000) = 960

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2734 independent reflections
Radiation source: fine-focus sealed tube	2282 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.064
ω scans	θmax = 26.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −8→7
Tmin = 0.98, Tmax = 0.99	k = −8→7
13513 measured reflections	l = −56→60

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.067	H-atom parameters constrained
wR(F^2) = 0.131	w = 1/[σ^2(Fo^2) + (0.0295P)^2 + 0.4167P] where P = (Fo^2 + 2Fc^2)/3
S = 1.19	(Δ/σ)max = 0.023
2734 reflections	Δρmax = 0.20 e Å^−3
489 parameters	Δρmin = −0.15 e Å^−3
324 restraints	Absolute structure: Flack (1983), with how many Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0 (10)

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	0.2037 (4)	0.9058 (4)	0.22151 (5)	0.0365 (7)
O2A	0.4971 (8)	0.3496 (7)	0.09074 (10)	0.0274 (12)	0.499 (2)
O3A	0.4242 (7)	0.4910 (7)	0.05025 (10)	0.0343 (13)	0.499 (2)
O4A	0.5944 (7)	0.2045 (7)	0.02180 (9)	0.0295 (12)	0.499 (2)
O5A	0.7556 (8)	0.0368 (8)	−0.01025 (10)	0.0443 (15)	0.499 (2)
O2B	0.6073 (8)	0.3151 (7)	0.09938 (12)	0.0315 (13)	0.501 (2)
O3B	0.8611 (7)	0.4875 (7)	0.08615 (11)	0.0418 (14)	0.501 (2)
O4B	0.808 (2)	−0.009 (3)	0.0883 (4)	0.038 (4)	0.501 (2)
O5B	0.8106 (7)	−0.3348 (6)	0.07809 (10)	0.0321 (12)	0.501 (2)
C1	0.3467 (5)	1.0097 (5)	0.20951 (7)	0.0294 (8)
C2	0.4712 (6)	1.1012 (5)	0.22744 (8)	0.0358 (9)
H2	0.4543	1.0867	0.2463	0.043*
C3	0.6179 (6)	1.2119 (5)	0.21794 (8)	0.0380 (10)
H3	0.6995	1.2729	0.2302	0.046*
C4	0.6443 (6)	1.2329 (5)	0.19001 (8)	0.0374 (9)
H4	0.7450	1.3061	0.1833	0.045*
C5	0.5196 (6)	1.1441 (5)	0.17219 (8)	0.0365 (10)
H5	0.5363	1.1609	0.1534	0.044*
C6	0.3699 (5)	1.0302 (4)	0.18141 (7)	0.0268 (8)
C7	0.2296 (6)	0.9401 (5)	0.16103 (7)	0.0368 (10)
C8	0.1578 (8)	1.1024 (6)	0.14153 (9)	0.0599 (15)
H11A	0.1254	1.2161	0.1521	0.090*
H11B	0.0481	1.0569	0.1319	0.090*
H11C	0.2553	1.1349	0.1286	0.090*
C9	0.0592 (6)	0.8626 (5)	0.17724 (8)	0.0398 (10)
H9A	−0.0265	0.9706	0.1806	0.048*
H9B	−0.0070	0.7689	0.1658	0.048*
C10	0.1031 (5)	0.7661 (5)	0.20458 (7)	0.0320 (9)
C11	0.2215 (7)	0.5821 (5)	0.20246 (8)	0.0462 (11)
H12A	0.3452	0.6145	0.1957	0.069*
H12B	0.1619	0.4923	0.1900	0.069*
H12C	0.2322	0.5229	0.2203	0.069*
C12	−0.0781 (6)	0.7256 (7)	0.22024 (9)	0.0500 (11)
H7A	−0.0479	0.6778	0.2382	0.075*
H7B	−0.1511	0.6294	0.2106	0.075*
H7C	−0.1501	0.8439	0.2218	0.075*
C13A	0.2858 (13)	0.7889 (18)	0.1430 (3)	0.021 (2)	0.499 (2)
C14A	0.1719 (12)	0.7071 (13)	0.12248 (19)	0.0252 (17)	0.499 (2)
H25	0.0468	0.7473	0.1208	0.030*	0.499 (2)
C15A	0.2426 (13)	0.5663 (11)	0.10452 (16)	0.0273 (16)	0.499 (2)
H24	0.1652	0.5130	0.0910	0.033*	0.499 (2)
C16A	0.4272 (15)	0.5069 (15)	0.1070 (2)	0.024 (2)	0.499 (2)
C17A	0.5417 (12)	0.5793 (13)	0.12682 (18)	0.0241 (16)	0.499 (2)
H22	0.6652	0.5343	0.1287	0.029*	0.499 (2)
C18A	0.4709 (15)	0.7231 (15)	0.14455 (19)	0.019 (2)	0.499 (2)
H21	0.5506	0.7760	0.1578	0.023*	0.499 (2)
C19A	0.4878 (10)	0.3604 (10)	0.06311 (14)	0.0234 (15)	0.499 (2)
C20A	0.5669 (11)	0.1716 (13)	0.05113 (15)	0.0224 (17)	0.499 (2)
C21A	0.7046 (10)	0.0531 (9)	0.01326 (14)	0.0254 (15)	0.499 (2)
C22A	0.7498 (12)	−0.0733 (12)	0.03762 (17)	0.0225 (16)	0.499 (2)
C23A	0.9171 (10)	−0.2070 (11)	0.03356 (15)	0.0313 (18)	0.499 (2)
H36A	1.0215	−0.1336	0.0263	0.047*	0.499 (2)
H36B	0.8839	−0.3088	0.0209	0.047*	0.499 (2)
H36C	0.9523	−0.2635	0.0508	0.047*	0.499 (2)
C24A	0.5573 (10)	−0.1740 (10)	0.04406 (14)	0.0273 (15)	0.499 (2)
H41A	0.5072	−0.2393	0.0280	0.033*	0.499 (2)
H41B	0.5704	−0.2681	0.0588	0.033*	0.499 (2)
C25A	0.4314 (13)	−0.0036 (12)	0.05265 (18)	0.0282 (19)	0.499 (2)
H33A	0.3833	−0.0215	0.0711	0.034*	0.499 (2)
H33B	0.3258	0.0122	0.0401	0.034*	0.499 (2)
C26A	0.7585 (11)	0.0886 (11)	0.0603 (2)	0.0227 (15)	0.499 (2)
C27A	0.9196 (11)	0.2236 (13)	0.0573 (2)	0.042 (2)	0.499 (2)
H37A	1.0353	0.1553	0.0611	0.063*	0.499 (2)
H37B	0.9058	0.3301	0.0700	0.063*	0.499 (2)
H37C	0.9228	0.2732	0.0389	0.063*	0.499 (2)
C28A	0.765 (3)	−0.006 (3)	0.0887 (5)	0.029 (4)	0.499 (2)
H31A	0.8735	−0.0896	0.0899	0.043*	0.499 (2)
H31B	0.6522	−0.0815	0.0915	0.043*	0.499 (2)
H31C	0.7730	0.0937	0.1025	0.043*	0.499 (2)
C13B	0.3552 (15)	0.7706 (16)	0.1437 (2)	0.0156 (19)	0.501 (2)
C14B	0.5421 (13)	0.7091 (16)	0.1495 (2)	0.023 (2)	0.501 (2)
H15	0.6082	0.7681	0.1637	0.027*	0.501 (2)
C15B	0.6284 (12)	0.5640 (12)	0.13444 (16)	0.0280 (17)	0.501 (2)
H16	0.7521	0.5270	0.1383	0.034*	0.501 (2)
C16B	0.5303 (14)	0.4750 (12)	0.11382 (18)	0.0285 (16)	0.501 (2)
C17B	0.3500 (16)	0.5289 (16)	0.1071 (2)	0.027 (2)	0.501 (2)
H18	0.2873	0.4685	0.0927	0.032*	0.501 (2)
C18B	0.2603 (12)	0.6767 (13)	0.12240 (18)	0.0253 (17)	0.501 (2)
H19	0.1366	0.7120	0.1182	0.030*	0.501 (2)
C19B	0.7709 (10)	0.3366 (10)	0.08623 (13)	0.0219 (15)	0.501 (2)
C20B	0.8297 (12)	0.1562 (11)	0.07056 (15)	0.0202 (15)	0.501 (2)
C21B	0.8111 (9)	−0.1708 (10)	0.06967 (14)	0.0232 (15)	0.501 (2)
C22B	0.8324 (12)	−0.0899 (12)	0.04133 (16)	0.0188 (15)	0.501 (2)
C23B	0.7777 (10)	−0.2321 (10)	0.01850 (15)	0.0317 (17)	0.501 (2)
H45A	0.8546	−0.3473	0.0198	0.048*	0.501 (2)
H45B	0.7972	−0.1712	0.0010	0.048*	0.501 (2)
H45C	0.6469	−0.2672	0.0204	0.048*	0.501 (2)
C24B	1.0378 (9)	−0.0161 (10)	0.04071 (14)	0.0251 (14)	0.501 (2)
H28A	1.0727	0.0275	0.0225	0.030*	0.501 (2)
H28B	1.1249	−0.1175	0.0465	0.030*	0.501 (2)
C25B	1.0374 (10)	0.1568 (11)	0.06133 (16)	0.0228 (14)	0.501 (2)
H13A	1.1225	0.1332	0.0766	0.027*	0.501 (2)
H13B	1.0712	0.2787	0.0525	0.027*	0.501 (2)
C26B	0.7133 (10)	0.1025 (10)	0.04439 (16)	0.0200 (15)	0.501 (2)
C27B	0.5033 (12)	0.0701 (16)	0.04965 (17)	0.030 (2)	0.501 (2)
H39A	0.4425	0.1936	0.0526	0.045*	0.501 (2)
H39B	0.4876	−0.0106	0.0656	0.045*	0.501 (2)
H39C	0.4475	0.0068	0.0340	0.045*	0.501 (2)
C28B	0.7365 (12)	0.2463 (11)	0.02115 (15)	0.0327 (17)	0.501 (2)
H26A	0.6964	0.1869	0.0043	0.049*	0.501 (2)
H26B	0.8670	0.2836	0.0197	0.049*	0.501 (2)
H26C	0.6608	0.3599	0.0247	0.049*	0.501 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0437 (16)	0.0394 (14)	0.0264 (14)	−0.0017 (14)	0.0001 (12)	−0.0041 (12)
O2A	0.033 (3)	0.027 (3)	0.022 (3)	0.008 (3)	0.002 (2)	−0.004 (2)
O3A	0.037 (3)	0.032 (3)	0.034 (3)	0.012 (3)	−0.002 (2)	0.003 (2)
O4A	0.033 (3)	0.034 (3)	0.022 (3)	0.010 (3)	−0.004 (2)	0.002 (2)
O5A	0.059 (4)	0.049 (3)	0.025 (3)	0.013 (3)	0.013 (3)	0.002 (2)
O2B	0.029 (3)	0.022 (3)	0.043 (3)	−0.006 (3)	0.011 (3)	−0.015 (2)
O3B	0.041 (3)	0.026 (3)	0.059 (4)	−0.011 (3)	0.025 (3)	−0.010 (3)
O4B	0.035 (6)	0.047 (6)	0.032 (6)	0.002 (5)	0.003 (4)	0.001 (5)
O5B	0.034 (3)	0.023 (3)	0.039 (3)	0.001 (2)	0.010 (2)	0.003 (2)
C1	0.039 (2)	0.0233 (17)	0.0263 (19)	0.0082 (18)	−0.0047 (16)	−0.0065 (15)
C2	0.045 (2)	0.035 (2)	0.027 (2)	0.009 (2)	−0.0045 (18)	−0.0066 (17)
C3	0.046 (2)	0.029 (2)	0.039 (2)	0.004 (2)	−0.0141 (19)	−0.0130 (17)
C4	0.039 (2)	0.0296 (19)	0.043 (2)	−0.0002 (19)	0.0012 (19)	−0.0029 (17)
C5	0.057 (3)	0.0229 (18)	0.030 (2)	0.008 (2)	−0.0001 (19)	−0.0022 (16)
C6	0.041 (2)	0.0136 (16)	0.0263 (18)	0.0043 (17)	−0.0037 (16)	−0.0021 (14)
C7	0.062 (3)	0.0196 (18)	0.029 (2)	−0.004 (2)	−0.0135 (19)	0.0012 (15)
C8	0.098 (4)	0.033 (2)	0.049 (3)	−0.011 (3)	−0.040 (3)	0.008 (2)
C9	0.050 (3)	0.026 (2)	0.043 (2)	0.001 (2)	−0.016 (2)	−0.0072 (18)
C10	0.040 (2)	0.0255 (19)	0.031 (2)	0.0019 (18)	−0.0029 (17)	−0.0049 (16)
C11	0.064 (3)	0.031 (2)	0.044 (2)	0.008 (2)	0.009 (2)	0.0098 (18)
C12	0.051 (3)	0.048 (3)	0.051 (3)	−0.001 (2)	0.007 (2)	−0.007 (2)
C13A	0.017 (4)	0.019 (4)	0.026 (4)	0.000 (4)	0.004 (4)	0.005 (3)
C14A	0.016 (3)	0.030 (4)	0.029 (3)	0.006 (3)	−0.001 (3)	−0.001 (3)
C15A	0.026 (4)	0.027 (3)	0.028 (3)	0.002 (3)	−0.003 (3)	−0.006 (3)
C16A	0.022 (5)	0.021 (4)	0.027 (3)	0.002 (4)	−0.001 (4)	−0.003 (3)
C17A	0.017 (3)	0.025 (3)	0.031 (4)	0.006 (3)	−0.004 (3)	0.004 (3)
C18A	0.017 (4)	0.018 (4)	0.023 (4)	0.003 (4)	−0.003 (4)	−0.004 (3)
C19A	0.024 (4)	0.022 (3)	0.024 (4)	−0.002 (3)	0.000 (3)	0.005 (3)
C20A	0.008 (4)	0.039 (5)	0.020 (4)	−0.004 (4)	0.000 (3)	0.008 (4)
C21A	0.024 (3)	0.028 (3)	0.024 (3)	0.000 (3)	0.001 (3)	−0.002 (3)
C22A	0.019 (3)	0.024 (3)	0.024 (3)	−0.001 (3)	−0.003 (3)	−0.005 (3)
C23A	0.031 (4)	0.031 (4)	0.032 (4)	0.007 (4)	0.004 (3)	−0.003 (3)
C24A	0.031 (3)	0.026 (3)	0.025 (3)	−0.009 (3)	0.002 (3)	−0.010 (3)
C25A	0.033 (5)	0.024 (4)	0.028 (4)	−0.007 (4)	0.004 (3)	−0.008 (3)
C26A	0.012 (3)	0.022 (3)	0.034 (4)	0.000 (3)	−0.012 (3)	−0.009 (3)
C27A	0.007 (4)	0.041 (5)	0.077 (6)	0.006 (4)	−0.006 (4)	−0.029 (5)
C28A	0.051 (10)	0.016 (6)	0.019 (7)	−0.006 (6)	−0.025 (7)	−0.001 (5)
C13B	0.014 (5)	0.013 (3)	0.020 (3)	0.009 (4)	0.002 (4)	−0.003 (3)
C14B	0.023 (4)	0.023 (3)	0.022 (4)	0.008 (4)	−0.001 (3)	0.002 (3)
C15B	0.024 (4)	0.032 (4)	0.028 (4)	0.003 (3)	0.000 (3)	0.003 (3)
C16B	0.031 (4)	0.024 (4)	0.031 (4)	−0.008 (4)	0.006 (3)	0.001 (3)
C17B	0.024 (5)	0.026 (4)	0.030 (4)	−0.004 (4)	0.002 (4)	−0.006 (3)
C18B	0.019 (4)	0.026 (3)	0.031 (4)	0.002 (3)	−0.002 (4)	−0.002 (3)
C19B	0.024 (4)	0.025 (4)	0.017 (3)	0.005 (3)	0.004 (3)	0.002 (3)
C20B	0.009 (4)	0.029 (4)	0.022 (4)	−0.006 (3)	−0.003 (3)	0.000 (3)
C21B	0.013 (3)	0.024 (3)	0.033 (3)	−0.004 (3)	−0.001 (3)	−0.011 (3)
C22B	0.015 (3)	0.020 (3)	0.022 (3)	−0.003 (3)	0.000 (3)	−0.006 (3)
C23B	0.029 (4)	0.034 (4)	0.033 (4)	−0.008 (3)	−0.002 (3)	−0.012 (3)
C24B	0.020 (3)	0.029 (3)	0.027 (3)	−0.002 (3)	0.000 (2)	−0.009 (3)
C25B	0.012 (3)	0.030 (3)	0.027 (3)	−0.002 (3)	−0.001 (3)	−0.005 (3)
C26B	0.011 (3)	0.026 (3)	0.023 (3)	−0.006 (3)	−0.003 (3)	−0.004 (3)
C27B	0.017 (5)	0.045 (7)	0.029 (5)	−0.008 (4)	0.000 (4)	0.003 (5)
C28B	0.028 (4)	0.037 (4)	0.033 (4)	0.005 (4)	−0.003 (3)	0.009 (3)

Geometric parameters (Å, º)

O1—C1	1.368 (4)	C20A—C25A	1.537 (11)
O1—C10	1.450 (4)	C20A—C26A	1.536 (11)
O2A—C19A	1.350 (8)	C21A—C22A	1.503 (10)
O2A—C16A	1.424 (11)	C22A—C23A	1.509 (10)
O3A—C19A	1.181 (8)	C22A—C24A	1.557 (11)
O4A—C21A	1.362 (8)	C22A—C26A	1.568 (12)
O4A—C20A	1.460 (9)	C23A—H36A	0.9600
O5A—C21A	1.206 (8)	C23A—H36B	0.9600
O2B—C19B	1.331 (8)	C23A—H36C	0.9600
O2B—C16B	1.411 (10)	C24A—C25A	1.527 (11)
O3B—C19B	1.215 (8)	C24A—H41A	0.9700
O3B—O5B^i	1.328 (7)	C24A—H41B	0.9700
O4B—C20B	1.43 (2)	C25A—H33A	0.9700
O4B—C21B	1.429 (18)	C25A—H33B	0.9700
O5B—C21B	1.196 (8)	C26A—C27A	1.475 (11)
O5B—O3B^ii	1.328 (7)	C26A—C28A	1.53 (3)
C1—C6	1.386 (5)	C27A—H37A	0.9600
C1—C2	1.389 (5)	C27A—H37B	0.9600
C2—C3	1.366 (5)	C27A—H37C	0.9600
C2—H2	0.9300	C28A—H31A	0.9600
C3—C4	1.381 (5)	C28A—H31B	0.9600
C3—H3	0.9300	C28A—H31C	0.9600
C4—C5	1.379 (5)	C13B—C18B	1.394 (13)
C4—H4	0.9300	C13B—C14B	1.415 (11)
C5—C6	1.390 (5)	C14B—C15B	1.378 (12)
C5—H5	0.9300	C14B—H15	0.9300
C6—C7	1.533 (5)	C15B—C16B	1.364 (12)
C7—C13A	1.417 (13)	C15B—H16	0.9300
C7—C9	1.535 (6)	C16B—C17B	1.367 (12)
C7—C8	1.548 (5)	C17B—C18B	1.407 (14)
C7—C13B	1.688 (11)	C17B—H18	0.9300
C8—H11A	0.9600	C18B—H19	0.9300
C8—H11B	0.9600	C19B—C20B	1.511 (10)
C8—H11C	0.9600	C20B—C25B	1.536 (10)
C9—C10	1.519 (5)	C20B—C26B	1.561 (10)
C9—H9A	0.9700	C21B—C22B	1.495 (10)
C9—H9B	0.9700	C22B—C23B	1.529 (10)
C10—C12	1.517 (5)	C22B—C24B	1.538 (10)
C10—C11	1.517 (5)	C22B—C26B	1.571 (11)
C11—H12A	0.9600	C23B—H45A	0.9600
C11—H12B	0.9600	C23B—H45B	0.9600
C11—H12C	0.9600	C23B—H45C	0.9600
C12—H7A	0.9600	C24B—C25B	1.553 (10)
C12—H7B	0.9600	C24B—H28A	0.9700
C12—H7C	0.9600	C24B—H28B	0.9700
C13A—C18A	1.386 (11)	C25B—H13A	0.9700
C13A—C14A	1.399 (14)	C25B—H13B	0.9700
C14A—C15A	1.395 (11)	C26B—C28B	1.509 (10)
C14A—H25	0.9300	C26B—C27B	1.523 (10)
C15A—C16A	1.372 (11)	C27B—H39A	0.9600
C15A—H24	0.9300	C27B—H39B	0.9600
C16A—C17A	1.356 (14)	C27B—H39C	0.9600
C17A—C18A	1.403 (13)	C28B—H26A	0.9600
C17A—H22	0.9300	C28B—H26B	0.9600
C18A—H21	0.9300	C28B—H26C	0.9600
C19A—C20A	1.525 (11)
C1—O1—C10	117.6 (3)	C21A—C22A—C24A	103.2 (6)
C19A—O2A—C16A	119.6 (7)	C23A—C22A—C24A	116.3 (6)
C21A—O4A—C20A	104.9 (5)	C21A—C22A—C26A	99.1 (7)
C19B—O2B—C16B	119.3 (6)	C23A—C22A—C26A	119.4 (7)
C19B—O3B—O5B^i	129.8 (6)	C24A—C22A—C26A	101.8 (6)
C20B—O4B—C21B	103.3 (12)	C22A—C23A—H36A	109.5
C21B—O5B—O3B^ii	164.1 (6)	C22A—C23A—H36B	109.5
O1—C1—C6	124.2 (3)	H36A—C23A—H36B	109.5
O1—C1—C2	115.7 (3)	C22A—C23A—H36C	109.5
C6—C1—C2	120.0 (4)	H36A—C23A—H36C	109.5
C3—C2—C1	121.3 (4)	H36B—C23A—H36C	109.5
C3—C2—H2	119.4	C25A—C24A—C22A	103.1 (6)
C1—C2—H2	119.4	C25A—C24A—H41A	111.1
C2—C3—C4	119.6 (4)	C22A—C24A—H41A	111.1
C2—C3—H3	120.2	C25A—C24A—H41B	111.1
C4—C3—H3	120.2	C22A—C24A—H41B	111.1
C5—C4—C3	119.2 (4)	H41A—C24A—H41B	109.1
C5—C4—H4	120.4	C24A—C25A—C20A	102.7 (7)
C3—C4—H4	120.4	C24A—C25A—H33A	111.2
C4—C5—C6	122.1 (4)	C20A—C25A—H33A	111.2
C4—C5—H5	119.0	C24A—C25A—H33B	111.2
C6—C5—H5	119.0	C20A—C25A—H33B	111.2
C1—C6—C5	117.8 (3)	H33A—C25A—H33B	109.1
C1—C6—C7	121.5 (3)	C27A—C26A—C28A	109.5 (11)
C5—C6—C7	120.6 (3)	C27A—C26A—C20A	114.8 (7)
C13A—C7—C6	121.0 (5)	C28A—C26A—C20A	116.6 (11)
C13A—C7—C9	106.7 (5)	C27A—C26A—C22A	113.8 (7)
C6—C7—C9	108.3 (3)	C28A—C26A—C22A	109.9 (10)
C13A—C7—C8	103.6 (6)	C20A—C26A—C22A	91.2 (7)
C6—C7—C8	108.7 (3)	C26A—C27A—H37A	109.5
C9—C7—C8	107.9 (4)	C26A—C27A—H37B	109.5
C13A—C7—C13B	16.0 (6)	H37A—C27A—H37B	109.5
C6—C7—C13B	105.0 (5)	C26A—C27A—H37C	109.5
C9—C7—C13B	115.6 (5)	H37A—C27A—H37C	109.5
C8—C7—C13B	111.1 (5)	H37B—C27A—H37C	109.5
C7—C8—H11A	109.5	C26A—C28A—H31A	109.5
C7—C8—H11B	109.5	C26A—C28A—H31B	109.5
H11A—C8—H11B	109.5	H31A—C28A—H31B	109.5
C7—C8—H11C	109.5	C26A—C28A—H31C	109.5
H11A—C8—H11C	109.5	H31A—C28A—H31C	109.5
H11B—C8—H11C	109.5	H31B—C28A—H31C	109.5
C10—C9—C7	116.2 (3)	C18B—C13B—C14B	117.4 (9)
C10—C9—H9A	108.2	C18B—C13B—C7	115.9 (7)
C7—C9—H9A	108.2	C14B—C13B—C7	126.7 (8)
C10—C9—H9B	108.2	C15B—C14B—C13B	121.5 (9)
C7—C9—H9B	108.2	C15B—C14B—H15	119.2
H9A—C9—H9B	107.4	C13B—C14B—H15	119.2
O1—C10—C12	104.4 (3)	C16B—C15B—C14B	119.3 (8)
O1—C10—C11	108.5 (3)	C16B—C15B—H16	120.4
C12—C10—C11	110.4 (3)	C14B—C15B—H16	120.4
O1—C10—C9	108.2 (3)	C15B—C16B—C17B	121.9 (9)
C12—C10—C9	110.4 (3)	C15B—C16B—O2B	121.2 (8)
C11—C10—C9	114.5 (3)	C17B—C16B—O2B	116.8 (9)
C10—C11—H12A	109.5	C16B—C17B—C18B	119.3 (10)
C10—C11—H12B	109.5	C16B—C17B—H18	120.4
H12A—C11—H12B	109.5	C18B—C17B—H18	120.4
C10—C11—H12C	109.5	C13B—C18B—C17B	120.6 (8)
H12A—C11—H12C	109.5	C13B—C18B—H19	119.7
H12B—C11—H12C	109.5	C17B—C18B—H19	119.7
C10—C12—H7A	109.5	O3B—C19B—O2B	123.5 (6)
C10—C12—H7B	109.5	O3B—C19B—C20B	123.4 (6)
H7A—C12—H7B	109.5	O2B—C19B—C20B	113.1 (6)
C10—C12—H7C	109.5	O4B—C20B—C19B	108.3 (9)
H7A—C12—H7C	109.5	O4B—C20B—C25B	106.2 (8)
H7B—C12—H7C	109.5	C19B—C20B—C25B	114.1 (7)
C18A—C13A—C14A	117.0 (10)	O4B—C20B—C26B	104.4 (9)
C18A—C13A—C7	117.9 (9)	C19B—C20B—C26B	117.4 (6)
C14A—C13A—C7	125.1 (8)	C25B—C20B—C26B	105.4 (6)
C15A—C14A—C13A	121.2 (8)	O5B—C21B—O4B	120.6 (10)
C15A—C14A—H25	119.4	O5B—C21B—C22B	131.7 (6)
C13A—C14A—H25	119.4	O4B—C21B—C22B	107.5 (9)
C16A—C15A—C14A	119.4 (8)	C21B—C22B—C23B	114.2 (6)
C16A—C15A—H24	120.3	C21B—C22B—C24B	103.6 (6)
C14A—C15A—H24	120.3	C23B—C22B—C24B	115.7 (7)
C17A—C16A—C15A	121.4 (9)	C21B—C22B—C26B	99.8 (6)
C17A—C16A—O2A	117.7 (9)	C23B—C22B—C26B	117.9 (7)
C15A—C16A—O2A	120.4 (9)	C24B—C22B—C26B	103.4 (6)
C16A—C17A—C18A	118.9 (8)	C22B—C24B—C25B	103.7 (5)
C16A—C17A—H22	120.5	C22B—C24B—H28A	111.0
C18A—C17A—H22	120.5	C25B—C24B—H28A	111.0
C13A—C18A—C17A	122.0 (9)	C22B—C24B—H28B	111.0
C13A—C18A—H21	119.0	C25B—C24B—H28B	111.0
C17A—C18A—H21	119.0	H28A—C24B—H28B	109.0
O3A—C19A—O2A	126.1 (7)	C20B—C25B—C24B	100.9 (6)
O3A—C19A—C20A	125.4 (6)	C20B—C25B—H13A	111.6
O2A—C19A—C20A	108.5 (6)	C24B—C25B—H13A	111.6
O4A—C20A—C19A	107.0 (6)	C20B—C25B—H13B	111.6
O4A—C20A—C25A	104.5 (7)	C24B—C25B—H13B	111.6
C19A—C20A—C25A	114.5 (7)	H13A—C25B—H13B	109.4
O4A—C20A—C26A	103.0 (6)	C28B—C26B—C27B	109.1 (7)
C19A—C20A—C26A	121.7 (7)	C28B—C26B—C20B	113.7 (6)
C25A—C20A—C26A	104.3 (7)	C27B—C26B—C20B	114.3 (6)
O5A—C21A—O4A	122.1 (6)	C28B—C26B—C22B	114.7 (6)
O5A—C21A—C22A	129.2 (7)	C27B—C26B—C22B	114.6 (7)
O4A—C21A—C22A	108.6 (6)	C20B—C26B—C22B	89.5 (6)
C21A—C22A—C23A	114.4 (7)
O4A—C20A—C19A—O2A	−167.5 (6)	O4B—C20B—C19B—O2B	−47.3 (11)
C20A—C19A—O2A—C16A	−178.5 (7)	C20B—C19B—O2B—C16B	−177.0 (7)
C14A—C13A—C7—C6	−175.5 (8)	C14B—C13B—C7—C6	7.4 (11)
C13A—C7—C6—C5	68.8 (7)	C13B—C7—C6—C5	68.2 (5)
C13A—C7—C9—C10	92.9 (6)	C13B—C7—C9—C10	78.6 (5)

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