(4aSR,7RS,9aRS)-7-tert-Butyl-9a-methyl-5,5-dioxo-1,2,4a,9a-tetra­hydro-8-oxa-5λ⁶-thia­benzocyclo­heptan-9-one

The title compound, C₁₄H₂₂O₄S, crystallizes with two crystallographically independent mol­ecules in the asymmetric unit. In both mol­ecules, the six-membered ring exhibits a sofa conformation while the seven-membered ring is in a boat-like conformation with the tert-butyl group in a pseudo-equatorial position.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.038
• wR factor = 0.100
• Data-to-parameter ratio = 20.5

checkCIF/PLATON results

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Alert level C
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          9

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
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   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
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   1 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

As detailed in an earlier series of articles (Zeller et al., 2004a,b,c,d; Chumachenko et al., 2005), two of the current authors (NC and PS) have been exploring the potential utility of sulfone-based tethers in intramolecular Diels–Alder cycloaddition reactions. This has resulted in the preparation of a series of bicyclic β-acyloxy sulfone cycloadducts, several of which have been subjected to analysis using single-crystal X-ray diffraction. In the present paper, the solid-state structure of the title cycloadduct, (I), as established by single-crystal X-ray diffraction methods, is described.

The title compound was isolated as one of three diastereomers from an intramolecular Diels–Alder cycloaddition reaction of 1-[(E)-butadienesulfonyl]-3,3-dimethyl-2-butyl methacrylate in toluene at 441 K (Chumachenko et al., 2005) (see scheme).

Compound (I) crystallizes in the monoclinic space group P2₁/c with Z = 8 and two crystallographically independent molecules in the asymmetric unit, as a racemic mixture of both enantiomers (Fig. 1). The conformations of the two independent molecules are almost identical. Bond lengths and angles differ only marginally, and the weighted r.m.s. deviation for the molecule fit is 0.0445 Å.

The six-membered ring may be described as in a sofa conformation with only C9a being non-coplanar with the other atoms of the ring. The deviation for C9a (or C9a') from the least-squares plane defined by C1 to C4a (or C1' to C4a') is 0.699 (2) Å, the largest deviation of any atom defining the plane is 0.1069 (9) Å for C2'. This differentiates the exo compound (I) from four similar endo cycloadducts described previously (Zeller et al., 2004a,b,c,d). Each of these compounds exhibited a half-chair conformation that is not easily accessible for the exo-adduct (I) described here. The angles at the unsaturated C atoms in (I) are 123.2 (1), 123.1 (1), 122.6 (1), and 122.8 (1)° for C4a—C4—C3, C4a'—C4'—C3', C4—C3—C2, and C4'—C3'—C2', respectively.

The seven-membered ring displays a boat-like conformation with the bulky tert-butyl group in a pseudo-equatorial position. In the crystal structure, some weak intermolecular C—H···O interactions with distances in the range 2.3–2.5 Å are found [O3···H4A'ⁱ = 2.39 Å, H6B'···O1'ⁱⁱ = 2.30 Å, O1···H6Bⁱⁱⁱ = 2.43 Å; symmetry codes: (i) x, y − 1, z; (ii) 2 − x, y − 1/2, 1/2 − z; (iii) 1 − x, y + 1/2, 1/2 − z]. These interactions seem to be somehow symmetrical, i.e. the interaction between S═O atom O1 and H6Bⁱⁱⁱ is similarly present for O1'ⁱⁱ and H6B' of the other symmetry-independent molecule, and for the interaction of C═O atom O3 with H4A'ⁱ a similar but less pronounced counterpart is also found (O3'···H4A = 2.68 Å). This symmetric arrangement of the short contacts can be seen an indication that these weak interactions may play a significant role as a driving force towards the kind of packing present in the crystal structure of (I). All bond lengths and angles of (I) are within their expected ranges.

S2. Experimental

The title compound was synthesized as described by Chumachenko et al. (2005) as a mixture of the exo- and two endo-cycloadducts, (I), (II) and (III), in a ratio of 12/100/4 as established by ¹H NMR of the crude reaction product (see scheme). The major endo compound (II) was removed from the mixture by selective crystallization in 1:3 e thyl acetate–hexanes. [The single-crystal structure of (II) is described in the next article of this series.] The mother liquor was then evaporated to dryness and the exo compound (I) was isolated by column chromatography (dichloromethane) and purified by recrystallization from a minimal amount of ethyl acetate to yield crystals suitable for X-ray structural analysis.

S3. Refinement

All H atoms were positioned geometrically, with a C—H bond distance of 1.00 or 0.99 Å. They were refined with isotropic displacement parameters of 1.5 (methyl) or 1.2 times (all others) that of the equivalent isotropic displacement parameter of the carrier C atom. Methyl H atoms were allowed to rotate to best fit the experimental data. The s.u. values of the cell parameters are taken from the software, recognizing that the values are unreasonably small (Herbstein, 2000).

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids. Both crystallographically independent molecules are shown.

(4aSR,7RS,9aRS)-7-tert-Butyl-9a-methyl-5,5-dioxo-1,2,4a,9a-tetrahydro-8-oxa- 5λ⁶-thiabenzocycloheptan-9-one

Crystal data

C14H22O4S	F(000) = 1232
Mr = 286.38	Dx = 1.314 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8187 reflections
a = 15.5204 (7) Å	θ = 2.3–30.5°
b = 9.8367 (4) Å	µ = 0.23 mm^−1
c = 23.0445 (10) Å	T = 100 K
β = 124.626 (1)°	Block, colourless
V = 2895.0 (2) Å^3	0.43 × 0.42 × 0.29 mm
Z = 8

Data collection

Bruker AXS SMART APEX CCD diffractometer	7195 independent reflections
Radiation source: fine-focus sealed tube	6801 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ω scans	θmax = 28.3°, θmin = 1.6°
Absorption correction: multi-scan (SADABS in SAINT-Plus; Bruker, 2003)	h = −20→20
Tmin = 0.891, Tmax = 0.935	k = −13→13
29131 measured reflections	l = −30→30

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0529P)^2 + 1.2868P] where P = (Fo^2 + 2Fc^2)/3
7195 reflections	(Δ/σ)max = 0.002
351 parameters	Δρmax = 0.49 e Å^−3
0 restraints	Δρmin = −0.52 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
C4A	0.56271 (9)	0.31776 (12)	0.15960 (6)	0.0150 (2)
H4A	0.6039	0.4000	0.1868	0.018*
C4	0.48733 (10)	0.36073 (13)	0.08363 (6)	0.0195 (2)
H4	0.4244	0.4052	0.0706	0.023*
C3	0.50479 (10)	0.33945 (15)	0.03439 (7)	0.0241 (3)
H3	0.4530	0.3666	−0.0126	0.029*
C2	0.60266 (11)	0.27443 (16)	0.04986 (7)	0.0276 (3)
H2A	0.6305	0.3288	0.0278	0.033*
H2B	0.5859	0.1826	0.0285	0.033*
C1	0.68671 (10)	0.26253 (15)	0.12893 (7)	0.0226 (3)
H1A	0.7187	0.3529	0.1477	0.027*
H1B	0.7424	0.2002	0.1366	0.027*
C9A	0.64168 (9)	0.20860 (12)	0.17001 (6)	0.0158 (2)
C9	0.73797 (9)	0.19288 (12)	0.24652 (6)	0.0175 (2)
C14	0.59384 (10)	0.06641 (13)	0.14206 (7)	0.0213 (2)
H14A	0.6439	0.0092	0.1401	0.032*
H14B	0.5292	0.0749	0.0947	0.032*
H14C	0.5780	0.0248	0.1736	0.032*
C6	0.57710 (9)	0.20183 (12)	0.27544 (6)	0.0163 (2)
H6A	0.5444	0.1921	0.3016	0.020*
H6B	0.5982	0.1102	0.2701	0.020*
C7	0.67399 (9)	0.29122 (12)	0.31767 (6)	0.0159 (2)
H10	0.6521	0.3884	0.3055	0.019*
C10	0.73170 (10)	0.27344 (12)	0.39810 (6)	0.0187 (2)
C12	0.82760 (11)	0.36743 (13)	0.43577 (7)	0.0233 (3)
H12A	0.8643	0.3573	0.4869	0.035*
H12B	0.8048	0.4619	0.4224	0.035*
H12C	0.8749	0.3430	0.4220	0.035*
C13	0.76640 (12)	0.12601 (14)	0.41940 (8)	0.0313 (3)
H13A	0.8026	0.1165	0.4705	0.047*
H13B	0.8139	0.1005	0.4060	0.047*
H13C	0.7049	0.0665	0.3953	0.047*
C11	0.65795 (12)	0.31652 (16)	0.41897 (8)	0.0297 (3)
H11A	0.6017	0.2494	0.4014	0.045*
H11B	0.6277	0.4056	0.3984	0.045*
H11C	0.6973	0.3221	0.4705	0.045*
O8	0.75025 (7)	0.26132 (11)	0.30171 (5)	0.0241 (2)
O3	0.81138 (7)	0.12546 (10)	0.25888 (5)	0.0272 (2)
O1	0.44413 (7)	0.39477 (9)	0.20021 (5)	0.02007 (19)
O2	0.41027 (7)	0.16524 (9)	0.14798 (5)	0.01922 (18)
S5	0.48443 (2)	0.27000 (3)	0.191055 (15)	0.01392 (8)
C4A'	0.91567 (9)	0.81879 (11)	0.30775 (6)	0.0133 (2)
H4A'	0.8856	0.9038	0.2792	0.016*
C4'	0.96606 (9)	0.85685 (12)	0.38410 (6)	0.0178 (2)
H4'	1.0342	0.8957	0.4095	0.021*
C3'	0.91974 (10)	0.83864 (13)	0.41727 (6)	0.0195 (2)
H3'	0.9565	0.8636	0.4656	0.023*
C2'	0.81195 (10)	0.78037 (13)	0.38187 (7)	0.0192 (2)
H2A'	0.7711	0.8365	0.3938	0.023*
H2B'	0.8169	0.6873	0.3999	0.023*
C1'	0.75484 (9)	0.77511 (13)	0.30203 (6)	0.0177 (2)
H1A'	0.7322	0.8680	0.2826	0.021*
H1B'	0.6914	0.7181	0.2818	0.021*
C9A'	0.82495 (9)	0.71631 (12)	0.27978 (6)	0.0146 (2)
C9'	0.75265 (10)	0.70549 (13)	0.19906 (6)	0.0182 (2)
C14'	0.85954 (10)	0.57153 (12)	0.30961 (7)	0.0186 (2)
H14D	0.7985	0.5192	0.2992	0.028*
H14E	0.9111	0.5762	0.3608	0.028*
H14F	0.8910	0.5270	0.2878	0.028*
C6'	0.94934 (9)	0.70437 (12)	0.21156 (6)	0.0152 (2)
H6A'	0.9989	0.6923	0.1979	0.018*
H6B'	0.9180	0.6147	0.2084	0.018*
C7'	0.86322 (9)	0.80257 (12)	0.16043 (6)	0.0150 (2)
H30	0.8883	0.8976	0.1766	0.018*
C10'	0.83126 (10)	0.78739 (13)	0.08382 (6)	0.0176 (2)
C11'	0.92497 (11)	0.82562 (17)	0.08147 (7)	0.0286 (3)
H11F	0.9803	0.7574	0.1072	0.043*
H11E	0.9516	0.9149	0.1034	0.043*
H11D	0.9029	0.8289	0.0323	0.043*
C12'	0.79615 (10)	0.64169 (13)	0.05758 (7)	0.0230 (3)
H12D	0.7379	0.6175	0.0609	0.035*
H12E	0.8547	0.5792	0.0866	0.035*
H12F	0.7734	0.6350	0.0084	0.035*
C13'	0.74216 (11)	0.88755 (13)	0.03734 (7)	0.0235 (3)
H13D	0.7227	0.8821	−0.0112	0.035*
H13E	0.7653	0.9801	0.0553	0.035*
H13F	0.6814	0.8645	0.0382	0.035*
O8'	0.76699 (7)	0.78213 (10)	0.15664 (5)	0.0226 (2)
O3'	0.67514 (8)	0.63644 (12)	0.17150 (5)	0.0334 (2)
O2'	1.07623 (7)	0.65207 (9)	0.34704 (5)	0.01866 (18)
O1'	1.07662 (6)	0.88352 (9)	0.30531 (5)	0.01784 (18)
S5'	1.01848 (2)	0.76324 (3)	0.299595 (15)	0.01311 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C4A	0.0138 (5)	0.0160 (5)	0.0163 (5)	0.0000 (4)	0.0094 (4)	0.0008 (4)
C4	0.0164 (5)	0.0210 (6)	0.0186 (6)	0.0011 (4)	0.0085 (5)	0.0034 (4)
C3	0.0212 (6)	0.0315 (7)	0.0177 (6)	−0.0029 (5)	0.0099 (5)	0.0030 (5)
C2	0.0268 (7)	0.0411 (8)	0.0211 (6)	−0.0016 (6)	0.0173 (6)	−0.0005 (6)
C1	0.0172 (6)	0.0329 (7)	0.0224 (6)	−0.0010 (5)	0.0140 (5)	−0.0007 (5)
C9A	0.0134 (5)	0.0177 (5)	0.0168 (5)	0.0003 (4)	0.0089 (4)	−0.0014 (4)
C9	0.0161 (5)	0.0160 (5)	0.0204 (6)	−0.0011 (4)	0.0104 (5)	−0.0005 (4)
C14	0.0201 (6)	0.0184 (6)	0.0248 (6)	−0.0003 (5)	0.0123 (5)	−0.0057 (5)
C6	0.0169 (5)	0.0158 (5)	0.0157 (5)	−0.0013 (4)	0.0089 (5)	0.0013 (4)
C7	0.0158 (5)	0.0157 (5)	0.0166 (5)	−0.0011 (4)	0.0095 (5)	0.0000 (4)
C10	0.0226 (6)	0.0154 (5)	0.0146 (5)	−0.0027 (4)	0.0084 (5)	0.0004 (4)
C12	0.0259 (6)	0.0209 (6)	0.0176 (6)	−0.0060 (5)	0.0090 (5)	−0.0024 (5)
C13	0.0355 (8)	0.0159 (6)	0.0219 (6)	−0.0021 (5)	0.0040 (6)	0.0035 (5)
C11	0.0359 (8)	0.0352 (8)	0.0244 (7)	−0.0109 (6)	0.0210 (6)	−0.0078 (6)
O8	0.0151 (4)	0.0364 (5)	0.0201 (5)	−0.0051 (4)	0.0096 (4)	−0.0087 (4)
O3	0.0194 (4)	0.0257 (5)	0.0300 (5)	0.0078 (4)	0.0103 (4)	0.0004 (4)
O1	0.0190 (4)	0.0184 (4)	0.0254 (5)	0.0034 (3)	0.0141 (4)	−0.0011 (3)
O2	0.0144 (4)	0.0210 (4)	0.0215 (4)	−0.0034 (3)	0.0097 (3)	−0.0034 (3)
S5	0.01186 (14)	0.01469 (14)	0.01596 (14)	0.00020 (9)	0.00835 (12)	−0.00056 (10)
C4A'	0.0125 (5)	0.0120 (5)	0.0171 (5)	0.0003 (4)	0.0093 (4)	0.0004 (4)
C4'	0.0154 (5)	0.0179 (5)	0.0169 (5)	−0.0015 (4)	0.0073 (5)	−0.0019 (4)
C3'	0.0213 (6)	0.0197 (6)	0.0159 (5)	0.0012 (5)	0.0095 (5)	−0.0001 (4)
C2'	0.0217 (6)	0.0204 (6)	0.0205 (6)	0.0010 (5)	0.0150 (5)	0.0003 (5)
C1'	0.0148 (5)	0.0203 (6)	0.0208 (6)	0.0009 (4)	0.0118 (5)	0.0011 (4)
C9A'	0.0133 (5)	0.0153 (5)	0.0157 (5)	−0.0012 (4)	0.0086 (4)	0.0000 (4)
C9'	0.0178 (5)	0.0198 (6)	0.0172 (6)	−0.0004 (4)	0.0100 (5)	−0.0005 (4)
C14'	0.0218 (6)	0.0139 (5)	0.0236 (6)	−0.0012 (4)	0.0150 (5)	0.0012 (4)
C6'	0.0156 (5)	0.0141 (5)	0.0162 (5)	0.0003 (4)	0.0092 (4)	−0.0004 (4)
C7'	0.0152 (5)	0.0158 (5)	0.0145 (5)	0.0007 (4)	0.0087 (4)	0.0009 (4)
C10'	0.0188 (6)	0.0192 (6)	0.0143 (5)	−0.0034 (4)	0.0091 (5)	−0.0023 (4)
C11'	0.0261 (7)	0.0445 (8)	0.0190 (6)	−0.0101 (6)	0.0151 (5)	−0.0028 (6)
C12'	0.0236 (6)	0.0195 (6)	0.0193 (6)	−0.0007 (5)	0.0082 (5)	−0.0050 (5)
C13'	0.0283 (6)	0.0206 (6)	0.0151 (5)	−0.0001 (5)	0.0085 (5)	0.0023 (5)
O8'	0.0161 (4)	0.0339 (5)	0.0197 (4)	0.0075 (4)	0.0113 (4)	0.0096 (4)
O3'	0.0278 (5)	0.0398 (6)	0.0228 (5)	−0.0160 (5)	0.0085 (4)	−0.0048 (4)
O2'	0.0157 (4)	0.0178 (4)	0.0206 (4)	0.0039 (3)	0.0092 (4)	0.0057 (3)
O1'	0.0150 (4)	0.0153 (4)	0.0234 (4)	−0.0022 (3)	0.0110 (4)	0.0009 (3)
S5'	0.01100 (13)	0.01231 (14)	0.01539 (14)	0.00071 (9)	0.00712 (11)	0.00184 (9)

Geometric parameters (Å, º)

C4A—C4	1.5116 (16)	C4A'—C4'	1.5113 (16)
C4A—C9A	1.5422 (16)	C4A'—C9A'	1.5437 (15)
C4A—S5	1.7953 (12)	C4A'—S5'	1.7945 (11)
C4A—H4A	1.0000	C4A'—H4A'	1.0000
C4—C3	1.3245 (18)	C4'—C3'	1.3256 (17)
C4—H4	0.9500	C4'—H4'	0.9500
C3—C2	1.493 (2)	C3'—C2'	1.4973 (18)
C3—H3	0.9500	C3'—H3'	0.9500
C2—C1	1.5278 (19)	C2'—C1'	1.5232 (17)
C2—H2A	0.9900	C2'—H2A'	0.9900
C2—H2B	0.9900	C2'—H2B'	0.9900
C1—C9A	1.5552 (17)	C1'—C9A'	1.5541 (16)
C1—H1A	0.9900	C1'—H1A'	0.9900
C1—H1B	0.9900	C1'—H1B'	0.9900
C9A—C9	1.5400 (16)	C9A'—C9'	1.5357 (16)
C9A—C14	1.5424 (17)	C9A'—C14'	1.5394 (16)
C9—O3	1.2043 (15)	C9'—O3'	1.2015 (16)
C9—O8	1.3534 (15)	C9'—O8'	1.3495 (15)
C14—H14A	0.9800	C14'—H14D	0.9800
C14—H14B	0.9800	C14'—H14E	0.9800
C14—H14C	0.9800	C14'—H14F	0.9800
C6—C7	1.5226 (16)	C6'—C7'	1.5226 (16)
C6—S5	1.7668 (12)	C6'—S5'	1.7689 (12)
C6—H6A	0.9900	C6'—H6A'	0.9900
C6—H6B	0.9900	C6'—H6B'	0.9900
C7—O8	1.4552 (15)	C7'—O8'	1.4596 (14)
C7—C10	1.5433 (16)	C7'—C10'	1.5459 (16)
C7—H10	1.0000	C7'—H30	1.0000
C10—C13	1.5276 (18)	C10'—C12'	1.5304 (17)
C10—C11	1.5318 (19)	C10'—C13'	1.5320 (18)
C10—C12	1.5347 (17)	C10'—C11'	1.5327 (18)
C12—H12A	0.9800	C11'—H11F	0.9800
C12—H12B	0.9800	C11'—H11E	0.9800
C12—H12C	0.9800	C11'—H11D	0.9800
C13—H13A	0.9800	C12'—H12D	0.9800
C13—H13B	0.9800	C12'—H12E	0.9800
C13—H13C	0.9800	C12'—H12F	0.9800
C11—H11A	0.9800	C13'—H13D	0.9800
C11—H11B	0.9800	C13'—H13E	0.9800
C11—H11C	0.9800	C13'—H13F	0.9800
O1—S5	1.4464 (9)	O2'—S5'	1.4426 (9)
O2—S5	1.4400 (9)	O1'—S5'	1.4479 (9)
C4—C4A—C9A	113.48 (10)	C4'—C4A'—C9A'	113.18 (9)
C4—C4A—S5	106.55 (8)	C4'—C4A'—S5'	107.14 (8)
C9A—C4A—S5	114.54 (8)	C9A'—C4A'—S5'	114.32 (8)
C4—C4A—H4A	107.3	C4'—C4A'—H4A'	107.3
C9A—C4A—H4A	107.3	C9A'—C4A'—H4A'	107.3
S5—C4A—H4A	107.3	S5'—C4A'—H4A'	107.3
C3—C4—C4A	123.20 (12)	C3'—C4'—C4A'	123.12 (11)
C3—C4—H4	118.4	C3'—C4'—H4'	118.4
C4A—C4—H4	118.4	C4A'—C4'—H4'	118.4
C4—C3—C2	122.61 (12)	C4'—C3'—C2'	122.80 (11)
C4—C3—H3	118.7	C4'—C3'—H3'	118.6
C2—C3—H3	118.7	C2'—C3'—H3'	118.6
C3—C2—C1	112.41 (11)	C3'—C2'—C1'	111.98 (10)
C3—C2—H2A	109.1	C3'—C2'—H2A'	109.2
C1—C2—H2A	109.1	C1'—C2'—H2A'	109.2
C3—C2—H2B	109.1	C3'—C2'—H2B'	109.2
C1—C2—H2B	109.1	C1'—C2'—H2B'	109.2
H2A—C2—H2B	107.9	H2A'—C2'—H2B'	107.9
C2—C1—C9A	112.18 (10)	C2'—C1'—C9A'	112.04 (10)
C2—C1—H1A	109.2	C2'—C1'—H1A'	109.2
C9A—C1—H1A	109.2	C9A'—C1'—H1A'	109.2
C2—C1—H1B	109.2	C2'—C1'—H1B'	109.2
C9A—C1—H1B	109.2	C9A'—C1'—H1B'	109.2
H1A—C1—H1B	107.9	H1A'—C1'—H1B'	107.9
C9—C9A—C4A	114.61 (10)	C9'—C9A'—C14'	107.83 (10)
C9—C9A—C14	108.10 (10)	C9'—C9A'—C4A'	114.60 (10)
C4A—C9A—C14	114.52 (10)	C14'—C9A'—C4A'	114.45 (10)
C9—C9A—C1	104.58 (10)	C9'—C9A'—C1'	104.99 (9)
C4A—C9A—C1	105.08 (10)	C14'—C9A'—C1'	109.20 (9)
C14—C9A—C1	109.35 (10)	C4A'—C9A'—C1'	105.24 (9)
O3—C9—O8	116.26 (11)	O3'—C9'—O8'	117.43 (11)
O3—C9—C9A	119.89 (11)	O3'—C9'—C9A'	120.16 (11)
O8—C9—C9A	123.56 (10)	O8'—C9'—C9A'	122.07 (11)
C9A—C14—H14A	109.5	C9A'—C14'—H14D	109.5
C9A—C14—H14B	109.5	C9A'—C14'—H14E	109.5
H14A—C14—H14B	109.5	H14D—C14'—H14E	109.5
C9A—C14—H14C	109.5	C9A'—C14'—H14F	109.5
H14A—C14—H14C	109.5	H14D—C14'—H14F	109.5
H14B—C14—H14C	109.5	H14E—C14'—H14F	109.5
C7—C6—S5	112.02 (8)	C7'—C6'—S5'	111.93 (8)
C7—C6—H6A	109.2	C7'—C6'—H6A'	109.2
S5—C6—H6A	109.2	S5'—C6'—H6A'	109.2
C7—C6—H6B	109.2	C7'—C6'—H6B'	109.2
S5—C6—H6B	109.2	S5'—C6'—H6B'	109.2
H6A—C6—H6B	107.9	H6A'—C6'—H6B'	107.9
O8—C7—C6	111.81 (10)	O8'—C7'—C6'	112.17 (9)
O8—C7—C10	106.28 (10)	O8'—C7'—C10'	105.36 (9)
C6—C7—C10	112.99 (10)	C6'—C7'—C10'	113.16 (10)
O8—C7—H10	108.5	O8'—C7'—H30	108.7
C6—C7—H10	108.5	C6'—C7'—H30	108.7
C10—C7—H10	108.5	C10'—C7'—H30	108.7
C13—C10—C11	110.59 (12)	C12'—C10'—C13'	110.41 (10)
C13—C10—C12	109.80 (11)	C12'—C10'—C11'	110.35 (11)
C11—C10—C12	108.26 (11)	C13'—C10'—C11'	108.37 (11)
C13—C10—C7	110.58 (10)	C12'—C10'—C7'	110.67 (10)
C11—C10—C7	108.57 (11)	C13'—C10'—C7'	108.23 (10)
C12—C10—C7	108.99 (10)	C11'—C10'—C7'	108.75 (10)
C10—C12—H12A	109.5	C10'—C11'—H11F	109.5
C10—C12—H12B	109.5	C10'—C11'—H11E	109.5
H12A—C12—H12B	109.5	H11F—C11'—H11E	109.5
C10—C12—H12C	109.5	C10'—C11'—H11D	109.5
H12A—C12—H12C	109.5	H11F—C11'—H11D	109.5
H12B—C12—H12C	109.5	H11E—C11'—H11D	109.5
C10—C13—H13A	109.5	C10'—C12'—H12D	109.5
C10—C13—H13B	109.5	C10'—C12'—H12E	109.5
H13A—C13—H13B	109.5	H12D—C12'—H12E	109.5
C10—C13—H13C	109.5	C10'—C12'—H12F	109.5
H13A—C13—H13C	109.5	H12D—C12'—H12F	109.5
H13B—C13—H13C	109.5	H12E—C12'—H12F	109.5
C10—C11—H11A	109.5	C10'—C13'—H13D	109.5
C10—C11—H11B	109.5	C10'—C13'—H13E	109.5
H11A—C11—H11B	109.5	H13D—C13'—H13E	109.5
C10—C11—H11C	109.5	C10'—C13'—H13F	109.5
H11A—C11—H11C	109.5	H13D—C13'—H13F	109.5
H11B—C11—H11C	109.5	H13E—C13'—H13F	109.5
C9—O8—C7	129.61 (10)	C9'—O8'—C7'	128.17 (10)
O2—S5—O1	117.73 (5)	O2'—S5'—O1'	117.63 (5)
O2—S5—C6	108.61 (5)	O2'—S5'—C6'	109.38 (5)
O1—S5—C6	108.10 (6)	O1'—S5'—C6'	108.20 (5)
O2—S5—C4A	111.60 (5)	O2'—S5'—C4A'	110.97 (5)
O1—S5—C4A	106.54 (5)	O1'—S5'—C4A'	106.67 (5)
C6—S5—C4A	103.26 (5)	C6'—S5'—C4A'	102.93 (5)
C9A—C4A—C4—C3	−18.83 (17)	C9A'—C4A'—C4'—C3'	−19.11 (16)
S5—C4A—C4—C3	−145.81 (12)	S5'—C4A'—C4'—C3'	−146.04 (11)
C4A—C4—C3—C2	−1.9 (2)	C4A'—C4'—C3'—C2'	−0.98 (19)
C4—C3—C2—C1	−11.5 (2)	C4'—C3'—C2'—C1'	−12.66 (17)
C3—C2—C1—C9A	45.44 (16)	C3'—C2'—C1'—C9A'	46.36 (14)
C4—C4A—C9A—C9	162.93 (10)	C4'—C4A'—C9A'—C9'	163.66 (10)
S5—C4A—C9A—C9	−74.41 (12)	S5'—C4A'—C9A'—C9'	−73.30 (11)
C4—C4A—C9A—C14	−71.29 (13)	C4'—C4A'—C9A'—C14'	−71.03 (12)
S5—C4A—C9A—C14	51.37 (12)	S5'—C4A'—C9A'—C14'	52.01 (12)
C4—C4A—C9A—C1	48.71 (13)	C4'—C4A'—C9A'—C1'	48.85 (12)
S5—C4A—C9A—C1	171.38 (8)	S5'—C4A'—C9A'—C1'	171.90 (8)
C2—C1—C9A—C9	175.64 (11)	C2'—C1'—C9A'—C9'	174.67 (10)
C2—C1—C9A—C4A	−63.31 (14)	C2'—C1'—C9A'—C14'	59.27 (13)
C2—C1—C9A—C14	60.07 (14)	C2'—C1'—C9A'—C4A'	−64.03 (12)
C4A—C9A—C9—O3	−169.14 (11)	C14'—C9A'—C9'—O3'	56.81 (16)
C14—C9A—C9—O3	61.82 (15)	C4A'—C9A'—C9'—O3'	−174.48 (12)
C1—C9A—C9—O3	−54.63 (15)	C1'—C9A'—C9'—O3'	−59.53 (15)
C4A—C9A—C9—O8	4.51 (16)	C14'—C9A'—C9'—O8'	−130.00 (12)
C14—C9A—C9—O8	−124.54 (12)	C4A'—C9A'—C9'—O8'	−1.30 (16)
C1—C9A—C9—O8	119.02 (12)	C1'—C9A'—C9'—O8'	113.65 (12)
S5—C6—C7—O8	−85.31 (11)	S5'—C6'—C7'—O8'	−83.72 (11)
S5—C6—C7—C10	154.84 (9)	S5'—C6'—C7'—C10'	157.24 (8)
O8—C7—C10—C13	−63.71 (13)	O8'—C7'—C10'—C12'	−65.89 (12)
C6—C7—C10—C13	59.27 (14)	C6'—C7'—C10'—C12'	57.02 (13)
O8—C7—C10—C11	174.80 (10)	O8'—C7'—C10'—C13'	55.22 (12)
C6—C7—C10—C11	−62.22 (13)	C6'—C7'—C10'—C13'	178.12 (10)
O8—C7—C10—C12	57.08 (13)	O8'—C7'—C10'—C11'	172.74 (10)
C6—C7—C10—C12	−179.94 (10)	C6'—C7'—C10'—C11'	−64.35 (13)
O3—C9—O8—C7	−144.94 (13)	O3'—C9'—O8'—C7'	−136.71 (13)
C9A—C9—O8—C7	41.20 (19)	C9A'—C9'—O8'—C7'	49.93 (18)
C6—C7—O8—C9	16.62 (17)	C6'—C7'—O8'—C9'	11.00 (17)
C10—C7—O8—C9	140.34 (12)	C10'—C7'—O8'—C9'	134.54 (12)
C7—C6—S5—O2	164.46 (8)	C7'—C6'—S5'—O2'	163.20 (8)
C7—C6—S5—O1	−66.75 (10)	C7'—C6'—S5'—O1'	−67.51 (9)
C7—C6—S5—C4A	45.88 (10)	C7'—C6'—S5'—C4A'	45.16 (9)
C4—C4A—S5—O2	56.44 (9)	C4'—C4A'—S5'—O2'	56.87 (9)
C9A—C4A—S5—O2	−69.90 (10)	C9A'—C4A'—S5'—O2'	−69.39 (9)
C4—C4A—S5—O1	−73.32 (9)	C4'—C4A'—S5'—O1'	−72.43 (9)
C9A—C4A—S5—O1	160.33 (8)	C9A'—C4A'—S5'—O1'	161.32 (8)
C4—C4A—S5—C6	172.92 (8)	C4'—C4A'—S5'—C6'	173.78 (8)
C9A—C4A—S5—C6	46.58 (10)	C9A'—C4A'—S5'—C6'	47.53 (9)