Dispiro[adamantane-2,2'-1',3',6',9',11',14'-hexathiacyclohexadecane-10',2''-adamantane]

The conformational features of the title compound, C₂₈H₄₄S₆, are compared with previously reported analogous macrocycles. The type of substituent affects considerably the conformation of the macrocycle. A ¹H NMR titration of the title compound with AgBF₄ indicated the formation of the 1:1 complex, which was not crystallized.

S1. Comment

Macrocyclic thiaethers have been a topic of interest because of their moderately low σ-donating and π-accepting properties. They also reveal increased thermodynamic stability over open-chain analogues as a result of the macrocyclic effect (Blake & Schroeder, 1990). These crown-like molecules have been extensively used as chelators for specific metal ions and phase-transfer catalysts. Recently, a series of cage-annulated sulfur-containing crown-ethers and cryptands were synthesized and their complexation properties evaluated (Williams et al., 2002). As a possible specific metal host system we have designed and prepared an adamantylidene-derived thiaether, (I) (Mlinarić-Majerski et al., 2002). The C—C bonds inside the 16-membered macrocycle [in the range 1.490 (13)–1.520 (15) Å] are considerably shorter than expected for Csp³—Csp³ linkages (Allen et al., 1987; Allen, 2002). This phenomenon has already been observed in numerous macrocyclic structures (Hill & Feller, 2000; Maverick et al., 1980; Dunitz & Seiler, 1974).

Generally, the conformation of a macrocyclic thiaether is determined by the torsional angles along the [–S—CH₂—CH₂]-S-[CH₂—CH₂—S–] moieties designated as brackets according to De Groot and Loeb (1989). These brackets are formed because S—C bonds tend to adopt a gauche conformation, and C—C bonds tend to favor an anti conformation inside the bracket. The molecule of (I) consists of two brackets (S11—C12—C13—S14—C15—C16—S1 and S3—C4—C5—S6—C7—C8—S9) joined by two methylene bridges at atoms C2 and C10 in a spiro junction to the two adamantyl moieties. According to DeSimone & Glick (1976) the orientations of the S atoms in macrocyclic thiaethers can be described as endo- or exodentate. In the structure of (I), atoms S6 and S14 are exodentate, whereas the remaining four S atoms (S1, S3, S9 and S11) are endodentate. Four endocyclic C—C bonds (C4—C5, C7—C8, C12—C13 and C15—C16) strictly obey the above-quoted rule with an anti conformation about four S—C—C—S units. Consequently, the exodentate orientation of atoms S6 and S14 occurred. Four out of eight S—C bonds inside the brackets (involving bonds with two central sulfur atoms, viz. S6—C5, S6—C7, S14—C13 and S14—C15) adopt the gauche conformation. The remaining four S—C bonds (involving bonds with the side S atoms, viz. S1—C16, S3—C4, S9—C8 and S11—C12) adopt an anti conformation; these S atoms are endodentate. The conformations about the four S—C bonds involving two bridging methylene groups (C2—S1, C2—S3, C10—S11 and C10—S9) are all gauche. This arrangement generates a rectangular projection of the 16-macrocyclic ring of an approximate D₂ symmetry (with S6, S14, C2 and C10 at the corners). The approximate D₂ symmetry is valid for the complete molecule as well. The average length? of the 'square' edge is 5.570 (15) Å and the diagonals are 8.240 (12) Å (C2—C10) and 7.514 (11) Å (S6—S14). The opposite endodentate S atoms are separated by 6.449 (10) (S1—S9) and 6.257 (13) Å (S3—S11). Thus, the cavity of (I) might be suitable for complexation of Ag⁺ or Cu⁺.

The presence of the adamantane cages at positions 2 and 10 greatly affects the conformation of the [16]ane-S6 macrocycle. In order to evaluate its structural characteristics and to analyze its conformation and complexation properties, an inspection of the Cambridge Structural Database (CSD; Version 5.23 of April 2002; Allen, 2002) was performed. It revealed four structures of 1,3,6,9,11,14-hexathiacyclohexadecane derivatives and two structures of their metal complexes with Cu⁺ and Ag⁺. The structure of 7,10,13,20,23,26-hexathiadispiro[5.7.5.7]hexacosane (CSD refcode WEKXIT; Xianming et al., 1994) is the only spiro-derivative of 1,3,6,9,11,14-hexathiacyclohexadecane reported so far. The overall conformation of this compound shows remarkable similarity with (I). It also possesses two exodentate S atoms at the 'square' corners, and the gauche–anti arrangements are similar to (I). The C—C endocyclic linkages show even larger discrepancies from the values expected for Csp³—Csp³ bond lengths than those in (I). In contrast to these two spiro-derivatives, the structure of the unsubstituted 1,3,6,9,11,14-hexathiacyclohexadecane (CSD refcode KAVYIP) (De Groot & Loeb, 1989) has two crystallographically independent half molecules in the asymmetric unit, located around crystallographic inversion centres. Thus, their molecular symmetry is C_i in contrast to (I) and WEKXIT, where C₁ symmetry was observed. The conformational features of trans-2,10-diphenyl-1,3,6,9,11,14-hexathiacyclohexadecane (CSD refcode WEKWUE; Xianming et al., 1994) are similar to the features of the unsubstituted KAVYIP but differ from the spiro derivatives WEKXIT and (I). The interatomic distances between the opposite endocyclic S atoms for the set of six 1,3,6,9,11,14-hexathiacyclohexadecane derivatives from the CSD and (I) are given in Table 1. (Refcode KAVYIP has two independent halves in the assymetric unit and hence two entries in Table 1.) The refcodes KAVYOV (De Groot & Loeb, 1989) and SOLHIK (De Groot & Loeb, 1991) correspond to the Cu⁺ and Ag⁺ complexes of KAVYIP, respectively. Four out of six S atoms are involved in the metal complexation in these structures, with a reduction of S···S distances compared with the ligand.

Complexation of a ligand with a metal ion causes ¹H NMR shifts (Ishikawa et al., 1999). In order to prove the complexation of (I) with Ag⁺, an NMR titration experiment was performed. Ligand (I) was dissolved in CDCl₃ and a solution of AgBF₄ in CD₃CN was added in molar amounts of 10%, 25%, 50%, 75%, 100%, 150% and 200%, respectively. As depicted in Fig. 2, the NMR chemical shifts gradually changed until 100% of the molar amount of AgBF₄ was added, indicating the formation of the 1:1 complex. However, attempts to isolate and crystallize the complex were unsuccesful. In the ¹H NMR spectra of complex Ag⁺[(I)], downfield shifts were observed for all H atoms except for the anti H3 atom (Fig. 2).

S2. Experimental

Compound (I) was prepared according to the procedure reported by Mlinarić-Majerski et al. (2002). Suitable single crystals of (I) were obtained by slow evaporation from a mixture of dichloromethane and water in a 1:1 molar ratio.

Computing details

Data collection: CAD-4 EXPRESS (Enraf Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: HELENA (Spek, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The molecular structure of (I), with the displacement ellipsoids shown at the 50% probability level.
	Fig. 2. ^1H NMR chemical shifts during the titration of (I) with AgBF4. The chemical shifts of atoms H2 and H4 were only partially observable because of overlap with the CD3CN signal. H atoms are labelled according to the chemical diagram.

2,10-Bis-spiro(2-adamantiliden)-1,3,6,9,11,14-hexathiacyclohexadecane

Crystal data

C28H44S6	F(000) = 2464
Mr = 572.99	Dx = 1.302 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 15.154 (4) Å	θ = 5.6–10.2°
b = 10.499 (3) Å	µ = 0.49 mm^−1
c = 36.743 (8) Å	T = 293 K
V = 5846 (3) Å^3	Prism, colourless
Z = 8	0.36 × 0.25 × 0.18 mm

Data collection

Enraf Nonius CAD4 diffractometer	1913 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.014
Graphite monochromator	θmax = 26.3°, θmin = 2.2°
non–profiled ω/2θ scans	h = −18→0
Absorption correction: ψ scan (North et al., 1968)	k = −13→0
Tmin = 0.765, Tmax = 0.915	l = 0→45
5907 measured reflections	3 standard reflections every 120 min
5907 independent reflections	intensity decay: 3%

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.063	w = 1/[σ^2(Fo^2) + (0.0826P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.204	(Δ/σ)max = 0.001
S = 0.92	Δρmax = 0.39 e Å^−3
5907 reflections	Δρmin = −0.44 e Å^−3
307 parameters

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.31965 (13)	0.38786 (16)	−0.03968 (5)	0.0531 (5)
S3	0.43655 (11)	0.15845 (15)	−0.04541 (5)	0.0470 (5)
S6	0.62503 (11)	0.3163 (2)	−0.12416 (5)	0.0623 (5)
S9	0.43528 (12)	0.48220 (15)	−0.20082 (5)	0.0481 (5)
S11	0.32232 (13)	0.25192 (17)	−0.21217 (6)	0.0594 (5)
S14	0.12906 (13)	0.3036 (3)	−0.12567 (6)	0.1140 (11)
C2	0.3780 (4)	0.2633 (5)	−0.01374 (16)	0.0372 (15)
C4	0.5115 (5)	0.2665 (6)	−0.0676 (2)	0.058 (2)
H4A	0.4802	0.3439	−0.0740	0.069*
H4B	0.5585	0.2890	−0.0509	0.069*
C5	0.5507 (5)	0.2096 (7)	−0.10122 (18)	0.061 (2)
H5A	0.5035	0.1861	−0.1178	0.073*
H5B	0.5823	0.1325	−0.0947	0.073*
C7	0.5501 (4)	0.4251 (6)	−0.14628 (17)	0.0546 (19)
H7A	0.5027	0.4464	−0.1296	0.065*
H7B	0.5813	0.5031	−0.1521	0.065*
C8	0.5114 (4)	0.3703 (6)	−0.18051 (18)	0.0537 (19)
H8A	0.4808	0.2916	−0.1749	0.064*
H8B	0.5583	0.3510	−0.1976	0.064*
C10	0.3796 (4)	0.3828 (5)	−0.23524 (16)	0.0365 (15)
C12	0.2462 (5)	0.3343 (8)	−0.1822 (2)	0.075 (2)
H12A	0.2772	0.3997	−0.1687	0.090*
H12B	0.2001	0.3749	−0.1964	0.090*
C13	0.2067 (5)	0.2392 (8)	−0.1566 (2)	0.087 (3)
H13A	0.2539	0.1994	−0.1429	0.104*
H13B	0.1780	0.1731	−0.1708	0.104*
C15	0.1999 (5)	0.3836 (8)	−0.09413 (19)	0.083 (3)
H15A	0.2439	0.4312	−0.1076	0.099*
H15B	0.1652	0.4440	−0.0802	0.099*
C16	0.2461 (5)	0.2943 (8)	−0.0681 (2)	0.071 (2)
H16A	0.2796	0.2312	−0.0816	0.086*
H16B	0.2031	0.2503	−0.0531	0.086*
C17	0.4396 (4)	0.3352 (5)	0.01240 (16)	0.0390 (15)
H17	0.4796	0.3899	−0.0016	0.047*
C18	0.4937 (4)	0.2398 (6)	0.03509 (19)	0.0517 (19)
H18A	0.5287	0.1866	0.0191	0.062*
H18B	0.5335	0.2855	0.0511	0.062*
C19	0.4316 (5)	0.1565 (6)	0.05764 (17)	0.0499 (17)
H19	0.4662	0.0954	0.0719	0.060*
C20	0.3772 (4)	0.2407 (7)	0.08343 (19)	0.057 (2)
H20A	0.3384	0.1883	0.0981	0.068*
H20B	0.4162	0.2871	0.0996	0.068*
C21	0.3228 (5)	0.3345 (6)	0.06058 (17)	0.0538 (18)
H21	0.2877	0.3887	0.0768	0.065*
C22	0.2622 (4)	0.2631 (6)	0.0354 (2)	0.056 (2)
H22A	0.2270	0.3231	0.0215	0.068*
H22B	0.2225	0.2101	0.0495	0.068*
C23	0.3160 (4)	0.1799 (6)	0.00935 (16)	0.0413 (15)
H23	0.2760	0.1326	−0.0067	0.050*
C24	0.3700 (4)	0.0856 (6)	0.03250 (17)	0.0478 (17)
H24A	0.3303	0.0329	0.0467	0.057*
H24B	0.4040	0.0303	0.0166	0.057*
C25	0.3866 (4)	0.4163 (6)	0.03924 (17)	0.0485 (17)
H25A	0.4266	0.4588	0.0559	0.058*
H25B	0.3542	0.4812	0.0260	0.058*
C26	0.4432 (4)	0.3233 (6)	−0.26240 (16)	0.0434 (16)
H26	0.4839	0.2663	−0.2496	0.052*
C27	0.4959 (4)	0.4285 (7)	−0.28194 (18)	0.0567 (19)
H27A	0.5288	0.4778	−0.2642	0.068*
H27B	0.5377	0.3902	−0.2987	0.068*
C28	0.4341 (5)	0.5153 (7)	−0.30265 (19)	0.062 (2)
H28	0.4683	0.5822	−0.3147	0.075*
C29	0.3832 (5)	0.4410 (7)	−0.33084 (19)	0.066 (2)
H29A	0.4237	0.4022	−0.3480	0.080*
H29B	0.3444	0.4978	−0.3442	0.080*
C30	0.3285 (5)	0.3373 (7)	−0.31188 (19)	0.0557 (19)
H30	0.2952	0.2887	−0.3300	0.067*
C31	0.2654 (4)	0.3969 (7)	−0.28460 (19)	0.0561 (19)
H31A	0.2316	0.3306	−0.2726	0.067*
H31B	0.2245	0.4527	−0.2972	0.067*
C32	0.3172 (4)	0.4729 (5)	−0.25630 (18)	0.0436 (16)
H32	0.2760	0.5132	−0.2393	0.052*
C33	0.3706 (5)	0.5753 (6)	−0.2759 (2)	0.0607 (19)
H33A	0.3310	0.6323	−0.2887	0.073*
H33B	0.4034	0.6250	−0.2582	0.073*
C34	0.3914 (5)	0.2475 (6)	−0.2910 (2)	0.057 (2)
H34A	0.3575	0.1809	−0.2791	0.069*
H34B	0.4320	0.2075	−0.3079	0.069*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0652 (12)	0.0451 (10)	0.0491 (10)	0.0137 (9)	−0.0053 (10)	0.0006 (9)
S3	0.0440 (9)	0.0398 (9)	0.0572 (11)	−0.0002 (8)	0.0094 (9)	−0.0127 (8)
S6	0.0393 (9)	0.0970 (14)	0.0506 (10)	−0.0012 (12)	0.0022 (10)	0.0119 (11)
S9	0.0499 (10)	0.0394 (9)	0.0549 (10)	−0.0006 (9)	−0.0090 (9)	−0.0120 (8)
S11	0.0614 (13)	0.0489 (11)	0.0679 (12)	−0.0168 (10)	0.0037 (11)	0.0005 (9)
S14	0.0434 (11)	0.245 (3)	0.0538 (12)	−0.0162 (19)	−0.0043 (12)	0.0184 (18)
C2	0.036 (4)	0.035 (3)	0.040 (4)	0.000 (3)	0.007 (3)	0.001 (3)
C4	0.051 (5)	0.056 (5)	0.066 (5)	−0.015 (4)	0.009 (4)	−0.012 (4)
C5	0.073 (5)	0.060 (4)	0.049 (4)	0.001 (4)	0.015 (4)	−0.013 (4)
C7	0.053 (4)	0.060 (4)	0.051 (4)	−0.020 (4)	−0.008 (4)	0.000 (4)
C8	0.044 (4)	0.060 (4)	0.057 (4)	−0.001 (4)	−0.009 (4)	−0.021 (4)
C10	0.031 (3)	0.037 (3)	0.041 (4)	−0.006 (3)	0.002 (3)	−0.002 (3)
C12	0.052 (5)	0.089 (6)	0.084 (5)	−0.012 (4)	0.011 (4)	0.014 (5)
C13	0.080 (6)	0.121 (8)	0.059 (5)	−0.052 (6)	0.002 (5)	−0.003 (5)
C15	0.078 (6)	0.122 (7)	0.048 (4)	0.056 (5)	0.004 (4)	−0.001 (5)
C16	0.069 (5)	0.086 (6)	0.060 (5)	0.008 (5)	−0.015 (4)	−0.004 (5)
C17	0.039 (3)	0.033 (3)	0.045 (4)	−0.005 (3)	−0.006 (3)	0.001 (3)
C18	0.043 (4)	0.050 (4)	0.063 (5)	0.003 (3)	−0.007 (4)	−0.010 (4)
C19	0.053 (4)	0.046 (4)	0.051 (4)	0.008 (4)	−0.001 (4)	0.011 (4)
C20	0.049 (4)	0.069 (5)	0.052 (4)	−0.004 (4)	−0.010 (4)	0.013 (4)
C21	0.054 (4)	0.060 (5)	0.047 (4)	0.004 (4)	−0.002 (4)	−0.006 (4)
C22	0.036 (4)	0.056 (5)	0.077 (5)	0.000 (3)	0.015 (4)	0.000 (4)
C23	0.030 (3)	0.049 (4)	0.045 (4)	−0.004 (3)	0.005 (3)	−0.002 (3)
C24	0.058 (4)	0.034 (4)	0.052 (4)	0.002 (3)	−0.002 (4)	0.009 (3)
C25	0.063 (5)	0.036 (4)	0.046 (4)	0.007 (3)	−0.001 (4)	−0.013 (3)
C26	0.040 (3)	0.037 (4)	0.053 (4)	0.017 (3)	−0.008 (3)	−0.006 (3)
C27	0.043 (4)	0.070 (5)	0.056 (4)	−0.007 (4)	0.006 (4)	−0.010 (4)
C28	0.057 (5)	0.066 (5)	0.065 (5)	−0.015 (4)	−0.004 (5)	0.002 (4)
C29	0.082 (6)	0.065 (5)	0.052 (4)	−0.001 (5)	−0.002 (4)	0.006 (4)
C30	0.056 (4)	0.056 (5)	0.055 (4)	0.000 (4)	−0.013 (4)	−0.013 (4)
C31	0.040 (4)	0.056 (5)	0.072 (5)	0.006 (4)	−0.011 (4)	−0.001 (4)
C32	0.032 (3)	0.032 (3)	0.067 (5)	0.005 (3)	−0.008 (3)	−0.012 (3)
C33	0.063 (5)	0.042 (4)	0.078 (5)	0.004 (4)	−0.009 (4)	0.003 (4)
C34	0.067 (5)	0.045 (4)	0.060 (5)	0.009 (4)	−0.010 (4)	−0.020 (3)

Geometric parameters (Å, º)

S1—C16	1.816 (8)	C19—C24	1.509 (8)
S1—C2	1.844 (6)	C19—C20	1.535 (9)
S3—C4	1.801 (6)	C19—H19	0.9800
S3—C2	1.831 (6)	C20—C21	1.535 (9)
S6—C5	1.798 (7)	C20—H20A	0.9700
S6—C7	1.805 (7)	C20—H20B	0.9700
S9—C8	1.808 (7)	C21—C22	1.504 (9)
S9—C10	1.844 (6)	C21—C25	1.513 (9)
S11—C12	1.813 (8)	C21—H21	0.9800
S11—C10	1.833 (6)	C22—C23	1.531 (8)
S14—C13	1.771 (8)	C22—H22A	0.9700
S14—C15	1.789 (8)	C22—H22B	0.9700
C2—C17	1.538 (8)	C23—C24	1.540 (8)
C2—C23	1.540 (8)	C23—H23	0.9800
C4—C5	1.495 (9)	C24—H24A	0.9700
C4—H4A	0.9700	C24—H24B	0.9700
C4—H4B	0.9700	C25—H25A	0.9700
C5—H5A	0.9700	C25—H25B	0.9700
C5—H5B	0.9700	C26—C34	1.534 (8)
C7—C8	1.502 (8)	C26—C27	1.541 (8)
C7—H7A	0.9700	C26—H26	0.9800
C7—H7B	0.9700	C27—C28	1.512 (9)
C8—H8A	0.9700	C27—H27A	0.9700
C8—H8B	0.9700	C27—H27B	0.9700
C10—C26	1.521 (8)	C28—C29	1.509 (9)
C10—C32	1.546 (8)	C28—C33	1.513 (9)
C12—C13	1.498 (9)	C28—H28	0.9800
C12—H12A	0.9700	C29—C30	1.535 (9)
C12—H12B	0.9700	C29—H29A	0.9700
C13—H13A	0.9700	C29—H29B	0.9700
C13—H13B	0.9700	C30—C31	1.520 (9)
C15—C16	1.511 (10)	C30—C34	1.545 (9)
C15—H15A	0.9700	C30—H30	0.9800
C15—H15B	0.9700	C31—C32	1.527 (8)
C16—H16A	0.9700	C31—H31A	0.9700
C16—H16B	0.9700	C31—H31B	0.9700
C17—C25	1.531 (8)	C32—C33	1.527 (8)
C17—C18	1.539 (8)	C32—H32	0.9800
C17—H17	0.9800	C33—H33A	0.9700
C18—C19	1.528 (8)	C33—H33B	0.9700
C18—H18A	0.9700	C34—H34A	0.9700
C18—H18B	0.9700	C34—H34B	0.9700
C16—S1—C2	102.0 (3)	C21—C20—H20B	110.0
C4—S3—C2	102.4 (3)	C19—C20—H20B	110.0
C5—S6—C7	102.2 (3)	H20A—C20—H20B	108.3
C8—S9—C10	101.9 (3)	C22—C21—C25	110.7 (6)
C12—S11—C10	102.9 (3)	C22—C21—C20	110.2 (6)
C13—S14—C15	101.4 (3)	C25—C21—C20	107.7 (6)
C17—C2—C23	107.8 (5)	C22—C21—H21	109.4
C17—C2—S3	113.4 (4)	C25—C21—H21	109.4
C23—C2—S3	107.7 (4)	C20—C21—H21	109.4
C17—C2—S1	105.4 (4)	C21—C22—C23	110.1 (5)
C23—C2—S1	113.3 (4)	C21—C22—H22A	109.6
S3—C2—S1	109.3 (3)	C23—C22—H22A	109.6
C5—C4—S3	111.9 (5)	C21—C22—H22B	109.6
C5—C4—H4A	109.2	C23—C22—H22B	109.6
S3—C4—H4A	109.2	H22A—C22—H22B	108.2
C5—C4—H4B	109.2	C22—C23—C2	110.1 (5)
S3—C4—H4B	109.2	C22—C23—C24	107.8 (5)
H4A—C4—H4B	107.9	C2—C23—C24	110.2 (5)
C4—C5—S6	112.8 (5)	C22—C23—H23	109.6
C4—C5—H5A	109.0	C2—C23—H23	109.6
S6—C5—H5A	109.0	C24—C23—H23	109.6
C4—C5—H5B	109.0	C19—C24—C23	110.5 (5)
S6—C5—H5B	109.0	C19—C24—H24A	109.6
H5A—C5—H5B	107.8	C23—C24—H24A	109.6
C8—C7—S6	112.3 (5)	C19—C24—H24B	109.6
C8—C7—H7A	109.1	C23—C24—H24B	109.6
S6—C7—H7A	109.1	H24A—C24—H24B	108.1
C8—C7—H7B	109.1	C21—C25—C17	110.7 (5)
S6—C7—H7B	109.1	C21—C25—H25A	109.5
H7A—C7—H7B	107.9	C17—C25—H25A	109.5
C7—C8—S9	110.2 (5)	C21—C25—H25B	109.5
C7—C8—H8A	109.6	C17—C25—H25B	109.5
S9—C8—H8A	109.6	H25A—C25—H25B	108.1
C7—C8—H8B	109.6	C10—C26—C34	109.7 (5)
S9—C8—H8B	109.6	C10—C26—C27	109.8 (5)
H8A—C8—H8B	108.1	C34—C26—C27	108.6 (5)
C26—C10—C32	108.1 (5)	C10—C26—H26	109.6
C26—C10—S11	107.2 (4)	C34—C26—H26	109.6
C32—C10—S11	113.6 (4)	C27—C26—H26	109.6
C26—C10—S9	113.1 (4)	C28—C27—C26	110.2 (5)
C32—C10—S9	106.1 (4)	C28—C27—H27A	109.6
S11—C10—S9	108.9 (3)	C26—C27—H27A	109.6
C13—C12—S11	108.5 (6)	C28—C27—H27B	109.6
C13—C12—H12A	110.0	C26—C27—H27B	109.6
S11—C12—H12A	110.0	H27A—C27—H27B	108.1
C13—C12—H12B	110.0	C29—C28—C27	110.6 (6)
S11—C12—H12B	110.0	C29—C28—C33	109.7 (6)
H12A—C12—H12B	108.4	C27—C28—C33	108.5 (6)
C12—C13—S14	114.5 (6)	C29—C28—H28	109.3
C12—C13—H13A	108.6	C27—C28—H28	109.3
S14—C13—H13A	108.6	C33—C28—H28	109.3
C12—C13—H13B	108.6	C28—C29—C30	109.3 (6)
S14—C13—H13B	108.6	C28—C29—H29A	109.8
H13A—C13—H13B	107.6	C30—C29—H29A	109.8
C16—C15—S14	113.4 (6)	C28—C29—H29B	109.8
C16—C15—H15A	108.9	C30—C29—H29B	109.8
S14—C15—H15A	108.9	H29A—C29—H29B	108.3
C16—C15—H15B	108.9	C31—C30—C29	110.3 (6)
S14—C15—H15B	108.9	C31—C30—C34	108.1 (6)
H15A—C15—H15B	107.7	C29—C30—C34	109.0 (6)
C15—C16—S1	108.2 (6)	C31—C30—H30	109.8
C15—C16—H16A	110.1	C29—C30—H30	109.8
S1—C16—H16A	110.1	C34—C30—H30	109.8
C15—C16—H16B	110.1	C30—C31—C32	109.9 (5)
S1—C16—H16B	110.1	C30—C31—H31A	109.7
H16A—C16—H16B	108.4	C32—C31—H31A	109.7
C25—C17—C2	110.9 (5)	C30—C31—H31B	109.7
C25—C17—C18	107.0 (5)	C32—C31—H31B	109.7
C2—C17—C18	110.0 (5)	H31A—C31—H31B	108.2
C25—C17—H17	109.6	C33—C32—C31	108.7 (6)
C2—C17—H17	109.6	C33—C32—C10	110.0 (5)
C18—C17—H17	109.6	C31—C32—C10	109.6 (5)
C19—C18—C17	109.7 (5)	C33—C32—H32	109.5
C19—C18—H18A	109.7	C31—C32—H32	109.5
C17—C18—H18A	109.7	C10—C32—H32	109.5
C19—C18—H18B	109.7	C28—C33—C32	110.5 (6)
C17—C18—H18B	109.7	C28—C33—H33A	109.6
H18A—C18—H18B	108.2	C32—C33—H33A	109.6
C24—C19—C18	109.3 (5)	C28—C33—H33B	109.6
C24—C19—C20	109.3 (6)	C32—C33—H33B	109.6
C18—C19—C20	109.6 (5)	H33A—C33—H33B	108.1
C24—C19—H19	109.5	C26—C34—C30	109.8 (5)
C18—C19—H19	109.5	C26—C34—H34A	109.7
C20—C19—H19	109.5	C30—C34—H34A	109.7
C21—C20—C19	108.6 (6)	C26—C34—H34B	109.7
C21—C20—H20A	110.0	C30—C34—H34B	109.7
C19—C20—H20A	110.0	H34A—C34—H34B	108.2
C4—S3—C2—C17	−56.5 (5)	S1—C2—C23—C22	−56.6 (6)
C4—S3—C2—C23	−175.7 (4)	C17—C2—C23—C24	−59.1 (6)
C4—S3—C2—S1	60.8 (4)	S3—C2—C23—C24	63.6 (5)
C16—S1—C2—C17	−177.8 (4)	S1—C2—C23—C24	−175.4 (4)
C16—S1—C2—C23	−60.1 (5)	C18—C19—C24—C23	−59.0 (7)
C16—S1—C2—S3	60.0 (4)	C20—C19—C24—C23	60.9 (7)
C2—S3—C4—C5	−165.6 (5)	C22—C23—C24—C19	−60.4 (7)
S3—C4—C5—S6	179.4 (4)	C2—C23—C24—C19	59.9 (7)
C7—S6—C5—C4	−76.3 (6)	C22—C21—C25—C17	−56.8 (7)
C5—S6—C7—C8	−79.1 (5)	C20—C21—C25—C17	63.8 (7)
S6—C7—C8—S9	178.8 (3)	C2—C17—C25—C21	57.5 (7)
C10—S9—C8—C7	−168.0 (5)	C18—C17—C25—C21	−62.5 (7)
C12—S11—C10—C26	−177.8 (4)	C32—C10—C26—C34	−60.3 (6)
C12—S11—C10—C32	−58.4 (5)	S11—C10—C26—C34	62.5 (5)
C12—S11—C10—S9	59.5 (4)	S9—C10—C26—C34	−177.4 (4)
C8—S9—C10—C26	−57.6 (5)	C32—C10—C26—C27	59.1 (6)
C8—S9—C10—C32	−176.0 (4)	S11—C10—C26—C27	−178.2 (4)
C8—S9—C10—S11	61.4 (4)	S9—C10—C26—C27	−58.1 (6)
C10—S11—C12—C13	−169.6 (5)	C10—C26—C27—C28	−61.1 (7)
S11—C12—C13—S14	−179.2 (4)	C34—C26—C27—C28	58.9 (7)
C15—S14—C13—C12	−75.2 (7)	C26—C27—C28—C29	−60.2 (7)
C13—S14—C15—C16	−76.0 (7)	C26—C27—C28—C33	60.2 (7)
S14—C15—C16—S1	176.9 (4)	C27—C28—C29—C30	60.4 (8)
C2—S1—C16—C15	−174.2 (5)	C33—C28—C29—C30	−59.3 (8)
C23—C2—C17—C25	−58.3 (6)	C28—C29—C30—C31	58.8 (8)
S3—C2—C17—C25	−177.4 (4)	C28—C29—C30—C34	−59.8 (7)
S1—C2—C17—C25	63.0 (5)	C29—C30—C31—C32	−58.8 (7)
C23—C2—C17—C18	59.9 (6)	C34—C30—C31—C32	60.3 (7)
S3—C2—C17—C18	−59.2 (6)	C30—C31—C32—C33	58.7 (7)
S1—C2—C17—C18	−178.8 (4)	C30—C31—C32—C10	−61.6 (7)
C25—C17—C18—C19	59.8 (6)	C26—C10—C32—C33	−58.9 (6)
C2—C17—C18—C19	−60.8 (7)	S11—C10—C32—C33	−177.7 (4)
C17—C18—C19—C24	59.5 (6)	S9—C10—C32—C33	62.8 (6)
C17—C18—C19—C20	−60.3 (7)	C26—C10—C32—C31	60.5 (6)
C24—C19—C20—C21	−59.3 (7)	S11—C10—C32—C31	−58.3 (6)
C18—C19—C20—C21	60.5 (7)	S9—C10—C32—C31	−177.8 (4)
C19—C20—C21—C22	59.6 (7)	C29—C28—C33—C32	60.8 (7)
C19—C20—C21—C25	−61.3 (7)	C27—C28—C33—C32	−60.1 (8)
C25—C21—C22—C23	58.3 (7)	C31—C32—C33—C28	−59.9 (7)
C20—C21—C22—C23	−60.8 (7)	C10—C32—C33—C28	60.1 (7)
C21—C22—C23—C2	−60.5 (7)	C10—C26—C34—C30	61.0 (7)
C21—C22—C23—C24	59.8 (7)	C27—C26—C34—C30	−59.1 (7)
C17—C2—C23—C22	59.6 (6)	C31—C30—C34—C26	−59.9 (7)
S3—C2—C23—C22	−177.6 (4)	C29—C30—C34—C26	60.0 (7)