An anthracene dimer with a fused 1,3-dithiole ring at 193 K

The first butterfly-shaped anthracene dimer including S atoms,8,9-di­hydro-3a,8[1',2']:9,13b[1'',2'']­di­benzeno­dibenzo­[3,4:7,8]cyclo­octa­[1,2-d]-1,3-di­thiole, C₂₉H₂₀S₂, contains an exceptionally long Csp³-Csp³ bond of 1.672 (2) Å in the fused 1,3-di­thiole ring. The length of the other bond bridging the anthracene moieties is 1.604 (3) Å.

S1. Comment

The title compound (1) is the only anthracene dimer reported so far where the S-atoms are bonded to the anthryl groups and additionally form a fused heterocyclic ring. According to the CA Index nomenclature (1) is called 8,9-dihydro-3a,8[1,2]:9,13b[1¨,2¨]- dibenzenodibenzo-[3,4:7,8]cycloocta[1,2-d]-1,3-dithiole. The synthesis and photochemical studies of an analogous anthracene dimer with a fused 1,3-dioxole ring have been published, but unfortunately without X-ray data (Desvergne et al., 1992, 1995).

A typical feature of the highly strained butterfly shaped anthracene dimers is the remarkable elongation of the central C–C bonds connecting the anthracene moieties compared to the C–C single bond standard of 1.54 Å (Battersby et al., 1995). Even in unsubstituted 9,9:10,10-bianthracene the central bond is reported to reach the value of 1.620 Å at 120 K (Batsanov & Howard, 2000, private communication), 1.618 Å at 198 K (Abboud et al., 1990), 1.612 Å (Ehrenberg, 1966) and 1.623 Å (Choi & Marinkas, 1980) at 295 K (DPANTH in Cambridge Structural Database (CSD), Version 5.21; Allen & Kennard, 1993). The longest reported central C–C bonds of 1.669 and 1.670 Å for 9,9:10,10-bianthracene derivatives are in the asymmetric photodimer of (Z)-1-(9-anthryloxy)-1,2-bis(9- anthryl)-2-methoxyethene (2) (HAVTAZ) (Langer & Becker, 1993a) and in symmetric 9,10-(10-methoxy-9-methylanthraceno-9-methoxy-10-methylanthracene (HAVVEF) (Langer & Becker, 1993b), respectively. The even longer C3a–C13b bond of 1.672 (3) Å in (1) (Fig. 1, Table 1) is apparently due to the greater steric demand of the fused heterocyclic 1,3-dithiole ring. The length of the other central bond (C8–C9) is only 1.604 (3) Å in (1) and 1.619 Å in (2). Similar large differences in the central bond lengths appear also in the anthracene dimer with the fused cyclobutadione ring, 1.655 (5) and 1.607 (6) Å (SIWDOR) (Becker et al., 1991) and with the fused cyclohexene ring 1.663 and 1.614 Å (REFVED) (Kammermeier et al., 1996). Several discussions based on experimental results and their comparison with theoretical calculations have been presented on the lengthening of the bridging C–C bond in anthracene dimers and related molecules (Dougherty et al., 1986; Battersby et al., 1995; Baldridge et al., 1997).

The bond angles in the 1,3-dithiole ring of (1) are rather close to those in the nonfused 4,5-tetrasubstituted 1,3-dithiole derivatives found in CSD. The main difference is the shape of the ring. They all posses more or less twisted envelope conformation but (1) is the only compound where the S atoms are in the same plane with the two C–atoms between them. This is clearly seen in the torsion angle S–C–C–S value which is only 0.69 (15)° in (1), but 38.4° in SOSHIR (Mloston et al., 1991), 49.0° in ZAMLOO (Leino et al., 1995), 44.5° in LEVFAT (Mloston et al., 1999), 52.4° in HASBIM and 53.6° in HASBEI (Kagi et al., 1993). The torsion angles C–S–C–C in (1) are 27.15 (14) and -28.03 (14)° thus proving the ring to be almost symmetric with a pseudo mirror plane.

The C–C distances of the 1,3-dithiole fragment in the above mentioned structures are mostly only slightly longer than normal, the longest being, however, 1.617 Å in LEVFAT (Mloston et al., 1999) probably due to bulky adamantyl and two phenyl groups. In compound (1) the S–C2 bonds are clearly shorter than the S–C bonds to the anthryl groups and both pairs of S–C bonds are shorter than the corresponding S–C bonds in the 1,3-dithiole structures of comparison.

In butterfly shaped dimers the anthracene moieties are typically bent at the central carbon atoms where the molecules are joined. The bent halves within each anthryl group in (1) form interplanar angles of 136.32 (8) and 130.72 (8)° which agree well with the values of 136.2 (2) and 129.7 (2)° found in SIDWOR (Becker et al., 1991). Due to the small torsion angle S–C–C–S value of 0.69° in (1) the S atoms and C2 deviate 0.029 (3), 0.056 (3) and -0.761 (4) Å from the plane defined by atoms C8, C9, C3a and C13b, respectively. According to the present data the 1,3-dithiole ring in (1) is strained.

Molecular packing of (1) shows tubular channels and separate molecule columns in the a axis direction. Molecules are oriented in such a way that the inversion related S-atoms seem to form rows of four S, one row passing the origin and the other the center of the cell through the crystal (Fig. 2).

S2. Experimental

Compound 1 was obtained as a minor side product in the synthesis of 2-[(9-anthracenyl)thiomethylthio]tetrahydropyran (Sipilä et al., 2001) from 2-(acetylthio)tetrahydropyran and 9-chloromethylthioanthracene. The thioester was hydrolysed with 2.2 eq. KOH in dimethyl sulfoxide–water solution at 273 K, 9-chloromethylthioanthracene was added at the same temperature in a one-pot reaction and the mixture was allowed to reach the room temperature by stirring overnight. Water was added and the mixture was extracted with diethyl ether. The organic phase was washed with water and brine, dried with Na₂SO₄, evaporated to dryness and purified with flash chromatography (Silica gel, CH₂Cl₂). The fractions containing compound 1 were evaporated and recrystallized from CH₂Cl₂ – ethanol, m.p. 454–455 K.

¹H, ¹³C, DEPT and HETCOR NMR spectra were taken for samples in CDCl₃ with a Varian GEMINI 200 and a Varian Inova 300 spectrometer with SiMe₄ as an internal reference. The assignments are based on DEPT and HETCOR measurements. ¹H NMR: δ4.50, s, (SCH₂), 4.56, s, (H8, H9), 6.8–6.9, m, (12H, arom.), 7.7–7.8, m, (4H, arom.) ¹³C NMR: δ 36.0 (SCH₂S), 53.7 (C8, C9), 125.53, 126.55, 126.70, 127.32, 142.27, 142.34.

S3. Refinement

All hydrogen atoms in 1 are at calculated positions and they are refined using a riding model with fixed distances and angles.

Computing details

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf-Nonius, 1994); data reduction: WinGX (Farrugia, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. View of (1) showing atom labels. Displacement ellipsoids are drawn at the 50% probability level and hydrogen atoms are omitted for clarity.
	Fig. 2. Packing of (1) seen in the a axis direction.

(1)

Crystal data

C29H20S2	Dx = 1.408 Mg m^−3
Mr = 432.57	Melting point = 454–455 K
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54180 Å
a = 10.619 (2) Å	Cell parameters from 25 reflections
b = 16.605 (3) Å	θ = 5–10°
c = 11.966 (2) Å	µ = 2.46 mm^−1
β = 104.67 (3)°	T = 193 K
V = 2041.2 (7) Å^3	Prismatic, light brown
Z = 4	0.24 × 0.22 × 0.21 mm
F(000) = 904

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.044
Radiation source: fine-focus sealed tube	θmax = 65.0°, θmin = 4.3°
Graphite monochromator	h = −12→0
ω/2θ scans	k = 0→19
3681 measured reflections	l = −13→14
3460 independent reflections	3 standard reflections every 100 reflections
3057 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.113	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0652P)^2 + 1.5819P] where P = (Fo^2 + 2Fc^2)/3
3460 reflections	(Δ/σ)max < 0.001
280 parameters	Δρmax = 0.61 e Å^−3
0 restraints	Δρmin = −0.47 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
S1	0.28760 (5)	1.05662 (3)	0.11707 (5)	0.02406 (16)
S3	0.27661 (5)	0.92906 (3)	−0.04435 (4)	0.02488 (16)
C2	0.1955 (2)	1.01884 (14)	−0.01808 (19)	0.0274 (5)
H2B	0.1927	1.0588	−0.0801	0.033*
H2C	0.1053	1.0067	−0.0148	0.033*
C3a	0.29629 (19)	0.88556 (12)	0.09968 (17)	0.0185 (4)
C3b	0.42299 (18)	0.83649 (12)	0.12984 (18)	0.0187 (4)
C4	0.5245 (2)	0.84691 (14)	0.0766 (2)	0.0251 (5)
H4B	0.5159	0.8847	0.0155	0.030*
C5	0.6379 (2)	0.80241 (14)	0.1124 (2)	0.0292 (5)
H5B	0.7059	0.8094	0.0748	0.035*
C6	0.6533 (2)	0.74802 (14)	0.2021 (2)	0.0293 (5)
H6B	0.7317	0.7181	0.2268	0.035*
C7	0.5531 (2)	0.73757 (13)	0.25552 (19)	0.0239 (5)
H7B	0.5630	0.7002	0.3172	0.029*
C7a	0.43861 (19)	0.78101 (12)	0.22010 (18)	0.0192 (4)
C8	0.33196 (18)	0.77423 (12)	0.28210 (18)	0.0188 (4)
H8B	0.3427	0.7220	0.3251	0.023*
C9	0.34004 (18)	0.84602 (12)	0.37335 (17)	0.0185 (4)
H9A	0.3539	0.8221	0.4522	0.022*
C9a	0.45069 (19)	0.90322 (13)	0.37410 (17)	0.0192 (4)
C10	0.5668 (2)	0.90078 (14)	0.46031 (19)	0.0245 (5)
H10C	0.5768	0.8629	0.5214	0.029*
C11	0.6675 (2)	0.95283 (15)	0.4579 (2)	0.0288 (5)
H11A	0.7461	0.9510	0.5174	0.035*
C12	0.6536 (2)	1.00771 (15)	0.3686 (2)	0.0278 (5)
H12A	0.7229	1.0433	0.3664	0.033*
C13	0.5384 (2)	1.01081 (14)	0.28227 (19)	0.0239 (5)
H13A	0.5298	1.0483	0.2208	0.029*
C13a	0.43593 (18)	0.95988 (13)	0.28469 (17)	0.0183 (4)
C13b	0.30394 (19)	0.96045 (12)	0.19461 (17)	0.0178 (4)
C14	0.18304 (19)	0.82842 (12)	0.10234 (18)	0.0186 (4)
C15	0.06354 (19)	0.82889 (13)	0.02061 (19)	0.0227 (5)
H15A	0.0488	0.8662	−0.0416	0.027*
C16	−0.0341 (2)	0.77566 (14)	0.0289 (2)	0.0283 (5)
H16A	−0.1152	0.7769	−0.0274	0.034*
C17	−0.0146 (2)	0.72079 (14)	0.1184 (2)	0.0285 (5)
H17A	−0.0816	0.6843	0.1237	0.034*
C18	0.1044 (2)	0.71963 (13)	0.2006 (2)	0.0249 (5)
H18A	0.1186	0.6821	0.2624	0.030*
C19	0.20260 (18)	0.77288 (12)	0.19294 (18)	0.0193 (4)
C20	0.21582 (19)	0.89387 (12)	0.34745 (18)	0.0187 (4)
C21	0.1227 (2)	0.88262 (13)	0.40882 (18)	0.0231 (5)
H21A	0.1360	0.8429	0.4677	0.028*
C22	0.0107 (2)	0.92867 (15)	0.3852 (2)	0.0287 (5)
H22A	−0.0535	0.9201	0.4267	0.034*
C23	−0.0073 (2)	0.98713 (15)	0.3009 (2)	0.0292 (5)
H23A	−0.0832	1.0198	0.2855	0.035*
C24	0.0853 (2)	0.99856 (14)	0.23817 (18)	0.0229 (5)
H24A	0.0718	1.0389	0.1801	0.027*
C25	0.19644 (19)	0.95182 (12)	0.25945 (17)	0.0173 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0265 (3)	0.0192 (3)	0.0249 (3)	−0.0018 (2)	0.0035 (2)	0.0037 (2)
S3	0.0289 (3)	0.0276 (3)	0.0189 (3)	0.0039 (2)	0.0074 (2)	0.0037 (2)
C2	0.0257 (11)	0.0259 (12)	0.0272 (12)	−0.0005 (9)	0.0007 (9)	0.0016 (9)
C3a	0.0155 (10)	0.0209 (10)	0.0191 (10)	0.0023 (8)	0.0046 (8)	0.0012 (8)
C3b	0.0147 (10)	0.0192 (10)	0.0228 (11)	0.0018 (8)	0.0057 (8)	−0.0012 (8)
C4	0.0233 (11)	0.0261 (11)	0.0297 (12)	0.0013 (9)	0.0139 (9)	0.0010 (9)
C5	0.0203 (11)	0.0317 (12)	0.0406 (13)	0.0015 (9)	0.0172 (10)	−0.0030 (10)
C6	0.0189 (11)	0.0299 (12)	0.0397 (13)	0.0083 (9)	0.0084 (9)	−0.0021 (11)
C7	0.0207 (10)	0.0226 (11)	0.0281 (11)	0.0056 (9)	0.0057 (9)	0.0009 (9)
C7a	0.0156 (10)	0.0187 (10)	0.0235 (11)	0.0023 (8)	0.0056 (8)	−0.0006 (8)
C8	0.0162 (10)	0.0166 (10)	0.0241 (11)	0.0017 (8)	0.0062 (8)	0.0036 (8)
C9	0.0150 (9)	0.0229 (11)	0.0181 (10)	0.0035 (8)	0.0048 (8)	0.0038 (8)
C9a	0.0118 (9)	0.0253 (11)	0.0207 (10)	0.0036 (8)	0.0044 (8)	−0.0018 (8)
C10	0.0181 (10)	0.0316 (12)	0.0219 (11)	0.0078 (9)	0.0015 (8)	−0.0020 (9)
C11	0.0123 (10)	0.0407 (13)	0.0306 (12)	0.0028 (9)	0.0001 (9)	−0.0101 (10)
C12	0.0132 (10)	0.0375 (13)	0.0331 (12)	−0.0053 (9)	0.0064 (9)	−0.0087 (10)
C13	0.0186 (10)	0.0297 (12)	0.0255 (11)	−0.0027 (9)	0.0091 (9)	−0.0034 (9)
C13a	0.0117 (9)	0.0231 (10)	0.0203 (10)	0.0018 (8)	0.0042 (8)	−0.0020 (8)
C13b	0.0140 (9)	0.0188 (10)	0.0198 (10)	0.0007 (7)	0.0030 (8)	0.0005 (8)
C14	0.0151 (9)	0.0194 (10)	0.0221 (10)	0.0014 (8)	0.0059 (8)	−0.0028 (8)
C15	0.0169 (10)	0.0240 (11)	0.0258 (11)	0.0062 (8)	0.0030 (8)	−0.0021 (9)
C16	0.0140 (10)	0.0331 (13)	0.0363 (13)	0.0026 (9)	0.0038 (9)	−0.0093 (10)
C17	0.0172 (10)	0.0309 (12)	0.0412 (14)	−0.0054 (9)	0.0145 (10)	−0.0087 (10)
C18	0.0210 (10)	0.0259 (11)	0.0315 (12)	−0.0013 (9)	0.0134 (9)	−0.0019 (9)
C19	0.0142 (10)	0.0205 (10)	0.0245 (11)	0.0020 (8)	0.0074 (8)	−0.0020 (8)
C20	0.0137 (9)	0.0217 (11)	0.0212 (10)	−0.0015 (8)	0.0052 (8)	−0.0021 (8)
C21	0.0206 (10)	0.0271 (11)	0.0236 (11)	−0.0025 (9)	0.0089 (9)	−0.0012 (9)
C22	0.0172 (10)	0.0409 (14)	0.0322 (12)	−0.0011 (9)	0.0139 (9)	−0.0061 (10)
C23	0.0164 (10)	0.0379 (13)	0.0333 (12)	0.0077 (9)	0.0065 (9)	−0.0054 (10)
C24	0.0178 (10)	0.0269 (11)	0.0224 (11)	0.0038 (8)	0.0024 (8)	−0.0016 (9)
C25	0.0132 (9)	0.0191 (10)	0.0189 (10)	−0.0012 (8)	0.0029 (8)	−0.0030 (8)

Geometric parameters (Å, º)

S1—C2	1.779 (2)	C10—H10C	0.9500
S1—C13b	1.833 (2)	C11—C12	1.384 (4)
S3—C2	1.789 (2)	C11—H11A	0.9500
S3—C3a	1.831 (2)	C12—C13	1.387 (3)
C2—H2B	0.9900	C12—H12A	0.9500
C2—H2C	0.9900	C13—C13a	1.385 (3)
C3a—C3b	1.536 (3)	C13—H13A	0.9500
C3a—C14	1.539 (3)	C13a—C13b	1.537 (3)
C3a—C13b	1.672 (3)	C13b—C25	1.541 (3)
C3b—C4	1.395 (3)	C14—C15	1.392 (3)
C3b—C7a	1.397 (3)	C14—C19	1.398 (3)
C4—C5	1.385 (3)	C15—C16	1.385 (3)
C4—H4B	0.9500	C15—H15A	0.9500
C5—C6	1.380 (3)	C16—C17	1.381 (3)
C5—H5B	0.9500	C16—H16A	0.9500
C6—C7	1.384 (3)	C17—C18	1.391 (3)
C6—H6B	0.9500	C17—H17A	0.9500
C7—C7a	1.385 (3)	C18—C19	1.388 (3)
C7—H7B	0.9500	C18—H18A	0.9500
C7a—C8	1.507 (3)	C20—C21	1.386 (3)
C8—C19	1.511 (3)	C20—C25	1.403 (3)
C8—C9	1.604 (3)	C21—C22	1.382 (3)
C8—H8B	1.0000	C21—H21A	0.9500
C9—C20	1.503 (3)	C22—C23	1.378 (3)
C9—C9a	1.509 (3)	C22—H22A	0.9500
C9—H9A	1.0000	C23—C24	1.393 (3)
C9a—C10	1.393 (3)	C23—H23A	0.9500
C9a—C13a	1.403 (3)	C24—C25	1.382 (3)
C10—C11	1.381 (3)	C24—H24A	0.9500
C2—S1—C13b	96.47 (10)	C12—C11—H11A	120.1
C2—S3—C3a	96.24 (10)	C11—C12—C13	120.1 (2)
S1—C2—S3	106.00 (12)	C11—C12—H12A	119.9
S1—C2—H2B	110.5	C13—C12—H12A	119.9
S3—C2—H2B	110.5	C13a—C13—C12	120.7 (2)
S1—C2—H2C	110.5	C13a—C13—H13A	119.6
S3—C2—H2C	110.5	C12—C13—H13A	119.6
H2B—C2—H2C	108.7	C13—C13a—C9a	119.26 (19)
C3b—C3a—C14	108.11 (16)	C13—C13a—C13b	124.32 (19)
C3b—C3a—C13b	110.24 (15)	C9a—C13a—C13b	116.42 (18)
C14—C3a—C13b	110.38 (15)	C13a—C13b—C25	107.86 (16)
C3b—C3a—S3	108.35 (14)	C13a—C13b—C3a	110.52 (15)
C14—C3a—S3	111.05 (14)	C25—C13b—C3a	110.98 (15)
C13b—C3a—S3	108.68 (13)	C13a—C13b—S1	108.25 (14)
C4—C3b—C7a	118.72 (19)	C25—C13b—S1	110.41 (14)
C4—C3b—C3a	124.01 (19)	C3a—C13b—S1	108.78 (13)
C7a—C3b—C3a	117.19 (17)	C15—C14—C19	118.58 (19)
C5—C4—C3b	120.3 (2)	C15—C14—C3a	124.07 (19)
C5—C4—H4B	119.8	C19—C14—C3a	117.35 (17)
C3b—C4—H4B	119.8	C16—C15—C14	120.8 (2)
C6—C5—C4	120.8 (2)	C16—C15—H15A	119.6
C6—C5—H5B	119.6	C14—C15—H15A	119.6
C4—C5—H5B	119.6	C17—C16—C15	120.6 (2)
C5—C6—C7	119.2 (2)	C17—C16—H16A	119.7
C5—C6—H6B	120.4	C15—C16—H16A	119.7
C7—C6—H6B	120.4	C16—C17—C18	119.2 (2)
C6—C7—C7a	120.7 (2)	C16—C17—H17A	120.4
C6—C7—H7B	119.6	C18—C17—H17A	120.4
C7a—C7—H7B	119.6	C19—C18—C17	120.5 (2)
C7—C7a—C3b	120.22 (19)	C19—C18—H18A	119.7
C7—C7a—C8	121.42 (19)	C17—C18—H18A	119.7
C3b—C7a—C8	118.23 (17)	C18—C19—C14	120.31 (19)
C7a—C8—C19	108.40 (17)	C18—C19—C8	121.79 (19)
C7a—C8—C9	111.23 (16)	C14—C19—C8	117.88 (18)
C19—C8—C9	111.96 (16)	C21—C20—C25	120.11 (19)
C7a—C8—H8B	108.4	C21—C20—C9	121.76 (19)
C19—C8—H8B	108.4	C25—C20—C9	118.13 (18)
C9—C8—H8B	108.4	C22—C21—C20	120.7 (2)
C20—C9—C9a	108.05 (16)	C22—C21—H21A	119.7
C20—C9—C8	111.07 (16)	C20—C21—H21A	119.7
C9a—C9—C8	112.28 (16)	C23—C22—C21	119.5 (2)
C20—C9—H9A	108.4	C23—C22—H22A	120.2
C9a—C9—H9A	108.4	C21—C22—H22A	120.2
C8—C9—H9A	108.4	C22—C23—C24	120.3 (2)
C10—C9a—C13a	119.41 (19)	C22—C23—H23A	119.9
C10—C9a—C9	121.85 (19)	C24—C23—H23A	119.9
C13a—C9a—C9	118.74 (17)	C25—C24—C23	120.7 (2)
C11—C10—C9a	120.8 (2)	C25—C24—H24A	119.6
C11—C10—H10C	119.6	C23—C24—H24A	119.6
C9a—C10—H10C	119.6	C24—C25—C20	118.67 (19)
C10—C11—C12	119.7 (2)	C24—C25—C13b	124.22 (19)
C10—C11—H11A	120.1	C20—C25—C13b	117.09 (17)
C13b—S1—C2—S3	−46.59 (13)	S3—C3a—C13b—C13a	−118.02 (15)
C3a—S3—C2—S1	46.98 (13)	C3b—C3a—C13b—C25	−119.03 (18)
C2—S3—C3a—C3b	−147.83 (14)	C14—C3a—C13b—C25	0.3 (2)
C2—S3—C3a—C14	93.57 (15)	S3—C3a—C13b—C25	122.36 (15)
C2—S3—C3a—C13b	−28.03 (14)	C3b—C3a—C13b—S1	119.31 (15)
C14—C3a—C3b—C4	140.8 (2)	C14—C3a—C13b—S1	−121.32 (15)
C13b—C3a—C3b—C4	−98.4 (2)	S3—C3a—C13b—S1	0.69 (15)
S3—C3a—C3b—C4	20.4 (3)	C2—S1—C13b—C13a	147.28 (15)
C14—C3a—C3b—C7a	−42.4 (2)	C2—S1—C13b—C25	−94.87 (15)
C13b—C3a—C3b—C7a	78.3 (2)	C2—S1—C13b—C3a	27.15 (14)
S3—C3a—C3b—C7a	−162.84 (16)	C3b—C3a—C14—C15	−137.7 (2)
C7a—C3b—C4—C5	0.5 (3)	C13b—C3a—C14—C15	101.6 (2)
C3a—C3b—C4—C5	177.3 (2)	S3—C3a—C14—C15	−19.0 (2)
C3b—C4—C5—C6	−0.9 (4)	C3b—C3a—C14—C19	42.3 (2)
C4—C5—C6—C7	0.7 (4)	C13b—C3a—C14—C19	−78.3 (2)
C5—C6—C7—C7a	−0.1 (3)	S3—C3a—C14—C19	161.06 (15)
C6—C7—C7a—C3b	−0.3 (3)	C19—C14—C15—C16	0.2 (3)
C6—C7—C7a—C8	−176.1 (2)	C3a—C14—C15—C16	−179.81 (19)
C4—C3b—C7a—C7	0.1 (3)	C14—C15—C16—C17	−0.2 (3)
C3a—C3b—C7a—C7	−176.88 (19)	C15—C16—C17—C18	0.2 (3)
C4—C3b—C7a—C8	176.03 (19)	C16—C17—C18—C19	−0.1 (3)
C3a—C3b—C7a—C8	−0.9 (3)	C17—C18—C19—C14	0.0 (3)
C7—C7a—C8—C19	−139.4 (2)	C17—C18—C19—C8	178.79 (19)
C3b—C7a—C8—C19	44.7 (2)	C15—C14—C19—C18	0.0 (3)
C7—C7a—C8—C9	97.1 (2)	C3a—C14—C19—C18	179.94 (18)
C3b—C7a—C8—C9	−78.8 (2)	C15—C14—C19—C8	−178.89 (18)
C7a—C8—C9—C20	121.80 (18)	C3a—C14—C19—C8	1.1 (3)
C19—C8—C9—C20	0.4 (2)	C7a—C8—C19—C18	136.5 (2)
C7a—C8—C9—C9a	0.7 (2)	C9—C8—C19—C18	−100.5 (2)
C19—C8—C9—C9a	−120.77 (18)	C7a—C8—C19—C14	−44.7 (2)
C20—C9—C9a—C10	134.9 (2)	C9—C8—C19—C14	78.4 (2)
C8—C9—C9a—C10	−102.3 (2)	C9a—C9—C20—C21	−135.6 (2)
C20—C9—C9a—C13a	−45.6 (2)	C8—C9—C20—C21	100.8 (2)
C8—C9—C9a—C13a	77.2 (2)	C9a—C9—C20—C25	43.6 (2)
C13a—C9a—C10—C11	−0.7 (3)	C8—C9—C20—C25	−80.0 (2)
C9—C9a—C10—C11	178.82 (19)	C25—C20—C21—C22	−0.7 (3)
C9a—C10—C11—C12	−0.4 (3)	C9—C20—C21—C22	178.5 (2)
C10—C11—C12—C13	0.5 (3)	C20—C21—C22—C23	−1.0 (3)
C11—C12—C13—C13a	0.6 (3)	C21—C22—C23—C24	1.4 (3)
C12—C13—C13a—C9a	−1.7 (3)	C22—C23—C24—C25	−0.2 (3)
C12—C13—C13a—C13b	178.44 (19)	C23—C24—C25—C20	−1.5 (3)
C10—C9a—C13a—C13	1.7 (3)	C23—C24—C25—C13b	−179.82 (19)
C9—C9a—C13a—C13	−177.78 (18)	C21—C20—C25—C24	1.9 (3)
C10—C9a—C13a—C13b	−178.41 (18)	C9—C20—C25—C24	−177.26 (18)
C9—C9a—C13a—C13b	2.1 (3)	C21—C20—C25—C13b	−179.64 (18)
C13—C13a—C13b—C25	−137.7 (2)	C9—C20—C25—C13b	1.2 (3)
C9a—C13a—C13b—C25	42.5 (2)	C13a—C13b—C25—C24	133.9 (2)
C13—C13a—C13b—C3a	100.8 (2)	C3a—C13b—C25—C24	−104.9 (2)
C9a—C13a—C13b—C3a	−79.0 (2)	S1—C13b—C25—C24	15.8 (3)
C13—C13a—C13b—S1	−18.2 (2)	C13a—C13b—C25—C20	−44.5 (2)
C9a—C13a—C13b—S1	161.94 (15)	C3a—C13b—C25—C20	76.7 (2)
C3b—C3a—C13b—C13a	0.6 (2)	S1—C13b—C25—C20	−162.55 (15)
C14—C3a—C13b—C13a	119.96 (18)