Asymmetric ruthenium-catalysed [2+2] cyclo­additions between bicyclic alkenes and chiral aryl-substituted acetyl­enic acyl camphorsultam alkynes

The regio- and absolute stereochemistry of (7S)-N-[4-(3-thien­yl)tricyclo­[4.2.1.0^2,5]non-3-en-3-ylcarbon­yl]-2,10-camphorsultam tetra­hydro­furan hemisolvate, C₂₄H₂₉NO₃S₂·0.5C₄H₈O, and (7S)-N-[4-(4-tol­yl)tricyclo­[4.2.1.0^2,5]non-3-en-3-ylcarbon­yl]-2,10-camphorsultam, C₂₇H₃₃NO₃S, have been established. One contains a half-occupancy tetra­hydro­furan solvent mol­ecule located on a twofold axis and the other contains two crystallographically unique mol­ecules which are nearly identical. The extended structures of both complexes can be explained via weak C—H...O interactions, which link the molecules together into two-dimensional sheets in the ab plane for the thienyl complex and ultimately into a three-dimensional structure for the tolyl derivative. The stereochemistry of both structures confirms that [2+2] cyclo­additions of bicyclic alkenes and alkynes catalysed by ruthenium are exclusively exo.

S1. Comment

Recently, the metal-catalyzed [2+2] cycloaddition reaction between bicyclic alkenes and alkynes has been utilized by several research groups as a means to generate cyclobutene rings. In terms of an asymmetric version of this process, both a chiral rhodium catalyst (Shibata et al., 2006) and a ruthenium-catalyzed (Villeneuve & Tam, 2004) reaction involving a chiral precursor have produced chiral [2+2] cyclobutene products. The ruthenium-catalyzed [2+2] cycloaddition between norbornene and a phenylactyleneacyl camphorsultam (chiral) yielded two diastereomers in a 131:1 ratio. The absolute stereochemistry of the major diastereomer (V) was established by single-crystal X-ray diffraction (Lough et al.,2004).

As an extension of this study, the Tam group is investigating the selectivity effect of different organic groups attached at the acetylenic position (see scheme). In this paper, we present the results of ruthenium-catalyzed [2+2] cycloadditions of norbornene, (I), with 3-thiophenylacteyleneacylcamphorsultam, (III), and 4-tolylacteyleneacylcamphorsultam, (IV). This yielded the expected complexes C₂₄H₂₉NO₃S₂.0.5C₄H₈O, (VI), and C₂₇H₃₃NO₃S, (VII). Two diastereomers of (VI) were obtained in a 20:1 ratio, whereas the major stereoisomer of (VII) was obtained in a 104:1 ratio over the minor isomer. The absolute stereochemistry of the major isomers, (VI) and (VII), were established by the single-crystal X-ray diffraction analysis described here.

A view of (VI) is shown in Fig. 1. Elucidation of the X-ray structure establishes the absolute configuration of the following atoms in Fig. 1: C2-S, C5-R, C8-R, C14-S, C15-R, C18-S and C19-R. This is the same configuration as that observed for the phenyl derivative (V). There is a tetrahydrofuran (THF) solvent molecule occluded in the structure. It was modeled at half-occupancy, as it is located on a symmetry element, and was refined giving reasonable displacement parameters; this molecule is involved in the extended structure as discussed below.

There are two chemically identical molecules of (VII) in the asymmetric unit. They are very similar structurally with an r.m.s. fit of 0.207 Å (PLATON; Spek, 2009). As expected, both have the same configuration as that observed for (VI). The absolute configuration, as determined by anomalous dispersion, is as follows: C2-S, C5-R, C8-R, C14-S, C15-R, C18-S and C19-R for one molecule, and C32-S, C35-R, C38-R, C44-S, C45-R, C48-S and C49-R for the second. A structure of one of the molecules of (VII) is shown in Fig. 2. The difference in the two molecules is attributed to their spatially different orientations with respect to one another (see below). The geometric data for both structures (VI) and (VII) are in the normal ranges.

Weak C—H···O interactions in (VI) (see Table 1 for geometric parameters and symmetry codes) tie the molecules together. Perhaps the simplest method to describe the packing is using two `classical model' graph-set descriptors (Bernstein et al., 1995). Firstly, a `chain of rings' is formed between two weak interactions (C8—H8A···O2ⁱ and C1—H1B···O3ⁱⁱ) that link molecules together into ribbons along the a axis {motif C²₂(10)[R²₂(9)]; Fig. 3}. Secondly, adjacent ribbons are linked together via reciprocating C14—H14A···O1ⁱⁱⁱ interactions, forming a two-dimensional network [motif R²₂(16)]. There are two further layers in the extension along the c axis, each of which is rotated by 120° with respect to the previous layer. The THF molecule of solvation was refined at half-occupancy, as it is located on a rotational axis; the O atom serves to link the layers together via another weak interaction (C1—H1A···O31).

As with (VI), it is the weak C—H···O interactions that control the geometry observed in the crystal structure of (VII) (Table 2). The nine weak interactions lead to a very extensive set of hydrogen-bonding motifs so only the key graph-set descriptors are noted here. The asymmetric unit contains two molecules, which couple together via two weak interactions (C3—H3B···O31 and C31—H31B···O3) to form an 11-membered ring, and, adjacent to this, a nine-membered ring is formed via C38—H38A···O1ⁱ and C1—H1B···O33ⁱⁱ interactions. This quaternary graph set, somewhat similar to (VI), has the motifs C²₂(10)[R²₂(11)R²₂(9)]: a `chain of rings' yielding ribbons along the a axis (Fig. 4). These a-axis ribbons are connected up and down the c axis according to the binary graph-set descriptor C²₂(12) via C50—H50A···O2ⁱⁱⁱ and C9—H9A···O3^iv interactions, thus forming parallel ribbons in the [010] plane. Finally, a full three-dimensional network is established via C27—H27A···O32^v and C9—H9A···O3^iv interactions, making C²₂(25) connections along the b axis. For completeness, the last two interactions in Table 2 can be described as motif S(7).

While there are no classical hydrogen-bonding networks in either of these structures, the weak interactions do seem to explain the observed geometry, which is understandable as even a weak hydrogen bond will be stronger than the van der Waals interactions. Unlike the previously published phenyl cycloadduct which shows partial π–π stacking between neighbouring phenyl rings (closest contact 3.64 Å) through secondary orbital overlap interactions (Lough et al., 2004), no such π-stacking interactions between either thiophenyl rings or tolyl rings are observed in these crystal structures.

In the case of the [2+2] cycloaddition, these crystal structures have unambiguously identified which are the major diastereomers formed in the asymmetric cycloaddition. The previous phenyl derivative combined with both the thiophenyl and tolyl derivatives herein reaffirm that [2+2] cycloadditions of bicyclic alkenes and alkynes catalyzed by ruthenium are exclusively exo with respect to their stereochemistry.

Related literature

For related literature, see: Lough et al. (2004); Shibata et al. (2006); Spek (2009); Villeneuve & Tam (2004).

S2. Experimental

Preparation of compound (VI) was achieved by addition of norbornene (72.0 mg, 765 mmol), (I), and chiral alkyne (III) (52.2 mg, 0.149 mmol) to Cp*Ru(cod)Cl (please define; 7.6 mg, 0.020 mmol) in THF (0.6 ml). The mixture was stirred for 18 h at 298 K, and subsequent column chromatography of the crude reaction mixture provided a 98% yield of the two diastereomeric cycloadducts in a 20:1 ratio. Evaporative recrystallization of the column-purified product in THF provided the major diastereomer (VI), giving colourless crystals suitable for X-ray analysis.

Similarly, compound (VII) was prepared by addition of norbornene (83.0 mg, 0.881 mmol), (I), and chiral alkyne (IV) (63.2 mg, 0.177 mmol) to Cp*Ru(cod)Cl (7.1 mg, 0.018 mmol) in THF (0.5 ml). The mixture was stirred for 17 h at 298 K, and subsequent column chromatography of the crude reaction mixture provided a 79% yield of the two diastereomeric cycloadducts in a 104:1 ratio. Evaporative recrystallization of the column-purified product in THF provided major diastereomer (VII), giving colourless crystals suitable for X-ray analysis.

Both diastereomeric ratios were back-calculated from the corresponding enantiomeric excesses obtained through cleavage of the chiral auxiliary under reductive conditions (LiAlH₄, AlCl₃), giving an enantiomeric mixture of cycloadduct alcohols that can be resolved using a Chiralcel OJ-H high-performance liquid chromatography column.

S3. Refinement

Standard SADI restraints were used for the dimensions of the disordered solvent (THF), which was refined at half-occupancy. H atoms were positioned geometrically and refined using a riding model with C—H distances of 0.98 Å (CH₃), 0.99 Å (CH₂), 1.00 Å (CH) or 0.95 Å (aromatic CH). U_iso(H) were set at 1.2 times U_eq(C) for all except the methyl H atoms, where U_iso(H) = 1.5U_eq(C).

Computing details

For both compounds, data collection: COLLECT (Nonius, 1997); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008).

Figures

	Fig. 1. A view of the structure of (VI), showing the crystallographic labelling scheme. Displacement ellipsoids are drawn at the 50% probablility level. For the sake of clarity, non-chiral H atoms have been omitted, as has the partial-occupancy THF molecule of solvation.
	Fig. 2. The molecular structure of one of the molecules of (VII), showing the atom-labelling scheme and with displacement ellipsoids drawn at the 50% probablility level. For the sake of clarity, the non-chiral H atoms have been omitted.
	Fig. 3. The packing of (I), showing weak C—H···O interactions as dashed lines. All H atoms, except those attached to atoms involved in weak interactions, have been omitted for clarity. The view is down the c axis, showing the ribbons along the a axis.
	Fig. 4. The packing of (II), showing the weak C—H···O interactions as dashed lines. All H atoms, except those involved in the displayed weak interactions, have been omitted for clarity. The view is down the c axis, showing the formation of a chain along the a axis.

(VI) (7S)-N-[4-(3-thienyl)tricyclo[4.2.1.0^2,5]non-3-ene-3- carbonyl]-2,10-camphorsultam tetrahydrofuran hemisolvate

Crystal data

C24H29NO3S2·0.5C4H8O	Dx = 1.335 Mg m^−3
Mr = 479.65	Melting point: 199 K
Trigonal, P3221	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 32 2"	Cell parameters from 19735 reflections
a = 12.0797 (17) Å	θ = 2.0–27.5°
c = 28.326 (6) Å	µ = 0.25 mm^−1
V = 3579.5 (10) Å^3	T = 150 K
Z = 6	Plate, colourless
F(000) = 1536	0.35 × 0.22 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer	4207 independent reflections
Radiation source: fine-focus sealed tube	3310 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
ϕ scans, and ω scans with κ offsets	θmax = 25.0°, θmin = 2.9°
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997)	h = −14→14
Tmin = 0.916, Tmax = 0.963	k = −11→11
8354 measured reflections	l = −33→33

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)] = 0.038	H-atom parameters constrained
wR(F^2) = 0.084	w = 1/[σ^2^(Fo^2^) + (0.0432P)^2^] where P = (Fo^2^ + 2Fc^2^)/3
S = 1.01	(Δ/σ)max < 0.001
4207 reflections	Δρmax = 0.19 e Å^−3
318 parameters	Δρmin = −0.31 e Å^−3
4 restraints	Absolute structure: Flack (1983), 1788 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.03 (7)

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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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	0.60309 (17)	0.69194 (15)	0.12342 (5)	0.0322 (5)
S1	0.62469 (6)	0.60943 (6)	0.15376 (2)	0.02461 (16)
N1	0.52685 (17)	0.57178 (19)	0.20119 (6)	0.0208 (5)
C1	0.5534 (2)	0.4517 (2)	0.13028 (8)	0.0260 (6)
H1A	0.5087	0.4462	0.1003	0.031*
H1B	0.6198	0.4283	0.1239	0.031*
O2	0.75321 (16)	0.65168 (16)	0.16832 (6)	0.0321 (4)
S2	0.33154 (8)	0.91996 (7)	0.31771 (2)	0.0390 (2)
C2	0.4595 (2)	0.3623 (2)	0.16665 (8)	0.0221 (6)
O3	0.39805 (16)	0.62130 (17)	0.24296 (6)	0.0281 (4)
C3	0.3339 (3)	0.2492 (3)	0.14789 (9)	0.0357 (7)
H3A	0.3505	0.1991	0.1241	0.043*
H3B	0.2779	0.2786	0.1339	0.043*
C4	0.2753 (3)	0.1710 (3)	0.19347 (10)	0.0436 (8)
H4A	0.1946	0.1690	0.2017	0.052*
H4B	0.2578	0.0822	0.1897	0.052*
C5	0.3773 (3)	0.2418 (2)	0.23128 (9)	0.0345 (7)
H5A	0.3715	0.1878	0.2590	0.041*
C6	0.5030 (3)	0.2946 (2)	0.20299 (9)	0.0282 (6)
C7	0.3740 (3)	0.3634 (2)	0.24425 (9)	0.0334 (7)
H7A	0.4341	0.4104	0.2703	0.040*
H7B	0.2869	0.3436	0.2534	0.040*
C8	0.4166 (2)	0.4394 (2)	0.19764 (8)	0.0236 (6)
H8A	0.3424	0.4407	0.1826	0.028*
C9	0.6237 (3)	0.3820 (3)	0.23148 (9)	0.0376 (8)
H9A	0.6310	0.3341	0.2581	0.056*
H9B	0.6182	0.4552	0.2435	0.056*
H9C	0.6990	0.4125	0.2111	0.056*
C10	0.5244 (3)	0.1911 (3)	0.18097 (9)	0.0387 (8)
H10A	0.5978	0.2308	0.1595	0.058*
H10B	0.4480	0.1308	0.1633	0.058*
H10C	0.5412	0.1453	0.2060	0.058*
C11	0.5041 (2)	0.6601 (2)	0.22510 (8)	0.0215 (6)
C12	0.6077 (2)	0.7928 (2)	0.23004 (8)	0.0234 (6)
C13	0.6085 (2)	0.8955 (2)	0.25049 (8)	0.0231 (6)
C14	0.7498 (2)	0.9844 (2)	0.24120 (8)	0.0237 (6)
H14A	0.7692	1.0548	0.2183	0.028*
C15	0.8422 (2)	1.0227 (2)	0.28271 (8)	0.0234 (6)
H15A	0.8345	1.0793	0.3066	0.028*
C16	0.9761 (2)	1.0750 (2)	0.26124 (9)	0.0267 (6)
H16A	1.0433	1.1187	0.2854	0.032*
H16B	0.9906	1.1355	0.2352	0.032*
C17	0.9743 (2)	0.9525 (3)	0.24244 (9)	0.0287 (7)
H17A	0.9913	0.9586	0.2081	0.034*
H17B	1.0384	0.9383	0.2590	0.034*
C18	0.8373 (2)	0.8452 (2)	0.25365 (8)	0.0240 (6)
H18A	0.8250	0.7570	0.2537	0.029*
C19	0.7505 (2)	0.8655 (2)	0.21943 (8)	0.0221 (6)
H19A	0.7743	0.8727	0.1853	0.027*
C20	0.8139 (3)	0.8906 (2)	0.30137 (8)	0.0259 (6)
H20A	0.8749	0.8971	0.3261	0.031*
H20B	0.7249	0.8374	0.3127	0.031*
C21	0.5224 (2)	0.9252 (2)	0.27616 (8)	0.0238 (6)
C22	0.3957 (3)	0.8448 (3)	0.28677 (8)	0.0304 (7)
H22A	0.3493	0.7573	0.2779	0.036*
C23	0.4727 (3)	1.0620 (3)	0.31785 (8)	0.0291 (6)
H23A	0.4850	1.1383	0.3323	0.035*
C24	0.5655 (3)	1.0508 (3)	0.29432 (9)	0.0309 (7)
H24A	0.6503	1.1197	0.2904	0.037*
O31	0.4857 (5)	0.3920 (5)	0.01939 (16)	0.0602 (14)	0.50
C32	0.3989 (9)	0.4359 (10)	0.0075 (6)	0.096 (6)	0.50
H32A	0.3277	0.4022	0.0305	0.115*	0.50
H32B	0.3625	0.4046	−0.0243	0.115*	0.50
C33	0.4687 (16)	0.5782 (14)	0.0082 (8)	0.084 (7)	0.50
H33A	0.4517	0.6108	0.0378	0.101*	0.50
H33B	0.4443	0.6127	−0.0190	0.101*	0.50
C34	0.6067 (13)	0.6130 (13)	0.0051 (13)	0.051 (4)	0.50
H34A	0.6497	0.6712	−0.0218	0.061*	0.50
H34B	0.6530	0.6546	0.0346	0.061*	0.50
C35	0.6007 (13)	0.4869 (16)	−0.0020 (6)	0.054 (4)	0.50
H35A	0.6006	0.4691	−0.0362	0.065*	0.50
H35B	0.6755	0.4880	0.0128	0.065*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0450 (12)	0.0249 (11)	0.0283 (9)	0.0187 (10)	0.0033 (8)	0.0076 (8)
S1	0.0238 (4)	0.0212 (4)	0.0264 (3)	0.0094 (3)	0.0036 (3)	−0.0015 (3)
N1	0.0170 (11)	0.0187 (12)	0.0228 (10)	0.0060 (10)	0.0044 (8)	−0.0026 (9)
C1	0.0289 (16)	0.0247 (14)	0.0252 (14)	0.0141 (13)	−0.0006 (12)	−0.0050 (11)
O2	0.0179 (10)	0.0315 (11)	0.0447 (10)	0.0107 (8)	0.0006 (8)	−0.0082 (9)
S2	0.0400 (5)	0.0405 (5)	0.0433 (4)	0.0252 (4)	0.0084 (4)	−0.0032 (4)
C2	0.0196 (14)	0.0179 (13)	0.0256 (13)	0.0070 (12)	0.0041 (11)	−0.0012 (11)
O3	0.0198 (10)	0.0269 (11)	0.0351 (11)	0.0099 (9)	0.0052 (9)	−0.0035 (9)
C3	0.0295 (17)	0.0261 (17)	0.0422 (17)	0.0069 (14)	0.0008 (14)	−0.0128 (14)
C4	0.0345 (19)	0.0233 (17)	0.0572 (19)	0.0027 (15)	0.0126 (16)	−0.0094 (15)
C5	0.0431 (19)	0.0220 (16)	0.0334 (15)	0.0125 (14)	0.0099 (14)	0.0021 (13)
C6	0.0339 (17)	0.0228 (15)	0.0303 (14)	0.0161 (14)	0.0042 (13)	0.0016 (12)
C7	0.0351 (18)	0.0240 (16)	0.0334 (16)	0.0090 (14)	0.0119 (14)	−0.0001 (13)
C8	0.0182 (14)	0.0174 (15)	0.0279 (14)	0.0035 (12)	−0.0001 (11)	−0.0046 (11)
C9	0.0433 (19)	0.0416 (19)	0.0338 (16)	0.0256 (16)	−0.0045 (15)	0.0029 (14)
C10	0.049 (2)	0.0316 (17)	0.0431 (17)	0.0258 (16)	0.0092 (15)	0.0035 (14)
C11	0.0248 (15)	0.0228 (15)	0.0207 (13)	0.0148 (12)	−0.0042 (11)	−0.0044 (11)
C12	0.0259 (16)	0.0220 (15)	0.0240 (13)	0.0134 (13)	−0.0002 (12)	−0.0012 (12)
C13	0.0222 (15)	0.0277 (16)	0.0209 (13)	0.0137 (13)	−0.0036 (11)	−0.0017 (12)
C14	0.0268 (16)	0.0201 (15)	0.0244 (14)	0.0119 (13)	−0.0004 (12)	0.0020 (11)
C15	0.0250 (15)	0.0186 (14)	0.0242 (13)	0.0092 (12)	−0.0013 (11)	−0.0029 (11)
C16	0.0229 (16)	0.0211 (15)	0.0317 (14)	0.0077 (13)	−0.0016 (12)	−0.0009 (12)
C17	0.0216 (15)	0.0295 (17)	0.0343 (15)	0.0124 (13)	−0.0008 (13)	−0.0027 (13)
C18	0.0230 (15)	0.0201 (14)	0.0280 (14)	0.0101 (12)	0.0021 (11)	0.0026 (11)
C19	0.0232 (15)	0.0206 (13)	0.0212 (13)	0.0099 (13)	−0.0012 (11)	−0.0028 (11)
C20	0.0263 (16)	0.0254 (15)	0.0248 (13)	0.0120 (13)	−0.0034 (12)	0.0000 (12)
C21	0.0239 (16)	0.0265 (16)	0.0251 (13)	0.0157 (13)	−0.0013 (11)	−0.0006 (12)
C22	0.0316 (17)	0.0285 (16)	0.0348 (15)	0.0178 (14)	0.0046 (13)	−0.0058 (13)
C23	0.0392 (17)	0.0277 (16)	0.0294 (15)	0.0235 (14)	−0.0038 (13)	−0.0065 (12)
C24	0.0328 (16)	0.0275 (17)	0.0355 (15)	0.0173 (14)	−0.0033 (13)	−0.0037 (13)
O31	0.061 (4)	0.053 (3)	0.048 (3)	0.014 (3)	−0.001 (3)	0.007 (3)
C32	0.051 (6)	0.158 (14)	0.066 (11)	0.043 (7)	−0.008 (5)	0.040 (11)
C33	0.076 (11)	0.163 (17)	0.062 (10)	0.096 (12)	0.012 (8)	0.025 (9)
C34	0.074 (9)	0.051 (7)	0.028 (12)	0.032 (3)	0.010 (6)	−0.006 (5)
C35	0.045 (6)	0.080 (10)	0.027 (5)	0.022 (6)	0.018 (5)	−0.005 (6)

Geometric parameters (Å, º)

O1—S1	1.4354 (17)	C13—C21	1.454 (3)
S1—O2	1.4313 (18)	C13—C14	1.517 (3)
S1—N1	1.6944 (18)	C14—C15	1.525 (3)
S1—C1	1.782 (2)	C14—C19	1.567 (3)
N1—C11	1.402 (3)	C14—H14A	1.0000
N1—C8	1.487 (3)	C15—C16	1.537 (3)
C1—C2	1.513 (3)	C15—C20	1.548 (3)
C1—H1A	0.9900	C15—H15A	1.0000
C1—H1B	0.9900	C16—C17	1.563 (3)
S2—C22	1.702 (2)	C16—H16A	0.9900
S2—C23	1.710 (3)	C16—H16B	0.9900
C2—C3	1.542 (3)	C17—C18	1.541 (3)
C2—C8	1.546 (3)	C17—H17A	0.9900
C2—C6	1.560 (3)	C17—H17B	0.9900
O3—C11	1.232 (3)	C18—C19	1.535 (3)
C3—C4	1.546 (4)	C18—C20	1.537 (3)
C3—H3A	0.9900	C18—H18A	1.0000
C3—H3B	0.9900	C19—H19A	1.0000
C4—C5	1.531 (4)	C20—H20A	0.9900
C4—H4A	0.9900	C20—H20B	0.9900
C4—H4B	0.9900	C21—C22	1.374 (4)
C5—C7	1.533 (3)	C21—C24	1.431 (3)
C5—C6	1.545 (4)	C22—H22A	0.9500
C5—H5A	1.0000	C23—C24	1.367 (4)
C6—C10	1.531 (4)	C23—H23A	0.9500
C6—C9	1.534 (3)	C24—H24A	0.9500
C7—C8	1.543 (3)	O31—C35	1.422 (12)
C7—H7A	0.9900	O31—C32	1.431 (12)
C7—H7B	0.9900	C32—C33	1.489 (14)
C8—H8A	1.0000	C32—H32A	0.9900
C9—H9A	0.9800	C32—H32B	0.9900
C9—H9B	0.9800	C33—C34	1.504 (11)
C9—H9C	0.9800	C33—H33A	0.9900
C10—H10A	0.9800	C33—H33B	0.9900
C10—H10B	0.9800	C34—C35	1.502 (12)
C10—H10C	0.9800	C34—H34A	0.9900
C11—C12	1.466 (4)	C34—H34B	0.9900
C12—C13	1.365 (3)	C35—H35A	0.9900
C12—C19	1.524 (3)	C35—H35B	0.9900
O2—S1—O1	117.80 (11)	C13—C14—C15	118.3 (2)
O2—S1—N1	110.72 (10)	C13—C14—C19	86.51 (19)
O1—S1—N1	108.45 (10)	C15—C14—C19	104.01 (19)
O2—S1—C1	110.29 (11)	C13—C14—H14A	114.7
O1—S1—C1	111.15 (11)	C15—C14—H14A	114.7
N1—S1—C1	96.30 (11)	C19—C14—H14A	114.7
C11—N1—C8	116.10 (18)	C14—C15—C16	106.25 (19)
C11—N1—S1	123.68 (16)	C14—C15—C20	101.5 (2)
C8—N1—S1	111.38 (14)	C16—C15—C20	101.7 (2)
C2—C1—S1	107.33 (16)	C14—C15—H15A	115.2
C2—C1—H1A	110.2	C16—C15—H15A	115.2
S1—C1—H1A	110.2	C20—C15—H15A	115.2
C2—C1—H1B	110.2	C15—C16—C17	103.43 (19)
S1—C1—H1B	110.2	C15—C16—H16A	111.1
H1A—C1—H1B	108.5	C17—C16—H16A	111.1
C22—S2—C23	92.56 (14)	C15—C16—H16B	111.1
C1—C2—C3	116.88 (19)	C17—C16—H16B	111.1
C1—C2—C8	108.33 (19)	H16A—C16—H16B	109.0
C3—C2—C8	104.6 (2)	C18—C17—C16	103.1 (2)
C1—C2—C6	119.6 (2)	C18—C17—H17A	111.2
C3—C2—C6	101.7 (2)	C16—C17—H17A	111.2
C8—C2—C6	104.09 (19)	C18—C17—H17B	111.2
C2—C3—C4	101.6 (2)	C16—C17—H17B	111.2
C2—C3—H3A	111.5	H17A—C17—H17B	109.1
C4—C3—H3A	111.5	C19—C18—C20	103.7 (2)
C2—C3—H3B	111.5	C19—C18—C17	105.5 (2)
C4—C3—H3B	111.5	C20—C18—C17	101.2 (2)
H3A—C3—H3B	109.3	C19—C18—H18A	115.0
C5—C4—C3	104.4 (2)	C20—C18—H18A	115.0
C5—C4—H4A	110.9	C17—C18—H18A	115.0
C3—C4—H4A	110.9	C12—C19—C18	116.75 (19)
C5—C4—H4B	110.9	C12—C19—C14	85.83 (18)
C3—C4—H4B	110.9	C18—C19—C14	102.42 (18)
H4A—C4—H4B	108.9	C12—C19—H19A	115.7
C4—C5—C7	107.7 (2)	C18—C19—H19A	115.7
C4—C5—C6	102.6 (2)	C14—C19—H19A	115.7
C7—C5—C6	102.7 (2)	C18—C20—C15	94.70 (18)
C4—C5—H5A	114.2	C18—C20—H20A	112.8
C7—C5—H5A	114.2	C15—C20—H20A	112.8
C6—C5—H5A	114.2	C18—C20—H20B	112.8
C10—C6—C9	106.6 (2)	C15—C20—H20B	112.8
C10—C6—C5	114.0 (2)	H20A—C20—H20B	110.2
C9—C6—C5	114.3 (2)	C22—C21—C24	110.9 (2)
C10—C6—C2	113.5 (2)	C22—C21—C13	128.0 (2)
C9—C6—C2	116.1 (2)	C24—C21—C13	121.1 (2)
C5—C6—C2	92.3 (2)	C21—C22—S2	112.2 (2)
C5—C7—C8	101.8 (2)	C21—C22—H22A	123.9
C5—C7—H7A	111.4	S2—C22—H22A	123.9
C8—C7—H7A	111.4	C24—C23—S2	110.8 (2)
C5—C7—H7B	111.4	C24—C23—H23A	124.6
C8—C7—H7B	111.4	S2—C23—H23A	124.6
H7A—C7—H7B	109.3	C23—C24—C21	113.5 (3)
N1—C8—C7	115.79 (19)	C23—C24—H24A	123.3
N1—C8—C2	107.22 (18)	C21—C24—H24A	123.3
C7—C8—C2	103.9 (2)	C35—O31—C32	101.7 (10)
N1—C8—H8A	109.9	O31—C32—C33	109.1 (10)
C7—C8—H8A	109.9	O31—C32—H32A	109.9
C2—C8—H8A	109.9	C33—C32—H32A	109.9
C6—C9—H9A	109.5	O31—C32—H32B	109.9
C6—C9—H9B	109.5	C33—C32—H32B	109.9
H9A—C9—H9B	109.5	H32A—C32—H32B	108.3
C6—C9—H9C	109.5	C32—C33—C34	103.4 (9)
H9A—C9—H9C	109.5	C32—C33—H33A	111.1
H9B—C9—H9C	109.5	C34—C33—H33A	111.1
C6—C10—H10A	109.5	C32—C33—H33B	111.1
C6—C10—H10B	109.5	C34—C33—H33B	111.1
H10A—C10—H10B	109.5	H33A—C33—H33B	109.1
C6—C10—H10C	109.5	C35—C34—C33	103.8 (6)
H10A—C10—H10C	109.5	C35—C34—H34A	111.0
H10B—C10—H10C	109.5	C33—C34—H34A	111.0
O3—C11—N1	118.1 (2)	C35—C34—H34B	111.0
O3—C11—C12	122.3 (2)	C33—C34—H34B	111.0
N1—C11—C12	119.5 (2)	H34A—C34—H34B	109.0
C13—C12—C11	130.4 (2)	O31—C35—C34	107.0 (9)
C13—C12—C19	93.9 (2)	O31—C35—H35A	110.3
C11—C12—C19	135.5 (2)	C34—C35—H35A	110.3
C12—C13—C21	139.1 (3)	O31—C35—H35B	110.3
C12—C13—C14	93.7 (2)	C34—C35—H35B	110.3
C21—C13—C14	127.0 (2)	H35A—C35—H35B	108.6
O2—S1—N1—C11	88.8 (2)	N1—C11—C12—C13	178.4 (2)
O1—S1—N1—C11	−41.9 (2)	O3—C11—C12—C19	169.1 (2)
C1—S1—N1—C11	−156.72 (19)	N1—C11—C12—C19	−7.9 (4)
O2—S1—N1—C8	−125.26 (16)	C11—C12—C13—C21	2.5 (5)
O1—S1—N1—C8	104.06 (17)	C19—C12—C13—C21	−173.2 (3)
C1—S1—N1—C8	−10.75 (18)	C11—C12—C13—C14	177.7 (3)
O2—S1—C1—C2	106.05 (18)	C19—C12—C13—C14	2.10 (19)
O1—S1—C1—C2	−121.40 (18)	C12—C13—C14—C15	−106.1 (2)
N1—S1—C1—C2	−8.80 (19)	C21—C13—C14—C15	70.0 (3)
S1—C1—C2—C3	142.6 (2)	C12—C13—C14—C19	−2.04 (19)
S1—C1—C2—C8	24.9 (2)	C21—C13—C14—C19	174.1 (2)
S1—C1—C2—C6	−94.0 (2)	C13—C14—C15—C16	162.6 (2)
C1—C2—C3—C4	171.7 (2)	C19—C14—C15—C16	69.0 (2)
C8—C2—C3—C4	−68.6 (2)	C13—C14—C15—C20	56.6 (3)
C6—C2—C3—C4	39.5 (2)	C19—C14—C15—C20	−37.0 (2)
C2—C3—C4—C5	−4.3 (3)	C14—C15—C16—C17	−72.8 (2)
C3—C4—C5—C7	75.2 (3)	C20—C15—C16—C17	33.0 (2)
C3—C4—C5—C6	−32.7 (3)	C15—C16—C17—C18	2.2 (2)
C4—C5—C6—C10	−62.5 (3)	C16—C17—C18—C19	70.7 (2)
C7—C5—C6—C10	−174.1 (2)	C16—C17—C18—C20	−37.0 (2)
C4—C5—C6—C9	174.6 (2)	C13—C12—C19—C18	99.8 (2)
C7—C5—C6—C9	62.9 (3)	C11—C12—C19—C18	−75.4 (3)
C4—C5—C6—C2	54.5 (2)	C13—C12—C19—C14	−2.04 (19)
C7—C5—C6—C2	−57.1 (2)	C11—C12—C19—C14	−177.3 (3)
C1—C2—C6—C10	−70.6 (3)	C20—C18—C19—C12	−60.2 (3)
C3—C2—C6—C10	59.8 (3)	C17—C18—C19—C12	−166.12 (19)
C8—C2—C6—C10	168.3 (2)	C20—C18—C19—C14	31.4 (2)
C1—C2—C6—C9	53.4 (3)	C17—C18—C19—C14	−74.5 (2)
C3—C2—C6—C9	−176.2 (2)	C13—C14—C19—C12	1.83 (17)
C8—C2—C6—C9	−67.7 (3)	C15—C14—C19—C12	120.17 (19)
C1—C2—C6—C5	171.9 (2)	C13—C14—C19—C18	−114.66 (19)
C3—C2—C6—C5	−57.6 (2)	C15—C14—C19—C18	3.7 (2)
C8—C2—C6—C5	50.8 (2)	C19—C18—C20—C15	−53.0 (2)
C4—C5—C7—C8	−65.1 (3)	C17—C18—C20—C15	56.2 (2)
C6—C5—C7—C8	42.8 (3)	C14—C15—C20—C18	54.6 (2)
C11—N1—C8—C7	−69.3 (3)	C16—C15—C20—C18	−54.9 (2)
S1—N1—C8—C7	141.92 (19)	C12—C13—C21—C22	−2.8 (5)
C11—N1—C8—C2	175.32 (19)	C14—C13—C21—C22	−176.9 (2)
S1—N1—C8—C2	26.6 (2)	C12—C13—C21—C24	176.8 (3)
C5—C7—C8—N1	−126.1 (2)	C14—C13—C21—C24	2.8 (4)
C5—C7—C8—C2	−8.8 (3)	C24—C21—C22—S2	0.1 (3)
C1—C2—C8—N1	−32.7 (3)	C13—C21—C22—S2	179.8 (2)
C3—C2—C8—N1	−158.00 (19)	C23—S2—C22—C21	−0.3 (2)
C6—C2—C8—N1	95.7 (2)	C22—S2—C23—C24	0.5 (2)
C1—C2—C8—C7	−155.7 (2)	S2—C23—C24—C21	−0.5 (3)
C3—C2—C8—C7	78.9 (2)	C22—C21—C24—C23	0.3 (3)
C6—C2—C8—C7	−27.4 (3)	C13—C21—C24—C23	−179.4 (2)
C8—N1—C11—O3	3.1 (3)	C35—O31—C32—C33	−35.6 (13)
S1—N1—C11—O3	147.63 (18)	O31—C32—C33—C34	18 (2)
C8—N1—C11—C12	−179.8 (2)	C32—C33—C34—C35	6 (3)
S1—N1—C11—C12	−35.3 (3)	C32—O31—C35—C34	38.8 (19)
O3—C11—C12—C13	−4.7 (4)	C33—C34—C35—O31	−28 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O2^i	1.0	2.59	3.516 (3)	154
C1—H1B···O3^ii	0.99	2.45	3.422 (3)	168
C14—H14A···O1^iii	1.00	2.66	3.500 (3)	141
C1—H1A···O31	0.99	2.36	3.235 (14)	147

Symmetry codes: (i) x−y, −y+1, −z+1/3; (ii) x−y+1, −y+1, −z+1/3; (iii) x−y+1, −y+2, −z+1/3.

(VII) (7S)-N-[4-(4-tolyl)tricyclo[4.2.1.0^2,5]non-3-ene-3-carbonyl]- 2,10-camphorsultam

Crystal data

C27H33NO3S	Dx = 1.266 Mg m^−3
Mr = 451.60	Melting point: 186 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 43635 reflections
a = 11.687 (2) Å	θ = 1.7–27.5°
b = 12.849 (3) Å	µ = 0.17 mm^−1
c = 31.547 (6) Å	T = 150 K
V = 4737.2 (16) Å^3	Block, colourless
Z = 8	0.40 × 0.35 × 0.17 mm
F(000) = 1936

Data collection

Nonius KappaCCD diffractometer	9673 independent reflections
Radiation source: fine-focus sealed tube	7676 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.068
ϕ scans, and ω scans with κ offsets	θmax = 26.4°, θmin = 2.6°
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997)	h = −14→14
Tmin = 0.937, Tmax = 0.972	k = −16→16
44242 measured reflections	l = −39→39

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)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.096	w = 1/[σ^2(Fo^2) + (0.052P)^2 + 0.1513P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
9673 reflections	Δρmax = 0.19 e Å^−3
583 parameters	Δρmin = −0.31 e Å^−3
0 restraints	Absolute structure: Flack (1983), 4291 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (5)

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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

To verify the positions of the C27 methyl hydrogen atoms, they were refined to reliable, stable positions with Uavg = 0.0478.

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

	x	y	z	Uiso*/Ueq
O1	0.81519 (13)	0.82842 (12)	0.87280 (5)	0.0391 (4)
S1	0.70189 (5)	0.78856 (4)	0.868799 (17)	0.02823 (13)
C1	0.70490 (19)	0.65036 (16)	0.86702 (7)	0.0305 (5)
H1A	0.6520	0.6244	0.8449	0.037*
H1B	0.7831	0.6256	0.8604	0.037*
N1	0.63077 (14)	0.79703 (13)	0.91532 (5)	0.0228 (4)
O2	0.63070 (14)	0.83102 (13)	0.83626 (5)	0.0404 (4)
C2	0.66810 (18)	0.61133 (17)	0.91030 (7)	0.0264 (5)
C3	0.6002 (2)	0.50883 (17)	0.91136 (8)	0.0341 (6)
H3A	0.6413	0.4526	0.8962	0.041*
H3B	0.5232	0.5175	0.8988	0.041*
O3	0.47143 (12)	0.86942 (11)	0.94353 (5)	0.0292 (4)
C4	0.5927 (2)	0.48613 (19)	0.95972 (8)	0.0401 (6)
H4A	0.5124	0.4884	0.9697	0.048*
H4B	0.6257	0.4171	0.9665	0.048*
C5	0.6638 (2)	0.57418 (17)	0.97980 (8)	0.0358 (6)
H5A	0.6931	0.5580	1.0088	0.043*
C6	0.7588 (2)	0.59377 (17)	0.94655 (7)	0.0320 (5)
C7	0.5918 (2)	0.67435 (18)	0.97728 (7)	0.0329 (5)
H7A	0.6295	0.7326	0.9924	0.040*
H7B	0.5144	0.6637	0.9892	0.040*
C8	0.58690 (18)	0.69448 (16)	0.92906 (6)	0.0262 (5)
H8A	0.5073	0.6838	0.9183	0.031*
C9	0.8369 (2)	0.68475 (19)	0.95728 (8)	0.0401 (6)
H9A	0.8795	0.6691	0.9833	0.060*
H9B	0.7908	0.7476	0.9616	0.060*
H9C	0.8908	0.6962	0.9339	0.060*
C10	0.8372 (2)	0.49984 (19)	0.93830 (9)	0.0431 (6)
H10A	0.8834	0.5128	0.9129	0.065*
H10B	0.7904	0.4374	0.9340	0.065*
H10C	0.8877	0.4894	0.9627	0.065*
C11	0.56299 (18)	0.88439 (16)	0.92545 (6)	0.0236 (5)
C12	0.61030 (17)	0.98763 (16)	0.91705 (6)	0.0232 (5)
C13	0.56549 (18)	1.08492 (16)	0.92125 (6)	0.0243 (5)
C14	0.68049 (17)	1.13723 (16)	0.91663 (6)	0.0245 (5)
H14A	0.6879	1.1865	0.8922	0.029*
C15	0.73742 (18)	1.17224 (17)	0.95815 (7)	0.0286 (5)
H15A	0.6948	1.2273	0.9740	0.034*
C16	0.86076 (18)	1.20032 (19)	0.94685 (8)	0.0367 (6)
H16A	0.9001	1.2342	0.9710	0.044*
H16B	0.8638	1.2470	0.9219	0.044*
C17	0.91466 (18)	1.09233 (18)	0.93672 (8)	0.0353 (6)
H17A	0.9386	1.0882	0.9067	0.042*
H17B	0.9818	1.0787	0.9550	0.042*
C18	0.81748 (18)	1.01510 (18)	0.94609 (7)	0.0294 (5)
H18A	0.8426	0.9422	0.9522	0.035*
C19	0.73200 (17)	1.02632 (16)	0.90952 (7)	0.0250 (5)
H19A	0.7636	1.0129	0.8806	0.030*
C20	0.7550 (2)	1.07006 (17)	0.98262 (7)	0.0313 (5)
H20A	0.8035	1.0787	1.0081	0.038*
H20B	0.6820	1.0358	0.9903	0.038*
C21	0.45561 (17)	1.13654 (16)	0.92709 (6)	0.0223 (5)
C22	0.35456 (18)	1.08700 (17)	0.93909 (7)	0.0275 (5)
H22A	0.3556	1.0148	0.9456	0.033*
C23	0.25308 (18)	1.14160 (16)	0.94155 (7)	0.0272 (5)
H23A	0.1856	1.1062	0.9501	0.033*
C24	0.24691 (18)	1.24753 (17)	0.93178 (6)	0.0252 (5)
C25	0.34828 (17)	1.29767 (17)	0.92094 (6)	0.0267 (5)
H25A	0.3472	1.3701	0.9149	0.032*
C26	0.45045 (18)	1.24384 (16)	0.91889 (6)	0.0269 (5)
H26A	0.5186	1.2802	0.9118	0.032*
C27	0.13450 (17)	1.30333 (18)	0.93233 (7)	0.0304 (5)
H27A	0.1469	1.3773	0.9264	0.046*
H27B	0.0990	1.2956	0.9603	0.046*
H27C	0.0841	1.2736	0.9107	0.046*
O31	0.34129 (15)	0.59886 (15)	0.86620 (7)	0.0638 (6)
S31	0.23370 (6)	0.62631 (5)	0.88508 (2)	0.04078 (17)
C31	0.2371 (2)	0.75909 (18)	0.90151 (7)	0.0337 (5)
H31A	0.1979	0.7675	0.9291	0.040*
H31B	0.3172	0.7833	0.9045	0.040*
N31	0.13308 (15)	0.64214 (14)	0.84736 (5)	0.0265 (4)
O32	0.1911 (2)	0.56063 (14)	0.91745 (6)	0.0692 (7)
C32	0.17624 (18)	0.82052 (16)	0.86750 (6)	0.0269 (5)
C33	0.1095 (2)	0.91680 (18)	0.88247 (8)	0.0366 (6)
H33A	0.0414	0.8967	0.8993	0.044*
H33B	0.1584	0.9634	0.8997	0.044*
O33	−0.04204 (13)	0.58735 (12)	0.82572 (5)	0.0352 (4)
C34	0.0750 (2)	0.9685 (2)	0.84054 (9)	0.0456 (7)
H34A	−0.0093	0.9697	0.8373	0.055*
H34B	0.1044	1.0407	0.8389	0.055*
C35	0.1307 (2)	0.8996 (2)	0.80669 (8)	0.0407 (6)
H35A	0.1418	0.9350	0.7788	0.049*
C36	0.2439 (2)	0.86511 (18)	0.82844 (7)	0.0325 (5)
C37	0.0622 (2)	0.79756 (18)	0.80405 (7)	0.0376 (6)
H37A	−0.0204	0.8111	0.7998	0.045*
H37B	0.0906	0.7524	0.7809	0.045*
C38	0.08545 (18)	0.74915 (17)	0.84772 (7)	0.0272 (5)
H38A	0.0141	0.7509	0.8652	0.033*
C39	0.3137 (2)	0.7869 (2)	0.80242 (8)	0.0444 (6)
H39A	0.3353	0.8184	0.7753	0.067*
H39B	0.2676	0.7245	0.7972	0.067*
H39C	0.3829	0.7677	0.8181	0.067*
C40	0.3246 (2)	0.9547 (2)	0.83956 (9)	0.0447 (7)
H40A	0.3852	0.9293	0.8584	0.067*
H40B	0.2815	1.0099	0.8539	0.067*
H40C	0.3589	0.9824	0.8135	0.067*
C41	0.0557 (2)	0.56291 (17)	0.83499 (7)	0.0266 (5)
C42	0.10053 (18)	0.45719 (17)	0.83037 (7)	0.0256 (5)
C43	0.04976 (18)	0.36382 (17)	0.82181 (6)	0.0258 (5)
C44	0.16350 (17)	0.30849 (17)	0.81514 (7)	0.0272 (5)
H44A	0.1809	0.2518	0.8359	0.033*
C45	0.20066 (18)	0.28688 (17)	0.76923 (7)	0.0306 (5)
H45A	0.1525	0.2352	0.7536	0.037*
C46	0.32879 (18)	0.26056 (19)	0.77134 (8)	0.0381 (6)
H46A	0.3561	0.2312	0.7442	0.046*
H46B	0.3449	0.2104	0.7944	0.046*
C47	0.3854 (2)	0.3682 (2)	0.78050 (9)	0.0430 (6)
H47A	0.4287	0.3667	0.8075	0.052*
H47B	0.4377	0.3886	0.7573	0.052*
C48	0.28339 (19)	0.44268 (18)	0.78337 (7)	0.0315 (5)
H48A	0.3024	0.5179	0.7794	0.038*
C49	0.22163 (18)	0.41645 (17)	0.82486 (7)	0.0286 (5)
H49A	0.2704	0.4184	0.8509	0.034*
C50	0.2030 (2)	0.39671 (18)	0.74987 (7)	0.0331 (5)
H50A	0.2364	0.3979	0.7210	0.040*
H50B	0.1268	0.4303	0.7498	0.040*
C51	−0.06397 (19)	0.31822 (17)	0.81778 (6)	0.0263 (5)
C52	−0.16743 (18)	0.37249 (18)	0.82097 (7)	0.0308 (5)
H52A	−0.1665	0.4453	0.8261	0.037*
C53	−0.27067 (19)	0.32178 (18)	0.81681 (7)	0.0331 (5)
H53A	−0.3395	0.3606	0.8191	0.040*
C54	−0.27698 (18)	0.21476 (18)	0.80924 (6)	0.0294 (5)
C55	−0.17470 (19)	0.16141 (18)	0.80577 (7)	0.0311 (5)
H55A	−0.1760	0.0887	0.8004	0.037*
C56	−0.07091 (19)	0.21139 (17)	0.80990 (7)	0.0299 (5)
H56A	−0.0023	0.1722	0.8073	0.036*
C57	−0.3900 (2)	0.1602 (2)	0.80431 (8)	0.0407 (6)
H57A	−0.4180	0.1696	0.7753	0.061*
H57B	−0.4453	0.1898	0.8243	0.061*
H57C	−0.3803	0.0859	0.8101	0.061*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0289 (8)	0.0299 (9)	0.0586 (11)	−0.0047 (7)	0.0163 (8)	−0.0051 (8)
S1	0.0301 (3)	0.0258 (3)	0.0287 (3)	0.0023 (2)	0.0071 (2)	0.0004 (2)
C1	0.0336 (12)	0.0285 (12)	0.0294 (11)	−0.0011 (10)	0.0041 (10)	−0.0037 (10)
N1	0.0233 (9)	0.0186 (9)	0.0266 (9)	0.0012 (8)	0.0026 (7)	0.0015 (7)
O2	0.0521 (10)	0.0441 (10)	0.0251 (8)	0.0144 (9)	0.0014 (7)	0.0071 (7)
C2	0.0277 (11)	0.0225 (11)	0.0290 (11)	0.0023 (9)	0.0008 (9)	−0.0024 (9)
C3	0.0341 (13)	0.0242 (12)	0.0439 (15)	0.0002 (11)	0.0007 (11)	−0.0054 (11)
O3	0.0263 (8)	0.0240 (8)	0.0373 (9)	−0.0007 (7)	0.0088 (7)	0.0008 (7)
C4	0.0499 (16)	0.0267 (13)	0.0437 (15)	−0.0008 (12)	0.0022 (12)	0.0065 (11)
C5	0.0468 (15)	0.0252 (12)	0.0354 (13)	0.0033 (11)	−0.0043 (11)	0.0055 (10)
C6	0.0350 (13)	0.0270 (12)	0.0341 (12)	0.0045 (11)	−0.0061 (10)	0.0020 (10)
C7	0.0436 (14)	0.0252 (12)	0.0300 (12)	0.0026 (11)	0.0071 (10)	0.0028 (9)
C8	0.0267 (12)	0.0207 (12)	0.0311 (12)	0.0002 (9)	0.0021 (9)	0.0002 (9)
C9	0.0386 (14)	0.0371 (15)	0.0444 (14)	−0.0009 (12)	−0.0143 (11)	0.0032 (11)
C10	0.0407 (14)	0.0337 (14)	0.0548 (16)	0.0135 (12)	−0.0066 (13)	0.0024 (12)
C11	0.0226 (11)	0.0254 (12)	0.0228 (11)	0.0011 (10)	−0.0005 (9)	0.0011 (9)
C12	0.0233 (11)	0.0223 (12)	0.0239 (11)	−0.0042 (9)	0.0018 (9)	0.0003 (9)
C13	0.0242 (11)	0.0255 (11)	0.0233 (11)	−0.0010 (10)	0.0001 (9)	0.0024 (9)
C14	0.0265 (11)	0.0203 (11)	0.0267 (11)	−0.0007 (9)	0.0046 (9)	0.0012 (9)
C15	0.0253 (12)	0.0249 (12)	0.0358 (12)	−0.0006 (10)	0.0021 (10)	−0.0063 (9)
C16	0.0274 (12)	0.0300 (14)	0.0525 (15)	−0.0057 (11)	0.0007 (11)	−0.0027 (11)
C17	0.0228 (12)	0.0329 (14)	0.0502 (15)	−0.0023 (11)	0.0001 (11)	−0.0011 (11)
C18	0.0249 (12)	0.0260 (12)	0.0374 (13)	0.0012 (10)	−0.0013 (10)	−0.0002 (10)
C19	0.0247 (11)	0.0214 (11)	0.0289 (11)	−0.0019 (9)	0.0043 (9)	−0.0004 (9)
C20	0.0314 (12)	0.0328 (13)	0.0295 (12)	−0.0020 (11)	−0.0036 (10)	−0.0043 (10)
C21	0.0220 (11)	0.0228 (11)	0.0222 (11)	−0.0016 (9)	−0.0019 (8)	−0.0004 (9)
C22	0.0279 (12)	0.0201 (11)	0.0343 (12)	−0.0017 (10)	0.0042 (10)	−0.0001 (9)
C23	0.0243 (11)	0.0239 (12)	0.0334 (12)	−0.0040 (10)	0.0050 (9)	0.0005 (9)
C24	0.0256 (11)	0.0256 (11)	0.0246 (11)	0.0014 (10)	−0.0034 (9)	−0.0006 (9)
C25	0.0286 (12)	0.0194 (11)	0.0322 (12)	0.0011 (10)	−0.0028 (9)	0.0026 (10)
C26	0.0275 (12)	0.0242 (11)	0.0290 (11)	−0.0036 (10)	0.0001 (10)	0.0024 (9)
C27	0.0262 (11)	0.0282 (13)	0.0367 (12)	0.0022 (10)	−0.0015 (9)	0.0006 (10)
O31	0.0364 (10)	0.0484 (12)	0.1067 (17)	0.0185 (9)	−0.0333 (11)	−0.0334 (11)
S31	0.0509 (4)	0.0242 (3)	0.0473 (4)	0.0014 (3)	−0.0262 (3)	−0.0016 (3)
C31	0.0390 (13)	0.0290 (13)	0.0331 (12)	−0.0010 (11)	−0.0095 (11)	−0.0028 (10)
N31	0.0276 (10)	0.0218 (10)	0.0302 (10)	0.0020 (8)	−0.0061 (8)	−0.0035 (8)
O32	0.1203 (18)	0.0377 (11)	0.0497 (12)	−0.0267 (12)	−0.0399 (12)	0.0164 (9)
C32	0.0290 (11)	0.0254 (11)	0.0263 (11)	0.0019 (9)	−0.0055 (10)	−0.0027 (9)
C33	0.0378 (13)	0.0279 (13)	0.0442 (14)	0.0027 (11)	−0.0023 (11)	−0.0083 (11)
O33	0.0241 (9)	0.0283 (9)	0.0530 (10)	0.0034 (7)	−0.0067 (7)	−0.0076 (8)
C34	0.0451 (16)	0.0261 (14)	0.0655 (19)	0.0037 (12)	−0.0179 (14)	−0.0020 (12)
C35	0.0491 (15)	0.0366 (15)	0.0366 (14)	−0.0011 (13)	−0.0129 (12)	0.0083 (11)
C36	0.0367 (13)	0.0313 (13)	0.0296 (12)	−0.0031 (11)	−0.0018 (10)	0.0014 (10)
C37	0.0416 (13)	0.0319 (14)	0.0391 (13)	0.0018 (12)	−0.0153 (11)	0.0014 (11)
C38	0.0256 (12)	0.0241 (12)	0.0319 (12)	0.0037 (9)	−0.0007 (10)	−0.0053 (9)
C39	0.0442 (15)	0.0507 (17)	0.0384 (14)	−0.0015 (14)	0.0081 (12)	−0.0072 (12)
C40	0.0434 (15)	0.0394 (15)	0.0513 (16)	−0.0125 (13)	0.0004 (13)	0.0061 (12)
C41	0.0268 (12)	0.0261 (12)	0.0269 (11)	0.0000 (10)	−0.0011 (10)	−0.0026 (9)
C42	0.0268 (12)	0.0241 (12)	0.0258 (11)	0.0030 (10)	−0.0018 (9)	−0.0031 (9)
C43	0.0296 (12)	0.0258 (12)	0.0219 (11)	0.0025 (10)	−0.0008 (9)	0.0003 (9)
C44	0.0287 (12)	0.0243 (12)	0.0287 (11)	0.0024 (10)	−0.0043 (9)	−0.0008 (9)
C45	0.0319 (12)	0.0245 (12)	0.0354 (12)	0.0052 (11)	−0.0031 (10)	−0.0069 (10)
C46	0.0341 (13)	0.0343 (14)	0.0458 (14)	0.0075 (11)	0.0046 (11)	−0.0072 (11)
C47	0.0271 (13)	0.0420 (16)	0.0600 (17)	0.0027 (12)	0.0037 (12)	−0.0097 (13)
C48	0.0269 (12)	0.0270 (13)	0.0407 (13)	0.0009 (10)	0.0043 (10)	−0.0027 (10)
C49	0.0294 (12)	0.0265 (12)	0.0298 (12)	0.0046 (10)	−0.0062 (10)	−0.0030 (9)
C50	0.0355 (13)	0.0353 (14)	0.0285 (12)	0.0033 (11)	0.0038 (10)	−0.0032 (10)
C51	0.0302 (12)	0.0260 (12)	0.0226 (11)	−0.0015 (10)	−0.0014 (9)	0.0005 (9)
C52	0.0317 (12)	0.0283 (12)	0.0325 (12)	0.0023 (11)	0.0010 (10)	−0.0042 (10)
C53	0.0273 (12)	0.0354 (14)	0.0367 (13)	0.0003 (11)	0.0016 (10)	−0.0039 (10)
C54	0.0309 (12)	0.0335 (13)	0.0237 (11)	−0.0047 (11)	−0.0022 (9)	−0.0015 (10)
C55	0.0369 (14)	0.0238 (12)	0.0326 (12)	−0.0012 (11)	0.0001 (10)	−0.0008 (9)
C56	0.0283 (11)	0.0277 (12)	0.0338 (12)	0.0033 (11)	0.0000 (10)	0.0024 (10)
C57	0.0354 (13)	0.0442 (16)	0.0426 (14)	−0.0056 (12)	−0.0019 (11)	−0.0037 (12)

Geometric parameters (Å, º)

O1—S1	1.4253 (16)	O31—S31	1.435 (2)
S1—O2	1.4296 (16)	S31—O32	1.415 (2)
S1—N1	1.6902 (17)	S31—N31	1.6852 (18)
S1—C1	1.777 (2)	S31—C31	1.784 (2)
C1—C2	1.517 (3)	C31—C32	1.510 (3)
C1—H1A	0.9900	C31—H31A	0.9900
C1—H1B	0.9900	C31—H31B	0.9900
N1—C11	1.410 (3)	N31—C41	1.417 (3)
N1—C8	1.479 (3)	N31—C38	1.483 (3)
C2—C3	1.538 (3)	C32—C38	1.535 (3)
C2—C8	1.547 (3)	C32—C33	1.537 (3)
C2—C6	1.575 (3)	C32—C36	1.572 (3)
C3—C4	1.556 (3)	C33—C34	1.534 (4)
C3—H3A	0.9900	C33—H33A	0.9900
C3—H3B	0.9900	C33—H33B	0.9900
O3—C11	1.228 (2)	O33—C41	1.220 (3)
C4—C5	1.540 (3)	C34—C35	1.532 (4)
C4—H4A	0.9900	C34—H34A	0.9900
C4—H4B	0.9900	C34—H34B	0.9900
C5—C7	1.539 (3)	C35—C37	1.539 (3)
C5—C6	1.548 (3)	C35—C36	1.555 (3)
C5—H5A	1.0000	C35—H35A	1.0000
C6—C9	1.522 (3)	C36—C40	1.529 (3)
C6—C10	1.538 (3)	C36—C39	1.533 (3)
C7—C8	1.544 (3)	C37—C38	1.536 (3)
C7—H7A	0.9900	C37—H37A	0.9900
C7—H7B	0.9900	C37—H37B	0.9900
C8—H8A	1.0000	C38—H38A	1.0000
C9—H9A	0.9800	C39—H39A	0.9800
C9—H9B	0.9800	C39—H39B	0.9800
C9—H9C	0.9800	C39—H39C	0.9800
C10—H10A	0.9800	C40—H40A	0.9800
C10—H10B	0.9800	C40—H40B	0.9800
C10—H10C	0.9800	C40—H40C	0.9800
C11—C12	1.461 (3)	C41—C42	1.463 (3)
C12—C13	1.362 (3)	C42—C43	1.365 (3)
C12—C19	1.525 (3)	C42—C49	1.519 (3)
C13—C21	1.457 (3)	C43—C51	1.458 (3)
C13—C14	1.510 (3)	C43—C44	1.522 (3)
C14—C15	1.536 (3)	C44—C45	1.537 (3)
C14—C19	1.563 (3)	C44—C49	1.575 (3)
C14—H14A	1.0000	C44—H44A	1.0000
C15—C16	1.528 (3)	C45—C46	1.537 (3)
C15—C20	1.537 (3)	C45—C50	1.538 (3)
C15—H15A	1.0000	C45—H45A	1.0000
C16—C17	1.557 (3)	C46—C47	1.560 (3)
C16—H16A	0.9900	C46—H46A	0.9900
C16—H16B	0.9900	C46—H46B	0.9900
C17—C18	1.537 (3)	C47—C48	1.532 (3)
C17—H17A	0.9900	C47—H47A	0.9900
C17—H17B	0.9900	C47—H47B	0.9900
C18—C19	1.533 (3)	C48—C49	1.532 (3)
C18—C20	1.536 (3)	C48—C50	1.532 (3)
C18—H18A	1.0000	C48—H48A	1.0000
C19—H19A	1.0000	C49—H49A	1.0000
C20—H20A	0.9900	C50—H50A	0.9900
C20—H20B	0.9900	C50—H50B	0.9900
C21—C22	1.394 (3)	C51—C56	1.397 (3)
C21—C26	1.404 (3)	C51—C52	1.399 (3)
C22—C23	1.380 (3)	C52—C53	1.378 (3)
C22—H22A	0.9500	C52—H52A	0.9500
C23—C24	1.398 (3)	C53—C54	1.398 (3)
C23—H23A	0.9500	C53—H53A	0.9500
C24—C25	1.391 (3)	C54—C55	1.382 (3)
C24—C27	1.497 (3)	C54—C57	1.503 (3)
C25—C26	1.381 (3)	C55—C56	1.379 (3)
C25—H25A	0.9500	C55—H55A	0.9500
C26—H26A	0.9500	C56—H56A	0.9500
C27—H27A	0.9800	C57—H57A	0.9800
C27—H27B	0.9800	C57—H57B	0.9800
C27—H27C	0.9800	C57—H57C	0.9800
O1—S1—O2	117.85 (11)	O32—S31—O31	117.47 (14)
O1—S1—N1	110.90 (9)	O32—S31—N31	109.61 (11)
O2—S1—N1	108.23 (9)	O31—S31—N31	110.36 (11)
O1—S1—C1	110.09 (11)	O32—S31—C31	111.64 (12)
O2—S1—C1	111.73 (11)	O31—S31—C31	109.63 (12)
N1—S1—C1	95.82 (9)	N31—S31—C31	96.06 (10)
C2—C1—S1	107.24 (14)	C32—C31—S31	106.43 (15)
C2—C1—H1A	110.3	C32—C31—H31A	110.4
S1—C1—H1A	110.3	S31—C31—H31A	110.4
C2—C1—H1B	110.3	C32—C31—H31B	110.4
S1—C1—H1B	110.3	S31—C31—H31B	110.4
H1A—C1—H1B	108.5	H31A—C31—H31B	108.6
C11—N1—C8	116.61 (16)	C41—N31—C38	115.37 (17)
C11—N1—S1	121.60 (14)	C41—N31—S31	123.60 (15)
C8—N1—S1	111.56 (13)	C38—N31—S31	111.61 (13)
C1—C2—C3	116.68 (18)	C31—C32—C38	107.59 (18)
C1—C2—C8	106.85 (17)	C31—C32—C33	116.21 (18)
C3—C2—C8	105.46 (17)	C38—C32—C33	104.78 (17)
C1—C2—C6	120.67 (18)	C31—C32—C36	120.67 (19)
C3—C2—C6	102.05 (17)	C38—C32—C36	104.29 (17)
C8—C2—C6	103.53 (17)	C33—C32—C36	101.69 (18)
C2—C3—C4	102.16 (18)	C34—C33—C32	102.55 (18)
C2—C3—H3A	111.3	C34—C33—H33A	111.3
C4—C3—H3A	111.3	C32—C33—H33A	111.3
C2—C3—H3B	111.3	C34—C33—H33B	111.3
C4—C3—H3B	111.3	C32—C33—H33B	111.3
H3A—C3—H3B	109.2	H33A—C33—H33B	109.2
C5—C4—C3	103.62 (19)	C35—C34—C33	103.82 (19)
C5—C4—H4A	111.0	C35—C34—H34A	111.0
C3—C4—H4A	111.0	C33—C34—H34A	111.0
C5—C4—H4B	111.0	C35—C34—H34B	111.0
C3—C4—H4B	111.0	C33—C34—H34B	111.0
H4A—C4—H4B	109.0	H34A—C34—H34B	109.0
C7—C5—C4	107.39 (19)	C34—C35—C37	108.0 (2)
C7—C5—C6	102.76 (17)	C34—C35—C36	102.63 (19)
C4—C5—C6	103.16 (19)	C37—C35—C36	102.91 (19)
C7—C5—H5A	114.1	C34—C35—H35A	114.0
C4—C5—H5A	114.1	C37—C35—H35A	114.0
C6—C5—H5A	114.1	C36—C35—H35A	114.0
C9—C6—C10	106.44 (19)	C40—C36—C39	106.8 (2)
C9—C6—C5	113.88 (19)	C40—C36—C35	114.3 (2)
C10—C6—C5	114.49 (19)	C39—C36—C35	113.8 (2)
C9—C6—C2	117.08 (18)	C40—C36—C32	113.88 (18)
C10—C6—C2	112.98 (19)	C39—C36—C32	116.6 (2)
C5—C6—C2	91.86 (17)	C35—C36—C32	91.24 (17)
C5—C7—C8	102.19 (17)	C38—C37—C35	101.81 (17)
C5—C7—H7A	111.3	C38—C37—H37A	111.4
C8—C7—H7A	111.3	C35—C37—H37A	111.4
C5—C7—H7B	111.3	C38—C37—H37B	111.4
C8—C7—H7B	111.3	C35—C37—H37B	111.4
H7A—C7—H7B	109.2	H37A—C37—H37B	109.3
N1—C8—C7	115.15 (17)	N31—C38—C32	107.31 (16)
N1—C8—C2	106.90 (16)	N31—C38—C37	115.78 (18)
C7—C8—C2	103.78 (17)	C32—C38—C37	104.18 (18)
N1—C8—H8A	110.2	N31—C38—H38A	109.8
C7—C8—H8A	110.2	C32—C38—H38A	109.8
C2—C8—H8A	110.2	C37—C38—H38A	109.8
C6—C9—H9A	109.5	C36—C39—H39A	109.5
C6—C9—H9B	109.5	C36—C39—H39B	109.5
H9A—C9—H9B	109.5	H39A—C39—H39B	109.5
C6—C9—H9C	109.5	C36—C39—H39C	109.5
H9A—C9—H9C	109.5	H39A—C39—H39C	109.5
H9B—C9—H9C	109.5	H39B—C39—H39C	109.5
C6—C10—H10A	109.5	C36—C40—H40A	109.5
C6—C10—H10B	109.5	C36—C40—H40B	109.5
H10A—C10—H10B	109.5	H40A—C40—H40B	109.5
C6—C10—H10C	109.5	C36—C40—H40C	109.5
H10A—C10—H10C	109.5	H40A—C40—H40C	109.5
H10B—C10—H10C	109.5	H40B—C40—H40C	109.5
O3—C11—N1	118.04 (18)	O33—C41—N31	118.61 (19)
O3—C11—C12	123.79 (19)	O33—C41—C42	123.4 (2)
N1—C11—C12	117.96 (18)	N31—C41—C42	117.74 (19)
C13—C12—C11	132.08 (19)	C43—C42—C41	132.8 (2)
C13—C12—C19	94.27 (17)	C43—C42—C49	94.56 (17)
C11—C12—C19	132.60 (18)	C41—C42—C49	131.7 (2)
C12—C13—C21	140.3 (2)	C42—C43—C51	140.0 (2)
C12—C13—C14	93.26 (16)	C42—C43—C44	93.34 (17)
C21—C13—C14	126.45 (18)	C51—C43—C44	126.60 (19)
C13—C14—C15	115.69 (17)	C43—C44—C45	117.48 (17)
C13—C14—C19	87.19 (15)	C43—C44—C49	86.47 (16)
C15—C14—C19	102.86 (16)	C45—C44—C49	102.75 (18)
C13—C14—H14A	115.7	C43—C44—H44A	115.3
C15—C14—H14A	115.7	C45—C44—H44A	115.3
C19—C14—H14A	115.7	C49—C44—H44A	115.3
C16—C15—C14	106.19 (18)	C46—C45—C44	105.91 (18)
C16—C15—C20	101.13 (18)	C46—C45—C50	101.65 (19)
C14—C15—C20	103.63 (17)	C44—C45—C50	102.32 (17)
C16—C15—H15A	114.8	C46—C45—H45A	115.1
C14—C15—H15A	114.8	C44—C45—H45A	115.1
C20—C15—H15A	114.8	C50—C45—H45A	115.1
C15—C16—C17	102.65 (18)	C45—C46—C47	103.09 (18)
C15—C16—H16A	111.2	C45—C46—H46A	111.1
C17—C16—H16A	111.2	C47—C46—H46A	111.1
C15—C16—H16B	111.2	C45—C46—H46B	111.1
C17—C16—H16B	111.2	C47—C46—H46B	111.1
H16A—C16—H16B	109.1	H46A—C46—H46B	109.1
C18—C17—C16	103.71 (18)	C48—C47—C46	103.56 (17)
C18—C17—H17A	111.0	C48—C47—H47A	111.0
C16—C17—H17A	111.0	C46—C47—H47A	111.0
C18—C17—H17B	111.0	C48—C47—H47B	111.0
C16—C17—H17B	111.0	C46—C47—H47B	111.0
H17A—C17—H17B	109.0	H47A—C47—H47B	109.0
C19—C18—C20	102.20 (17)	C47—C48—C49	106.24 (19)
C19—C18—C17	106.04 (18)	C47—C48—C50	101.29 (18)
C20—C18—C17	101.47 (18)	C49—C48—C50	102.45 (17)
C19—C18—H18A	115.1	C47—C48—H48A	115.1
C20—C18—H18A	115.1	C49—C48—H48A	115.1
C17—C18—H18A	115.1	C50—C48—H48A	115.1
C12—C19—C18	117.38 (17)	C42—C49—C48	117.44 (18)
C12—C19—C14	85.16 (15)	C42—C49—C44	85.63 (16)
C18—C19—C14	103.22 (17)	C48—C49—C44	103.33 (17)
C12—C19—H19A	115.5	C42—C49—H49A	115.3
C18—C19—H19A	115.5	C48—C49—H49A	115.3
C14—C19—H19A	115.5	C44—C49—H49A	115.3
C18—C20—C15	94.56 (17)	C48—C50—C45	95.21 (17)
C18—C20—H20A	112.8	C48—C50—H50A	112.7
C15—C20—H20A	112.8	C45—C50—H50A	112.7
C18—C20—H20B	112.8	C48—C50—H50B	112.7
C15—C20—H20B	112.8	C45—C50—H50B	112.7
H20A—C20—H20B	110.3	H50A—C50—H50B	110.2
C22—C21—C26	117.5 (2)	C56—C51—C52	116.9 (2)
C22—C21—C13	124.97 (19)	C56—C51—C43	117.6 (2)
C26—C21—C13	117.49 (19)	C52—C51—C43	125.5 (2)
C23—C22—C21	120.7 (2)	C53—C52—C51	120.9 (2)
C23—C22—H22A	119.6	C53—C52—H52A	119.5
C21—C22—H22A	119.6	C51—C52—H52A	119.5
C22—C23—C24	121.8 (2)	C52—C53—C54	121.9 (2)
C22—C23—H23A	119.1	C52—C53—H53A	119.1
C24—C23—H23A	119.1	C54—C53—H53A	119.1
C25—C24—C23	117.5 (2)	C55—C54—C53	117.1 (2)
C25—C24—C27	121.91 (19)	C55—C54—C57	121.4 (2)
C23—C24—C27	120.6 (2)	C53—C54—C57	121.5 (2)
C26—C25—C24	121.1 (2)	C56—C55—C54	121.5 (2)
C26—C25—H25A	119.5	C56—C55—H55A	119.3
C24—C25—H25A	119.5	C54—C55—H55A	119.3
C25—C26—C21	121.3 (2)	C55—C56—C51	121.7 (2)
C25—C26—H26A	119.3	C55—C56—H56A	119.2
C21—C26—H26A	119.3	C51—C56—H56A	119.2
C24—C27—H27A	109.5	C54—C57—H57A	109.5
C24—C27—H27B	109.5	C54—C57—H57B	109.5
H27A—C27—H27B	109.5	H57A—C57—H57B	109.5
C24—C27—H27C	109.5	C54—C57—H57C	109.5
H27A—C27—H27C	109.5	H57A—C57—H57C	109.5
H27B—C27—H27C	109.5	H57B—C57—H57C	109.5
O1—S1—C1—C2	102.92 (16)	O32—S31—C31—C32	−128.40 (17)
O2—S1—C1—C2	−124.13 (15)	O31—S31—C31—C32	99.65 (18)
N1—S1—C1—C2	−11.85 (16)	N31—S31—C31—C32	−14.50 (17)
O1—S1—N1—C11	92.08 (17)	O32—S31—N31—C41	−35.3 (2)
O2—S1—N1—C11	−38.64 (18)	O31—S31—N31—C41	95.59 (19)
C1—S1—N1—C11	−153.81 (17)	C31—S31—N31—C41	−150.86 (18)
O1—S1—N1—C8	−123.95 (14)	O32—S31—N31—C38	109.44 (17)
O2—S1—N1—C8	105.34 (15)	O31—S31—N31—C38	−119.68 (16)
C1—S1—N1—C8	−9.84 (16)	C31—S31—N31—C38	−6.12 (17)
S1—C1—C2—C3	146.51 (17)	S31—C31—C32—C38	30.1 (2)
S1—C1—C2—C8	28.9 (2)	S31—C31—C32—C33	147.16 (17)
S1—C1—C2—C6	−88.8 (2)	S31—C31—C32—C36	−89.2 (2)
C1—C2—C3—C4	172.51 (19)	C31—C32—C33—C34	171.8 (2)
C8—C2—C3—C4	−69.1 (2)	C38—C32—C33—C34	−69.6 (2)
C6—C2—C3—C4	38.8 (2)	C36—C32—C33—C34	38.8 (2)
C2—C3—C4—C5	−3.6 (2)	C32—C33—C34—C35	−2.8 (2)
C3—C4—C5—C7	74.6 (2)	C33—C34—C35—C37	73.7 (2)
C3—C4—C5—C6	−33.6 (2)	C33—C34—C35—C36	−34.6 (2)
C7—C5—C6—C9	63.9 (2)	C34—C35—C36—C40	−61.6 (3)
C4—C5—C6—C9	175.46 (19)	C37—C35—C36—C40	−173.73 (19)
C7—C5—C6—C10	−173.30 (19)	C34—C35—C36—C39	175.4 (2)
C4—C5—C6—C10	−61.7 (2)	C37—C35—C36—C39	63.3 (2)
C7—C5—C6—C2	−56.95 (19)	C34—C35—C36—C32	55.4 (2)
C4—C5—C6—C2	54.62 (19)	C37—C35—C36—C32	−56.7 (2)
C1—C2—C6—C9	53.4 (3)	C31—C32—C36—C40	−70.2 (3)
C3—C2—C6—C9	−175.2 (2)	C38—C32—C36—C40	168.91 (19)
C8—C2—C6—C9	−65.9 (2)	C33—C32—C36—C40	60.1 (2)
C1—C2—C6—C10	−70.8 (3)	C31—C32—C36—C39	54.9 (3)
C3—C2—C6—C10	60.6 (2)	C38—C32—C36—C39	−66.0 (2)
C8—C2—C6—C10	169.93 (19)	C33—C32—C36—C39	−174.77 (19)
C1—C2—C6—C5	171.57 (19)	C31—C32—C36—C35	172.46 (19)
C3—C2—C6—C5	−57.10 (19)	C38—C32—C36—C35	51.55 (19)
C8—C2—C6—C5	52.27 (18)	C33—C32—C36—C35	−57.21 (19)
C4—C5—C7—C8	−66.9 (2)	C34—C35—C37—C38	−65.9 (2)
C6—C5—C7—C8	41.5 (2)	C36—C35—C37—C38	42.1 (2)
C11—N1—C8—C7	−71.3 (2)	C41—N31—C38—C32	172.48 (17)
S1—N1—C8—C7	142.75 (15)	S31—N31—C38—C32	24.6 (2)
C11—N1—C8—C2	173.99 (17)	C41—N31—C38—C37	−71.7 (2)
S1—N1—C8—C2	28.06 (19)	S31—N31—C38—C37	140.45 (17)
C5—C7—C8—N1	−122.93 (19)	C31—C32—C38—N31	−35.0 (2)
C5—C7—C8—C2	−6.5 (2)	C33—C32—C38—N31	−159.22 (17)
C1—C2—C8—N1	−36.0 (2)	C36—C32—C38—N31	94.31 (19)
C3—C2—C8—N1	−160.78 (17)	C31—C32—C38—C37	−158.23 (18)
C6—C2—C8—N1	92.41 (19)	C33—C32—C38—C37	77.5 (2)
C1—C2—C8—C7	−158.12 (18)	C36—C32—C38—C37	−29.0 (2)
C3—C2—C8—C7	77.1 (2)	C35—C37—C38—N31	−125.1 (2)
C6—C2—C8—C7	−29.7 (2)	C35—C37—C38—C32	−7.5 (2)
C8—N1—C11—O3	−2.3 (3)	C38—N31—C41—O33	0.0 (3)
S1—N1—C11—O3	139.98 (16)	S31—N31—C41—O33	143.59 (18)
C8—N1—C11—C12	172.59 (17)	C38—N31—C41—C42	174.63 (18)
S1—N1—C11—C12	−45.1 (2)	S31—N31—C41—C42	−41.8 (3)
O3—C11—C12—C13	−9.0 (4)	O33—C41—C42—C43	−10.5 (4)
N1—C11—C12—C13	176.4 (2)	N31—C41—C42—C43	175.2 (2)
O3—C11—C12—C19	156.2 (2)	O33—C41—C42—C49	155.5 (2)
N1—C11—C12—C19	−18.4 (3)	N31—C41—C42—C49	−18.8 (3)
C11—C12—C13—C21	−14.9 (4)	C41—C42—C43—C51	−8.6 (4)
C19—C12—C13—C21	176.0 (3)	C49—C42—C43—C51	−178.2 (3)
C11—C12—C13—C14	166.4 (2)	C41—C42—C43—C44	169.8 (2)
C19—C12—C13—C14	−2.70 (17)	C49—C42—C43—C44	0.20 (17)
C12—C13—C14—C15	−100.3 (2)	C42—C43—C44—C45	−102.7 (2)
C21—C13—C14—C15	80.7 (3)	C51—C43—C44—C45	76.0 (3)
C12—C13—C14—C19	2.63 (17)	C42—C43—C44—C49	−0.19 (16)
C21—C13—C14—C19	−176.4 (2)	C51—C43—C44—C49	178.5 (2)
C13—C14—C15—C16	168.01 (18)	C43—C44—C45—C46	164.30 (18)
C19—C14—C15—C16	74.9 (2)	C49—C44—C45—C46	71.6 (2)
C13—C14—C15—C20	61.9 (2)	C43—C44—C45—C50	58.2 (2)
C19—C14—C15—C20	−31.2 (2)	C49—C44—C45—C50	−34.5 (2)
C14—C15—C16—C17	−69.9 (2)	C44—C45—C46—C47	−72.8 (2)
C20—C15—C16—C17	38.0 (2)	C50—C45—C46—C47	33.8 (2)
C15—C16—C17—C18	−3.3 (2)	C45—C46—C47—C48	1.0 (2)
C16—C17—C18—C19	73.9 (2)	C46—C47—C48—C49	71.1 (2)
C16—C17—C18—C20	−32.5 (2)	C46—C47—C48—C50	−35.6 (2)
C13—C12—C19—C18	105.0 (2)	C43—C42—C49—C48	102.6 (2)
C11—C12—C19—C18	−64.0 (3)	C41—C42—C49—C48	−67.2 (3)
C13—C12—C19—C14	2.61 (17)	C43—C42—C49—C44	−0.19 (17)
C11—C12—C19—C14	−166.4 (2)	C41—C42—C49—C44	−170.0 (2)
C20—C18—C19—C12	−54.2 (2)	C47—C48—C49—C42	−163.88 (19)
C17—C18—C19—C12	−160.10 (18)	C50—C48—C49—C42	−58.0 (2)
C20—C18—C19—C14	37.2 (2)	C47—C48—C49—C44	−71.9 (2)
C17—C18—C19—C14	−68.7 (2)	C50—C48—C49—C44	34.0 (2)
C13—C14—C19—C12	−2.35 (15)	C43—C44—C49—C42	0.17 (15)
C15—C14—C19—C12	113.37 (16)	C45—C44—C49—C42	117.56 (17)
C13—C14—C19—C18	−119.37 (16)	C43—C44—C49—C48	−117.01 (17)
C15—C14—C19—C18	−3.65 (19)	C45—C44—C49—C48	0.4 (2)
C19—C18—C20—C15	−54.77 (19)	C47—C48—C50—C45	55.5 (2)
C17—C18—C20—C15	54.63 (19)	C49—C48—C50—C45	−54.19 (19)
C16—C15—C20—C18	−57.16 (19)	C46—C45—C50—C48	−54.90 (19)
C14—C15—C20—C18	52.72 (19)	C44—C45—C50—C48	54.46 (19)
C12—C13—C21—C22	14.2 (4)	C42—C43—C51—C56	−177.2 (2)
C14—C13—C21—C22	−167.4 (2)	C44—C43—C51—C56	4.8 (3)
C12—C13—C21—C26	−164.0 (3)	C42—C43—C51—C52	3.1 (4)
C14—C13—C21—C26	14.4 (3)	C44—C43—C51—C52	−174.9 (2)
C26—C21—C22—C23	1.8 (3)	C56—C51—C52—C53	0.5 (3)
C13—C21—C22—C23	−176.4 (2)	C43—C51—C52—C53	−179.8 (2)
C21—C22—C23—C24	0.7 (3)	C51—C52—C53—C54	0.0 (3)
C22—C23—C24—C25	−2.4 (3)	C52—C53—C54—C55	−0.4 (3)
C22—C23—C24—C27	176.5 (2)	C52—C53—C54—C57	−179.4 (2)
C23—C24—C25—C26	1.7 (3)	C53—C54—C55—C56	0.5 (3)
C27—C24—C25—C26	−177.25 (19)	C57—C54—C55—C56	179.4 (2)
C24—C25—C26—C21	0.8 (3)	C54—C55—C56—C51	0.0 (3)
C22—C21—C26—C25	−2.6 (3)	C52—C51—C56—C55	−0.5 (3)
C13—C21—C26—C25	175.77 (19)	C43—C51—C56—C55	179.76 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···O31	0.99	2.58	3.539 (3)	163
C31—H31B···O3	0.99	2.45	3.356 (2)	152
C38—H38A···O1^i	1.00	2.54	3.412 (2)	146
C1—H1B···O33^ii	0.99	2.37	3.332 (3)	164
C50—H50A···O2^iii	0.99	2.53	3.446 (2)	153
C9—H9A···O3^iv	0.98	2.59	3.570 (3)	174
C27—H27A···O32^v	0.98	2.43	3.404 (3)	174
C22—H22A···O3	0.95	2.31	3.115 (3)	142
C52—H52A···O33	0.95	2.33	3.129 (3)	141

Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) −x+1, y−1/2, −z+3/2; (iv) x+1/2, −y+3/2, −z+2; (v) x, y+1, z.