cis-1-Ethyl-4,4,10-trimethyl-2-tosyl-1,2,3,3a,4,11b-hexa­hydro-11H-pyrrolo[3,4-c]pyrano[5,6-c]quinolin-11-one

The mol­ecule of the title compound, C₂₆H₃₀N₂O₄S, adopts a folded conformation, with the sulfonyl-bound benzene ring lying over the pyridinone ring [centroid-to-centroid distance = 3.893 (1) Å], forming a dihedral angle of 23.87 (5)°. The pyrrolidine ring adopts a twist conformation and the dihydro­pyran ring is in a half-chair conformation. The pyrrolidine and dihydro­pyran rings are cis-fused. The sulfonyl group has a distorted tetra­hedral geometry. In the crystal structure, the mol­ecules are linked into a centrosymmetric R₂²(12) dimer by C—H...O hydrogen bonds. The dimers are cross-linked into a sheet parallel to the bc plane via C—H...π inter­actions involving the benzene ring of the quinolinone ring system. The ethyl group is disordered over two positions; the site-occupancy factors are ca 0.8 and 0.2.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in main residue
• R factor = 0.059
• wR factor = 0.163
• Data-to-parameter ratio = 21.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT301_ALERT_3_C Main Residue  Disorder .........................       6.00 Perc.

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of C2     = ...          R
PLAT793_ALERT_1_G Check the Absolute Configuration of C3     = ...          R
PLAT793_ALERT_1_G Check the Absolute Configuration of C4     = ...          R
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

Some pyranoquinolone derivatives exhibit anti-inflammatory activity (Keenan, 1994; Wasserman 1995). Pyranoquinolone alkaloids exhibit photo-activated antimicrobial activity (Hanawa et al., 2004) and SRS-A antagonist action (Kamikawa et al., 1996). Pyranoquinolinones act as blockers of the voltage-gated potassium channel Kv1.3 (Butenschön et al., 2001). 2H-pyrano[3,2-g]quinolin-2-one derivatives are found to modulate the transcriptional activity of the human androgen receptor (Edwards et al., 1999). We report here the crystal structure of the title compound, a pyranoquinolinone derivative.

Bond lengths and angles in the title molecule (Fig. 1) are comparable to those observed in a related compound, 6,6-dimethyl-4-tosylpyrrolo[3,4-c]pyrano[5,6-c]-1- methylquinolin-2-one hemihydrate (Chinnakali et al., 2007).

The pyrrolidine ring adopts a twist conformation, with the local twofold rotation axis passing through atom N1 and the mid-point of the opposite bond C2—C3; the asymmetry parameter (Duax et al., 1976) ΔC₂[C2—C3] is 2.3 (2)°, and the puckering parameters (Cremer & Pople, 1975) are q₂ = 0.370 (2) Å and φ = 92.2 (3)°. The tosyl group is attached to the pyrrolidine ring in a biaxial position. The dihydropyran ring is in a half-chair conformation, with a local pseudo-twofold rotation axis running through the midpoints of the C2—C5 and C6—C7 bonds. The puckering parameters Q, θ and φ, and the smallest displacement asymmetry parameter ΔC₂[C2—C5] are 0.438 (2) Å, 50.6 (3)°, 87.1 (3)° and 4.6 (3)°, respectively. The pyrrolidine ring is cis-fused to the dihydropyran ring. The quinolinone ring system is planar, with an r.m.s. deviation of 0.030 Å, and atoms O4 and C24 deviating from the mean plane by 0.171 (2) and 0.084 (3) Å, respectively.

As expected, the sulfonyl group has a distorted tetrahedral geometry, with the O1—S1—O2 [119.40 (9)°] angle deviating significantly from the ideal tetrahedral value. The molecule is in a folded conformation, with the sulfonyl-bound benzene ring lying over the pyridinone ring. The centroid-centroid distance [3.893 (1) Å] and the dihedral angle [23.87 (5)°] between the two rings indicate the presence of weak π–π interactions between them.

In the crystal structure, centrosymmetrically related molecules are linked by a pair of C2—H2···O1ⁱ hydrogen bonds (Table 1) into a R₂²(12) dimer. The dimers are linked into a sheet parallel to the bc plane (Fig. 2) via C25A—H25A···π interactions involving the C17–C22 ring (centroid Cg1) of the molecule at (1 - x, -1/2 + y, 1/2 - z).

Related literature

The structure of the title molecule is quite similar to that of 6,6-dimethyl-4-tosylpyrrolo[3,4-c]pyrano[5,6-c]-1- methylquinolin-2-one (Chinnakali et al., 2007). For biological activities of pyranoquinolinones, see: Butenschön et al. (2001); Edwards et al. (1999); Hanawa et al. (2004); Kamikawa et al. (1996); Keenan (1994); Wasserman (1995). For ring-puckering parameters, see: Cremer & Pople (1975). For asymmetry parameters, see: Duax et al. (1976).

S2. Experimental

To a solution of 1-methylquinoline-2,4-dione (1 mmol) in dry toluene (20 ml), 2-[N-(3-methylbut-2-enyl)-N-tosylamino]butanal (1 mmol) and a catalytic amount of the base ethylenediamine-N,N'-diacetate (EDDA) were added and the reaction mixture was refluxed for 12 h. After completion of the reaction, the solvent was evaporated under reduced pressure and the crude product was chromatographed using a hexane–ethyl acetate (8:2 v/v) mixture to obtain the title compound. The compound was recrystallized from ethyl acetate solution by slow evaporation.

S3. Refinement

The ethyl group is disordered over two orientations (C25A,C26A/C25B,C26B) with refined occupancies of 0.760 (5) and 0.240 (5). The corresponding C—C distances in the disordered components were restrained to be equal. H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93–0.98 Å. The U_iso values were set equal to 1.5U_eq of the carrier atom for methyl H atoms and 1.2U_eq for the remaining H atoms. A rotating group model was used for the methyl groups attached to aromatic rings.

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL (Sheldrick, 1998); molecular graphics: SHELXTL (Sheldrick, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 1998) and PLATON (Spek, 2003).

Figures

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 80% probability level. Only one disorder component is shown.
	Fig. 2. View of a hydrogen-bonded sheet in the title compound. Dashed and dotted lines indicate C—H···O and C—H···π interactions, respectively. For the sake of clarity, H atoms not involved in the interactions have been omitted. Only one disorder component is shown.

cis-1-Ethyl-4,4,10-trimethyl-2-tosyl-1,2,3,3a,4,11b-hexahydro- 11H-pyrrolo[3,4-c]pyrano[5,6-c]quinolin-11-one

Crystal data

C26H30N2O4S	F(000) = 992
Mr = 466.58	Dx = 1.346 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6924 reflections
a = 10.4111 (2) Å	θ = 2.2–28.4°
b = 13.8576 (2) Å	µ = 0.18 mm^−1
c = 18.0460 (3) Å	T = 100 K
β = 117.834 (1)°	Block, light yellow
V = 2302.33 (7) Å^3	0.52 × 0.43 × 0.33 mm
Z = 4

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	6709 independent reflections
Radiation source: fine-focus sealed tube	4846 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
Detector resolution: 8.33 pixels mm^-1	θmax = 30.1°, θmin = 2.0°
ω scans	h = −14→14
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −15→19
Tmin = 0.874, Tmax = 0.944	l = −25→24
28627 measured reflections

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.163	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0874P)^2 + 0.4457P] where P = (Fo^2 + 2Fc^2)/3
6709 reflections	(Δ/σ)max = 0.001
319 parameters	Δρmax = 0.85 e Å^−3
2 restraints	Δρmin = −0.43 e Å^−3

Special details

Experimental. The low-temparture data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.21372 (5)	0.08412 (3)	0.39792 (3)	0.02235 (13)
O1	0.24491 (14)	0.04611 (10)	0.47870 (8)	0.0265 (3)
O2	0.10426 (14)	0.03882 (10)	0.32371 (8)	0.0309 (3)
O3	0.60238 (13)	0.32271 (10)	0.44037 (8)	0.0258 (3)
O4	0.25960 (15)	0.22331 (11)	0.16712 (8)	0.0316 (3)
N1	0.36407 (16)	0.07947 (11)	0.39179 (9)	0.0225 (3)
N2	0.25256 (16)	0.37742 (12)	0.20890 (9)	0.0238 (3)
C1	0.49235 (19)	0.12860 (14)	0.45792 (11)	0.0233 (4)
H1A	0.5415	0.0874	0.5067	0.028*
H1B	0.4646	0.1882	0.4748	0.028*
C2	0.5894 (2)	0.14873 (14)	0.41714 (11)	0.0256 (4)
H2	0.6491	0.0915	0.4237	0.031*
C3	0.4814 (2)	0.16080 (14)	0.32352 (11)	0.0260 (4)
H3	0.5295	0.1451	0.2896	0.031*
C4	0.3652 (2)	0.08486 (14)	0.30939 (11)	0.0292 (4)
H4	0.2700	0.1024	0.2635	0.035*	0.760 (5)
H4B	0.2776	0.1202	0.2762	0.035*	0.240 (5)
C5	0.68972 (19)	0.23514 (15)	0.45482 (12)	0.0276 (4)
C6	0.48668 (18)	0.33451 (14)	0.36317 (11)	0.0224 (4)
C7	0.42612 (19)	0.26299 (14)	0.30625 (11)	0.0229 (4)
C8	0.16642 (18)	0.20637 (13)	0.39735 (11)	0.0212 (4)
C9	0.09429 (19)	0.25587 (15)	0.32132 (11)	0.0252 (4)
H9	0.0673	0.2241	0.2708	0.030*
C10	0.06369 (19)	0.35297 (15)	0.32241 (11)	0.0255 (4)
H10	0.0164	0.3864	0.2720	0.031*
C11	0.10221 (19)	0.40159 (14)	0.39735 (12)	0.0238 (4)
C12	0.17227 (18)	0.35032 (14)	0.47219 (11)	0.0233 (4)
H12	0.1971	0.3817	0.5226	0.028*
C13	0.20556 (19)	0.25356 (14)	0.47281 (10)	0.0219 (4)
H13	0.2537	0.2204	0.5233	0.026*
C14	0.0690 (2)	0.50723 (15)	0.39761 (13)	0.0346 (5)
H14A	0.0508	0.5355	0.3450	0.052*
H14B	0.1502	0.5389	0.4423	0.052*
H14C	−0.0154	0.5147	0.4057	0.052*
C15	0.7767 (2)	0.22697 (16)	0.54924 (12)	0.0322 (5)
H15A	0.7118	0.2179	0.5728	0.048*
H15B	0.8319	0.2849	0.5714	0.048*
H15C	0.8414	0.1728	0.5633	0.048*
C16	0.7889 (2)	0.24952 (18)	0.41481 (14)	0.0376 (5)
H16A	0.8506	0.3043	0.4398	0.056*
H16B	0.7311	0.2604	0.3558	0.056*
H16C	0.8476	0.1930	0.4237	0.056*
C17	0.43063 (18)	0.43151 (14)	0.34636 (11)	0.0215 (4)
C18	0.4934 (2)	0.50710 (15)	0.40380 (11)	0.0259 (4)
H18	0.5740	0.4948	0.4551	0.031*
C19	0.4376 (2)	0.59907 (15)	0.38551 (12)	0.0291 (4)
H19	0.4804	0.6488	0.4239	0.035*
C20	0.3159 (2)	0.61680 (15)	0.30867 (12)	0.0280 (4)
H20	0.2766	0.6786	0.2965	0.034*
C21	0.2532 (2)	0.54446 (14)	0.25068 (11)	0.0261 (4)
H21	0.1727	0.5578	0.1996	0.031*
C22	0.30974 (18)	0.45094 (14)	0.26793 (11)	0.0223 (4)
C23	0.3089 (2)	0.28460 (14)	0.22321 (11)	0.0249 (4)
C24	0.1320 (2)	0.39954 (15)	0.12554 (11)	0.0283 (4)
H24A	0.0997	0.3412	0.0934	0.042*
H24B	0.1646	0.4443	0.0973	0.042*
H24C	0.0532	0.4275	0.1317	0.042*
C25A	0.4228 (3)	−0.0123 (2)	0.29271 (17)	0.0268 (7)	0.760 (5)
H25A	0.4308	−0.0063	0.2415	0.032*	0.760 (5)
H25B	0.5194	−0.0241	0.3382	0.032*	0.760 (5)
C26A	0.3273 (3)	−0.0979 (2)	0.28484 (17)	0.0316 (7)	0.760 (5)
H26A	0.3686	−0.1552	0.2747	0.047*	0.760 (5)
H26B	0.2321	−0.0876	0.2390	0.047*	0.760 (5)
H26C	0.3205	−0.1054	0.3358	0.047*	0.760 (5)
C25B	0.3309 (9)	−0.0119 (5)	0.2635 (4)	0.026 (2)	0.240 (5)
H25C	0.2400	−0.0377	0.2576	0.032*	0.240 (5)
H25D	0.3237	−0.0046	0.2083	0.032*	0.240 (5)
C26B	0.4553 (8)	−0.0771 (6)	0.3171 (5)	0.027 (2)	0.240 (5)
H26D	0.4402	−0.1395	0.2914	0.041*	0.240 (5)
H26E	0.4609	−0.0832	0.3715	0.041*	0.240 (5)
H26F	0.5443	−0.0501	0.3226	0.041*	0.240 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0256 (2)	0.0191 (2)	0.0208 (2)	−0.00014 (17)	0.00949 (17)	−0.00027 (17)
O1	0.0326 (7)	0.0232 (7)	0.0264 (7)	0.0026 (6)	0.0160 (6)	0.0050 (5)
O2	0.0288 (7)	0.0279 (8)	0.0293 (7)	−0.0029 (6)	0.0080 (6)	−0.0069 (6)
O3	0.0232 (6)	0.0245 (7)	0.0237 (6)	0.0032 (5)	0.0060 (5)	0.0050 (5)
O4	0.0423 (8)	0.0292 (8)	0.0215 (6)	0.0011 (6)	0.0136 (6)	−0.0016 (6)
N1	0.0275 (7)	0.0218 (8)	0.0174 (7)	0.0012 (6)	0.0099 (6)	−0.0003 (6)
N2	0.0244 (7)	0.0260 (9)	0.0198 (7)	−0.0011 (6)	0.0094 (6)	0.0018 (6)
C1	0.0259 (8)	0.0226 (10)	0.0200 (8)	0.0003 (7)	0.0097 (7)	0.0018 (7)
C2	0.0287 (9)	0.0242 (10)	0.0263 (9)	0.0070 (8)	0.0149 (8)	0.0049 (7)
C3	0.0319 (9)	0.0276 (11)	0.0230 (8)	0.0069 (8)	0.0167 (8)	0.0042 (7)
C4	0.0464 (11)	0.0250 (11)	0.0200 (8)	−0.0038 (9)	0.0187 (8)	−0.0016 (7)
C5	0.0231 (8)	0.0275 (11)	0.0319 (10)	0.0062 (8)	0.0126 (8)	0.0069 (8)
C6	0.0207 (8)	0.0252 (10)	0.0221 (8)	0.0005 (7)	0.0107 (7)	0.0069 (7)
C7	0.0254 (8)	0.0233 (10)	0.0234 (8)	0.0005 (7)	0.0143 (7)	0.0038 (7)
C8	0.0224 (8)	0.0195 (9)	0.0214 (8)	0.0012 (7)	0.0099 (7)	0.0026 (7)
C9	0.0249 (9)	0.0285 (11)	0.0198 (8)	0.0033 (8)	0.0086 (7)	0.0012 (7)
C10	0.0257 (8)	0.0281 (11)	0.0225 (8)	0.0046 (8)	0.0112 (7)	0.0077 (7)
C11	0.0204 (8)	0.0239 (10)	0.0284 (9)	0.0005 (7)	0.0125 (7)	0.0028 (7)
C12	0.0243 (8)	0.0232 (10)	0.0220 (8)	−0.0009 (7)	0.0104 (7)	−0.0021 (7)
C13	0.0232 (8)	0.0228 (10)	0.0179 (8)	−0.0004 (7)	0.0080 (6)	0.0017 (7)
C14	0.0391 (11)	0.0237 (11)	0.0366 (11)	0.0042 (9)	0.0141 (9)	0.0026 (9)
C15	0.0256 (9)	0.0325 (12)	0.0306 (10)	0.0044 (8)	0.0065 (8)	0.0078 (9)
C16	0.0269 (10)	0.0438 (14)	0.0459 (12)	0.0022 (9)	0.0202 (9)	0.0074 (10)
C17	0.0210 (8)	0.0219 (10)	0.0228 (8)	−0.0001 (7)	0.0113 (7)	0.0042 (7)
C18	0.0246 (8)	0.0264 (11)	0.0241 (8)	−0.0014 (8)	0.0092 (7)	0.0047 (8)
C19	0.0293 (9)	0.0272 (11)	0.0278 (9)	−0.0015 (8)	0.0107 (8)	0.0019 (8)
C20	0.0285 (9)	0.0242 (10)	0.0297 (9)	0.0016 (8)	0.0122 (8)	0.0052 (8)
C21	0.0238 (8)	0.0272 (11)	0.0241 (9)	0.0020 (8)	0.0086 (7)	0.0070 (8)
C22	0.0221 (8)	0.0237 (10)	0.0226 (8)	−0.0029 (7)	0.0116 (7)	0.0024 (7)
C23	0.0296 (9)	0.0259 (10)	0.0228 (8)	0.0001 (8)	0.0153 (7)	0.0035 (7)
C24	0.0256 (9)	0.0340 (12)	0.0212 (8)	0.0024 (8)	0.0075 (7)	0.0014 (8)
C25A	0.0324 (16)	0.0238 (16)	0.0284 (13)	−0.0023 (12)	0.0176 (13)	−0.0056 (11)
C26A	0.0366 (15)	0.0271 (16)	0.0337 (14)	−0.0033 (11)	0.0187 (12)	−0.0077 (11)
C25B	0.018 (4)	0.039 (5)	0.017 (3)	−0.007 (3)	0.004 (3)	−0.001 (3)
C26B	0.034 (4)	0.029 (5)	0.023 (4)	−0.003 (4)	0.017 (3)	−0.007 (3)

Geometric parameters (Å, º)

S1—O2	1.4356 (13)	C12—C13	1.384 (3)
S1—O1	1.4374 (13)	C12—H12	0.93
S1—N1	1.6212 (16)	C13—H13	0.93
S1—C8	1.7629 (19)	C14—H14A	0.96
O3—C6	1.361 (2)	C14—H14B	0.96
O3—C5	1.465 (2)	C14—H14C	0.96
O4—C23	1.235 (2)	C15—H15A	0.96
N1—C1	1.478 (2)	C15—H15B	0.96
N1—C4	1.494 (2)	C15—H15C	0.96
N2—C23	1.387 (3)	C16—H16A	0.96
N2—C22	1.391 (2)	C16—H16B	0.96
N2—C24	1.473 (2)	C16—H16C	0.96
C1—C2	1.528 (2)	C17—C18	1.402 (3)
C1—H1A	0.97	C17—C22	1.413 (2)
C1—H1B	0.97	C18—C19	1.375 (3)
C2—C5	1.524 (3)	C18—H18	0.93
C2—C3	1.540 (2)	C19—C20	1.395 (3)
C2—H2	0.98	C19—H19	0.93
C3—C7	1.505 (3)	C20—C21	1.374 (3)
C3—C4	1.532 (3)	C20—H20	0.93
C3—H3	0.98	C21—C22	1.397 (3)
C4—C25B	1.527 (7)	C21—H21	0.93
C4—C25A	1.559 (3)	C24—H24A	0.96
C4—H4	0.98	C24—H24B	0.96
C4—H4B	0.96	C24—H24C	0.96
C5—C15	1.515 (3)	C25A—C26A	1.512 (4)
C5—C16	1.525 (3)	C25A—H25A	0.97
C6—C7	1.353 (3)	C25A—H25B	0.97
C6—C17	1.440 (3)	C26A—H26A	0.96
C7—C23	1.455 (2)	C26A—H26B	0.96
C8—C13	1.389 (2)	C26A—H26C	0.96
C8—C9	1.398 (2)	C25B—C26B	1.503 (8)
C9—C10	1.385 (3)	C25B—H25C	0.97
C9—H9	0.93	C25B—H25D	0.97
C10—C11	1.392 (3)	C26B—H26D	0.96
C10—H10	0.93	C26B—H26E	0.96
C11—C12	1.393 (2)	C26B—H26F	0.96
C11—C14	1.505 (3)
O2—S1—O1	119.40 (9)	C12—C13—H13	120.3
O2—S1—N1	106.87 (8)	C8—C13—H13	120.3
O1—S1—N1	106.65 (8)	C11—C14—H14A	109.5
O2—S1—C8	108.47 (8)	C11—C14—H14B	109.5
O1—S1—C8	106.76 (8)	H14A—C14—H14B	109.5
N1—S1—C8	108.29 (8)	C11—C14—H14C	109.5
C6—O3—C5	117.44 (14)	H14A—C14—H14C	109.5
C1—N1—C4	110.90 (14)	H14B—C14—H14C	109.5
C1—N1—S1	117.64 (12)	C5—C15—H15A	109.5
C4—N1—S1	121.48 (13)	C5—C15—H15B	109.5
C23—N2—C22	122.96 (15)	H15A—C15—H15B	109.5
C23—N2—C24	117.89 (16)	C5—C15—H15C	109.5
C22—N2—C24	119.06 (16)	H15A—C15—H15C	109.5
N1—C1—C2	104.28 (14)	H15B—C15—H15C	109.5
N1—C1—H1A	110.9	C5—C16—H16A	109.5
C2—C1—H1A	110.9	C5—C16—H16B	109.5
N1—C1—H1B	110.9	H16A—C16—H16B	109.5
C2—C1—H1B	110.9	C5—C16—H16C	109.5
H1A—C1—H1B	108.9	H16A—C16—H16C	109.5
C5—C2—C1	113.45 (16)	H16B—C16—H16C	109.5
C5—C2—C3	113.65 (16)	C18—C17—C22	119.19 (17)
C1—C2—C3	103.88 (14)	C18—C17—C6	122.58 (16)
C5—C2—H2	108.5	C22—C17—C6	118.21 (17)
C1—C2—H2	108.5	C19—C18—C17	121.08 (17)
C3—C2—H2	108.5	C19—C18—H18	119.5
C7—C3—C4	114.57 (16)	C17—C18—H18	119.5
C7—C3—C2	110.00 (16)	C18—C19—C20	119.16 (19)
C4—C3—C2	102.90 (15)	C18—C19—H19	120.4
C7—C3—H3	109.7	C20—C19—H19	120.4
C4—C3—H3	109.7	C21—C20—C19	121.09 (19)
C2—C3—H3	109.7	C21—C20—H20	119.5
N1—C4—C25B	112.8 (3)	C19—C20—H20	119.5
N1—C4—C3	103.94 (14)	C20—C21—C22	120.41 (17)
C25B—C4—C3	131.3 (3)	C20—C21—H21	119.8
N1—C4—C25A	109.35 (17)	C22—C21—H21	119.8
C3—C4—C25A	106.26 (18)	N2—C22—C21	121.58 (16)
N1—C4—H4	112.3	N2—C22—C17	119.35 (17)
C25B—C4—H4	82.6	C21—C22—C17	119.05 (17)
C3—C4—H4	112.3	O4—C23—N2	120.50 (17)
C25A—C4—H4	112.3	O4—C23—C7	122.04 (18)
N1—C4—H4B	101.6	N2—C23—C7	117.46 (17)
C25B—C4—H4B	101.3	N2—C24—H24A	109.5
C3—C4—H4B	101.5	N2—C24—H24B	109.5
C25A—C4—H4B	131.3	H24A—C24—H24B	109.5
O3—C5—C15	104.91 (16)	N2—C24—H24C	109.5
O3—C5—C2	109.40 (14)	H24A—C24—H24C	109.5
C15—C5—C2	111.60 (16)	H24B—C24—H24C	109.5
O3—C5—C16	107.99 (16)	C26A—C25A—C4	113.6 (2)
C15—C5—C16	111.17 (16)	C26A—C25A—H25A	108.8
C2—C5—C16	111.47 (17)	C4—C25A—H25A	108.8
C7—C6—O3	124.43 (17)	C26A—C25A—H25B	108.8
C7—C6—C17	121.63 (16)	C4—C25A—H25B	108.8
O3—C6—C17	113.94 (16)	H25A—C25A—H25B	107.7
C6—C7—C23	120.05 (17)	C25A—C26A—H26A	109.5
C6—C7—C3	122.30 (16)	C25A—C26A—H26B	109.5
C23—C7—C3	117.56 (17)	H26A—C26A—H26B	109.5
C13—C8—C9	120.55 (18)	C25A—C26A—H26C	109.5
C13—C8—S1	119.56 (13)	H26A—C26A—H26C	109.5
C9—C8—S1	119.86 (14)	H26B—C26A—H26C	109.5
C10—C9—C8	118.98 (17)	C26B—C25B—C4	105.4 (5)
C10—C9—H9	120.5	C26B—C25B—H25C	110.7
C8—C9—H9	120.5	C4—C25B—H25C	110.7
C9—C10—C11	121.35 (17)	C26B—C25B—H25D	110.7
C9—C10—H10	119.3	C4—C25B—H25D	110.7
C11—C10—H10	119.3	H25C—C25B—H25D	108.8
C10—C11—C12	118.55 (18)	C25B—C26B—H26D	109.5
C10—C11—C14	120.77 (17)	C25B—C26B—H26E	109.5
C12—C11—C14	120.68 (17)	H26D—C26B—H26E	109.5
C13—C12—C11	121.18 (17)	C25B—C26B—H26F	109.5
C13—C12—H12	119.4	H26D—C26B—H26F	109.5
C11—C12—H12	119.4	H26E—C26B—H26F	109.5
C12—C13—C8	119.38 (16)
O2—S1—N1—C1	175.21 (13)	N1—S1—C8—C13	−95.57 (15)
O1—S1—N1—C1	−56.03 (15)	O2—S1—C8—C9	−33.33 (17)
C8—S1—N1—C1	58.53 (15)	O1—S1—C8—C9	−163.20 (14)
O2—S1—N1—C4	32.76 (16)	N1—S1—C8—C9	82.31 (16)
O1—S1—N1—C4	161.52 (14)	C13—C8—C9—C10	0.6 (3)
C8—S1—N1—C4	−83.92 (15)	S1—C8—C9—C10	−177.22 (14)
C4—N1—C1—C2	−10.4 (2)	C8—C9—C10—C11	−0.5 (3)
S1—N1—C1—C2	−156.59 (12)	C9—C10—C11—C12	−0.3 (3)
N1—C1—C2—C5	153.67 (15)	C9—C10—C11—C14	179.68 (18)
N1—C1—C2—C3	29.77 (19)	C10—C11—C12—C13	1.1 (3)
C5—C2—C3—C7	−39.1 (2)	C14—C11—C12—C13	−178.91 (17)
C1—C2—C3—C7	84.63 (18)	C11—C12—C13—C8	−1.0 (3)
C5—C2—C3—C4	−161.64 (15)	C9—C8—C13—C12	0.1 (3)
C1—C2—C3—C4	−37.87 (18)	S1—C8—C13—C12	177.97 (13)
C1—N1—C4—C25B	134.0 (4)	C7—C6—C17—C18	−178.76 (17)
S1—N1—C4—C25B	−81.3 (4)	O3—C6—C17—C18	1.9 (2)
C1—N1—C4—C3	−13.2 (2)	C7—C6—C17—C22	−0.3 (3)
S1—N1—C4—C3	131.45 (14)	O3—C6—C17—C22	−179.61 (15)
C1—N1—C4—C25A	99.89 (19)	C22—C17—C18—C19	1.1 (3)
S1—N1—C4—C25A	−115.41 (18)	C6—C17—C18—C19	179.58 (17)
C7—C3—C4—N1	−88.26 (18)	C17—C18—C19—C20	0.5 (3)
C2—C3—C4—N1	31.12 (18)	C18—C19—C20—C21	−1.3 (3)
C7—C3—C4—C25B	133.3 (4)	C19—C20—C21—C22	0.6 (3)
C2—C3—C4—C25B	−107.3 (4)	C23—N2—C22—C21	178.04 (16)
C7—C3—C4—C25A	156.40 (17)	C24—N2—C22—C21	1.6 (3)
C2—C3—C4—C25A	−84.23 (18)	C23—N2—C22—C17	0.0 (3)
C6—O3—C5—C15	−163.06 (15)	C24—N2—C22—C17	−176.48 (16)
C6—O3—C5—C2	−43.2 (2)	C20—C21—C22—N2	−177.01 (17)
C6—O3—C5—C16	78.29 (19)	C20—C21—C22—C17	1.1 (3)
C1—C2—C5—O3	−63.18 (19)	C18—C17—C22—N2	176.24 (16)
C3—C2—C5—O3	55.21 (19)	C6—C17—C22—N2	−2.3 (2)
C1—C2—C5—C15	52.5 (2)	C18—C17—C22—C21	−1.9 (3)
C3—C2—C5—C15	170.86 (16)	C6—C17—C22—C21	179.59 (16)
C1—C2—C5—C16	177.44 (16)	C22—N2—C23—O4	−175.84 (17)
C3—C2—C5—C16	−64.2 (2)	C24—N2—C23—O4	0.6 (3)
C5—O3—C6—C7	16.5 (2)	C22—N2—C23—C7	4.6 (2)
C5—O3—C6—C17	−164.19 (14)	C24—N2—C23—C7	−178.86 (15)
O3—C6—C7—C23	−175.72 (15)	C6—C7—C23—O4	173.38 (17)
C17—C6—C7—C23	5.0 (3)	C3—C7—C23—O4	−3.1 (3)
O3—C6—C7—C3	0.6 (3)	C6—C7—C23—N2	−7.1 (3)
C17—C6—C7—C3	−178.68 (16)	C3—C7—C23—N2	176.42 (15)
C4—C3—C7—C6	126.67 (18)	N1—C4—C25A—C26A	63.3 (3)
C2—C3—C7—C6	11.4 (2)	C25B—C4—C25A—C26A	−38.9 (6)
C4—C3—C7—C23	−56.9 (2)	C3—C4—C25A—C26A	174.9 (2)
C2—C3—C7—C23	−172.27 (15)	N1—C4—C25B—C26B	−65.5 (6)
O2—S1—C8—C13	148.80 (14)	C3—C4—C25B—C26B	70.1 (6)
O1—S1—C8—C13	18.93 (17)	C25A—C4—C25B—C26B	24.8 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1^i	0.98	2.48	3.282 (2)	139
C4—H4···O4	0.98	2.38	2.974 (2)	118
C25A—H25A···Cg1^ii	0.97	2.87	3.706 (3)	145

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