4,4-Dimethyl-2-tosyl-2,3,3a,4-tetra­hydro-1H,10H-pyrrolo[3,4-c]pyrano[6,5-b]indan-10-one

The mol­ecule of the title compound, C₂₃H₂₃NO₄S, adopts a folded conformation, with the cyclo­penta­dienone ring and tosyl groups arranged in an almost face-to-face fashion. The pyrrolidine ring has an envelope conformation and the dihydro­pyran ring is in a half-chair conformation. The pyrrolidine and dihydro­pyran rings are cis-fused. The indenone ring system is essentially planar, and the indene plane forms a dihedral angle of 25.12 (3)° with the sulfonyl-bound benzene ring. In the crystal structure, mol­ecules translated by one unit cell along the a-axis direction are linked into a chain by C—H...O hydrogen bonds. The inversion-related mol­ecules of adjacent chains are linked along the c axis by C—H...O hydrogen bonds into a sheet-like structure parallel to the ac plane.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.001 Å
• R factor = 0.034
• wR factor = 0.105
• Data-to-parameter ratio = 32.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        100 Deg.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          3
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.52 Ratio

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of C2     = ...          S
PLAT793_ALERT_1_G Check the Absolute Configuration of C3     = ...          S

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

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 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

As part of our ongoing studies on pyrrolo[3,4-c]pyran derivatives (Chinnakali et al., 2007a,b), we report here the crystal structure of the title compound (Fig. 1).

Bond lengths and angles show normal values (Allen et al., 1987), and are comparable with those in related structures (Chinnakali et al., 2007a,b). As a result of the repulsive interaction between the short S═O bonds, atom S1 has a distorted tetrahedral configuration, with the O2—S1—O1 [120.17 (4)°] angle deviating significantly from the ideal tetrahedral value.

The pyrrolidine ring (N1/C1–C4) has an envelope conformation with atom C2 deviating by 0.586 (1) Å from the least-squares plane formed by the remaining four ring atoms. The puckering parameters (q₂, φ₂; Cremer & Pople, 1975) and the smallest displacement asymmetry parameters (Duax et al., 1976) for the pyrrolidine ring are q₂ = 0.3821 (8) Å, φ₂ = 260.23 (11)° and ΔC_s[C2] = 6.18 (7)°. The tosyl group is equatorially attached to the pyrrolidine ring. The dihydropyran ring adopts a half-chair conformation with a local twofold rotation axis passing through the C2—C5 and C6—C7 bonds; the puckering (Q, θ, φ) and asymmetry (ΔC₂[C2–C5]) parameters are 0.4439 (8) Å, 129.98 (10)°, 276.03 (12)° and 3.45 (9)°, respectively. The pyrrolidine and dihydropyran rings are cis-fused.

The indenone ring system is essentially planar, with atom O4 deviating from the indene plane by 0.088 (1) Å. The dihedral angle between the indene ring system and the C8–C13 benzene ring is 25.12 (3)°. The molecule adopts a folded conformation, with the cyclopentadienone and C8–C13 benzene rings arranged in an almost face-to-face fashion. However, no significant π–π interactions are observed between these rings as their centroids are separated by 3.9135 (5) Å.

In the crystal structure, molecules translated by one unit cell along the a-axis direction are linked by C3—H3···O1ⁱ and C16—H16C···O1ⁱ [symmetry code: (i) 1 + x, y, z] hydrogen-bonding interactions to form a chain. These interactions together constitute a pair of bifurcated acceptor bonds, generating an R¹₂(7) motif (Bernstein et al., 1995). The inversion-related molecules of adjacent chains are alternately linked along the c axis by pairs of C16—H16A···O3ⁱⁱ and C21—H21···O4ⁱⁱⁱ [symmetry codes: (ii) 2 - x, 2 - y, -z; (iii) 2 - x, 2 - y, 1 - z] hydrogen bonds (Table 1) into a sheet-like structure parallel to the ac plane (Fig. 2). The pairs of C16—H16A···O3ⁱⁱ and C21—H21···O4ⁱⁱⁱ interactions generate rings of graph-set motif R²₂(10) and R²₂(8), respectively.

Related literature

For bond-length data, see: Allen et al. (1987). For related pyrrolo[3,4-c]pyran structures, see: Chinnakali et al. (2007a,b). For ring-puckering parameters, see: Cremer & Pople (1975). For asymmetry parameters, see: Duax et al. (1976). For notation of hydrogen-bonding motifs, see: Bernstein et al. (1995).

S2. Experimental

To a solution of 2H-indene-1,3-dione (1 mmol) in dry toluene (20 ml), 2-[N-(3-methylbut-2-enyl)-N-tosylamino]acetaldehyde (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

H atoms were positioned geometrically (C—H = 0.93–0.98 Å) and allowed to ride on their parent atoms, with U_iso(H) = 1.5U_eq(C_methyl) or 1.2U_eq(C). A rotating group model was used for the methyl group attached to the aromatic ring.

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, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 80% probability level.
	Fig. 2. View of a hydrogen-bonded (dashed lines) sheet of the title compound. For the sake of clarity, H atoms not involved in the interactions have been omitted. Symmetry codes: (i) 1 + x, y, z; (iii) 2 - x, 2 - y, 1 - z; (iv) x, y, 1 + z.

4,4-Dimethyl-2-tosyl-2,3,3a,4-tetrahydro-1H,10H- pyrrolo[3,4-c]pyrano[6,5-b]indan-10-one

Crystal data

C23H23NO4S	Z = 2
Mr = 409.48	F(000) = 432
Triclinic, P1	Dx = 1.377 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0219 (2) Å	Cell parameters from 8302 reflections
b = 8.6106 (2) Å	θ = 2.5–40.2°
c = 15.0432 (4) Å	µ = 0.19 mm^−1
α = 104.557 (1)°	T = 100 K
β = 99.182 (1)°	Block, light yellow
γ = 93.192 (1)°	0.60 × 0.56 × 0.37 mm
V = 987.84 (4) Å^3

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	8635 independent reflections
Radiation source: fine-focus sealed tube	7903 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
Detector resolution: 8.33 pixels mm^-1	θmax = 35.0°, θmin = 1.4°
ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −13→13
Tmin = 0.862, Tmax = 0.932	l = −24→24
42977 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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0596P)^2 + 0.2351P] where P = (Fo^2 + 2Fc^2)/3
8635 reflections	(Δ/σ)max = 0.001
263 parameters	Δρmax = 0.58 e Å^−3
0 restraints	Δρmin = −0.36 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
S1	0.39580 (2)	0.63360 (2)	0.220153 (13)	0.01541 (5)
O1	0.23678 (8)	0.62916 (8)	0.15941 (5)	0.02275 (12)
O2	0.41576 (9)	0.52386 (7)	0.27782 (5)	0.02174 (12)
O3	0.83313 (8)	0.95635 (6)	0.09401 (4)	0.01588 (10)
O4	0.99483 (9)	0.77446 (7)	0.36449 (4)	0.02030 (11)
N1	0.53669 (8)	0.59825 (7)	0.15218 (4)	0.01406 (10)
C1	0.55116 (9)	0.69996 (9)	0.08746 (5)	0.01553 (12)
H1A	0.5482	0.8129	0.1182	0.019*
H1B	0.4608	0.6678	0.0334	0.019*
C2	0.72446 (9)	0.66848 (8)	0.05984 (5)	0.01418 (11)
H2	0.7114	0.5658	0.0118	0.017*
C3	0.83158 (9)	0.64700 (8)	0.15018 (5)	0.01296 (11)
H3	0.9272	0.5848	0.1361	0.016*
C4	0.70506 (9)	0.55341 (8)	0.18884 (5)	0.01496 (11)
H4A	0.7108	0.4381	0.1671	0.018*
H4B	0.7277	0.5847	0.2566	0.018*
C5	0.80278 (10)	0.79956 (8)	0.02205 (5)	0.01600 (12)
C6	0.88902 (9)	0.94690 (8)	0.18073 (5)	0.01282 (11)
C7	0.89279 (9)	0.81174 (8)	0.21169 (5)	0.01246 (11)
C8	0.44908 (9)	0.83213 (9)	0.29019 (5)	0.01570 (12)
C9	0.56938 (10)	0.86295 (10)	0.37214 (5)	0.01873 (13)
H9	0.6141	0.7784	0.3930	0.022*
C10	0.62124 (11)	1.02188 (10)	0.42204 (6)	0.02109 (14)
H10	0.7008	1.0433	0.4769	0.025*
C11	0.55587 (11)	1.15034 (10)	0.39124 (6)	0.02036 (14)
C12	0.43419 (11)	1.11695 (10)	0.30990 (6)	0.02146 (14)
H12	0.3886	1.2014	0.2893	0.026*
C13	0.38025 (10)	0.95850 (10)	0.25916 (6)	0.01916 (13)
H13	0.2989	0.9370	0.2050	0.023*
C14	0.61644 (14)	1.32121 (11)	0.44569 (8)	0.0315 (2)
H14A	0.5504	1.3937	0.4193	0.047*
H14B	0.7338	1.3436	0.4430	0.047*
H14C	0.6038	1.3354	0.5095	0.047*
C15	0.68402 (13)	0.83273 (10)	−0.05901 (6)	0.02343 (16)
H15A	0.7383	0.9153	−0.0803	0.035*
H15B	0.5815	0.8679	−0.0388	0.035*
H15C	0.6573	0.7359	−0.1091	0.035*
C16	0.97315 (11)	0.75615 (10)	−0.00403 (6)	0.02156 (15)
H16A	1.0209	0.8391	−0.0276	0.032*
H16B	0.9573	0.6554	−0.0512	0.032*
H16C	1.0488	0.7466	0.0502	0.032*
C17	0.95601 (9)	1.09335 (8)	0.25648 (5)	0.01349 (11)
C18	0.97941 (10)	1.25424 (9)	0.25762 (5)	0.01705 (12)
H18	0.9517	1.2876	0.2034	0.020*
C19	1.04670 (11)	1.36602 (9)	0.34373 (6)	0.02031 (14)
H19	1.0648	1.4749	0.3465	0.024*
C20	1.08615 (11)	1.31523 (10)	0.42432 (6)	0.02093 (14)
H20	1.1278	1.3910	0.4808	0.025*
C21	1.06429 (10)	1.15118 (9)	0.42228 (5)	0.01811 (13)
H21	1.0919	1.1172	0.4763	0.022*
C22	1.00078 (9)	1.04233 (8)	0.33774 (5)	0.01415 (11)
C23	0.96614 (9)	0.86138 (8)	0.31201 (5)	0.01398 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.01277 (8)	0.01370 (8)	0.01945 (8)	−0.00091 (5)	0.00437 (6)	0.00339 (6)
O1	0.0122 (2)	0.0237 (3)	0.0283 (3)	−0.0010 (2)	0.0010 (2)	0.0016 (2)
O2	0.0258 (3)	0.0168 (2)	0.0261 (3)	0.0000 (2)	0.0109 (2)	0.0087 (2)
O3	0.0234 (3)	0.0116 (2)	0.0113 (2)	−0.00181 (18)	0.00137 (17)	0.00251 (16)
O4	0.0277 (3)	0.0166 (2)	0.0169 (2)	0.0031 (2)	0.0006 (2)	0.00693 (19)
N1	0.0124 (2)	0.0139 (2)	0.0163 (2)	0.00059 (18)	0.00296 (18)	0.00469 (19)
C1	0.0147 (3)	0.0155 (3)	0.0161 (3)	−0.0007 (2)	0.0002 (2)	0.0056 (2)
C2	0.0165 (3)	0.0118 (3)	0.0131 (3)	−0.0018 (2)	0.0026 (2)	0.0020 (2)
C3	0.0131 (3)	0.0104 (2)	0.0150 (3)	0.00002 (19)	0.0033 (2)	0.00229 (19)
C4	0.0133 (3)	0.0129 (3)	0.0198 (3)	0.0007 (2)	0.0031 (2)	0.0065 (2)
C5	0.0226 (3)	0.0125 (3)	0.0115 (3)	−0.0027 (2)	0.0032 (2)	0.0013 (2)
C6	0.0145 (3)	0.0111 (2)	0.0121 (2)	−0.0003 (2)	0.0023 (2)	0.00204 (19)
C7	0.0133 (3)	0.0106 (2)	0.0129 (3)	0.00010 (19)	0.0021 (2)	0.00233 (19)
C8	0.0144 (3)	0.0150 (3)	0.0176 (3)	0.0017 (2)	0.0040 (2)	0.0034 (2)
C9	0.0201 (3)	0.0172 (3)	0.0182 (3)	0.0039 (2)	0.0030 (2)	0.0033 (2)
C10	0.0208 (3)	0.0194 (3)	0.0199 (3)	0.0032 (3)	0.0021 (3)	0.0000 (2)
C11	0.0198 (3)	0.0160 (3)	0.0237 (3)	0.0021 (2)	0.0071 (3)	0.0001 (2)
C12	0.0225 (3)	0.0159 (3)	0.0265 (4)	0.0051 (3)	0.0059 (3)	0.0050 (3)
C13	0.0177 (3)	0.0171 (3)	0.0221 (3)	0.0040 (2)	0.0023 (2)	0.0045 (2)
C14	0.0332 (5)	0.0175 (4)	0.0372 (5)	0.0005 (3)	0.0063 (4)	−0.0044 (3)
C15	0.0344 (4)	0.0192 (3)	0.0143 (3)	−0.0040 (3)	−0.0016 (3)	0.0051 (2)
C16	0.0268 (4)	0.0185 (3)	0.0202 (3)	−0.0023 (3)	0.0116 (3)	0.0030 (2)
C17	0.0154 (3)	0.0106 (2)	0.0135 (3)	0.0005 (2)	0.0023 (2)	0.00183 (19)
C18	0.0216 (3)	0.0115 (3)	0.0172 (3)	0.0007 (2)	0.0032 (2)	0.0028 (2)
C19	0.0257 (4)	0.0115 (3)	0.0210 (3)	−0.0008 (2)	0.0032 (3)	0.0006 (2)
C20	0.0256 (4)	0.0147 (3)	0.0178 (3)	−0.0013 (3)	0.0010 (3)	−0.0018 (2)
C21	0.0212 (3)	0.0162 (3)	0.0139 (3)	−0.0002 (2)	0.0001 (2)	0.0008 (2)
C22	0.0155 (3)	0.0123 (3)	0.0134 (3)	0.0005 (2)	0.0015 (2)	0.0019 (2)
C23	0.0148 (3)	0.0126 (3)	0.0139 (3)	0.0011 (2)	0.0019 (2)	0.0029 (2)

Geometric parameters (Å, º)

S1—O2	1.4337 (6)	C9—H9	0.93
S1—O1	1.4383 (7)	C10—C11	1.3992 (12)
S1—N1	1.6329 (6)	C10—H10	0.93
S1—C8	1.7563 (8)	C11—C12	1.3942 (13)
O3—C6	1.3343 (8)	C11—C14	1.5031 (12)
O3—C5	1.4827 (9)	C12—C13	1.3916 (12)
O4—C23	1.2226 (9)	C12—H12	0.93
N1—C1	1.4770 (9)	C13—H13	0.93
N1—C4	1.4849 (9)	C14—H14A	0.96
C1—C2	1.5325 (10)	C14—H14B	0.96
C1—H1A	0.97	C14—H14C	0.96
C1—H1B	0.97	C15—H15A	0.96
C2—C5	1.5328 (10)	C15—H15B	0.96
C2—C3	1.5462 (10)	C15—H15C	0.96
C2—H2	0.98	C16—H16A	0.96
C3—C7	1.4923 (9)	C16—H16B	0.96
C3—C4	1.5332 (10)	C16—H16C	0.96
C3—H3	0.98	C17—C18	1.3831 (10)
C4—H4A	0.97	C17—C22	1.4012 (10)
C4—H4B	0.97	C18—C19	1.4099 (11)
C5—C15	1.5202 (11)	C18—H18	0.93
C5—C16	1.5217 (12)	C19—C20	1.3859 (12)
C6—C7	1.3581 (9)	C19—H19	0.93
C6—C17	1.4779 (9)	C20—C21	1.4057 (11)
C7—C23	1.4734 (10)	C20—H20	0.93
C8—C13	1.3953 (11)	C21—C22	1.3770 (10)
C8—C9	1.3960 (11)	C21—H21	0.93
C9—C10	1.3892 (11)	C22—C23	1.5063 (10)
O2—S1—O1	120.17 (4)	C9—C10—C11	121.18 (8)
O2—S1—N1	106.46 (4)	C9—C10—H10	119.4
O1—S1—N1	105.76 (4)	C11—C10—H10	119.4
O2—S1—C8	109.35 (4)	C12—C11—C10	118.97 (7)
O1—S1—C8	107.78 (4)	C12—C11—C14	120.94 (8)
N1—S1—C8	106.52 (3)	C10—C11—C14	120.09 (8)
C6—O3—C5	114.81 (6)	C13—C12—C11	120.66 (8)
C1—N1—C4	111.34 (6)	C13—C12—H12	119.7
C1—N1—S1	118.53 (5)	C11—C12—H12	119.7
C4—N1—S1	119.42 (5)	C12—C13—C8	119.49 (7)
N1—C1—C2	103.05 (6)	C12—C13—H13	120.3
N1—C1—H1A	111.2	C8—C13—H13	120.3
C2—C1—H1A	111.2	C11—C14—H14A	109.5
N1—C1—H1B	111.2	C11—C14—H14B	109.5
C2—C1—H1B	111.2	H14A—C14—H14B	109.5
H1A—C1—H1B	109.1	C11—C14—H14C	109.5
C1—C2—C5	114.46 (6)	H14A—C14—H14C	109.5
C1—C2—C3	103.08 (5)	H14B—C14—H14C	109.5
C5—C2—C3	113.88 (6)	C5—C15—H15A	109.5
C1—C2—H2	108.4	C5—C15—H15B	109.5
C5—C2—H2	108.4	H15A—C15—H15B	109.5
C3—C2—H2	108.4	C5—C15—H15C	109.5
C7—C3—C4	113.62 (6)	H15A—C15—H15C	109.5
C7—C3—C2	107.12 (5)	H15B—C15—H15C	109.5
C4—C3—C2	103.12 (6)	C5—C16—H16A	109.5
C7—C3—H3	110.9	C5—C16—H16B	109.5
C4—C3—H3	110.9	H16A—C16—H16B	109.5
C2—C3—H3	110.9	C5—C16—H16C	109.5
N1—C4—C3	104.45 (6)	H16A—C16—H16C	109.5
N1—C4—H4A	110.9	H16B—C16—H16C	109.5
C3—C4—H4A	110.9	C18—C17—C22	121.23 (6)
N1—C4—H4B	110.9	C18—C17—C6	132.27 (7)
C3—C4—H4B	110.9	C22—C17—C6	106.50 (6)
H4A—C4—H4B	108.9	C17—C18—C19	117.81 (7)
O3—C5—C15	104.14 (6)	C17—C18—H18	121.1
O3—C5—C16	107.55 (6)	C19—C18—H18	121.1
C15—C5—C16	111.62 (7)	C20—C19—C18	120.64 (7)
O3—C5—C2	110.56 (5)	C20—C19—H19	119.7
C15—C5—C2	112.44 (6)	C18—C19—H19	119.7
C16—C5—C2	110.27 (6)	C19—C20—C21	121.16 (7)
O3—C6—C7	127.24 (6)	C19—C20—H20	119.4
O3—C6—C17	120.89 (6)	C21—C20—H20	119.4
C7—C6—C17	111.87 (6)	C22—C21—C20	117.92 (7)
C6—C7—C23	107.48 (6)	C22—C21—H21	121.0
C6—C7—C3	123.28 (6)	C20—C21—H21	121.0
C23—C7—C3	129.24 (6)	C21—C22—C17	121.20 (7)
C13—C8—C9	120.73 (7)	C21—C22—C23	130.91 (7)
C13—C8—S1	119.21 (6)	C17—C22—C23	107.89 (6)
C9—C8—S1	119.85 (6)	O4—C23—C7	127.46 (6)
C10—C9—C8	118.95 (7)	O4—C23—C22	126.32 (7)
C10—C9—H9	120.5	C7—C23—C22	106.23 (6)
C8—C9—H9	120.5
O2—S1—N1—C1	−177.15 (5)	O1—S1—C8—C13	−23.07 (7)
O1—S1—N1—C1	53.96 (6)	N1—S1—C8—C13	90.05 (7)
C8—S1—N1—C1	−60.54 (6)	O2—S1—C8—C9	29.79 (7)
O2—S1—N1—C4	−35.69 (6)	O1—S1—C8—C9	162.01 (6)
O1—S1—N1—C4	−164.58 (5)	N1—S1—C8—C9	−84.87 (7)
C8—S1—N1—C4	80.92 (6)	C13—C8—C9—C10	−0.70 (12)
C4—N1—C1—C2	18.78 (7)	S1—C8—C9—C10	174.14 (6)
S1—N1—C1—C2	163.14 (5)	C8—C9—C10—C11	−0.40 (12)
N1—C1—C2—C5	−159.04 (6)	C9—C10—C11—C12	1.24 (13)
N1—C1—C2—C3	−34.83 (6)	C9—C10—C11—C14	−178.93 (8)
C1—C2—C3—C7	−81.83 (6)	C10—C11—C12—C13	−0.99 (13)
C5—C2—C3—C7	42.77 (8)	C14—C11—C12—C13	179.17 (8)
C1—C2—C3—C4	38.33 (6)	C11—C12—C13—C8	−0.07 (13)
C5—C2—C3—C4	162.92 (6)	C9—C8—C13—C12	0.93 (12)
C1—N1—C4—C3	5.19 (7)	S1—C8—C13—C12	−173.94 (6)
S1—N1—C4—C3	−138.82 (5)	O3—C6—C17—C18	−1.65 (12)
C7—C3—C4—N1	88.79 (7)	C7—C6—C17—C18	178.60 (8)
C2—C3—C4—N1	−26.79 (7)	O3—C6—C17—C22	179.12 (6)
C6—O3—C5—C15	160.01 (6)	C7—C6—C17—C22	−0.63 (8)
C6—O3—C5—C16	−81.43 (7)	C22—C17—C18—C19	−1.27 (11)
C6—O3—C5—C2	39.02 (9)	C6—C17—C18—C19	179.59 (8)
C1—C2—C5—O3	61.71 (8)	C17—C18—C19—C20	−0.60 (12)
C3—C2—C5—O3	−56.54 (8)	C18—C19—C20—C21	1.57 (13)
C1—C2—C5—C15	−54.22 (8)	C19—C20—C21—C22	−0.63 (13)
C3—C2—C5—C15	−172.46 (6)	C20—C21—C22—C17	−1.25 (12)
C1—C2—C5—C16	−179.49 (6)	C20—C21—C22—C23	178.69 (8)
C3—C2—C5—C16	62.27 (8)	C18—C17—C22—C21	2.25 (11)
C5—O3—C6—C7	−12.17 (10)	C6—C17—C22—C21	−178.42 (7)
C5—O3—C6—C17	168.12 (6)	C18—C17—C22—C23	−177.71 (7)
O3—C6—C7—C23	179.60 (7)	C6—C17—C22—C23	1.63 (8)
C17—C6—C7—C23	−0.67 (8)	C6—C7—C23—O4	−177.94 (8)
O3—C6—C7—C3	−0.19 (11)	C3—C7—C23—O4	1.83 (12)
C17—C6—C7—C3	179.54 (6)	C6—C7—C23—C22	1.63 (8)
C4—C3—C7—C6	−128.50 (7)	C3—C7—C23—C22	−178.61 (7)
C2—C3—C7—C6	−15.31 (9)	C21—C22—C23—O4	−2.41 (13)
C4—C3—C7—C23	51.76 (10)	C17—C22—C23—O4	177.54 (7)
C2—C3—C7—C23	164.96 (7)	C21—C22—C23—C7	178.01 (8)
O2—S1—C8—C13	−155.29 (6)	C17—C22—C23—C7	−2.03 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1^i	0.98	2.45	3.2451 (10)	138
C16—H16A···O3^ii	0.96	2.55	3.5075 (11)	175
C16—H16C···O1^i	0.96	2.49	3.4151 (11)	161
C21—H21···O4^iii	0.93	2.56	3.2266 (9)	129

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