Methyl (1SR,8RS,10SR)-3,5-di­chloro-1-(4-methoxy­phenyl)-8-(phenyl­thio)-11-oxa-4-aza­tri­cyclo­[6.2.1.0^2,7]­undeca-2,4,6-triene-10-carboxyl­ate

In the title mol­ecule, C₂₄H₁₉Cl₂NO₄S, the cyclo­hexane ring tends towards a boat conformation and the two tetra­hydro­furan rings adopt envelope conformations. The crystal packing structure is built from infinite molecular chains, stabilized by an intermolecular C—H...O close contact, running along the b direction.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.030
• wR factor = 0.078
• Data-to-parameter ratio = 19.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           28.29
         From the CIF: _reflns_number_total               5601
         Count of symmetry unique reflns         3193
         Completeness (_total/calc)            175.41%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured      2408
         Fraction of Friedel pairs measured     0.754
         Are heavy atom types Z>Si present          yes
          Please check that the estimate of the number of Friedel pairs is
          correct. If it is not, please give the correct count in the
          _publ_section_exptl_refinement section of the submitted CIF.

---

S1. Comment

In contrast to the remarkable growth of the chemistry of o-quinoid 10-π electron isobenzofuran ring systems, isobenzofurans having a heterocyclic ring, e.g. furo[3,4-c]pyridines have not been studied so well (Padwa, 1998; Rodrigo, 1988; Bailey et al., 1995; Friedrichsen, 1999). Recently, in a series of papers, Sarkar et al. have addressed this issue including development of novel techniques for the generation and trapping of both stable and unstable furo[3,4-c]pyridines for the synthesis of polycyclic heteroaromatic ring systems (Sarkar et al., 1999; Sarkar, Ghosh & Chow, 2000; Sarkar, Basak & Ghosh, 2000; Sarkar, Basak & Panda, 2002). In this context, the title compound (2) was synthesized by Pummerer reaction of a pyridylmethyl substituted sulfoxide and trapping of the in situ generated furo[3,4-c]pyridine (1) in Diels-Alder reaction with methyl acrylate. The X-ray crystal structure determination of (2) was undertaken in order to elucidate its regio- and stereochemistry which could not be done unambiguously by NMR spectroscopy.

The title compound (2) has three chiral atoms; the C6 atom is the R-chiral center and the atoms C8 and C9 are the S-chiral centers (Fig. 1). The absolute configuration was determined by the Flack parameter (Flack, 1983). Since the title compound was prepared from achiral reagents, the chiral space group is the result of spontaneous resolution. All the chiral atoms belong to the oxabicycloheptane [O1, C3, C4, C6—C9]. The average C—O and C—C bond distances in this moiety are 1.455 Å and 1.520 Å, respectively. As a result of the bulky substituents attached on the oxabicycloheptane in (2), the average C—O bond distance is slightly longer, whereas that of C—C is shorter compared with the corresponding values in the related structure methyl 7-oxabicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylate [C—O 1.433 Å and C—C 1.555 Å; Kohnke et al., 1988]. The cyclohexane ring (C3, C4, C6—C9) tends towards a boat conformation and the two tetrahydrofuran rings [O1, C3, C4, C6, C9 and O1, C6—C9] adopt envelope conformations, which are similar to those in the related structure. Also comparable are the dihedral angles between the O1/C6/C9 and C3/C4/C6/C9 planes [127.6 (1)°], the O1/C6/C9 and C6/C7/C8/C9 planes [121.5 (1)°], and the C3/C4/C6/C9 and C6/C7/C8/C9 planes [110.9 (1)°]; the corresponding values in the related structure are 124°, 124° and 112° (Kohnke et al., 1988).

The pyridine ring (N1, C1—C5) makes a dihedral angle of 40.1 (1)° with the cyclohexane main plane. Atoms Cl1 and Cl2 are displaced on opposite sides of the pyridine ring by 0.046 (1) Å and 0.142 (1) Å. The relative configuration of the other three substituents, methyl carboxylate (O2, O3, C17, C18), thiophenyl (S1, C19—C24) and methoxy phenyl (O4, C10—C16), with respect to the oxabicycloheptane are conditioned by the sp³ hybridization of atoms C6, C8 and C9. The methyl carboxylate is twisted about the C8—C17 bond by an angle of 78.8 (1)° out of the cyclohexane mean plane. The aromatic ring of the thiophenyl and methoxy phenyl make dihedral angles of 38.3 (1) and 29.0 (1)°, respectively, with the cyclohexane.

Within these substituents, the sulfur atom S1 exhibits sp³ hybridization; the angle subtended at this atom is 104.4 (1)°, while the methoxy substituent (atoms O4 and C16) tends to be coplanar with the attached phenyl [being twisted by 5.3 (1)°], as is usually observed in the anysoles (Domiano et al., 1979).

An intramolecular C—H···O close contact is observed in (2), linking atom H24 of the thiophenyl to O1 of the oxabicycloheptane (Fig. 1). In the crystal packing, the molecules are linked by intermolecular C16—H16B···O2ⁱ (i: x, y − 1, z) close contacts (Table 2) into one-dimensional molecular chains: in this manner a C(11) (Bernstein et al., 1995) is generated running along the b direction (Fig. 2). Short contacts of Cl2···O3ⁱⁱ [3.20 Å; ii: −1/2 + x, 3/2 − y, −z] are observed in the crystal, interconnecting the molecular chains into a three-dimensional network.

S2. Experimental

A mixture of 5 ml of dry toluene and 0.13 ml acetic anhydride containing catalytic amount of p-toluene sulfonic acid and 0.1 ml me thyl acrylate was refluxed under argon. To this mixture, 60 mg of o-benzoyl substituted pyridylmethyl sulfoxide in 5 ml toluene was added dropwise over a period of 10 min. The yellow solution was refluxed for an additional 1 h. The bright yellow solution was cooled and washed with saturated aqueous NaHCO₃ and dried (Na₂SO₄). After removal of solvent, the residue was purified by preparative thin-layer chromatography and finally crystallized from ethyl acetate–petroleum ether (1:20) to give colorless crystals of (2) (m.p. 390–392 K).

S3. Refinement

All the H-atoms were fixed geometrically and were treated as riding atoms, with C—H distances 0.93–0.98 Å and U_iso(H) = 1.2–1.5U_eq(C). The methyl H atoms were constrained, but allowed to rotate about the C—C bonds.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Figures

	Fig. 1. The structure of (2), showing 50% probability displacement ellipsoids and the atom-numbering scheme. Dashed lines denote the intramolecular C—H.·O close contact.
	Fig. 2. The packing structure of (2), viewed down the a axis showing the molecular chains running along the b-direction. Dashed lines denote the intermolecular C—H···O close contacts.

Methyl (1SR,8RS,10SR)-3,5-dichloro-1-(4-methoxyphenyl)-8-(phenylthio)-11- oxa-4-azatricyclo[6.2.1.0^2,7]undeca-2,4,6-triene-10-carboxylate

Crystal data

C24H19Cl2NO4S	Dx = 1.433 Mg m^−3
Mr = 488.36	Melting point: 391(1)K K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
a = 9.0330 (4) Å	Cell parameters from 8828 reflections
b = 10.2107 (5) Å	θ = 2.6–28.3°
c = 24.5414 (12) Å	µ = 0.41 mm^−1
V = 2263.53 (19) Å^3	T = 293 K
Z = 4	Block, colorless
F(000) = 1008	0.42 × 0.40 × 0.40 mm

Data collection

Siemens SMART CCD area-detector diffractometer	5601 independent reflections
Radiation source: fine-focus sealed tube	5068 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
Detector resolution: 8.33 pixels mm^-1	θmax = 28.3°, θmin = 2.6°
ω scans	h = −12→10
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −13→13
Tmin = 0.846, Tmax = 0.853	l = −32→26
14401 measured reflections

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)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.078	w = 1/[σ^2(Fo^2) + (0.0388P)^2 + 0.2526P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
5601 reflections	Δρmax = 0.22 e Å^−3
291 parameters	Δρmin = −0.19 e Å^−3
0 restraints	Absolute structure: (Flack, 1983), 2408 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (4)

Special details

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 30 s covered 0.3° in ω. The crystal-to-detector distance was 5 cm and the detector swing angle was −35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible.

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
Cl1	0.56367 (6)	1.20472 (5)	0.23745 (2)	0.06307 (14)
Cl2	0.40714 (5)	0.86087 (5)	0.09270 (2)	0.05639 (12)
S1	1.08814 (4)	0.85032 (5)	0.197703 (18)	0.04903 (11)
O1	0.87533 (12)	0.71753 (12)	0.14305 (4)	0.0391 (2)
O2	0.74361 (17)	1.02534 (13)	0.03342 (6)	0.0575 (3)
O3	0.73125 (15)	0.85444 (12)	−0.02341 (5)	0.0502 (3)
O4	0.43275 (18)	0.28787 (14)	0.07125 (7)	0.0681 (4)
N1	0.50890 (15)	1.02107 (15)	0.16700 (6)	0.0449 (3)
C1	0.61473 (19)	1.07107 (16)	0.19714 (7)	0.0437 (4)
C2	0.76129 (19)	1.02881 (17)	0.19935 (7)	0.0431 (3)
H2	0.8328	1.0703	0.2204	0.052*
C3	0.79138 (17)	0.92120 (16)	0.16792 (7)	0.0382 (3)
C4	0.68269 (16)	0.86277 (16)	0.13577 (6)	0.0356 (3)
C5	0.54480 (17)	0.91943 (17)	0.13572 (7)	0.0394 (3)
C6	0.93223 (16)	0.84800 (16)	0.15330 (6)	0.0391 (3)
C7	0.97466 (18)	0.89269 (17)	0.09475 (7)	0.0433 (4)
H7A	0.9672	0.9870	0.0909	0.052*
H7B	1.0742	0.8652	0.0853	0.052*
C8	0.85776 (17)	0.82165 (16)	0.05931 (6)	0.0382 (3)
H8A	0.9066	0.7547	0.0370	0.046*
C9	0.75956 (16)	0.75301 (15)	0.10425 (6)	0.0357 (3)
C10	0.67251 (17)	0.63143 (15)	0.09112 (6)	0.0380 (3)
C11	0.5911 (2)	0.57482 (19)	0.13310 (7)	0.0506 (4)
H11	0.5893	0.6149	0.1671	0.061*
C12	0.5135 (2)	0.4610 (2)	0.12523 (8)	0.0566 (5)
H12	0.4597	0.4247	0.1538	0.068*
C13	0.5148 (2)	0.39961 (17)	0.07473 (8)	0.0482 (4)
C14	0.5951 (2)	0.45447 (17)	0.03272 (7)	0.0465 (4)
H14	0.5972	0.4141	−0.0012	0.056*
C15	0.67281 (19)	0.57019 (17)	0.04120 (7)	0.0417 (3)
H15	0.7260	0.6069	0.0126	0.050*
C16	0.4390 (3)	0.2152 (2)	0.02227 (11)	0.0728 (6)
H16A	0.3830	0.1359	0.0263	0.109*
H16B	0.5401	0.1940	0.0141	0.109*
H16C	0.3981	0.2664	−0.0069	0.109*
C17	0.77146 (17)	0.91378 (16)	0.02265 (7)	0.0399 (3)
C18	0.6537 (3)	0.9364 (2)	−0.06226 (9)	0.0609 (5)
H18A	0.6383	0.8885	−0.0954	0.091*
H18B	0.7117	1.0132	−0.0697	0.091*
H18C	0.5598	0.9619	−0.0474	0.091*
C19	1.01318 (18)	0.81905 (16)	0.26325 (7)	0.0423 (3)
C20	1.0917 (2)	0.8708 (2)	0.30682 (8)	0.0557 (4)
H20	1.1732	0.9245	0.3005	0.067*
C21	1.0488 (3)	0.8426 (2)	0.35956 (8)	0.0683 (6)
H21	1.1033	0.8750	0.3887	0.082*
C22	0.9255 (3)	0.7665 (2)	0.36913 (8)	0.0646 (5)
H22	0.8962	0.7488	0.4047	0.078*
C23	0.8459 (2)	0.7168 (2)	0.32625 (9)	0.0584 (5)
H23	0.7613	0.6674	0.3328	0.070*
C24	0.8913 (2)	0.74007 (19)	0.27318 (8)	0.0510 (4)
H24	0.8401	0.7027	0.2442	0.061*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0665 (3)	0.0595 (3)	0.0632 (3)	0.0067 (2)	0.0121 (2)	−0.0171 (2)
Cl2	0.03264 (18)	0.0751 (3)	0.0614 (3)	0.0003 (2)	−0.01142 (18)	−0.0094 (2)
S1	0.02987 (18)	0.0676 (3)	0.0496 (2)	−0.00260 (19)	−0.00715 (17)	0.0056 (2)
O1	0.0332 (5)	0.0445 (6)	0.0396 (6)	0.0034 (4)	−0.0050 (4)	0.0020 (5)
O2	0.0687 (9)	0.0462 (7)	0.0575 (8)	0.0110 (6)	−0.0064 (7)	−0.0009 (6)
O3	0.0603 (7)	0.0467 (6)	0.0435 (6)	0.0001 (6)	−0.0109 (5)	0.0037 (5)
O4	0.0705 (9)	0.0507 (7)	0.0832 (10)	−0.0176 (7)	0.0038 (8)	−0.0032 (7)
N1	0.0355 (7)	0.0514 (8)	0.0479 (8)	0.0038 (6)	0.0039 (6)	−0.0002 (6)
C1	0.0455 (9)	0.0429 (8)	0.0428 (8)	0.0012 (7)	0.0070 (7)	−0.0031 (7)
C2	0.0404 (8)	0.0451 (8)	0.0437 (8)	−0.0033 (7)	−0.0031 (7)	−0.0026 (7)
C3	0.0308 (7)	0.0428 (8)	0.0410 (8)	−0.0007 (6)	−0.0026 (6)	0.0027 (7)
C4	0.0302 (7)	0.0418 (8)	0.0346 (7)	−0.0017 (6)	0.0007 (5)	0.0004 (6)
C5	0.0293 (7)	0.0486 (8)	0.0403 (8)	−0.0011 (6)	−0.0015 (6)	−0.0005 (7)
C6	0.0295 (7)	0.0464 (8)	0.0415 (8)	0.0001 (7)	−0.0055 (6)	0.0024 (7)
C7	0.0312 (7)	0.0533 (9)	0.0454 (8)	−0.0024 (6)	0.0009 (6)	0.0056 (7)
C8	0.0326 (7)	0.0438 (9)	0.0384 (8)	0.0034 (6)	0.0031 (6)	0.0031 (6)
C9	0.0317 (7)	0.0418 (8)	0.0335 (7)	0.0028 (6)	0.0003 (6)	0.0015 (6)
C10	0.0356 (7)	0.0398 (8)	0.0386 (7)	0.0033 (6)	−0.0005 (6)	0.0016 (7)
C11	0.0570 (10)	0.0554 (10)	0.0393 (9)	−0.0093 (9)	0.0053 (8)	−0.0010 (7)
C12	0.0627 (12)	0.0581 (11)	0.0491 (10)	−0.0134 (9)	0.0093 (9)	0.0083 (8)
C13	0.0427 (9)	0.0407 (8)	0.0611 (11)	−0.0012 (7)	−0.0030 (8)	0.0031 (8)
C14	0.0476 (9)	0.0470 (9)	0.0448 (9)	0.0028 (8)	−0.0022 (8)	−0.0059 (7)
C15	0.0413 (8)	0.0452 (9)	0.0385 (8)	0.0018 (7)	0.0022 (7)	0.0001 (7)
C16	0.0665 (13)	0.0458 (10)	0.1061 (18)	−0.0047 (10)	−0.0079 (13)	−0.0169 (11)
C17	0.0336 (8)	0.0450 (9)	0.0411 (8)	0.0006 (6)	0.0030 (6)	0.0047 (7)
C18	0.0671 (12)	0.0580 (12)	0.0575 (12)	−0.0053 (9)	−0.0215 (10)	0.0151 (9)
C19	0.0367 (8)	0.0444 (8)	0.0458 (8)	0.0053 (6)	−0.0056 (7)	−0.0022 (7)
C20	0.0492 (10)	0.0607 (11)	0.0573 (10)	−0.0047 (9)	−0.0061 (9)	−0.0125 (9)
C21	0.0732 (13)	0.0817 (15)	0.0501 (11)	−0.0018 (12)	−0.0090 (10)	−0.0184 (10)
C22	0.0759 (14)	0.0713 (13)	0.0468 (10)	0.0081 (12)	0.0047 (10)	−0.0032 (9)
C23	0.0569 (11)	0.0565 (11)	0.0619 (12)	−0.0030 (9)	0.0009 (9)	0.0071 (10)
C24	0.0486 (10)	0.0559 (10)	0.0486 (10)	−0.0078 (8)	−0.0106 (8)	0.0028 (8)

Geometric parameters (Å, º)

Cl1—C1	1.7475 (17)	C10—C15	1.375 (2)
Cl2—C5	1.7375 (16)	C10—C11	1.392 (2)
S1—C19	1.7744 (18)	C11—C12	1.371 (3)
S1—C6	1.7808 (15)	C11—H11	0.9300
O1—C6	1.450 (2)	C12—C13	1.389 (3)
O1—C9	1.4600 (18)	C12—H12	0.9300
O2—C17	1.196 (2)	C13—C14	1.380 (3)
O3—C17	1.333 (2)	C14—C15	1.390 (2)
O3—C18	1.449 (2)	C14—H14	0.9300
O4—C13	1.363 (2)	C15—H15	0.9300
O4—C16	1.414 (3)	C16—H16A	0.9600
N1—C1	1.312 (2)	C16—H16B	0.9600
N1—C5	1.331 (2)	C16—H16C	0.9600
C1—C2	1.393 (2)	C18—H18A	0.9600
C2—C3	1.370 (2)	C18—H18B	0.9600
C2—H2	0.9300	C18—H18C	0.9600
C3—C4	1.394 (2)	C19—C24	1.386 (2)
C3—C6	1.519 (2)	C19—C20	1.388 (2)
C4—C5	1.373 (2)	C20—C21	1.382 (3)
C4—C9	1.529 (2)	C20—H20	0.9300
C6—C7	1.556 (2)	C21—C22	1.378 (3)
C7—C8	1.548 (2)	C21—H21	0.9300
C7—H7A	0.9700	C22—C23	1.372 (3)
C7—H7B	0.9700	C22—H22	0.9300
C8—C17	1.517 (2)	C23—C24	1.386 (3)
C8—C9	1.579 (2)	C23—H23	0.9300
C8—H8A	0.9800	C24—H24	0.9300
C9—C10	1.504 (2)
C19—S1—C6	104.51 (8)	C12—C11—H11	119.4
C6—O1—C9	98.00 (11)	C10—C11—H11	119.4
C17—O3—C18	115.28 (14)	C11—C12—C13	120.25 (17)
C13—O4—C16	118.10 (17)	C11—C12—H12	119.9
C1—N1—C5	116.80 (14)	C13—C12—H12	119.9
N1—C1—C2	126.42 (16)	O4—C13—C14	125.37 (17)
N1—C1—Cl1	115.51 (13)	O4—C13—C12	115.40 (17)
C2—C1—Cl1	118.06 (14)	C14—C13—C12	119.23 (16)
C3—C2—C1	114.51 (15)	C13—C14—C15	119.92 (16)
C3—C2—H2	122.7	C13—C14—H14	120.0
C1—C2—H2	122.7	C15—C14—H14	120.0
C2—C3—C4	121.50 (15)	C10—C15—C14	121.25 (16)
C2—C3—C6	133.96 (15)	C10—C15—H15	119.4
C4—C3—C6	104.22 (13)	C14—C15—H15	119.4
C5—C4—C3	117.32 (15)	O4—C16—H16A	109.5
C5—C4—C9	136.10 (14)	O4—C16—H16B	109.5
C3—C4—C9	106.28 (13)	H16A—C16—H16B	109.5
N1—C5—C4	123.30 (15)	O4—C16—H16C	109.5
N1—C5—Cl2	116.39 (12)	H16A—C16—H16C	109.5
C4—C5—Cl2	120.30 (13)	H16B—C16—H16C	109.5
O1—C6—C3	101.32 (11)	O2—C17—O3	124.26 (16)
O1—C6—C7	101.34 (12)	O2—C17—C8	124.58 (16)
C3—C6—C7	106.27 (13)	O3—C17—C8	111.16 (14)
O1—C6—S1	113.50 (10)	O3—C18—H18A	109.5
C3—C6—S1	120.76 (12)	O3—C18—H18B	109.5
C7—C6—S1	111.50 (11)	H18A—C18—H18B	109.5
C8—C7—C6	102.32 (12)	O3—C18—H18C	109.5
C8—C7—H7A	111.3	H18A—C18—H18C	109.5
C6—C7—H7A	111.3	H18B—C18—H18C	109.5
C8—C7—H7B	111.3	C24—C19—C20	119.50 (17)
C6—C7—H7B	111.3	C24—C19—S1	124.55 (13)
H7A—C7—H7B	109.2	C20—C19—S1	115.77 (14)
C17—C8—C7	113.14 (14)	C21—C20—C19	119.89 (19)
C17—C8—C9	113.62 (12)	C21—C20—H20	120.1
C7—C8—C9	101.46 (12)	C19—C20—H20	120.1
C17—C8—H8A	109.4	C22—C21—C20	120.3 (2)
C7—C8—H8A	109.4	C22—C21—H21	119.9
C9—C8—H8A	109.4	C20—C21—H21	119.9
O1—C9—C10	108.02 (12)	C23—C22—C21	120.1 (2)
O1—C9—C4	100.21 (11)	C23—C22—H22	119.9
C10—C9—C4	118.42 (13)	C21—C22—H22	119.9
O1—C9—C8	99.39 (11)	C22—C23—C24	120.1 (2)
C10—C9—C8	120.68 (13)	C22—C23—H23	119.9
C4—C9—C8	106.45 (12)	C24—C23—H23	119.9
C15—C10—C11	118.14 (16)	C19—C24—C23	120.00 (18)
C15—C10—C9	124.39 (14)	C19—C24—H24	120.0
C11—C10—C9	117.42 (14)	C23—C24—H24	120.0
C12—C11—C10	121.20 (17)
C5—N1—C1—C2	0.5 (3)	C3—C4—C9—C8	−72.97 (15)
C5—N1—C1—Cl1	179.77 (12)	C17—C8—C9—O1	−158.87 (13)
N1—C1—C2—C3	−2.7 (3)	C7—C8—C9—O1	−37.12 (14)
Cl1—C1—C2—C3	178.06 (13)	C17—C8—C9—C10	83.56 (17)
C1—C2—C3—C4	1.4 (2)	C7—C8—C9—C10	−154.68 (13)
C1—C2—C3—C6	173.80 (17)	C17—C8—C9—C4	−55.21 (17)
C2—C3—C4—C5	1.6 (2)	C7—C8—C9—C4	66.54 (14)
C6—C3—C4—C5	−172.70 (14)	O1—C9—C10—C15	−111.84 (16)
C2—C3—C4—C9	176.32 (15)	C4—C9—C10—C15	135.33 (16)
C6—C3—C4—C9	1.99 (16)	C8—C9—C10—C15	1.3 (2)
C1—N1—C5—C4	3.1 (3)	O1—C9—C10—C11	65.52 (18)
C1—N1—C5—Cl2	−175.91 (13)	C4—C9—C10—C11	−47.3 (2)
C3—C4—C5—N1	−4.1 (3)	C8—C9—C10—C11	178.64 (15)
C9—C4—C5—N1	−176.75 (16)	C15—C10—C11—C12	0.2 (3)
C3—C4—C5—Cl2	174.85 (12)	C9—C10—C11—C12	−177.33 (18)
C9—C4—C5—Cl2	2.2 (3)	C10—C11—C12—C13	0.0 (3)
C9—O1—C6—C3	52.18 (13)	C16—O4—C13—C14	5.6 (3)
C9—O1—C6—C7	−57.19 (12)	C16—O4—C13—C12	−175.04 (19)
C9—O1—C6—S1	−176.84 (10)	C11—C12—C13—O4	−179.37 (19)
C2—C3—C6—O1	152.88 (18)	C11—C12—C13—C14	0.1 (3)
C4—C3—C6—O1	−33.84 (15)	O4—C13—C14—C15	179.06 (17)
C2—C3—C6—C7	−101.6 (2)	C12—C13—C14—C15	−0.3 (3)
C4—C3—C6—C7	71.66 (15)	C11—C10—C15—C14	−0.4 (3)
C2—C3—C6—S1	26.6 (3)	C9—C10—C15—C14	176.90 (15)
C4—C3—C6—S1	−160.16 (12)	C13—C14—C15—C10	0.5 (3)
C19—S1—C6—O1	−74.10 (12)	C18—O3—C17—O2	2.3 (3)
C19—S1—C6—C3	46.42 (14)	C18—O3—C17—C8	−177.37 (15)
C19—S1—C6—C7	172.22 (12)	C7—C8—C17—O2	−30.9 (2)
O1—C6—C7—C8	32.08 (14)	C9—C8—C17—O2	84.1 (2)
C3—C6—C7—C8	−73.40 (15)	C7—C8—C17—O3	148.76 (14)
S1—C6—C7—C8	153.15 (11)	C9—C8—C17—O3	−96.23 (16)
C6—C7—C8—C17	125.30 (14)	C6—S1—C19—C24	32.80 (17)
C6—C7—C8—C9	3.22 (15)	C6—S1—C19—C20	−152.29 (14)
C6—O1—C9—C10	−174.65 (12)	C24—C19—C20—C21	0.5 (3)
C6—O1—C9—C4	−50.10 (13)	S1—C19—C20—C21	−174.68 (17)
C6—O1—C9—C8	58.64 (12)	C19—C20—C21—C22	−2.0 (3)
C5—C4—C9—O1	−156.72 (18)	C20—C21—C22—C23	0.9 (3)
C3—C4—C9—O1	30.09 (15)	C21—C22—C23—C24	1.7 (3)
C5—C4—C9—C10	−39.7 (3)	C20—C19—C24—C23	2.1 (3)
C3—C4—C9—C10	147.15 (14)	S1—C19—C24—C23	176.84 (16)
C5—C4—C9—C8	100.2 (2)	C22—C23—C24—C19	−3.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16B···O2^i	0.96	2.56	3.377 (3)	142
C24—H24···O1	0.93	2.51	3.205 (2)	132

Symmetry code: (i) x, y−1, z.