Fine-tuning of bi­aryl dihedral angles: structural characterization of five homologous three-atom bridged bi­phenyls by X-ray crystallography

The homologous series of three-atom bridged biaryls comprising 5,7-dihydro-1,2,3,9,10,11-hexamethoxydibenzo[c,e]oxepine, 6,7-dihydro-1,2,3,9,10,11-hexamethoxy-6-methyl-5H-dibenzo[c,e]azepinium chloride, 5,7-dihydro-1,2,3,9,10,11-hexamethoxydibenzo[c,e]thiepine, and the 6-oxide and 6,6-dioxide derivatives of the latter have been characterized by X-ray crystal structure analysis. Within this series the endocyclic and exocyclic biaryl dihedral angles vary over 10° ranges, reflecting the changing balance of intramolecular (steric, geometric) and intermolecular (crystal packing) forces, the former being potential control elements for fine-tuning the helicity of the biaryl system.

1. Introduction

Biaryls with three-atom bridges connecting the 2,2′-positions have been the subject of continuing interest since the pioneering studies by Mislow and others in the 1960s into their chiroptical properties and the features which determine their configurational stability (Mislow et al., 1962, 1964; Kurland et al., 1964; Hall, 1969); more recently their biological effects have become increasingly significant. The alkaloid (−)-colchicine (1) (Fig. 1) binds strongly to the protein tubulin, thereby disrupting microtubule-dependent cell functions (Boyé & Brossi, 1992; Brossi, 1990; Le Hello, 2000), and although the therapeutic value of (1) is compromised by its toxicity, a number of related structures such as the allocolchicine derivatives (2) and (3) have similar or enhanced tubulin-binding ability (Kang et al., 1990; Boyé et al., 1993; Shi et al., 1997, 1998; Lee, 1999). From this series a phosphate pro-drug, ZD6126, derived from (3), has been identified as a promising candidate for clinical use in targeting the vascular systems of solid tumours (Davis et al., 2002). It has been established that colchicine analogues only bind efficiently to tubulin if they possess, or can achieve, the same sense of helicity as the natural product (Brossi et al., 1990; Berg & Bladh, 1999; Brossi et al., 1999). The nature of the bridging B-ring influences the conformational mobility of the A–C axis, and in (−)-(1) the preference of the 7-substituent for an equatorial orientation effectively induces the (aR) configuration depicted. However, structures with an unsubstituted B-ring such as (4) (Banwell et al., 1992) and (5) (Boyé et al., 1989) are also efficient tubulin binders and these exist in solution as mixtures of (aR)- and (aS)-atropisomers, of which the former is the active conformation (Cavazza et al., 2000; Bergemann et al., 2003). The discovery that open-chain biaryls also bind to the colchicine binding site of tubulin has led to further speculation about the role of inter-aryl flexibility in the binding process (Janik & Bane, 2002).

Figure 1 Structures of three-atom bridged biaryls (1)–(12).

Our interest in these and other aspects of biaryl conformation, in particular the principle of fine tuning the dihedral angles, led us to seek new ways of controlling this property. Using complementary kinetic and thermodynamic resolution processes we prepared the first examples, (6) and (7), of a new type of conformationally restrained bridged biaryl lactam (Edwards et al., 2003). To gain further insight into the structural characteristics of three-atom bridged biaryls, we prepared the homologous series of polymethoxylated structures (8)–(12) for analysis by X-ray crystallography. We herein describe the results of this study, which provide some direct comparison of the factors that contribute to the final three-dimensional structure of such molecules.

2. Experimental

All compounds are racemic. Melting points were determined using a Buchi 512 or an Electrothermal 9100 apparatus and are uncorrected. IR spectra were of neat thin films on NaCl plates, recorded on Perkin-Elmer 1710FT or Nicolet Nexus 670/870 spectrometers. NMR spectra were measured on Bruker DPX200 (¹H at 200 MHz), DPX300 (¹H at 300 MHz, ¹³C at 75 MHz) or DPX400 (¹H at 400 MHz, ¹³C at 100 MHz) instruments for solutions in deuteriochloroform; J values are quoted to the nearest 0.5 Hz. NMR spectra were assigned with the aid of HMQC and DEPT-135 spectra where appropriate. Mass spectra were measured on a Micromass LCT instrument using a Waters 2790 separations module with electrospray ionization and TOF fragment detection. Starting materials and solvents were either used as supplied or purified by conventional techniques (Perrin et al., 1980) and most reactions were carried out under nitrogen or argon. Organic solutions were dried using anhydrous magnesium sulfate and concentrated by rotary evaporation. TLC was carried out using Merck silica gel 60 on aluminium plates and the chromatograms visualized using UV light (254 nm) and/or the following developing agents: ethanolic vanillin or acidified aqueous potassium permanganate. Preparative (flash) chromatography (Still et al., 1978) was carried out on 60 H silica gel (Merck 9385). Compositions of solvent mixtures are quoted as ratios of volume. `Ether' refers to diethyl ether.

2.1. Dimethyl 4,4′,5,5′,6,6′-hexamethoxy-2,2′-diphenate (±)-(14)

To a suspension of ellagic acid (13) (8.8 g, 29.1 mmol) in water (170 ml) at room temperature tetrabutylammonium iodide (537 mg, 1.45 mmol, 5 mol %) and dimethyl sulfate (29 ml, 38.66 g, 0.3 mol) were added. To the vigorously stirred suspension was slowly added a solution of KOH (28.6 g, 0.5 mol) in water (56 ml) over 3 h and the mixture was then heated under reflux for 12 h. After cooling to room temperature, the mixture was acidified with concentrated HCl and extracted with DCM (3 × 100 ml). The organic layer was dried and evaporated to give a crude solid (8 g), which was dissolved in DMF (70 ml) and treated at 273 K with NaH (4.79 g, 60% dispersion in mineral oil, 0.12 mol). After stirring for 0.5 h, iodomethane (10 ml, 22.8 g, 0.16 mol) was added and the mixture was stirred overnight at room temperature. The reaction was quenched by the addition of 2 M hydrochloric acid (20 ml) at 273 K and the mixture extracted with ether (3 × 100 ml). The combined extracts were dried and evaporated. Purification of the crude material by flash chromatography over silica gel (200 g), eluting with hexane–ethyl acetate (3:1), followed by recrystallization from ether–hexane gave the title compound (14) (5.07 g, 39%) as a colourless solid, m.p. 352–354 K, lit. 353 K (Itoh et al., 1996); δ_H (300 MHz, CDCl₃) 7.38 (2H, s, 3 and 3′-H), 3.97 (6H, s, 2 × OMe), 3.95 (6H, s, 2 × OMe), 3.65 (12H, s, 2 × OMe and 2 × CO₂Me); δ_C (75 MHz, CDCl₃) 52.2, 56.3, 60.9, 61.2, 109.2, 125.4, 127.0, 145.8, 151.6, 152.4, 167.3.

2.2. 4,4′,5,5′,6,6′-Hexamethoxy-1,1′-biphenyl-2,2′-dimethanol (±)-(15)

To a suspension of LiAlH₄ (1.14 g, 30 mmol) in dry THF (20 ml) under argon was added a solution of (14) (4.5 g, 10.0 mmol) in dry THF (20 ml) and the mixture was then heated under reflux for 3 h. After being cooled to room temperature, the mixture was cautiously acidified with concentrated hydrochloric acid (5 ml) and extracted with ether (3 × 100 ml). The combined extracts were dried and evaporated to give a crude solid (3.8 g), which was purified by flash chromatography over silica gel (200 g), eluting with hexane–ethyl acetate (1:1; R_f = 0.29), followed by recrystallization from ethyl acetate–hexane, which gave the diol (15) (3.6 g, 91%), m.p. 380–382 K, lit. 378–379 K (benzene–ether; Kochetkov et al., 1962); δ_H (400 MHz, CDCl₃) 6.87 (2H, s, 3-H, 3′-H), 4.16 (4H, s, 2 × CH₂), 3.91 (6H, s, 2 × OMe), 3.87 (6H, s, 2 × OMe), 3.65 (6H, s, 2 × OMe), 2.78 (2H, br. s, 2 × OH); δ_C (100 MHz, CDCl₃) 56.04, 61.03, 61.05, 63.73 (CH₂), 108.84 (3-H, 3′-H), 121.68, 135.77, 141.69, 151.07, 153.38, consistent with published data (Warshawsky & Meyers, 1990); ν_max (cm^–1) 3402, 2936, 2835, 1600, 1488, 1464, 1402, 1324, 1192, 1130, 1099, 1014, 917; m/z (ES) 347 (50%, MH⁺—CH₂O), 377 (4%, MH⁺—H₂O), 417 (3%, MNa⁺), 458 (100%, MNa₂H₂O⁺).

2.3. 5,7-Dihydro-1,2,3,9,10,11-hexamethoxydibenzo[c,e]oxepine (±)-(8)

Concentrated hydrochloric acid (0.2 ml) was added to a solution of the diol (15) (160 mg, 0.41 mmol) in THF (3 ml) and 2 M hydrochloric acid (3 ml), and the mixture was heated under reflux for 4 h. The mixture was then cooled to room temperature, diluted with water (30 ml) and extracted with ether (3 × 30 ml). The combined extracts were dried and evaporated to give a crude solid (142 mg), which was purified by flash chromatography over silica gel (20 g), eluting with hexane–ethyl acetate (1:1; R_f = 0.33) to obtain the title compound (±)-(8) (130 mg, 85%) as colourless crystals, m.p. 417–419 K (EtOAc), lit. 420–421 K (MeOH; Kashiwada et al., 1994). Found: C 63.70, H 6.55; C₂₀H₂₄O₇ requires C 63.82, H 6.43%; δ_H (200 MHz, CDCl₃) 6.72 (2H, s, 4-H, 8-H), 4.38 (2H, d, J = 11 Hz, 5-H_A, 7-H_A), 4.05 (2H, d, J = 11 Hz, 5-H_B, 7-H_B), 3.92 (6H, s, 2 × OMe), 3.91 (6H, s, 2 × OMe), 3.72 (6H, s, 2 × OMe); δ_C (100 MHz, CDCl₃) 56.16, 60.88, 61.12, 67.59 (5-C, 7-C), 107.98 (4-C, 8-C), 123.18, 130.94, 142.40, 151.36, 153.40; ν_max (cm⁻¹) 2983, 2940, 2855, 1599, 1492, 1463, 1403, 1318, 1238, 1191, 1127, 1097; m/z (ES) 347 (8%, MH⁺—CH₂O), 377 (2%, MH⁺), 399 (3%, MNa⁺), 440 (100%, MNa₂H₂O⁺).

2.4. (±)-2,2′-Bis(bromomethyl)-5,7-dihydro-4,4′,5,5′,6,6′-hexamethoxy-1,1′-biphenyl (16)

Phosphorus tribromide (417 mg, 1.54 mmol) was added to a solution of the diol (15) (0.92 g, 2.33 mmol) in DCM (20 ml) and the mixture was stirred for 1 h. TLC indicated complete conversion and water (30 ml) was then added. The organic phase was then separated and the aqueous phase extracted with DCM (2 × 30 ml). The combined extracts were dried and evaporated in vacuo to give the crude dibromide (16), which was used without further purification.

2.5. 6,7-Dihydro-1,2,3,9,10,11-hexamethoxy-6-methyl-5H-dibenzo[c,e]azepine (±)-(9)

Methylamine hydrochloride (0.181 g, 2.68 mmol) and tri­ethylamine (0.475 g, 4.7 mmol) were added to a solution of the dibromide (16), prepared as described above from the diol (15) (0.67 mmol), in dry DMF (2 ml) at 273 K under argon, and the mixture was stirred overnight at room temperature. Water (20 ml) was added and the mixture was extracted with ethyl acetate (3 × 20 ml). The combined organic extract was washed with brine (20 ml), dried and evaporated in vacuo. Flash chromatography of the residue over silica gel (50 g), eluting with ethyl acetate, followed by crystallization from ethyl acetate yielded the title compound (9) (166 mg, 64%) as a colourless solid, m.p. 401–402 K. Found: C 64.7, H 6.6, N 4.0; C₂₁H₂₇NO₆ requires C 64.77, H, 6.99, N 3.60%; δ_H (400 MHz, CDCl₃) 6.64 (2H, s, 4-H, 8-H), 3.90 (6H, s, 2 × OMe), 3.89 (6H, s, 2 × OMe), 3.69 (6H, s, 2 × OMe), 3.34 (2H, d, J = 12.5 Hz, 5-H_A, 7-H_A), 3.09 (2H, d, J = 12.5 Hz, 5-H_B, 7-H_B), 2.36 (3H, s, NMe); δ_C (100 MHz, CDCl₃) 43.00, 56.15, 57.19 (5-C, 7-C), 60.82, 61.12, 108.21 (4-C, 8-C), 122.73, 130.03, 141.76, 151.48, 152.88; ν_max (cm⁻¹) 2940, 2835, 2788, 1596, 1487, 1464, 1410, 1363, 1320, 1243, 1130, 1107; m/z (ES) 390 (100%, MH⁺).

2.6. 5,7-Dihydro-1,2,3,9,10,11-hexamethoxydibenzo[c,e]thiepine (±)-(10)

Sodium sulfide nonahydrate (0.483 g, 2.0 mmol) and tri­ethylamine (0.204 g, 2.0 mmol) was added to a solution of the dibromide (16), prepared as described above from the diol (15) (0.67 mmol), in dry DMF (2 ml) at 273 K under argon, and the mixture stirred overnight at room temperature. Water (20 ml) was added and the mixture extracted with ethyl acetate (3 × 20 ml). The combined organic extract was washed with brine (20 ml), dried and evaporated in vacuo. Flash chromatography of the residue over silica gel (50 g), eluting with ethyl acetate, followed by crystallization from ethyl acetate yielded the title compound (10) (230 mg, 87%) as a colourless solid, m.p. 482–484 K. Found: C 61.2, H 6.1, S 8.1; C₂₀H₂₄O₆S requires C 61.21, H 6.16, S 8.17%; δ_H (400 MHz, CDCl₃) 6.63 (2H, s, 4-H, 8-H), 3.90 (6H, s, 2 × OMe), 3.88 (6H, s, 2 × OMe), 3.67 (6H, s, 2 × OMe), 3.40 (2H, d, J = 12.5 Hz, 5-H_A, 7-H_A), 3.23 (2H, d, J = 12.5 Hz, 5-H_B, 7-H_B); δ_C (100 MHz, CDCl₃) 32.21 (5-C, 7-C), 56.09, 60.67, 61.10, 106.68 (4-C, 8-C), 122.01, 131.45, 141.45, 151.39, 153.62; ν_max (cm⁻¹) 2928, 1594, 1488, 1458, 1399, 1318, 1242, 1199, 1093, 1008; m/z (ES) 393 (8%, MH⁺), 415 (4%, MNa⁺), 456 (100%, MNa₂H₂O⁺).

2.7. 5,7-Dihydro-1,2,3,9,10,11-hexamethoxydibenzo[c,e]thiepine 6-oxide (±)-(11) and 5,7-dihydro-1,2,3,9,10,11-hexamethoxydibenzo[c,e]thiepine 6,6-dioxide (±)-(12)

m-Chloroperbenzoic acid (41 mg, purity ca 70%, 0.17 mmol) was added to a solution of (±)-(10) (66 mg, 0.17 mmol) in acetone (1 ml). The mixture was stirred at 273 K for 5 h, then cooled to room temperature, diluted with water (10 ml) and extracted with ether (3 × 10 ml). The combined extracts were dried and evaporated to give a crude solid (62 mg) which was purified by flash chromatography over silica gel (10 g), eluting initially with ethyl acetate and later with ethyl acetate–methanol (10:1). The first fractions gave the title sulfone (12) (18 mg, 25%) as colourless crystals, m.p. 497 K (EtOAc). Found: C 56.7, H 5.8, S 7.5; C₂₀H₂₄O₈S requires C 56.59, H 5.70, S 7.55%; δ_H (400 MHz, CDCl₃) 6.75 (2H, s, 4-H, 8-H), 3.98 (2H, d, J = 13.5 Hz, 5-H_A, 7-H_A), 3.92 (6H, s, 2 × OMe), 3.90 (6H, s, 2 × OMe), 3.86 (2H, d, J = 13.5 Hz, 5-H_B, 7-H_B), 3.71 (6H, s, 2 × OMe); δ_C (100 MHz, CDCl₃) 56.27, 57.77 (5-C, 7-C), 61.12, 61.17, 109.08 (4-C, 8-C), 122.51, 124.12, 142.78, 152.19, 154.15; m/z (ES) 425 (31%, MH⁺), 447 (4%, MNa⁺), 488 (100%, MNa₂H₂O⁺); R_f = 0.60 (EtOAc). Later fractions afforded the title sulfoxide (11) (43 mg, 63%) as colourless crystals, m.p. 435 K (EtOAc). Found: C 58.8, H 6.0, S 7.8; C₂₀H₂₄O₇S requires C 58.81, H 5.92, S 7.85%; δ_H (400 MHz, CDCl₃) 6.72 (1H, s, 4-H or 8-H), 6.66 (1H, s, 8-H or 4-H), 4.13 (1H, d, J = 12.0 Hz, 5-H or 7-H), 3.93 (3H, s, OMe), 3.91 (3H, s, OMe), 3.905 (3H, s, OMe), 3.90 (3H, s, OMe), 3.74 (3H, s, OMe), 3.71 (3H, s, OMe), 3.68 (1H, d, J = 14.0 Hz, 5-H or 7-H), 3.40 (1H, d, J = 14.0 Hz, 5-H or 7-H), 3.17 (1H, d, J = 12.0 Hz, 5-H or 7-H); δ_C (75 MHz, CDCl₃) 53.88, 55.97 (5-C, 7-C), 56.20, 56.28, 61.00, 61.03, 61.05, 61.12 (6 × OCH₃), 108.45, 110.12 (4-C, 8-C), 122.28, 122.38, 123.90, 125.43 (4a-C, 7a-C, 11a-C and 11b-C), 142.52, 142.98, 151.82, 152.39, 153.23, 153.41 (6 × OC_Ar); ν_max (cm⁻¹) 2944, 2839, 1596, 1577, 1487, 1464, 1406, 1328, 1243, 1200, 1130, 1099, 1041; m/z (ES) 409 (34%, MH⁺), 431 (4%, MNa⁺), 472 (100%, MNa₂H₂O⁺); R_f = 0.20 (EtOAc).

2.8. X-ray crystallography

All measurements were carried out using a Nonius KappaCCD diffractometer with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å). Details of cell parameters, data collection and refinement are summarized in Table 1, together with a list of software employed. The structures were solved by direct methods and refined with all data on F². A weighting scheme based on P = [F²_o + 2F²_c]/3 was employed in order to reduce statistical bias (Wilson, 1976). The H atoms were isotropically refined.¹

Table 1
Crystallographic data for (8)–(12)

	(8)	(9)·HCl	(10)	(11)	(12)
Crystal data
Chemical formula	C20H24O7	C21H29ClNO6.5	C20H24O6S	C20H24O7S	C20H24O8S
Mr	376.39	434.9	392.45	408.45	424.45
Cell setting, space group	Monoclinic, C2/c	Monoclinic, C2/c	Monoclinic, C2/c	Monoclinic, C2/c	Monoclinic, P21/n
a, b, c (Å)	15.3519 (4), 10.4044 (3), 11.8506 (4)	36.0403 (12), 7.8165 (2), 17.0066 (5)	8.6029 (2), 12.2965 (3), 17.6032 (4)	8.8113 (3), 12.2699 (3), 17.5640 (6)	8.7886 (2), 15.3454 (3), 15.4972 (4)
β (°)	109.607 (2)	111.7920	104.0380	103.988 (2)	106.2770
V (Å^3)	1783.11 (9)	4448.5 (2)	1806.55 (7)	1842.60 (10)	2006.25 (8)
Z	4	8	4	4	4
Dx (Mg m^−3)	1.402	1.299	1.443	1.472	1.405
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα	Mo Kα
No. of reflections for cell parameters	5472	52 930	10 338	14 600	21 800
θ range (°)	2.8–27.5	3.2–27.3	3.0–29.1	3.3–27.5	3.1–27.5
μ (mm^−1)	0.11	0.21	0.22	0.22	0.21
Temperature (K)	150 (2)	150 (2)	150 (2)	150 (2)	150 (2)
Crystal form, colour	Plate, colourless	Needle, colourless	Needle, colourless	Prism, colourless	Prism, colourless
Crystal size (mm)	0.2 × 0.2 × 0.1	0.25 × 0.15 × 0.1	0.2 × 0.1 × 0.1	0.2 × 0.2 × 0.2	0.25 × 0.2 × 0.15
Data collection
Diffractometer	KappaCCD	KappaCCD	KappaCCD	KappaCCD	KappaCCD
Data collection method	CCD rotation images, thick slices	CCD rotation images, thick slices	CCD rotation images, thick slices	CCD rotation images, thick slices	CCD rotation images, thick slices
Absorption correction	Multi-scan (based on symmetry-related measurements)	Multi-scan (based on symmetry-related measurements)	Multi-scan (based on symmetry-related measurements)	Multi-scan (based on symmetry-related measurements)	Multi-scan (based on symmetry-related measurements)
Tmin	0.99	0.97	0.98	0.96	0.98
Tmax	1.0	1.0	1.0	1.0	1.0
No. of measured, independent and observed reflections	9423, 2043, 1501	36 698, 4945, 3299	15 259, 2388, 2003	14 844, 2111, 1775	30 410, 4583, 3388
Criterion for observed reflections	I > 2σ(I)	I > 2σ(I)	I > 2σ(I)	I > 2σ(I)	I > 2σ(I)
Rint	0.063	0.082	0.054	0.110	0.057
θmax (°)	27.5	27.3	29.1	27.5	27.5
Range of h, k, l	−16 → h → 19	−45 → h → 46	−11 → h → 11	−11 → h → 11	−11 → h → 11
	−13 → k → 13	−10 → k → 10	−16 → k → 16	−15 → k → 15	−19 → k → 19
	−15 → l → 15	−21 → l → 21	−23 → l → 24	−22 → l → 22	−18 → l → 20
Refinement
Refinement on	F^2	F^2	F^2	F^2	F^2
R[F^2 > 2σ(F^2)], wR(F^2), S	0.044, 0.125, 1.08	0.047, 0.112, 1.03	0.037, 0.099, 1.04	0.048, 0.135, 1.12	0.041, 0.104, 1.02
No. of reflections	2043	4945	2388	2111	4583
No. of parameters	172	392	172	180	359
H-atom treatment	Mixture of independent and constrained refinement	Mixture of independent and constrained refinement	Mixture of independent and constrained refinement	Mixture of independent and constrained refinement	Mixture of independent and constrained refinement
Weighting scheme	w = 1/[σ^2(Fo^2) + (0.0729P)^2 + 0.0661P], where P = (Fo^2 + 2Fc^2)/3	w = 1/[σ^2(Fo^2) + (0.0477P)^2 + 2.813P], where P = (Fo^2 + 2Fc^2)/3	w = 1/[σ^2(Fo^2) + (0.0508P)^2 + 1.3323P], where P = (Fo^2 + 2Fc^2)/3	w = 1/[σ^2(Fo^2) + (0.0619P)^2 + 1.7711P], where P = (Fo^2 + 2Fc^2)/3	w = 1/[σ^2(Fo^2) + (0.0451P)^2 + 0.9601P], where P = (Fo^2 + 2Fc^2)/3
(Δ/σ)max	0.012	0.019	0.003	0.006	0.005
Δρmax, Δρmin (e Å^−3)	0.29, −0.23	0.28, −0.29	0.32, −0.30	0.30, −0.39	0.26, −0.39
Extinction method	SHELXL	SHELXL	SHELXL	None	SHELXL
Extinction coefficient	0.013 (3)	0.0017 (3)	0.0074 (13)		0.0072 (11)
Computer programs used: COLLECT (Nonius BV, 1998), HKL DENZO (Otwinowski & Minor, 1997), HKL SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP3 for Windows (Farrugia, 1997), WinGX publication routines (Farrugia, 1999).

3. Results and discussion

3.1. Synthesis

A convenient starting point for the preparation of the bridged systems (8)–(12) is the commercially available tannin ellagic acid (13), which can be polymethylated to obtain the hexamethoxydiphenate (14) (Itoh et al., 1996). The reduction of (14) to the diol (15) and subsequent acid-induced cyclization to (8) were achieved using the published methods (Insole, 1990a,b). The preparation of (9) and (10) also followed conventional routes, the diol (15) being converted into the corresponding bis(bromomethyl)biaryl (16) which was then treated with methylamine to obtain (9) or sodium sulfide to obtain (10). Oxidation of (10) with m-chloroperbenzoic acid gave a mixture from which the sulfoxide (11) and sulfone (12) were isolated by chromatography (see Fig. 2).

Figure 2 Synthesis of compounds (8)–(12). Reagents and conditions: (a) Me2SO4, Bu4NI, KOH, then NaH, DMF, MeI (38% over two steps). (b) LiAlH4, THF (91%). (c) PBr3, ether. (d), 2 M aq. HCl–THF (1:1), heat [93% (8) from (15)]. (e) MeNH2 [64% (9) over two steps via (16)]. (f) Na2S [87% (10) over two steps via (16)]. (g) mCPBA [60% (11), 26% (12)].

3.2. X -ray crystal structures

The synthesized biaryls all formed crystals which were suitable for analysis by X-ray diffraction. A numbering guide and the derived structures are shown in Figures 3–8, with selected molecular parameters provided in Tables 2 and 3. Each system crystallized in a monoclinic space group with both enantiomeric forms in the unit cell. The azepine (9) (as the hydrochloride) crystallized with one molecule of water associated with each molecular pair. The oxepine (8), thiepine (10) and sulfoxide (11) exhibit C₂ molecular symmetry, with the C1 and C2 methoxyl groups in a mutually eclipsed arrangement which is replicated at C11 and C10. In the sulfone (12) the corresponding methoxyl groups are splayed apart in arrangements which differ with respect to the aromatic rings, although the seven-membered ring effectively retains local C₂ symmetry. The azepinium salt (9)·HCl differs significantly from the other structures in that not only are the methoxyl groups arranged differently in each aromatic ring, but the seven-membered ring no longer possesses local C₂ symmetry and the C1–C11B aromatic ring is displaced from the expected plane. These features are discussed in detail below.

Table 2
Selected interatomic distances (Å) for (8)–(12)

Here and in other tables, standard uncertainties are given in parentheses for individual results obtained in this work; values in italics are those derived using symmetry transformations to generate equivalent atoms.

		(8) X = O	(9) X = NHMe	(10) X = S	(11) X = SO	(12) X = SO2
(1)	C4A—C5	1.510 (2)	1.503 (3)	1.505 (2)	1.500 (2)	1.507 (2)
(2)	C5—X6	1.440 (2)	1.512 (2)	1.827 (2)	1.829 (2)	1.789 (2)
(3)	C7—X6	1.440 (2)	1.514 (3)	1.827 (2)	1.829 (2)	1.783 (2)
(4)	C7—C7A	1.510 (2)	1.500 (3)	1.505 (2)	1.500 (2)	1.497 (2)
(5)	C11A—C11B	1.479 (3)	1.485 (3)	1.489 (2)	1.489 (3)	1.490 (2)
(6)	O6—S6				1.378 (3)
(7)	O6A—S6					1.443 (2)
(8)	O6B—S6					1.447 (2)
(9)	O1—O11 non-bonded	2.786	2.878	3.052	3.034	2.928
(10)	C5—C7 non-bonded	2.418	2.535	2.804	2.780	2.790

Table 3
Selected bond and dihedral angles (°) for (8)–(12)

		(8) X = O	(9) X = NHMe	(10) X = S	(11) X = SO	(12) X = SO2
(1)	C5—X6—C7	114.2 (2)	113.9 (2)	100.3 (1)	98.9 (2)	102.7 (1)
(2)	C5—C4A—C11B—C11A	0.8 (2)	7.7 (3)	1.4 (2)	0.9 (3)	0.8 (3)
(3)	C4A—C5—X6—C7	−43.6 (1)	–50.4 (2)	−44.5 (1)	−45.0 (1)	−44.6 (2)
(4)	C7A—C7—X6—C5	−43.6 (1)	−35.2 (2)	−44.5 (1)	−45.0 (1)	−44.4 (2)
(5)	C7—C7A—C11A—C11B	0.8 (2)	−6.7 (3)	1.4 (2)	0.9 (3)	−6.0 (2)
(6)	C7A—C11A—C11B—C4A	−49.8 (3)	−51.1 (3)	−59.9 (3)	−58.8 (3)	−54.9 (2)
(7)	C11—C11A—C11B—C1	−57.0 (3)	−53.6 (3)	−61.9 (3)	−63.6 (3)	−61.4 (2)
(8)	C11—C11A—C11B—C4A	126.6 (3)	121.7 (2)	119.0 (3)	118.8 (3)	122.1 (2)
(9)	C7A—C11A—C11B—C1	126.6 (3)	133.6 (2)	119.0 (3)	118.8 (3)	121.5 (2)
(10)	O1—C1—C2—O2	4.2 (2)	6.5 (3)	4.5 (2)	4.9 (2)	3.4 (2)
(11)	O1—C1—C2—C3	179.3 (2)	−175.1 (2)	−178.7 (2)	−179.2 (2)	−177.1 (2)
(12)	O1—C1—C11B—C4A	176.3 (2)	170.0 (2)	177.2 (2)	176.9 (2)	173.7 (2)
(13)	O1—C1—C11B—C11A	−0.1 (2)	−14.8 (3)	−1.9 (2)	−0.7 (3)	−2.8 (2)
(14)	O2—C2—C3—O3	0.4 (2)	1.0 (2)	−3.9 (2)	−4.1 (3)	1.3 (2)
(15)	O3—C3—C4—C4A	174.1 (2)	178.1 (2)	−179.5 (2)	−179.5 (2)	–179.5 (2)
(16)	O3—C3—C2—C1	−174.7 (2)	−177.4 (2)	179.3 (2)	−179.8 (2)	−178.3 (2)
(17)	O11—C11—C10—O10	4.2 (2)	−1.1 (3)	4.5 (2)	4.9 (2)	0.3 (3)
(18)	O10—C10—C9—O9	0.4 (2)	3.1 (3)	−3.9 (2)	−4.1 (3)	1.4 (3)
(19)	C1—C2—C3—C4	3.6 (2)	5.2 (3)	0.4 (2)	1.6 (3)	3.6 (3)
(20)	C2—C3—C4—C4A	−4.0 (2)	−4.7 (3)	−0.7 (2)	−1.1 (3)	−1.6 (3)
(21)	C3—C4—C4A—C11B	−0.4 (2)	−0.8 (3)	−0.9 (2)	−1.2 (3)	−2.0 (3)
(22)	C4—C4A—C11B—C1	5.1 (2)	5.8 (3)	2.7 (2)	2.9 (3)	3.5 (3)
(23)	C4A—C11B—C1—C2	−5.5 (2)	−5.3 (3)	−3.1 (2)	−2.4 (3)	−1.5 (3)
(24)	C11B—C1—C2—C3	1.2 (2)	−0.1 (3)	1.5 (2)	0.1 (3)	−2.1 (3)
(25)	C11—C10—C9—C8	3.6 (2)	1.1 (3)	0.4 (2)	1.6 (3)	–2.7 (3)
(26)	C10—C9—C8—C7A	−4.0 (2)	−1.9 (3)	−0.7 (2)	−1.1 (3)	0.3 (3)
(27)	C9—C8—C7A—C11A	−0.4 (2)	0.1 (3)	−0.9 (2)	−1.2 (3)	2.5 (3)
(28)	C8—C7A—C11A—C11	5.1 (2)	2.4 (3)	2.7 (2)	2.9 (3)	−2.8 (3)
(29)	C7A—C11A—C11—C10	−5.5 (2)	−3.2 (3)	−3.1 (2)	−2.4 (3)	0.3 (3)
(30)	C11A—C11—C10—C9	1.2 (2)	1.5 (3)	1.5 (2)	0.1 (3)	2.4 (3)
(31)	C8—C7A—C11A—C11B	−178.4 (2)	175.4 (2)	−178.2 (1)	−179.4 (2)	174.4 (2)
(32)	C10—C11—C11A—C11B	178.1 (1)	−176.3 (2)	177.9 (1)	180.0 (2)	−176.8 (2)
(33)	C4—C4A—C11B—C11A	−178.4 (2)	−169.6 (2)	−178.2 (1)	−179.4 (2)	179.9 (2)
(34)	C2—C1—C11B—C11A	178.1 (1)	170.0 (2)	177.9 (1)	180.0 (2)	−178.0 (2)

Figure 3 The numbering system for the structures in Figs. 4–8, which were all generated with C7A, C11A and C11B in the viewed plane and the C11A—C11B bond aligned horizontally.

Figure 4 5,7-Dihydro-1,2,3,9,10,11-hexamethoxydibenzo[c,e]oxepine (8). Displacement ellipsoids in Figs. 4–8 are drawn at the 50% probability level.

Figure 5 6,7-Dihydro-1,2,3,9,10,11-hexamethoxy-6-methyl-5H-dibenzo[c,e]azepinium chloride (9)·HCl hemihydrate.

Figure 6 5,7-Dihydro-1,2,3,9,10,11-hexamethoxydibenzo[c,e]thiepine (10).

Figure 7 5,7-Dihydro-1,2,3,9,10,11-hexamethoxydibenzo[c,e]thiepine 6-oxide (11).

Figure 8 5,7-Dihydro-1,2,3,9,10,11-hexamethoxydibenzo[c,e]thiepine 6,6-dioxide (12).

The structure of the sulfoxide (11) is disordered in that, while the position of the S atom is fixed, the attached O6 atom is distributed equally between the two possible locations. The ¹H NMR spectrum of (11) also reflects its distinctive symmetry properties. Although the S atom is not a stereogenic centre, the combined presence of the stereogenic axis and the single O6 atom renders the C5 and C7 methylene groups non-equivalent and diastereotopic. Each of these four H atoms thus appears as an individual doublet in the ¹H NMR spectrum of (11), as has been described for a related system (Fraser & Schuber, 1970).

For the reasons outlined above, our interest in structures (8)–(12) is centred on the helicity of the respective biaryl moieties, which is viewed in Fig. 9. In each case the seven-membered ring has taken up a helical conformation in which the flexibility of the biaryl axis must be subject to upper and lower limits dictated by the geometric constraints of the three-atom bridge and the interaction of the 1- and 11-substituents, which are obliged to move towards each other if the system moves towards planarity. It is therefore pertinent to examine four sets of parameters, viz. the C—X bond lengths (Table 2, rows 2, 3), the O1—O11 distances (Table 2, row 9), the endocyclic biaryl dihedral angles (Table 3, row 6) and the exocyclic biaryl dihedral angles (Table 3, row 7). From a comparison of the C—X bond lengths with the biaryl dihedral angles through the series it is evident that the more pronounced helicity of the thiepines (10)–(12) is primarily a consequence of the seven-membered ring twisting more in order to accommodate the longer C—S bonds; the smaller C—S—C bond angles (Table 3, row 1) will counteract this effect slightly. The oxepine (8) and azepinium chloride (9)·HCl, with their shorter C—X bonds, exhibit degrees of twist some 10° lower than observed in the sulfur series.

Figure 9 Views of (8)–(12) along the C11A—C11B bond. The plane defined by C7A, C11A and C11B is perpendicular to the viewed plane. H atoms are omitted.

It is notable that in each of the structures (8)–(12) the endocyclic and exocyclic dihedral angles are unequal, the latter invariably exceeding the former, and that neither series runs entirely in parallel with the C—X bond length. In a non-bridged biphenyl with perfectly planar trigonal C atoms the two biaryl dihedral angles should be equal, so the difference between them in a bridged structure might be viewed as an indicator of the distortion around the biaryl axis. In the systems (8)–(12) this difference would be expected to arise from steric repulsion between the 1- and 11-methoxyl groups, which operates on the exocyclic quadrants of the biaryl axis and opposes the constraining effect of the three-atom bridge. The close proximity of these methoxyl groups is evident in the O1—O11 distance (Table 2, row 9), which reaches twice the van der Waals radius for oxygen, 1.52 Å (Bondi, 1964; Bott et al., 1980), only in the cases of (10) and (11). This steric compression, reinforced by the buttressing effect of the adjacent methoxyl groups (Insole, 1990a,b; Charton, 1977), is maximal in the oxepine (8) and would account, at least in part, for the relatively large (7.2°) difference between the endocyclic and exocyclic dihedral angles in this structure and for the dihedral angles of more than 5° associated with C1, C11B and C4A (Table 3, rows 22, 23), through which its levering effects are dissipated. By the dihedral angle criterion the thiepine (10) incorporates a much less distorted biaryl axis, consistent with the longer C—S bonds inducing a more pronounced twist in the seven-membered ring and, as a consequence, alleviating the steric interaction between O1 and O11. The structural parameters for the sulfoxide (11) are very similar to those of the thiepine (10), but the difference between the endocyclic and exocyclic dihedral angles rises from 2.0 to 4.8°. The sulfone (12) manifests rather more distortion at the biaryl axis than the other thiepine derivatives, the dihedral angle difference now being 6.5°. The reduced endocyclic dihedral angle in (12) [by 5° compared with the thiepine (10)] is consistent with its shorter C—S bonds (Table 2, rows 2, 3), but the flattening in the seven-membered ring is not reciprocated in the exocyclic region, where the dihedral angle remains above 61° even though the O1—O11 distance (Table 2, row 9) shortens significantly. The extent to which intermolecular (crystal packing) effects might contribute to these structural features of (12) is discussed later.

In the case of the azepinium salt (9)·HCl the relatively small difference between the biaryl endocyclic and exocyclic dihedral angles (2.5°) is not a useful guide to the forces operating in this region of the molecule. The C1—C2 and C4A—C4 bonds are both 10° out of alignment with the inter-aryl bond (Table 3, rows 33, 34), as is perceptible in Fig. 9. The dihedral angles of more than 5° around C1, C11B and C4A (Table 3, rows 22, 23) are consistent with the effects of 1,11-methoxyl repulsion, as observed in the oxepine (8), but there is also a twisting of the seven-membered ring, unique in the series and manifested by a difference of 15° in the dihedral angles spanning the endocyclic C—N bonds (Table 3, rows 3, 4) and 12° in those spanning the two aryl rings (Table 3, rows 8, 9). The ultimate origins of the distortion in the crystal structure of (9)·HCl are obscure, although the association of the chloride ion with one face of the seven-membered ring is a potentially significant desymmetrizing factor.

To broaden this analysis, the ConQuest software (Allen, 2002; Bruno et al., 2002) was used to search the Cambridge Structural Database for substructures containing a 1,1′-biaryl with a 2,2′-bridge of the form CH₂XCH₂, where X = O, N or S, and most of the structures recovered are listed in Fig. 10 in order of increasing endocyclic dihedral angle for each heteroatom series. In the oxygen series the endocyclic biaryl dihedral angles vary over more than 18° in going from the parent system present in (17) to the bis(phosphine) (20). Throughout this series the exocyclic dihedral angle remains responsive to the steric size of the 6- and 6′-substituents, increases in the exocyclic dihedral angle being possible through bending processes, whereas the endocyclic dihedral angle is constrained by bond-length requirements.

Figure 10 Dihedral angles (°) around the aryl–aryl bond in biaryl-fused oxepines, azepines and thiepines (taken from published X-ray data). The numerical values of the exocyclic and endocyclic biaryl dihedral angles are indicated. Symbols: (*) highest of four per unit cell; (†) lowest of four per unit cell; (‡) highest of three per unit cell; (§) lowest of three per unit cell; (¶) highest of two per unit cell; (¥) lowest of two per unit cell. CSD six-letter codes: (17), DIFTAN (Engelhardt et al., 1985); (18), JAFLAE (Bringmann et al., 2003); (19), TICTOO (Roszak et al., 1996); (20), GEDYOD (Schmid et al., 1988); (21), GAVKET (Nyburg et al., 1988); (22), GAVKAP (Nyburg et al., 1988); (23), NUBGOG (Mrvoš-Sermek et al., 1998); (24), XEBNOH (Arroyo et al., 2000); (25), WOBMIJ (Schneider et al., 2000); (26), WOBMEF (Schneider et al., 2000); (27), HOVGEE (Widhalm et al., 1999); (28), XEBNIB (Arroyo et al., 2000); (29), HOVGOO (Widhalm et al., 1999); (30), SIZQOH (Kiupel et al., 1998); (31), YIPREU01 (Miyake et al., 2002); (32), YIPREU (Bandarage et al., 1995); (33), KIRPOQ (Loncar-Tomascovic et al., 2000); (34), KIRKOL (Loncar-Tomascovic et al., 2000).

A similar trend is seen in the nitrogen series, where the endocyclic dihedral angle does not exceed 55.0°, while the exocyclic dihedral angle is forced up by bulky ortho groups and reaches 67.8° in the binaphthyl (29). The underlying flexibility of the biaryl system can be seen in the variation, by 5° or more, of the respective dihedral angles in analogous molecules, e.g. (21) and (22) or (24) and (29). In the sulfur series the longer (C—S) bonds in the seven-membered ring permit larger endocyclic dihedral angles and a framework capable of accommodating larger ortho-substituents (Me, naphthyl) with minimal distortion at the axis. Axial flexibility is illustrated in the thiepine series by (30) and (31), whose respective unit cells contain three or more equivalent biaryl axes with varying dihedral angles.

The distinction between the geometry of a molecule in the crystalline state, where it is subject to intermolecular (crystal packing) forces, and its conformation in solution is of fundamental importance in the context of biological effects. The crystal structure dihedral angles for the tubulin binding agents colchicine (1) (Lessinger & Margulis, 1978) and N-acetyl­colchinol (3) (Margulis & Lessinger, 1978) are shown in Fig. 11. Although the multiple dihedral angles for (3) reveal some flexibility in its biaryl axis, each of these structures crystallizes as a hydrated system with a packing arrangement involving complex hydrogen bonding. The situation is simpler in the cases of the oxepine (8) and sulfone (12), and it was considered that computational modelling of these molecules might provide a means of estimating the contribution made by crystal packing effects to their solid-state structures. Accordingly, the structures (8) and (12) were allowed to `relax' by using semi-empirical (force field) methods to minimize their steric energies, starting from the atomic coordinates provided by X-ray crystallography. The minimized structures (8′) and (12′) indicate less distortion in the region of the biaryl axis, primarily through a reduced exocyclic biaryl dihedral angle in (8′) and an increased endocyclic dihedral angle in (12′) (Fig. 11), the inference being that these parameters are particularly affected by crystal packing forces within the respective solid-state structures. However, while the geometries of the energy-minimized structures may be more representative of the dominant solution conformations of such molecules, it can be speculated that the conformational flexibility of the bridged biaryl unit, implicit in the results reported here and in the X-ray diffraction data cited, is a more significant factor in the large number of colchicine analogues that retain the tubulin-binding capability of the natural product.

Figure 11 Dihedral angles (°) around the aryl–aryl bond in (1), (3) (from published X-ray data), (8′) and (12′). To generate (8′) and (12′), models of (8) and (12) were assembled from their crystal structure atom coordinates using Quantum CAChe4.5 (Fujitsu) and their geometries optimized with the Mechanics application using an augmented MM3 force field. The structures (8′) and (12′) are assumed to be nearby (but not necessarily global) steric energy minima. The number inside the seven-membered ring is the C7A—C11A—C11B—C4A dihedral angle; the other number is the C11—C11A—C11B—C1 dihedral angle. Symbols: (¶) highest of the two per unit cell; (¥) lowest of the two per unit cell.

4. Conclusions

The biaryls (8), (9)·HCl, (10), (11) and (12), each incorporating a three-atom bridge of the form CH₂—X—CH₂ (X = O, N or S), have been characterized by X-ray crystal structure analysis. Within this series the endocyclic and exocyclic biaryl dihedral angles vary over slightly offset but roughly parallel 10° ranges in a manner which is consistent with each structure being subject to a variable blend of intramolecular (steric, geometric) and intermolecular (crystal packing) forces of comparable strength. The results are consistent with the expectation that the major determinant of the degree of helicity in the seven-membered ring, and hence in the biaryl chromophore, is the C—X bond length. The results also suggest that there is a significant degree of conformational flexibility within the biaryl unit, despite the presence of the three-atom bridge.

Supporting information

Computing details

For all compounds, data collection: Collect (Nonius BV, 1997-2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).

Figures

(oxepine) 5,7-dihydro-1,2,3,9,10,11-hexamethoxydibenzo[c,e]oxepine

Crystal data

C20H24O7	F(000) = 800
Mr = 376.39	Dx = 1.402 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5472 reflections
a = 15.3519 (4) Å	θ = 1.0–27.5°
b = 10.4044 (3) Å	µ = 0.11 mm^−1
c = 11.8506 (4) Å	T = 150 K
β = 109.607 (2)°	Plate, colourless
V = 1783.11 (9) Å^3	0.2 × 0.2 × 0.1 mm
Z = 4

Data collection

KappaCCD diffractometer	2043 independent reflections
Radiation source: Enraf Nonius FR590	1501 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.063
CCD rotation images, thick slices scans	θmax = 27.5°, θmin = 2.8°
Absorption correction: multi-scan R.H. Blessing, Acta Cryst. (1995), A51, 33-38	h = −16→19
Tmin = 0.992, Tmax = 1.014	k = −13→13
9423 measured reflections	l = −15→15

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)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.125	w = 1/[σ^2(Fo^2) + (0.0729P)^2 + 0.0661P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.012
2043 reflections	Δρmax = 0.29 e Å^−3
172 parameters	Δρmin = −0.23 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.013 (3)

Special details

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

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

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

	x	y	z	Uiso*/Ueq
C1	0.60555 (10)	0.54245 (12)	0.33594 (11)	0.0206 (3)
C2	0.70119 (10)	0.54458 (12)	0.36558 (11)	0.0218 (4)
C3	0.74416 (10)	0.64879 (13)	0.32986 (12)	0.0231 (3)
C4	0.69164 (10)	0.75234 (13)	0.27117 (12)	0.0238 (4)
C4A	0.59581 (10)	0.74971 (13)	0.24088 (12)	0.0223 (4)
C5	0.53841 (11)	0.86214 (14)	0.17609 (13)	0.0251 (4)
C11B	0.55105 (10)	0.64278 (13)	0.26840 (11)	0.0209 (3)
C12	0.59447 (13)	0.40214 (17)	0.49088 (13)	0.0299 (4)
C13	0.82017 (13)	0.46454 (18)	0.53795 (14)	0.0349 (4)
C14	0.88365 (12)	0.73873 (17)	0.31678 (18)	0.0355 (4)
O1	0.56046 (7)	0.44207 (9)	0.36779 (8)	0.0244 (3)
O2	0.75238 (7)	0.43965 (8)	0.42204 (9)	0.0255 (3)
O3	0.83726 (7)	0.63638 (9)	0.35454 (9)	0.0298 (3)
O6	0.5	0.93726 (12)	0.25	0.0262 (4)
H4	0.7190 (11)	0.8232 (16)	0.2455 (14)	0.026 (4)*
H5A	0.5747 (11)	0.9227 (16)	0.1488 (14)	0.027 (4)*
H5B	0.4883 (11)	0.8307 (14)	0.1045 (13)	0.018 (3)*
H12A	0.6399 (14)	0.3340 (18)	0.5043 (15)	0.041 (5)*
H12B	0.6205 (13)	0.4753 (18)	0.5448 (17)	0.045 (5)*
H12C	0.5432 (13)	0.3687 (16)	0.5087 (15)	0.036 (5)*
H13A	0.8330 (17)	0.558 (3)	0.554 (2)	0.084 (8)*
H13B	0.869 (2)	0.416 (3)	0.548 (3)	0.113 (11)*
H13C	0.7937 (16)	0.451 (2)	0.604 (2)	0.069 (7)*
H14A	0.8520 (12)	0.7605 (16)	0.2259 (16)	0.035 (5)*
H14B	0.8857 (13)	0.815 (2)	0.3615 (17)	0.044 (5)*
H14C	0.9483 (13)	0.7045 (18)	0.3358 (14)	0.039 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0243 (8)	0.0194 (7)	0.0180 (6)	−0.0022 (5)	0.0070 (6)	−0.0018 (5)
C2	0.0252 (8)	0.0199 (7)	0.0194 (7)	0.0024 (6)	0.0063 (6)	−0.0020 (5)
C3	0.0199 (8)	0.0258 (7)	0.0242 (7)	−0.0004 (6)	0.0083 (6)	−0.0036 (6)
C4	0.0270 (8)	0.0219 (7)	0.0233 (7)	−0.0024 (6)	0.0095 (6)	0.0000 (6)
C4A	0.0248 (8)	0.0225 (7)	0.0193 (7)	−0.0003 (6)	0.0072 (6)	−0.0009 (5)
C5	0.0256 (9)	0.0240 (7)	0.0256 (7)	−0.0001 (6)	0.0085 (6)	0.0016 (6)
C11B	0.0234 (8)	0.0215 (7)	0.0176 (6)	−0.0007 (6)	0.0068 (6)	−0.0025 (5)
C12	0.0349 (10)	0.0312 (8)	0.0231 (8)	−0.0028 (8)	0.0093 (7)	0.0050 (7)
C13	0.0326 (10)	0.0367 (9)	0.0275 (8)	0.0048 (8)	−0.0004 (7)	0.0010 (7)
C14	0.0252 (9)	0.0301 (9)	0.0524 (11)	−0.0046 (7)	0.0147 (8)	−0.0015 (8)
O1	0.0263 (6)	0.0236 (5)	0.0216 (5)	−0.0039 (4)	0.0059 (4)	0.0033 (4)
O2	0.0248 (6)	0.0229 (5)	0.0256 (5)	0.0043 (4)	0.0042 (4)	0.0003 (4)
O3	0.0206 (6)	0.0301 (6)	0.0393 (6)	0.0002 (4)	0.0108 (5)	0.0038 (5)
O6	0.0284 (8)	0.0189 (7)	0.0321 (8)	0	0.0115 (6)	0

Geometric parameters (Å, º)

C1—O1	1.3740 (16)	C11B—C11B^i	1.479 (3)
C1—C2	1.391 (2)	C12—O1	1.4359 (17)
C1—C11B	1.4074 (19)	C12—H12A	0.97 (2)
C2—O2	1.3799 (16)	C12—H12B	0.99 (2)
C2—C3	1.406 (2)	C12—H12C	0.947 (19)
C3—O3	1.3654 (18)	C13—O2	1.4414 (18)
C3—C4	1.385 (2)	C13—H13A	1.00 (3)
C4—C4A	1.393 (2)	C13—H13B	0.88 (3)
C4—H4	0.948 (17)	C13—H13C	1.00 (2)
C4A—C11B	1.4023 (19)	C14—O3	1.4337 (19)
C4A—C5	1.5101 (19)	C14—H14A	1.047 (17)
C5—O6	1.4395 (16)	C14—H14B	0.95 (2)
C5—H5A	0.966 (17)	C14—H14C	1.006 (19)
C5—H5B	0.990 (15)	O6—C5^i	1.4395 (16)
O1—C1—C2	121.96 (12)	C1—C11B—C11B^i	122.45 (10)
O1—C1—C11B	117.51 (12)	O1—C12—H12A	112.0 (10)
C2—C1—C11B	120.51 (12)	O1—C12—H12B	111.3 (11)
O2—C2—C1	119.42 (12)	H12A—C12—H12B	110.2 (16)
O2—C2—C3	120.51 (13)	O1—C12—H12C	106.7 (10)
C1—C2—C3	119.89 (12)	H12A—C12—H12C	107.5 (15)
O3—C3—C4	124.91 (13)	H12B—C12—H12C	109.0 (15)
O3—C3—C2	115.19 (12)	O2—C13—H13A	112.9 (14)
C4—C3—C2	119.88 (13)	O2—C13—H13B	109 (2)
C3—C4—C4A	120.05 (13)	H13A—C13—H13B	116 (3)
C3—C4—H4	121.3 (10)	O2—C13—H13C	111.4 (14)
C4A—C4—H4	118.5 (10)	H13A—C13—H13C	95.3 (17)
C4—C4A—C11B	120.88 (13)	H13B—C13—H13C	112 (2)
C4—C4A—C5	120.10 (12)	O3—C14—H14A	112.0 (9)
C11B—C4A—C5	119.01 (13)	O3—C14—H14B	112.0 (11)
O6—C5—C4A	113.55 (11)	H14A—C14—H14B	108.0 (15)
O6—C5—H5A	104.4 (9)	O3—C14—H14C	102.9 (10)
C4A—C5—H5A	111.8 (9)	H14A—C14—H14C	112.9 (13)
O6—C5—H5B	110.0 (9)	H14B—C14—H14C	109.0 (15)
C4A—C5—H5B	109.4 (8)	C1—O1—C12	117.01 (11)
H5A—C5—H5B	107.4 (12)	C2—O2—C13	115.57 (11)
C4A—C11B—C1	118.46 (13)	C3—O3—C14	117.19 (12)
C4A—C11B—C11B^i	119.00 (10)	C5—O6—C5^i	114.24 (14)
O1—C1—C2—O2	4.15 (18)	C5—C4A—C11B—C1	−175.72 (12)
C11B—C1—C2—O2	−173.97 (11)	C4—C4A—C11B—C11B^i	−178.37 (13)
O1—C1—C2—C3	179.30 (12)	C5—C4A—C11B—C11B^i	0.8 (2)
C11B—C1—C2—C3	1.19 (19)	O1—C1—C11B—C4A	176.34 (11)
O2—C2—C3—O3	0.43 (18)	C2—C1—C11B—C4A	−5.46 (19)
C1—C2—C3—O3	−174.67 (11)	O1—C1—C11B—C11B^i	−0.1 (2)
O2—C2—C3—C4	178.73 (12)	C2—C1—C11B—C11B^i	178.10 (13)
C1—C2—C3—C4	3.6 (2)	C2—C1—O1—C12	50.03 (18)
O3—C3—C4—C4A	174.07 (12)	C11B—C1—O1—C12	−131.79 (14)
C2—C3—C4—C4A	−4.0 (2)	C1—C2—O2—C13	−120.19 (14)
C3—C4—C4A—C11B	−0.4 (2)	C3—C2—O2—C13	64.69 (17)
C3—C4—C4A—C5	−179.56 (13)	C4—C3—O3—C14	0.1 (2)
C4—C4A—C5—O6	−108.00 (14)	C2—C3—O3—C14	178.33 (13)
C11B—C4A—C5—O6	72.78 (16)	C4A—C5—O6—C5^i	−43.57 (9)
C4—C4A—C11B—C1	5.07 (19)

Symmetry code: (i) −x+1, y, −z+1/2.

(azepine) 6,7-dihydro-1,2,3,9,10,11-hexamethoxy-6-methyl-5H-dibenzo[c,e]azepinium chloride

Crystal data

C21H29ClNO6	F(000) = 1848
Mr = 434.9	Dx = 1.299 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 52930 reflections
a = 36.0403 (12) Å	θ = 1.0–27.5°
b = 7.8165 (2) Å	µ = 0.21 mm^−1
c = 17.0066 (5) Å	T = 150 K
β = 111.7920°	Needle, colourless
V = 4448.5 (2) Å^3	0.25 × 0.15 × 0.1 mm
Z = 8

Data collection

KappaCCD diffractometer	4945 independent reflections
Radiation source: Enraf Nonius FR590	3299 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.082
CCD rotation images, thick slices scans	θmax = 27.3°, θmin = 3.2°
Absorption correction: multi-scan R.H. Blessing, Acta Cryst. (1995), A51, 33-38	h = −45→46
Tmin = 0.973, Tmax = 1.015	k = −10→10
36698 measured reflections	l = −21→21

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)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.112	w = 1/[σ^2(Fo^2) + (0.0477P)^2 + 2.813P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.019
4945 reflections	Δρmax = 0.28 e Å^−3
392 parameters	Δρmin = −0.29 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0017 (3)

Special details

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

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.68102 (5)	0.6598 (2)	0.58223 (12)	0.0230 (4)
C2	0.69278 (5)	0.5570 (2)	0.65436 (12)	0.0238 (4)
C3	0.66395 (5)	0.4941 (2)	0.68409 (12)	0.0241 (4)
C4	0.62380 (6)	0.5223 (2)	0.63852 (12)	0.0248 (4)
C4A	0.61219 (5)	0.6240 (2)	0.56628 (12)	0.0235 (4)
C5	0.56852 (6)	0.6585 (3)	0.51870 (12)	0.0255 (4)
C7	0.57796 (6)	0.6216 (3)	0.37918 (13)	0.0255 (4)
C7A	0.59552 (5)	0.7981 (2)	0.39492 (12)	0.0244 (4)
C8	0.58130 (6)	0.9250 (3)	0.33339 (13)	0.0271 (5)
C9	0.59851 (6)	1.0858 (2)	0.34706 (13)	0.0280 (5)
C10	0.62961 (6)	1.1218 (2)	0.42439 (13)	0.0275 (5)
C11	0.64324 (6)	0.9960 (2)	0.48552 (12)	0.0266 (4)
C11A	0.62726 (5)	0.8304 (2)	0.47142 (12)	0.0235 (4)
C11B	0.64053 (5)	0.6998 (2)	0.53969 (11)	0.0226 (4)
C12	0.74333 (7)	0.7999 (3)	0.60016 (16)	0.0353 (5)
C13	0.74706 (8)	0.3788 (4)	0.66441 (19)	0.0457 (6)
C14	0.64945 (7)	0.3361 (3)	0.78873 (15)	0.0357 (5)
C15	0.55478 (8)	1.1886 (4)	0.21296 (16)	0.0434 (6)
C16	0.68161 (7)	1.3068 (3)	0.42899 (18)	0.0414 (6)
C17	0.65697 (9)	1.0696 (4)	0.62684 (16)	0.0429 (6)
C18	0.54776 (7)	0.3913 (3)	0.43460 (16)	0.0325 (5)
O1	0.70720 (4)	0.71479 (17)	0.54644 (8)	0.0273 (3)
O2	0.73253 (4)	0.51848 (18)	0.69880 (8)	0.0298 (3)
O3	0.67858 (4)	0.40029 (17)	0.75722 (8)	0.0276 (3)
O9	0.58700 (4)	1.21986 (17)	0.29158 (9)	0.0352 (4)
O10	0.64468 (4)	1.28628 (16)	0.44066 (9)	0.0320 (3)
O11	0.67256 (4)	1.03867 (17)	0.56190 (8)	0.0322 (3)
O12	0.5145 (2)	1.0434 (6)	0.4664 (4)	0.0887 (15)	0.5
N6	0.55294 (5)	0.5802 (2)	0.43118 (10)	0.0254 (4)
Cl1	0.467597 (15)	0.70067 (8)	0.36456 (3)	0.04043 (18)
H4	0.6047 (6)	0.473 (3)	0.6540 (12)	0.026 (5)*
H5A	0.5527 (6)	0.605 (2)	0.5506 (12)	0.020 (5)*
H5B	0.5642 (6)	0.778 (3)	0.5122 (12)	0.022 (5)*
H6	0.5273 (7)	0.625 (3)	0.4031 (14)	0.034 (6)*
H7A	0.5602 (6)	0.608 (2)	0.3220 (13)	0.023 (5)*
H7B	0.5999 (6)	0.538 (3)	0.3952 (12)	0.023 (5)*
H8	0.5608 (6)	0.898 (3)	0.2829 (14)	0.026 (5)*
H12A	0.7646 (9)	0.715 (3)	0.6254 (18)	0.061 (8)*
H12B	0.7524 (8)	0.870 (3)	0.5613 (17)	0.057 (8)*
H12C	0.7382 (7)	0.863 (3)	0.6430 (16)	0.046 (7)*
H12D	0.493 (3)	0.931 (12)	0.448 (5)	0.13 (3)*	0.5
H12E	0.5280 (19)	1.036 (8)	0.522 (5)	0.07 (2)*	0.5
H13A	0.7456 (9)	0.410 (4)	0.606 (2)	0.079 (10)*
H13B	0.7313 (10)	0.284 (4)	0.658 (2)	0.075 (10)*
H13C	0.7752 (8)	0.357 (3)	0.7045 (17)	0.056 (7)*
H14A	0.6316 (7)	0.254 (3)	0.7481 (15)	0.036 (6)*
H14B	0.6349 (7)	0.424 (3)	0.8011 (15)	0.043 (7)*
H14C	0.6638 (7)	0.280 (3)	0.8425 (16)	0.044 (6)*
H15A	0.5613 (7)	1.099 (4)	0.1807 (17)	0.052 (8)*
H15B	0.5290 (8)	1.146 (3)	0.2186 (15)	0.047 (7)*
H15C	0.5498 (7)	1.294 (3)	0.1842 (15)	0.044 (7)*
H16A	0.7017 (8)	1.223 (4)	0.4660 (18)	0.061 (8)*
H16B	0.6754 (7)	1.290 (3)	0.3657 (18)	0.052 (7)*
H16C	0.6896 (7)	1.422 (4)	0.4455 (15)	0.053 (7)*
H17A	0.6451 (8)	0.965 (4)	0.6373 (17)	0.062 (8)*
H17B	0.6385 (8)	1.160 (4)	0.6071 (16)	0.054 (8)*
H17C	0.6805 (8)	1.103 (3)	0.6770 (16)	0.050 (7)*
H18A	0.5737 (7)	0.342 (3)	0.4657 (14)	0.039 (6)*
H18B	0.5364 (6)	0.347 (3)	0.3732 (14)	0.032 (6)*
H18C	0.5298 (7)	0.372 (3)	0.4623 (15)	0.040 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0227 (9)	0.0229 (10)	0.0242 (10)	−0.0036 (8)	0.0094 (8)	−0.0053 (8)
C2	0.0182 (9)	0.0255 (10)	0.0253 (10)	0.0001 (8)	0.0054 (8)	−0.0031 (8)
C3	0.0255 (10)	0.0238 (10)	0.0209 (10)	0.0019 (8)	0.0064 (8)	−0.0001 (8)
C4	0.0216 (10)	0.0282 (10)	0.0251 (11)	−0.0015 (8)	0.0094 (8)	−0.0007 (8)
C4A	0.0219 (9)	0.0240 (10)	0.0225 (10)	−0.0011 (8)	0.0059 (8)	−0.0030 (8)
C5	0.0238 (10)	0.0289 (11)	0.0229 (10)	0.0017 (9)	0.0075 (8)	−0.0009 (8)
C7	0.0254 (10)	0.0284 (10)	0.0218 (11)	−0.0011 (9)	0.0076 (9)	−0.0014 (8)
C7A	0.0248 (10)	0.0248 (10)	0.0242 (10)	0.0016 (8)	0.0098 (8)	−0.0003 (8)
C8	0.0261 (10)	0.0317 (11)	0.0227 (11)	0.0006 (9)	0.0080 (9)	−0.0018 (9)
C9	0.0318 (10)	0.0269 (10)	0.0261 (11)	0.0053 (9)	0.0116 (9)	0.0048 (8)
C10	0.0306 (10)	0.0222 (10)	0.0319 (12)	−0.0001 (8)	0.0143 (9)	−0.0014 (8)
C11	0.0256 (10)	0.0268 (10)	0.0247 (10)	−0.0010 (8)	0.0063 (8)	−0.0019 (8)
C11A	0.0223 (9)	0.0248 (10)	0.0236 (10)	0.0022 (8)	0.0085 (8)	0.0013 (8)
C11B	0.0244 (9)	0.0219 (9)	0.0198 (9)	−0.0003 (8)	0.0062 (8)	−0.0031 (8)
C12	0.0246 (11)	0.0398 (13)	0.0376 (13)	−0.0098 (10)	0.0068 (10)	−0.0006 (11)
C13	0.0328 (13)	0.0451 (15)	0.0549 (18)	0.0121 (12)	0.0112 (12)	−0.0060 (13)
C14	0.0314 (11)	0.0480 (14)	0.0293 (13)	0.0026 (11)	0.0130 (10)	0.0105 (11)
C15	0.0452 (15)	0.0428 (14)	0.0334 (13)	0.0030 (12)	0.0043 (11)	0.0123 (12)
C16	0.0419 (13)	0.0340 (13)	0.0525 (17)	−0.0099 (11)	0.0221 (12)	−0.0010 (12)
C17	0.0546 (16)	0.0381 (14)	0.0328 (14)	−0.0001 (13)	0.0127 (12)	−0.0088 (11)
C18	0.0348 (12)	0.0285 (11)	0.0358 (13)	−0.0065 (10)	0.0152 (11)	−0.0016 (9)
O1	0.0222 (7)	0.0328 (8)	0.0271 (7)	−0.0063 (6)	0.0095 (6)	−0.0011 (6)
O2	0.0196 (7)	0.0374 (8)	0.0290 (8)	0.0021 (6)	0.0050 (6)	0.0012 (6)
O3	0.0236 (7)	0.0341 (8)	0.0243 (7)	0.0024 (6)	0.0080 (6)	0.0068 (6)
O9	0.0415 (8)	0.0291 (8)	0.0296 (8)	0.0022 (6)	0.0069 (7)	0.0071 (6)
O10	0.0364 (8)	0.0208 (7)	0.0381 (8)	−0.0013 (6)	0.0131 (7)	−0.0013 (6)
O11	0.0354 (8)	0.0301 (7)	0.0260 (8)	−0.0047 (6)	0.0054 (6)	−0.0035 (6)
O12	0.122 (4)	0.052 (3)	0.094 (4)	−0.020 (3)	0.043 (4)	−0.009 (3)
N6	0.0206 (8)	0.0288 (9)	0.0242 (9)	−0.0005 (7)	0.0052 (7)	−0.0009 (7)
Cl1	0.0256 (3)	0.0552 (4)	0.0358 (3)	0.0024 (2)	0.0059 (2)	0.0110 (3)

Geometric parameters (Å, º)

C1—O1	1.368 (2)	C12—H12A	0.98 (3)
C1—C2	1.394 (3)	C12—H12B	1.00 (3)
C1—C11B	1.402 (3)	C12—H12C	0.95 (3)
C2—O2	1.382 (2)	C13—O2	1.427 (3)
C2—C3	1.403 (3)	C13—H13A	1.01 (3)
C3—O3	1.370 (2)	C13—H13B	0.91 (3)
C3—C4	1.382 (3)	C13—H13C	1.00 (3)
C4—C4A	1.391 (3)	C14—O3	1.435 (3)
C4—H4	0.91 (2)	C14—H14A	0.99 (2)
C4A—C11B	1.393 (3)	C14—H14B	0.94 (3)
C4A—C5	1.503 (3)	C14—H14C	0.97 (3)
C5—N6	1.512 (2)	C15—O9	1.429 (3)
C5—H5A	1.01 (2)	C15—H15A	0.97 (3)
C5—H5B	0.95 (2)	C15—H15B	1.02 (3)
C7—C7A	1.500 (3)	C15—H15C	0.94 (3)
C7—N6	1.514 (3)	C16—O10	1.426 (3)
C7—H7A	0.95 (2)	C16—H16A	1.01 (3)
C7—H7B	0.98 (2)	C16—H16B	1.02 (3)
C7A—C8	1.394 (3)	C16—H16C	0.96 (3)
C7A—C11A	1.400 (3)	C17—O11	1.433 (3)
C8—C9	1.383 (3)	C17—H17A	0.97 (3)
C8—H8	0.93 (2)	C17—H17B	0.94 (3)
C9—O9	1.367 (2)	C17—H17C	0.99 (3)
C9—C10	1.404 (3)	C18—N6	1.492 (3)
C10—C11	1.382 (3)	C18—H18A	0.97 (2)
C10—O10	1.383 (2)	C18—H18B	1.03 (2)
C11—O11	1.377 (2)	C18—H18C	0.94 (3)
C11—C11A	1.401 (3)	O12—H12D	1.13 (10)
C11A—C11B	1.485 (3)	O12—H12E	0.89 (7)
C12—O1	1.446 (2)	N6—H6	0.94 (2)
O1—C1—C2	122.52 (16)	H12A—C12—H12C	111 (2)
O1—C1—C11B	117.25 (16)	H12B—C12—H12C	115 (2)
C2—C1—C11B	120.06 (17)	O2—C13—H13A	109.2 (18)
O2—C2—C1	121.44 (17)	O2—C13—H13B	111 (2)
O2—C2—C3	118.88 (16)	H13A—C13—H13B	106 (3)
C1—C2—C3	119.67 (16)	O2—C13—H13C	106.4 (15)
O3—C3—C4	124.38 (18)	H13A—C13—H13C	112 (2)
O3—C3—C2	115.34 (15)	H13B—C13—H13C	112 (2)
C4—C3—C2	120.23 (17)	O3—C14—H14A	110.1 (13)
C3—C4—C4A	119.71 (19)	O3—C14—H14B	112.2 (15)
C3—C4—H4	121.3 (12)	H14A—C14—H14B	111.2 (19)
C4A—C4—H4	119.0 (12)	O3—C14—H14C	107.7 (14)
C4—C4A—C11B	120.88 (17)	H14A—C14—H14C	110.0 (19)
C4—C4A—C5	119.31 (18)	H14B—C14—H14C	106 (2)
C11B—C4A—C5	119.75 (17)	O9—C15—H15A	111.7 (15)
C4A—C5—N6	112.92 (16)	O9—C15—H15B	114.7 (14)
C4A—C5—H5A	108.9 (10)	H15A—C15—H15B	104 (2)
N6—C5—H5A	106.4 (11)	O9—C15—H15C	105.7 (14)
C4A—C5—H5B	109.4 (12)	H15A—C15—H15C	112 (2)
N6—C5—H5B	107.5 (12)	H15B—C15—H15C	109 (2)
H5A—C5—H5B	111.8 (16)	O10—C16—H16A	109.4 (16)
C7A—C7—N6	113.30 (16)	O10—C16—H16B	106.4 (14)
C7A—C7—H7A	111.5 (12)	H16A—C16—H16B	114 (2)
N6—C7—H7A	104.5 (12)	O10—C16—H16C	105.0 (15)
C7A—C7—H7B	108.5 (11)	H16A—C16—H16C	111 (2)
N6—C7—H7B	106.8 (11)	H16B—C16—H16C	111 (2)
H7A—C7—H7B	112.0 (16)	O11—C17—H17A	108.8 (16)
C8—C7A—C11A	121.02 (17)	O11—C17—H17B	106.2 (16)
C8—C7A—C7	120.47 (17)	H17A—C17—H17B	114 (2)
C11A—C7A—C7	118.47 (17)	O11—C17—H17C	104.6 (14)
C9—C8—C7A	120.23 (18)	H17A—C17—H17C	111 (2)
C9—C8—H8	121.3 (13)	H17B—C17—H17C	112 (2)
C7A—C8—H8	118.4 (13)	N6—C18—H18A	107.8 (13)
O9—C9—C8	125.35 (18)	N6—C18—H18B	107.7 (12)
O9—C9—C10	115.15 (17)	H18A—C18—H18B	111.0 (18)
C8—C9—C10	119.47 (18)	N6—C18—H18C	107.4 (14)
C11—C10—O10	120.48 (17)	H18A—C18—H18C	112 (2)
C11—C10—C9	119.97 (17)	H18B—C18—H18C	111.2 (18)
O10—C10—C9	119.43 (17)	C1—O1—C12	118.14 (16)
O11—C11—C10	118.14 (17)	C2—O2—C13	113.95 (16)
O11—C11—C11A	120.52 (17)	C3—O3—C14	115.97 (15)
C10—C11—C11A	121.33 (17)	C9—O9—C15	116.59 (17)
C7A—C11A—C11	117.89 (17)	C10—O10—C16	113.22 (17)
C7A—C11A—C11B	121.15 (16)	C11—O11—C17	112.63 (17)
C11—C11A—C11B	120.58 (16)	H12D—O12—H12E	107 (6)
C4A—C11B—C1	119.03 (17)	C18—N6—C5	111.63 (16)
C4A—C11B—C11A	118.94 (16)	C18—N6—C7	110.15 (16)
C1—C11B—C11A	121.86 (17)	C5—N6—C7	113.86 (15)
O1—C12—H12A	109.9 (15)	C18—N6—H6	106.0 (13)
O1—C12—H12B	105.9 (14)	C5—N6—H6	106.7 (13)
H12A—C12—H12B	105 (2)	C7—N6—H6	108.2 (13)
O1—C12—H12C	109.6 (15)
O1—C1—C2—O2	6.5 (3)	O11—C11—C11A—C7A	175.39 (17)
C11B—C1—C2—O2	−178.50 (16)	C10—C11—C11A—C7A	−3.2 (3)
O1—C1—C2—C3	−175.10 (17)	O11—C11—C11A—C11B	2.4 (3)
C11B—C1—C2—C3	−0.1 (3)	C10—C11—C11A—C11B	−176.25 (18)
O2—C2—C3—O3	1.0 (2)	C4—C4A—C11B—C1	5.8 (3)
C1—C2—C3—O3	−177.41 (16)	C5—C4A—C11B—C1	−176.93 (17)
O2—C2—C3—C4	−176.38 (17)	C4—C4A—C11B—C11A	−169.61 (17)
C1—C2—C3—C4	5.2 (3)	C5—C4A—C11B—C11A	7.7 (3)
O3—C3—C4—C4A	178.09 (17)	O1—C1—C11B—C4A	169.95 (16)
C2—C3—C4—C4A	−4.7 (3)	C2—C1—C11B—C4A	−5.3 (3)
C3—C4—C4A—C11B	−0.8 (3)	O1—C1—C11B—C11A	−14.8 (3)
C3—C4—C4A—C5	−178.07 (18)	C2—C1—C11B—C11A	169.96 (17)
C4—C4A—C5—N6	−114.1 (2)	C7A—C11A—C11B—C4A	−51.1 (3)
C11B—C4A—C5—N6	68.6 (2)	C11—C11A—C11B—C4A	121.7 (2)
N6—C7—C7A—C8	−109.0 (2)	C7A—C11A—C11B—C1	133.6 (2)
N6—C7—C7A—C11A	73.1 (2)	C11—C11A—C11B—C1	−53.6 (3)
C11A—C7A—C8—C9	0.1 (3)	C2—C1—O1—C12	−52.5 (2)
C7—C7A—C8—C9	−177.77 (19)	C11B—C1—O1—C12	132.34 (19)
C7A—C8—C9—O9	−179.75 (18)	C1—C2—O2—C13	−83.1 (2)
C7A—C8—C9—C10	−1.9 (3)	C3—C2—O2—C13	98.4 (2)
O9—C9—C10—C11	179.20 (18)	C4—C3—O3—C14	−3.1 (3)
C8—C9—C10—C11	1.1 (3)	C2—C3—O3—C14	179.58 (18)
O9—C9—C10—O10	3.1 (3)	C8—C9—O9—C15	−0.7 (3)
C8—C9—C10—O10	−174.96 (18)	C10—C9—O9—C15	−178.6 (2)
O10—C10—C11—O11	−1.1 (3)	C11—C10—O10—C16	82.4 (2)
C9—C10—C11—O11	−177.17 (18)	C9—C10—O10—C16	−101.5 (2)
O10—C10—C11—C11A	177.52 (18)	C10—C11—O11—C17	100.4 (2)
C9—C10—C11—C11A	1.5 (3)	C11A—C11—O11—C17	−78.3 (2)
C8—C7A—C11A—C11	2.4 (3)	C4A—C5—N6—C18	75.0 (2)
C7—C7A—C11A—C11	−179.67 (18)	C4A—C5—N6—C7	−50.4 (2)
C8—C7A—C11A—C11B	175.44 (18)	C7A—C7—N6—C18	−161.48 (17)
C7—C7A—C11A—C11B	−6.7 (3)	C7A—C7—N6—C5	−35.2 (2)

(sulfide) 5,7-dihydro-1,2,3,9,10,11-hexamethoxydibenzo[c,e]thiepine

Crystal data

C20H24O6S	F(000) = 832
Mr = 392.45	Dx = 1.443 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 10338 reflections
a = 8.6029 (2) Å	θ = 0–0°
b = 12.2965 (3) Å	µ = 0.22 mm^−1
c = 17.6032 (4) Å	T = 150 K
β = 104.0380°	Needle, colourless
V = 1806.55 (7) Å^3	0.2 × 0.1 × 0.1 mm
Z = 4

Data collection

KappaCCD diffractometer	2388 independent reflections
Radiation source: Enraf Nonius FR590	2003 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
CCD rotation images, thick slices scans	θmax = 29.1°, θmin = 3.0°
Absorption correction: multi-scan R.H. Blessing, Acta Cryst. (1995), A51, 33-38	h = −11→11
Tmin = 0.975, Tmax = 1.016	k = −16→16
15259 measured reflections	l = −23→24

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)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.099	w = 1/[σ^2(Fo^2) + (0.0508P)^2 + 1.3323P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.003
2388 reflections	Δρmax = 0.32 e Å^−3
172 parameters	Δρmin = −0.30 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0074 (13)

Special details

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

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

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

	x	y	z	Uiso*/Ueq
C1	0.55184 (14)	0.58168 (9)	0.66847 (7)	0.0135 (3)
C2	0.65913 (15)	0.58284 (9)	0.62049 (7)	0.0142 (3)
C3	0.77012 (15)	0.49775 (10)	0.62572 (7)	0.0146 (3)
C4	0.77115 (15)	0.41306 (10)	0.67830 (7)	0.0146 (3)
C4A	0.66397 (15)	0.41269 (9)	0.72640 (7)	0.0138 (3)
C5	0.66577 (16)	0.32012 (10)	0.78250 (8)	0.0163 (3)
C11B	0.55516 (14)	0.49830 (9)	0.72330 (7)	0.0138 (3)
C12	0.28299 (17)	0.63325 (13)	0.62107 (10)	0.0263 (3)
C13	0.5804 (2)	0.65199 (13)	0.49157 (8)	0.0279 (3)
C14	0.98301 (18)	0.41644 (12)	0.58250 (9)	0.0251 (3)
O1	0.44194 (11)	0.66526 (7)	0.66090 (5)	0.0177 (2)
O2	0.66061 (11)	0.66986 (7)	0.57123 (5)	0.0178 (2)
O3	0.87013 (11)	0.50350 (7)	0.57639 (5)	0.0193 (2)
S6	0.5	0.22488 (3)	0.75	0.01952 (15)
H14B	1.044 (2)	0.4347 (14)	0.5450 (10)	0.031 (5)*
H4	0.847 (2)	0.3561 (14)	0.6814 (10)	0.023 (4)*
H14A	0.928 (2)	0.3476 (15)	0.5698 (10)	0.031 (5)*
H13C	0.594 (2)	0.7161 (15)	0.4628 (11)	0.030 (5)*
H8B	0.6576 (18)	0.3479 (13)	0.8335 (9)	0.019 (4)*
H8A	0.759 (2)	0.2756 (13)	0.7889 (9)	0.020 (4)*
H14C	1.058 (2)	0.4178 (14)	0.6363 (11)	0.027 (4)*
H12A	0.280 (3)	0.6008 (19)	0.5714 (14)	0.055 (6)*
H13B	0.465 (3)	0.6393 (18)	0.4877 (13)	0.051 (6)*
H12C	0.211 (3)	0.6965 (17)	0.6134 (11)	0.043 (5)*
H13A	0.629 (3)	0.591 (2)	0.4700 (14)	0.065 (7)*
H12B	0.241 (3)	0.5780 (19)	0.6481 (14)	0.059 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0152 (6)	0.0100 (5)	0.0149 (5)	0.0001 (4)	0.0026 (5)	−0.0015 (4)
C2	0.0179 (6)	0.0112 (5)	0.0130 (5)	−0.0027 (4)	0.0028 (5)	0.0008 (4)
C3	0.0153 (6)	0.0153 (6)	0.0140 (5)	−0.0017 (4)	0.0051 (5)	−0.0008 (4)
C4	0.0153 (6)	0.0128 (6)	0.0159 (6)	0.0014 (4)	0.0039 (5)	0.0001 (4)
C4A	0.0152 (6)	0.0125 (5)	0.0136 (5)	−0.0010 (4)	0.0031 (5)	0.0010 (4)
C5	0.0170 (6)	0.0145 (6)	0.0180 (6)	0.0020 (5)	0.0056 (5)	0.0033 (5)
C11B	0.0151 (6)	0.0124 (5)	0.0144 (6)	−0.0015 (4)	0.0047 (5)	−0.0009 (4)
C12	0.0194 (7)	0.0228 (7)	0.0336 (8)	0.0045 (5)	0.0007 (6)	−0.0032 (6)
C13	0.0416 (9)	0.0247 (7)	0.0148 (6)	−0.0045 (6)	0.0022 (6)	0.0036 (5)
C14	0.0225 (7)	0.0273 (8)	0.0304 (7)	0.0100 (6)	0.0159 (6)	0.0097 (6)
O1	0.0173 (5)	0.0122 (4)	0.0232 (5)	0.0031 (3)	0.0042 (4)	0.0001 (3)
O2	0.0253 (5)	0.0135 (4)	0.0141 (4)	−0.0021 (3)	0.0040 (4)	0.0033 (3)
O3	0.0208 (5)	0.0198 (5)	0.0209 (5)	0.0049 (4)	0.0123 (4)	0.0052 (4)
S6	0.0200 (2)	0.0112 (2)	0.0291 (3)	0	0.00936 (19)	0

Geometric parameters (Å, º)

C1—O1	1.3809 (14)	C11B—C11B^i	1.489 (2)
C1—C2	1.3942 (17)	C12—O1	1.4323 (17)
C1—C11B	1.4037 (16)	C12—H12A	0.96 (2)
C2—O2	1.3792 (14)	C12—H12C	0.99 (2)
C2—C3	1.4044 (17)	C12—H12B	0.95 (2)
C3—O3	1.3644 (15)	C13—O2	1.4218 (16)
C3—C4	1.3919 (17)	C13—H13C	0.960 (18)
C4—C4A	1.3949 (17)	C13—H13B	0.99 (2)
C4—H4	0.947 (17)	C13—H13A	0.98 (3)
C4A—C11B	1.4010 (17)	C14—O3	1.4318 (16)
C4A—C5	1.5046 (17)	C14—H14B	0.967 (18)
C5—S6	1.8267 (13)	C14—H14A	0.969 (18)
C5—H8B	0.980 (16)	C14—H14C	1.010 (18)
C5—H8A	0.958 (17)	S6—C5^i	1.8267 (13)
O1—C1—C2	118.19 (10)	C1—C11B—C11B^i	121.63 (9)
O1—C1—C11B	120.61 (11)	O1—C12—H12A	111.7 (14)
C2—C1—C11B	121.20 (11)	O1—C12—H12C	110.3 (12)
O2—C2—C1	119.81 (11)	H12A—C12—H12C	109.3 (17)
O2—C2—C3	120.63 (11)	O1—C12—H12B	112.8 (14)
C1—C2—C3	119.48 (11)	H12A—C12—H12B	103.4 (19)
O3—C3—C4	123.97 (11)	H12C—C12—H12B	109.0 (18)
O3—C3—C2	116.31 (11)	O2—C13—H13C	107.5 (11)
C4—C3—C2	119.71 (11)	O2—C13—H13B	109.3 (13)
C3—C4—C4A	120.50 (11)	H13C—C13—H13B	110.0 (17)
C3—C4—H4	119.1 (10)	O2—C13—H13A	110.5 (14)
C4A—C4—H4	120.4 (10)	H13C—C13—H13A	107.7 (18)
C4—C4A—C11B	120.52 (11)	H13B—C13—H13A	111.8 (19)
C4—C4A—C5	119.85 (11)	O3—C14—H14B	104.4 (11)
C11B—C4A—C5	119.63 (11)	O3—C14—H14A	110.6 (11)
C4A—C5—S6	113.36 (9)	H14B—C14—H14A	111.3 (15)
C4A—C5—H8B	110.3 (9)	O3—C14—H14C	109.1 (10)
S6—C5—H8B	106.6 (9)	H14B—C14—H14C	107.7 (14)
C4A—C5—H8A	112.6 (10)	H14A—C14—H14C	113.4 (14)
S6—C5—H8A	104.0 (10)	C1—O1—C12	113.13 (10)
H8B—C5—H8A	109.7 (13)	C2—O2—C13	115.07 (10)
C4A—C11B—C1	118.52 (11)	C3—O3—C14	115.74 (10)
C4A—C11B—C11B^i	119.84 (9)	C5—S6—C5^i	100.25 (8)
O1—C1—C2—O2	4.46 (17)	C5—C4A—C11B—C1	−177.70 (11)
C11B—C1—C2—O2	−175.30 (11)	C4—C4A—C11B—C11B^i	−178.19 (12)
O1—C1—C2—C3	−178.70 (10)	C5—C4A—C11B—C11B^i	1.38 (19)
C11B—C1—C2—C3	1.53 (18)	O1—C1—C11B—C4A	177.17 (10)
O2—C2—C3—O3	−3.94 (17)	C2—C1—C11B—C4A	−3.07 (18)
C1—C2—C3—O3	179.25 (10)	O1—C1—C11B—C11B^i	−1.89 (19)
O2—C2—C3—C4	177.19 (11)	C2—C1—C11B—C11B^i	177.87 (12)
C1—C2—C3—C4	0.38 (18)	C2—C1—O1—C12	105.35 (13)
O3—C3—C4—C4A	−179.48 (11)	C11B—C1—O1—C12	−74.88 (15)
C2—C3—C4—C4A	−0.70 (19)	C1—C2—O2—C13	−101.06 (14)
C3—C4—C4A—C11B	−0.89 (19)	C3—C2—O2—C13	82.14 (15)
C3—C4—C4A—C5	179.54 (11)	C4—C3—O3—C14	−1.37 (18)
C4—C4A—C5—S6	−104.20 (12)	C2—C3—O3—C14	179.81 (11)
C11B—C4A—C5—S6	76.23 (13)	C4A—C5—S6—C5^i	−44.52 (7)
C4—C4A—C11B—C1	2.73 (18)

Symmetry code: (i) −x+1, y, −z+3/2.

(sulfoxide) 5,7-dihydro-1,2,3,9,10,11-hexamethoxydibenzo[c,e]thiepine 6-oxide

Crystal data

C20H24O7S	F(000) = 864
Mr = 408.45	Dx = 1.472 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 14600 reflections
a = 8.8113 (3) Å	θ = 1.0–27.5°
b = 12.2699 (3) Å	µ = 0.22 mm^−1
c = 17.5640 (6) Å	T = 150 K
β = 103.988 (2)°	Prism, colourless
V = 1842.60 (10) Å^3	0.2 × 0.2 × 0.2 mm
Z = 4

Data collection

KappaCCD diffractometer	2111 independent reflections
Radiation source: Enraf Nonius FR590	1775 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.110
CCD rotation images, thick slices scans	θmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan R.H. Blessing, Acta Cryst. (1995), A51, 33-38	h = −11→11
Tmin = 0.96, Tmax = 1.033	k = −15→15
14844 measured reflections	l = −22→22

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0619P)^2 + 1.7711P] where P = (Fo^2 + 2Fc^2)/3
2111 reflections	(Δ/σ)max = 0.006
180 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.39 e Å^−3

Special details

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

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.1307 (2)	0.16085 (14)	0.33121 (10)	0.0212 (4)
C2	0.2817 (2)	0.16099 (14)	0.38027 (10)	0.0219 (4)
C3	0.3846 (2)	0.24607 (15)	0.37397 (10)	0.0228 (4)
C4	0.3340 (2)	0.32981 (14)	0.32078 (10)	0.0221 (4)
C4A	0.1828 (2)	0.32929 (14)	0.27266 (10)	0.0209 (4)
C5	0.1282 (2)	0.42173 (14)	0.21689 (11)	0.0241 (4)
C11B	0.08030 (19)	0.24316 (14)	0.27612 (10)	0.0210 (4)
C12	−0.0606 (3)	0.1030 (2)	0.39317 (18)	0.0457 (6)
C13	0.3584 (3)	0.0963 (2)	0.51153 (12)	0.0368 (5)
C14	0.6423 (2)	0.31688 (19)	0.40804 (14)	0.0337 (5)
O1	0.03009 (15)	0.07741 (10)	0.33878 (7)	0.0246 (3)
O2	0.32735 (16)	0.07378 (10)	0.42962 (7)	0.0270 (3)
O3	0.53039 (14)	0.24138 (11)	0.42333 (7)	0.0287 (3)
O6	0.0871 (3)	0.5785 (2)	0.31160 (17)	0.0299 (6)	0.5
S1	0	0.51860 (5)	0.25	0.0332 (2)
H4	0.401 (3)	0.3897 (18)	0.3150 (13)	0.027 (5)*
H5A	0.216 (3)	0.4675 (18)	0.2093 (12)	0.028 (5)*
H5B	0.070 (3)	0.3939 (18)	0.1668 (13)	0.028 (5)*
H12A	−0.127 (4)	0.039 (3)	0.3966 (17)	0.066 (9)*
H12B	−0.004 (4)	0.111 (3)	0.441 (2)	0.085 (12)*
H12C	−0.112 (4)	0.174 (3)	0.382 (2)	0.082 (11)*
H13A	0.265 (5)	0.128 (3)	0.523 (2)	0.090 (12)*
H13B	0.456 (4)	0.149 (3)	0.526 (2)	0.079 (10)*
H13C	0.370 (3)	0.030 (2)	0.5379 (15)	0.040 (6)*
H14A	0.748 (3)	0.298 (2)	0.4450 (15)	0.041 (6)*
H14B	0.615 (3)	0.390 (2)	0.4154 (16)	0.049 (7)*
H14C	0.651 (3)	0.308 (2)	0.3549 (16)	0.038 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0197 (8)	0.0197 (8)	0.0242 (9)	−0.0013 (6)	0.0051 (7)	−0.0024 (6)
C2	0.0229 (9)	0.0203 (8)	0.0216 (8)	0.0026 (7)	0.0038 (7)	0.0003 (6)
C3	0.0164 (8)	0.0256 (8)	0.0249 (9)	0.0007 (7)	0.0022 (7)	−0.0026 (7)
C4	0.0185 (8)	0.0218 (8)	0.0256 (9)	−0.0013 (7)	0.0047 (7)	−0.0011 (7)
C4A	0.0176 (8)	0.0224 (8)	0.0223 (8)	0.0017 (6)	0.0042 (6)	0.0002 (7)
C5	0.0201 (9)	0.0239 (8)	0.0274 (9)	0.0007 (7)	0.0039 (7)	0.0034 (7)
C11B	0.0177 (9)	0.0217 (8)	0.0226 (8)	0.0016 (6)	0.0031 (7)	−0.0022 (6)
C12	0.0459 (14)	0.0396 (13)	0.0619 (17)	−0.0165 (11)	0.0332 (13)	−0.0159 (11)
C13	0.0491 (14)	0.0359 (11)	0.0246 (10)	0.0063 (10)	0.0073 (9)	0.0057 (8)
C14	0.0175 (9)	0.0410 (12)	0.0398 (12)	−0.0031 (8)	0.0014 (8)	0.0095 (9)
O1	0.0230 (7)	0.0216 (6)	0.0295 (7)	−0.0037 (5)	0.0069 (5)	−0.0003 (5)
O2	0.0307 (7)	0.0224 (7)	0.0247 (7)	0.0024 (5)	0.0003 (5)	0.0027 (5)
O3	0.0176 (7)	0.0322 (7)	0.0318 (7)	−0.0027 (5)	−0.0026 (5)	0.0066 (5)
O6	0.0215 (13)	0.0262 (13)	0.0417 (15)	−0.0076 (10)	0.0070 (11)	−0.0150 (11)
S1	0.0210 (3)	0.0208 (3)	0.0577 (5)	0	0.0093 (3)	0

Geometric parameters (Å, º)

C1—O1	1.382 (2)	C12—O1	1.421 (3)
C1—C11B	1.395 (2)	C12—H12A	0.99 (3)
C1—C2	1.399 (2)	C12—H12B	0.88 (4)
C2—O2	1.375 (2)	C12—H12C	0.98 (4)
C2—C3	1.405 (3)	C13—O2	1.425 (2)
C3—O3	1.366 (2)	C13—H13A	0.98 (4)
C3—C4	1.388 (3)	C13—H13B	1.05 (4)
C4—C4A	1.395 (2)	C13—H13C	0.93 (3)
C4—H4	0.96 (2)	C14—O3	1.425 (2)
C4A—C11B	1.401 (2)	C14—H14A	1.02 (3)
C4A—C5	1.500 (2)	C14—H14B	0.94 (3)
C5—S1	1.8289 (19)	C14—H14C	0.96 (3)
C5—H5A	0.99 (2)	O6—S1	1.378 (3)
C5—H5B	0.97 (2)	S1—O6^i	1.378 (3)
C11B—C11B^i	1.489 (3)	S1—C5^i	1.8289 (19)
O1—C1—C11B	119.94 (15)	H12A—C12—H12B	104 (3)
O1—C1—C2	118.59 (15)	O1—C12—H12C	112 (2)
C11B—C1—C2	121.47 (16)	H12A—C12—H12C	118 (3)
O2—C2—C1	118.48 (15)	H12B—C12—H12C	103 (3)
O2—C2—C3	122.16 (16)	O2—C13—H13A	109 (2)
C1—C2—C3	119.23 (16)	O2—C13—H13B	108.3 (19)
O3—C3—C4	123.96 (16)	H13A—C13—H13B	113 (3)
O3—C3—C2	116.40 (15)	O2—C13—H13C	107.8 (15)
C4—C3—C2	119.63 (16)	H13A—C13—H13C	104 (3)
C3—C4—C4A	120.62 (16)	H13B—C13—H13C	115 (3)
C3—C4—H4	122.0 (13)	O3—C14—H14A	107.3 (14)
C4A—C4—H4	117.3 (13)	O3—C14—H14B	112.3 (17)
C4—C4A—C11B	120.56 (16)	H14A—C14—H14B	111 (2)
C4—C4A—C5	120.05 (16)	O3—C14—H14C	109.2 (15)
C11B—C4A—C5	119.39 (15)	H14A—C14—H14C	109 (2)
C4A—C5—S1	114.13 (13)	H14B—C14—H14C	109 (2)
C4A—C5—H5A	112.2 (12)	C1—O1—C12	112.31 (15)
S1—C5—H5A	103.8 (13)	C2—O2—C13	116.20 (15)
C4A—C5—H5B	110.1 (13)	C3—O3—C14	116.12 (14)
S1—C5—H5B	106.5 (13)	O6—S1—O6^i	115.5 (2)
H5A—C5—H5B	109.8 (18)	O6—S1—C5	109.07 (13)
C1—C11B—C4A	118.41 (15)	O6^i—S1—C5	111.52 (13)
C1—C11B—C11B^i	121.56 (13)	O6—S1—C5^i	111.52 (13)
C4A—C11B—C11B^i	119.99 (13)	O6^i—S1—C5^i	109.07 (13)
O1—C12—H12A	107.5 (18)	C5—S1—C5^i	98.93 (12)
O1—C12—H12B	113 (3)
O1—C1—C2—O2	4.9 (2)	O1—C1—C11B—C11B^i	−0.7 (3)
C11B—C1—C2—O2	−175.77 (15)	C2—C1—C11B—C11B^i	180.00 (17)
O1—C1—C2—C3	−179.16 (15)	C4—C4A—C11B—C1	2.9 (3)
C11B—C1—C2—C3	0.1 (3)	C5—C4A—C11B—C1	−176.77 (16)
O2—C2—C3—O3	−4.1 (3)	C4—C4A—C11B—C11B^i	−179.43 (17)
C1—C2—C3—O3	−179.84 (15)	C5—C4A—C11B—C11B^i	0.9 (3)
O2—C2—C3—C4	177.34 (15)	C11B—C1—O1—C12	−88.6 (2)
C1—C2—C3—C4	1.6 (3)	C2—C1—O1—C12	90.7 (2)
O3—C3—C4—C4A	−179.52 (16)	C1—C2—O2—C13	−115.0 (2)
C2—C3—C4—C4A	−1.1 (3)	C3—C2—O2—C13	69.2 (2)
C3—C4—C4A—C11B	−1.2 (3)	C4—C3—O3—C14	−11.7 (3)
C3—C4—C4A—C5	178.45 (16)	C2—C3—O3—C14	169.83 (17)
C4—C4A—C5—S1	−102.63 (17)	C4A—C5—S1—O6	71.57 (19)
C11B—C4A—C5—S1	77.04 (19)	C4A—C5—S1—O6^i	−159.66 (17)
O1—C1—C11B—C4A	176.92 (15)	C4A—C5—S1—C5^i	−44.99 (11)
C2—C1—C11B—C4A	−2.4 (3)

Symmetry code: (i) −x, y, −z+1/2.

(sulfone) 5,7-dihydro-1,2,3,9,10,11-hexamethoxydibenzo[c,e]thiepine 6,6-dioxide

Crystal data

C20H24O8S	F(000) = 896
Mr = 424.45	Dx = 1.405 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 21800 reflections
a = 8.7886 (2) Å	θ = 1.0–27.5°
b = 15.3454 (3) Å	µ = 0.21 mm^−1
c = 15.4972 (4) Å	T = 150 K
β = 106.2770°	Prism, colourless
V = 2006.25 (8) Å^3	0.25 × 0.2 × 0.15 mm
Z = 4

Data collection

KappaCCD diffractometer	4583 independent reflections
Radiation source: Enraf Nonius FR590	3388 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
CCD rotation images, thick slices scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan R.H. Blessing, Acta Cryst. (1995), A51, 33-38	h = −11→11
Tmin = 0.98, Tmax = 1.014	k = −19→19
30410 measured reflections	l = −18→20

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 atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.104	w = 1/[σ^2(Fo^2) + (0.0451P)^2 + 0.9601P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.005
4583 reflections	Δρmax = 0.26 e Å^−3
359 parameters	Δρmin = −0.39 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0072 (11)

Special details

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

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

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

	x	y	z	Uiso*/Ueq
C1	0.7995 (2)	0.34436 (11)	0.49995 (11)	0.0218 (4)
C2	0.9578 (2)	0.36152 (11)	0.54564 (12)	0.0226 (4)
C3	1.0768 (2)	0.30216 (11)	0.54148 (12)	0.0238 (4)
C4	1.0359 (2)	0.22407 (11)	0.49598 (12)	0.0241 (4)
C4A	0.8777 (2)	0.20595 (11)	0.45292 (11)	0.0222 (4)
C5	0.8376 (2)	0.11862 (11)	0.40784 (13)	0.0245 (4)
C7	0.6126 (2)	0.11438 (12)	0.50394 (12)	0.0240 (4)
C7A	0.5201 (2)	0.16875 (11)	0.42681 (12)	0.0233 (4)
C8	0.3672 (2)	0.14309 (12)	0.37870 (13)	0.0269 (4)
C9	0.2787 (2)	0.19511 (12)	0.30995 (13)	0.0305 (4)
C010	0.7574 (2)	0.26612 (11)	0.45174 (12)	0.0225 (4)
C10	0.3419 (2)	0.27306 (12)	0.28921 (12)	0.0287 (4)
C11	0.4969 (2)	0.29688 (11)	0.33510 (12)	0.0254 (4)
C11A	0.5891 (2)	0.24470 (11)	0.40486 (12)	0.0234 (4)
C12	0.6937 (3)	0.48870 (12)	0.47979 (15)	0.0315 (4)
C13	1.0371 (5)	0.42582 (19)	0.68788 (16)	0.0565 (8)
C14	1.3515 (3)	0.27458 (17)	0.5670 (2)	0.0456 (6)
C15	0.0835 (3)	0.08715 (15)	0.24673 (16)	0.0404 (5)
C16	0.1442 (3)	0.37914 (16)	0.25046 (17)	0.0453 (6)
C17	0.6114 (3)	0.36332 (18)	0.23188 (17)	0.0478 (6)
O1	0.68036 (14)	0.39925 (7)	0.50612 (8)	0.0256 (3)
O2	0.99568 (15)	0.43757 (8)	0.59425 (8)	0.0286 (3)
O3	1.22822 (14)	0.32560 (8)	0.58625 (9)	0.0305 (3)
O6A	0.86896 (15)	0.01927 (8)	0.55267 (9)	0.0320 (3)
O6B	0.66782 (16)	−0.02143 (8)	0.41224 (9)	0.0344 (3)
O9	0.12642 (17)	0.17617 (9)	0.26091 (11)	0.0463 (4)
O10	0.25441 (16)	0.32601 (9)	0.22129 (9)	0.0362 (3)
O11	0.56027 (16)	0.37245 (8)	0.31174 (9)	0.0318 (3)
S6	0.75182 (5)	0.04630 (3)	0.47175 (3)	0.02502 (14)
H4	1.118 (2)	0.1820 (12)	0.4945 (13)	0.025 (5)*
H5A	0.757 (2)	0.1224 (12)	0.3486 (14)	0.026 (5)*
H5B	0.926 (3)	0.0871 (13)	0.4014 (13)	0.030 (5)*
H7A	0.543 (2)	0.0736 (13)	0.5257 (13)	0.027 (5)*
H7B	0.671 (2)	0.1491 (13)	0.5517 (14)	0.029 (5)*
H8	0.322 (3)	0.0888 (14)	0.3948 (15)	0.039 (6)*
H12A	0.585 (4)	0.5101 (18)	0.4482 (19)	0.071 (8)*
H12B	0.732 (3)	0.5230 (18)	0.533 (2)	0.069 (8)*
H12C	0.764 (3)	0.4942 (17)	0.4404 (18)	0.061 (8)*
H13A	0.946 (4)	0.408 (2)	0.699 (2)	0.081 (12)*
H13B	1.061 (3)	0.4816 (17)	0.7175 (16)	0.051 (7)*
H13C	1.122 (5)	0.379 (2)	0.709 (3)	0.111 (13)*
H14A	1.351 (3)	0.2169 (17)	0.5937 (17)	0.051 (7)*
H14B	1.449 (3)	0.3019 (16)	0.5963 (17)	0.050 (7)*
H14C	1.334 (3)	0.2751 (15)	0.4961 (19)	0.051 (7)*
H15A	0.155 (4)	0.0632 (19)	0.210 (2)	0.077 (9)*
H15B	−0.028 (3)	0.0859 (14)	0.2125 (15)	0.043 (6)*
H15C	0.091 (3)	0.0574 (17)	0.3031 (19)	0.061 (8)*
H16A	0.061 (4)	0.342 (2)	0.273 (2)	0.080 (10)*
H16B	0.087 (3)	0.4181 (16)	0.1982 (18)	0.054 (7)*
H16C	0.198 (3)	0.4162 (17)	0.3017 (18)	0.054 (7)*
H17A	0.697 (3)	0.3171 (19)	0.2422 (19)	0.068 (8)*
H17B	0.521 (4)	0.341 (2)	0.181 (2)	0.080 (10)*
H17C	0.659 (3)	0.4188 (19)	0.2214 (18)	0.065 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0217 (8)	0.0216 (8)	0.0226 (9)	0.0040 (7)	0.0068 (7)	0.0048 (7)
C2	0.0253 (9)	0.0202 (8)	0.0221 (9)	−0.0011 (7)	0.0062 (7)	0.0002 (7)
C3	0.0206 (9)	0.0255 (9)	0.0230 (9)	−0.0009 (7)	0.0025 (7)	−0.0004 (7)
C4	0.0215 (9)	0.0247 (9)	0.0254 (9)	0.0042 (7)	0.0053 (7)	0.0004 (7)
C4A	0.0217 (9)	0.0229 (8)	0.0199 (9)	0.0010 (7)	0.0022 (7)	0.0001 (7)
C5	0.0224 (9)	0.0231 (9)	0.0258 (10)	0.0022 (7)	0.0031 (8)	−0.0020 (7)
C7	0.0208 (9)	0.0240 (9)	0.0251 (9)	0.0007 (7)	0.0028 (8)	−0.0003 (7)
C7A	0.0209 (9)	0.0235 (8)	0.0235 (9)	0.0039 (7)	0.0030 (7)	−0.0026 (7)
C8	0.0216 (9)	0.0265 (9)	0.0303 (10)	0.0009 (7)	0.0036 (8)	−0.0030 (8)
C9	0.0223 (9)	0.0334 (10)	0.0301 (10)	0.0039 (8)	−0.0019 (8)	−0.0079 (8)
C010	0.0214 (9)	0.0231 (8)	0.0213 (9)	0.0019 (7)	0.0030 (7)	0.0038 (7)
C10	0.0275 (10)	0.0328 (10)	0.0210 (9)	0.0094 (8)	−0.0012 (8)	−0.0018 (7)
C11	0.0274 (9)	0.0236 (9)	0.0242 (9)	0.0046 (7)	0.0057 (8)	−0.0009 (7)
C11A	0.0209 (8)	0.0247 (9)	0.0225 (9)	0.0036 (7)	0.0026 (7)	−0.0031 (7)
C12	0.0347 (11)	0.0210 (9)	0.0378 (12)	0.0045 (8)	0.0082 (10)	0.0051 (8)
C13	0.096 (2)	0.0431 (14)	0.0278 (12)	0.0129 (15)	0.0129 (14)	−0.0085 (10)
C14	0.0190 (10)	0.0484 (14)	0.0636 (17)	0.0026 (10)	0.0020 (10)	−0.0235 (13)
C15	0.0336 (12)	0.0444 (13)	0.0354 (12)	−0.0108 (10)	−0.0032 (10)	0.0043 (10)
C16	0.0464 (14)	0.0421 (13)	0.0407 (13)	0.0216 (11)	0.0011 (11)	−0.0017 (11)
C17	0.0549 (15)	0.0520 (15)	0.0411 (14)	0.0045 (13)	0.0210 (12)	0.0092 (11)
O1	0.0242 (6)	0.0209 (6)	0.0325 (7)	0.0038 (5)	0.0094 (5)	0.0018 (5)
O2	0.0312 (7)	0.0249 (6)	0.0280 (7)	−0.0021 (5)	0.0057 (6)	−0.0048 (5)
O3	0.0194 (6)	0.0333 (7)	0.0356 (8)	0.0004 (5)	0.0027 (6)	−0.0107 (6)
O6A	0.0284 (7)	0.0319 (7)	0.0321 (7)	0.0085 (6)	0.0030 (6)	0.0074 (6)
O6B	0.0325 (7)	0.0268 (7)	0.0417 (8)	−0.0047 (6)	0.0068 (6)	−0.0089 (6)
O9	0.0270 (7)	0.0386 (8)	0.0565 (10)	0.0029 (6)	−0.0158 (7)	−0.0092 (7)
O10	0.0341 (8)	0.0401 (8)	0.0274 (7)	0.0156 (6)	−0.0027 (6)	0.0025 (6)
O11	0.0375 (8)	0.0290 (7)	0.0275 (7)	0.0035 (6)	0.0067 (6)	0.0057 (5)
S6	0.0228 (2)	0.0213 (2)	0.0281 (3)	0.00192 (17)	0.00245 (18)	−0.00060 (17)

Geometric parameters (Å, º)

C1—O1	1.368 (2)	C11—C11A	1.406 (2)
C1—C2	1.398 (2)	C12—O1	1.446 (2)
C1—C010	1.408 (2)	C12—H12A	1.00 (3)
C2—O2	1.378 (2)	C12—H12B	0.96 (3)
C2—C3	1.402 (2)	C12—H12C	0.98 (3)
C3—O3	1.365 (2)	C13—O2	1.405 (3)
C3—C4	1.386 (2)	C13—H13A	0.91 (3)
C4—C4A	1.391 (2)	C13—H13B	0.97 (3)
C4—H4	0.97 (2)	C13—H13C	1.02 (4)
C4A—C010	1.400 (2)	C14—O3	1.435 (2)
C4A—C5	1.507 (2)	C14—H14A	0.98 (3)
C5—S6	1.7886 (19)	C14—H14B	0.94 (3)
C5—H5A	0.99 (2)	C14—H14C	1.07 (3)
C5—H5B	0.95 (2)	C15—O9	1.418 (3)
C7—C7A	1.497 (2)	C15—H15A	1.02 (3)
C7—S6	1.7830 (18)	C15—H15B	0.97 (2)
C7—H7A	1.00 (2)	C15—H15C	0.97 (3)
C7—H7B	0.94 (2)	C16—O10	1.433 (3)
C7A—C8	1.398 (2)	C16—H16A	1.05 (3)
C7A—C11A	1.399 (3)	C16—H16B	1.02 (3)
C8—C9	1.383 (3)	C16—H16C	0.98 (3)
C8—H8	0.98 (2)	C17—O11	1.437 (3)
C9—O9	1.372 (2)	C17—H17A	1.01 (3)
C9—C10	1.394 (3)	C17—H17B	1.00 (3)
C010—C11A	1.490 (2)	C17—H17C	0.98 (3)
C10—O10	1.381 (2)	O6A—S6	1.4425 (13)
C10—C11	1.397 (3)	O6B—S6	1.4472 (13)
C11—O11	1.378 (2)
O1—C1—C2	121.41 (15)	O1—C12—H12A	108.0 (16)
O1—C1—C010	118.02 (15)	O1—C12—H12B	108.4 (17)
C2—C1—C010	120.39 (16)	H12A—C12—H12B	107 (2)
O2—C2—C1	119.35 (15)	O1—C12—H12C	111.8 (15)
O2—C2—C3	120.41 (15)	H12A—C12—H12C	110 (2)
C1—C2—C3	120.24 (15)	H12B—C12—H12C	111 (2)
O3—C3—C4	124.29 (16)	O2—C13—H13A	105 (2)
O3—C3—C2	116.03 (15)	O2—C13—H13B	109.6 (14)
C4—C3—C2	119.65 (16)	H13A—C13—H13B	105 (3)
C3—C4—C4A	119.92 (16)	O2—C13—H13C	112 (2)
C3—C4—H4	119.8 (11)	H13A—C13—H13C	109 (3)
C4A—C4—H4	120.2 (11)	H13B—C13—H13C	115 (3)
C4—C4A—C010	121.60 (16)	O3—C14—H14A	108.3 (15)
C4—C4A—C5	118.22 (16)	O3—C14—H14B	106.9 (15)
C010—C4A—C5	120.18 (15)	H14A—C14—H14B	108 (2)
C4A—C5—S6	112.05 (13)	O3—C14—H14C	108.0 (13)
C4A—C5—H5A	113.0 (11)	H14A—C14—H14C	115 (2)
S6—C5—H5A	104.1 (11)	H14B—C14—H14C	110 (2)
C4A—C5—H5B	114.2 (12)	O9—C15—H15A	104.7 (17)
S6—C5—H5B	103.2 (12)	O9—C15—H15B	106.7 (13)
H5A—C5—H5B	109.4 (16)	H15A—C15—H15B	112 (2)
C7A—C7—S6	111.40 (13)	O9—C15—H15C	111.4 (15)
C7A—C7—H7A	112.0 (11)	H15A—C15—H15C	115 (2)
S6—C7—H7A	105.0 (11)	H15B—C15—H15C	107 (2)
C7A—C7—H7B	111.6 (12)	O10—C16—H16A	112.8 (17)
S6—C7—H7B	106.6 (12)	O10—C16—H16B	108.0 (15)
H7A—C7—H7B	110.0 (17)	H16A—C16—H16B	110 (2)
C8—C7A—C11A	121.48 (16)	O10—C16—H16C	111.5 (15)
C8—C7A—C7	119.63 (16)	H16A—C16—H16C	106 (2)
C11A—C7A—C7	118.88 (15)	H16B—C16—H16C	109 (2)
C9—C8—C7A	119.83 (18)	O11—C17—H17A	109.2 (16)
C9—C8—H8	120.3 (13)	O11—C17—H17B	109.6 (18)
C7A—C8—H8	119.8 (13)	H17A—C17—H17B	106 (2)
O9—C9—C8	123.73 (18)	O11—C17—H17C	107.9 (17)
O9—C9—C10	116.37 (17)	H17A—C17—H17C	108 (2)
C8—C9—C10	119.87 (17)	H17B—C17—H17C	116 (2)
C4A—C010—C1	118.05 (15)	C1—O1—C12	116.14 (14)
C4A—C010—C11A	120.24 (15)	C2—O2—C13	114.13 (16)
C1—C010—C11A	121.62 (15)	C3—O3—C14	115.84 (15)
O10—C10—C9	120.51 (16)	C9—O9—C15	117.77 (16)
O10—C10—C11	119.31 (17)	C10—O10—C16	112.08 (16)
C9—C10—C11	120.14 (16)	C11—O11—C17	113.04 (17)
O11—C11—C10	119.65 (16)	O6A—S6—O6B	117.37 (8)
O11—C11—C11A	119.53 (16)	O6A—S6—C7	107.69 (8)
C10—C11—C11A	120.82 (17)	O6B—S6—C7	109.37 (9)
C7A—C11A—C11	117.76 (16)	O6A—S6—C5	110.55 (9)
C7A—C11A—C010	120.25 (15)	O6B—S6—C5	108.15 (9)
C11—C11A—C010	121.93 (16)	C7—S6—C5	102.71 (9)
O1—C1—C2—O2	−3.4 (2)	C9—C10—C11—O11	177.56 (17)
C010—C1—C2—O2	−178.37 (15)	O10—C10—C11—C11A	179.73 (16)
O1—C1—C2—C3	177.05 (16)	C9—C10—C11—C11A	−2.4 (3)
C010—C1—C2—C3	2.1 (3)	C8—C7A—C11A—C11	2.8 (3)
O2—C2—C3—O3	−1.3 (2)	C7—C7A—C11A—C11	−176.87 (16)
C1—C2—C3—O3	178.30 (15)	C8—C7A—C11A—C010	−174.35 (16)
O2—C2—C3—C4	176.85 (16)	C7—C7A—C11A—C010	6.0 (2)
C1—C2—C3—C4	−3.6 (3)	O11—C11—C11A—C7A	179.69 (16)
O3—C3—C4—C4A	179.51 (17)	C10—C11—C11A—C7A	−0.3 (3)
C2—C3—C4—C4A	1.6 (3)	O11—C11—C11A—C010	−3.2 (3)
C3—C4—C4A—C010	2.0 (3)	C10—C11—C11A—C010	176.77 (17)
C3—C4—C4A—C5	−177.24 (16)	C4A—C010—C11A—C7A	54.9 (2)
C4—C4A—C5—S6	104.21 (17)	C1—C010—C11A—C7A	−121.53 (19)
C010—C4A—C5—S6	−75.08 (19)	C4A—C010—C11A—C11	−122.14 (19)
S6—C7—C7A—C8	99.79 (18)	C1—C010—C11A—C11	61.4 (2)
S6—C7—C7A—C11A	−80.52 (18)	C2—C1—O1—C12	57.4 (2)
C11A—C7A—C8—C9	−2.5 (3)	C010—C1—O1—C12	−127.54 (17)
C7—C7A—C8—C9	177.14 (17)	C1—C2—O2—C13	106.9 (2)
C7A—C8—C9—O9	−178.22 (18)	C3—C2—O2—C13	−73.5 (3)
C7A—C8—C9—C10	−0.3 (3)	C4—C3—O3—C14	14.4 (3)
C4—C4A—C010—C1	−3.5 (3)	C2—C3—O3—C14	−167.5 (2)
C5—C4A—C010—C1	175.74 (15)	C8—C9—O9—C15	−31.5 (3)
C4—C4A—C010—C11A	179.91 (16)	C10—C9—O9—C15	150.5 (2)
C5—C4A—C010—C11A	−0.8 (3)	C9—C10—O10—C16	81.1 (2)
O1—C1—C010—C4A	−173.71 (15)	C11—C10—O10—C16	−101.1 (2)
C2—C1—C010—C4A	1.5 (3)	C10—C11—O11—C17	−78.3 (2)
O1—C1—C010—C11A	2.8 (2)	C11A—C11—O11—C17	101.7 (2)
C2—C1—C010—C11A	177.97 (16)	C7A—C7—S6—O6A	161.07 (12)
O9—C9—C10—O10	−1.4 (3)	C7A—C7—S6—O6B	−70.34 (15)
C8—C9—C10—O10	−179.44 (17)	C7A—C7—S6—C5	44.36 (15)
O9—C9—C10—C11	−179.20 (17)	C4A—C5—S6—O6A	−70.03 (14)
C8—C9—C10—C11	2.7 (3)	C4A—C5—S6—O6B	160.20 (12)
O10—C10—C11—O11	−0.3 (3)	C4A—C5—S6—C7	44.62 (15)

 

Footnotes

¹Supplementary data for this paper are available from the IUCr electronic archives (Reference: SX5028 ). Services for accessing these data are described at the back of the journal.