13,13a-Di­hydro-13-methoxy-9-methyl-1-benzo­pyrano­[4,3-i]­dinaphtho­[2,1-c;1',2'-f]-2,8-dioxa­bicyclo­[3.3.1]­nonane

The crystal structure of the title compound, C₃₂H₂₄O₄, contains three fused di­hydro­pyran rings (A, B and C); ring A is fused with a benzene ring while the other two rings, B and C, are fused with naphthalene rings. Ring A adopts a half-chair conformation with an equatorial methoxy group, whereas ring B assumes a distorted half-chair conformation, the A/B ring junction being trans. Ring C adopts a distorted half-boat conformation and is nearly orthogonal to ring B. Ring C is inclined to the best plane of ring A at an angle of 112.1 (1)°.

S1. Comment

Recently, some coumarin-based inhibitors of HIV-integrase (Zhao et al., 1997) have been synthesized which have some structural resemblance to the compounds obtained by the reaction of β-naphthol with simple aldehydes (Sirkecioglue et al., 1995), and by the reaction of 4-hydroxycoumarins with vinyl acetate (Balasubramanian et al., 1996) and with isatin (Jain et al., 1997). The synthesis of an analogous chromone-based compound by reacting 6-methyl-4-oxo-4H-1-benzopyran-3-carboxaldehyde with β-naphthol was attempted. The present study has revealed that the structure of the compound as determined by spectroscopic analysis and reported earlier (Bandyopadhyay & Sur, 2000) was erroneous. Here we describe the actual structure of the compound, (I), as determined by X-ray crystal structure analysis. \sch

The compound contains three fused dihydropyran rings. Two of these dihydropyran rings (B and C) are attached to naphthalene rings and the third (A) is attached to a benzene ring. According to ring puckering parameters [Q = 0.480 (2) Å, ϕ = −92.8 (4)°, θ = 131.3 (3)°] (Cremer & Pople, 1975) and ring torsion angles (Nashipuri, 1991) (Table 1), the dihydropyran ring A adopts a half-chair conformation with atoms C13 and C13A out of the best plane containing the remaining atoms by 0.346 (3) Å and −0.390 (3) Å, respectively. The asymmetry parameter (Nardelli, 1983) ΔC₂(C13—C13A) = 0.008 (1) also reveals the half-chair conformation with a twofold pseudoaxis passing through the midpoints of the C13—C13A and C7B—C11A bonds. The best plane through the fused dihydropyran ring forms a dihedral angle of 5.1 (1)° with the benzene ring.

The half-chair conformation of ring B (O20,C19A,C13C,C13B,C13A,C7A) is evident from the ring puckering parameters [Q = 0.544 (2) Å, ϕ = −101.5 (3)°, θ = 49.0 (2)°] and also from the torsion angles (Table 1). The asymmetry parameter ΔC₂(C13C—C19A) = 0.043 (1) indicates the presence of a twofold pseudoaxis passing through the midpoints of C13C– C19A and C7A—C13A bonds. The fused naphthalene ring makes a dihedral angle of 5.2 (1)° with the best plane through ring B.

Ring C adopts a distorted half-boat conformation [ring puckering parameters: Q = 0.556 (2) Å, ϕ = 147.0 (2)°, θ = 56.7 (2)°]. The atoms C13A and C7A are out of the best plane passing through the remaining atoms of the ring by −0.938 (3) Å and −0.375 (3) Å, respectively. The asymmetry parameter ΔC₂(O7—C6A) = 0.013 (1) indicates the presence of the twofold pseudoaxis across the O7—C6A and C13A—C13B bonds.

The torsion angle C7B—C7A—C13A—C13B of 171.2 (1)° indicates that the A/B ring junction is trans. The angles between the best planes through rings A and B, rings B and C, and rings A and C are 18.0 (1), 94.1 (1) and 112.1 (1)°, respectively.

S2. Experimental

To a stirred solution of β-naphthol (8 mmoles) in glacial acetic acid (10 ml) at 333–353 K, concentrated HCl (1 ml) was added dropwise. The mixture was stirred at that temperature for 15 min. A solution of 6-methyl-4-oxo-4H-1-benzopyran-3-carboxaldehyde in glacial acetic acid (8 ml) was added dropwise to the reaction mixture which gradually turned red. The deep red solution solidified on stirring at 333–353 K within 1 h. The whole mass was poured into crushed ice (200 g). The solid obtained was filtered, washed with water, dried in air, and digested with chloroform. The major red insoluble mass obtained after the chloroform extraction was digested with methanol. The methanolic solution produced a white crystalline compound, (I), in more than 50% yield. The compound was recrystallized by slow evaporation at room temperature from a solution in an ethanol/chloroform mixture.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and PARST93 (Nardelli, 1993).

Figures

Fig. 1. Molecular structure showing 30% probability displacement ellipsoids (Farrugia, 1997).

13,13a-Dihydro-9-methyl-13-methoxy-1-benzopyrano[4,3-i]- dinaphtho[2,1 − c;1',2'-f]-2,8-dioxabicyclo[3,3,1]nonane

Crystal data

C32H24O4	F(000) = 496
Mr = 472.51	Dx = 1.316 Mg m^−3
Triclinic, P1	Melting point: 248° K
a = 10.191 (7) Å	Cu Kα radiation, λ = 1.54180 Å
b = 10.963 (10) Å	Cell parameters from 25 reflections
c = 12.6210 (11) Å	θ = 15–20°
α = 102.23 (6)°	µ = 0.69 mm^−1
β = 114.58 (3)°	T = 293 K
γ = 100.64 (6)°	Irregular, colourless
V = 1192.7 (14) Å^3	0.35 × 0.27 × 0.23 mm
Z = 2

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.000
Radiation source: fine-focus sealed tube	θmax = 70.0°, θmin = 4.1°
Graphite monochromator	h = −12→11
ω–2θ scans	k = 0→13
4396 measured reflections	l = −15→15
4396 independent reflections	2 standard reflections every 60 min
3505 reflections with I > 2σ(I)	intensity decay: 0.3

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)] = 0.050	H-atom parameters constrained
wR(F^2) = 0.151	w = 1/[σ^2(Fo^2) + (0.0968P)^2 + 0.1715P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.030
4396 reflections	Δρmax = 0.21 e Å^−3
328 parameters	Δρmin = −0.22 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0060 (19)

Special details

Experimental. θ scan width (1.2 + 1.4θ)°

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	0.5534 (2)	0.91517 (18)	0.67123 (17)	0.0516 (4)
H1	0.5883	0.8592	0.6307	0.062*
C2	0.5695 (2)	1.03949 (19)	0.66477 (19)	0.0610 (5)
H2	0.6148	1.0665	0.6197	0.073*
C3	0.5188 (2)	1.12687 (19)	0.7250 (2)	0.0665 (6)
H3	0.5314	1.2115	0.7205	0.080*
C4	0.4515 (2)	1.08757 (18)	0.7897 (2)	0.0598 (5)
H4	0.4190	1.1463	0.8300	0.072*
C4A	0.42937 (19)	0.95886 (16)	0.79740 (16)	0.0476 (4)
C5	0.3493 (2)	0.91408 (17)	0.85679 (16)	0.0518 (4)
H5	0.3207	0.9731	0.9009	0.062*
C6	0.3131 (2)	0.78666 (17)	0.85089 (15)	0.0496 (4)
H6	0.2537	0.7572	0.8852	0.060*
C6A	0.36634 (19)	0.69919 (16)	0.79228 (14)	0.0429 (4)
C6B	0.45968 (18)	0.74027 (15)	0.74465 (14)	0.0406 (4)
C6C	0.48445 (18)	0.87000 (15)	0.73863 (14)	0.0426 (4)
O7	0.31670 (15)	0.57111 (11)	0.78547 (11)	0.0509 (3)
C7A	0.3403 (2)	0.46687 (16)	0.71026 (15)	0.0445 (4)
C7B	0.1969 (2)	0.35453 (17)	0.64277 (16)	0.0484 (4)
C8	0.1518 (2)	0.27384 (17)	0.70107 (18)	0.0520 (4)
H8	0.2111	0.2926	0.7853	0.062*
C9	0.0222 (2)	0.16700 (19)	0.6382 (2)	0.0595 (5)
C10	−0.0663 (2)	0.1436 (2)	0.5130 (2)	0.0664 (6)
H10	−0.1549	0.0731	0.4689	0.080*
C11	−0.0264 (2)	0.2219 (2)	0.4528 (2)	0.0671 (6)
H11	−0.0885	0.2046	0.3692	0.080*
C11A	0.1061 (2)	0.32665 (18)	0.51627 (17)	0.0552 (5)
O12	0.14453 (17)	0.39520 (13)	0.44872 (12)	0.0667 (4)
C13	0.2582 (2)	0.52019 (17)	0.51599 (15)	0.0475 (4)
H13	0.2160	0.5851	0.5451	0.057*
C13A	0.39196 (19)	0.51037 (16)	0.62346 (14)	0.0436 (4)
H13A	0.4303	0.4436	0.5917	0.052*
C13B	0.52295 (19)	0.63722 (16)	0.69998 (14)	0.0421 (4)
H13B	0.5673	0.6651	0.6502	0.050*
C13C	0.64161 (19)	0.61160 (16)	0.80950 (14)	0.0421 (4)
C13D	0.79745 (19)	0.69091 (16)	0.87501 (15)	0.0443 (4)
C14	0.8556 (2)	0.79546 (19)	0.84275 (18)	0.0554 (5)
H14	0.7909	0.8147	0.7752	0.066*
C15	1.0043 (2)	0.8693 (2)	0.9079 (2)	0.0621 (5)
H15	1.0389	0.9381	0.8845	0.075*
C16	1.1061 (2)	0.8433 (2)	1.00995 (19)	0.0604 (5)
H16	1.2070	0.8951	1.0548	0.072*
C17	1.0552 (2)	0.7416 (2)	1.04213 (17)	0.0572 (5)
H17	1.1231	0.7229	1.1085	0.069*
C17A	0.9016 (2)	0.66299 (18)	0.97767 (16)	0.0497 (4)
C18	0.8483 (2)	0.55849 (19)	1.01279 (17)	0.0574 (5)
H18	0.9156	0.5405	1.0799	0.069*
C19	0.7017 (2)	0.48430 (18)	0.95103 (17)	0.0552 (5)
H19	0.6684	0.4157	0.9754	0.066*
C19A	0.5988 (2)	0.51136 (16)	0.84899 (15)	0.0463 (4)
O20	0.45309 (14)	0.42633 (11)	0.79345 (11)	0.0508 (3)
O21	0.30724 (15)	0.55631 (13)	0.43687 (11)	0.0571 (4)
C22	0.1957 (3)	0.5867 (3)	0.33994 (19)	0.0730 (6)
H22A	0.2398	0.6193	0.2935	0.109*
H22B	0.1611	0.6522	0.3747	0.109*
H22C	0.1116	0.5089	0.2867	0.109*
C23	−0.0195 (3)	0.0778 (2)	0.7027 (3)	0.0790 (7)
H23A	0.0706	0.0657	0.7606	0.118*
H23B	−0.0873	−0.0056	0.6431	0.118*
H23C	−0.0683	0.1164	0.7454	0.118*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0563 (10)	0.0533 (10)	0.0468 (10)	0.0198 (8)	0.0232 (9)	0.0193 (8)
C2	0.0606 (11)	0.0573 (11)	0.0586 (12)	0.0125 (9)	0.0215 (10)	0.0257 (9)
C3	0.0663 (12)	0.0415 (10)	0.0768 (14)	0.0141 (9)	0.0203 (11)	0.0215 (9)
C4	0.0560 (11)	0.0429 (9)	0.0660 (13)	0.0178 (8)	0.0193 (10)	0.0083 (8)
C4A	0.0431 (8)	0.0421 (9)	0.0439 (9)	0.0149 (7)	0.0113 (7)	0.0060 (7)
C5	0.0522 (10)	0.0511 (10)	0.0465 (10)	0.0217 (8)	0.0221 (8)	0.0031 (7)
C6	0.0519 (10)	0.0567 (10)	0.0408 (9)	0.0204 (8)	0.0239 (8)	0.0096 (7)
C6A	0.0517 (9)	0.0453 (9)	0.0318 (8)	0.0187 (7)	0.0185 (7)	0.0118 (6)
C6B	0.0474 (9)	0.0455 (8)	0.0295 (8)	0.0198 (7)	0.0165 (7)	0.0118 (6)
C6C	0.0427 (8)	0.0434 (8)	0.0346 (8)	0.0156 (7)	0.0124 (7)	0.0099 (6)
O7	0.0740 (8)	0.0460 (7)	0.0442 (7)	0.0215 (6)	0.0369 (6)	0.0149 (5)
C7A	0.0561 (10)	0.0440 (9)	0.0351 (8)	0.0231 (7)	0.0192 (8)	0.0141 (7)
C7B	0.0549 (10)	0.0460 (9)	0.0435 (10)	0.0222 (8)	0.0208 (8)	0.0121 (7)
C8	0.0590 (10)	0.0511 (10)	0.0520 (10)	0.0230 (8)	0.0299 (9)	0.0151 (8)
C9	0.0625 (11)	0.0527 (10)	0.0712 (13)	0.0231 (9)	0.0393 (11)	0.0143 (9)
C10	0.0599 (12)	0.0531 (11)	0.0715 (14)	0.0133 (9)	0.0259 (11)	0.0067 (10)
C11	0.0661 (12)	0.0594 (12)	0.0517 (12)	0.0175 (10)	0.0128 (10)	0.0057 (9)
C11A	0.0643 (11)	0.0493 (10)	0.0449 (10)	0.0215 (9)	0.0196 (9)	0.0115 (8)
O12	0.0794 (10)	0.0599 (8)	0.0363 (7)	0.0112 (7)	0.0114 (7)	0.0123 (6)
C13	0.0603 (10)	0.0508 (9)	0.0346 (9)	0.0253 (8)	0.0222 (8)	0.0134 (7)
C13A	0.0555 (10)	0.0462 (9)	0.0347 (8)	0.0259 (7)	0.0222 (8)	0.0126 (7)
C13B	0.0531 (9)	0.0486 (9)	0.0351 (8)	0.0260 (8)	0.0244 (8)	0.0176 (7)
C13C	0.0513 (9)	0.0479 (9)	0.0332 (8)	0.0246 (7)	0.0215 (7)	0.0131 (7)
C13D	0.0525 (9)	0.0501 (9)	0.0380 (9)	0.0269 (8)	0.0251 (8)	0.0117 (7)
C14	0.0541 (10)	0.0683 (12)	0.0547 (11)	0.0254 (9)	0.0306 (9)	0.0246 (9)
C15	0.0571 (11)	0.0738 (13)	0.0667 (13)	0.0222 (10)	0.0361 (10)	0.0280 (10)
C16	0.0495 (10)	0.0713 (13)	0.0574 (12)	0.0203 (9)	0.0268 (9)	0.0110 (9)
C17	0.0543 (10)	0.0683 (12)	0.0440 (10)	0.0267 (9)	0.0187 (9)	0.0116 (9)
C17A	0.0546 (10)	0.0553 (10)	0.0386 (9)	0.0264 (8)	0.0204 (8)	0.0097 (7)
C18	0.0615 (11)	0.0609 (11)	0.0408 (10)	0.0260 (9)	0.0127 (9)	0.0176 (8)
C19	0.0682 (12)	0.0531 (10)	0.0432 (10)	0.0240 (9)	0.0200 (9)	0.0223 (8)
C19A	0.0544 (10)	0.0462 (9)	0.0379 (9)	0.0211 (8)	0.0196 (8)	0.0131 (7)
O20	0.0558 (7)	0.0487 (7)	0.0436 (7)	0.0181 (6)	0.0161 (6)	0.0208 (5)
O21	0.0710 (8)	0.0784 (9)	0.0373 (7)	0.0395 (7)	0.0290 (6)	0.0264 (6)
C22	0.0953 (16)	0.1011 (17)	0.0489 (12)	0.0591 (14)	0.0371 (12)	0.0426 (11)
C23	0.0875 (16)	0.0661 (13)	0.0949 (18)	0.0158 (12)	0.0589 (15)	0.0215 (12)

Geometric parameters (Å, º)

C1—C2	1.366 (3)	O12—C13	1.429 (3)
C1—C6C	1.418 (2)	C13—O21	1.383 (2)
C1—H1	0.9300	C13—C13A	1.512 (2)
C2—C3	1.401 (3)	C13—H13	0.9800
C2—H2	0.9300	C13A—C13B	1.524 (3)
C3—C4	1.352 (3)	C13A—H13A	0.9800
C3—H3	0.9300	C13B—C13C	1.533 (2)
C4—C4A	1.418 (3)	C13B—H13B	0.9800
C4—H4	0.9300	C13C—C19A	1.372 (3)
C4A—C5	1.409 (3)	C13C—C13D	1.434 (3)
C4A—C6C	1.434 (2)	C13D—C14	1.406 (3)
C5—C6	1.355 (3)	C13D—C17A	1.429 (2)
C5—H5	0.9300	C14—C15	1.362 (3)
C6—C6A	1.409 (2)	C14—H14	0.9300
C6—H6	0.9300	C15—C16	1.403 (3)
C6A—O7	1.373 (2)	C15—H15	0.9300
C6A—C6B	1.379 (2)	C16—C17	1.353 (3)
C6B—C6C	1.422 (3)	C16—H16	0.9300
C6B—C13B	1.520 (2)	C17—C17A	1.414 (3)
O7—C7A	1.448 (2)	C17—H17	0.9300
C7A—O20	1.416 (2)	C17A—C18	1.411 (3)
C7A—C7B	1.495 (3)	C18—C19	1.347 (3)
C7A—C13A	1.521 (2)	C18—H18	0.9300
C7B—C8	1.394 (3)	C19—C19A	1.414 (2)
C7B—C11A	1.399 (3)	C19—H19	0.9300
C8—C9	1.382 (3)	C19A—O20	1.382 (3)
C8—H8	0.9300	O21—C22	1.433 (2)
C9—C10	1.391 (3)	C22—H22A	0.9600
C9—C23	1.507 (3)	C22—H22B	0.9600
C10—C11	1.371 (3)	C22—H22C	0.9600
C10—H10	0.9300	C23—H23A	0.9600
C11—C11A	1.386 (3)	C23—H23B	0.9600
C11—H11	0.9300	C23—H23C	0.9600
C11A—O12	1.373 (2)
C2—C1—C6C	121.21 (18)	O21—C13—H13	110.3
C2—C1—H1	119.4	O12—C13—H13	110.3
C6C—C1—H1	119.4	C13A—C13—H13	110.3
C1—C2—C3	121.1 (2)	C13—C13A—C7A	109.47 (15)
C1—C2—H2	119.5	C13—C13A—C13B	115.12 (15)
C3—C2—H2	119.5	C7A—C13A—C13B	107.00 (14)
C4—C3—C2	119.69 (18)	C13—C13A—H13A	108.4
C4—C3—H3	120.2	C7A—C13A—H13A	108.4
C2—C3—H3	120.2	C13B—C13A—H13A	108.4
C3—C4—C4A	121.55 (19)	C6B—C13B—C13A	107.35 (15)
C3—C4—H4	119.2	C6B—C13B—C13C	110.42 (13)
C4A—C4—H4	119.2	C13A—C13B—C13C	107.80 (14)
C5—C4A—C4	121.85 (17)	C6B—C13B—H13B	110.4
C5—C4A—C6C	119.05 (16)	C13A—C13B—H13B	110.4
C4—C4A—C6C	119.04 (18)	C13C—C13B—H13B	110.4
C6—C5—C4A	121.23 (16)	C19A—C13C—C13D	117.98 (16)
C6—C5—H5	119.4	C19A—C13C—C13B	119.76 (17)
C4A—C5—H5	119.4	C13D—C13C—C13B	122.24 (15)
C5—C6—C6A	119.47 (17)	C14—C13D—C17A	117.27 (18)
C5—C6—H6	120.3	C14—C13D—C13C	123.37 (17)
C6A—C6—H6	120.3	C17A—C13D—C13C	119.35 (17)
O7—C6A—C6B	123.19 (15)	C15—C14—C13D	121.63 (19)
O7—C6A—C6	114.85 (16)	C15—C14—H14	119.2
C6B—C6A—C6	121.96 (16)	C13D—C14—H14	119.2
C6A—C6B—C6C	118.56 (15)	C14—C15—C16	121.1 (2)
C6A—C6B—C13B	114.89 (15)	C14—C15—H15	119.4
C6C—C6B—C13B	126.53 (15)	C16—C15—H15	119.4
C1—C6C—C6B	123.57 (16)	C17—C16—C15	119.0 (2)
C1—C6C—C4A	117.41 (16)	C17—C16—H16	120.5
C6B—C6C—C4A	118.92 (16)	C15—C16—H16	120.5
C6A—O7—C7A	121.06 (13)	C16—C17—C17A	121.80 (19)
O20—C7A—O7	105.96 (14)	C16—C17—H17	119.1
O20—C7A—C7B	107.79 (15)	C17A—C17—H17	119.1
O7—C7A—C7B	107.91 (15)	C18—C17A—C17	121.69 (18)
O20—C7A—C13A	109.80 (14)	C18—C17A—C13D	119.14 (18)
O7—C7A—C13A	112.98 (14)	C17—C17A—C13D	119.16 (18)
C7B—C7A—C13A	112.09 (15)	C19—C18—C17A	121.30 (18)
C8—C7B—C11A	118.47 (19)	C19—C18—H18	119.3
C8—C7B—C7A	122.14 (17)	C17A—C18—H18	119.3
C11A—C7B—C7A	119.37 (17)	C18—C19—C19A	119.58 (18)
C9—C8—C7B	122.36 (19)	C18—C19—H19	120.2
C9—C8—H8	118.8	C19A—C19—H19	120.2
C7B—C8—H8	118.8	C13C—C19A—O20	124.07 (16)
C8—C9—C10	117.5 (2)	C13C—C19A—C19	122.64 (18)
C8—C9—C23	121.1 (2)	O20—C19A—C19	113.29 (16)
C10—C9—C23	121.4 (2)	C19A—O20—C7A	115.02 (14)
C11—C10—C9	121.8 (2)	C13—O21—C22	113.59 (15)
C11—C10—H10	119.1	O21—C22—H22A	109.5
C9—C10—H10	119.1	O21—C22—H22B	109.5
C10—C11—C11A	120.2 (2)	H22A—C22—H22B	109.5
C10—C11—H11	119.9	O21—C22—H22C	109.5
C11A—C11—H11	119.9	H22A—C22—H22C	109.5
O12—C11A—C11	117.12 (18)	H22B—C22—H22C	109.5
O12—C11A—C7B	123.13 (19)	C9—C23—H23A	109.5
C11—C11A—C7B	119.7 (2)	C9—C23—H23B	109.5
C11A—O12—C13	116.80 (15)	H23A—C23—H23B	109.5
O21—C13—O12	107.24 (15)	C9—C23—H23C	109.5
O21—C13—C13A	108.34 (15)	H23A—C23—H23C	109.5
O12—C13—C13A	110.36 (16)	H23B—C23—H23C	109.5
C6C—C1—C2—C3	0.2 (3)	O12—C13—C13A—C7A	−61.24 (18)
C1—C2—C3—C4	−0.6 (3)	O21—C13—C13A—C13B	61.09 (18)
C2—C3—C4—C4A	−0.6 (3)	O12—C13—C13A—C13B	178.22 (13)
C3—C4—C4A—C5	−175.14 (19)	O20—C7A—C13A—C13	165.64 (13)
C3—C4—C4A—C6C	2.2 (3)	O7—C7A—C13A—C13	−76.32 (19)
C4—C4A—C5—C6	171.98 (17)	C7B—C7A—C13A—C13	45.86 (18)
C6C—C4A—C5—C6	−5.3 (3)	O20—C7A—C13A—C13B	−69.00 (17)
C4A—C5—C6—C6A	4.9 (3)	O7—C7A—C13A—C13B	49.05 (18)
C5—C6—C6A—O7	−176.66 (15)	C7B—C7A—C13A—C13B	171.22 (12)
C5—C6—C6A—C6B	2.7 (3)	C6A—C6B—C13B—C13A	46.13 (18)
O7—C6A—C6B—C6C	169.90 (15)	C6C—C6B—C13B—C13A	−132.09 (17)
C6—C6A—C6B—C6C	−9.4 (2)	C6A—C6B—C13B—C13C	−71.13 (19)
O7—C6A—C6B—C13B	−8.5 (2)	C6C—C6B—C13B—C13C	110.65 (19)
C6—C6A—C6B—C13B	172.28 (15)	C13—C13A—C13B—C6B	56.68 (17)
C2—C1—C6C—C6B	177.56 (17)	C7A—C13A—C13B—C6B	−65.20 (15)
C2—C1—C6C—C4A	1.3 (3)	C13—C13A—C13B—C13C	175.65 (13)
C6A—C6B—C6C—C1	−167.59 (16)	C7A—C13A—C13B—C13C	53.76 (16)
C13B—C6B—C6C—C1	10.6 (3)	C6B—C13B—C13C—C19A	93.70 (19)
C6A—C6B—C6C—C4A	8.6 (2)	C13A—C13B—C13C—C19A	−23.28 (19)
C13B—C6B—C6C—C4A	−173.26 (14)	C6B—C13B—C13C—C13D	−85.02 (19)
C5—C4A—C6C—C1	174.90 (16)	C13A—C13B—C13C—C13D	158.00 (14)
C4—C4A—C6C—C1	−2.5 (2)	C19A—C13C—C13D—C14	179.29 (15)
C5—C4A—C6C—C6B	−1.5 (2)	C13B—C13C—C13D—C14	−2.0 (2)
C4—C4A—C6C—C6B	−178.88 (15)	C19A—C13C—C13D—C17A	0.2 (2)
C6B—C6A—O7—C7A	−9.9 (2)	C13B—C13C—C13D—C17A	178.92 (13)
C6—C6A—O7—C7A	169.42 (14)	C17A—C13D—C14—C15	−1.4 (3)
C6A—O7—C7A—O20	108.17 (17)	C13C—C13D—C14—C15	179.48 (16)
C6A—O7—C7A—C7B	−136.59 (15)	C13D—C14—C15—C16	0.4 (3)
C6A—O7—C7A—C13A	−12.1 (2)	C14—C15—C16—C17	1.1 (3)
O20—C7A—C7B—C8	39.7 (2)	C15—C16—C17—C17A	−1.6 (3)
O7—C7A—C7B—C8	−74.28 (19)	C16—C17—C17A—C18	−178.82 (17)
C13A—C7A—C7B—C8	160.69 (15)	C16—C17—C17A—C13D	0.6 (3)
O20—C7A—C7B—C11A	−138.60 (16)	C14—C13D—C17A—C18	−179.67 (15)
O7—C7A—C7B—C11A	107.37 (18)	C13C—C13D—C17A—C18	−0.5 (2)
C13A—C7A—C7B—C11A	−17.7 (2)	C14—C13D—C17A—C17	0.9 (2)
C11A—C7B—C8—C9	0.8 (3)	C13C—C13D—C17A—C17	−179.91 (14)
C7A—C7B—C8—C9	−177.58 (15)	C17—C17A—C18—C19	179.84 (17)
C7B—C8—C9—C10	−1.7 (3)	C13D—C17A—C18—C19	0.5 (3)
C7B—C8—C9—C23	176.99 (17)	C17A—C18—C19—C19A	−0.1 (3)
C8—C9—C10—C11	0.9 (3)	C13D—C13C—C19A—O20	−179.04 (13)
C23—C9—C10—C11	−177.80 (19)	C13B—C13C—C19A—O20	2.2 (2)
C9—C10—C11—C11A	0.8 (3)	C13D—C13C—C19A—C19	0.2 (2)
C10—C11—C11A—O12	175.51 (17)	C13B—C13C—C19A—C19	−178.55 (15)
C10—C11—C11A—C7B	−1.8 (3)	C18—C19—C19A—C13C	−0.3 (3)
C8—C7B—C11A—O12	−176.13 (16)	C18—C19—C19A—O20	179.05 (16)
C7A—C7B—C11A—O12	2.3 (3)	C13C—C19A—O20—C7A	−14.6 (2)
C8—C7B—C11A—C11	1.0 (3)	C19—C19A—O20—C7A	166.11 (14)
C7A—C7B—C11A—C11	179.42 (17)	O7—C7A—O20—C19A	−74.65 (18)
C11—C11A—O12—C13	165.15 (16)	C7B—C7A—O20—C19A	170.03 (13)
C7B—C11A—O12—C13	−17.6 (3)	C13A—C7A—O20—C19A	47.67 (18)
C11A—O12—C13—O21	164.91 (15)	O12—C13—O21—C22	69.1 (2)
C11A—O12—C13—C13A	47.1 (2)	C13A—C13—O21—C22	−171.78 (15)
O21—C13—C13A—C7A	−178.37 (13)