(1SR,2SR,3SR,4RS,5RS,6RS,7SR,8RS)-7,8-Dichloro­bicyclo­[4.2.0]octa-2,3,4,5-tetrayl tetra­acetate

In the title compound, C₁₆H₂₀Cl₂O₈, the bicyclic system contains a central non-planar cyclo­hexane ring which is fused to a cyclo­butane moiety. The cyclo­hexane ring has a chair conformation and the whole system adopts a syn conformation. The structure provides information on the stereochemical course of the chlorination, photo-oxidation and hydrox­ylation steps of the reaction.

S1. Comment

Carbohydrates are densely functionalized molecules and, as a result, their synthesis often requires many reaction steps, usually including the manipulation of different protecting groups. There are many synthetic strategies leading to the various conduritol isomers and their derivatives (Gültekin et al., 2004). We have previously used a photo-oxygenation reaction to introduce two oxygen functionalities in the 1,4-positions of the appropriate dienes, followed by cleavage of the peroxide linkage (Sütbeyaz et al., 1990; Seçen et al., 1990, 1992, 1993; Salamci et al., 1997; Kara & Balci, 2003). cis-Dichlorobicyclooctadiene, (1), was synthesized as described in the literature (Gözel et al., 1991). Photooxidation of (1) with singlet oxygen gave the expected endoperoxide, (2) (see scheme) (Reppe et al., 1948). Reduction of the peroxide bond in (2) was performed with thiourea under very mild conditions to give the diol, (3a) (Kelebekli et al., 2005; Balci, 1981). For further proof of the structure, (3a) was converted into the corresponding diacetate, (3 b), which was fully characterized by spectroscopic methods. cis-Hydroxylation of (3b) with KMnO4 at 263 K gave a mixture of diols (4a) and (5a) in a ratio of 1:1. These were converted into the tetraacetate derivatives, (4b) and (5b), which were separated by fractional crystallization from hexane–CH₂Cl₂. The title compound, isomer (4b), crystallized out first (Kelebekli et al., 2005). The exact configuration of compound (4b) has now been determined by X-ray diffraction analysis. The structure provides information on the stereochemical course of the chlorination, photo-oxidation and hydroxylation of the reaction.

Compound (4b) crystallizes in space group P1, with Z = 2. It contains a central non-planar cyclohexane ring with a cyclobutane fused to it. Each C atom is tetrahedral. The all-cis stereochemistry of the four acetate groups was determined unequivocally. The same cis stereochemistry was also seen in the dibromotetraacetate compound (Kara et al., 1994), but there the Br atoms had a trans conformation.

All the substituents, including the acetoxy and chloro groups, are on the same side of the bicycle (syn conformation). In addition to this, the Cl atoms have cis stereochemistry. The six-membered ring adopts a chair conformation, with puckering parameters (Cremer & Pople, 1975) Q_T = 0.525 (2) Å, θ = 151.1 (2)° and ϕ = 185.7 (5)° (Fig. 1).

The cyclobutane moiety is appreciably distorted, with C—C distances in the range 1.534 (3)–1.567 (3) Å. The strong electronegativity of the Cl atoms along the C3—C7—Cl1 and C4—C8—Cl2 chains causes elongation of the C3—C4 bond.

Intermolecular C—H···O hydrogen bonds between cyclohexane H atoms of the cyclic system and the acetyl O atom are effective in determining the molecular conformation of (4b) [C2···O8ⁱ = 3.279 (2) Å and C8···O8ⁱ = 3.339 (3) Å; symmetry code: (i) 1 − x, 1 − y, 1 − z]. The molecules are elongated approximately parallel to the (001) plane and are stacked approximately along the a direction (Fig.2).

S2. Experimental

1R(S),2S(R),3S(R),4R(S),5R(S),6S(R)-3,4-Dichloro-7,8-dioxatricyclo[4.2.2.0^2,5]-dec-9-ene, (2) (Gözel et al., 1991), was prepared as follows. To a stirred solution of the dichlorodiene (1) (Reppe et al., 1948) (3.0 g, 17 mmol) in CCl₄ (100 ml) was added tetraphenylporphyrin (TPP; 30 mg). The resulting mixture was irradiated with a projection lamp (500 W) while oxygen was passed through the solution, and the mixture was stirred at room temperature for 8 h. Evaporation of the solvent (303 K, 20 mm H g; 1 mm H g = 133.322 Pa) and chromatography of the residue on a silica-gel column (50 g) eluted with hexane–CH₂Cl₂ (1:1) gave pure endoperoxide, (2) (2.67 g, 75%, m.p. 364–365 K). The compound was recrystallized from CHCl₃–hexane (Ratio?). Analysis, found: C 46.17, H 3.95%; C₁₆H₂₀Cl₂O₈ requires: C 46.41, H 3.89%. Spectroscopic analysis: IR (KBr, ν_max, cm⁻¹): 3469, 3079, 3016, 2979, 1369, 1331, 1296, 1266, 1250, 1026, 958; ¹H NMR (200 MHz, CDCl₃, δ, p.p.m.): 6.88 (quasi dd, J = 4.4 and 1.0 Hz, 2H, C═CH), 4.90 (m, 2H, CH—O), 4.13 (d, 2H, J = 3.5 Hz, CH—Cl), 3.37 (m, 2H); ¹³C NMR (50 MHz, CDCl₃, δ, p.p.m.): 134.6, 72.9, 57.3, 45.1.

1R(S),2S(R),5R(S),6S(R),7S(R),8R(S)-7,8-Dichlorobicyclo[4.2.0]oct-3-ene-2,5-diol, (3a), was prepared as follows. To a magnetically stirred slurry of thiourea (0.44 g, 5.79 mmol) in methanol (30 ml) was added a solution of endoperoxide (2) (1.20 g, 5.79 mmol) in CHCl₃ (30 ml) at room temperature. After completion of the addition (ca 10 min), the mixture was stirred for 1 h and the solid was removed by filtration. Evaporation of the solvent gave diol (3a) (1.15 g, 95%) as a colourless oil. Spectroscopic analysis: ¹H NMR (200 MHz, CD₃OD, δ, p.p.m.): 5.81 (s, 2H, C═CH), 4.51 (dd, 2H, J = 3.0 and 1.2 Hz, CH—O), 4.11 (m, 2H, CH—Cl), 2.69 (m, 2H, CH); ¹³C NMR (50 MHz, CD₃OD, δ, p.p.m.): 134.8,68.8, 62.0, 50.9.

1R(S),2S(R),5R(S),6S(R),7S(R),8R(S)-5-(Acetyloxy)-7,8-dichlorobicyclo[4.2.0]-oct-3-en-2-yl acetate, (3b), was prepared as follows. Diol (3a) (0.81 g, 3.87 mmol) was dissolved in acetyl chloride (10 ml) and the resulting solution was stirred at room temperature overnight. The excess of unreacted acetyl chloride was evaporated (333 K, 20 mm H g). The residue was dissolved in CHCl₃ and filtered through silica gel. Evaporation of the solvent gave (3b) (1.08 g, 94%, m.p. 327–328 K). The compound was recrystallized from CHCl₃–hexane (Ratio?). Analysis, found: C 49.65, H 5.08%; C₁₂H₁₄Cl₂O₄ requires: C 49.17, H 4.81%. Spectroscopic analysis: IR (KBr, ν_max, cm⁻¹): 3020, 2969, 2935, 1731, 1434, 1373, 1234, 1029, 917, 755; ¹H NMR (200 MHz, CDCl₃, δ, p.p.m.): 5.92 (s, 2H, C═CH), 5.18 (br s, 2H, CH—O), 4.44 (d, 2H, J = 4.5 Hz, CH—Cl), 2.88 (m, 2H, CH), 2.07 (s, 6H, CH₃); ¹³C NMR (50 MHz, CDCl₃, δ, p.p.m.): 172.2, 130.9, 68.9 60.4, 46.5, 22.9.

1S(R),2S(R),3S(R),4R(S),5R(S),6R(S),7S(R),8R(S)-2,4,5-Tris(acetyloxy)-7,8-dichlorobicyclo[4.2.0]oct-3-yl acetate, (4b), and 1S(R),2S(R),3R(S),4S(R),5R(S),6R(S),7S(R),8R(S)-2,4,5-Tris(acetyloxy)-7,8-dichlorobicyclo[4.2.0]oct-3-yl acetate, (5b) (Kelebekli et al., 2005), were prepared as follows. To a stirred solution of dichlorodiacetate (3b) (0.55 g, 1.88 mmol) in EtOH (50 ml) was added a solution of KMnO₄ (0.3 g, 1.88 mmol) and MgSO₄ (0.23 g, 1.88 mmol) in water (20 ml) at 263 K over a period of 5 h. After completeion of the addition, the reaction mixture was stirred for an additional 15 h at 268 K and then filtered. The precipitate was washed several times with hot water. The combined filtrates were concentrated to 20 ml by rotary evaporation (333 K, 20 mm H g). The aqueous solution was extracted with ethyl acetate (3 × 75 ml) and the extracts were dried (Na₂SO₄). After removal of the solvent, the crude mixture was acetylated as described above to give compounds (5b) and (4b) in a ratio of 1:1 (according to ¹H NMR) (0.59 g, 77%). Compounds (4b) and (5b) were separated by recrystallization from hexane–CH₂Cl₂ (Ratio?). The title compound, (4b), formed colourless crystals from hexane–CH₂Cl₂ (Ratio?) (m.p. 444–446 K). Analysis, found: C 46.68, H 4.87%; C₁₆H₂₀Cl₂O₈ requires: C 46.73, H 4.90%. Spectroscopic analysis: IR (KBr, ν_max, cm⁻¹): 3025, 2979, 2948, 1751, 1431, 1370, 1235, 1081, 1041, 758; ¹H NMR (200 MHz, CDCl₃, δ, p.p.m.): 5.30–5.20 (m, 4H, –CHO), 4.55 (m, 2H, –CHCl), 3.05 (m, 2H, –CH), 2.05 (s, 6H, CH3), 2.03 (s, 6H, –CH3); ¹³C NMR (50 MHz, CDCl₃, δ, p.p.m.): 171.8, 171.6, 70.1, 69.7, 59.0, 47.0, 22.6, 22.5.

S3. Refinement

Methyl atoms were treated as riding, with C—H = 0.96 Å and with U_iso(H) = 1.5U_eq(C). [Please check added text] All other H atoms were located in a difference synthesis and refined isotropically [C—H = 0.89 (3)–1.00 (2) Å].

Computing details

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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 (Farrugia, 1999).

Figures

	Fig. 1. A drawing of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The crystal structure of (4b), viewed down the a axis. Hydrogen bonds are indicated by dashed lines. H atoms not involved in the hydrogen bonding have been omitted for clarity.

(1SR,2SR,3SR,4RS,5RS,6RS,7SR,8RS)-7,8-Dichlorobicyclo[4.2.0]octa-2,3,4,5-tetrayl tetraacetate

Crystal data

C16H20Cl2O8	Z = 2
Mr = 411.22	F(000) = 428
Triclinic, P1	Dx = 1.458 Mg m^−3
Hall symbol: -P1	Mo Kα radiation, λ = 0.71073 Å
a = 8.9489 (5) Å	Cell parameters from 7762 reflections
b = 11.0230 (8) Å	θ = 2.5–33.2°
c = 11.2885 (7) Å	µ = 0.39 mm^−1
α = 111.427 (2)°	T = 295 K
β = 98.281 (1)°	Block, white
γ = 108.834 (1)°	0.32 × 0.21 × 0.20 mm
V = 936.70 (10) Å^3

Data collection

Rigaku R-AXIS RAPID S diffractometer	6532 reflections with I > 2σ(I)
oscillation scans	Rint = 0.045
Absorption correction: multi-scan (Blessing, 1995)	θmax = 33.2°, θmin = 2.2°
Tmin = 0.909, Tmax = 0.926	h = −13→13
64683 measured reflections	k = −16→16
7145 independent reflections	l = −17→17

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.076	w = 1/[σ^2(Fo^2) + (0.0595P)^2 + 0.3756P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.190	(Δ/σ)max = 0.002
S = 1.32	Δρmax = 0.33 e Å^−3
7145 reflections	Δρmin = −0.26 e Å^−3
271 parameters

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.

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

	x	y	z	Uiso*/Ueq
C1	0.4965 (2)	0.61022 (19)	0.77019 (17)	0.0309 (3)
C2	0.4544 (2)	0.4592 (2)	0.75323 (18)	0.0330 (3)
C3	0.2891 (2)	0.3968 (2)	0.7761 (2)	0.0360 (4)
C4	0.1506 (2)	0.4225 (2)	0.69984 (19)	0.0356 (4)
C5	0.1919 (2)	0.5522 (2)	0.67124 (18)	0.0334 (3)
C6	0.3678 (2)	0.60502 (19)	0.66193 (17)	0.0314 (3)
C7	0.1893 (3)	0.2346 (2)	0.6858 (2)	0.0447 (4)
C8	0.1028 (2)	0.2742 (2)	0.5867 (2)	0.0430 (4)
C9	0.6381 (3)	0.3577 (2)	0.8030 (2)	0.0423 (4)
C10	0.7875 (3)	0.3840 (3)	0.9028 (3)	0.0567 (6)
C11	0.5991 (2)	0.8355 (2)	0.96058 (19)	0.0388 (4)
C12	0.5772 (4)	0.9116 (3)	1.0926 (2)	0.0553 (6)
C13	0.0206 (3)	0.6635 (2)	0.7595 (2)	0.0463 (5)
C14	0.0142 (3)	0.7843 (3)	0.8721 (3)	0.0739 (9)
C15	0.5351 (3)	0.7849 (2)	0.61363 (18)	0.0380 (4)
C16	0.5744 (3)	0.9313 (3)	0.6258 (3)	0.0543 (6)
Cl1	0.05627 (9)	0.15421 (8)	0.76460 (9)	0.0702 (2)
Cl2	−0.10859 (8)	0.17212 (8)	0.49481 (9)	0.0731 (2)
O1	0.58777 (17)	0.46418 (16)	0.84715 (14)	0.0399 (3)
O2	0.5674 (3)	0.2543 (2)	0.6982 (2)	0.0718 (6)
O3	0.49473 (16)	0.69586 (14)	0.90194 (12)	0.0343 (3)
O4	0.6945 (2)	0.88949 (18)	0.91157 (17)	0.0556 (4)
O5	0.17410 (16)	0.66642 (15)	0.77633 (14)	0.0384 (3)
O6	−0.0960 (2)	0.5712 (2)	0.6667 (2)	0.0735 (6)
O7	0.40837 (17)	0.74260 (14)	0.66243 (14)	0.0364 (3)
O8	0.6049 (2)	0.71054 (18)	0.56760 (16)	0.0477 (4)
H1	0.603 (3)	0.648 (2)	0.761 (2)	0.030 (5)*
H10A	0.7554	0.3623	0.9728	0.085*
H10B	0.863	0.4824	0.9397	0.085*
H10C	0.8402	0.3243	0.8603	0.085*
H12A	0.6503	1.0109	1.1315	0.083*
H12B	0.6024	0.8708	1.1506	0.083*
H12C	0.4649	0.9021	1.0803	0.083*
H14A	−0.0098	0.8477	0.8403	0.111*
H14B	0.119	0.8352	0.9401	0.111*
H14C	−0.0708	0.7477	0.9085	0.111*
H16A	0.6382	0.947	0.5672	0.082*
H16B	0.6368	0.9997	0.716	0.082*
H16C	0.4735	0.9419	0.6019	0.082*
H2	0.460 (3)	0.405 (3)	0.662 (2)	0.037 (6)*
H3	0.306 (3)	0.426 (3)	0.872 (3)	0.044 (6)*
H4	0.066 (3)	0.414 (3)	0.743 (2)	0.040 (6)*
H5	0.111 (3)	0.525 (3)	0.586 (3)	0.045 (6)*
H6	0.368 (3)	0.537 (2)	0.575 (2)	0.031 (5)*
H7	0.246 (3)	0.172 (3)	0.654 (2)	0.042 (6)*
H8	0.157 (3)	0.272 (3)	0.526 (2)	0.043 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0288 (7)	0.0342 (8)	0.0293 (7)	0.0153 (6)	0.0097 (6)	0.0109 (6)
C2	0.0306 (7)	0.0367 (8)	0.0322 (8)	0.0175 (7)	0.0087 (6)	0.0128 (7)
C3	0.0357 (8)	0.0364 (9)	0.0397 (9)	0.0178 (7)	0.0138 (7)	0.0170 (7)
C4	0.0303 (7)	0.0372 (9)	0.0404 (9)	0.0164 (7)	0.0143 (7)	0.0144 (7)
C5	0.0311 (7)	0.0365 (8)	0.0325 (8)	0.0179 (7)	0.0088 (6)	0.0117 (7)
C6	0.0326 (7)	0.0343 (8)	0.0304 (8)	0.0173 (7)	0.0108 (6)	0.0137 (7)
C7	0.0382 (9)	0.0355 (9)	0.0614 (13)	0.0159 (8)	0.0214 (9)	0.0191 (9)
C8	0.0308 (8)	0.0382 (10)	0.0479 (11)	0.0103 (7)	0.0101 (8)	0.0104 (8)
C9	0.0411 (10)	0.0470 (11)	0.0485 (11)	0.0255 (9)	0.0149 (8)	0.0237 (9)
C10	0.0444 (11)	0.0725 (16)	0.0654 (15)	0.0354 (12)	0.0124 (10)	0.0342 (13)
C11	0.0385 (9)	0.0352 (9)	0.0370 (9)	0.0157 (7)	0.0079 (7)	0.0107 (7)
C12	0.0708 (16)	0.0443 (12)	0.0393 (11)	0.0212 (11)	0.0183 (10)	0.0080 (9)
C13	0.0326 (9)	0.0477 (11)	0.0588 (12)	0.0223 (8)	0.0154 (8)	0.0177 (10)
C14	0.0474 (13)	0.0565 (15)	0.097 (2)	0.0285 (12)	0.0269 (14)	0.0039 (15)
C15	0.0428 (9)	0.0437 (10)	0.0325 (8)	0.0201 (8)	0.0151 (7)	0.0183 (8)
C16	0.0671 (15)	0.0442 (12)	0.0623 (14)	0.0233 (11)	0.0318 (12)	0.0291 (11)
Cl1	0.0631 (4)	0.0624 (4)	0.1061 (6)	0.0247 (3)	0.0432 (4)	0.0528 (4)
Cl2	0.0371 (3)	0.0549 (4)	0.0883 (5)	0.0043 (2)	−0.0033 (3)	0.0119 (3)
O1	0.0394 (7)	0.0447 (7)	0.0364 (7)	0.0250 (6)	0.0060 (5)	0.0139 (6)
O2	0.0830 (14)	0.0575 (11)	0.0653 (12)	0.0481 (11)	0.0000 (10)	0.0083 (9)
O3	0.0349 (6)	0.0345 (6)	0.0300 (6)	0.0146 (5)	0.0111 (5)	0.0098 (5)
O4	0.0546 (9)	0.0407 (8)	0.0522 (9)	0.0061 (7)	0.0211 (8)	0.0101 (7)
O5	0.0306 (6)	0.0404 (7)	0.0406 (7)	0.0192 (5)	0.0103 (5)	0.0100 (6)
O6	0.0353 (8)	0.0773 (13)	0.0762 (13)	0.0265 (9)	0.0035 (8)	0.0027 (10)
O7	0.0384 (6)	0.0381 (7)	0.0407 (7)	0.0207 (6)	0.0167 (5)	0.0193 (6)
O8	0.0563 (9)	0.0538 (9)	0.0487 (8)	0.0308 (8)	0.0313 (7)	0.0257 (7)

Geometric parameters (Å, º)

C1—H1	0.95 (2)	C12—H12C	0.96
C2—C1	1.514 (3)	C13—C14	1.492 (3)
C2—C3	1.520 (3)	C14—H14A	0.96
C2—H2	1.00 (2)	C14—H14B	0.96
C3—C4	1.567 (3)	C14—H14C	0.96
C3—C7	1.552 (3)	C15—C16	1.485 (3)
C3—H3	0.99 (3)	C16—H16A	0.96
C4—C8	1.534 (3)	C16—H16B	0.96
C4—H4	0.96 (2)	C16—H16C	0.96
C5—C4	1.522 (3)	Cl1—C7	1.788 (2)
C5—C6	1.526 (2)	Cl2—C8	1.769 (2)
C5—H5	1.00 (3)	O1—C2	1.450 (2)
C6—C1	1.525 (2)	O1—C9	1.344 (2)
C6—H6	0.99 (2)	O2—C9	1.197 (3)
C7—C8	1.538 (3)	O3—C1	1.447 (2)
C7—H7	0.98 (3)	O3—C11	1.353 (2)
C8—H8	0.89 (3)	O4—C11	1.199 (3)
C9—C10	1.489 (3)	O5—C13	1.348 (2)
C10—H10A	0.96	O5—C5	1.453 (2)
C10—H10B	0.96	O6—C13	1.201 (3)
C10—H10C	0.96	O7—C15	1.354 (2)
C11—C12	1.497 (3)	O7—C6	1.439 (2)
C12—H12A	0.96	O8—C15	1.202 (2)
C12—H12B	0.96
C1—C2—C3	111.84 (14)	C13—C14—H14C	109.5
C1—C2—H2	105.7 (14)	C13—O5—C5	115.46 (15)
C1—C6—C5	114.24 (14)	C15—C16—H16A	109.5
C1—C6—H6	107.0 (13)	C15—C16—H16B	109.5
C2—C1—C6	107.87 (14)	C15—C16—H16C	109.5
C2—C1—H1	109.8 (13)	C15—O7—C6	115.49 (14)
C2—C3—C4	112.11 (15)	Cl1—C7—H7	105.0 (15)
C2—C3—C7	114.09 (15)	Cl2—C8—H8	105.7 (17)
C2—C3—H3	109.3 (15)	O1—C2—C1	107.03 (14)
C3—C2—H2	114.2 (14)	O1—C2—C3	111.15 (15)
C3—C4—H4	106.9 (14)	O1—C2—H2	106.5 (13)
C3—C7—Cl1	110.86 (15)	O1—C9—C10	111.2 (2)
C3—C7—H7	120.7 (15)	O2—C9—C10	125.4 (2)
C4—C3—H3	117.5 (15)	O2—C9—O1	123.35 (19)
C4—C5—C6	111.59 (14)	O3—C1—C2	108.45 (14)
C4—C5—H5	108.2 (15)	O3—C1—C6	111.42 (13)
C4—C8—C7	89.45 (16)	O3—C1—H1	109.6 (13)
C4—C8—Cl2	117.74 (14)	O3—C11—C12	110.73 (18)
C4—C8—H8	115.2 (17)	O4—C11—C12	125.4 (2)
C5—C4—C3	121.16 (15)	O4—C11—O3	123.87 (18)
C5—C4—C8	120.03 (17)	O5—C13—C14	111.6 (2)
C5—C4—H4	111.6 (14)	O5—C5—C4	109.55 (15)
C5—C6—H6	107.4 (13)	O5—C5—C6	109.17 (15)
C6—C1—H1	109.6 (13)	O5—C5—H5	108.1 (15)
C6—C5—H5	110.1 (15)	O6—C13—C14	125.2 (2)
C7—C3—C4	87.73 (15)	O6—C13—O5	123.1 (2)
C7—C3—H3	114.9 (15)	O7—C15—C16	111.57 (17)
C7—C8—Cl2	121.08 (16)	O7—C6—C1	111.41 (14)
C7—C8—H8	107.2 (16)	O7—C6—C5	107.94 (13)
C8—C4—C3	87.36 (14)	O7—C6—H6	108.6 (13)
C8—C4—H4	106.8 (15)	O8—C15—C16	125.86 (19)
C8—C7—C3	87.74 (15)	O8—C15—O7	122.57 (18)
C8—C7—Cl1	113.82 (15)	H10A—C10—H10B	109.5
C8—C7—H7	118.4 (15)	H10A—C10—H10C	109.5
C9—C10—H10A	109.5	H10B—C10—H10C	109.5
C9—C10—H10B	109.5	H12A—C12—H12B	109.5
C9—C10—H10C	109.5	H12A—C12—H12C	109.5
C9—O1—C2	116.51 (15)	H12B—C12—H12C	109.5
C11—C12—H12A	109.5	H14A—C14—H14B	109.5
C11—C12—H12B	109.5	H14A—C14—H14C	109.5
C11—C12—H12C	109.5	H14B—C14—H14C	109.5
C11—O3—C1	116.81 (14)	H16A—C16—H16B	109.5
C13—C14—H14A	109.5	H16A—C16—H16C	109.5
C13—C14—H14B	109.5	H16B—C16—H16C	109.5
C1—C2—C3—C4	47.1 (2)	C6—C5—C4—C3	27.2 (2)
C1—C2—C3—C7	144.89 (17)	C6—C5—C4—C8	−79.5 (2)
C1—O3—C11—C12	177.04 (17)	C6—O7—C15—C16	−176.54 (18)
C1—O3—C11—O4	−2.4 (3)	C6—O7—C15—O8	3.1 (3)
C2—C3—C4—C5	−29.4 (2)	C7—C3—C4—C5	−144.56 (17)
C2—C3—C4—C8	94.47 (17)	C7—C3—C4—C8	−20.67 (15)
C2—C3—C7—C8	−92.65 (17)	C9—O1—C2—C1	−138.95 (17)
C2—C3—C7—Cl1	152.67 (14)	C9—O1—C2—C3	98.66 (19)
C2—O1—C9—C10	173.39 (18)	C11—O3—C1—C2	149.13 (15)
C2—O1—C9—O2	−8.5 (3)	C11—O3—C1—C6	−92.29 (18)
C3—C2—C1—C6	−64.25 (18)	C13—O5—C5—C4	−86.5 (2)
C3—C2—C1—O3	56.56 (18)	C13—O5—C5—C6	151.07 (17)
C3—C4—C8—C7	20.85 (14)	C15—O7—C6—C1	73.77 (18)
C3—C4—C8—Cl2	146.18 (16)	C15—O7—C6—C5	−160.03 (15)
C3—C7—C8—C4	−21.06 (14)	Cl1—C7—C8—C4	90.79 (16)
C3—C7—C8—Cl2	−143.59 (16)	Cl1—C7—C8—Cl2	−31.7 (2)
C4—C3—C7—C8	20.60 (14)	O1—C2—C1—C6	173.79 (13)
C4—C3—C7—Cl1	−94.08 (15)	O1—C2—C1—O3	−65.40 (16)
C4—C5—C6—C1	−43.8 (2)	O1—C2—C3—C4	166.70 (14)
C4—C5—C6—O7	−168.35 (14)	O1—C2—C3—C7	−95.55 (19)
C5—C4—C8—C7	145.72 (17)	O5—C5—C4—C3	−93.81 (18)
C5—C4—C8—Cl2	−89.0 (2)	O5—C5—C4—C8	159.49 (15)
C5—C6—C1—C2	63.27 (18)	O5—C5—C6—C1	77.40 (18)
C5—C6—C1—O3	−55.66 (19)	O5—C5—C6—O7	−47.11 (18)
C5—O5—C13—C14	179.9 (2)	O7—C6—C1—C2	−174.09 (13)
C5—O5—C13—O6	2.2 (3)	O7—C6—C1—O3	66.98 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O4	0.95 (3)	2.35 (2)	2.690 (3)	100.5 (17)
C1—H1···O8	0.95 (3)	2.52 (2)	3.031 (3)	114.1 (17)
C2—H2···O2	1.00 (2)	2.29 (3)	2.672 (3)	100.9 (18)
C2—H2···O8^i	1.00 (2)	2.31 (2)	3.279 (2)	161 (2)
C8—H8···O8^i	0.89 (3)	2.50 (3)	3.339 (3)	158 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.