2,3,3',6-Tetra-O-acetyl-4,1',6'-trichloro-4,1',4',6'-tetradeoxygalactosucrose

At 160 K, one of the Cl atoms in the furanoid moiety of 3-O-acetyl-1,6-di­chloro-1,4,6-tri­deoxy-[beta]-D-fructo­furan­osyl 2,3,6-tri-O-acetyl-4-chloro-4-deoxy-[alpha]-D-galacto­pyran­oside, C₂₀H₂₇­Cl₃O₁₁, is disordered over two orientations, which differ by a rotation of about 107° about the parent C-C bond. The conformation of the core of the mol­ecule is very similar to that of 3-O-acetyl-1,4,6-tri­chloro-1,4,6-tri­deoxy-[beta]-D-tagato­furanos­yl 2,3,6-tri-O-acetyl-4-chloro-4-deoxy-[alpha]-D-galacto­pyran­oside, particularly with regard to the conformation about the glycosidic linkage.

S1. Comment

Halogenated analogues of sucrose are unique among sugar compounds in that they are generally intensely sweet, and some of these compounds are several thousand times sweeter than sucrose (Lee, 1982, 1983, 1987). There is still no clear explanation for this. Although the Shallenberger & Acree-Kier AH,B,γ hypothesis (Shallenberger & Acree, 1967; Kier, 1972) is currently the most accepted model for explaining the sweetness of a compound, the location of this tripartite glucophore for this group of compounds is still being debated intensely. It is fairly widely accepted that the intense sweetness of the halodeoxy sucrose analogues is directly related to the presence of one or more of the halogen substituents. For this reason, we are interested in the syntheses and structures of these analogues and, as part of this programme, the crystal structure of the title compound, (I), has been determined. \sch

The absolute configuration of (I) has been determined confidently by refinement of the absolute structure parameter (Flack, 1983) and is shown in Fig. 1. The Cl atom of the chloromethyl substituent at C7 in the furanoid moiety is disordered over two orientations, which differ by a rotation of approximately 107° about the parent C7—C12 bond. The major conformation is present in approximately 94% of the molecules. The bond lengths and angles exhibit normal values, and generally agree with those of sucrose (Brown & Levy, 1963, 1973; Hanson et al., 1973) and the related chlorinated derivatives 3-O-acetyl-1,4,6-trichloro-1,4,6-trideoxy-β-D-fructofuranosyl 2,3,6-tri-O-acetyl-4-chloro-4-deoxy-α-D-galactopyranoside, (II) (Lee, 1982, 1983) and 3-O-acetyl-1,4,6-trichloro-1,4,6-trideoxy-β-D-tagatofuranosyl 2,3,6-tri-O-acetyl-4-chloro-4-deoxy-α-D-galactopyranoside, (III) (Lee et al., 1999). The torsion angles about the anomeric O1 atom (Table 1) are also very similar to those in sucrose and compound (III), but differ from those in compound (II).

The C5 hydroxymethyl and C10 chloromethyl substituents have gauche-trans conformations, while the major conformation of the C7 chloromethyl substituent is gauche-gauche. These conformations are the same as in the related chlorinated derivatives, (II) and (III), and sucralose (Kanters et al., 1988). In sucrose, however, both the C5 and C10 hydroxymethyl substituents are gauche-gauche, while that at C7 is trans-gauche. The gauche-trans conformation for O6 in (I) avoids any 1,3-peri interaction between atoms O6 and Cl4. For the major conformation of the C7 chloromethyl substituent, the gauche-gauche conformation places atom Cl2A under the furanose ring, thereby avoiding both possible peri interactions with atoms O10 and O8, and also a repulsive dipole-dipole interaction between atom Cl2A and the anomeric O1 atom.

The minor conformation of the C7 chloromethyl substituent has the trans-gauche conformation, as found in sucrose. This actually brings atom Cl2B within 2.589 (10) Å of atom O19 of the acetyl substituent at C8, which is unreasonably close. However, the enlarged atomic displacement ellipsoids for atoms O19 and C20 suggest that these atoms might also be disordered, thereby alleviating the short Cl2B···O19 contact caused by the use of averaged positions for the latter atom. However, due to the very low proportion of this disordered component in the structure, no attempt was made to define disordered positions for atoms O19 and C20.

The glucopyranosyl ring in compound (I) adopts the ⁴C₁ chair conformation. The puckering parameters (Cremer & Pople, 1975) are Q = 0.5832 (18) Å, q₂ = 0.0288 (18) Å, q₃ = 0.5825 (18) Å, θ = 2.84 (18)° and ϕ₂ = 113 (3)°. The puckering amplitudes (q₃ >> q₂) of the pyranose ring describe a slightly distorted chair. Indeed, the total puckering amplitude (Q) is only slightly lower than that of the ideal cyclohexane chair [0.63 Å for δ(C—C) = 1.54 Å]. The magnitude of the distortion is significantly less than in the related fructofuranosyl and tagatofuranosyl derivatives, (II) and (III) [θ = 4.7 (4) and 5.0 (3)°, respectively; Lee et al., 1999], but comparable with that of sucralose (θ = 1.9°; Kanters et al., 1988). With ϕ₂ being close to 120°, the distortion is towards the boat ^2,5B conformation. The furanoid ring in (I) has the envelope ⁹E conformation (i.e. ⁴E with conventional furanosyl ring numbering), with puckering parameters θ₂ = 0.410 (2) Å and ϕ₂ = 283.4 (3)°. Atom C9 lies 0.632 (3) Å from the plane defined by atoms C7, C8, C10 and O10. The same conformation is found in (III) [ϕ₂ = 291.3 (4)°], whereas a twisted conformation is present in (II) [ϕ₂ = 268.1 (6)°] (Lee et al., 1999).

S2. Experimental

Carbon tetrachloride (1 ml, 6.49 mmol) was added dropwise to a stirred solution of 3-O-acetyl-4-deoxy-β-D-fructofuranosyl 2,3,6-tri-O-acetyl-α-D-glucopyranoside (0.39 g, 0.79 mmol) and triphenylphosphine (1.65 g, 6.29 mmol) in pyridine (25 ml) under an argon atmosphere at room temperature. The reaction mixture was stirred for 30 min at room temperature, before being heated at ~358 K for 1 h. After all starting material had reacted, as indicated by thin layer chromatography (ethyl acetate-hexane, 1:2), the reaction mixture was diluted with dichloromethane and then washed with dilute HCl (10%), saturated aqueous NaHCO₃ and brine, dried (Na₂SO₄) and concentrated. The crude product was flash chromatographed (ethyl acetate-hexane, 1:2) to give the title compound, (I) (0.41 g, 87%), m.p. 381–382 K (CH₂Cl₂). Spectroscopic analysis: [α]_D +70.2° (c 0.83, CHCl₃); ¹H NMR (300.13 MHz, CDCl₃, δ, p.p.m., the assignments employ the crystallographic atom numbering used in Fig. 1): 1.93–2.01 (m, 1H, H9A), 2.00–2.07 (4 × s, 12H, 4 × CH₃), 2.50–2.59 (m, 1H, H9B), 3.39–3.72 (m, 4H, H11A,B, H12A,B), 4.10–4.32 (m, 3H, H6A,B, H10), 4.47–4.52 (m, 2H, H4, H5), 5.19 (dd, 1H, J_2,3 = 10.8, J_3,4 = 3.0 Hz, H3), 5.25 (dd, 1H, J_1,2 = 3.1, J_2,3 = 10.8 Hz, H2), 5.45 (dd, 1H, J_8,9a = 7.3, J_{8,9 b} = 9.7 Hz, H8), 5.56 (d, 1H, J_1,2 = 3.1 Hz, H1); ¹³C NMR (75.47 MHz, CDCl₃, δ, p.p.m.): 170.3, 170.1, 169.9, 169.7 (COCH₃), 104.5, (C7), 89.7 (C1), 78.4 (C10), 72.7 (C8), 68.2 (C3), 67.6 (C5), 66.8 (C2), 64.0 (C6), 59.0 (C4), 45.4, 45.1 (C11, C12), 33.0 (C9), 20.7, 20.6 (COCH₃); HRMS-ESI (positive mode), calculated for [M + Na]⁺: 571.0517:573.0487:575.0457; found: 571.0496:573.0481:575.0469. Suitable crystals were obtained by slow evaporation of a dilute solution of (I) in dichloromethane.

S3. Refinement

One Cl atom in the furanoid moiety, Cl2, is disordered over two positions, A and B. The site occupancy factors of the disordered atoms were refined, while constraining their sum for the two conformations to 1.0. The major conformation was found to be present in 93.9 (2)% of the molecules. A bond-length restraint was applied to the C—Cl bond involving the minor conformation so as to maintain reasonable geometry. The methyl H atoms were constrained to an ideal geometry (C—H = 0.98 Å) with U_iso(H) = 1.5U_eq(C), but were allowed to rotate freely about the C—C bonds. All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.99–1.00 Å and U_iso(H) = 1.2U_eq(C). The determined absolute configuration agreed with that expected for a natural sucrose derivative. Ten low-angle reflections were omitted from the final cycles of refinement because their observed intensities were much lower than the calculated values, as a result of being partially obscured by the beam stop.

Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2002).

Figures

Fig. 1. A view of the major conformation (94% contribution) of the molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are represented by spheres of arbitrary size.

3-O-acetyl-1,6-dichloro-1,4,6-trideoxy-β-D-fructofuranosyl 2,3,6-tri-O-acetyl-4-chloro-4-deoxy-α-D-galactopyranoside

Crystal data

C20H27Cl3O11	Z = 1
Mr = 549.78	F(000) = 286
Triclinic, P1	Dx = 1.439 Mg m^−3
Hall symbol: P 1	Melting point: 381 K
a = 8.2962 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.4622 (1) Å	Cell parameters from 38452 reflections
c = 9.9471 (3) Å	θ = 2.0–30.0°
α = 61.6508 (6)°	µ = 0.42 mm^−1
β = 69.9690 (6)°	T = 160 K
γ = 71.4651 (11)°	Prism, colourless
V = 634.15 (2) Å^3	0.20 × 0.15 × 0.12 mm

Data collection

Nonius KappaCCD area-detector diffractometer	7135 independent reflections
Radiation source: Nonius FR591 sealed-tube generator	6346 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.039
Detector resolution: 9 pixels mm^-1	θmax = 30.1°, θmin = 3.1°
ϕ and ω scans with κ offsets	h = −11→11
Absorption correction: multi-scan (Blessing, 1995)	k = −13→13
Tmin = 0.922, Tmax = 0.953	l = −13→13
33175 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.035	w = 1/[σ^2(Fo^2) + (0.047P)^2 + 0.0721P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.089	(Δ/σ)max = 0.004
S = 1.03	Δρmax = 0.28 e Å^−3
7125 reflections	Δρmin = −0.32 e Å^−3
322 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
4 restraints	Extinction coefficient: 0.050 (6)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), with 3437 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.00 (3)

Special details

Experimental. Solvent used: dichloromethane Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.720 (1) Frames collected: 745 Seconds exposure per frame: 76 Degrees rotation per frame: 2.0 Crystal-Detector distance (mm): 28.0

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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

-5.9275 (0.0070) x + 2.7978 (0.0094) y + 3.3519 (0.0115) z = 0.3620 (0.0112)

* 0.0140 (0.0009) C7 * -0.0083 (0.0006) C8 * 0.0091 (0.0006) C10 * -0.0148 (0.0010) O10 0.6320 (0.0032) C9

Rms deviation of fitted atoms = 0.0119

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)
Cl1	0.43354 (8)	0.99824 (6)	0.00901 (6)	0.05466 (15)
Cl2A	0.76785 (9)	0.41824 (13)	0.31788 (9)	0.0899 (4)	0.939 (2)
Cl2B	0.6732 (12)	0.2268 (4)	0.5997 (9)	0.050 (3)	0.061 (2)
Cl4	−0.03086 (5)	0.73662 (5)	0.96425 (4)	0.03585 (11)
O1	0.30508 (14)	0.52271 (13)	0.58022 (12)	0.0252 (2)
O2	0.47169 (14)	0.42697 (13)	0.81349 (13)	0.0275 (2)
O3	0.17515 (16)	0.38638 (13)	1.05903 (12)	0.0287 (2)
O5	0.15087 (14)	0.75899 (12)	0.61582 (12)	0.0254 (2)
O6	−0.15965 (16)	0.89790 (15)	0.50270 (15)	0.0354 (3)
O8	0.24965 (18)	0.31466 (14)	0.51232 (14)	0.0361 (3)
O10	0.43913 (16)	0.67042 (14)	0.32055 (13)	0.0314 (2)
O13	0.56438 (19)	0.51534 (19)	0.94349 (18)	0.0452 (3)
O15	0.02643 (18)	0.20418 (16)	1.09766 (15)	0.0386 (3)
O17	−0.3037 (2)	0.70493 (19)	0.56221 (17)	0.0486 (4)
O19	0.4749 (3)	0.1085 (2)	0.5424 (3)	0.0866 (7)
C1	0.30645 (19)	0.63970 (17)	0.62988 (17)	0.0228 (3)
H1	0.4099	0.6935	0.5647	0.027*
C2	0.3174 (2)	0.55123 (18)	0.80190 (17)	0.0239 (3)
H2	0.3223	0.6301	0.8400	0.029*
C3	0.1585 (2)	0.47152 (18)	0.89880 (17)	0.0244 (3)
H3	0.1594	0.3899	0.8615	0.029*
C4	−0.0092 (2)	0.59921 (19)	0.87865 (19)	0.0273 (3)
H4	−0.1112	0.5422	0.9323	0.033*
C5	−0.0045 (2)	0.69145 (18)	0.70263 (18)	0.0254 (3)
H5	−0.0071	0.6129	0.6632	0.031*
C6	−0.1573 (2)	0.8326 (2)	0.6660 (2)	0.0330 (3)
H61	−0.2680	0.7942	0.7326	0.040*
H62	−0.1473	0.9194	0.6899	0.040*
C7	0.4296 (2)	0.51396 (19)	0.44298 (18)	0.0277 (3)
C8	0.3591 (3)	0.4245 (2)	0.38620 (19)	0.0334 (4)
H8	0.4575	0.3648	0.3293	0.040*
C9	0.2537 (3)	0.5647 (2)	0.2739 (2)	0.0401 (4)
H91	0.1383	0.6050	0.3302	0.048*
H92	0.2377	0.5340	0.1977	0.048*
C10	0.3729 (3)	0.6887 (2)	0.19539 (19)	0.0352 (4)
H10	0.4717	0.6612	0.1144	0.042*
C11	0.2806 (3)	0.8619 (2)	0.1223 (3)	0.0473 (5)
H111	0.1977	0.8951	0.2058	0.057*
H112	0.2128	0.8692	0.0537	0.057*
C12	0.6069 (2)	0.4345 (2)	0.4834 (2)	0.0407 (4)
H121	0.6011	0.3243	0.5697	0.049*	0.939 (2)
H122	0.6388	0.5007	0.5198	0.049*	0.939 (2)
H123	0.6238	0.4961	0.5332	0.049*	0.061 (2)
H124	0.6937	0.4590	0.3816	0.049*	0.061 (2)
C13	0.5877 (2)	0.4248 (2)	0.8835 (2)	0.0326 (3)
C14	0.7458 (3)	0.2969 (3)	0.8715 (3)	0.0464 (5)
H141	0.8230	0.3386	0.7671	0.070*
H142	0.7106	0.1993	0.8880	0.070*
H143	0.8077	0.2688	0.9515	0.070*
C15	0.1100 (2)	0.24643 (19)	1.14500 (19)	0.0303 (3)
C16	0.1575 (3)	0.1572 (2)	1.3004 (2)	0.0414 (4)
H161	0.1019	0.0610	1.3634	0.062*
H162	0.1172	0.2295	1.3551	0.062*
H163	0.2846	0.1223	1.2847	0.062*
C17	−0.2449 (2)	0.8257 (2)	0.4678 (2)	0.0379 (4)
C18	−0.2555 (3)	0.9118 (3)	0.2991 (2)	0.0551 (6)
H181	−0.2355	0.8310	0.2573	0.083*
H182	−0.1663	0.9805	0.2387	0.083*
H183	−0.3715	0.9804	0.2910	0.083*
C19	0.3244 (3)	0.1578 (2)	0.5815 (3)	0.0477 (5)
C20	0.1972 (4)	0.0598 (3)	0.7106 (3)	0.0640 (7)
H201	0.2574	−0.0526	0.7613	0.096*
H202	0.1067	0.0594	0.6683	0.096*
H203	0.1432	0.1076	0.7878	0.096*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0654 (4)	0.0388 (2)	0.0507 (3)	−0.0224 (2)	−0.0123 (3)	−0.0041 (2)
Cl2A	0.0404 (4)	0.1366 (8)	0.0526 (4)	0.0162 (4)	0.0066 (3)	−0.0398 (4)
Cl2B	0.048 (5)	0.051 (5)	0.063 (6)	0.005 (4)	−0.025 (4)	−0.034 (4)
Cl4	0.0396 (2)	0.0386 (2)	0.0333 (2)	−0.00736 (16)	−0.00477 (16)	−0.02029 (16)
O1	0.0283 (5)	0.0282 (5)	0.0217 (5)	−0.0090 (4)	−0.0045 (4)	−0.0109 (4)
O2	0.0273 (5)	0.0297 (5)	0.0288 (5)	−0.0042 (4)	−0.0126 (4)	−0.0113 (4)
O3	0.0400 (6)	0.0288 (5)	0.0202 (5)	−0.0136 (5)	−0.0088 (4)	−0.0065 (4)
O5	0.0255 (5)	0.0234 (5)	0.0265 (5)	−0.0080 (4)	−0.0058 (4)	−0.0076 (4)
O6	0.0308 (6)	0.0343 (6)	0.0356 (6)	−0.0107 (5)	−0.0140 (5)	−0.0030 (5)
O8	0.0548 (8)	0.0268 (5)	0.0301 (6)	−0.0137 (5)	−0.0105 (5)	−0.0102 (5)
O10	0.0409 (7)	0.0326 (6)	0.0212 (5)	−0.0137 (5)	−0.0073 (4)	−0.0071 (4)
O13	0.0438 (7)	0.0618 (9)	0.0484 (8)	−0.0075 (6)	−0.0209 (6)	−0.0316 (7)
O15	0.0470 (7)	0.0362 (6)	0.0355 (6)	−0.0201 (5)	−0.0170 (5)	−0.0041 (5)
O17	0.0520 (9)	0.0574 (9)	0.0395 (7)	−0.0298 (7)	−0.0131 (6)	−0.0085 (7)
O19	0.0793 (15)	0.0364 (9)	0.0933 (15)	0.0034 (9)	−0.0090 (12)	−0.0034 (9)
C1	0.0240 (7)	0.0243 (7)	0.0217 (7)	−0.0065 (5)	−0.0072 (5)	−0.0082 (5)
C2	0.0257 (7)	0.0241 (7)	0.0236 (7)	−0.0058 (5)	−0.0066 (6)	−0.0098 (6)
C3	0.0307 (8)	0.0255 (7)	0.0187 (6)	−0.0094 (6)	−0.0074 (5)	−0.0066 (5)
C4	0.0277 (7)	0.0300 (7)	0.0266 (7)	−0.0096 (6)	−0.0052 (6)	−0.0115 (6)
C5	0.0246 (7)	0.0268 (7)	0.0251 (7)	−0.0080 (6)	−0.0065 (5)	−0.0084 (6)
C6	0.0285 (8)	0.0341 (8)	0.0355 (9)	−0.0039 (6)	−0.0109 (7)	−0.0124 (7)
C7	0.0290 (8)	0.0289 (7)	0.0224 (7)	−0.0044 (6)	−0.0037 (6)	−0.0105 (6)
C8	0.0508 (10)	0.0266 (7)	0.0234 (7)	−0.0106 (7)	−0.0058 (7)	−0.0104 (6)
C9	0.0659 (13)	0.0308 (8)	0.0326 (9)	−0.0146 (8)	−0.0235 (8)	−0.0084 (7)
C10	0.0553 (11)	0.0308 (8)	0.0227 (7)	−0.0118 (7)	−0.0117 (7)	−0.0093 (6)
C11	0.0583 (13)	0.0308 (9)	0.0500 (12)	−0.0163 (9)	−0.0248 (10)	−0.0010 (8)
C12	0.0303 (9)	0.0495 (11)	0.0333 (9)	−0.0011 (8)	−0.0044 (7)	−0.0158 (8)
C13	0.0310 (8)	0.0395 (8)	0.0290 (8)	−0.0105 (7)	−0.0117 (6)	−0.0099 (7)
C14	0.0372 (10)	0.0489 (11)	0.0576 (13)	0.0020 (8)	−0.0264 (9)	−0.0212 (10)
C15	0.0357 (9)	0.0283 (8)	0.0253 (7)	−0.0112 (6)	−0.0081 (6)	−0.0057 (6)
C16	0.0582 (12)	0.0387 (10)	0.0262 (8)	−0.0184 (9)	−0.0157 (8)	−0.0026 (7)
C17	0.0294 (9)	0.0466 (10)	0.0341 (9)	−0.0121 (7)	−0.0104 (7)	−0.0085 (8)
C18	0.0509 (13)	0.0746 (15)	0.0358 (10)	−0.0256 (11)	−0.0180 (9)	−0.0055 (10)
C19	0.0702 (15)	0.0285 (9)	0.0414 (10)	−0.0098 (9)	−0.0186 (10)	−0.0078 (8)
C20	0.107 (2)	0.0429 (11)	0.0456 (12)	−0.0383 (13)	−0.0262 (13)	0.0002 (10)

Geometric parameters (Å, º)

Cl1—C11	1.796 (2)	C6—H62	0.9900
Cl2A—C12	1.7664 (19)	C7—C12	1.518 (2)
Cl2B—C12	1.7586 (10)	C7—C8	1.541 (2)
Cl4—C4	1.8017 (16)	C8—C9	1.515 (3)
O1—C1	1.4144 (17)	C8—H8	1.0000
O1—C7	1.4230 (18)	C9—C10	1.517 (3)
O2—C13	1.3583 (19)	C9—H91	0.9900
O2—C2	1.4317 (18)	C9—H92	0.9900
O3—C15	1.3564 (18)	C10—C11	1.501 (3)
O3—C3	1.4385 (18)	C10—H10	1.0000
O5—C1	1.4168 (18)	C11—H111	0.9900
O5—C5	1.4330 (18)	C11—H112	0.9900
O6—C17	1.337 (2)	C12—H121	0.9900
O6—C6	1.443 (2)	C12—H122	0.9900
O8—C19	1.341 (2)	C12—H123	0.9900
O8—C8	1.435 (2)	C12—H124	0.9900
O10—C7	1.4062 (19)	C13—C14	1.490 (3)
O10—C10	1.444 (2)	C14—H141	0.9800
O13—C13	1.195 (2)	C14—H142	0.9800
O15—C15	1.200 (2)	C14—H143	0.9800
O17—C17	1.203 (2)	C15—C16	1.491 (2)
O19—C19	1.182 (3)	C16—H161	0.9800
C1—C2	1.5280 (19)	C16—H162	0.9800
C1—H1	1.0000	C16—H163	0.9800
C2—C3	1.519 (2)	C17—C18	1.498 (3)
C2—H2	1.0000	C18—H181	0.9800
C3—C4	1.526 (2)	C18—H182	0.9800
C3—H3	1.0000	C18—H183	0.9800
C4—C5	1.534 (2)	C19—C20	1.478 (3)
C4—H4	1.0000	C20—H201	0.9800
C5—C6	1.517 (2)	C20—H202	0.9800
C5—H5	1.0000	C20—H203	0.9800
C6—H61	0.9900
C1—O1—C7	118.44 (11)	O10—C10—C11	109.26 (14)
C13—O2—C2	118.29 (13)	O10—C10—C9	104.57 (13)
C15—O3—C3	115.87 (11)	C11—C10—C9	113.50 (17)
C1—O5—C5	113.42 (11)	O10—C10—H10	109.8
C17—O6—C6	115.85 (14)	C11—C10—H10	109.8
C19—O8—C8	117.72 (17)	C9—C10—H10	109.8
C7—O10—C10	110.01 (12)	C10—C11—Cl1	111.00 (16)
O1—C1—O5	110.08 (11)	C10—C11—H111	109.4
O1—C1—C2	108.16 (11)	Cl1—C11—H111	109.4
O5—C1—C2	109.24 (12)	C10—C11—H112	109.4
O1—C1—H1	109.8	Cl1—C11—H112	109.4
O5—C1—H1	109.8	H111—C11—H112	108.0
C2—C1—H1	109.8	C7—C12—Cl2B	126.1 (3)
O2—C2—C3	109.13 (12)	C7—C12—Cl2A	110.53 (13)
O2—C2—C1	108.00 (12)	C7—C12—H121	109.5
C3—C2—C1	108.88 (12)	Cl2A—C12—H121	109.5
O2—C2—H2	110.3	C7—C12—H122	109.5
C3—C2—H2	110.3	Cl2A—C12—H122	109.5
C1—C2—H2	110.3	H121—C12—H122	108.1
O3—C3—C2	107.36 (11)	C7—C12—H123	105.8
O3—C3—C4	112.90 (13)	Cl2B—C12—H123	105.8
C2—C3—C4	110.53 (12)	C7—C12—H124	105.8
O3—C3—H3	108.7	Cl2B—C12—H124	105.8
C2—C3—H3	108.7	H123—C12—H124	106.2
C4—C3—H3	108.7	O13—C13—O2	123.80 (17)
C3—C4—C5	108.04 (13)	O13—C13—C14	125.97 (16)
C3—C4—Cl4	110.82 (11)	O2—C13—C14	110.22 (15)
C5—C4—Cl4	111.35 (11)	C13—C14—H141	109.5
C3—C4—H4	108.9	C13—C14—H142	109.5
C5—C4—H4	108.9	H141—C14—H142	109.5
Cl4—C4—H4	108.9	C13—C14—H143	109.5
O5—C5—C6	106.59 (12)	H141—C14—H143	109.5
O5—C5—C4	111.67 (12)	H142—C14—H143	109.5
C6—C5—C4	113.10 (13)	O15—C15—O3	122.71 (15)
O5—C5—H5	108.4	O15—C15—C16	126.40 (15)
C6—C5—H5	108.4	O3—C15—C16	110.89 (14)
C4—C5—H5	108.4	C15—C16—H161	109.5
O6—C6—C5	110.17 (14)	C15—C16—H162	109.5
O6—C6—H61	109.6	H161—C16—H162	109.5
C5—C6—H61	109.6	C15—C16—H163	109.5
O6—C6—H62	109.6	H161—C16—H163	109.5
C5—C6—H62	109.6	H162—C16—H163	109.5
H61—C6—H62	108.1	O17—C17—O6	123.02 (17)
O10—C7—O1	111.27 (12)	O17—C17—C18	124.99 (18)
O10—C7—C12	109.11 (14)	O6—C17—C18	111.98 (17)
O1—C7—C12	108.18 (13)	C17—C18—H181	109.5
O10—C7—C8	105.72 (12)	C17—C18—H182	109.5
O1—C7—C8	106.38 (13)	H181—C18—H182	109.5
C12—C7—C8	116.17 (15)	C17—C18—H183	109.5
O8—C8—C9	110.67 (16)	H181—C18—H183	109.5
O8—C8—C7	112.29 (13)	H182—C18—H183	109.5
C9—C8—C7	102.21 (13)	O19—C19—O8	122.5 (2)
O8—C8—H8	110.5	O19—C19—C20	125.7 (2)
C9—C8—H8	110.5	O8—C19—C20	111.8 (2)
C7—C8—H8	110.5	C19—C20—H201	109.5
C8—C9—C10	99.94 (16)	C19—C20—H202	109.5
C8—C9—H91	111.8	H201—C20—H202	109.5
C10—C9—H91	111.8	C19—C20—H203	109.5
C8—C9—H92	111.8	H201—C20—H203	109.5
C10—C9—H92	111.8	H202—C20—H203	109.5
H91—C9—H92	109.5
C7—O1—C1—O5	113.88 (13)	C1—O1—C7—C8	−160.75 (12)
C7—O1—C1—C2	−126.82 (13)	C1—O1—C7—C12	73.76 (17)
C5—O5—C1—O1	57.49 (15)	C19—O8—C8—C9	152.62 (16)
C5—O5—C1—C2	−61.14 (15)	C19—O8—C8—C7	−93.87 (18)
C13—O2—C2—C3	−115.53 (14)	O10—C7—C8—O8	−145.90 (14)
C13—O2—C2—C1	126.24 (14)	O1—C7—C8—O8	−27.51 (18)
O1—C1—C2—O2	57.73 (15)	C12—C7—C8—O8	92.95 (18)
O5—C1—C2—O2	177.55 (11)	O10—C7—C8—C9	−27.27 (18)
O1—C1—C2—C3	−60.65 (15)	O1—C7—C8—C9	91.12 (15)
O5—C1—C2—C3	59.17 (14)	C12—C7—C8—C9	−148.43 (16)
C15—O3—C3—C2	−146.46 (14)	O8—C8—C9—C10	159.28 (13)
C15—O3—C3—C4	91.47 (16)	C7—C8—C9—C10	39.52 (17)
O2—C2—C3—O3	61.00 (14)	C7—O10—C10—C11	145.06 (15)
C1—C2—C3—O3	178.66 (11)	C7—O10—C10—C9	23.23 (18)
O2—C2—C3—C4	−175.47 (12)	C8—C9—C10—O10	−38.96 (17)
C1—C2—C3—C4	−57.80 (15)	C8—C9—C10—C11	−157.96 (16)
O3—C3—C4—C5	175.10 (11)	O10—C10—C11—Cl1	71.71 (19)
C2—C3—C4—C5	54.83 (15)	C9—C10—C11—Cl1	−172.02 (13)
O3—C3—C4—Cl4	52.86 (15)	O1—C7—C12—Cl2A	179.51 (12)
C2—C3—C4—Cl4	−67.41 (14)	O10—C7—C12—Cl2A	−59.30 (17)
C1—O5—C5—C6	−176.16 (12)	C8—C7—C12—Cl2A	60.03 (18)
C1—O5—C5—C4	59.86 (15)	O1—C7—C12—Cl2B	72.2 (4)
C3—C4—C5—O5	−54.61 (16)	O10—C7—C12—Cl2B	−166.6 (4)
Cl4—C4—C5—O5	67.31 (14)	C8—C7—C12—Cl2B	−47.3 (4)
C3—C4—C5—C6	−174.84 (13)	C2—O2—C13—O13	4.1 (2)
Cl4—C4—C5—C6	−52.92 (16)	C2—O2—C13—C14	−174.98 (15)
O5—C5—C6—O6	65.61 (16)	C3—O3—C15—O15	−8.0 (2)
C4—C5—C6—O6	−171.30 (12)	C3—O3—C15—C16	171.76 (15)
C17—O6—C6—C5	87.23 (18)	C6—O6—C17—O17	−6.3 (3)
C10—O10—C7—O1	−112.45 (15)	C6—O6—C17—C18	174.35 (17)
C10—O10—C7—C12	128.26 (15)	C8—O8—C19—O19	0.2 (3)
C10—O10—C7—C8	2.63 (17)	C8—O8—C19—C20	179.07 (17)
C1—O1—C7—O10	−46.08 (17)