Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107035858/hj3047sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107035858/hj3047Isup2.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S0108270107035858/hj3047sup3.pdf |
CCDC reference: 645558
For related literature, see: Allen (2002); Allen et al. (1998); Desiraju (1989); Desiraju & Steiner (1999); Erlanson et al. (2000); Hof & Diedrich (2004); Maccallum et al. (1995); Manoj et al. (2005, 2006); Potter & Lampe (1995); Sureshan et al. (2003).
The preparation of 2,4(6)-di-O-benzoyl-6(4)-O-[(1S)-10-camphorsulfonyl]-myo-inositol 1,3,5-orthoacetate, a mixture of diastereomers (I) and (II), was carried out as follows. A mixture of pyridine (10 ml), racemic 2,4-di-O-benzoyl-myo-inositol 1,3,5-orthoacetate (0.412 g, 1 mmol) and (1S)-10-camphorsulfonyl chloride (0.751 g, 3 mmol) was stirred at room temperature for 24 h. Pyridine was evaporated under reduced pressure and the residue obtained was worked up with chloroform. The crude product was purified (0.451 g, 72%) by flash column chromatography over silica (eluent: ethyl acetate–petroleum ether 1:9 v/v). The mixture of diastereomers (I) and (II) was crystallized from a mixture of dichloromethane and methanol (4:1 v/v) in a closed container at room temperature (m.p. 426–427 K). Spectroscopic analysis: IR (CHCl3, ν, cm-1): 1718, 1733; 1H NMR (CDCl3, 200 MHz, δ, p.p.m.): 0.71–0.77 (2s, 3H), 0.92–1.02 (2s, 3H), 1.43 (s, 1H), 1.62 (s, 3H), 1.64–1.73 (m, 1H), 1.88–2.10 (m, 3H), 2.26–2.42 (m, 2H), 2.81–2.98 (m, 1H), 3.46–3.59 (2d, 1H), 4.61–4.76 (m, 2H), 4.76–4.83 (m, 1H), 5.47–5.59 (m, 2H), 5.78–5.86 (m, 1H), 7.43–7.63 (m, 6H), 8.10–8.18 (m, 4H); 13C NMR (CDCl3, 50 MHz, δ, p.p.m.): 19.4, 19.5, 23.9, 24.7, 26.7, 26.8, 42.2, 42.6, 47.9, 48.0, 48.1, 57.7, 57.8, 62.3, 67.3, 67.4, 67.5, 69.8, 70.0, 70.3, 72.4, 72.6, 109.2, 128.4, 128.6, 128.8, 129.3, 129.9, 130.0, 133.5, 133.6, 165.1, 165.9, 213.9. Analysis, calculated for C32H34O11S: C 61.33, H 5.47%; found: C 61.49, H 5.42%.
All H atoms were placed in idealized positions, with C—H = 0.98 Å for atoms H27 and H27' and inositol ring H atoms, 0.93 Å for phenyl H atoms, 0.97 Å for methylene H atoms and 0.96 Å for methyl H atoms, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Version 1.5; Macrae et al., 2006); software used to prepare material for publication: SHELXTL97 (Sheldrick, 1997), PLATON (Spek, 2003) and publCIF (Westrip, 2007).
C32H34O11S | Z = 2 |
Mr = 626.65 | F(000) = 660 |
Triclinic, P1 | Dx = 1.444 Mg m−3 |
a = 11.5241 (16) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.6958 (16) Å | Cell parameters from 5336 reflections |
c = 12.453 (2) Å | θ = 2.4–28.1° |
α = 80.499 (3)° | µ = 0.18 mm−1 |
β = 62.449 (2)° | T = 298 K |
γ = 75.937 (2)° | Irregular, colourless |
V = 1440.8 (4) Å3 | 0.68 × 0.25 × 0.14 mm |
Bruker SMART APEX CCD area-detector diffractometer | 7596 independent reflections |
Radiation source: fine-focus sealed tube | 7284 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
ω and ϕ scans | θmax = 25.0°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −13→13 |
Tmin = 0.889, Tmax = 0.976 | k = −13→13 |
9388 measured reflections | l = −14→13 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.052 | H-atom parameters constrained |
wR(F2) = 0.136 | w = 1/[σ2(Fo2) + (0.0711P)2 + 0.3482P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
7596 reflections | Δρmax = 0.54 e Å−3 |
799 parameters | Δρmin = −0.29 e Å−3 |
3 restraints | Absolute structure: Flack H D (1983),2944 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.00 (8) |
C32H34O11S | γ = 75.937 (2)° |
Mr = 626.65 | V = 1440.8 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.5241 (16) Å | Mo Kα radiation |
b = 11.6958 (16) Å | µ = 0.18 mm−1 |
c = 12.453 (2) Å | T = 298 K |
α = 80.499 (3)° | 0.68 × 0.25 × 0.14 mm |
β = 62.449 (2)° |
Bruker SMART APEX CCD area-detector diffractometer | 7596 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 7284 reflections with I > 2σ(I) |
Tmin = 0.889, Tmax = 0.976 | Rint = 0.039 |
9388 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | H-atom parameters constrained |
wR(F2) = 0.136 | Δρmax = 0.54 e Å−3 |
S = 1.09 | Δρmin = −0.29 e Å−3 |
7596 reflections | Absolute structure: Flack H D (1983),2944 Friedel pairs |
799 parameters | Absolute structure parameter: 0.00 (8) |
3 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.91377 (9) | 0.76272 (8) | 0.14984 (9) | 0.0187 (2) | |
O1 | 1.1465 (3) | 0.8970 (2) | 0.4284 (3) | 0.0218 (7) | |
O2 | 1.2987 (3) | 0.8939 (2) | 0.1723 (3) | 0.0212 (7) | |
O3 | 1.0279 (3) | 1.0056 (2) | 0.3264 (3) | 0.0232 (7) | |
O4 | 0.9564 (3) | 0.7425 (2) | 0.2576 (3) | 0.0206 (7) | |
O5 | 0.9213 (3) | 0.8977 (2) | 0.5043 (3) | 0.0187 (6) | |
O6 | 1.1021 (3) | 0.6146 (2) | 0.3732 (3) | 0.0177 (6) | |
O7 | 1.3022 (3) | 0.8645 (3) | −0.0028 (3) | 0.0322 (8) | |
O8 | 1.2234 (3) | 0.5181 (2) | 0.4719 (3) | 0.0280 (7) | |
O9 | 0.8311 (3) | 0.6800 (3) | 0.1748 (3) | 0.0313 (7) | |
O10 | 0.8645 (3) | 0.8859 (2) | 0.1355 (3) | 0.0308 (8) | |
O11 | 1.0921 (4) | 0.4874 (3) | −0.0338 (3) | 0.0497 (9) | |
C1 | 1.1835 (4) | 0.7927 (3) | 0.3621 (4) | 0.0192 (9) | |
H1 | 1.2699 | 0.7471 | 0.3549 | 0.023* | |
C2 | 1.1899 (4) | 0.8301 (3) | 0.2382 (4) | 0.0196 (9) | |
H2 | 1.2065 | 0.7604 | 0.1954 | 0.024* | |
C3 | 1.0576 (4) | 0.9099 (3) | 0.2517 (4) | 0.0190 (9) | |
H3 | 1.0619 | 0.9407 | 0.1720 | 0.023* | |
C4 | 0.9437 (4) | 0.8420 (3) | 0.3213 (4) | 0.0176 (9) | |
H4 | 0.8589 | 0.8959 | 0.3355 | 0.021* | |
C5 | 0.9430 (4) | 0.7942 (3) | 0.4431 (4) | 0.0160 (8) | |
H5 | 0.8707 | 0.7501 | 0.4899 | 0.019* | |
C6 | 1.0754 (4) | 0.7193 (3) | 0.4329 (4) | 0.0199 (9) | |
H6 | 1.0698 | 0.6973 | 0.5143 | 0.024* | |
C7 | 1.0234 (4) | 0.9648 (3) | 0.4408 (4) | 0.0162 (8) | |
C8 | 0.9899 (5) | 1.0694 (3) | 0.5118 (5) | 0.0268 (10) | |
H8A | 1.0549 | 1.1188 | 0.4677 | 0.040* | |
H8B | 0.9902 | 1.0430 | 0.5889 | 0.040* | |
H8C | 0.9031 | 1.1135 | 0.5243 | 0.040* | |
C9 | 1.3508 (4) | 0.8991 (3) | 0.0496 (4) | 0.0220 (9) | |
C10 | 1.4749 (4) | 0.9513 (3) | −0.0109 (4) | 0.0225 (9) | |
C11 | 1.5425 (4) | 0.9631 (3) | 0.0534 (4) | 0.0239 (9) | |
H11 | 1.5095 | 0.9424 | 0.1361 | 0.029* | |
C12 | 1.6594 (5) | 1.0060 (4) | −0.0079 (5) | 0.0352 (12) | |
H12 | 1.7062 | 1.0141 | 0.0335 | 0.042* | |
C13 | 1.7070 (5) | 1.0368 (4) | −0.1300 (5) | 0.0371 (12) | |
H13 | 1.7850 | 1.0671 | −0.1704 | 0.044* | |
C14 | 1.6399 (5) | 1.0233 (4) | −0.1934 (5) | 0.0353 (11) | |
H14 | 1.6736 | 1.0433 | −0.2763 | 0.042* | |
C15 | 1.5228 (5) | 0.9802 (4) | −0.1333 (5) | 0.0327 (11) | |
H15 | 1.4770 | 0.9709 | −0.1753 | 0.039* | |
C16 | 1.1759 (4) | 0.5173 (3) | 0.4041 (4) | 0.0190 (9) | |
C17 | 1.1870 (4) | 0.4132 (3) | 0.3434 (4) | 0.0196 (9) | |
C18 | 1.2755 (5) | 0.3100 (4) | 0.3499 (5) | 0.0284 (11) | |
H18 | 1.3237 | 0.3062 | 0.3935 | 0.034* | |
C19 | 1.2905 (5) | 0.2130 (4) | 0.2902 (5) | 0.0314 (11) | |
H19 | 1.3496 | 0.1441 | 0.2937 | 0.038* | |
C20 | 1.2194 (5) | 0.2179 (4) | 0.2265 (5) | 0.0310 (11) | |
H20 | 1.2305 | 0.1521 | 0.1873 | 0.037* | |
C21 | 1.1308 (5) | 0.3199 (4) | 0.2196 (5) | 0.0295 (11) | |
H21 | 1.0820 | 0.3225 | 0.1768 | 0.035* | |
C22 | 1.1160 (4) | 0.4176 (4) | 0.2771 (4) | 0.0244 (10) | |
H22 | 1.0583 | 0.4868 | 0.2716 | 0.029* | |
C23 | 1.0712 (4) | 0.7183 (4) | 0.0281 (4) | 0.0248 (9) | |
H23A | 1.1243 | 0.7778 | 0.0108 | 0.030* | |
H23B | 1.1156 | 0.6455 | 0.0541 | 0.030* | |
C24 | 1.0697 (4) | 0.6985 (3) | −0.0893 (4) | 0.0195 (9) | |
C25 | 0.9431 (5) | 0.7463 (4) | −0.1082 (5) | 0.0341 (11) | |
H25A | 0.9038 | 0.8260 | −0.0818 | 0.041* | |
H25B | 0.8775 | 0.6963 | −0.0637 | 0.041* | |
C26 | 0.9919 (5) | 0.7444 (4) | −0.2460 (5) | 0.0338 (11) | |
H26A | 0.9459 | 0.6962 | −0.2637 | 0.041* | |
H26B | 0.9795 | 0.8235 | −0.2826 | 0.041* | |
C27 | 1.1405 (4) | 0.6895 (4) | −0.2906 (4) | 0.0245 (10) | |
H27 | 1.1950 | 0.7029 | −0.3779 | 0.029* | |
C28 | 1.1464 (5) | 0.5605 (4) | −0.2457 (5) | 0.0359 (12) | |
H28A | 1.2363 | 0.5154 | −0.2840 | 0.043* | |
H28B | 1.0871 | 0.5257 | −0.2605 | 0.043* | |
C29 | 1.1001 (5) | 0.5668 (4) | −0.1109 (5) | 0.0280 (10) | |
C30 | 1.1810 (5) | 0.7413 (4) | −0.2087 (4) | 0.0267 (10) | |
C31 | 1.1679 (7) | 0.8752 (4) | −0.2262 (5) | 0.0506 (16) | |
H31A | 1.1836 | 0.9031 | −0.1667 | 0.076* | |
H31B | 1.0797 | 0.9108 | −0.2170 | 0.076* | |
H31C | 1.2321 | 0.8960 | −0.3060 | 0.076* | |
C32 | 1.3205 (5) | 0.6866 (5) | −0.2222 (5) | 0.0423 (13) | |
H32A | 1.3839 | 0.6969 | −0.3053 | 0.064* | |
H32B | 1.3254 | 0.6039 | −0.1984 | 0.064* | |
H32C | 1.3402 | 0.7245 | −0.1714 | 0.064* | |
S1' | 0.81494 (9) | 0.46341 (8) | 0.63126 (9) | 0.0208 (2) | |
O1' | 0.7006 (3) | 0.2121 (2) | 0.4593 (3) | 0.0199 (6) | |
O2' | 0.4280 (3) | 0.3135 (2) | 0.6174 (3) | 0.0238 (7) | |
O3' | 0.5755 (3) | 0.3181 (2) | 0.3608 (3) | 0.0222 (7) | |
O4' | 0.6051 (3) | 0.6030 (2) | 0.4216 (3) | 0.0214 (7) | |
O5' | 0.8007 (3) | 0.3266 (2) | 0.2820 (3) | 0.0214 (7) | |
O6' | 0.7551 (3) | 0.4798 (2) | 0.5350 (3) | 0.0198 (6) | |
O7' | 0.4382 (3) | 0.3268 (3) | 0.7903 (3) | 0.0328 (8) | |
O8' | 0.4940 (3) | 0.7009 (2) | 0.3161 (3) | 0.0281 (7) | |
O9' | 0.8589 (3) | 0.5701 (3) | 0.6179 (3) | 0.0352 (8) | |
O10' | 0.9053 (4) | 0.3527 (3) | 0.6134 (3) | 0.0405 (9) | |
O11' | 0.8954 (3) | 0.4269 (3) | 0.8309 (3) | 0.0387 (8) | |
C1' | 0.6679 (4) | 0.3069 (3) | 0.5344 (4) | 0.0199 (9) | |
H1' | 0.6672 | 0.2750 | 0.6126 | 0.024* | |
C2' | 0.5324 (4) | 0.3805 (3) | 0.5546 (4) | 0.0201 (9) | |
H2' | 0.5133 | 0.4496 | 0.5993 | 0.024* | |
C3' | 0.5346 (4) | 0.4192 (3) | 0.4316 (4) | 0.0211 (9) | |
H3' | 0.4458 | 0.4615 | 0.4419 | 0.025* | |
C4' | 0.6375 (4) | 0.4988 (3) | 0.3580 (4) | 0.0190 (9) | |
H4' | 0.6406 | 0.5206 | 0.2774 | 0.023* | |
C5' | 0.7727 (4) | 0.4288 (3) | 0.3469 (4) | 0.0201 (9) | |
H5' | 0.8414 | 0.4767 | 0.3009 | 0.024* | |
C6' | 0.7773 (4) | 0.3804 (3) | 0.4664 (4) | 0.0197 (9) | |
H6' | 0.8646 | 0.3304 | 0.4506 | 0.024* | |
C7' | 0.7036 (4) | 0.2547 (3) | 0.3456 (5) | 0.0240 (10) | |
C8' | 0.7406 (5) | 0.1515 (3) | 0.2699 (4) | 0.0273 (11) | |
H8D | 0.6760 | 0.1013 | 0.3109 | 0.041* | |
H8E | 0.8272 | 0.1075 | 0.2582 | 0.041* | |
H8F | 0.7422 | 0.1802 | 0.1925 | 0.041* | |
C9' | 0.3850 (5) | 0.2968 (3) | 0.7391 (4) | 0.0255 (10) | |
C10' | 0.2662 (4) | 0.2417 (3) | 0.7985 (4) | 0.0255 (10) | |
C11' | 0.1943 (5) | 0.2289 (4) | 0.7383 (5) | 0.0335 (12) | |
H11' | 0.2241 | 0.2507 | 0.6559 | 0.040* | |
C12' | 0.0775 (5) | 0.1834 (4) | 0.8019 (6) | 0.0385 (13) | |
H12' | 0.0285 | 0.1767 | 0.7622 | 0.046* | |
C13' | 0.0344 (5) | 0.1485 (4) | 0.9228 (6) | 0.0473 (16) | |
H13' | −0.0423 | 0.1164 | 0.9643 | 0.057* | |
C14' | 0.1069 (6) | 0.1616 (4) | 0.9835 (5) | 0.0417 (13) | |
H14' | 0.0782 | 0.1391 | 1.0656 | 0.050* | |
C15' | 0.2194 (5) | 0.2076 (4) | 0.9207 (5) | 0.0324 (11) | |
H15' | 0.2667 | 0.2165 | 0.9614 | 0.039* | |
C16' | 0.5395 (4) | 0.7011 (3) | 0.3851 (4) | 0.0196 (9) | |
C17' | 0.5288 (4) | 0.8061 (3) | 0.4450 (4) | 0.0200 (9) | |
C18' | 0.4413 (5) | 0.9095 (4) | 0.4368 (4) | 0.0278 (10) | |
H18' | 0.3918 | 0.9122 | 0.3946 | 0.033* | |
C19' | 0.4291 (5) | 1.0080 (4) | 0.4923 (5) | 0.0329 (12) | |
H19' | 0.3702 | 1.0770 | 0.4887 | 0.039* | |
C20' | 0.5052 (5) | 1.0034 (4) | 0.5534 (5) | 0.0322 (11) | |
H20' | 0.4977 | 1.0700 | 0.5897 | 0.039* | |
C21' | 0.5923 (5) | 0.9007 (4) | 0.5607 (5) | 0.0318 (11) | |
H21' | 0.6428 | 0.8982 | 0.6019 | 0.038* | |
C22' | 0.6035 (4) | 0.8020 (4) | 0.5065 (4) | 0.0247 (10) | |
H22' | 0.6615 | 0.7327 | 0.5113 | 0.030* | |
C23' | 0.6658 (5) | 0.4595 (4) | 0.7695 (4) | 0.0328 (11) | |
H23C | 0.5927 | 0.5094 | 0.7558 | 0.039* | |
H23D | 0.6497 | 0.3794 | 0.7855 | 0.039* | |
C24' | 0.6589 (5) | 0.4964 (4) | 0.8832 (5) | 0.0287 (10) | |
C25' | 0.6281 (5) | 0.6323 (4) | 0.8969 (5) | 0.0329 (11) | |
H25C | 0.7083 | 0.6654 | 0.8523 | 0.039* | |
H25D | 0.5625 | 0.6727 | 0.8684 | 0.039* | |
C26' | 0.5727 (6) | 0.6411 (4) | 1.0353 (5) | 0.0405 (13) | |
H26C | 0.6244 | 0.6829 | 1.0531 | 0.049* | |
H26D | 0.4800 | 0.6808 | 1.0704 | 0.049* | |
C27' | 0.5878 (5) | 0.5104 (4) | 1.0825 (5) | 0.0297 (11) | |
H27' | 0.5336 | 0.4968 | 1.1698 | 0.036* | |
C28' | 0.7357 (5) | 0.4632 (4) | 1.0393 (5) | 0.0327 (11) | |
H28C | 0.7779 | 0.5165 | 1.0551 | 0.039* | |
H28D | 0.7521 | 0.3859 | 1.0779 | 0.039* | |
C29' | 0.7847 (5) | 0.4562 (3) | 0.9047 (5) | 0.0267 (10) | |
C30' | 0.5541 (5) | 0.4511 (4) | 1.0013 (5) | 0.0320 (11) | |
C31' | 0.4102 (5) | 0.4943 (5) | 1.0185 (5) | 0.0441 (13) | |
H31D | 0.3947 | 0.5782 | 1.0013 | 0.066* | |
H31E | 0.3497 | 0.4757 | 1.1007 | 0.066* | |
H31F | 0.3960 | 0.4560 | 0.9642 | 0.066* | |
C32' | 0.5785 (6) | 0.3155 (4) | 1.0181 (5) | 0.0418 (13) | |
H32D | 0.5489 | 0.2846 | 0.9703 | 0.063* | |
H32E | 0.5298 | 0.2920 | 1.1022 | 0.063* | |
H32F | 0.6720 | 0.2852 | 0.9925 | 0.063* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O9 | 0.0272 (16) | 0.0479 (18) | 0.0230 (18) | −0.0136 (14) | −0.0115 (14) | −0.0020 (14) |
S1 | 0.0194 (5) | 0.0210 (4) | 0.0156 (6) | −0.0023 (4) | −0.0083 (4) | −0.0014 (4) |
O1 | 0.0216 (15) | 0.0209 (13) | 0.0243 (18) | −0.0006 (11) | −0.0114 (14) | −0.0066 (13) |
O2 | 0.0182 (15) | 0.0223 (13) | 0.0193 (18) | −0.0049 (11) | −0.0040 (13) | −0.0029 (12) |
O3 | 0.0285 (17) | 0.0172 (13) | 0.0229 (18) | −0.0032 (12) | −0.0116 (15) | 0.0002 (12) |
O4 | 0.0259 (16) | 0.0187 (13) | 0.0217 (17) | −0.0021 (11) | −0.0137 (14) | −0.0061 (12) |
O5 | 0.0217 (15) | 0.0207 (13) | 0.0126 (16) | −0.0014 (11) | −0.0068 (13) | −0.0051 (12) |
O6 | 0.0222 (15) | 0.0163 (12) | 0.0146 (15) | −0.0012 (11) | −0.0101 (12) | 0.0011 (11) |
O7 | 0.0292 (17) | 0.0442 (18) | 0.0229 (19) | −0.0162 (14) | −0.0057 (15) | −0.0055 (14) |
O8 | 0.0282 (17) | 0.0256 (15) | 0.033 (2) | 0.0065 (13) | −0.0198 (16) | −0.0070 (14) |
O10 | 0.0459 (19) | 0.0250 (14) | 0.0236 (18) | 0.0078 (13) | −0.0230 (15) | −0.0046 (13) |
O11 | 0.082 (3) | 0.0256 (15) | 0.044 (2) | −0.0147 (16) | −0.032 (2) | 0.0098 (16) |
C1 | 0.020 (2) | 0.0182 (18) | 0.021 (2) | 0.0029 (16) | −0.0123 (19) | −0.0055 (17) |
C2 | 0.015 (2) | 0.0174 (17) | 0.025 (3) | −0.0048 (15) | −0.0071 (19) | −0.0010 (17) |
C3 | 0.021 (2) | 0.0150 (17) | 0.017 (2) | −0.0010 (16) | −0.0066 (19) | −0.0015 (17) |
C4 | 0.018 (2) | 0.0162 (17) | 0.015 (2) | −0.0030 (15) | −0.0048 (18) | −0.0015 (16) |
C5 | 0.0168 (19) | 0.0171 (17) | 0.014 (2) | −0.0035 (15) | −0.0073 (17) | 0.0004 (16) |
C6 | 0.025 (2) | 0.0187 (18) | 0.019 (2) | −0.0038 (16) | −0.0119 (19) | −0.0026 (17) |
C7 | 0.0143 (19) | 0.0223 (18) | 0.008 (2) | −0.0024 (15) | −0.0028 (17) | 0.0013 (16) |
C8 | 0.029 (2) | 0.021 (2) | 0.030 (3) | −0.0038 (18) | −0.012 (2) | −0.005 (2) |
C9 | 0.020 (2) | 0.0209 (18) | 0.023 (2) | −0.0007 (16) | −0.0084 (19) | −0.0051 (17) |
C10 | 0.018 (2) | 0.0190 (18) | 0.024 (2) | −0.0012 (15) | −0.0039 (18) | −0.0066 (17) |
C11 | 0.019 (2) | 0.0240 (19) | 0.023 (2) | −0.0027 (16) | −0.0059 (19) | −0.0001 (18) |
C12 | 0.031 (3) | 0.031 (2) | 0.050 (4) | −0.0077 (19) | −0.021 (2) | −0.007 (2) |
C13 | 0.027 (3) | 0.038 (2) | 0.039 (3) | −0.012 (2) | −0.004 (2) | −0.008 (2) |
C14 | 0.031 (2) | 0.043 (2) | 0.020 (3) | −0.020 (2) | 0.003 (2) | 0.004 (2) |
C15 | 0.037 (3) | 0.033 (2) | 0.030 (3) | −0.013 (2) | −0.013 (2) | −0.005 (2) |
C16 | 0.0115 (19) | 0.0174 (18) | 0.020 (3) | −0.0020 (15) | −0.0019 (18) | 0.0023 (17) |
C17 | 0.015 (2) | 0.0180 (18) | 0.018 (2) | −0.0064 (15) | −0.0007 (18) | 0.0033 (17) |
C18 | 0.034 (3) | 0.0199 (19) | 0.031 (3) | −0.0024 (18) | −0.016 (2) | 0.000 (2) |
C19 | 0.037 (3) | 0.0168 (19) | 0.030 (3) | 0.0040 (18) | −0.011 (2) | −0.0008 (19) |
C20 | 0.038 (3) | 0.019 (2) | 0.033 (3) | −0.0085 (19) | −0.010 (2) | −0.005 (2) |
C21 | 0.028 (2) | 0.033 (2) | 0.029 (3) | −0.0096 (19) | −0.010 (2) | −0.009 (2) |
C22 | 0.024 (2) | 0.0242 (19) | 0.025 (3) | −0.0027 (17) | −0.012 (2) | −0.0018 (19) |
C23 | 0.019 (2) | 0.033 (2) | 0.022 (2) | −0.0069 (16) | −0.0077 (18) | −0.0032 (18) |
C24 | 0.022 (2) | 0.027 (2) | 0.012 (2) | −0.0121 (16) | −0.0074 (18) | 0.0035 (17) |
C25 | 0.027 (2) | 0.046 (3) | 0.025 (3) | 0.006 (2) | −0.014 (2) | −0.005 (2) |
C26 | 0.036 (3) | 0.039 (2) | 0.027 (3) | 0.005 (2) | −0.019 (2) | −0.006 (2) |
C27 | 0.025 (2) | 0.032 (2) | 0.016 (2) | −0.0045 (17) | −0.0087 (19) | −0.0037 (18) |
C28 | 0.043 (3) | 0.031 (2) | 0.037 (3) | −0.007 (2) | −0.018 (2) | −0.010 (2) |
C29 | 0.036 (3) | 0.024 (2) | 0.026 (3) | −0.0111 (18) | −0.013 (2) | 0.0010 (19) |
C30 | 0.029 (2) | 0.030 (2) | 0.025 (3) | −0.0086 (17) | −0.012 (2) | −0.0055 (19) |
C31 | 0.091 (5) | 0.039 (3) | 0.028 (3) | −0.029 (3) | −0.026 (3) | 0.004 (2) |
C32 | 0.028 (3) | 0.078 (4) | 0.026 (3) | −0.018 (2) | −0.009 (2) | −0.013 (3) |
S1' | 0.0224 (6) | 0.0225 (5) | 0.0182 (6) | −0.0034 (4) | −0.0103 (5) | 0.0002 (4) |
O1' | 0.0207 (15) | 0.0175 (12) | 0.0202 (17) | −0.0026 (11) | −0.0077 (13) | −0.0040 (12) |
O2' | 0.0208 (16) | 0.0220 (13) | 0.0259 (19) | −0.0057 (12) | −0.0062 (14) | −0.0048 (13) |
O3' | 0.0238 (15) | 0.0156 (12) | 0.0283 (19) | −0.0016 (11) | −0.0122 (14) | −0.0049 (12) |
O4' | 0.0262 (15) | 0.0150 (12) | 0.0248 (18) | 0.0006 (11) | −0.0139 (14) | −0.0048 (12) |
O5' | 0.0202 (15) | 0.0167 (13) | 0.0222 (18) | −0.0018 (11) | −0.0057 (13) | −0.0021 (12) |
O6' | 0.0239 (15) | 0.0171 (12) | 0.0169 (16) | −0.0014 (11) | −0.0094 (13) | 0.0004 (12) |
O7' | 0.0352 (18) | 0.0401 (17) | 0.0267 (19) | −0.0166 (14) | −0.0131 (16) | 0.0011 (15) |
O8' | 0.0284 (17) | 0.0241 (14) | 0.036 (2) | 0.0027 (12) | −0.0199 (16) | −0.0065 (14) |
O9' | 0.048 (2) | 0.0446 (18) | 0.0256 (18) | −0.0307 (16) | −0.0201 (16) | 0.0095 (15) |
O10' | 0.047 (2) | 0.0403 (18) | 0.038 (2) | 0.0131 (15) | −0.0290 (18) | −0.0121 (16) |
O11' | 0.0302 (17) | 0.0480 (18) | 0.0333 (19) | 0.0003 (14) | −0.0124 (15) | −0.0075 (15) |
C1' | 0.022 (2) | 0.0211 (19) | 0.017 (2) | −0.0023 (16) | −0.0098 (19) | 0.0000 (17) |
C2' | 0.020 (2) | 0.0189 (18) | 0.017 (2) | −0.0033 (16) | −0.0047 (19) | −0.0025 (16) |
C3' | 0.019 (2) | 0.0146 (17) | 0.029 (3) | 0.0024 (15) | −0.0116 (19) | −0.0067 (18) |
C4' | 0.021 (2) | 0.0151 (17) | 0.022 (2) | −0.0002 (16) | −0.0118 (19) | −0.0025 (17) |
C5' | 0.020 (2) | 0.0172 (18) | 0.020 (2) | −0.0054 (15) | −0.0055 (18) | −0.0031 (17) |
C6' | 0.021 (2) | 0.0188 (18) | 0.020 (2) | −0.0020 (16) | −0.0106 (19) | −0.0018 (17) |
C7' | 0.024 (2) | 0.0150 (18) | 0.035 (3) | 0.0007 (16) | −0.016 (2) | −0.0051 (19) |
C8' | 0.035 (3) | 0.0194 (19) | 0.026 (3) | 0.0001 (18) | −0.014 (2) | −0.0059 (19) |
C9' | 0.029 (2) | 0.0160 (18) | 0.023 (3) | −0.0001 (16) | −0.005 (2) | −0.0055 (17) |
C10' | 0.021 (2) | 0.0185 (18) | 0.031 (3) | 0.0022 (15) | −0.008 (2) | −0.0064 (18) |
C11' | 0.035 (3) | 0.0196 (19) | 0.039 (3) | −0.0031 (17) | −0.010 (2) | −0.0062 (19) |
C12' | 0.026 (2) | 0.033 (2) | 0.049 (3) | −0.0093 (19) | −0.004 (2) | −0.013 (2) |
C13' | 0.029 (3) | 0.028 (2) | 0.061 (4) | −0.014 (2) | 0.008 (3) | −0.012 (2) |
C14' | 0.049 (3) | 0.025 (2) | 0.038 (3) | −0.009 (2) | −0.008 (3) | 0.001 (2) |
C15' | 0.033 (3) | 0.022 (2) | 0.033 (3) | −0.0039 (18) | −0.007 (2) | −0.0027 (19) |
C16' | 0.023 (2) | 0.0203 (19) | 0.018 (2) | −0.0019 (16) | −0.0128 (19) | −0.0017 (17) |
C17' | 0.019 (2) | 0.0178 (18) | 0.017 (2) | −0.0023 (16) | −0.0038 (18) | −0.0007 (17) |
C18' | 0.031 (2) | 0.023 (2) | 0.025 (3) | −0.0009 (18) | −0.011 (2) | −0.0018 (19) |
C19' | 0.043 (3) | 0.0184 (19) | 0.033 (3) | 0.0019 (19) | −0.016 (2) | −0.001 (2) |
C20' | 0.037 (3) | 0.023 (2) | 0.027 (3) | −0.0081 (19) | −0.002 (2) | −0.008 (2) |
C21' | 0.025 (2) | 0.035 (2) | 0.039 (3) | −0.0104 (19) | −0.012 (2) | −0.009 (2) |
C22' | 0.014 (2) | 0.024 (2) | 0.030 (3) | −0.0044 (16) | −0.005 (2) | −0.0013 (19) |
C23' | 0.026 (2) | 0.052 (3) | 0.021 (2) | −0.016 (2) | −0.0054 (19) | −0.008 (2) |
C24' | 0.029 (2) | 0.029 (2) | 0.027 (3) | −0.0077 (18) | −0.010 (2) | −0.0051 (19) |
C25' | 0.038 (3) | 0.024 (2) | 0.036 (3) | 0.0009 (19) | −0.019 (2) | −0.002 (2) |
C26' | 0.040 (3) | 0.036 (3) | 0.045 (4) | 0.003 (2) | −0.019 (3) | −0.016 (2) |
C27' | 0.036 (3) | 0.035 (2) | 0.016 (2) | −0.014 (2) | −0.007 (2) | 0.0001 (19) |
C28' | 0.037 (3) | 0.036 (2) | 0.029 (3) | −0.012 (2) | −0.018 (2) | 0.004 (2) |
C29' | 0.029 (2) | 0.023 (2) | 0.029 (3) | −0.0025 (17) | −0.014 (2) | −0.0024 (19) |
C30' | 0.038 (3) | 0.038 (2) | 0.019 (3) | −0.015 (2) | −0.010 (2) | 0.002 (2) |
C31' | 0.032 (3) | 0.069 (3) | 0.024 (3) | −0.020 (2) | −0.002 (2) | −0.001 (3) |
C32' | 0.054 (3) | 0.035 (2) | 0.036 (3) | −0.028 (2) | −0.012 (3) | 0.002 (2) |
O9—S1 | 1.419 (3) | S1'—O9' | 1.415 (3) |
S1—O10 | 1.428 (3) | S1'—O10' | 1.427 (3) |
S1—O4 | 1.596 (3) | S1'—O6' | 1.605 (3) |
S1—C23 | 1.766 (4) | S1'—C23' | 1.787 (5) |
O1—C7 | 1.399 (5) | O1'—C7' | 1.409 (6) |
O1—C1 | 1.451 (4) | O1'—C1' | 1.436 (5) |
O2—C9 | 1.355 (6) | O2'—C9' | 1.355 (6) |
O2—C2 | 1.450 (5) | O2'—C2' | 1.435 (5) |
O3—C7 | 1.407 (5) | O3'—C7' | 1.422 (5) |
O3—C3 | 1.449 (5) | O3'—C3' | 1.446 (5) |
O4—C4 | 1.455 (4) | O4'—C16' | 1.349 (5) |
O5—C7 | 1.417 (5) | O4'—C4' | 1.441 (4) |
O5—C5 | 1.445 (4) | O5'—C7' | 1.415 (5) |
O6—C16 | 1.361 (5) | O5'—C5' | 1.441 (5) |
O6—C6 | 1.433 (4) | O6'—C6' | 1.458 (5) |
O7—C9 | 1.200 (5) | O7'—C9' | 1.203 (6) |
O8—C16 | 1.203 (5) | O8'—C16' | 1.196 (5) |
O11—C29 | 1.207 (6) | O11'—C29' | 1.181 (6) |
C1—C2 | 1.505 (6) | C1'—C2' | 1.515 (6) |
C1—C6 | 1.523 (6) | C1'—C6' | 1.531 (6) |
C1—H1 | 0.9800 | C1'—H1' | 0.9800 |
C2—C3 | 1.533 (5) | C2'—C3' | 1.514 (6) |
C2—H2 | 0.9800 | C2'—H2' | 0.9800 |
C3—C4 | 1.528 (6) | C3'—C4' | 1.537 (6) |
C3—H3 | 0.9800 | C3'—H3' | 0.9800 |
C4—C5 | 1.525 (6) | C4'—C5' | 1.528 (6) |
C4—H4 | 0.9800 | C4'—H4' | 0.9800 |
C5—C6 | 1.523 (5) | C5'—C6' | 1.522 (6) |
C5—H5 | 0.9800 | C5'—H5' | 0.9800 |
C6—H6 | 0.9800 | C6'—H6' | 0.9800 |
C7—C8 | 1.496 (5) | C7'—C8' | 1.510 (5) |
C8—H8A | 0.9600 | C8'—H8D | 0.9600 |
C8—H8B | 0.9600 | C8'—H8E | 0.9600 |
C8—H8C | 0.9600 | C8'—H8F | 0.9600 |
C9—C10 | 1.504 (6) | C9'—C10' | 1.473 (6) |
C10—C15 | 1.373 (7) | C10'—C15' | 1.382 (7) |
C10—C11 | 1.390 (6) | C10'—C11' | 1.395 (7) |
C11—C12 | 1.379 (7) | C11'—C12' | 1.394 (7) |
C11—H11 | 0.9300 | C11'—H11' | 0.9300 |
C12—C13 | 1.373 (8) | C12'—C13' | 1.372 (8) |
C12—H12 | 0.9300 | C12'—H12' | 0.9300 |
C13—C14 | 1.382 (8) | C13'—C14' | 1.406 (8) |
C13—H13 | 0.9300 | C13'—H13' | 0.9300 |
C14—C15 | 1.382 (7) | C14'—C15' | 1.358 (7) |
C14—H14 | 0.9300 | C14'—H14' | 0.9300 |
C15—H15 | 0.9300 | C15'—H15' | 0.9300 |
C16—C17 | 1.486 (5) | C16'—C17' | 1.490 (5) |
C17—C22 | 1.394 (6) | C17'—C22' | 1.381 (6) |
C17—C18 | 1.396 (6) | C17'—C18' | 1.397 (6) |
C18—C19 | 1.390 (6) | C18'—C19' | 1.385 (6) |
C18—H18 | 0.9300 | C18'—H18' | 0.9300 |
C19—C20 | 1.367 (7) | C19'—C20' | 1.390 (7) |
C19—H19 | 0.9300 | C19'—H19' | 0.9300 |
C20—C21 | 1.389 (7) | C20'—C21' | 1.386 (7) |
C20—H20 | 0.9300 | C20'—H20' | 0.9300 |
C21—C22 | 1.382 (6) | C21'—C22' | 1.382 (6) |
C21—H21 | 0.9300 | C21'—H21' | 0.9300 |
C22—H22 | 0.9300 | C22'—H22' | 0.9300 |
C23—C24 | 1.527 (6) | C23'—C24' | 1.510 (7) |
C23—H23A | 0.9700 | C23'—H23C | 0.9700 |
C23—H23B | 0.9700 | C23'—H23D | 0.9700 |
C24—C29 | 1.534 (5) | C24'—C30' | 1.520 (7) |
C24—C25 | 1.541 (6) | C24'—C29' | 1.543 (6) |
C24—C30 | 1.552 (6) | C24'—C25' | 1.562 (6) |
C25—C26 | 1.541 (7) | C25'—C26' | 1.549 (8) |
C25—H25A | 0.9700 | C25'—H25C | 0.9700 |
C25—H25B | 0.9700 | C25'—H25D | 0.9700 |
C26—C27 | 1.535 (7) | C26'—C27' | 1.543 (7) |
C26—H26A | 0.9700 | C26'—H26C | 0.9700 |
C26—H26B | 0.9700 | C26'—H26D | 0.9700 |
C27—C28 | 1.516 (6) | C27'—C28' | 1.514 (7) |
C27—C30 | 1.552 (6) | C27'—C30' | 1.542 (6) |
C27—H27 | 0.9800 | C27'—H27' | 0.9800 |
C28—C29 | 1.517 (7) | C28'—C29' | 1.510 (7) |
C28—H28A | 0.9700 | C28'—H28C | 0.9700 |
C28—H28B | 0.9700 | C28'—H28D | 0.9700 |
C30—C32 | 1.518 (7) | C30'—C31' | 1.534 (8) |
C30—C31 | 1.525 (6) | C30'—C32' | 1.539 (7) |
C31—H31A | 0.9600 | C31'—H31D | 0.9600 |
C31—H31B | 0.9600 | C31'—H31E | 0.9600 |
C31—H31C | 0.9600 | C31'—H31F | 0.9600 |
C32—H32A | 0.9600 | C32'—H32D | 0.9600 |
C32—H32B | 0.9600 | C32'—H32E | 0.9600 |
C32—H32C | 0.9600 | C32'—H32F | 0.9600 |
O9—S1—O10 | 119.8 (2) | O9'—S1'—O10' | 121.0 (2) |
O9—S1—O4 | 106.13 (18) | O9'—S1'—O6' | 104.70 (18) |
O10—S1—O4 | 108.44 (16) | O10'—S1'—O6' | 107.53 (17) |
O9—S1—C23 | 110.07 (19) | O9'—S1'—C23' | 109.6 (2) |
O10—S1—C23 | 110.9 (2) | O10'—S1'—C23' | 111.7 (2) |
O4—S1—C23 | 99.38 (18) | O6'—S1'—C23' | 99.89 (19) |
C7—O1—C1 | 112.1 (3) | C7'—O1'—C1' | 111.5 (3) |
C9—O2—C2 | 116.3 (3) | C9'—O2'—C2' | 115.6 (3) |
C7—O3—C3 | 112.4 (3) | C7'—O3'—C3' | 110.8 (3) |
C4—O4—S1 | 120.5 (2) | C16'—O4'—C4' | 116.0 (3) |
C7—O5—C5 | 113.0 (3) | C7'—O5'—C5' | 111.7 (3) |
C16—O6—C6 | 116.0 (3) | C6'—O6'—S1' | 119.8 (2) |
O1—C1—C2 | 109.0 (3) | O1'—C1'—C2' | 109.8 (3) |
O1—C1—C6 | 107.4 (3) | O1'—C1'—C6' | 106.3 (3) |
C2—C1—C6 | 109.7 (3) | C2'—C1'—C6' | 111.0 (3) |
O1—C1—H1 | 110.2 | O1'—C1'—H1' | 109.9 |
C2—C1—H1 | 110.2 | C2'—C1'—H1' | 109.9 |
C6—C1—H1 | 110.2 | C6'—C1'—H1' | 109.9 |
O2—C2—C1 | 107.6 (3) | O2'—C2'—C3' | 106.0 (3) |
O2—C2—C3 | 110.4 (3) | O2'—C2'—C1' | 112.2 (3) |
C1—C2—C3 | 109.3 (4) | C3'—C2'—C1' | 108.0 (4) |
O2—C2—H2 | 109.8 | O2'—C2'—H2' | 110.2 |
C1—C2—H2 | 109.8 | C3'—C2'—H2' | 110.2 |
C3—C2—H2 | 109.8 | C1'—C2'—H2' | 110.2 |
O3—C3—C4 | 105.4 (3) | O3'—C3'—C2' | 110.3 (3) |
O3—C3—C2 | 109.0 (3) | O3'—C3'—C4' | 105.9 (3) |
C4—C3—C2 | 110.0 (3) | C2'—C3'—C4' | 111.1 (3) |
O3—C3—H3 | 110.8 | O3'—C3'—H3' | 109.8 |
C4—C3—H3 | 110.8 | C2'—C3'—H3' | 109.8 |
C2—C3—H3 | 110.8 | C4'—C3'—H3' | 109.8 |
O4—C4—C5 | 107.9 (3) | O4'—C4'—C5' | 108.4 (3) |
O4—C4—C3 | 112.9 (3) | O4'—C4'—C3' | 110.1 (3) |
C5—C4—C3 | 108.7 (3) | C5'—C4'—C3' | 107.2 (3) |
O4—C4—H4 | 109.1 | O4'—C4'—H4' | 110.4 |
C5—C4—H4 | 109.1 | C5'—C4'—H4' | 110.4 |
C3—C4—H4 | 109.1 | C3'—C4'—H4' | 110.4 |
O5—C5—C6 | 106.4 (3) | O5'—C5'—C6' | 105.5 (3) |
O5—C5—C4 | 104.9 (3) | O5'—C5'—C4' | 106.0 (3) |
C6—C5—C4 | 113.9 (3) | C6'—C5'—C4' | 115.4 (4) |
O5—C5—H5 | 110.5 | O5'—C5'—H5' | 109.9 |
C6—C5—H5 | 110.5 | C6'—C5'—H5' | 109.9 |
C4—C5—H5 | 110.5 | C4'—C5'—H5' | 109.9 |
O6—C6—C1 | 111.5 (3) | O6'—C6'—C5' | 108.4 (3) |
O6—C6—C5 | 109.0 (3) | O6'—C6'—C1' | 111.3 (3) |
C1—C6—C5 | 108.3 (3) | C5'—C6'—C1' | 107.6 (3) |
O6—C6—H6 | 109.3 | O6'—C6'—H6' | 109.8 |
C1—C6—H6 | 109.3 | C5'—C6'—H6' | 109.8 |
C5—C6—H6 | 109.3 | C1'—C6'—H6' | 109.8 |
O1—C7—O3 | 110.7 (3) | O1'—C7'—O5' | 111.1 (3) |
O1—C7—O5 | 110.5 (3) | O1'—C7'—O3' | 110.1 (4) |
O3—C7—O5 | 109.6 (3) | O5'—C7'—O3' | 110.7 (3) |
O1—C7—C8 | 109.5 (3) | O1'—C7'—C8' | 109.2 (3) |
O3—C7—C8 | 108.5 (3) | O5'—C7'—C8' | 107.7 (4) |
O5—C7—C8 | 108.1 (3) | O3'—C7'—C8' | 108.0 (3) |
C7—C8—H8A | 109.5 | C7'—C8'—H8D | 109.5 |
C7—C8—H8B | 109.5 | C7'—C8'—H8E | 109.5 |
H8A—C8—H8B | 109.5 | H8D—C8'—H8E | 109.5 |
C7—C8—H8C | 109.5 | C7'—C8'—H8F | 109.5 |
H8A—C8—H8C | 109.5 | H8D—C8'—H8F | 109.5 |
H8B—C8—H8C | 109.5 | H8E—C8'—H8F | 109.5 |
O7—C9—O2 | 122.7 (4) | O7'—C9'—O2' | 122.4 (4) |
O7—C9—C10 | 124.9 (4) | O7'—C9'—C10' | 125.3 (5) |
O2—C9—C10 | 112.4 (4) | O2'—C9'—C10' | 112.2 (4) |
C15—C10—C11 | 121.5 (4) | C15'—C10'—C11' | 118.5 (4) |
C15—C10—C9 | 117.3 (4) | C15'—C10'—C9' | 118.8 (4) |
C11—C10—C9 | 121.1 (4) | C11'—C10'—C9' | 122.6 (5) |
C12—C11—C10 | 118.7 (5) | C12'—C11'—C10' | 119.8 (5) |
C12—C11—H11 | 120.7 | C12'—C11'—H11' | 120.1 |
C10—C11—H11 | 120.7 | C10'—C11'—H11' | 120.1 |
C13—C12—C11 | 120.2 (5) | C13'—C12'—C11' | 120.5 (5) |
C13—C12—H12 | 119.9 | C13'—C12'—H12' | 119.7 |
C11—C12—H12 | 119.9 | C11'—C12'—H12' | 119.7 |
C12—C13—C14 | 120.6 (5) | C12'—C13'—C14' | 119.6 (5) |
C12—C13—H13 | 119.7 | C12'—C13'—H13' | 120.2 |
C14—C13—H13 | 119.7 | C14'—C13'—H13' | 120.2 |
C13—C14—C15 | 119.9 (5) | C15'—C14'—C13' | 119.1 (5) |
C13—C14—H14 | 120.1 | C15'—C14'—H14' | 120.4 |
C15—C14—H14 | 120.1 | C13'—C14'—H14' | 120.4 |
C10—C15—C14 | 119.1 (5) | C14'—C15'—C10' | 122.4 (5) |
C10—C15—H15 | 120.5 | C14'—C15'—H15' | 118.8 |
C14—C15—H15 | 120.5 | C10'—C15'—H15' | 118.8 |
O8—C16—O6 | 123.4 (4) | O8'—C16'—O4' | 123.3 (3) |
O8—C16—C17 | 126.1 (4) | O8'—C16'—C17' | 125.8 (4) |
O6—C16—C17 | 110.5 (4) | O4'—C16'—C17' | 110.9 (3) |
C22—C17—C18 | 119.7 (4) | C22'—C17'—C18' | 120.6 (4) |
C22—C17—C16 | 121.9 (4) | C22'—C17'—C16' | 121.2 (3) |
C18—C17—C16 | 118.3 (4) | C18'—C17'—C16' | 118.1 (4) |
C19—C18—C17 | 119.1 (4) | C19'—C18'—C17' | 119.1 (4) |
C19—C18—H18 | 120.5 | C19'—C18'—H18' | 120.4 |
C17—C18—H18 | 120.5 | C17'—C18'—H18' | 120.4 |
C20—C19—C18 | 120.8 (4) | C18'—C19'—C20' | 119.9 (4) |
C20—C19—H19 | 119.6 | C18'—C19'—H19' | 120.1 |
C18—C19—H19 | 119.6 | C20'—C19'—H19' | 120.1 |
C19—C20—C21 | 120.8 (4) | C21'—C20'—C19' | 120.7 (4) |
C19—C20—H20 | 119.6 | C21'—C20'—H20' | 119.7 |
C21—C20—H20 | 119.6 | C19'—C20'—H20' | 119.7 |
C22—C21—C20 | 119.2 (5) | C22'—C21'—C20' | 119.5 (5) |
C22—C21—H21 | 120.4 | C22'—C21'—H21' | 120.2 |
C20—C21—H21 | 120.4 | C20'—C21'—H21' | 120.2 |
C21—C22—C17 | 120.5 (4) | C17'—C22'—C21' | 120.1 (4) |
C21—C22—H22 | 119.8 | C17'—C22'—H22' | 119.9 |
C17—C22—H22 | 119.8 | C21'—C22'—H22' | 119.9 |
C24—C23—S1 | 115.8 (3) | C24'—C23'—S1' | 118.8 (3) |
C24—C23—H23A | 108.3 | C24'—C23'—H23C | 107.6 |
S1—C23—H23A | 108.3 | S1'—C23'—H23C | 107.6 |
C24—C23—H23B | 108.3 | C24'—C23'—H23D | 107.6 |
S1—C23—H23B | 108.3 | S1'—C23'—H23D | 107.6 |
H23A—C23—H23B | 107.4 | H23C—C23'—H23D | 107.1 |
C23—C24—C29 | 112.0 (4) | C23'—C24'—C30' | 115.0 (4) |
C23—C24—C25 | 120.2 (4) | C23'—C24'—C29' | 117.4 (4) |
C29—C24—C25 | 103.1 (3) | C30'—C24'—C29' | 101.3 (4) |
C23—C24—C30 | 116.1 (3) | C23'—C24'—C25' | 115.9 (4) |
C29—C24—C30 | 99.8 (3) | C30'—C24'—C25' | 103.4 (4) |
C25—C24—C30 | 103.0 (4) | C29'—C24'—C25' | 101.7 (3) |
C24—C25—C26 | 104.5 (4) | C26'—C25'—C24' | 103.1 (4) |
C24—C25—H25A | 110.9 | C26'—C25'—H25C | 111.1 |
C26—C25—H25A | 110.9 | C24'—C25'—H25C | 111.1 |
C24—C25—H25B | 110.9 | C26'—C25'—H25D | 111.1 |
C26—C25—H25B | 110.9 | C24'—C25'—H25D | 111.1 |
H25A—C25—H25B | 108.9 | H25C—C25'—H25D | 109.1 |
C27—C26—C25 | 102.6 (4) | C27'—C26'—C25' | 102.7 (4) |
C27—C26—H26A | 111.3 | C27'—C26'—H26C | 111.2 |
C25—C26—H26A | 111.3 | C25'—C26'—H26C | 111.2 |
C27—C26—H26B | 111.3 | C27'—C26'—H26D | 111.2 |
C25—C26—H26B | 111.3 | C25'—C26'—H26D | 111.2 |
H26A—C26—H26B | 109.2 | H26C—C26'—H26D | 109.1 |
C28—C27—C26 | 105.9 (4) | C28'—C27'—C30' | 102.8 (4) |
C28—C27—C30 | 102.8 (4) | C28'—C27'—C26' | 106.7 (4) |
C26—C27—C30 | 103.3 (4) | C30'—C27'—C26' | 102.5 (4) |
C28—C27—H27 | 114.5 | C28'—C27'—H27' | 114.5 |
C26—C27—H27 | 114.5 | C30'—C27'—H27' | 114.5 |
C30—C27—H27 | 114.5 | C26'—C27'—H27' | 114.5 |
C27—C28—C29 | 102.3 (3) | C29'—C28'—C27' | 102.6 (4) |
C27—C28—H28A | 111.3 | C29'—C28'—H28C | 111.2 |
C29—C28—H28A | 111.3 | C27'—C28'—H28C | 111.2 |
C27—C28—H28B | 111.3 | C29'—C28'—H28D | 111.2 |
C29—C28—H28B | 111.3 | C27'—C28'—H28D | 111.2 |
H28A—C28—H28B | 109.2 | H28C—C28'—H28D | 109.2 |
O11—C29—C28 | 129.2 (4) | O11'—C29'—C28' | 127.9 (4) |
O11—C29—C24 | 124.9 (4) | O11'—C29'—C24' | 126.9 (4) |
C28—C29—C24 | 105.9 (4) | C28'—C29'—C24' | 105.2 (4) |
C32—C30—C31 | 108.8 (4) | C24'—C30'—C31' | 114.7 (4) |
C32—C30—C24 | 113.1 (4) | C24'—C30'—C32' | 112.9 (4) |
C31—C30—C24 | 113.8 (4) | C31'—C30'—C32' | 107.7 (4) |
C32—C30—C27 | 113.8 (4) | C24'—C30'—C27' | 94.3 (4) |
C31—C30—C27 | 113.2 (4) | C31'—C30'—C27' | 113.3 (4) |
C24—C30—C27 | 93.5 (3) | C32'—C30'—C27' | 113.7 (4) |
C30—C31—H31A | 109.5 | C30'—C31'—H31D | 109.5 |
C30—C31—H31B | 109.5 | C30'—C31'—H31E | 109.5 |
H31A—C31—H31B | 109.5 | H31D—C31'—H31E | 109.5 |
C30—C31—H31C | 109.5 | C30'—C31'—H31F | 109.5 |
H31A—C31—H31C | 109.5 | H31D—C31'—H31F | 109.5 |
H31B—C31—H31C | 109.5 | H31E—C31'—H31F | 109.5 |
C30—C32—H32A | 109.5 | C30'—C32'—H32D | 109.5 |
C30—C32—H32B | 109.5 | C30'—C32'—H32E | 109.5 |
H32A—C32—H32B | 109.5 | H32D—C32'—H32E | 109.5 |
C30—C32—H32C | 109.5 | C30'—C32'—H32F | 109.5 |
H32A—C32—H32C | 109.5 | H32D—C32'—H32F | 109.5 |
H32B—C32—H32C | 109.5 | H32E—C32'—H32F | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O9′ | 0.98 | 2.41 | 3.153 (5) | 132 |
C23—H23A···O7 | 0.97 | 2.43 | 3.347 (5) | 158 |
C5′—H5′···O9 | 0.98 | 2.63 | 3.351 (5) | 130 |
C23′—H23D···O7′ | 0.97 | 2.63 | 3.252 (5) | 122 |
C8′—H8E···O3i | 0.96 | 2.76 | 3.658 (6) | 155 |
C8—H8C···O1′ii | 0.96 | 2.75 | 3.644 (5) | 155 |
C12—H12···O10iii | 0.93 | 2.72 | 3.495 (6) | 142 |
C1—H1···O8′iii | 0.98 | 2.33 | 3.275 (5) | 161 |
C28—H28B···O11′iv | 0.97 | 2.45 | 3.297 (6) | 146 |
C18′—H18′···O1v | 0.93 | 2.71 | 3.485 (6) | 142 |
C3′—H3′···O8v | 0.98 | 2.35 | 3.310 (5) | 167 |
C31′—H31E···Cg1vi | 0.96 | 2.86 | 3.724 | 151 |
C31—H31C···Cg2vii | 0.96 | 3.06 | 3.943 | 153 |
Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z; (iii) x+1, y, z; (iv) x, y, z−1; (v) x−1, y, z; (vi) x−1, y, z+1; (vii) x+1, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | C32H34O11S |
Mr | 626.65 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 11.5241 (16), 11.6958 (16), 12.453 (2) |
α, β, γ (°) | 80.499 (3), 62.449 (2), 75.937 (2) |
V (Å3) | 1440.8 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.18 |
Crystal size (mm) | 0.68 × 0.25 × 0.14 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.889, 0.976 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9388, 7596, 7284 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.136, 1.09 |
No. of reflections | 7596 |
No. of parameters | 799 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.54, −0.29 |
Absolute structure | Flack H D (1983),2944 Friedel pairs |
Absolute structure parameter | 0.00 (8) |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and Mercury (Version 1.5; Macrae et al., 2006), SHELXTL97 (Sheldrick, 1997), PLATON (Spek, 2003) and publCIF (Westrip, 2007).
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O9' | 0.98 | 2.41 | 3.153 (5) | 132.0 |
C23—H23A···O7 | 0.97 | 2.43 | 3.347 (5) | 158.2 |
C5'—H5'···O9 | 0.98 | 2.63 | 3.351 (5) | 130.2 |
C23'—H23D···O7' | 0.97 | 2.63 | 3.252 (5) | 122.4 |
C8'—H8E···O3i | 0.96 | 2.76 | 3.658 (6) | 155.4 |
C8—H8C···O1'ii | 0.96 | 2.75 | 3.644 (5) | 155.2 |
C12—H12···O10iii | 0.93 | 2.72 | 3.495 (6) | 141.9 |
C1—H1···O8'iii | 0.98 | 2.33 | 3.275 (5) | 160.8 |
C28—H28B···O11'iv | 0.97 | 2.45 | 3.297 (6) | 145.9 |
C18'—H18'···O1v | 0.93 | 2.71 | 3.485 (6) | 142.0 |
C3'—H3'···O8v | 0.98 | 2.35 | 3.310 (5) | 166.6 |
C31'—H31E···Cg1vi | 0.96 | 2.86 | 3.724 | 151 |
C31—H31C···Cg2vii | 0.96 | 3.06 | 3.943 | 153 |
Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z; (iii) x+1, y, z; (iv) x, y, z−1; (v) x−1, y, z; (vi) x−1, y, z+1; (vii) x+1, y, z−1. |
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The importance of non-covalent intermolecular interactions is being increasingly recognized because of their role in crystal engineering, host–guest complexes, enzyme–substrate binding and drug design (Desiraju & Steiner, 1999). The understanding of weak interactions in molecular crystals can be utilized for the design and synthesis of functional supramolecular assemblies (Desiraju, 1989). Amongst these, dipolar contacts are of considerable interest because of their involvement in the conformational stabilization of proteins (Maccallum et al., 1995) and the structure-based design of drugs (Hof & Diedrich, 2004). The geometrical preferences of S═O···C═O contacts and their role in the formation of inclusion crystals of 2,4(6)-di-O-benzoyl-6(4)-O-[(1S)-10-camphorsulfonyl]-myo-inositol 1,3,5-orthoformate were first recognized by us (Manoj et al., 2005, 2006). In order to explore the dipolar association of this framework, a diastereomeric mixture, (I) and (II), of the orthoacetate derivative was prepared. Suitable single crystals containing a 1:1 mixture of (I) and (II) were obtained from a dichloromethane–methanol mixture. We did not observe any (pseudo)polymorphic modifications under different crystallization methods or solvents. Synthetically protected myo-inositol 1,3,5-orthoester derivatives also serve as key intermediates (Sureshan et al., 2003) for the preparation of biologically relevant myo-inositol phosphates, which play a significant role in cellular signal transduction (Potter & Lampe, 1995).
The crystal structure of the title compound shows short intramolecular C—H···O interactions (Fig. 1) between atom H23A (H23D) of the camphorsulfonyl methylene group and atom O7 (O7') of the equatorial benzoyl group in both diastereomers (Table 1). Compared with the conformation of the orthoformate derivative (Manoj et al., 2005, 2006), the orthoacetate shows a significant orientational change in the camphorsulfonate group (see supplementary figures for molecular overlapping), which could be due to this intramolecular C—H···O interaction.
In the absence of conventional hydrogen bonding, diastereomers (I) and (II) are associated via dipolar S═O···C═O short contacts and weak hydrogen bonds. The crystal structure shows dimeric bridging (Fig. 1) and the contacts between the diastereomers are asymmetric. The (S═)O···C(═O) distances are 3.144 (5) and 3.556 (5) Å [O9···C16' = 3.144 (5) Å, O9···C16'═O8' = 92.2 (1)° and S1═O9···C16' = 123.6 (1)°; O9'···C16 = 3.556 (5) Å, O9'···C16═O8 = 94.7 (1)° and S1'═ O9'···C16 = 103.6 (1)°], with complementary C—H···O contacts of 2.63 and 2.41 Å, respectively (Table 1). These complementary interactions (the shorter of the S═O···C═O contacts is accompanied by a longer C—H···O interaction and vice versa) between diastereomers were also seen in the solvates of the orthoformate derivative (Manoj et al., 2005, 2006).
The basic difference in the association of the diastereomers in the title compound and its orthoformate analogue (Manoj et al., 2005, 2006) is in the geometry of the dipolar S═O···C═O contacts. We have classified the S═O···C═O interaction motifs as Types I, II and III (Fig. 2a), similar to carbonyl–carbonyl interactions (Allen et al., 1998). In all the crystalline solvates of orthoformate (Manoj et al., 2005, 2006), the contacts were of Type I (Fig. 2b), whereas in the orthoacetate crystals they are of Type III (Fig. 2c). In the case of C═O···C═ O contacts, the frequency of occurrence of the various motifs is of the order Type II > Type III > Type I (Allen et al., 1998). A survey of the Cambridge Structural Database (CSD, Version 5.28; Allen, 2002) was carried out to see how S═ O···C═O contacts are distributed amongst these three types. The CSD was used for the geometric analysis of non-covalent intermolecular interactions with a distance (D) cut-off of 3.6 Å (twice the van der Waals radius of carbon, with a tolerance of 0.2 Å). The angle criteria for Type I were A1 = 90±10° and A2 = 160±20°, for Type II they were A1 = 90±10° and A2 = 90±20°, and for Type III they were A1 = 90±10° and A2 = 120±20°. All searches were carried out with error-free coordinates and restricted entries of disordered, ionic, polymeric and powdered structures. Interestingly, the maximum number of hits (235) was found for Type III, followed by Type I (111 hits) and Type II contacts (21 hits). The preferred Type III motif (and also the less preferred Type II) in S═O···C═ O contacts may be due to the heterodipoles having different van der Waals radii for S and C atoms. The Type III dipolar S═O···C═O interaction motif is indeed observed in the binding of N-tosyl-D-proline (ligand) to thymidylate synthase (from Escherichia coli), an essential enzyme in pyrimidine metabolism with therapeutic applications in cancer and infectious diseases (Erlanson et al., 2000).
Diastereomers (I) and (II), associated via S═O···C═O (and C—H···O) interactions, are packed in the crystal structure only via weak intermolecular interactions such as C—H···π and C—H···O by translation. These dimeric units, translated along the diagonal to the a and c axes, form somewhat off-centred C—H···π interactions between the methyl H atoms (H31E and H31C) of the camphor moiety and the phenyl ring of the axial benzoyl groups, as shown in Fig. 3; details are given in Table 1. [Please check additions to Table 1]. These molecular rows are linked to unit-translated ones along the b axis by very weak head-to-head C—H···O contacts, forming layers as shown in Fig. 3; details are given in Table 1. [Please check additions to Table 1]. These layers are linked along the third dimension via symmetric C—H···O contacts (Table 1) between the axial benzoyl atoms O8 and O8' and inositol ring atoms H3' and H1, respectively (see supplementary figures). Additionally, they are also linked via C18'—H18'···O1 and C12—H12···O10 contacts (Table 1) along the b axis.
The rectangular net of each of the diastereomers interlocks into the other via the equatorial benzoyl groups (Fig. 4), leaving no possibility of any guest inclusion, whereas the orthoformate derivative (Manoj et al., 2005, 2006) had the diastereomers organized in such a way that they created voids for the guests (see supplementary figures).
In conclusion, different motifs of association of S═O and C═O were observed in the crystals of 2,4(6)-di-O-benzoyl-6(4)-O-[(1S)-10-camphorsulfonyl]-myo-inositol 1,3,5-orthoformate and its orthoacetate analogue. The experimentally observed motifs of these S═O···C═O contacts are expected to be of considerable interest in the context of improved binding of drug molecules containing S═O groups to their receptors (Erlanson et al., 2000).