The crystal structure of 5-O-tert-butyldimethylsilyl-3,4-O-carbonyl-1,2-O-cyclohexylidene-2-oxo-3-oxa-4-bornanylcarbonyl-D-myo-inositol has been studied by single-crystal X-ray diffraction at both room temperature and 173 K. At room temperature, the tert-butyldimethylsilyl group exhibits dynamical disorder. A molecular dynamics simulation was used to model the disorder and this indicates that the group librates between two stable conformations in the crystal. Approximate relative energies of the different forms and energy barriers for the transition were obtained by empirical force field methods. Calculations of the thermal motion of the atoms are in good qualitative, but fair to poor quantitative agreement with the X-ray data.
Supporting information
CCDC references: 148927; 148928
For both compounds, data collection: "Collect" data collection software, Nonius B.V., 1998.; data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).
Crystal data top
C29H44O10Si | F(000) = 624 |
Mr = 580.73 | Dx = 1.210 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: P 2y1 | Cell parameters from 6915 reflections |
a = 7.537 (1) Å | θ = 2.2–27.5° |
b = 10.183 (1) Å | µ = 0.13 mm−1 |
c = 20.843 (1) Å | T = 173 K |
β = 94.93 (1)° | Block, colourless |
V = 1593.8 (3) Å3 | 0.20 × 0.15 × 0.13 mm |
Z = 2 | |
Data collection top
Enraf Nonius Kappa CCD diffractometer | 3310 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.029 |
Graphite monochromator | θmax = 27.5°, θmin = 2.2° |
a 175° ψ–scan and 2 ω | h = −8→9 |
6915 measured reflections | k = −7→11 |
4237 independent reflections | l = −23→23 |
Refinement top
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)] = 0.051 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.128 | w = 1/[σ2(Fo2) + (0.0643P)2 + 0.7367P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.011 |
4237 reflections | Δρmax = 0.33 e Å−3 |
433 parameters | Δρmin = −0.30 e Å−3 |
1 restraint | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.0 (2) |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.5376 (6) | 0.8283 (4) | 0.2125 (2) | 0.0412 (11) | |
O2 | 0.3726 (3) | 0.8806 (3) | 0.21383 (13) | 0.0388 (7) | |
C3 | 0.2486 (5) | 0.7721 (4) | 0.21512 (19) | 0.0346 (9) | |
H3 | 0.2104 | 0.7437 | 0.1701 | 0.104 (3)* | |
C4 | 0.0877 (5) | 0.7939 (4) | 0.25159 (19) | 0.0387 (10) | |
H4 | 0.0026 | 0.8574 | 0.2290 | 0.104 (3)* | |
O5 | 0.1396 (4) | 0.8342 (3) | 0.31560 (14) | 0.0478 (8) | |
C6 | 0.0466 (6) | 0.7549 (5) | 0.3584 (2) | 0.0501 (12) | |
C7 | −0.1324 (7) | 0.8161 (6) | 0.3694 (3) | 0.0702 (16) | |
H7A | −0.2062 | 0.8228 | 0.3279 | 0.104 (3)* | |
H7B | −0.1138 | 0.9058 | 0.3870 | 0.104 (3)* | |
C8 | −0.2297 (9) | 0.7332 (7) | 0.4164 (4) | 0.099 (2) | |
H8A | −0.3403 | 0.7789 | 0.4261 | 0.104 (3)* | |
H8B | −0.2637 | 0.6480 | 0.3960 | 0.104 (3)* | |
C9 | −0.1145 (13) | 0.7085 (8) | 0.4789 (3) | 0.122 (3) | |
H9A | −0.0933 | 0.7926 | 0.5022 | 0.104 (3)* | |
H9B | −0.1782 | 0.6491 | 0.5067 | 0.104 (3)* | |
C10 | 0.0632 (10) | 0.6475 (7) | 0.4660 (3) | 0.100 (2) | |
H10A | 0.1373 | 0.6365 | 0.5072 | 0.104 (3)* | |
H10B | 0.0425 | 0.5595 | 0.4466 | 0.104 (3)* | |
C11 | 0.1609 (8) | 0.7323 (6) | 0.4212 (2) | 0.0740 (17) | |
H11A | 0.2735 | 0.6888 | 0.4121 | 0.104 (3)* | |
H11B | 0.1906 | 0.8177 | 0.4420 | 0.104 (3)* | |
O12 | 0.0253 (4) | 0.6324 (3) | 0.32671 (13) | 0.0437 (7) | |
C13 | 0.0001 (5) | 0.6551 (4) | 0.2593 (2) | 0.0379 (10) | |
H13 | −0.1300 | 0.6592 | 0.2452 | 0.104 (3)* | |
C14 | 0.0851 (5) | 0.5387 (4) | 0.22745 (18) | 0.0361 (10) | |
H14 | 0.0364 | 0.4558 | 0.2447 | 0.104 (3)* | |
C15 | 0.2936 (5) | 0.5305 (4) | 0.23423 (19) | 0.0349 (10) | |
H15 | 0.3376 | 0.4967 | 0.1934 | 0.104 (3)* | |
C16 | 0.3646 (5) | 0.6677 (4) | 0.2483 (2) | 0.0329 (9) | |
H16 | 0.3728 | 0.6832 | 0.2959 | 0.104 (3)* | |
O17 | 0.5365 (3) | 0.6971 (3) | 0.22414 (14) | 0.0417 (7) | |
O18 | 0.6659 (4) | 0.8887 (3) | 0.20132 (16) | 0.0573 (9) | |
O19 | 0.3526 (3) | 0.4494 (3) | 0.28583 (12) | 0.0403 (7) | |
Si20 | 0.39989 (18) | 0.29041 (13) | 0.28804 (6) | 0.0517 (4) | |
C21 | 0.4731 (13) | 0.2360 (6) | 0.2125 (3) | 0.132 (4) | |
H21A | 0.3843 | 0.2605 | 0.1774 | 0.104 (3)* | |
H21B | 0.4876 | 0.1404 | 0.2133 | 0.104 (3)* | |
H21C | 0.5873 | 0.2776 | 0.2057 | 0.104 (3)* | |
C22 | 0.1941 (9) | 0.1977 (7) | 0.3020 (5) | 0.136 (3) | |
H22A | 0.1586 | 0.2181 | 0.3451 | 0.104 (3)* | |
H22B | 0.2170 | 0.1033 | 0.2988 | 0.104 (3)* | |
H22C | 0.0984 | 0.2230 | 0.2696 | 0.104 (3)* | |
C23 | 0.5590 (9) | 0.2701 (6) | 0.3575 (3) | 0.096 (2) | |
C24 | 0.5895 (14) | 0.1220 (8) | 0.3710 (4) | 0.188 (6) | |
H24A | 0.6846 | 0.0897 | 0.3459 | 0.104 (3)* | |
H24B | 0.4795 | 0.0735 | 0.3588 | 0.104 (3)* | |
H24C | 0.6240 | 0.1088 | 0.4170 | 0.104 (3)* | |
C25 | 0.4983 (13) | 0.3345 (9) | 0.4172 (3) | 0.134 (3) | |
H25A | 0.3765 | 0.3065 | 0.4233 | 0.104 (3)* | |
H25B | 0.5014 | 0.4301 | 0.4123 | 0.104 (3)* | |
H25C | 0.5778 | 0.3085 | 0.4548 | 0.104 (3)* | |
C26 | 0.7331 (9) | 0.3442 (10) | 0.3408 (6) | 0.228 (7) | |
H26A | 0.7506 | 0.3312 | 0.2952 | 0.104 (3)* | |
H26B | 0.8359 | 0.3092 | 0.3674 | 0.104 (3)* | |
H26C | 0.7209 | 0.4382 | 0.3495 | 0.104 (3)* | |
O27 | 0.0223 (3) | 0.5502 (3) | 0.15949 (13) | 0.0379 (7) | |
C28 | −0.0098 (5) | 0.4380 (5) | 0.1265 (2) | 0.0433 (11) | |
O29 | 0.0191 (6) | 0.3328 (4) | 0.14909 (18) | 0.0965 (16) | |
C30 | −0.0844 (5) | 0.4660 (4) | 0.05944 (19) | 0.0313 (9) | |
O31 | −0.1429 (3) | 0.3402 (2) | 0.03029 (12) | 0.0345 (7) | |
C32 | −0.2592 (5) | 0.3710 (4) | −0.02114 (18) | 0.0320 (9) | |
C33 | −0.2752 (5) | 0.5170 (4) | −0.02418 (19) | 0.0359 (10) | |
C34 | −0.0892 (6) | 0.5582 (5) | −0.0459 (2) | 0.0533 (12) | |
H34A | −0.0606 | 0.5079 | −0.0843 | 0.104 (3)* | |
H34B | −0.0863 | 0.6532 | −0.0558 | 0.104 (3)* | |
C35 | 0.0419 (5) | 0.5248 (4) | 0.0126 (2) | 0.0459 (12) | |
H35A | 0.1026 | 0.6044 | 0.0307 | 0.104 (3)* | |
H35B | 0.1321 | 0.4601 | 0.0013 | 0.104 (3)* | |
C36 | −0.2534 (4) | 0.5524 (4) | 0.04849 (18) | 0.0304 (9) | |
C37 | −0.4073 (5) | 0.5001 (4) | 0.0850 (2) | 0.0457 (12) | |
H37A | −0.3767 | 0.5091 | 0.1314 | 0.104 (3)* | |
H37B | −0.4279 | 0.4073 | 0.0743 | 0.104 (3)* | |
H37C | −0.5155 | 0.5505 | 0.0725 | 0.104 (3)* | |
C38 | −0.2265 (6) | 0.6970 (4) | 0.0627 (2) | 0.0413 (11) | |
H38A | −0.1249 | 0.7294 | 0.0410 | 0.104 (3)* | |
H38B | −0.2034 | 0.7098 | 0.1093 | 0.104 (3)* | |
H38C | −0.3339 | 0.7456 | 0.0471 | 0.104 (3)* | |
O39 | −0.3239 (3) | 0.2874 (3) | −0.05710 (13) | 0.0412 (7) | |
C40 | −0.4383 (7) | 0.5672 (5) | −0.0645 (2) | 0.0604 (14) | |
H40A | −0.5459 | 0.5398 | −0.0449 | 0.104 (3)* | |
H40B | −0.4401 | 0.5309 | −0.1081 | 0.104 (3)* | |
H40C | −0.4341 | 0.6633 | −0.0666 | 0.104 (3)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.035 (2) | 0.036 (3) | 0.051 (3) | 0.004 (2) | −0.006 (2) | −0.005 (2) |
O2 | 0.0368 (15) | 0.0263 (16) | 0.0519 (18) | 0.0034 (12) | −0.0041 (12) | −0.0016 (13) |
C3 | 0.035 (2) | 0.026 (2) | 0.043 (2) | −0.0012 (18) | −0.0014 (17) | −0.001 (2) |
C4 | 0.036 (2) | 0.036 (2) | 0.043 (3) | 0.003 (2) | −0.0011 (18) | −0.004 (2) |
O5 | 0.0480 (16) | 0.048 (2) | 0.0482 (19) | −0.0041 (14) | 0.0054 (14) | −0.0150 (15) |
C6 | 0.056 (3) | 0.055 (3) | 0.039 (3) | 0.001 (2) | 0.002 (2) | −0.015 (2) |
C7 | 0.062 (3) | 0.071 (4) | 0.080 (4) | 0.002 (3) | 0.025 (3) | −0.021 (3) |
C8 | 0.096 (5) | 0.109 (6) | 0.098 (6) | −0.009 (4) | 0.049 (4) | −0.029 (4) |
C9 | 0.188 (8) | 0.118 (6) | 0.067 (5) | −0.046 (6) | 0.060 (5) | −0.029 (4) |
C10 | 0.151 (6) | 0.112 (6) | 0.034 (3) | −0.011 (5) | −0.002 (4) | 0.002 (4) |
C11 | 0.094 (4) | 0.084 (5) | 0.041 (3) | −0.008 (3) | −0.013 (3) | −0.012 (3) |
O12 | 0.0531 (17) | 0.0392 (18) | 0.0383 (19) | −0.0015 (14) | 0.0005 (13) | −0.0028 (14) |
C13 | 0.033 (2) | 0.038 (3) | 0.041 (3) | 0.0005 (19) | −0.0035 (18) | −0.003 (2) |
C14 | 0.040 (2) | 0.036 (3) | 0.030 (2) | 0.0008 (19) | −0.0093 (17) | −0.004 (2) |
C15 | 0.037 (2) | 0.029 (2) | 0.038 (2) | 0.0064 (18) | −0.0063 (18) | 0.002 (2) |
C16 | 0.031 (2) | 0.022 (2) | 0.044 (3) | 0.0028 (17) | −0.0043 (18) | −0.0016 (18) |
O17 | 0.0321 (15) | 0.0300 (18) | 0.062 (2) | 0.0051 (12) | −0.0018 (13) | −0.0054 (15) |
O18 | 0.0379 (17) | 0.049 (2) | 0.084 (2) | −0.0075 (16) | 0.0026 (16) | 0.0013 (18) |
O19 | 0.0515 (16) | 0.0308 (16) | 0.0362 (17) | 0.0096 (13) | −0.0104 (13) | 0.0015 (14) |
Si20 | 0.0705 (8) | 0.0325 (7) | 0.0497 (8) | 0.0120 (6) | −0.0089 (6) | 0.0034 (6) |
C21 | 0.274 (11) | 0.050 (4) | 0.073 (5) | 0.059 (5) | 0.030 (5) | 0.002 (3) |
C22 | 0.083 (5) | 0.054 (4) | 0.265 (11) | −0.015 (3) | −0.013 (6) | 0.018 (6) |
C23 | 0.135 (6) | 0.063 (4) | 0.082 (5) | 0.046 (4) | −0.040 (4) | 0.002 (4) |
C24 | 0.281 (12) | 0.091 (6) | 0.163 (9) | 0.078 (7) | −0.148 (9) | −0.002 (6) |
C25 | 0.221 (9) | 0.115 (7) | 0.056 (4) | 0.001 (6) | −0.044 (5) | 0.016 (5) |
C26 | 0.048 (4) | 0.175 (10) | 0.45 (2) | 0.000 (5) | −0.030 (7) | −0.150 (12) |
O27 | 0.0449 (15) | 0.0276 (17) | 0.0384 (17) | −0.0034 (12) | −0.0117 (12) | −0.0056 (14) |
C28 | 0.046 (2) | 0.022 (3) | 0.059 (3) | 0.0086 (19) | −0.009 (2) | −0.006 (3) |
O29 | 0.177 (4) | 0.030 (2) | 0.070 (3) | 0.016 (2) | −0.067 (3) | −0.0081 (18) |
C30 | 0.033 (2) | 0.022 (2) | 0.038 (2) | −0.0054 (17) | −0.0044 (18) | −0.0077 (19) |
O31 | 0.0355 (14) | 0.0262 (16) | 0.0397 (16) | −0.0003 (11) | −0.0095 (12) | −0.0064 (13) |
C32 | 0.031 (2) | 0.033 (3) | 0.031 (2) | −0.0032 (18) | −0.0029 (18) | −0.002 (2) |
C33 | 0.049 (2) | 0.025 (3) | 0.032 (2) | −0.0026 (19) | −0.0034 (18) | 0.0027 (19) |
C34 | 0.070 (3) | 0.051 (3) | 0.040 (3) | −0.020 (2) | 0.013 (2) | −0.005 (2) |
C35 | 0.036 (2) | 0.042 (3) | 0.061 (3) | −0.010 (2) | 0.011 (2) | −0.014 (2) |
C36 | 0.031 (2) | 0.022 (2) | 0.037 (2) | 0.0009 (17) | −0.0050 (17) | 0.0024 (18) |
C37 | 0.039 (2) | 0.044 (3) | 0.055 (3) | 0.0031 (19) | 0.007 (2) | −0.006 (2) |
C38 | 0.049 (2) | 0.024 (2) | 0.049 (3) | 0.0049 (18) | −0.004 (2) | −0.003 (2) |
O39 | 0.0443 (15) | 0.0370 (17) | 0.0404 (16) | −0.0086 (14) | −0.0075 (12) | −0.0076 (15) |
C40 | 0.087 (3) | 0.039 (3) | 0.049 (3) | 0.008 (3) | −0.027 (3) | −0.002 (2) |
Geometric parameters (Å, º) top
C1—O18 | 1.186 (5) | O19—Si20 | 1.658 (3) |
C1—O2 | 1.356 (5) | Si20—C21 | 1.799 (7) |
C1—O17 | 1.358 (5) | Si20—C23 | 1.811 (6) |
O2—C3 | 1.449 (5) | Si20—C22 | 1.860 (7) |
C3—C4 | 1.502 (5) | C23—C25 | 1.511 (10) |
C3—C16 | 1.506 (5) | C23—C24 | 1.548 (9) |
C4—O5 | 1.418 (5) | C23—C26 | 1.579 (11) |
C4—C13 | 1.574 (6) | O27—C28 | 1.345 (5) |
O5—C6 | 1.430 (5) | C28—O29 | 1.184 (5) |
C6—O12 | 1.414 (5) | C28—C30 | 1.488 (6) |
C6—C7 | 1.521 (7) | C30—O31 | 1.469 (4) |
C6—C11 | 1.521 (7) | C30—C35 | 1.542 (6) |
C7—C8 | 1.526 (8) | C30—C36 | 1.548 (5) |
C8—C9 | 1.524 (10) | O31—C32 | 1.362 (4) |
C9—C10 | 1.521 (10) | C32—O39 | 1.209 (5) |
C10—C11 | 1.509 (9) | C32—C33 | 1.493 (5) |
O12—C13 | 1.420 (5) | C33—C40 | 1.517 (6) |
C13—C14 | 1.526 (5) | C33—C36 | 1.552 (5) |
C14—O27 | 1.459 (4) | C33—C34 | 1.566 (6) |
C14—C15 | 1.568 (5) | C34—C35 | 1.538 (6) |
C15—O19 | 1.398 (5) | C36—C38 | 1.513 (5) |
C15—C16 | 1.516 (5) | C36—C37 | 1.536 (5) |
C16—O17 | 1.461 (5) | | |
| | | |
O18—C1—O2 | 124.4 (4) | C21—Si20—C23 | 115.6 (4) |
O18—C1—O17 | 124.3 (4) | O19—Si20—C22 | 108.6 (3) |
O2—C1—O17 | 111.3 (4) | C21—Si20—C22 | 107.7 (4) |
C1—O2—C3 | 107.1 (3) | C23—Si20—C22 | 108.7 (4) |
O2—C3—C4 | 116.5 (3) | C25—C23—C24 | 108.9 (6) |
O2—C3—C16 | 101.4 (3) | C25—C23—C26 | 106.9 (7) |
C4—C3—C16 | 109.5 (3) | C24—C23—C26 | 113.1 (7) |
O5—C4—C3 | 110.5 (3) | C25—C23—Si20 | 112.5 (5) |
O5—C4—C13 | 104.3 (3) | C24—C23—Si20 | 109.5 (5) |
C3—C4—C13 | 106.4 (3) | C26—C23—Si20 | 105.9 (6) |
C4—O5—C6 | 108.2 (3) | C28—O27—C14 | 117.2 (3) |
O12—C6—O5 | 104.5 (3) | O29—C28—O27 | 123.1 (4) |
O12—C6—C7 | 111.4 (4) | O29—C28—C30 | 126.1 (4) |
O5—C6—C7 | 110.6 (4) | O27—C28—C30 | 110.8 (4) |
O12—C6—C11 | 107.5 (4) | O31—C30—C28 | 107.3 (3) |
O5—C6—C11 | 110.5 (4) | O31—C30—C35 | 104.8 (3) |
C7—C6—C11 | 112.1 (4) | C28—C30—C35 | 117.7 (3) |
C6—C7—C8 | 110.6 (5) | O31—C30—C36 | 102.7 (3) |
C9—C8—C7 | 111.7 (6) | C28—C30—C36 | 119.1 (3) |
C10—C9—C8 | 111.1 (5) | C35—C30—C36 | 103.3 (3) |
C11—C10—C9 | 111.1 (6) | C32—O31—C30 | 105.9 (3) |
C10—C11—C6 | 110.4 (5) | O39—C32—O31 | 121.6 (4) |
C6—O12—C13 | 108.5 (3) | O39—C32—C33 | 130.4 (4) |
O12—C13—C14 | 106.1 (3) | O31—C32—C33 | 107.9 (3) |
O12—C13—C4 | 103.1 (3) | C32—C33—C40 | 114.7 (3) |
C14—C13—C4 | 117.2 (3) | C32—C33—C36 | 100.8 (3) |
O27—C14—C13 | 104.3 (3) | C40—C33—C36 | 118.4 (4) |
O27—C14—C15 | 109.3 (3) | C32—C33—C34 | 102.0 (3) |
C13—C14—C15 | 117.2 (3) | C40—C33—C34 | 116.9 (4) |
O19—C15—C16 | 108.2 (3) | C36—C33—C34 | 101.4 (3) |
O19—C15—C14 | 110.5 (3) | C35—C34—C33 | 104.0 (3) |
C16—C15—C14 | 107.6 (3) | C34—C35—C30 | 101.4 (3) |
O17—C16—C3 | 101.2 (3) | C38—C36—C37 | 109.5 (3) |
O17—C16—C15 | 115.5 (3) | C38—C36—C30 | 115.4 (3) |
C3—C16—C15 | 112.4 (3) | C37—C36—C30 | 112.1 (3) |
C1—O17—C16 | 106.4 (3) | C38—C36—C33 | 114.7 (3) |
C15—O19—Si20 | 130.7 (2) | C37—C36—C33 | 112.5 (3) |
O19—Si20—C21 | 111.0 (2) | C30—C36—C33 | 91.7 (3) |
O19—Si20—C23 | 105.0 (2) | | |
Crystal data top
C29H44O10Si | F(000) = 624 |
Mr = 580.73 | Dx = 1.184 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: P 2y1 | Cell parameters from 6199 reflections |
a = 7.5722 (4) Å | θ = 3.4–26.4° |
b = 10.2402 (5) Å | µ = 0.12 mm−1 |
c = 21.1352 (9) Å | T = 298 K |
β = 96.188 (2)° | Block, colourless |
V = 1629.29 (14) Å3 | 0.5 × 0.4 × 0.3 mm |
Z = 2 | |
Data collection top
Enraf Nonius Kappa CCD diffractometer | 5230 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.019 |
Graphite monochromator | θmax = 26.4°, θmin = 3.4° |
a 175° ψ–scan and 2 ω | h = 0→9 |
6439 measured reflections | k = −12→12 |
6199 independent reflections | l = −26→26 |
Refinement top
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)] = 0.073 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.198 | w = 1/[σ2(Fo2) + (0.0996P)2 + 0.6765P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max = 0.049 |
6199 reflections | Δρmax = 0.55 e Å−3 |
435 parameters | Δρmin = −0.80 e Å−3 |
7 restraints | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.4 (3) |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.5463 (5) | 0.8249 (4) | 0.2097 (2) | 0.0655 (10) | |
O2 | 0.3830 (3) | 0.8758 (2) | 0.21123 (13) | 0.0590 (6) | |
C3 | 0.2591 (4) | 0.7685 (3) | 0.21270 (18) | 0.0515 (7) | |
H3 | 0.2196 | 0.7406 | 0.1691 | 0.127 (3)* | |
C4 | 0.1003 (5) | 0.7903 (4) | 0.24825 (18) | 0.0590 (9) | |
H4 | 0.0165 | 0.8519 | 0.2257 | 0.127 (3)* | |
O5 | 0.1551 (4) | 0.8332 (3) | 0.31087 (15) | 0.0748 (8) | |
C6 | 0.0617 (6) | 0.7564 (5) | 0.3535 (2) | 0.0792 (13) | |
C7 | −0.1121 (8) | 0.8171 (7) | 0.3641 (3) | 0.106 (2) | |
H7A | −0.1865 | 0.8232 | 0.3239 | 0.127 (3)* | |
H7B | −0.0920 | 0.9049 | 0.3806 | 0.127 (3)* | |
C8 | −0.2074 (13) | 0.7366 (11) | 0.4110 (5) | 0.156 (4) | |
H8A | −0.3129 | 0.7828 | 0.4209 | 0.127 (3)* | |
H8B | −0.2443 | 0.6537 | 0.3917 | 0.127 (3)* | |
C9 | −0.0855 (17) | 0.7121 (13) | 0.4725 (4) | 0.193 (5) | |
H9A | −0.1454 | 0.6553 | 0.5001 | 0.127 (3)* | |
H9B | −0.0615 | 0.7944 | 0.4945 | 0.127 (3)* | |
C10 | 0.0842 (13) | 0.6516 (12) | 0.4599 (3) | 0.157 (4) | |
H10A | 0.0610 | 0.5657 | 0.4416 | 0.127 (3)* | |
H10B | 0.1590 | 0.6408 | 0.4998 | 0.127 (3)* | |
C11 | 0.1822 (10) | 0.7338 (9) | 0.4148 (3) | 0.120 (2) | |
H11A | 0.2161 | 0.8169 | 0.4345 | 0.127 (3)* | |
H11B | 0.2894 | 0.6890 | 0.4055 | 0.127 (3)* | |
O12 | 0.0401 (4) | 0.6329 (3) | 0.32271 (14) | 0.0718 (7) | |
C13 | 0.0128 (5) | 0.6547 (4) | 0.25581 (17) | 0.0569 (8) | |
H13 | −0.1145 | 0.6588 | 0.2415 | 0.127 (3)* | |
C14 | 0.0976 (4) | 0.5375 (4) | 0.22527 (16) | 0.0534 (8) | |
H14 | 0.0500 | 0.4571 | 0.2420 | 0.127 (3)* | |
C15 | 0.3034 (4) | 0.5284 (3) | 0.23272 (16) | 0.0506 (7) | |
H15 | 0.3444 | 0.4941 | 0.1936 | 0.127 (3)* | |
C16 | 0.3755 (4) | 0.6648 (3) | 0.24568 (17) | 0.0512 (8) | |
H16 | 0.3859 | 0.6808 | 0.2916 | 0.127 (3)* | |
O17 | 0.5461 (3) | 0.6937 (3) | 0.22228 (14) | 0.0648 (7) | |
O18 | 0.6728 (4) | 0.8837 (3) | 0.19854 (19) | 0.0860 (10) | |
O19 | 0.3622 (4) | 0.4481 (3) | 0.28416 (12) | 0.0633 (7) | |
Si20 | 0.4279 (3) | 0.29636 (16) | 0.28631 (7) | 0.1166 (7) | |
C21 | 0.4766 (19) | 0.2334 (8) | 0.2127 (3) | 0.205 (7) | |
H21A | 0.4202 | 0.2863 | 0.1789 | 0.127 (3)* | |
H21B | 0.4333 | 0.1454 | 0.2080 | 0.127 (3)* | |
H21C | 0.6028 | 0.2341 | 0.2111 | 0.127 (3)* | |
C22 | 0.2297 (13) | 0.2017 (11) | 0.2936 (12) | 0.43 (2) | |
H22A | 0.2302 | 0.1717 | 0.3366 | 0.127 (3)* | |
H22B | 0.2268 | 0.1279 | 0.2654 | 0.127 (3)* | |
H22C | 0.1268 | 0.2551 | 0.2825 | 0.127 (3)* | |
C23 | 0.5605 (16) | 0.2660 (8) | 0.3581 (3) | 0.252 (9) | |
C24 | 0.5776 (19) | 0.1140 (9) | 0.3705 (5) | 0.203 (6) | |
H24A | 0.6767 | 0.0805 | 0.3508 | 0.127 (3)* | |
H24B | 0.4707 | 0.0713 | 0.3528 | 0.127 (3)* | |
H24C | 0.5958 | 0.0979 | 0.4155 | 0.127 (3)* | |
C25 | 0.4790 (19) | 0.3250 (12) | 0.4167 (3) | 0.205 (6) | |
H25A | 0.3522 | 0.3159 | 0.4107 | 0.127 (3)* | |
H25B | 0.5095 | 0.4159 | 0.4207 | 0.127 (3)* | |
H25C | 0.5254 | 0.2796 | 0.4546 | 0.127 (3)* | |
C26 | 0.7268 (15) | 0.3513 (17) | 0.3384 (13) | 0.57 (3) | |
H26A | 0.7236 | 0.3534 | 0.2929 | 0.127 (3)* | |
H26B | 0.8360 | 0.3122 | 0.3564 | 0.127 (3)* | |
H26C | 0.7189 | 0.4387 | 0.3543 | 0.127 (3)* | |
O27 | 0.0327 (3) | 0.5484 (3) | 0.15776 (12) | 0.0594 (6) | |
C28 | −0.0094 (5) | 0.4382 (4) | 0.12628 (19) | 0.0616 (9) | |
O29 | 0.0141 (8) | 0.3343 (4) | 0.1486 (2) | 0.138 (2) | |
C30 | −0.0833 (4) | 0.4665 (3) | 0.05901 (16) | 0.0479 (7) | |
O31 | −0.1426 (3) | 0.3419 (2) | 0.03012 (11) | 0.0512 (5) | |
C32 | −0.2589 (4) | 0.3723 (3) | −0.02149 (16) | 0.0494 (7) | |
C33 | −0.2732 (5) | 0.5188 (4) | −0.02458 (17) | 0.0563 (8) | |
C34 | −0.0874 (7) | 0.5569 (5) | −0.0450 (2) | 0.0768 (12) | |
H34A | −0.0607 | 0.5066 | −0.0817 | 0.127 (3)* | |
H34B | −0.0828 | 0.6492 | −0.0551 | 0.127 (3)* | |
C35 | 0.0430 (5) | 0.5236 (5) | 0.0141 (2) | 0.0696 (11) | |
H35A | 0.1029 | 0.6010 | 0.0320 | 0.127 (3)* | |
H35B | 0.1308 | 0.4600 | 0.0041 | 0.127 (3)* | |
C36 | −0.2515 (4) | 0.5522 (3) | 0.04784 (15) | 0.0468 (7) | |
C37 | −0.4049 (5) | 0.5008 (5) | 0.0824 (2) | 0.0680 (10) | |
H37A | −0.3768 | 0.5119 | 0.1274 | 0.127 (3)* | |
H37B | −0.4230 | 0.4097 | 0.0729 | 0.127 (3)* | |
H37C | −0.5112 | 0.5484 | 0.0684 | 0.127 (3)* | |
C38 | −0.2234 (6) | 0.6969 (4) | 0.0617 (2) | 0.0640 (10) | |
H38A | −0.1262 | 0.7282 | 0.0402 | 0.127 (3)* | |
H38B | −0.1969 | 0.7096 | 0.1067 | 0.127 (3)* | |
H38C | −0.3293 | 0.7441 | 0.0468 | 0.127 (3)* | |
O39 | −0.3236 (4) | 0.2899 (3) | −0.05682 (13) | 0.0653 (7) | |
C40 | −0.4371 (8) | 0.5681 (5) | −0.0654 (2) | 0.0889 (15) | |
H40A | −0.5413 | 0.5294 | −0.0511 | 0.127 (3)* | |
H40B | −0.4297 | 0.5447 | −0.1090 | 0.127 (3)* | |
H40C | −0.4439 | 0.6614 | −0.0618 | 0.127 (3)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.055 (2) | 0.058 (2) | 0.082 (3) | 0.0043 (18) | −0.0011 (17) | −0.0049 (19) |
O2 | 0.0576 (14) | 0.0415 (13) | 0.0765 (16) | 0.0050 (11) | 0.0015 (11) | −0.0020 (12) |
C3 | 0.0504 (16) | 0.0408 (17) | 0.0618 (19) | 0.0058 (14) | −0.0014 (14) | −0.0012 (14) |
C4 | 0.0545 (18) | 0.054 (2) | 0.068 (2) | 0.0166 (16) | 0.0015 (15) | −0.0047 (17) |
O5 | 0.0763 (17) | 0.072 (2) | 0.0763 (18) | −0.0024 (14) | 0.0113 (14) | −0.0264 (15) |
C6 | 0.079 (3) | 0.094 (4) | 0.065 (2) | 0.009 (2) | 0.009 (2) | −0.027 (2) |
C7 | 0.095 (3) | 0.117 (5) | 0.109 (4) | 0.007 (3) | 0.030 (3) | −0.039 (4) |
C8 | 0.154 (7) | 0.182 (9) | 0.147 (8) | −0.008 (6) | 0.084 (6) | −0.042 (7) |
C9 | 0.282 (14) | 0.208 (11) | 0.107 (6) | −0.015 (10) | 0.100 (8) | −0.033 (7) |
C10 | 0.181 (8) | 0.226 (11) | 0.062 (4) | 0.014 (8) | 0.010 (4) | 0.000 (5) |
C11 | 0.130 (5) | 0.156 (7) | 0.070 (3) | 0.004 (5) | −0.012 (3) | −0.025 (4) |
O12 | 0.0848 (18) | 0.0720 (18) | 0.0592 (16) | 0.0020 (15) | 0.0102 (13) | −0.0072 (13) |
C13 | 0.0518 (18) | 0.062 (2) | 0.0552 (19) | 0.0056 (16) | −0.0018 (14) | −0.0079 (16) |
C14 | 0.0545 (17) | 0.0495 (19) | 0.0541 (18) | 0.0026 (15) | −0.0032 (14) | −0.0032 (15) |
C15 | 0.0574 (18) | 0.0410 (17) | 0.0520 (17) | 0.0068 (14) | −0.0003 (13) | −0.0007 (14) |
C16 | 0.0469 (16) | 0.0478 (19) | 0.0577 (19) | 0.0084 (14) | −0.0002 (13) | −0.0018 (15) |
O17 | 0.0505 (13) | 0.0555 (15) | 0.0879 (19) | 0.0127 (11) | 0.0056 (12) | 0.0007 (14) |
O18 | 0.0597 (16) | 0.072 (2) | 0.126 (3) | −0.0104 (15) | 0.0083 (17) | 0.003 (2) |
O19 | 0.0769 (16) | 0.0505 (14) | 0.0596 (14) | 0.0139 (13) | −0.0056 (11) | 0.0032 (12) |
Si20 | 0.207 (2) | 0.0690 (9) | 0.0717 (8) | 0.0648 (11) | 0.0035 (10) | 0.0114 (7) |
C21 | 0.413 (19) | 0.101 (6) | 0.099 (5) | 0.126 (9) | 0.019 (7) | −0.006 (4) |
C22 | 0.180 (12) | 0.078 (6) | 0.99 (7) | −0.023 (7) | −0.09 (2) | 0.042 (18) |
C23 | 0.50 (2) | 0.145 (9) | 0.089 (5) | 0.180 (13) | −0.054 (8) | 0.003 (5) |
C24 | 0.309 (15) | 0.127 (7) | 0.151 (8) | 0.092 (9) | −0.071 (9) | 0.027 (6) |
C25 | 0.357 (17) | 0.167 (10) | 0.082 (5) | 0.074 (11) | −0.017 (7) | 0.016 (5) |
C26 | 0.111 (8) | 0.176 (16) | 1.39 (10) | −0.014 (9) | −0.09 (2) | −0.12 (3) |
O27 | 0.0717 (15) | 0.0479 (14) | 0.0550 (13) | −0.0048 (12) | −0.0101 (11) | −0.0070 (11) |
C28 | 0.070 (2) | 0.0390 (18) | 0.071 (2) | 0.0088 (16) | −0.0144 (17) | −0.0085 (17) |
O29 | 0.246 (6) | 0.0476 (19) | 0.098 (3) | 0.013 (3) | −0.080 (3) | −0.0079 (18) |
C30 | 0.0511 (17) | 0.0351 (16) | 0.0555 (17) | −0.0002 (13) | −0.0026 (13) | −0.0118 (13) |
O31 | 0.0534 (12) | 0.0342 (11) | 0.0631 (13) | 0.0001 (9) | −0.0068 (10) | −0.0091 (10) |
C32 | 0.0492 (16) | 0.0455 (18) | 0.0528 (17) | −0.0048 (14) | 0.0018 (13) | −0.0054 (15) |
C33 | 0.073 (2) | 0.0417 (18) | 0.0509 (18) | −0.0055 (16) | −0.0065 (15) | 0.0022 (14) |
C34 | 0.106 (3) | 0.064 (3) | 0.063 (2) | −0.031 (2) | 0.021 (2) | −0.005 (2) |
C35 | 0.056 (2) | 0.068 (3) | 0.087 (3) | −0.0138 (19) | 0.0187 (18) | −0.024 (2) |
C36 | 0.0497 (16) | 0.0370 (16) | 0.0523 (16) | 0.0026 (13) | −0.0003 (13) | 0.0004 (13) |
C37 | 0.057 (2) | 0.072 (3) | 0.075 (2) | 0.0098 (19) | 0.0081 (17) | −0.005 (2) |
C38 | 0.083 (3) | 0.0363 (17) | 0.070 (2) | 0.0073 (17) | −0.0046 (19) | −0.0087 (16) |
O39 | 0.0745 (16) | 0.0501 (14) | 0.0680 (15) | −0.0100 (13) | −0.0084 (12) | −0.0106 (13) |
C40 | 0.119 (4) | 0.065 (3) | 0.074 (3) | 0.012 (3) | −0.033 (3) | 0.000 (2) |
Geometric parameters (Å, º) top
C1—O18 | 1.177 (5) | O19—Si20 | 1.630 (3) |
C1—O2 | 1.346 (5) | Si20—C23 | 1.755 (6) |
C1—O17 | 1.370 (5) | Si20—C21 | 1.760 (6) |
O2—C3 | 1.448 (4) | Si20—C22 | 1.807 (7) |
C3—C16 | 1.503 (5) | C23—C25 | 1.563 (10) |
C3—C4 | 1.502 (5) | C23—C26 | 1.622 (11) |
C4—O5 | 1.414 (5) | C23—C24 | 1.582 (9) |
C4—C13 | 1.554 (6) | O27—C28 | 1.331 (4) |
O5—C6 | 1.437 (6) | C28—O29 | 1.171 (6) |
C6—O12 | 1.423 (6) | C28—C30 | 1.499 (5) |
C6—C11 | 1.520 (7) | C30—O31 | 1.464 (4) |
C6—C7 | 1.494 (7) | C30—C36 | 1.544 (4) |
C7—C8 | 1.530 (11) | C30—C35 | 1.534 (5) |
C8—C9 | 1.531 (15) | O31—C32 | 1.362 (4) |
C9—C10 | 1.476 (13) | C32—O39 | 1.196 (4) |
C10—C11 | 1.525 (13) | C32—C33 | 1.505 (5) |
O12—C13 | 1.424 (5) | C33—C40 | 1.520 (6) |
C13—C14 | 1.536 (5) | C33—C36 | 1.560 (5) |
C14—O27 | 1.463 (4) | C33—C34 | 1.565 (6) |
C14—C15 | 1.552 (5) | C34—C35 | 1.544 (7) |
C15—O19 | 1.398 (4) | C36—C38 | 1.520 (5) |
C15—C16 | 1.513 (5) | C36—C37 | 1.530 (5) |
C16—O17 | 1.463 (4) | | |
| | | |
O18—C1—O2 | 125.2 (4) | C23—Si20—C21 | 123.0 (5) |
O18—C1—O17 | 124.0 (4) | O19—Si20—C22 | 105.1 (5) |
O2—C1—O17 | 110.8 (3) | C23—Si20—C22 | 103.6 (8) |
C1—O2—C3 | 107.8 (3) | C21—Si20—C22 | 97.7 (8) |
O2—C3—C16 | 101.4 (3) | C25—C23—C26 | 112.2 (12) |
O2—C3—C4 | 117.0 (3) | C25—C23—C24 | 106.4 (9) |
C16—C3—C4 | 109.5 (3) | C26—C23—C24 | 121.4 (12) |
O5—C4—C3 | 110.1 (3) | C25—C23—Si20 | 112.2 (6) |
O5—C4—C13 | 105.5 (3) | C26—C23—Si20 | 94.0 (8) |
C3—C4—C13 | 107.0 (3) | C24—C23—Si20 | 110.3 (6) |
C4—O5—C6 | 107.5 (3) | C28—O27—C14 | 117.4 (3) |
O12—C6—O5 | 103.9 (3) | O29—C28—O27 | 123.4 (4) |
O12—C6—C11 | 106.4 (5) | O29—C28—C30 | 125.7 (4) |
O5—C6—C11 | 109.1 (5) | O27—C28—C30 | 110.8 (3) |
O12—C6—C7 | 112.2 (4) | O31—C30—C28 | 107.1 (3) |
O5—C6—C7 | 111.5 (5) | O31—C30—C36 | 102.7 (2) |
C11—C6—C7 | 113.1 (5) | C28—C30—C36 | 118.2 (3) |
C6—C7—C8 | 111.0 (6) | O31—C30—C35 | 104.9 (3) |
C9—C8—C7 | 110.8 (8) | C28—C30—C35 | 117.9 (3) |
C8—C9—C10 | 111.9 (6) | C36—C30—C35 | 104.3 (3) |
C9—C10—C11 | 111.9 (9) | C32—O31—C30 | 106.1 (2) |
C6—C11—C10 | 109.3 (6) | O39—C32—O31 | 121.6 (3) |
C6—O12—C13 | 108.1 (3) | O39—C32—C33 | 130.8 (3) |
O12—C13—C14 | 105.8 (3) | O31—C32—C33 | 107.4 (3) |
O12—C13—C4 | 103.0 (3) | C40—C33—C32 | 114.0 (3) |
C14—C13—C4 | 116.9 (3) | C40—C33—C36 | 118.5 (4) |
O27—C14—C13 | 103.8 (3) | C32—C33—C36 | 100.2 (3) |
O27—C14—C15 | 109.4 (3) | C40—C33—C34 | 117.7 (4) |
C13—C14—C15 | 117.7 (3) | C32—C33—C34 | 101.4 (3) |
O19—C15—C16 | 108.9 (3) | C36—C33—C34 | 102.3 (3) |
O19—C15—C14 | 110.3 (3) | C35—C34—C33 | 103.7 (3) |
C16—C15—C14 | 107.6 (3) | C34—C35—C30 | 101.4 (3) |
O17—C16—C3 | 101.3 (3) | C38—C36—C37 | 110.0 (3) |
O17—C16—C15 | 116.1 (3) | C38—C36—C30 | 115.4 (3) |
C3—C16—C15 | 112.7 (3) | C37—C36—C30 | 112.8 (3) |
C1—O17—C16 | 106.5 (3) | C38—C36—C33 | 113.6 (3) |
C15—O19—Si20 | 130.8 (2) | C37—C36—C33 | 112.8 (3) |
O19—Si20—C23 | 109.7 (3) | C30—C36—C33 | 91.3 (3) |
O19—Si20—C21 | 114.6 (3) | | |