Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801000745/om6001sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801000745/om6001Isup2.hkl |
CCDC reference: 159741
A toluene solution of (I) (317 mg, 0.32 mmol, 10 ml) was added to high purity K lumps (25.0 mg, 0.64 mmol) and either sonicated or stirred vigorously for 4 h, or until no K was visible. Removal of volatiles under reduced pressure afforded a colourless solid. Extraction with pentane, followed by concentration and cooling to 243 K afforded colourless highly crystalline (II) (yield 231 mg, 74%). Crystals selected for data collection were grown at room temperature by ethanol diffusion into a diethyl ether solution of (II).
Although the crystal has a unit cell which is metrically close to monoclinic, merging of the data under 2/m symmetry gave a very high merging R of 0.584; we accordingly adopted the lower triclinic system where the corresponding value was 0.070. For its class, compound (II) displays a surprisingly low level of disorder in the peripheral groups. Positional disorder of one cyclopentyl group was modelled and refined satisfactorily upon application of geometric similarity restraints: the major and minor components comprise 0.76 (2) and 0.24 (2), respectively. H atoms were refined riding on their parent atoms with Uiso(H) = xUeq(C), where x = 1.5 for methyl H atoms and 1.2 for all others; C—H distances were restrained to 0.98, 0.99 and 1.00 Å for methyl, methylene and methine H atoms, respectively.
Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1999); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2000).
C41H78O11Si8 | Z = 2 |
Mr = 971.75 | F(000) = 1048 |
Triclinic, P1 | Dx = 1.267 Mg m−3 |
a = 11.9992 (8) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 14.6230 (9) Å | Cell parameters from 26509 reflections |
c = 15.0146 (13) Å | θ = 2.9–27.5° |
α = 75.182 (3)° | µ = 0.26 mm−1 |
β = 89.959 (3)° | T = 150 K |
γ = 89.793 (2)° | Block, colourless |
V = 2546.9 (3) Å3 | 0.25 × 0.10 × 0.08 mm |
Nonius kappaCCD area-detector diffractometer | 9603 independent reflections |
Radiation source: Nonius FR591 rotating anode | 5603 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.070 |
Detector resolution: 9.091 pixels/mm pixels mm-1 | θmax = 26.0°, θmin = 3.3° |
ϕ and ω scans | h = −15→15 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −18→18 |
Tmin = 0.87, Tmax = 0.99 | l = −16→19 |
195409 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.060 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.163 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0617P)2] where P = (Fo2 + 2Fc2)/3 |
9603 reflections | (Δ/σ)max = 0.001 |
541 parameters | Δρmax = 0.47 e Å−3 |
2 restraints | Δρmin = −0.38 e Å−3 |
C41H78O11Si8 | γ = 89.793 (2)° |
Mr = 971.75 | V = 2546.9 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.9992 (8) Å | Mo Kα radiation |
b = 14.6230 (9) Å | µ = 0.26 mm−1 |
c = 15.0146 (13) Å | T = 150 K |
α = 75.182 (3)° | 0.25 × 0.10 × 0.08 mm |
β = 89.959 (3)° |
Nonius kappaCCD area-detector diffractometer | 9603 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 5603 reflections with I > 2σ(I) |
Tmin = 0.87, Tmax = 0.99 | Rint = 0.070 |
195409 measured reflections |
R[F2 > 2σ(F2)] = 0.060 | 2 restraints |
wR(F2) = 0.163 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.47 e Å−3 |
9603 reflections | Δρmin = −0.38 e Å−3 |
541 parameters |
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 | Occ. (<1) | |
Si1 | 0.01225 (8) | 0.15604 (8) | 0.23254 (7) | 0.0282 (3) | |
Si2 | 0.02615 (8) | 0.36359 (8) | 0.15802 (7) | 0.0274 (3) | |
Si3 | 0.11064 (8) | 0.23690 (8) | 0.04756 (7) | 0.0279 (3) | |
Si4 | 0.33701 (8) | 0.23705 (8) | 0.13452 (7) | 0.0264 (3) | |
Si5 | 0.24491 (8) | 0.10733 (8) | 0.32140 (7) | 0.0266 (3) | |
Si6 | 0.26589 (8) | 0.39705 (8) | 0.22323 (7) | 0.0263 (3) | |
Si7 | 0.32435 (8) | 0.25818 (8) | 0.41658 (7) | 0.0269 (3) | |
Si10 | 0.18038 (9) | 0.31176 (8) | 0.57353 (8) | 0.0332 (3) | |
O1 | −0.02061 (18) | 0.26566 (18) | 0.22658 (17) | 0.0279 (6) | |
O2 | 0.06786 (19) | 0.33729 (18) | 0.06449 (16) | 0.0284 (6) | |
O3 | 0.05739 (19) | 0.15370 (18) | 0.13060 (17) | 0.0288 (6) | |
O4 | 0.24523 (18) | 0.23285 (18) | 0.05573 (16) | 0.0292 (6) | |
O5 | 0.11174 (19) | 0.12290 (19) | 0.30599 (17) | 0.0329 (7) | |
O6 | 0.13216 (18) | 0.39934 (18) | 0.20622 (17) | 0.0308 (6) | |
O7 | 0.2649 (2) | 0.27108 (19) | 0.50728 (17) | 0.0355 (7) | |
O8 | 0.30923 (19) | 0.15483 (18) | 0.22653 (17) | 0.0312 (6) | |
O9 | 0.32770 (19) | 0.33883 (18) | 0.15847 (17) | 0.0306 (6) | |
O10 | 0.28286 (19) | 0.15907 (18) | 0.39911 (17) | 0.0309 (6) | |
O11 | 0.28854 (19) | 0.34463 (18) | 0.32965 (16) | 0.0286 (6) | |
C10 | −0.1060 (3) | 0.0764 (3) | 0.2662 (3) | 0.0303 (9) | |
H10A | −0.0812 | 0.0125 | 0.2614 | 0.036* | |
C11 | −0.2121 (3) | 0.1014 (3) | 0.2078 (3) | 0.0410 (11) | |
H11A | −0.2029 | 0.0871 | 0.1473 | 0.049* | |
H11B | −0.2311 | 0.1693 | 0.1978 | 0.049* | |
C12 | −0.3022 (3) | 0.0385 (3) | 0.2655 (3) | 0.0448 (12) | |
H12A | −0.3106 | −0.0206 | 0.2456 | 0.054* | |
H12B | −0.3748 | 0.0720 | 0.2580 | 0.054* | |
C13 | −0.2639 (3) | 0.0162 (3) | 0.3666 (3) | 0.0425 (11) | |
H13A | −0.2569 | −0.0529 | 0.3928 | 0.051* | |
H13B | −0.3177 | 0.0417 | 0.4042 | 0.051* | |
C14 | −0.1498 (3) | 0.0647 (3) | 0.3644 (3) | 0.0362 (10) | |
H14A | −0.1580 | 0.1270 | 0.3783 | 0.043* | |
H14B | −0.0984 | 0.0250 | 0.4099 | 0.043* | |
C20 | −0.0823 (3) | 0.4545 (3) | 0.1294 (3) | 0.0310 (9) | |
H20A | −0.0487 | 0.5112 | 0.0860 | 0.037* | |
C21 | −0.1334 (3) | 0.4873 (3) | 0.2095 (3) | 0.0392 (11) | |
H21A | −0.0851 | 0.5346 | 0.2270 | 0.047* | |
H21B | −0.1442 | 0.4332 | 0.2639 | 0.047* | |
C22 | −0.2459 (3) | 0.5314 (3) | 0.1722 (3) | 0.0495 (12) | |
H22A | −0.3020 | 0.5207 | 0.2221 | 0.059* | |
H22B | −0.2380 | 0.6004 | 0.1456 | 0.059* | |
C23 | −0.2802 (4) | 0.4845 (5) | 0.1004 (4) | 0.081 (2) | |
H23A | −0.3013 | 0.5327 | 0.0436 | 0.097* | |
H23B | −0.3456 | 0.4439 | 0.1218 | 0.097* | |
C24 | −0.1840 (3) | 0.4250 (3) | 0.0804 (3) | 0.0469 (12) | |
H24A | −0.1708 | 0.4379 | 0.0132 | 0.056* | |
H24B | −0.1998 | 0.3568 | 0.1049 | 0.056* | |
C30 | 0.0645 (3) | 0.2222 (3) | −0.0637 (3) | 0.0328 (10) | |
H30A | 0.1028 | 0.2704 | −0.1136 | 0.039* | |
C31 | 0.0889 (3) | 0.1233 (3) | −0.0775 (3) | 0.0427 (11) | |
H31A | 0.1588 | 0.1235 | −0.1126 | 0.051* | |
H31B | 0.0957 | 0.0760 | −0.0174 | 0.051* | |
C32 | −0.0104 (3) | 0.1018 (3) | −0.1312 (3) | 0.0471 (12) | |
H32A | −0.0023 | 0.1318 | −0.1979 | 0.057* | |
H32B | −0.0200 | 0.0328 | −0.1218 | 0.057* | |
C33 | −0.1064 (4) | 0.1443 (4) | −0.0908 (4) | 0.0643 (16) | |
H33A | −0.1709 | 0.1554 | −0.1334 | 0.077* | |
H33B | −0.1298 | 0.1018 | −0.0313 | 0.077* | |
C34 | −0.0638 (3) | 0.2353 (3) | −0.0773 (3) | 0.0520 (13) | |
H34A | −0.0986 | 0.2494 | −0.0224 | 0.062* | |
H34B | −0.0806 | 0.2880 | −0.1318 | 0.062* | |
C40 | 0.4759 (3) | 0.2166 (3) | 0.0913 (3) | 0.0295 (9) | |
H40A | 0.5306 | 0.2136 | 0.1422 | 0.035* | |
C41 | 0.4846 (3) | 0.1230 (3) | 0.0624 (3) | 0.0410 (11) | |
H41A | 0.5048 | 0.0703 | 0.1160 | 0.049* | |
H41B | 0.4127 | 0.1080 | 0.0372 | 0.049* | |
C42 | 0.5752 (4) | 0.1374 (4) | −0.0109 (4) | 0.0640 (15) | |
H42A | 0.6377 | 0.0928 | 0.0102 | 0.077* | |
H42B | 0.5450 | 0.1267 | −0.0688 | 0.077* | |
C43 | 0.6146 (4) | 0.2385 (3) | −0.0264 (3) | 0.0539 (13) | |
H43A | 0.6301 | 0.2669 | −0.0924 | 0.065* | |
H43B | 0.6829 | 0.2415 | 0.0096 | 0.065* | |
C44 | 0.5178 (3) | 0.2890 (3) | 0.0068 (3) | 0.0428 (11) | |
H44A | 0.5434 | 0.3470 | 0.0230 | 0.051* | |
H44B | 0.4590 | 0.3061 | −0.0408 | 0.051* | |
C50 | 0.2806 (3) | −0.0181 (3) | 0.3565 (3) | 0.0331 (10) | |
H50A | 0.2422 | −0.0470 | 0.4161 | 0.040* | |
C51 | 0.2441 (3) | −0.0732 (3) | 0.2838 (3) | 0.0458 (12) | |
C52 | 0.3317 (5) | −0.1545 (6) | 0.3025 (7) | 0.059 (3)* | 0.76 (2) |
H52A | 0.3094 | −0.2056 | 0.3565 | 0.071* | 0.76 (2) |
H52B | 0.3381 | −0.1812 | 0.2484 | 0.071* | 0.76 (2) |
C56 | 0.3515 (12) | −0.111 (2) | 0.2521 (15) | 0.050 (8)* | 0.24 (2) |
H56A | 0.3391 | −0.1756 | 0.2445 | 0.059* | 0.24 (2) |
H56B | 0.3748 | −0.0699 | 0.1919 | 0.059* | 0.24 (2) |
C53 | 0.4381 (4) | −0.1136 (4) | 0.3201 (4) | 0.0656 (15) | |
C54 | 0.4080 (3) | −0.0374 (3) | 0.3698 (3) | 0.0467 (12) | |
H54A | 0.4505 | 0.0212 | 0.3434 | 0.056* | |
H54B | 0.4262 | −0.0596 | 0.4362 | 0.056* | |
C60 | 0.3177 (3) | 0.5183 (3) | 0.1988 (3) | 0.0291 (9) | |
H60A | 0.3015 | 0.5508 | 0.1329 | 0.035* | |
C61 | 0.4452 (3) | 0.5250 (3) | 0.2165 (3) | 0.0348 (10) | |
H61A | 0.4753 | 0.4622 | 0.2492 | 0.042* | |
H61B | 0.4857 | 0.5475 | 0.1575 | 0.042* | |
C62 | 0.4579 (3) | 0.5943 (3) | 0.2750 (3) | 0.0467 (12) | |
H62A | 0.5238 | 0.5786 | 0.3158 | 0.056* | |
H62B | 0.4656 | 0.6598 | 0.2361 | 0.056* | |
C63 | 0.3518 (3) | 0.5830 (3) | 0.3300 (3) | 0.0450 (12) | |
H63A | 0.3385 | 0.6384 | 0.3552 | 0.054* | |
H63B | 0.3543 | 0.5251 | 0.3815 | 0.054* | |
C64 | 0.2627 (3) | 0.5756 (3) | 0.2614 (3) | 0.0373 (10) | |
H64A | 0.2397 | 0.6392 | 0.2248 | 0.045* | |
H64B | 0.1965 | 0.5422 | 0.2932 | 0.045* | |
C70 | 0.4760 (3) | 0.2547 (3) | 0.4322 (3) | 0.0307 (9) | |
H70A | 0.4922 | 0.1974 | 0.4834 | 0.037* | |
C71 | 0.5280 (3) | 0.3392 (3) | 0.4609 (3) | 0.0418 (11) | |
H71A | 0.4863 | 0.3982 | 0.4332 | 0.050* | |
H71B | 0.5272 | 0.3282 | 0.5287 | 0.050* | |
C72 | 0.6481 (4) | 0.3460 (4) | 0.4247 (4) | 0.0635 (15) | |
H72A | 0.6617 | 0.4092 | 0.3828 | 0.076* | |
H72B | 0.7016 | 0.3359 | 0.4765 | 0.076* | |
C73 | 0.6621 (4) | 0.2727 (4) | 0.3753 (4) | 0.0712 (17) | |
H73A | 0.7008 | 0.2171 | 0.4148 | 0.085* | |
H73B | 0.7070 | 0.2970 | 0.3189 | 0.085* | |
C74 | 0.5467 (3) | 0.2451 (3) | 0.3502 (3) | 0.0412 (11) | |
H74A | 0.5460 | 0.1794 | 0.3439 | 0.049* | |
H74B | 0.5201 | 0.2883 | 0.2921 | 0.049* | |
C100 | 0.0338 (3) | 0.2892 (3) | 0.5441 (3) | 0.0375 (10) | |
C101 | 0.2153 (4) | 0.2508 (4) | 0.6935 (3) | 0.0506 (12) | |
H10B | 0.2000 | 0.1830 | 0.7042 | 0.076* | |
H10C | 0.1700 | 0.2769 | 0.7355 | 0.076* | |
H10D | 0.2944 | 0.2599 | 0.7047 | 0.076* | |
C102 | 0.2078 (4) | 0.4397 (3) | 0.5548 (3) | 0.0528 (13) | |
H10E | 0.2852 | 0.4490 | 0.5712 | 0.079* | |
H10F | 0.1575 | 0.4660 | 0.5934 | 0.079* | |
H10G | 0.1952 | 0.4719 | 0.4899 | 0.079* | |
C103 | 0.0074 (4) | 0.3438 (4) | 0.4439 (3) | 0.0577 (14) | |
H10H | −0.0697 | 0.3313 | 0.4291 | 0.087* | |
H10I | 0.0582 | 0.3228 | 0.4018 | 0.087* | |
H10J | 0.0171 | 0.4117 | 0.4371 | 0.087* | |
C104 | −0.0482 (3) | 0.3221 (4) | 0.6087 (3) | 0.0538 (13) | |
H10K | −0.1248 | 0.3100 | 0.5923 | 0.081* | |
H10L | −0.0386 | 0.3900 | 0.6024 | 0.081* | |
H10M | −0.0334 | 0.2873 | 0.6726 | 0.081* | |
C105 | 0.0162 (4) | 0.1835 (3) | 0.5531 (3) | 0.0553 (13) | |
H10N | −0.0610 | 0.1728 | 0.5372 | 0.083* | |
H10O | 0.0313 | 0.1479 | 0.6167 | 0.083* | |
H10P | 0.0670 | 0.1623 | 0.5113 | 0.083* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Si1 | 0.0259 (6) | 0.0304 (7) | 0.0288 (7) | −0.0001 (4) | 0.0011 (4) | −0.0085 (5) |
Si2 | 0.0244 (6) | 0.0306 (7) | 0.0288 (7) | 0.0012 (4) | −0.0004 (4) | −0.0104 (5) |
Si3 | 0.0278 (6) | 0.0318 (7) | 0.0255 (6) | 0.0004 (5) | 0.0001 (4) | −0.0099 (5) |
Si4 | 0.0253 (6) | 0.0292 (7) | 0.0260 (6) | 0.0008 (4) | 0.0019 (4) | −0.0096 (5) |
Si5 | 0.0263 (6) | 0.0271 (7) | 0.0265 (6) | 0.0000 (4) | −0.0003 (4) | −0.0071 (5) |
Si6 | 0.0249 (6) | 0.0262 (7) | 0.0289 (6) | 0.0011 (4) | −0.0008 (4) | −0.0092 (5) |
Si7 | 0.0288 (6) | 0.0282 (7) | 0.0255 (6) | 0.0018 (5) | −0.0003 (4) | −0.0100 (5) |
Si10 | 0.0381 (6) | 0.0339 (7) | 0.0299 (7) | 0.0019 (5) | 0.0054 (5) | −0.0121 (6) |
O1 | 0.0259 (13) | 0.0297 (16) | 0.0299 (16) | −0.0011 (11) | 0.0040 (11) | −0.0109 (13) |
O2 | 0.0314 (14) | 0.0292 (16) | 0.0251 (15) | 0.0019 (11) | 0.0029 (11) | −0.0077 (13) |
O3 | 0.0302 (14) | 0.0290 (16) | 0.0285 (16) | −0.0020 (11) | 0.0030 (11) | −0.0099 (13) |
O4 | 0.0277 (14) | 0.0351 (17) | 0.0269 (16) | 0.0020 (11) | −0.0014 (10) | −0.0117 (13) |
O5 | 0.0243 (14) | 0.0428 (18) | 0.0299 (16) | 0.0016 (12) | −0.0017 (11) | −0.0063 (14) |
O6 | 0.0254 (14) | 0.0349 (17) | 0.0355 (16) | 0.0021 (11) | −0.0028 (11) | −0.0156 (14) |
O7 | 0.0386 (16) | 0.0414 (19) | 0.0284 (16) | 0.0042 (13) | 0.0012 (12) | −0.0126 (14) |
O8 | 0.0301 (14) | 0.0330 (17) | 0.0291 (16) | −0.0004 (11) | 0.0045 (11) | −0.0053 (13) |
O9 | 0.0286 (14) | 0.0298 (17) | 0.0369 (17) | 0.0027 (11) | 0.0014 (11) | −0.0150 (13) |
O10 | 0.0396 (15) | 0.0263 (16) | 0.0289 (16) | −0.0031 (12) | −0.0009 (11) | −0.0109 (13) |
O11 | 0.0341 (14) | 0.0269 (16) | 0.0234 (15) | 0.0040 (11) | −0.0039 (11) | −0.0038 (12) |
C10 | 0.029 (2) | 0.028 (2) | 0.034 (2) | −0.0025 (17) | 0.0022 (17) | −0.009 (2) |
C11 | 0.034 (2) | 0.051 (3) | 0.038 (3) | −0.007 (2) | −0.0035 (18) | −0.010 (2) |
C12 | 0.032 (2) | 0.050 (3) | 0.053 (3) | −0.008 (2) | 0.003 (2) | −0.014 (2) |
C13 | 0.037 (2) | 0.042 (3) | 0.045 (3) | −0.005 (2) | 0.0106 (19) | −0.005 (2) |
C14 | 0.036 (2) | 0.037 (3) | 0.034 (3) | 0.0024 (18) | 0.0003 (18) | −0.005 (2) |
C20 | 0.028 (2) | 0.032 (2) | 0.033 (2) | 0.0010 (17) | −0.0020 (16) | −0.008 (2) |
C21 | 0.032 (2) | 0.044 (3) | 0.046 (3) | 0.0079 (19) | −0.0016 (18) | −0.020 (2) |
C22 | 0.038 (3) | 0.050 (3) | 0.064 (3) | 0.010 (2) | 0.001 (2) | −0.021 (3) |
C23 | 0.040 (3) | 0.125 (6) | 0.103 (5) | 0.037 (3) | −0.031 (3) | −0.076 (4) |
C24 | 0.035 (2) | 0.060 (3) | 0.052 (3) | 0.012 (2) | −0.013 (2) | −0.027 (3) |
C30 | 0.036 (2) | 0.031 (3) | 0.032 (2) | 0.0031 (18) | −0.0028 (17) | −0.010 (2) |
C31 | 0.059 (3) | 0.044 (3) | 0.028 (3) | 0.002 (2) | −0.001 (2) | −0.015 (2) |
C32 | 0.053 (3) | 0.050 (3) | 0.047 (3) | −0.012 (2) | 0.004 (2) | −0.027 (3) |
C33 | 0.045 (3) | 0.082 (4) | 0.081 (4) | −0.016 (3) | 0.013 (3) | −0.048 (3) |
C34 | 0.049 (3) | 0.060 (4) | 0.055 (3) | 0.012 (2) | −0.023 (2) | −0.029 (3) |
C40 | 0.029 (2) | 0.032 (3) | 0.029 (2) | 0.0026 (17) | 0.0023 (16) | −0.010 (2) |
C41 | 0.037 (2) | 0.039 (3) | 0.049 (3) | 0.0053 (19) | 0.0091 (19) | −0.014 (2) |
C42 | 0.069 (3) | 0.066 (4) | 0.065 (4) | −0.004 (3) | 0.027 (3) | −0.032 (3) |
C43 | 0.051 (3) | 0.056 (4) | 0.053 (3) | 0.000 (2) | 0.023 (2) | −0.012 (3) |
C44 | 0.041 (2) | 0.040 (3) | 0.044 (3) | −0.001 (2) | 0.010 (2) | −0.005 (2) |
C50 | 0.039 (2) | 0.026 (2) | 0.032 (2) | −0.0014 (18) | −0.0006 (17) | −0.004 (2) |
C51 | 0.051 (3) | 0.035 (3) | 0.061 (3) | 0.003 (2) | −0.003 (2) | −0.029 (3) |
C53 | 0.067 (3) | 0.063 (4) | 0.078 (4) | 0.028 (3) | −0.015 (3) | −0.040 (3) |
C54 | 0.044 (3) | 0.037 (3) | 0.059 (3) | 0.011 (2) | −0.014 (2) | −0.011 (2) |
C60 | 0.031 (2) | 0.026 (2) | 0.029 (2) | 0.0005 (17) | 0.0007 (16) | −0.0046 (19) |
C61 | 0.029 (2) | 0.033 (3) | 0.042 (3) | −0.0007 (17) | 0.0024 (17) | −0.009 (2) |
C62 | 0.037 (3) | 0.047 (3) | 0.059 (3) | −0.001 (2) | −0.010 (2) | −0.020 (3) |
C63 | 0.049 (3) | 0.045 (3) | 0.048 (3) | 0.007 (2) | −0.009 (2) | −0.023 (2) |
C64 | 0.034 (2) | 0.034 (3) | 0.046 (3) | 0.0008 (18) | 0.0008 (18) | −0.012 (2) |
C70 | 0.034 (2) | 0.027 (2) | 0.030 (2) | 0.0042 (17) | −0.0042 (17) | −0.0064 (19) |
C71 | 0.041 (2) | 0.040 (3) | 0.049 (3) | −0.002 (2) | −0.005 (2) | −0.019 (2) |
C72 | 0.043 (3) | 0.081 (4) | 0.076 (4) | −0.019 (3) | 0.007 (2) | −0.038 (3) |
C73 | 0.031 (3) | 0.080 (4) | 0.118 (5) | −0.004 (2) | 0.010 (3) | −0.054 (4) |
C74 | 0.036 (2) | 0.037 (3) | 0.055 (3) | −0.0025 (19) | 0.005 (2) | −0.020 (2) |
C100 | 0.037 (2) | 0.038 (3) | 0.036 (3) | 0.0032 (19) | 0.0054 (18) | −0.008 (2) |
C101 | 0.057 (3) | 0.063 (4) | 0.033 (3) | 0.004 (2) | 0.003 (2) | −0.015 (2) |
C102 | 0.057 (3) | 0.046 (3) | 0.061 (3) | −0.004 (2) | 0.009 (2) | −0.025 (3) |
C103 | 0.046 (3) | 0.076 (4) | 0.046 (3) | 0.001 (2) | 0.000 (2) | −0.006 (3) |
C104 | 0.047 (3) | 0.057 (3) | 0.058 (3) | 0.010 (2) | 0.014 (2) | −0.015 (3) |
C105 | 0.049 (3) | 0.058 (4) | 0.064 (4) | −0.009 (2) | 0.007 (2) | −0.026 (3) |
Si1—O1 | 1.629 (3) | C13—C14 | 1.540 (5) |
Si1—O3 | 1.632 (3) | C20—C21 | 1.531 (5) |
Si1—O5 | 1.613 (3) | C20—C24 | 1.544 (5) |
Si1—C10 | 1.826 (4) | C21—C22 | 1.537 (5) |
Si2—O1 | 1.636 (3) | C22—C23 | 1.476 (6) |
Si2—O2 | 1.626 (3) | C23—C24 | 1.518 (6) |
Si2—O6 | 1.617 (2) | C30—C31 | 1.540 (6) |
Si2—C20 | 1.828 (4) | C30—C34 | 1.558 (5) |
Si3—O2 | 1.634 (3) | C31—C32 | 1.518 (5) |
Si3—O3 | 1.635 (3) | C32—C33 | 1.506 (6) |
Si3—O4 | 1.619 (2) | C33—C34 | 1.489 (6) |
Si3—C30 | 1.825 (4) | C40—C44 | 1.516 (5) |
Si4—O4 | 1.630 (2) | C40—C41 | 1.541 (5) |
Si4—O8 | 1.618 (3) | C41—C42 | 1.523 (6) |
Si4—O9 | 1.621 (3) | C42—C43 | 1.514 (7) |
Si4—C40 | 1.839 (4) | C43—C44 | 1.525 (6) |
Si5—O5 | 1.622 (2) | C50—C54 | 1.558 (5) |
Si5—O8 | 1.613 (3) | C50—C51 | 1.575 (5) |
Si5—O10 | 1.611 (3) | C51—C56 | 1.526 (14) |
Si5—C50 | 1.823 (4) | C51—C52 | 1.555 (7) |
Si6—O6 | 1.624 (2) | C52—C53 | 1.465 (7) |
Si6—O9 | 1.624 (3) | C56—C53 | 1.451 (14) |
Si6—O11 | 1.609 (3) | C53—C54 | 1.534 (6) |
Si6—C60 | 1.828 (4) | C60—C64 | 1.556 (5) |
Si7—O7 | 1.590 (3) | C60—C61 | 1.562 (5) |
Si7—O10 | 1.618 (3) | C61—C62 | 1.510 (5) |
Si7—O11 | 1.625 (3) | C62—C63 | 1.504 (6) |
Si7—C70 | 1.833 (4) | C63—C64 | 1.508 (5) |
Si10—O7 | 1.634 (3) | C70—C74 | 1.531 (5) |
Si10—C101 | 1.842 (4) | C70—C71 | 1.542 (5) |
Si10—C102 | 1.851 (5) | C71—C72 | 1.536 (6) |
Si10—C100 | 1.865 (4) | C72—C73 | 1.460 (6) |
C10—C14 | 1.533 (5) | C73—C74 | 1.517 (6) |
C10—C11 | 1.535 (5) | C100—C105 | 1.531 (6) |
C11—C12 | 1.538 (5) | C100—C104 | 1.541 (6) |
C12—C13 | 1.539 (6) | C100—C103 | 1.545 (6) |
O1—Si1—O3 | 106.48 (14) | C14—C10—C11 | 102.5 (3) |
O1—Si1—O5 | 109.47 (14) | C14—C10—Si1 | 116.1 (3) |
O3—Si1—O5 | 108.77 (13) | C11—C10—Si1 | 116.5 (3) |
O5—Si1—C10 | 109.18 (16) | C10—C11—C12 | 104.0 (3) |
O1—Si1—C10 | 112.20 (16) | C11—C12—C13 | 106.9 (3) |
O3—Si1—C10 | 110.65 (16) | C12—C13—C14 | 105.3 (3) |
O1—Si2—O2 | 106.68 (14) | C10—C14—C13 | 105.3 (3) |
O1—Si2—O6 | 108.78 (14) | C21—C20—C24 | 103.9 (3) |
O2—Si2—O6 | 108.67 (13) | C21—C20—Si2 | 116.9 (3) |
O6—Si2—C20 | 111.45 (16) | C24—C20—Si2 | 113.5 (3) |
O2—Si2—C20 | 109.41 (16) | C20—C21—C22 | 104.5 (3) |
O1—Si2—C20 | 111.70 (16) | C23—C22—C21 | 106.4 (4) |
O2—Si3—O3 | 106.40 (13) | C22—C23—C24 | 109.2 (4) |
O2—Si3—O4 | 108.37 (13) | C23—C24—C20 | 105.1 (4) |
O3—Si3—O4 | 109.18 (14) | C31—C30—C34 | 104.8 (3) |
O4—Si3—C30 | 111.26 (16) | C31—C30—Si3 | 113.6 (3) |
O2—Si3—C30 | 111.62 (16) | C34—C30—Si3 | 112.4 (3) |
O3—Si3—C30 | 109.87 (17) | C32—C31—C30 | 104.7 (3) |
O4—Si4—O8 | 108.75 (13) | C33—C32—C31 | 102.9 (4) |
O4—Si4—O9 | 108.90 (14) | C34—C33—C32 | 105.4 (4) |
O8—Si4—O9 | 108.71 (14) | C33—C34—C30 | 106.0 (4) |
O8—Si4—C40 | 109.71 (16) | C44—C40—C41 | 102.9 (3) |
O9—Si4—C40 | 112.27 (15) | C44—C40—Si4 | 117.1 (3) |
O4—Si4—C40 | 108.44 (15) | C41—C40—Si4 | 113.2 (2) |
O5—Si5—O8 | 109.46 (14) | C42—C41—C40 | 106.3 (3) |
O5—Si5—O10 | 108.01 (14) | C43—C42—C41 | 106.6 (4) |
O8—Si5—O10 | 109.08 (14) | C42—C43—C44 | 104.2 (4) |
O10—Si5—C50 | 110.42 (16) | C40—C44—C43 | 103.5 (4) |
O8—Si5—C50 | 108.56 (17) | C54—C50—C51 | 104.9 (3) |
O5—Si5—C50 | 111.29 (16) | C54—C50—Si5 | 113.5 (3) |
O6—Si6—O9 | 110.35 (13) | C51—C50—Si5 | 113.0 (3) |
O6—Si6—O11 | 107.92 (13) | C56—C51—C50 | 105.7 (7) |
O9—Si6—O11 | 109.20 (14) | C52—C51—C50 | 100.9 (4) |
O11—Si6—C60 | 109.47 (16) | C53—C52—C51 | 107.0 (5) |
O6—Si6—C60 | 109.12 (16) | C53—C56—C51 | 109.3 (10) |
O9—Si6—C60 | 110.73 (16) | C56—C53—C54 | 106.6 (8) |
O7—Si7—O10 | 107.89 (15) | C52—C53—C54 | 105.4 (4) |
O7—Si7—O11 | 109.41 (15) | C53—C54—C50 | 107.2 (3) |
O10—Si7—O11 | 109.48 (14) | C64—C60—C61 | 104.1 (3) |
O7—Si7—C70 | 109.87 (16) | C64—C60—Si6 | 112.3 (3) |
O10—Si7—C70 | 109.43 (16) | C61—C60—Si6 | 113.7 (3) |
O11—Si7—C70 | 110.72 (16) | C62—C61—C60 | 106.4 (3) |
O7—Si10—C101 | 107.15 (18) | C63—C62—C61 | 103.6 (3) |
O7—Si10—C102 | 107.87 (18) | C62—C63—C64 | 104.0 (3) |
C101—Si10—C102 | 109.0 (2) | C63—C64—C60 | 104.9 (3) |
O7—Si10—C100 | 109.04 (17) | C74—C70—C71 | 104.1 (3) |
C101—Si10—C100 | 112.0 (2) | C74—C70—Si7 | 116.9 (3) |
C102—Si10—C100 | 111.6 (2) | C71—C70—Si7 | 116.2 (3) |
Si1—O1—Si2 | 129.99 (16) | C72—C71—C70 | 105.5 (4) |
Si1—O3—Si3 | 130.97 (17) | C73—C72—C71 | 107.2 (4) |
Si1—O5—Si5 | 146.39 (17) | C72—C73—C74 | 107.5 (4) |
Si2—O2—Si3 | 130.55 (17) | C73—C74—C70 | 102.8 (3) |
Si2—O6—Si6 | 148.56 (18) | C105—C100—C104 | 109.0 (4) |
Si3—O4—Si4 | 136.23 (16) | C105—C100—C103 | 108.4 (4) |
Si7—O7—Si10 | 160.06 (19) | C104—C100—C103 | 108.5 (4) |
Si4—O8—Si5 | 155.73 (18) | C105—C100—Si10 | 110.4 (3) |
Si4—O9—Si6 | 144.47 (17) | C104—C100—Si10 | 110.5 (3) |
Si5—O10—Si7 | 144.31 (18) | C103—C100—Si10 | 110.1 (3) |
Si6—O11—Si7 | 156.54 (18) |
Experimental details
Crystal data | |
Chemical formula | C41H78O11Si8 |
Mr | 971.75 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 11.9992 (8), 14.6230 (9), 15.0146 (13) |
α, β, γ (°) | 75.182 (3), 89.959 (3), 89.793 (2) |
V (Å3) | 2546.9 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.26 |
Crystal size (mm) | 0.25 × 0.10 × 0.08 |
Data collection | |
Diffractometer | Nonius kappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.87, 0.99 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 195409, 9603, 5603 |
Rint | 0.070 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.060, 0.163, 1.00 |
No. of reflections | 9603 |
No. of parameters | 541 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.47, −0.38 |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1999), DENZO and COLLECT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXL97 and PLATON (Spek, 2000).
Si1—O1 | 1.629 (3) | Si4—O9 | 1.621 (3) |
Si1—O3 | 1.632 (3) | Si5—O5 | 1.622 (2) |
Si1—O5 | 1.613 (3) | Si5—O8 | 1.613 (3) |
Si2—O1 | 1.636 (3) | Si5—O10 | 1.611 (3) |
Si2—O2 | 1.626 (3) | Si6—O6 | 1.624 (2) |
Si2—O6 | 1.617 (2) | Si6—O9 | 1.624 (3) |
Si3—O2 | 1.634 (3) | Si6—O11 | 1.609 (3) |
Si3—O3 | 1.635 (3) | Si7—O7 | 1.590 (3) |
Si3—O4 | 1.619 (2) | Si7—O10 | 1.618 (3) |
Si4—O4 | 1.630 (2) | Si7—O11 | 1.625 (3) |
Si4—O8 | 1.618 (3) | Si10—O7 | 1.634 (3) |
O1—Si1—O3 | 106.48 (14) | O6—Si6—O11 | 107.92 (13) |
O1—Si1—O5 | 109.47 (14) | O9—Si6—O11 | 109.20 (14) |
O3—Si1—O5 | 108.77 (13) | O7—Si7—O10 | 107.89 (15) |
O1—Si2—O2 | 106.68 (14) | O7—Si7—O11 | 109.41 (15) |
O1—Si2—O6 | 108.78 (14) | O10—Si7—O11 | 109.48 (14) |
O2—Si2—O6 | 108.67 (13) | Si1—O1—Si2 | 129.99 (16) |
O2—Si3—O3 | 106.40 (13) | Si1—O3—Si3 | 130.97 (17) |
O2—Si3—O4 | 108.37 (13) | Si1—O5—Si5 | 146.39 (17) |
O3—Si3—O4 | 109.18 (14) | Si2—O2—Si3 | 130.55 (17) |
O4—Si4—O8 | 108.75 (13) | Si2—O6—Si6 | 148.56 (18) |
O4—Si4—O9 | 108.90 (14) | Si3—O4—Si4 | 136.23 (16) |
O8—Si4—O9 | 108.71 (14) | Si7—O7—Si10 | 160.06 (19) |
O5—Si5—O8 | 109.46 (14) | Si4—O8—Si5 | 155.73 (18) |
O5—Si5—O10 | 108.01 (14) | Si4—O9—Si6 | 144.47 (17) |
O8—Si5—O10 | 109.08 (14) | Si5—O10—Si7 | 144.31 (18) |
O6—Si6—O9 | 110.35 (13) | Si6—O11—Si7 | 156.54 (18) |
Over the past year, a number of groups have found that under certain conditions lithiation of the siloxane triol (c-C5H9)7Si7O9(OH)3 proceeds smoothly, without the cage destruction which had been reported to arise during reactions to generate a sodium salt (Annand et al., 1999; Feher et al., 1992). The TBDMS (TBDMS is tert-butyldimethylsilyl) functionalization has provided us with a highly soluble tractable disilanol, (c-C5H9)7Si7O9(OH)2(OSiMe2But), (I), which we were able to convert quantitatively to a dilithio salt using tert-butyl lithium (Arnold et al., 2001). Treatment of a pentane or toluene solution of (I) with two equivalents of potassium metal results in dissolution of the metal over a few hours (the reaction is accelerated by sonication). This colourless solution contains the siloxane, (c-C5H9)7Si7O9(O)(OSiMe2But), (II), arising from the condensation of adjacent silanols to form a new six-membered siloxane ring in the complex. It is widely agreed that these classes of siloxanes crystallize readily but form poorly diffracting crystals that rarely yield satisfactory structural information (Herrmann et al., 1994; Abbenhuis, 2000). This held true for (II), with further complications arising from crystals that cracked upon cooling in the cold nitrogen stream on the diffractometer. A range of morphologies of crystals was obtained from different solvents and solvent mixtures, but the only crystals that diffracted reasonably were large colourless blocks grown by ethanol diffusion into an ether solution of (II); this too was mounted at room temperature to eliminate the problem of disintegration. Distances and angles for the compound are as anticipated; whilst the TBDMS anchoring vertex Si7 bends away from the cube, the tert-butyl group is folded back towards the siloxane oxygen O1, possibly facilitating the surprisingly highly ordered packing of the molecules.