Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801013265/om6038sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801013265/om6038Isup2.hkl |
CCDC reference: 172192
For the preparation of trans–Ph2(CH3)2C2(η5-C5H4)2Ca(DME), (I), calcium granules (1.33 g, 33.19 mmol; preactivated with HgCl2) were suspended in 100 ml of dry DME under an argon atmosphere. 6,6-Methylphenylfulvene (10.00 g, 59.44 mmol) was added gradually for a period of 15 min as the reaction was stirred at room temperature. The red color of the fulvene disappeared almost instantly and the reaction mixture appeared colorless within 6 h. The mixture was filtered to remove the gray precipitate and the solvent was removed under reduced pressure. The tan solid was washed with copious amounts of hexane yielding the product, a colorless solid (8.71 g, 61%). Roughly equal amounts of both the cis and trans isomers are present. The trans isomer was selectively precipitated as a colorless powder by dissolution and cooling to 195 K in a dry ice/acetone bath. Yield 2.66 g, 25%. X-ray quality crystals of the trans isomer were obtained from a saturated DME solution at room temperature after 3 d. 1H NMR (200 MHz, DMSO-d6): δ 1.92 (s, 6H, CH3), 3.24 (s, 6H, CH3—DME), 3.43 (s, 4H, CH2—DME), 5.44 (s, 2H, Cp), 5.63–5.69 (d, 4H, Cp), 6.20 (s, 2H, Cp), 7.06–7.34 (m, 10H, Ph); 13C{1H} NMR (50.3 MHz, DMSO-d6): δ 28.2 (CH3), 52.8 (MeCPH), 58.9 (CH3O-DME), 71.9 (OCH2CH2O), 104.1, 106.7, 107.5, 108.2, 125.5 (C5H4), 126.5, 128.6, 129.4, 130.3, 132.5, 150.0 (C6H5); C30H34CaO2 (calc/found%): C 77.21/77.17, H 7.34/7.31.
H atoms were placed geometrically and refined with a riding model, with the Uiso constrained to be 1.2Ueq of the carrier atom. There are voids of 48 Å3 present in (I).
Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: XS (Sheldrick, 1998); program(s) used to refine structure: XL (Sheldrick, 1998); molecular graphics: XP (Sheldrick, 1998); software used to prepare material for publication: XCIF (Sheldrick, 1998).
Fig. 1. The molecular structure of ((I)) with 30% probability ellipsoids. H atoms have been omitted for clarity. |
[Ca(C26H24)(C4H10O2)] | F(000) = 2000 |
Mr = 466.65 | Dx = 1.195 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 27.726 (3) Å | Cell parameters from 8192 reflections |
b = 12.412 (2) Å | θ = 1.8–25.0° |
c = 16.087 (3) Å | µ = 0.27 mm−1 |
β = 110.46 (2)° | T = 213 K |
V = 5186.7 (14) Å3 | Block, colorless |
Z = 8 | 0.25 × 0.20 × 0.15 mm |
Siemens SMART 1K diffractometer | 4564 independent reflections |
Radiation source: normal-focus sealed tube | 4294 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
Detector resolution: 8.3 pixels mm-1 | θmax = 25.0°, θmin = 1.8° |
ω scans | h = −32→32 |
Absorption correction: empirical (using intensity measurements) (XPREP; Sheldrick, 1998) | k = −7→14 |
Tmin = 0.937, Tmax = 0.961 | l = −19→19 |
14054 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)] = 0.062 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.29 | w = 1/[σ2(Fo2) + (0.0165P)2 + 8.9225P] where P = (Fo2 + 2Fc2)/3 |
4564 reflections | (Δ/σ)max = 0.001 |
302 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
[Ca(C26H24)(C4H10O2)] | V = 5186.7 (14) Å3 |
Mr = 466.65 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 27.726 (3) Å | µ = 0.27 mm−1 |
b = 12.412 (2) Å | T = 213 K |
c = 16.087 (3) Å | 0.25 × 0.20 × 0.15 mm |
β = 110.46 (2)° |
Siemens SMART 1K diffractometer | 4564 independent reflections |
Absorption correction: empirical (using intensity measurements) (XPREP; Sheldrick, 1998) | 4294 reflections with I > 2σ(I) |
Tmin = 0.937, Tmax = 0.961 | Rint = 0.028 |
14054 measured reflections |
R[F2 > 2σ(F2)] = 0.062 | 0 restraints |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.29 | Δρmax = 0.25 e Å−3 |
4564 reflections | Δρmin = −0.24 e Å−3 |
302 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 | ||
C1 | 0.38450 (12) | 0.2368 (2) | 0.29348 (17) | 0.0460 (7) | |
H1 | 0.4192 | 0.2207 | 0.3254 | 0.055* | |
C2 | 0.35100 (14) | 0.2918 (3) | 0.32724 (19) | 0.0561 (8) | |
H2 | 0.3595 | 0.3190 | 0.3851 | 0.067* | |
C3 | 0.30308 (13) | 0.2990 (2) | 0.2601 (2) | 0.0517 (8) | |
H3 | 0.2735 | 0.3316 | 0.2646 | 0.062* | |
C4 | 0.30698 (10) | 0.2488 (2) | 0.18423 (18) | 0.0400 (6) | |
H4 | 0.2801 | 0.2425 | 0.1292 | 0.048* | |
C5 | 0.35753 (9) | 0.2092 (2) | 0.20347 (16) | 0.0335 (6) | |
C6 | 0.43328 (11) | 0.3845 (2) | 0.13082 (19) | 0.0426 (7) | |
H6 | 0.4629 | 0.3476 | 0.1664 | 0.051* | |
C7 | 0.42732 (15) | 0.4974 (3) | 0.1259 (2) | 0.0585 (9) | |
H7 | 0.4521 | 0.5482 | 0.1574 | 0.070* | |
C8 | 0.37849 (15) | 0.5204 (2) | 0.0667 (2) | 0.0573 (9) | |
H8 | 0.3644 | 0.5896 | 0.0512 | 0.069* | |
C9 | 0.35378 (12) | 0.4225 (2) | 0.03404 (18) | 0.0430 (7) | |
H9 | 0.3202 | 0.4155 | −0.0074 | 0.052* | |
C10 | 0.38750 (9) | 0.3356 (2) | 0.07341 (16) | 0.0313 (5) | |
C11 | 0.38072 (9) | 0.14745 (19) | 0.14325 (15) | 0.0296 (5) | |
C12 | 0.37407 (9) | 0.21585 (19) | 0.05301 (15) | 0.0272 (5) | |
C13 | 0.25200 (13) | 0.5674 (3) | 0.1584 (3) | 0.0754 (11) | |
H13A | 0.2369 | 0.5340 | 0.1980 | 0.113* | |
H13B | 0.2434 | 0.5255 | 0.1043 | 0.113* | |
H13C | 0.2386 | 0.6399 | 0.1442 | 0.113* | |
C14 | 0.32294 (16) | 0.6384 (3) | 0.2767 (2) | 0.0800 (12) | |
H14A | 0.3118 | 0.6074 | 0.3231 | 0.096* | |
H14B | 0.3072 | 0.7098 | 0.2617 | 0.096* | |
C15 | 0.37921 (17) | 0.6483 (3) | 0.3093 (3) | 0.0881 (14) | |
H15A | 0.3899 | 0.6878 | 0.2659 | 0.106* | |
H15B | 0.3908 | 0.6888 | 0.3651 | 0.106* | |
C16 | 0.44406 (13) | 0.5315 (3) | 0.4031 (2) | 0.0662 (10) | |
H16A | 0.4714 | 0.5807 | 0.4038 | 0.099* | |
H16B | 0.4567 | 0.4580 | 0.4080 | 0.099* | |
H16C | 0.4329 | 0.5473 | 0.4526 | 0.099* | |
C17 | 0.30937 (11) | 0.0062 (2) | 0.12679 (19) | 0.0466 (7) | |
H17 | 0.2911 | 0.0581 | 0.1464 | 0.056* | |
C18 | 0.28880 (13) | −0.0970 (3) | 0.1054 (2) | 0.0595 (9) | |
H18 | 0.2567 | −0.1131 | 0.1102 | 0.071* | |
C19 | 0.31457 (15) | −0.1750 (3) | 0.0778 (2) | 0.0660 (10) | |
H19 | 0.3008 | −0.2447 | 0.0644 | 0.079* | |
C20 | 0.36100 (15) | −0.1497 (3) | 0.0698 (3) | 0.0708 (10) | |
H20 | 0.3790 | −0.2022 | 0.0501 | 0.085* | |
C21 | 0.38141 (12) | −0.0472 (2) | 0.0907 (2) | 0.0551 (8) | |
H21 | 0.4133 | −0.0318 | 0.0851 | 0.066* | |
C22 | 0.35646 (10) | 0.0337 (2) | 0.11957 (16) | 0.0341 (6) | |
C23 | 0.43838 (9) | 0.1298 (2) | 0.19634 (18) | 0.0410 (6) | |
H23A | 0.4546 | 0.1986 | 0.2173 | 0.061* | |
H23B | 0.4547 | 0.0963 | 0.1585 | 0.061* | |
H23C | 0.4421 | 0.0833 | 0.2467 | 0.061* | |
C24 | 0.38594 (11) | 0.0974 (2) | −0.0698 (2) | 0.0473 (7) | |
H24 | 0.3517 | 0.0747 | −0.0835 | 0.057* | |
C25 | 0.41374 (13) | 0.0588 (3) | −0.1206 (2) | 0.0631 (9) | |
H25 | 0.3981 | 0.0111 | −0.1678 | 0.076* | |
C26 | 0.46386 (13) | 0.0900 (3) | −0.1021 (2) | 0.0626 (9) | |
H26 | 0.4827 | 0.0651 | −0.1368 | 0.075* | |
C27 | 0.48622 (11) | 0.1584 (3) | −0.0317 (2) | 0.0523 (8) | |
H27 | 0.5208 | 0.1790 | −0.0175 | 0.063* | |
C28 | 0.45824 (10) | 0.1973 (2) | 0.01840 (17) | 0.0386 (6) | |
H28 | 0.4743 | 0.2445 | 0.0657 | 0.046* | |
C29 | 0.40698 (9) | 0.16856 (19) | 0.00069 (16) | 0.0311 (5) | |
C30 | 0.31725 (9) | 0.2097 (2) | −0.00820 (16) | 0.0345 (6) | |
H30A | 0.2963 | 0.2517 | 0.0172 | 0.052* | |
H30B | 0.3059 | 0.1353 | −0.0142 | 0.052* | |
H30C | 0.3137 | 0.2384 | −0.0661 | 0.052* | |
Ca1 | 0.36396 (2) | 0.42404 (4) | 0.20534 (4) | 0.03889 (16) | |
O1 | 0.30689 (8) | 0.57156 (16) | 0.20084 (13) | 0.0509 (5) | |
O2 | 0.40246 (9) | 0.54348 (18) | 0.32334 (14) | 0.0689 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0578 (18) | 0.0461 (17) | 0.0294 (14) | −0.0095 (14) | 0.0093 (13) | 0.0055 (12) |
C2 | 0.088 (2) | 0.0542 (19) | 0.0355 (16) | −0.0110 (18) | 0.0339 (17) | −0.0049 (14) |
C3 | 0.064 (2) | 0.0519 (18) | 0.0577 (19) | −0.0058 (16) | 0.0441 (17) | −0.0044 (15) |
C4 | 0.0394 (15) | 0.0455 (16) | 0.0398 (15) | −0.0049 (13) | 0.0197 (12) | −0.0029 (12) |
C5 | 0.0354 (14) | 0.0347 (14) | 0.0296 (13) | −0.0051 (11) | 0.0105 (11) | 0.0027 (11) |
C6 | 0.0429 (16) | 0.0427 (16) | 0.0489 (17) | −0.0114 (13) | 0.0246 (13) | −0.0107 (13) |
C7 | 0.082 (2) | 0.0428 (17) | 0.068 (2) | −0.0265 (17) | 0.049 (2) | −0.0194 (16) |
C8 | 0.103 (3) | 0.0299 (16) | 0.061 (2) | 0.0027 (17) | 0.056 (2) | 0.0014 (14) |
C9 | 0.0620 (18) | 0.0368 (15) | 0.0372 (15) | 0.0086 (14) | 0.0263 (14) | 0.0032 (12) |
C10 | 0.0377 (14) | 0.0316 (13) | 0.0300 (13) | −0.0005 (11) | 0.0186 (11) | 0.0001 (11) |
C11 | 0.0257 (12) | 0.0316 (13) | 0.0288 (12) | 0.0008 (10) | 0.0060 (10) | 0.0041 (10) |
C12 | 0.0259 (12) | 0.0296 (13) | 0.0254 (12) | −0.0008 (10) | 0.0081 (10) | 0.0003 (10) |
C13 | 0.058 (2) | 0.076 (3) | 0.086 (3) | 0.0066 (19) | 0.018 (2) | −0.008 (2) |
C14 | 0.099 (3) | 0.078 (3) | 0.050 (2) | 0.034 (2) | 0.009 (2) | −0.0222 (19) |
C15 | 0.106 (3) | 0.051 (2) | 0.072 (3) | 0.011 (2) | −0.013 (2) | −0.0288 (19) |
C16 | 0.052 (2) | 0.079 (3) | 0.059 (2) | 0.0045 (18) | 0.0091 (17) | −0.0122 (19) |
C17 | 0.0524 (18) | 0.0419 (16) | 0.0509 (17) | −0.0106 (14) | 0.0250 (14) | −0.0041 (13) |
C18 | 0.065 (2) | 0.054 (2) | 0.068 (2) | −0.0228 (17) | 0.0345 (18) | −0.0031 (17) |
C19 | 0.089 (3) | 0.0372 (18) | 0.076 (2) | −0.0178 (18) | 0.034 (2) | −0.0021 (17) |
C20 | 0.082 (3) | 0.0341 (17) | 0.108 (3) | −0.0004 (17) | 0.049 (2) | −0.0055 (18) |
C21 | 0.0536 (19) | 0.0357 (16) | 0.084 (2) | 0.0021 (14) | 0.0341 (18) | 0.0023 (16) |
C22 | 0.0356 (14) | 0.0339 (14) | 0.0310 (13) | −0.0007 (11) | 0.0094 (11) | 0.0070 (11) |
C23 | 0.0315 (14) | 0.0472 (16) | 0.0386 (15) | 0.0022 (12) | 0.0052 (12) | 0.0119 (13) |
C24 | 0.0459 (16) | 0.0424 (16) | 0.0564 (18) | −0.0027 (13) | 0.0213 (14) | −0.0162 (14) |
C25 | 0.066 (2) | 0.060 (2) | 0.067 (2) | 0.0040 (17) | 0.0278 (18) | −0.0266 (18) |
C26 | 0.066 (2) | 0.066 (2) | 0.069 (2) | 0.0134 (18) | 0.0395 (18) | −0.0143 (18) |
C27 | 0.0391 (16) | 0.060 (2) | 0.065 (2) | 0.0082 (14) | 0.0263 (15) | −0.0004 (17) |
C28 | 0.0349 (14) | 0.0414 (15) | 0.0402 (14) | 0.0057 (12) | 0.0140 (12) | 0.0003 (12) |
C29 | 0.0338 (13) | 0.0284 (13) | 0.0311 (13) | 0.0056 (11) | 0.0114 (11) | 0.0043 (10) |
C30 | 0.0277 (13) | 0.0438 (15) | 0.0300 (13) | 0.0023 (11) | 0.0078 (10) | 0.0037 (11) |
Ca1 | 0.0529 (3) | 0.0342 (3) | 0.0356 (3) | −0.0035 (3) | 0.0231 (3) | −0.0064 (2) |
O1 | 0.0579 (13) | 0.0513 (12) | 0.0438 (11) | 0.0047 (10) | 0.0181 (10) | −0.0120 (10) |
O2 | 0.0838 (17) | 0.0530 (14) | 0.0474 (13) | 0.0130 (12) | −0.0056 (12) | −0.0184 (11) |
C1—C2 | 1.406 (4) | C14—C15 | 1.467 (5) |
C1—C5 | 1.420 (4) | C14—H14A | 0.9800 |
C1—Ca1 | 2.678 (3) | C14—H14B | 0.9800 |
C1—H1 | 0.9400 | C15—O2 | 1.434 (4) |
C2—C3 | 1.392 (4) | C15—H15A | 0.9800 |
C2—Ca1 | 2.676 (3) | C15—H15B | 0.9800 |
C2—H2 | 0.9400 | C16—O2 | 1.401 (4) |
C3—C4 | 1.409 (4) | C16—H16A | 0.9700 |
C3—Ca1 | 2.660 (3) | C16—H16B | 0.9700 |
C3—H3 | 0.9400 | C16—H16C | 0.9700 |
C4—C5 | 1.414 (4) | C17—C22 | 1.393 (4) |
C4—Ca1 | 2.639 (3) | C17—C18 | 1.395 (4) |
C4—H4 | 0.9400 | C17—H17 | 0.9400 |
C5—C11 | 1.541 (3) | C18—C19 | 1.367 (5) |
C5—Ca1 | 2.672 (3) | C18—H18 | 0.9400 |
C6—C7 | 1.409 (4) | C19—C20 | 1.374 (5) |
C6—C10 | 1.419 (4) | C19—H19 | 0.9400 |
C6—Ca1 | 2.642 (3) | C20—C21 | 1.386 (4) |
C6—H6 | 0.9400 | C20—H20 | 0.9400 |
C7—C8 | 1.386 (5) | C21—C22 | 1.388 (4) |
C7—Ca1 | 2.667 (3) | C21—H21 | 0.9400 |
C7—H7 | 0.9400 | C23—H23A | 0.9700 |
C8—C9 | 1.404 (4) | C23—H23B | 0.9700 |
C8—Ca1 | 2.682 (3) | C23—H23C | 0.9700 |
C8—H8 | 0.9400 | C24—C25 | 1.391 (4) |
C9—C10 | 1.423 (4) | C24—C29 | 1.394 (4) |
C9—Ca1 | 2.670 (3) | C24—H24 | 0.9400 |
C9—H9 | 0.9400 | C25—C26 | 1.371 (5) |
C10—C12 | 1.540 (3) | C25—H25 | 0.9400 |
C10—Ca1 | 2.665 (2) | C26—C27 | 1.377 (4) |
C11—C23 | 1.542 (3) | C26—H26 | 0.9400 |
C11—C22 | 1.553 (3) | C27—C28 | 1.386 (4) |
C11—C12 | 1.636 (3) | C27—H27 | 0.9400 |
C12—C30 | 1.540 (3) | C28—C29 | 1.395 (3) |
C12—C29 | 1.556 (3) | C28—H28 | 0.9400 |
C13—O1 | 1.435 (4) | C30—H30A | 0.9700 |
C13—H13A | 0.9700 | C30—H30B | 0.9700 |
C13—H13B | 0.9700 | C30—H30C | 0.9700 |
C13—H13C | 0.9700 | Ca1—O2 | 2.350 (2) |
C14—O1 | 1.413 (4) | Ca1—O1 | 2.404 (2) |
C2—C1—C5 | 109.1 (3) | C18—C19—H19 | 120.6 |
C2—C1—Ca1 | 74.68 (17) | C20—C19—H19 | 120.6 |
C5—C1—Ca1 | 74.37 (15) | C19—C20—C21 | 120.3 (3) |
C2—C1—H1 | 125.4 | C19—C20—H20 | 119.9 |
C5—C1—H1 | 125.4 | C21—C20—H20 | 119.9 |
Ca1—C1—H1 | 117.4 | C20—C21—C22 | 122.4 (3) |
C3—C2—C1 | 108.2 (3) | C20—C21—H21 | 118.8 |
C3—C2—Ca1 | 74.23 (17) | C22—C21—H21 | 118.8 |
C1—C2—Ca1 | 74.88 (16) | C21—C22—C17 | 116.2 (3) |
C3—C2—H2 | 125.9 | C21—C22—C11 | 121.1 (2) |
C1—C2—H2 | 125.9 | C17—C22—C11 | 122.7 (2) |
Ca1—C2—H2 | 117.0 | C11—C23—H23A | 109.5 |
C2—C3—C4 | 107.6 (3) | C11—C23—H23B | 109.5 |
C2—C3—Ca1 | 75.53 (17) | H23A—C23—H23B | 109.5 |
C4—C3—Ca1 | 73.80 (15) | C11—C23—H23C | 109.5 |
C2—C3—H3 | 126.2 | H23A—C23—H23C | 109.5 |
C4—C3—H3 | 126.2 | H23B—C23—H23C | 109.5 |
Ca1—C3—H3 | 116.6 | C25—C24—C29 | 122.4 (3) |
C3—C4—C5 | 109.6 (3) | C25—C24—H24 | 118.8 |
C3—C4—Ca1 | 75.37 (16) | C29—C24—H24 | 118.8 |
C5—C4—Ca1 | 75.85 (15) | C26—C25—C24 | 120.1 (3) |
C3—C4—H4 | 125.2 | C26—C25—H25 | 119.9 |
C5—C4—H4 | 125.2 | C24—C25—H25 | 119.9 |
Ca1—C4—H4 | 115.5 | C25—C26—C27 | 119.0 (3) |
C4—C5—C1 | 105.5 (2) | C25—C26—H26 | 120.5 |
C4—C5—C11 | 129.4 (2) | C27—C26—H26 | 120.5 |
C1—C5—C11 | 125.1 (2) | C26—C27—C28 | 120.7 (3) |
C4—C5—Ca1 | 73.29 (15) | C26—C27—H27 | 119.7 |
C1—C5—Ca1 | 74.86 (16) | C28—C27—H27 | 119.7 |
C11—C5—Ca1 | 117.55 (15) | C27—C28—C29 | 122.0 (3) |
C7—C6—C10 | 109.2 (3) | C27—C28—H28 | 119.0 |
C7—C6—Ca1 | 75.59 (17) | C29—C28—H28 | 119.0 |
C10—C6—Ca1 | 75.39 (14) | C24—C29—C28 | 115.8 (2) |
C7—C6—H6 | 125.4 | C24—C29—C12 | 121.4 (2) |
C10—C6—H6 | 125.4 | C28—C29—C12 | 122.8 (2) |
Ca1—C6—H6 | 115.6 | C12—C30—H30A | 109.5 |
C8—C7—C6 | 108.1 (3) | C12—C30—H30B | 109.5 |
C8—C7—Ca1 | 75.58 (18) | H30A—C30—H30B | 109.5 |
C6—C7—Ca1 | 73.63 (16) | C12—C30—H30C | 109.5 |
C8—C7—H7 | 125.9 | H30A—C30—H30C | 109.5 |
C6—C7—H7 | 125.9 | H30B—C30—H30C | 109.5 |
Ca1—C7—H7 | 116.9 | O2—Ca1—O1 | 69.66 (8) |
C7—C8—C9 | 108.1 (3) | O2—Ca1—C4 | 134.92 (9) |
C7—C8—Ca1 | 74.39 (18) | O1—Ca1—C4 | 105.41 (8) |
C9—C8—Ca1 | 74.33 (16) | O2—Ca1—C6 | 106.64 (9) |
C7—C8—H8 | 126.0 | O1—Ca1—C6 | 134.67 (8) |
C9—C8—H8 | 126.0 | C4—Ca1—C6 | 106.63 (8) |
Ca1—C8—H8 | 117.3 | O2—Ca1—C3 | 105.19 (10) |
C8—C9—C10 | 109.3 (3) | O1—Ca1—C3 | 88.11 (9) |
C8—C9—Ca1 | 75.26 (16) | C6—Ca1—C3 | 133.53 (9) |
C10—C9—Ca1 | 74.34 (14) | O2—Ca1—C10 | 137.25 (9) |
C8—C9—H9 | 125.3 | O1—Ca1—C10 | 129.15 (8) |
C10—C9—H9 | 125.3 | C4—Ca1—C10 | 81.97 (8) |
Ca1—C9—H9 | 117.0 | C3—Ca1—C10 | 112.59 (8) |
C6—C10—C9 | 105.3 (2) | O2—Ca1—C7 | 88.98 (10) |
C6—C10—C12 | 130.3 (2) | O1—Ca1—C7 | 105.21 (9) |
C9—C10—C12 | 124.4 (2) | C4—Ca1—C7 | 133.19 (9) |
C6—C10—Ca1 | 73.61 (14) | C3—Ca1—C7 | 163.40 (9) |
C9—C10—Ca1 | 74.73 (14) | C10—Ca1—C7 | 51.22 (8) |
C12—C10—Ca1 | 117.33 (15) | O2—Ca1—C9 | 133.81 (9) |
C5—C11—C23 | 107.6 (2) | O1—Ca1—C9 | 98.24 (8) |
C5—C11—C22 | 111.5 (2) | C4—Ca1—C9 | 91.08 (9) |
C23—C11—C22 | 106.4 (2) | C6—Ca1—C9 | 50.33 (9) |
C5—C11—C12 | 110.95 (19) | C3—Ca1—C9 | 119.18 (10) |
C23—C11—C12 | 109.80 (19) | C7—Ca1—C9 | 50.05 (10) |
C22—C11—C12 | 110.45 (18) | O2—Ca1—C5 | 130.41 (8) |
C10—C12—C30 | 107.5 (2) | O1—Ca1—C5 | 135.98 (8) |
C10—C12—C29 | 109.60 (19) | C6—Ca1—C5 | 82.30 (8) |
C30—C12—C29 | 107.33 (19) | C3—Ca1—C5 | 51.25 (8) |
C10—C12—C11 | 111.60 (18) | C10—Ca1—C5 | 67.29 (7) |
C30—C12—C11 | 108.34 (18) | C7—Ca1—C5 | 112.81 (9) |
C29—C12—C11 | 112.25 (18) | C9—Ca1—C5 | 89.93 (8) |
O1—C13—H13A | 109.5 | O2—Ca1—C2 | 86.24 (9) |
O1—C13—H13B | 109.5 | O1—Ca1—C2 | 103.51 (9) |
H13A—C13—H13B | 109.5 | C4—Ca1—C2 | 50.30 (9) |
O1—C13—H13C | 109.5 | C6—Ca1—C2 | 121.59 (10) |
H13A—C13—H13C | 109.5 | C10—Ca1—C2 | 117.64 (9) |
H13B—C13—H13C | 109.5 | C7—Ca1—C2 | 147.12 (12) |
O1—C14—C15 | 109.4 (3) | C9—Ca1—C2 | 139.39 (9) |
O1—C14—H14A | 109.8 | C5—Ca1—C2 | 51.00 (8) |
C15—C14—H14A | 109.8 | O2—Ca1—C1 | 99.63 (8) |
O1—C14—H14B | 109.8 | O1—Ca1—C1 | 133.85 (9) |
C15—C14—H14B | 109.8 | C4—Ca1—C1 | 50.19 (9) |
H14A—C14—H14B | 108.2 | C6—Ca1—C1 | 91.45 (9) |
O2—C15—C14 | 110.1 (3) | C3—Ca1—C1 | 50.24 (10) |
O2—C15—H15A | 109.6 | C10—Ca1—C1 | 89.89 (8) |
C14—C15—H15A | 109.6 | C7—Ca1—C1 | 119.73 (11) |
O2—C15—H15B | 109.6 | C9—Ca1—C1 | 117.80 (8) |
C14—C15—H15B | 109.6 | O2—Ca1—C8 | 103.43 (10) |
H15A—C15—H15B | 108.1 | O1—Ca1—C8 | 85.63 (9) |
O2—C16—H16A | 109.5 | C4—Ca1—C8 | 121.18 (10) |
O2—C16—H16B | 109.5 | C6—Ca1—C8 | 50.29 (10) |
H16A—C16—H16B | 109.5 | C3—Ca1—C8 | 146.40 (11) |
O2—C16—H16C | 109.5 | C10—Ca1—C8 | 51.09 (8) |
H16A—C16—H16C | 109.5 | C5—Ca1—C8 | 117.68 (8) |
H16B—C16—H16C | 109.5 | C2—Ca1—C8 | 168.66 (9) |
C22—C17—C18 | 121.3 (3) | C1—Ca1—C8 | 139.58 (9) |
C22—C17—H17 | 119.4 | C14—O1—C13 | 113.2 (3) |
C18—C17—H17 | 119.4 | C14—O1—Ca1 | 114.58 (19) |
C19—C18—C17 | 121.0 (3) | C13—O1—Ca1 | 124.36 (19) |
C19—C18—H18 | 119.5 | C16—O2—C15 | 115.0 (3) |
C17—C18—H18 | 119.5 | C16—O2—Ca1 | 131.9 (2) |
C18—C19—C20 | 118.8 (3) | C15—O2—Ca1 | 113.09 (18) |
C5—C1—C2—C3 | 0.3 (3) | C6—C10—Ca1—C8 | 75.47 (19) |
Ca1—C1—C2—C3 | 67.3 (2) | C9—C10—Ca1—C8 | −35.98 (17) |
C5—C1—C2—Ca1 | −67.00 (19) | C12—C10—Ca1—C8 | −157.2 (2) |
C1—C2—C3—C4 | −0.4 (3) | C8—C7—Ca1—O2 | −119.68 (18) |
Ca1—C2—C3—C4 | 67.4 (2) | C6—C7—Ca1—O2 | 126.1 (2) |
C1—C2—C3—Ca1 | −67.8 (2) | C8—C7—Ca1—O1 | −51.09 (18) |
C2—C3—C4—C5 | 0.2 (3) | C6—C7—Ca1—O1 | −165.29 (18) |
Ca1—C3—C4—C5 | 68.84 (19) | C8—C7—Ca1—C4 | 78.2 (2) |
C2—C3—C4—Ca1 | −68.6 (2) | C6—C7—Ca1—C4 | −36.0 (3) |
C3—C4—C5—C1 | 0.0 (3) | C8—C7—Ca1—C6 | 114.2 (3) |
Ca1—C4—C5—C1 | 68.50 (18) | C8—C7—Ca1—C3 | 91.3 (4) |
C3—C4—C5—C11 | 179.2 (2) | C6—C7—Ca1—C3 | −22.9 (5) |
Ca1—C4—C5—C11 | −112.2 (3) | C8—C7—Ca1—C10 | 77.30 (19) |
C3—C4—C5—Ca1 | −68.5 (2) | C6—C7—Ca1—C10 | −36.90 (17) |
C2—C1—C5—C4 | −0.2 (3) | C8—C7—Ca1—C9 | 36.96 (17) |
Ca1—C1—C5—C4 | −67.40 (18) | C6—C7—Ca1—C9 | −77.23 (19) |
C2—C1—C5—C11 | −179.5 (2) | C8—C7—Ca1—C5 | 106.23 (18) |
Ca1—C1—C5—C11 | 113.3 (2) | C6—C7—Ca1—C5 | −8.0 (2) |
C2—C1—C5—Ca1 | 67.2 (2) | C8—C7—Ca1—C2 | 158.86 (19) |
C10—C6—C7—C8 | 0.2 (3) | C6—C7—Ca1—C2 | 44.7 (3) |
Ca1—C6—C7—C8 | −68.3 (2) | C8—C7—Ca1—C1 | 139.80 (17) |
C10—C6—C7—Ca1 | 68.58 (18) | C6—C7—Ca1—C1 | 25.6 (2) |
C6—C7—C8—C9 | −0.2 (3) | C6—C7—Ca1—C8 | −114.2 (3) |
Ca1—C7—C8—C9 | −67.3 (2) | C8—C9—Ca1—O2 | −3.1 (2) |
C6—C7—C8—Ca1 | 67.0 (2) | C10—C9—Ca1—O2 | 112.26 (17) |
C7—C8—C9—C10 | 0.2 (3) | C8—C9—Ca1—O1 | 66.5 (2) |
Ca1—C8—C9—C10 | −67.17 (18) | C10—C9—Ca1—O1 | −178.09 (15) |
C7—C8—C9—Ca1 | 67.3 (2) | C8—C9—Ca1—C4 | 172.2 (2) |
C7—C6—C10—C9 | −0.1 (3) | C10—C9—Ca1—C4 | −72.35 (16) |
Ca1—C6—C10—C9 | 68.58 (17) | C8—C9—Ca1—C6 | −76.9 (2) |
C7—C6—C10—C12 | 179.1 (2) | C10—C9—Ca1—C6 | 38.52 (15) |
Ca1—C6—C10—C12 | −112.2 (2) | C8—C9—Ca1—C3 | 158.94 (19) |
C7—C6—C10—Ca1 | −68.7 (2) | C10—C9—Ca1—C3 | −85.64 (18) |
C8—C9—C10—C6 | 0.0 (3) | C8—C9—Ca1—C10 | −115.4 (3) |
Ca1—C9—C10—C6 | −67.78 (17) | C8—C9—Ca1—C7 | −36.47 (19) |
C8—C9—C10—C12 | −179.3 (2) | C10—C9—Ca1—C7 | 78.94 (18) |
Ca1—C9—C10—C12 | 112.9 (2) | C8—C9—Ca1—C5 | −156.9 (2) |
C8—C9—C10—Ca1 | 67.77 (19) | C10—C9—Ca1—C5 | −41.51 (16) |
C4—C5—C11—C23 | 176.7 (3) | C8—C9—Ca1—C2 | −171.4 (2) |
C1—C5—C11—C23 | −4.2 (3) | C10—C9—Ca1—C2 | −56.0 (2) |
Ca1—C5—C11—C23 | 86.2 (2) | C8—C9—Ca1—C1 | −143.31 (19) |
C4—C5—C11—C22 | −67.0 (3) | C10—C9—Ca1—C1 | −27.90 (19) |
C1—C5—C11—C22 | 112.2 (3) | C10—C9—Ca1—C8 | 115.4 (3) |
Ca1—C5—C11—C22 | −157.49 (15) | C4—C5—Ca1—O2 | 112.54 (17) |
C4—C5—C11—C12 | 56.6 (3) | C1—C5—Ca1—O2 | 0.8 (2) |
C1—C5—C11—C12 | −124.3 (3) | C11—C5—Ca1—O2 | −121.23 (17) |
Ca1—C5—C11—C12 | −33.9 (2) | C4—C5—Ca1—O1 | 9.6 (2) |
C6—C10—C12—C30 | 175.2 (2) | C1—C5—Ca1—O1 | −102.17 (18) |
C9—C10—C12—C30 | −5.7 (3) | C11—C5—Ca1—O1 | 135.83 (16) |
Ca1—C10—C12—C30 | 83.9 (2) | C1—C5—Ca1—C4 | −111.8 (2) |
C6—C10—C12—C29 | −68.5 (3) | C11—C5—Ca1—C4 | 126.2 (2) |
C9—C10—C12—C29 | 110.6 (3) | C4—C5—Ca1—C6 | −142.14 (16) |
Ca1—C10—C12—C29 | −159.70 (15) | C1—C5—Ca1—C6 | 106.09 (17) |
C6—C10—C12—C11 | 56.5 (3) | C11—C5—Ca1—C6 | −15.91 (17) |
C9—C10—C12—C11 | −124.4 (2) | C4—C5—Ca1—C3 | 36.55 (16) |
Ca1—C10—C12—C11 | −34.7 (2) | C1—C5—Ca1—C3 | −75.22 (18) |
C5—C11—C12—C10 | 44.2 (3) | C11—C5—Ca1—C3 | 162.8 (2) |
C23—C11—C12—C10 | −74.6 (2) | C4—C5—Ca1—C10 | −113.90 (16) |
C22—C11—C12—C10 | 168.33 (19) | C1—C5—Ca1—C10 | 134.33 (18) |
C5—C11—C12—C30 | −74.0 (2) | C11—C5—Ca1—C10 | 12.33 (16) |
C23—C11—C12—C30 | 167.2 (2) | C4—C5—Ca1—C7 | −138.03 (16) |
C22—C11—C12—C30 | 50.2 (2) | C1—C5—Ca1—C7 | 110.20 (18) |
C5—C11—C12—C29 | 167.67 (19) | C11—C5—Ca1—C7 | −11.8 (2) |
C23—C11—C12—C29 | 48.9 (3) | C4—C5—Ca1—C9 | −92.23 (16) |
C22—C11—C12—C29 | −68.2 (2) | C1—C5—Ca1—C9 | 156.00 (17) |
O1—C14—C15—O2 | −53.9 (5) | C11—C5—Ca1—C9 | 34.00 (18) |
C22—C17—C18—C19 | 0.8 (5) | C4—C5—Ca1—C2 | 75.69 (17) |
C17—C18—C19—C20 | −1.0 (6) | C1—C5—Ca1—C2 | −36.08 (17) |
C18—C19—C20—C21 | 0.8 (6) | C11—C5—Ca1—C2 | −158.1 (2) |
C19—C20—C21—C22 | −0.4 (6) | C4—C5—Ca1—C1 | 111.8 (2) |
C20—C21—C22—C17 | 0.2 (5) | C11—C5—Ca1—C1 | −122.0 (3) |
C20—C21—C22—C11 | 179.4 (3) | C4—C5—Ca1—C8 | −105.17 (17) |
C18—C17—C22—C21 | −0.4 (4) | C1—C5—Ca1—C8 | 143.05 (18) |
C18—C17—C22—C11 | −179.6 (3) | C11—C5—Ca1—C8 | 21.1 (2) |
C5—C11—C22—C21 | −159.6 (2) | C3—C2—Ca1—O2 | 129.36 (19) |
C23—C11—C22—C21 | −42.6 (3) | C1—C2—Ca1—O2 | −116.28 (19) |
C12—C11—C22—C21 | 76.5 (3) | C3—C2—Ca1—O1 | 61.33 (19) |
C5—C11—C22—C17 | 19.6 (3) | C1—C2—Ca1—O1 | 175.69 (17) |
C23—C11—C22—C17 | 136.6 (3) | C3—C2—Ca1—C4 | −37.63 (17) |
C12—C11—C22—C17 | −104.3 (3) | C1—C2—Ca1—C4 | 76.73 (18) |
C29—C24—C25—C26 | 0.3 (5) | C3—C2—Ca1—C6 | −123.39 (18) |
C24—C25—C26—C27 | 1.1 (5) | C1—C2—Ca1—C6 | −9.0 (2) |
C25—C26—C27—C28 | −1.5 (5) | C1—C2—Ca1—C3 | 114.4 (3) |
C26—C27—C28—C29 | 0.6 (5) | C3—C2—Ca1—C10 | −87.86 (19) |
C25—C24—C29—C28 | −1.2 (4) | C1—C2—Ca1—C10 | 26.5 (2) |
C25—C24—C29—C12 | 176.4 (3) | C3—C2—Ca1—C7 | −148.37 (19) |
C27—C28—C29—C24 | 0.7 (4) | C1—C2—Ca1—C7 | −34.0 (3) |
C27—C28—C29—C12 | −176.8 (2) | C3—C2—Ca1—C9 | −59.1 (2) |
C10—C12—C29—C24 | −139.5 (2) | C1—C2—Ca1—C9 | 55.2 (3) |
C30—C12—C29—C24 | −23.0 (3) | C3—C2—Ca1—C5 | −77.87 (19) |
C11—C12—C29—C24 | 95.9 (3) | C1—C2—Ca1—C5 | 36.49 (16) |
C10—C12—C29—C28 | 37.8 (3) | C3—C2—Ca1—C1 | −114.4 (3) |
C30—C12—C29—C28 | 154.3 (2) | C3—C2—Ca1—C8 | −81.8 (6) |
C11—C12—C29—C28 | −86.8 (3) | C1—C2—Ca1—C8 | 32.6 (7) |
C3—C4—Ca1—O2 | 18.4 (2) | C2—C1—Ca1—O2 | 65.16 (19) |
C5—C4—Ca1—O2 | −96.65 (17) | C5—C1—Ca1—O2 | −179.41 (16) |
C3—C4—Ca1—O1 | −58.08 (19) | C2—C1—Ca1—O1 | −5.8 (2) |
C5—C4—Ca1—O1 | −173.10 (14) | C5—C1—Ca1—O1 | 109.61 (17) |
C3—C4—Ca1—C6 | 154.42 (18) | C2—C1—Ca1—C4 | −77.1 (2) |
C5—C4—Ca1—C6 | 39.40 (17) | C5—C1—Ca1—C4 | 38.32 (15) |
C5—C4—Ca1—C3 | −115.0 (2) | C2—C1—Ca1—C6 | 172.31 (19) |
C3—C4—Ca1—C10 | 173.42 (19) | C5—C1—Ca1—C6 | −72.26 (17) |
C5—C4—Ca1—C10 | 58.40 (15) | C2—C1—Ca1—C3 | −36.64 (18) |
C3—C4—Ca1—C7 | 172.73 (19) | C5—C1—Ca1—C3 | 78.79 (18) |
C5—C4—Ca1—C7 | 57.7 (2) | C2—C1—Ca1—C10 | −156.72 (19) |
C3—C4—Ca1—C9 | −156.93 (19) | C5—C1—Ca1—C10 | −41.29 (16) |
C5—C4—Ca1—C9 | 88.05 (15) | C2—C1—Ca1—C7 | 159.53 (18) |
C3—C4—Ca1—C5 | 115.0 (2) | C5—C1—Ca1—C7 | −85.04 (18) |
C3—C4—Ca1—C2 | 36.86 (18) | C2—C1—Ca1—C9 | −142.80 (18) |
C5—C4—Ca1—C2 | −78.15 (17) | C5—C1—Ca1—C9 | −27.4 (2) |
C3—C4—Ca1—C1 | 76.8 (2) | C2—C1—Ca1—C5 | −115.4 (3) |
C5—C4—Ca1—C1 | −38.21 (15) | C5—C1—Ca1—C2 | 115.4 (3) |
C3—C4—Ca1—C8 | −152.35 (19) | C2—C1—Ca1—C8 | −170.6 (2) |
C5—C4—Ca1—C8 | 92.64 (17) | C5—C1—Ca1—C8 | −55.2 (2) |
C7—C6—Ca1—O2 | −57.4 (2) | C7—C8—Ca1—O2 | 63.27 (19) |
C10—C6—Ca1—O2 | −172.12 (15) | C9—C8—Ca1—O2 | 177.66 (18) |
C7—C6—Ca1—O1 | 20.2 (2) | C7—C8—Ca1—O1 | 131.14 (18) |
C10—C6—Ca1—O1 | −94.53 (17) | C9—C8—Ca1—O1 | −114.47 (19) |
C7—C6—Ca1—C4 | 153.4 (2) | C7—C8—Ca1—C4 | −123.47 (18) |
C10—C6—Ca1—C4 | 38.73 (17) | C9—C8—Ca1—C4 | −9.1 (2) |
C7—C6—Ca1—C3 | 171.2 (2) | C7—C8—Ca1—C6 | −37.35 (17) |
C10—C6—Ca1—C3 | 56.5 (2) | C9—C8—Ca1—C6 | 77.04 (19) |
C7—C6—Ca1—C10 | 114.7 (3) | C7—C8—Ca1—C3 | −148.9 (2) |
C10—C6—Ca1—C7 | −114.7 (3) | C9—C8—Ca1—C3 | −34.5 (3) |
C7—C6—Ca1—C9 | 76.2 (2) | C7—C8—Ca1—C10 | −77.76 (19) |
C10—C6—Ca1—C9 | −38.43 (15) | C9—C8—Ca1—C10 | 36.64 (16) |
C7—C6—Ca1—C5 | 172.6 (2) | C9—C8—Ca1—C7 | 114.4 (3) |
C10—C6—Ca1—C5 | 57.92 (16) | C7—C8—Ca1—C9 | −114.4 (3) |
C7—C6—Ca1—C2 | −153.4 (2) | C7—C8—Ca1—C5 | −88.12 (19) |
C10—C6—Ca1—C2 | 91.94 (18) | C9—C8—Ca1—C5 | 26.3 (2) |
C7—C6—Ca1—C1 | −157.9 (2) | C7—C8—Ca1—C2 | −84.7 (6) |
C10—C6—Ca1—C1 | 87.37 (16) | C9—C8—Ca1—C2 | 29.7 (7) |
C7—C6—Ca1—C8 | 36.39 (19) | C7—C8—Ca1—C1 | −59.8 (2) |
C10—C6—Ca1—C8 | −78.28 (18) | C9—C8—Ca1—C1 | 54.6 (3) |
C2—C3—Ca1—O2 | −53.07 (19) | C15—C14—O1—C13 | −173.2 (3) |
C4—C3—Ca1—O2 | −166.63 (17) | C15—C14—O1—Ca1 | 36.2 (4) |
C2—C3—Ca1—O1 | −121.40 (18) | O2—Ca1—O1—C14 | −9.7 (2) |
C4—C3—Ca1—O1 | 125.04 (18) | C4—Ca1—O1—C14 | 123.0 (3) |
C2—C3—Ca1—C4 | 113.6 (3) | C6—Ca1—O1—C14 | −103.3 (3) |
C2—C3—Ca1—C6 | 78.8 (2) | C3—Ca1—O1—C14 | 97.3 (3) |
C4—C3—Ca1—C6 | −34.8 (2) | C10—Ca1—O1—C14 | −144.8 (2) |
C2—C3—Ca1—C10 | 106.50 (18) | C7—Ca1—O1—C14 | −92.8 (3) |
C4—C3—Ca1—C10 | −7.1 (2) | C9—Ca1—O1—C14 | −143.5 (3) |
C2—C3—Ca1—C7 | 94.7 (4) | C5—Ca1—O1—C14 | 118.0 (3) |
C4—C3—Ca1—C7 | −18.8 (5) | C2—Ca1—O1—C14 | 71.0 (3) |
C2—C3—Ca1—C9 | 140.22 (18) | C1—Ca1—O1—C14 | 74.0 (3) |
C4—C3—Ca1—C9 | 26.7 (2) | C8—Ca1—O1—C14 | −115.8 (3) |
C2—C3—Ca1—C5 | 76.97 (19) | O2—Ca1—O1—C13 | −156.5 (3) |
C4—C3—Ca1—C5 | −36.59 (16) | C4—Ca1—O1—C13 | −23.8 (3) |
C4—C3—Ca1—C2 | −113.6 (3) | C6—Ca1—O1—C13 | 109.9 (3) |
C2—C3—Ca1—C1 | 36.91 (17) | C3—Ca1—O1—C13 | −49.6 (3) |
C4—C3—Ca1—C1 | −76.65 (19) | C10—Ca1—O1—C13 | 68.4 (3) |
C2—C3—Ca1—C8 | 159.41 (19) | C7—Ca1—O1—C13 | 120.4 (3) |
C4—C3—Ca1—C8 | 45.8 (3) | C9—Ca1—O1—C13 | 69.7 (3) |
C6—C10—Ca1—O2 | 11.2 (2) | C5—Ca1—O1—C13 | −28.8 (3) |
C9—C10—Ca1—O2 | −100.30 (19) | C2—Ca1—O1—C13 | −75.8 (3) |
C12—C10—Ca1—O2 | 138.52 (16) | C1—Ca1—O1—C13 | −72.8 (3) |
C6—C10—Ca1—O1 | 113.89 (17) | C8—Ca1—O1—C13 | 97.4 (3) |
C9—C10—Ca1—O1 | 2.4 (2) | C14—C15—O2—C16 | −135.3 (3) |
C12—C10—Ca1—O1 | −118.75 (17) | C14—C15—O2—Ca1 | 45.8 (4) |
C6—C10—Ca1—C4 | −142.74 (17) | O1—Ca1—O2—C16 | 162.0 (3) |
C9—C10—Ca1—C4 | 105.81 (17) | C4—Ca1—O2—C16 | 70.3 (3) |
C12—C10—Ca1—C4 | −15.37 (17) | C6—Ca1—O2—C16 | −65.8 (3) |
C9—C10—Ca1—C6 | −111.5 (2) | C3—Ca1—O2—C16 | 79.9 (3) |
C12—C10—Ca1—C6 | 127.4 (3) | C10—Ca1—O2—C16 | −71.8 (3) |
C6—C10—Ca1—C3 | −139.09 (17) | C7—Ca1—O2—C16 | −91.3 (3) |
C9—C10—Ca1—C3 | 109.46 (17) | C9—Ca1—O2—C16 | −116.3 (3) |
C12—C10—Ca1—C3 | −11.7 (2) | C5—Ca1—O2—C16 | 28.3 (3) |
C6—C10—Ca1—C7 | 36.62 (18) | C2—Ca1—O2—C16 | 56.1 (3) |
C9—C10—Ca1—C7 | −74.84 (19) | C1—Ca1—O2—C16 | 28.7 (3) |
C12—C10—Ca1—C7 | 164.0 (2) | C8—Ca1—O2—C16 | −117.9 (3) |
C6—C10—Ca1—C9 | 111.5 (2) | O1—Ca1—O2—C15 | −19.3 (3) |
C12—C10—Ca1—C9 | −121.2 (3) | C4—Ca1—O2—C15 | −111.1 (3) |
C6—C10—Ca1—C5 | −114.47 (17) | C6—Ca1—O2—C15 | 112.9 (3) |
C9—C10—Ca1—C5 | 134.08 (18) | C3—Ca1—O2—C15 | −101.4 (3) |
C12—C10—Ca1—C5 | 12.90 (16) | C10—Ca1—O2—C15 | 106.9 (3) |
C6—C10—Ca1—C2 | −106.07 (18) | C7—Ca1—O2—C15 | 87.3 (3) |
C9—C10—Ca1—C2 | 142.48 (17) | C9—Ca1—O2—C15 | 62.4 (3) |
C12—C10—Ca1—C2 | 21.3 (2) | C5—Ca1—O2—C15 | −153.1 (3) |
C6—C10—Ca1—C1 | −93.00 (17) | C2—Ca1—O2—C15 | −125.2 (3) |
C9—C10—Ca1—C1 | 155.55 (17) | C1—Ca1—O2—C15 | −152.7 (3) |
C12—C10—Ca1—C1 | 34.37 (18) | C8—Ca1—O2—C15 | 60.8 (3) |
Experimental details
Crystal data | |
Chemical formula | [Ca(C26H24)(C4H10O2)] |
Mr | 466.65 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 213 |
a, b, c (Å) | 27.726 (3), 12.412 (2), 16.087 (3) |
β (°) | 110.46 (2) |
V (Å3) | 5186.7 (14) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.27 |
Crystal size (mm) | 0.25 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Siemens SMART 1K diffractometer |
Absorption correction | Empirical (using intensity measurements) (XPREP; Sheldrick, 1998) |
Tmin, Tmax | 0.937, 0.961 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14054, 4564, 4294 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.062, 0.117, 1.29 |
No. of reflections | 4564 |
No. of parameters | 302 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.24 |
Computer programs: SMART (Bruker, 1997), SMART, SAINT-Plus (Bruker, 1999), XS (Sheldrick, 1998), XL (Sheldrick, 1998), XP (Sheldrick, 1998), XCIF (Sheldrick, 1998).
The reductive coupling of fulvenes with active metals is a convenient method for generating ethanediyl-bridged dicyclopentadienyl-ligand frameworks for ansa-metallocene complexes (Tan et al., 1975; Schwemlein & Brintzinger, 1983; Eisch & Shi, 1998). We have examined the reductive coupling of 6-methyl-6-phenylfulvene with activated calcium and report on the structure of the unusual calcocene: trans-Ph2(CH3)2C2(η5-C5H4)2Ca(DME), (I).
The Ca atom in (I) is in a four-coordinate environment, η5-bonded η5 to both cyclopentadienyl (Cp) ligands and η1-bonded to each O atom of the solvent ligand. Compound (I) has a Cp(centroid)—Ca distance of 2.381 (3) Å and a Cp—Ca—Cp angle of 121.3 (2)°. The Ca—O distances are slightly asymmetric [2.404 (2) and 2.350 (2) Å]. The O—Ca—O angle [69.66 (7)°] is distorted from the ideal tetrahedral angle due to the geometrical constraint of the chelate DME ligand. The dihedral angle between the two cyclopentadienyl rings is 59.6 (1)°.
There are few structurally determined ansa-bridged calcocenes for comparison. The closely related cis and trans ansa-calcocenes Ph2C2H2(η5C5H4)2Ca(THF)2 have an average Cp—Ca distances of 2.40 and 2.42 Å, respectively with a Cp—Ca—Cp angle of 120.4 and 119.9° (Matare et al., 1998; Kane et al., 1997). The only other structurally reported carbon-bridged ansa-calcocene consists of the diiminoethane (DIE) coordinated calcocene (CH3)4C2(η5-C5H4)2Ca(tBu2DIE) which is closely related to (I) with asymmetric ligand N—Ca bonding of 2.503 (6) and 2.563 (6) Å, Cp—Ca distances of 2.396 (3) and 2.391 (3) Å, and a Cp—Ca—Cp angle of 119.0° (Reickhoff et al., 1993).