Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199012135/da1092sup1.cif | |
Structure factor file (SHELXL table format) https://doi.org/10.1107/S0108270199012135/da1092Isup2.sft |
CCDC reference: 143217
A glass tube was charged with [HC(CHNPh)2]AlMe2 (50 mg, 0.18 mmol; Radzewich et al., 1999), (Ph3C)[B(C6F5)4] (0.5 equivalents; 89 mg, 0.090 mmol) and C6H6 (10 ml). An orange oil was produced. Hexanes (20 ml) were added resulting in the formation of an orange solid. The tube was then flame sealed and heated to 323 K overnight to produce orange crystals of (I). The formation of (I) is believed to occur by reaction of a cationic aluminium methyl complex, [HC(CHNPh)2]AlMe+, with an LiCl impurity that is present in the neutral starting material.
Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SHELXTL (Sheldrick, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[AlCl(CH3)(C15H13N2)][Li(C24BF20)]2·C6H6 | Z = 2 |
Mr = 1748.83 | F(000) = 1724 |
Triclinic, P1 | Dx = 1.739 Mg m−3 |
a = 12.2522 (9) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 13.8727 (10) Å | Cell parameters from 4465 reflections |
c = 22.2931 (16) Å | θ = 2–28° |
α = 79.743 (1)° | µ = 0.23 mm−1 |
β = 80.829 (1)° | T = 173 K |
γ = 64.077 (1)° | Needle, pale yellow |
V = 3339.2 (4) Å3 | 0.50 × 0.34 × 0.25 mm |
Bruker CCD 1000 diffractometer | 12479 independent reflections |
Radiation source: fine-focus sealed tube | 7428 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ϕ and ω scans | θmax = 26.4°, θmin = 2.0° |
Absorption correction: empirical (using intensity measurements) (SADABS; Blessing, 1995) | h = −14→15 |
Tmin = 0.894, Tmax = 0.945 | k = −16→17 |
17369 measured reflections | l = −27→27 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 0.93 | w = 1/[σ2(Fo2) + (0.035P)2] where P = (Fo2 + 2Fc2)/3 |
12479 reflections | (Δ/σ)max < 0.001 |
1058 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
[AlCl(CH3)(C15H13N2)][Li(C24BF20)]2·C6H6 | γ = 64.077 (1)° |
Mr = 1748.83 | V = 3339.2 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 12.2522 (9) Å | Mo Kα radiation |
b = 13.8727 (10) Å | µ = 0.23 mm−1 |
c = 22.2931 (16) Å | T = 173 K |
α = 79.743 (1)° | 0.50 × 0.34 × 0.25 mm |
β = 80.829 (1)° |
Bruker CCD 1000 diffractometer | 12479 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Blessing, 1995) | 7428 reflections with I > 2σ(I) |
Tmin = 0.894, Tmax = 0.945 | Rint = 0.024 |
17369 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 0.93 | Δρmax = 0.34 e Å−3 |
12479 reflections | Δρmin = −0.29 e Å−3 |
1058 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 | ||
Al | 0.60242 (7) | 0.48358 (6) | 0.37347 (4) | 0.0280 (2) | |
Cl | 0.72590 (6) | 0.32505 (5) | 0.41791 (3) | 0.03762 (19) | |
F18 | 0.07391 (14) | 0.09000 (11) | 0.42009 (6) | 0.0351 (4) | |
F19 | 0.01388 (14) | 0.30094 (12) | 0.39297 (7) | 0.0385 (4) | |
F20 | −0.00675 (14) | 0.39508 (12) | 0.27423 (7) | 0.0416 (4) | |
F21 | 0.03232 (14) | 0.26980 (12) | 0.18379 (7) | 0.0390 (4) | |
F22 | 0.09310 (13) | 0.06389 (11) | 0.20839 (6) | 0.0326 (4) | |
F24 | 0.23122 (13) | −0.13582 (11) | 0.46754 (6) | 0.0318 (4) | |
F25 | 0.44483 (13) | −0.16507 (12) | 0.49076 (7) | 0.0374 (4) | |
F26 | 0.60912 (14) | −0.13254 (14) | 0.39995 (8) | 0.0492 (5) | |
F27 | 0.54934 (14) | −0.07929 (13) | 0.28096 (7) | 0.0450 (4) | |
F28 | 0.33475 (13) | −0.05670 (12) | 0.25560 (6) | 0.0371 (4) | |
F30 | −0.07156 (13) | −0.01786 (12) | 0.27381 (7) | 0.0369 (4) | |
F31 | −0.08569 (15) | −0.10635 (13) | 0.18053 (7) | 0.0441 (4) | |
F32 | 0.11052 (16) | −0.27591 (13) | 0.13748 (7) | 0.0488 (5) | |
F33 | 0.32534 (15) | −0.35398 (12) | 0.18999 (7) | 0.0473 (5) | |
F34 | 0.34340 (14) | −0.26531 (12) | 0.28140 (7) | 0.0395 (4) | |
F36 | −0.12851 (13) | 0.06669 (11) | 0.39485 (6) | 0.0310 (4) | |
F37 | −0.26211 (13) | −0.01169 (12) | 0.46921 (7) | 0.0350 (4) | |
F38 | −0.17501 (14) | −0.22529 (12) | 0.51398 (7) | 0.0413 (4) | |
F39 | 0.06221 (14) | −0.35909 (11) | 0.48142 (7) | 0.0390 (4) | |
F40 | 0.20138 (13) | −0.28241 (11) | 0.40197 (7) | 0.0345 (4) | |
F42 | 0.49328 (14) | 0.40836 (12) | 0.13922 (7) | 0.0377 (4) | |
F43 | 0.61152 (15) | 0.49865 (13) | 0.05473 (8) | 0.0471 (5) | |
F44 | 0.71946 (17) | 0.40914 (14) | −0.05028 (8) | 0.0546 (5) | |
F45 | 0.71174 (16) | 0.22087 (13) | −0.06671 (7) | 0.0487 (5) | |
F46 | 0.59736 (14) | 0.12964 (12) | 0.01564 (7) | 0.0361 (4) | |
F48 | 0.28843 (14) | 0.38388 (12) | 0.22430 (7) | 0.0423 (4) | |
F49 | 0.07837 (15) | 0.54357 (12) | 0.19933 (7) | 0.0478 (5) | |
F50 | −0.00859 (15) | 0.57620 (13) | 0.08914 (9) | 0.0583 (5) | |
F51 | 0.12445 (15) | 0.43764 (14) | 0.00433 (8) | 0.0562 (5) | |
F52 | 0.33117 (13) | 0.26880 (12) | 0.03052 (7) | 0.0383 (4) | |
F54 | 0.68651 (13) | 0.02540 (12) | 0.13052 (7) | 0.0398 (4) | |
F55 | 0.72013 (15) | −0.17577 (13) | 0.12445 (8) | 0.0522 (5) | |
F56 | 0.52655 (17) | −0.22162 (13) | 0.12054 (9) | 0.0594 (5) | |
F57 | 0.29541 (15) | −0.05566 (13) | 0.12346 (8) | 0.0469 (5) | |
F58 | 0.26051 (13) | 0.14056 (12) | 0.12930 (7) | 0.0354 (4) | |
F60 | 0.32668 (14) | 0.17031 (12) | 0.24918 (7) | 0.0393 (4) | |
F61 | 0.37869 (16) | 0.14458 (13) | 0.36448 (7) | 0.0504 (5) | |
F62 | 0.58664 (16) | 0.15289 (13) | 0.38812 (7) | 0.0495 (5) | |
F63 | 0.73948 (15) | 0.18764 (13) | 0.29326 (7) | 0.0481 (5) | |
F64 | 0.69147 (14) | 0.21207 (13) | 0.17864 (7) | 0.0399 (4) | |
N1 | 0.6960 (2) | 0.52573 (17) | 0.30786 (10) | 0.0310 (6) | |
N2 | 0.50606 (19) | 0.45562 (17) | 0.32695 (10) | 0.0285 (5) | |
B1 | 0.1351 (3) | −0.0687 (2) | 0.33776 (14) | 0.0269 (7) | |
B2 | 0.4604 (3) | 0.2167 (2) | 0.13751 (14) | 0.0261 (7) | |
C1 | 0.5151 (3) | 0.5906 (2) | 0.42860 (13) | 0.0368 (7) | |
H1A | 0.4744 | 0.6613 | 0.4050 | 0.055* | |
H1B | 0.5724 | 0.5936 | 0.4535 | 0.055* | |
H1C | 0.4542 | 0.5714 | 0.4554 | 0.055* | |
C2 | 0.7015 (3) | 0.5040 (2) | 0.25142 (13) | 0.0362 (7) | |
H2 | 0.7592 | 0.5182 | 0.2218 | 0.043* | |
C3 | 0.6311 (3) | 0.4626 (2) | 0.23211 (13) | 0.0372 (7) | |
H3 | 0.6497 | 0.4437 | 0.1916 | 0.045* | |
C4 | 0.5349 (3) | 0.4465 (2) | 0.26731 (12) | 0.0334 (7) | |
H4 | 0.4856 | 0.4274 | 0.2473 | 0.040* | |
C5 | 0.7574 (2) | 0.5883 (2) | 0.31723 (13) | 0.0302 (7) | |
C6 | 0.7605 (3) | 0.6728 (2) | 0.27394 (14) | 0.0392 (8) | |
H6 | 0.7225 | 0.6892 | 0.2372 | 0.047* | |
C7 | 0.8186 (3) | 0.7329 (3) | 0.28435 (15) | 0.0487 (9) | |
H7 | 0.8211 | 0.7902 | 0.2545 | 0.058* | |
C8 | 0.8729 (3) | 0.7108 (3) | 0.33732 (16) | 0.0463 (8) | |
H8 | 0.9138 | 0.7520 | 0.3438 | 0.056* | |
C9 | 0.8681 (3) | 0.6288 (2) | 0.38118 (14) | 0.0401 (8) | |
H9 | 0.9043 | 0.6145 | 0.4183 | 0.048* | |
C10 | 0.8108 (2) | 0.5674 (2) | 0.37134 (13) | 0.0331 (7) | |
H10 | 0.8079 | 0.5108 | 0.4016 | 0.040* | |
C11 | 0.3951 (2) | 0.4489 (2) | 0.35500 (12) | 0.0282 (7) | |
C12 | 0.3920 (3) | 0.4008 (2) | 0.41520 (13) | 0.0328 (7) | |
H12 | 0.4622 | 0.3738 | 0.4370 | 0.039* | |
C13 | 0.2875 (3) | 0.3921 (2) | 0.44346 (14) | 0.0387 (8) | |
H13 | 0.2861 | 0.3590 | 0.4846 | 0.046* | |
C14 | 0.1853 (3) | 0.4313 (2) | 0.41231 (14) | 0.0386 (8) | |
H14 | 0.1135 | 0.4247 | 0.4316 | 0.046* | |
C15 | 0.1877 (3) | 0.4803 (2) | 0.35295 (14) | 0.0384 (8) | |
H15 | 0.1172 | 0.5074 | 0.3314 | 0.046* | |
C16 | 0.2915 (3) | 0.4904 (2) | 0.32426 (13) | 0.0335 (7) | |
H16 | 0.2916 | 0.5258 | 0.2836 | 0.040* | |
C17 | 0.0843 (2) | 0.0633 (2) | 0.31723 (11) | 0.0246 (6) | |
C18 | 0.0636 (2) | 0.1327 (2) | 0.36038 (11) | 0.0264 (6) | |
C19 | 0.0325 (2) | 0.2411 (2) | 0.34791 (12) | 0.0275 (6) | |
C20 | 0.0213 (2) | 0.2895 (2) | 0.28866 (13) | 0.0287 (7) | |
C21 | 0.0408 (2) | 0.2257 (2) | 0.24365 (12) | 0.0285 (7) | |
C22 | 0.0717 (2) | 0.1184 (2) | 0.25866 (12) | 0.0265 (6) | |
C23 | 0.2705 (2) | −0.0982 (2) | 0.35881 (12) | 0.0270 (6) | |
C24 | 0.3069 (2) | −0.1228 (2) | 0.41726 (12) | 0.0260 (6) | |
C25 | 0.4181 (3) | −0.1362 (2) | 0.43125 (12) | 0.0288 (7) | |
C26 | 0.5018 (3) | −0.1222 (2) | 0.38626 (13) | 0.0323 (7) | |
C27 | 0.4716 (3) | −0.0958 (2) | 0.32692 (13) | 0.0322 (7) | |
C28 | 0.3593 (3) | −0.0848 (2) | 0.31485 (12) | 0.0290 (7) | |
C29 | 0.1373 (2) | −0.13369 (19) | 0.28175 (11) | 0.0256 (6) | |
C30 | 0.0309 (2) | −0.1019 (2) | 0.25428 (12) | 0.0286 (7) | |
C31 | 0.0206 (3) | −0.1463 (2) | 0.20626 (12) | 0.0323 (7) | |
C32 | 0.1206 (3) | −0.2318 (2) | 0.18444 (12) | 0.0346 (7) | |
C33 | 0.2271 (3) | −0.2701 (2) | 0.21055 (12) | 0.0334 (7) | |
C34 | 0.2336 (2) | −0.2211 (2) | 0.25814 (12) | 0.0297 (7) | |
C35 | 0.0472 (2) | −0.1039 (2) | 0.39313 (11) | 0.0233 (6) | |
C36 | −0.0721 (2) | −0.0419 (2) | 0.41325 (11) | 0.0242 (6) | |
C37 | −0.1454 (2) | −0.0813 (2) | 0.45284 (12) | 0.0259 (6) | |
C38 | −0.1022 (3) | −0.1877 (2) | 0.47581 (12) | 0.0282 (7) | |
C39 | 0.0164 (3) | −0.2542 (2) | 0.45919 (12) | 0.0267 (6) | |
C40 | 0.0864 (2) | −0.2119 (2) | 0.41815 (12) | 0.0257 (6) | |
C41 | 0.5420 (2) | 0.2618 (2) | 0.08402 (12) | 0.0275 (6) | |
C42 | 0.5484 (2) | 0.3582 (2) | 0.08833 (12) | 0.0278 (7) | |
C43 | 0.6069 (3) | 0.4075 (2) | 0.04529 (13) | 0.0332 (7) | |
C44 | 0.6626 (3) | 0.3617 (2) | −0.00734 (13) | 0.0344 (7) | |
C45 | 0.6575 (3) | 0.2675 (2) | −0.01526 (12) | 0.0350 (7) | |
C46 | 0.5982 (2) | 0.2210 (2) | 0.02929 (12) | 0.0294 (7) | |
C47 | 0.3215 (2) | 0.3135 (2) | 0.12963 (12) | 0.0261 (6) | |
C48 | 0.2505 (2) | 0.3892 (2) | 0.16956 (12) | 0.0310 (7) | |
C49 | 0.1414 (3) | 0.4749 (2) | 0.15746 (13) | 0.0346 (7) | |
C50 | 0.0970 (3) | 0.4916 (2) | 0.10213 (15) | 0.0387 (8) | |
C51 | 0.1640 (3) | 0.4209 (2) | 0.06029 (13) | 0.0363 (7) | |
C52 | 0.2710 (2) | 0.3363 (2) | 0.07441 (12) | 0.0306 (7) | |
C53 | 0.4730 (2) | 0.0961 (2) | 0.12885 (11) | 0.0254 (6) | |
C54 | 0.5867 (3) | 0.0083 (2) | 0.12812 (12) | 0.0308 (7) | |
C55 | 0.6066 (3) | −0.0961 (2) | 0.12488 (13) | 0.0351 (7) | |
C56 | 0.5093 (3) | −0.1200 (2) | 0.12255 (13) | 0.0386 (8) | |
C57 | 0.3958 (3) | −0.0376 (2) | 0.12358 (12) | 0.0345 (7) | |
C58 | 0.3812 (2) | 0.0656 (2) | 0.12681 (12) | 0.0282 (7) | |
C59 | 0.5029 (2) | 0.1974 (2) | 0.20719 (12) | 0.0278 (6) | |
C60 | 0.4313 (2) | 0.1763 (2) | 0.25780 (12) | 0.0305 (7) | |
C61 | 0.4552 (3) | 0.1624 (2) | 0.31781 (13) | 0.0361 (7) | |
C62 | 0.5597 (3) | 0.1664 (2) | 0.32901 (13) | 0.0371 (8) | |
C63 | 0.6372 (3) | 0.1827 (2) | 0.28162 (13) | 0.0341 (7) | |
C64 | 0.6082 (3) | 0.1967 (2) | 0.22253 (12) | 0.0305 (7) | |
C100 | 1.0445 (3) | 0.0412 (3) | 0.05656 (16) | 0.0557 (9) | |
H100 | 1.0663 | −0.0342 | 0.0612 | 0.067* | |
C101 | 1.1178 (3) | 0.0839 (3) | 0.01747 (15) | 0.0604 (10) | |
H101 | 1.1893 | 0.0376 | −0.0044 | 0.072* | |
C102 | 1.0866 (3) | 0.1931 (3) | 0.01061 (14) | 0.0541 (9) | |
H102 | 1.1356 | 0.2226 | −0.0164 | 0.065* | |
C103 | 0.9844 (3) | 0.2589 (3) | 0.04305 (14) | 0.0481 (9) | |
H103 | 0.9629 | 0.3342 | 0.0388 | 0.058* | |
C104 | 0.9123 (3) | 0.2164 (3) | 0.08192 (14) | 0.0479 (9) | |
H104 | 0.8420 | 0.2627 | 0.1046 | 0.057* | |
C105 | 0.9415 (2) | 0.1075 (2) | 0.08815 (11) | 0.0500 (9) | |
H105 | 0.8906 | 0.0788 | 0.1141 | 0.060* | |
Li1 | −0.2926 (2) | 0.1615 (2) | 0.44268 (11) | 0.0395 (12) | |
Li2 | 0.1203 (2) | 0.1192 (2) | 0.12298 (11) | 0.0536 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Al | 0.0306 (5) | 0.0298 (5) | 0.0276 (5) | −0.0154 (4) | −0.0022 (4) | −0.0063 (4) |
Cl | 0.0353 (4) | 0.0329 (4) | 0.0452 (4) | −0.0148 (3) | −0.0089 (3) | 0.0001 (3) |
F18 | 0.0494 (10) | 0.0347 (9) | 0.0238 (8) | −0.0193 (8) | −0.0041 (7) | −0.0051 (7) |
F19 | 0.0469 (11) | 0.0345 (9) | 0.0382 (9) | −0.0182 (8) | −0.0015 (8) | −0.0143 (8) |
F20 | 0.0477 (11) | 0.0278 (9) | 0.0469 (10) | −0.0157 (8) | −0.0001 (8) | −0.0029 (8) |
F21 | 0.0467 (10) | 0.0372 (9) | 0.0299 (9) | −0.0185 (8) | −0.0042 (8) | 0.0063 (7) |
F22 | 0.0414 (10) | 0.0348 (9) | 0.0228 (8) | −0.0171 (8) | −0.0025 (7) | −0.0045 (7) |
F24 | 0.0341 (9) | 0.0401 (9) | 0.0241 (8) | −0.0192 (8) | −0.0009 (7) | −0.0030 (7) |
F25 | 0.0368 (10) | 0.0440 (10) | 0.0290 (9) | −0.0116 (8) | −0.0099 (7) | −0.0067 (7) |
F26 | 0.0290 (10) | 0.0701 (12) | 0.0514 (11) | −0.0211 (9) | −0.0051 (8) | −0.0126 (9) |
F27 | 0.0350 (10) | 0.0580 (11) | 0.0397 (10) | −0.0224 (9) | 0.0053 (8) | −0.0010 (9) |
F28 | 0.0397 (10) | 0.0466 (10) | 0.0241 (9) | −0.0202 (8) | −0.0005 (7) | 0.0012 (7) |
F30 | 0.0297 (9) | 0.0423 (10) | 0.0395 (10) | −0.0134 (8) | −0.0030 (7) | −0.0118 (8) |
F31 | 0.0483 (11) | 0.0610 (11) | 0.0376 (10) | −0.0347 (9) | −0.0102 (8) | −0.0048 (8) |
F32 | 0.0754 (13) | 0.0571 (11) | 0.0325 (9) | −0.0432 (10) | 0.0045 (9) | −0.0184 (8) |
F33 | 0.0586 (12) | 0.0359 (10) | 0.0381 (10) | −0.0114 (9) | 0.0074 (9) | −0.0153 (8) |
F34 | 0.0364 (10) | 0.0356 (9) | 0.0383 (10) | −0.0055 (8) | −0.0034 (8) | −0.0099 (8) |
F36 | 0.0308 (9) | 0.0261 (8) | 0.0322 (9) | −0.0099 (7) | −0.0009 (7) | −0.0010 (7) |
F37 | 0.0286 (9) | 0.0390 (9) | 0.0365 (9) | −0.0148 (8) | 0.0043 (7) | −0.0077 (7) |
F38 | 0.0426 (10) | 0.0441 (10) | 0.0415 (10) | −0.0263 (9) | 0.0042 (8) | −0.0010 (8) |
F39 | 0.0467 (11) | 0.0277 (9) | 0.0417 (10) | −0.0169 (8) | 0.0005 (8) | −0.0030 (8) |
F40 | 0.0314 (10) | 0.0289 (8) | 0.0384 (9) | −0.0086 (7) | 0.0002 (7) | −0.0064 (7) |
F42 | 0.0441 (10) | 0.0426 (10) | 0.0344 (9) | −0.0230 (8) | 0.0007 (8) | −0.0155 (8) |
F43 | 0.0611 (12) | 0.0433 (10) | 0.0518 (11) | −0.0353 (9) | −0.0001 (9) | −0.0117 (9) |
F44 | 0.0720 (13) | 0.0575 (12) | 0.0485 (11) | −0.0464 (11) | 0.0171 (10) | −0.0104 (9) |
F45 | 0.0650 (12) | 0.0566 (11) | 0.0344 (10) | −0.0383 (10) | 0.0205 (9) | −0.0183 (9) |
F46 | 0.0487 (11) | 0.0393 (9) | 0.0303 (9) | −0.0275 (8) | 0.0048 (8) | −0.0120 (7) |
F48 | 0.0482 (11) | 0.0438 (10) | 0.0327 (9) | −0.0136 (8) | −0.0050 (8) | −0.0132 (8) |
F49 | 0.0483 (11) | 0.0353 (9) | 0.0502 (11) | −0.0114 (8) | 0.0096 (9) | −0.0107 (8) |
F50 | 0.0410 (11) | 0.0483 (11) | 0.0701 (13) | −0.0024 (9) | −0.0168 (10) | −0.0030 (10) |
F51 | 0.0480 (11) | 0.0642 (12) | 0.0512 (11) | −0.0133 (9) | −0.0259 (9) | −0.0027 (9) |
F52 | 0.0356 (10) | 0.0495 (10) | 0.0317 (9) | −0.0162 (8) | −0.0080 (8) | −0.0098 (8) |
F54 | 0.0273 (9) | 0.0439 (10) | 0.0492 (11) | −0.0149 (8) | −0.0071 (8) | −0.0052 (8) |
F55 | 0.0432 (11) | 0.0367 (10) | 0.0651 (12) | −0.0067 (9) | −0.0041 (9) | −0.0058 (9) |
F56 | 0.0721 (14) | 0.0374 (10) | 0.0733 (13) | −0.0276 (10) | 0.0028 (11) | −0.0142 (10) |
F57 | 0.0515 (12) | 0.0543 (11) | 0.0536 (11) | −0.0382 (9) | 0.0037 (9) | −0.0169 (9) |
F58 | 0.0262 (9) | 0.0391 (9) | 0.0465 (10) | −0.0173 (8) | 0.0004 (8) | −0.0129 (8) |
F60 | 0.0410 (10) | 0.0512 (10) | 0.0323 (9) | −0.0271 (9) | 0.0018 (8) | −0.0055 (8) |
F61 | 0.0665 (13) | 0.0576 (11) | 0.0288 (9) | −0.0316 (10) | 0.0051 (9) | −0.0029 (8) |
F62 | 0.0670 (12) | 0.0541 (11) | 0.0267 (9) | −0.0210 (9) | −0.0162 (8) | −0.0046 (8) |
F63 | 0.0437 (11) | 0.0549 (11) | 0.0491 (11) | −0.0157 (9) | −0.0226 (9) | −0.0114 (9) |
F64 | 0.0317 (10) | 0.0572 (11) | 0.0354 (9) | −0.0221 (8) | −0.0044 (8) | −0.0068 (8) |
N1 | 0.0324 (14) | 0.0330 (13) | 0.0311 (14) | −0.0164 (11) | −0.0014 (11) | −0.0068 (11) |
N2 | 0.0305 (14) | 0.0333 (13) | 0.0266 (13) | −0.0178 (11) | 0.0005 (11) | −0.0069 (10) |
B1 | 0.0314 (19) | 0.0265 (17) | 0.0224 (16) | −0.0122 (15) | 0.0006 (14) | −0.0048 (13) |
B2 | 0.0230 (18) | 0.0319 (18) | 0.0261 (17) | −0.0131 (15) | −0.0025 (14) | −0.0053 (14) |
C1 | 0.0424 (19) | 0.0347 (17) | 0.0382 (17) | −0.0198 (15) | 0.0000 (14) | −0.0104 (14) |
C2 | 0.0348 (18) | 0.0417 (18) | 0.0324 (17) | −0.0175 (15) | 0.0009 (14) | −0.0050 (14) |
C3 | 0.0408 (19) | 0.054 (2) | 0.0273 (16) | −0.0285 (16) | 0.0051 (15) | −0.0140 (15) |
C4 | 0.0372 (18) | 0.0378 (17) | 0.0329 (17) | −0.0199 (15) | −0.0062 (14) | −0.0093 (14) |
C5 | 0.0233 (16) | 0.0351 (17) | 0.0342 (17) | −0.0145 (13) | 0.0030 (13) | −0.0081 (14) |
C6 | 0.0391 (19) | 0.0452 (19) | 0.0399 (18) | −0.0258 (16) | −0.0038 (15) | 0.0003 (15) |
C7 | 0.047 (2) | 0.053 (2) | 0.054 (2) | −0.0328 (18) | 0.0005 (18) | 0.0004 (17) |
C8 | 0.0336 (19) | 0.050 (2) | 0.066 (2) | −0.0263 (16) | 0.0023 (18) | −0.0177 (19) |
C9 | 0.0340 (18) | 0.0476 (19) | 0.0457 (19) | −0.0206 (16) | −0.0040 (15) | −0.0131 (16) |
C10 | 0.0278 (17) | 0.0371 (17) | 0.0354 (17) | −0.0149 (14) | 0.0013 (14) | −0.0073 (14) |
C11 | 0.0327 (17) | 0.0244 (15) | 0.0312 (16) | −0.0151 (13) | −0.0003 (14) | −0.0066 (12) |
C12 | 0.0330 (18) | 0.0367 (17) | 0.0334 (17) | −0.0188 (14) | −0.0054 (14) | −0.0025 (13) |
C13 | 0.044 (2) | 0.0400 (18) | 0.0367 (17) | −0.0233 (16) | −0.0023 (16) | −0.0012 (14) |
C14 | 0.0359 (19) | 0.0400 (18) | 0.046 (2) | −0.0222 (15) | 0.0002 (16) | −0.0065 (15) |
C15 | 0.0315 (18) | 0.0398 (18) | 0.049 (2) | −0.0166 (15) | −0.0093 (15) | −0.0071 (15) |
C16 | 0.0354 (18) | 0.0360 (17) | 0.0328 (17) | −0.0171 (15) | −0.0047 (14) | −0.0060 (13) |
C17 | 0.0190 (15) | 0.0297 (15) | 0.0262 (15) | −0.0114 (12) | 0.0014 (12) | −0.0060 (12) |
C18 | 0.0279 (16) | 0.0307 (16) | 0.0213 (15) | −0.0141 (13) | −0.0031 (12) | 0.0010 (12) |
C19 | 0.0277 (16) | 0.0282 (16) | 0.0297 (16) | −0.0134 (13) | −0.0018 (13) | −0.0072 (13) |
C20 | 0.0224 (16) | 0.0224 (15) | 0.0403 (17) | −0.0097 (12) | −0.0007 (13) | −0.0029 (13) |
C21 | 0.0276 (16) | 0.0322 (16) | 0.0244 (15) | −0.0152 (13) | 0.0004 (13) | 0.0042 (13) |
C22 | 0.0278 (16) | 0.0283 (16) | 0.0247 (15) | −0.0125 (13) | −0.0003 (12) | −0.0068 (12) |
C23 | 0.0300 (16) | 0.0236 (14) | 0.0261 (15) | −0.0107 (13) | −0.0004 (13) | −0.0033 (12) |
C24 | 0.0263 (16) | 0.0242 (15) | 0.0256 (15) | −0.0105 (13) | 0.0026 (13) | −0.0030 (12) |
C25 | 0.0324 (17) | 0.0275 (15) | 0.0233 (15) | −0.0082 (13) | −0.0068 (14) | −0.0034 (12) |
C26 | 0.0239 (17) | 0.0337 (16) | 0.0396 (18) | −0.0109 (13) | −0.0046 (14) | −0.0070 (14) |
C27 | 0.0278 (17) | 0.0328 (16) | 0.0336 (17) | −0.0130 (14) | 0.0048 (14) | −0.0046 (13) |
C28 | 0.0356 (18) | 0.0304 (16) | 0.0191 (15) | −0.0130 (14) | −0.0026 (13) | −0.0010 (12) |
C29 | 0.0298 (16) | 0.0233 (14) | 0.0241 (15) | −0.0143 (13) | 0.0026 (13) | 0.0000 (12) |
C30 | 0.0312 (17) | 0.0289 (15) | 0.0270 (15) | −0.0150 (14) | 0.0017 (13) | −0.0045 (12) |
C31 | 0.0387 (19) | 0.0403 (17) | 0.0274 (16) | −0.0266 (15) | −0.0031 (14) | −0.0005 (13) |
C32 | 0.057 (2) | 0.0383 (17) | 0.0219 (15) | −0.0335 (17) | 0.0048 (15) | −0.0077 (13) |
C33 | 0.046 (2) | 0.0252 (16) | 0.0269 (16) | −0.0149 (15) | 0.0092 (15) | −0.0095 (13) |
C34 | 0.0313 (17) | 0.0281 (15) | 0.0269 (15) | −0.0114 (14) | −0.0020 (13) | 0.0005 (13) |
C35 | 0.0274 (16) | 0.0286 (15) | 0.0177 (14) | −0.0140 (13) | −0.0031 (12) | −0.0051 (11) |
C36 | 0.0312 (17) | 0.0242 (15) | 0.0195 (14) | −0.0127 (13) | −0.0060 (12) | −0.0023 (12) |
C37 | 0.0229 (16) | 0.0301 (16) | 0.0257 (15) | −0.0107 (13) | 0.0014 (13) | −0.0100 (12) |
C38 | 0.0356 (18) | 0.0344 (17) | 0.0215 (15) | −0.0233 (15) | 0.0026 (13) | −0.0023 (13) |
C39 | 0.0361 (18) | 0.0201 (15) | 0.0260 (15) | −0.0130 (14) | −0.0046 (13) | −0.0035 (12) |
C40 | 0.0259 (16) | 0.0285 (15) | 0.0252 (15) | −0.0118 (13) | −0.0019 (13) | −0.0087 (12) |
C41 | 0.0250 (16) | 0.0333 (16) | 0.0277 (15) | −0.0138 (13) | −0.0053 (12) | −0.0054 (13) |
C42 | 0.0275 (16) | 0.0343 (16) | 0.0234 (15) | −0.0124 (13) | −0.0044 (13) | −0.0073 (13) |
C43 | 0.0376 (18) | 0.0319 (17) | 0.0400 (18) | −0.0227 (14) | −0.0058 (15) | −0.0047 (14) |
C44 | 0.0343 (18) | 0.0417 (18) | 0.0337 (17) | −0.0255 (15) | 0.0026 (14) | −0.0002 (14) |
C45 | 0.0415 (19) | 0.0406 (18) | 0.0267 (16) | −0.0212 (15) | 0.0028 (14) | −0.0084 (14) |
C46 | 0.0296 (17) | 0.0321 (16) | 0.0335 (17) | −0.0178 (14) | −0.0051 (13) | −0.0064 (13) |
C47 | 0.0249 (16) | 0.0322 (16) | 0.0268 (15) | −0.0183 (13) | −0.0002 (12) | −0.0025 (12) |
C48 | 0.0336 (18) | 0.0352 (17) | 0.0288 (16) | −0.0187 (14) | −0.0053 (13) | −0.0018 (13) |
C49 | 0.0323 (18) | 0.0290 (16) | 0.0415 (18) | −0.0145 (14) | 0.0075 (15) | −0.0075 (14) |
C50 | 0.0240 (17) | 0.0358 (18) | 0.052 (2) | −0.0095 (14) | −0.0054 (15) | −0.0009 (15) |
C51 | 0.0316 (18) | 0.0465 (19) | 0.0354 (17) | −0.0193 (15) | −0.0139 (14) | 0.0014 (15) |
C52 | 0.0273 (17) | 0.0364 (17) | 0.0321 (16) | −0.0169 (14) | −0.0003 (13) | −0.0069 (13) |
C53 | 0.0239 (16) | 0.0347 (16) | 0.0206 (14) | −0.0152 (13) | −0.0014 (12) | −0.0032 (12) |
C54 | 0.0320 (18) | 0.0371 (17) | 0.0276 (16) | −0.0193 (15) | −0.0023 (13) | −0.0023 (13) |
C55 | 0.0334 (18) | 0.0293 (17) | 0.0332 (17) | −0.0060 (15) | 0.0021 (14) | −0.0052 (13) |
C56 | 0.052 (2) | 0.0293 (17) | 0.0377 (18) | −0.0208 (16) | 0.0010 (16) | −0.0060 (14) |
C57 | 0.0384 (19) | 0.0452 (19) | 0.0279 (16) | −0.0259 (17) | 0.0032 (14) | −0.0079 (14) |
C58 | 0.0244 (16) | 0.0321 (16) | 0.0258 (15) | −0.0093 (13) | 0.0008 (12) | −0.0075 (12) |
C59 | 0.0310 (17) | 0.0289 (15) | 0.0248 (15) | −0.0123 (13) | −0.0036 (13) | −0.0062 (12) |
C60 | 0.0304 (17) | 0.0327 (16) | 0.0317 (17) | −0.0138 (14) | −0.0090 (14) | −0.0053 (13) |
C61 | 0.047 (2) | 0.0331 (17) | 0.0254 (16) | −0.0156 (15) | 0.0040 (15) | −0.0059 (13) |
C62 | 0.050 (2) | 0.0331 (17) | 0.0251 (16) | −0.0095 (15) | −0.0171 (15) | −0.0042 (13) |
C63 | 0.0322 (18) | 0.0343 (17) | 0.0365 (18) | −0.0105 (14) | −0.0110 (15) | −0.0085 (14) |
C64 | 0.0302 (17) | 0.0340 (16) | 0.0270 (16) | −0.0126 (14) | −0.0026 (14) | −0.0054 (13) |
C100 | 0.064 (3) | 0.053 (2) | 0.056 (2) | −0.025 (2) | −0.019 (2) | −0.0098 (19) |
C101 | 0.053 (2) | 0.079 (3) | 0.040 (2) | −0.019 (2) | 0.0026 (18) | −0.017 (2) |
C102 | 0.052 (2) | 0.075 (3) | 0.0354 (19) | −0.032 (2) | −0.0013 (17) | 0.0040 (18) |
C103 | 0.047 (2) | 0.052 (2) | 0.046 (2) | −0.0220 (18) | −0.0080 (17) | 0.0011 (17) |
C104 | 0.0320 (19) | 0.064 (2) | 0.045 (2) | −0.0225 (18) | −0.0011 (16) | 0.0025 (17) |
C105 | 0.046 (2) | 0.070 (3) | 0.046 (2) | −0.038 (2) | −0.0135 (17) | 0.0068 (18) |
Li1 | 0.039 (3) | 0.041 (3) | 0.037 (3) | −0.016 (2) | −0.002 (2) | −0.003 (2) |
Li2 | 0.050 (4) | 0.091 (4) | 0.032 (3) | −0.044 (3) | −0.008 (3) | 0.003 (3) |
Al—N1 | 1.882 (2) | C11—C12 | 1.391 (4) |
Al—N2 | 1.885 (2) | C12—C13 | 1.379 (4) |
Al—C1 | 1.924 (3) | C13—C14 | 1.376 (4) |
Al—Cl | 2.2136 (11) | C14—C15 | 1.378 (4) |
Cl—Li1i | 2.338 (3) | C15—C16 | 1.382 (4) |
F18—C18 | 1.359 (3) | C17—C22 | 1.385 (3) |
F19—C19 | 1.345 (3) | C17—C18 | 1.399 (3) |
F20—C20 | 1.340 (3) | C18—C19 | 1.366 (3) |
F21—C21 | 1.365 (3) | C19—C20 | 1.370 (4) |
F21—Li2 | 2.436 (3) | C20—C21 | 1.379 (4) |
F22—C22 | 1.390 (3) | C21—C22 | 1.358 (3) |
F22—Li2 | 1.956 (3) | C23—C24 | 1.381 (4) |
F24—C24 | 1.376 (3) | C23—C28 | 1.397 (4) |
F24—Li1ii | 2.165 (3) | C24—C25 | 1.372 (4) |
F25—C25 | 1.365 (3) | C25—C26 | 1.367 (4) |
F25—Li1ii | 2.179 (3) | C26—C27 | 1.373 (4) |
F26—C26 | 1.338 (3) | C27—C28 | 1.381 (4) |
F27—C27 | 1.344 (3) | C29—C34 | 1.385 (3) |
F28—C28 | 1.352 (3) | C29—C30 | 1.388 (4) |
F30—C30 | 1.360 (3) | C30—C31 | 1.374 (4) |
F31—C31 | 1.351 (3) | C31—C32 | 1.375 (4) |
F32—C32 | 1.349 (3) | C32—C33 | 1.360 (4) |
F33—C33 | 1.343 (3) | C33—C34 | 1.387 (4) |
F34—C34 | 1.357 (3) | C35—C36 | 1.381 (3) |
F36—C36 | 1.370 (3) | C35—C40 | 1.395 (3) |
F36—Li1 | 2.100 (3) | C36—C37 | 1.374 (4) |
F37—C37 | 1.365 (3) | C37—C38 | 1.362 (4) |
F37—Li1 | 2.246 (3) | C38—C39 | 1.370 (3) |
F38—C38 | 1.341 (3) | C39—C40 | 1.384 (4) |
F39—C39 | 1.340 (3) | C41—C46 | 1.386 (3) |
F40—C40 | 1.353 (3) | C41—C42 | 1.394 (4) |
F42—C42 | 1.361 (3) | C42—C43 | 1.370 (4) |
F43—C43 | 1.345 (3) | C43—C44 | 1.370 (4) |
F44—C44 | 1.341 (3) | C44—C45 | 1.378 (4) |
F45—C45 | 1.350 (3) | C45—C46 | 1.372 (4) |
F46—C46 | 1.360 (3) | C47—C52 | 1.390 (4) |
F48—C48 | 1.353 (3) | C47—C48 | 1.393 (3) |
F49—C49 | 1.349 (3) | C48—C49 | 1.372 (4) |
F50—C50 | 1.344 (3) | C49—C50 | 1.368 (4) |
F51—C51 | 1.355 (3) | C50—C51 | 1.372 (4) |
F52—C52 | 1.367 (3) | C51—C52 | 1.360 (4) |
F54—C54 | 1.354 (3) | C53—C58 | 1.373 (4) |
F55—C55 | 1.347 (3) | C53—C54 | 1.394 (4) |
F56—C56 | 1.339 (3) | C54—C55 | 1.372 (4) |
F57—C57 | 1.358 (3) | C55—C56 | 1.380 (4) |
F57—Li2 | 2.436 (3) | C56—C57 | 1.360 (4) |
F58—C58 | 1.386 (3) | C57—C58 | 1.376 (4) |
F58—Li2 | 1.895 (3) | C59—C64 | 1.382 (4) |
F60—C60 | 1.365 (3) | C59—C60 | 1.385 (4) |
F61—C61 | 1.350 (3) | C60—C61 | 1.377 (4) |
F62—C62 | 1.370 (3) | C61—C62 | 1.370 (4) |
F62—Li1i | 2.113 (3) | C62—C63 | 1.361 (4) |
F63—C63 | 1.352 (3) | C63—C64 | 1.378 (4) |
F64—C64 | 1.357 (3) | C100—C105 | 1.366 (4) |
N1—C2 | 1.330 (3) | C100—C101 | 1.396 (5) |
N1—C5 | 1.431 (3) | C100—Li2i | 2.473 (4) |
N2—C4 | 1.334 (3) | C101—C102 | 1.376 (5) |
N2—C11 | 1.438 (3) | C101—Li2i | 2.494 (4) |
B1—C23 | 1.651 (4) | C102—C103 | 1.368 (4) |
B1—C29 | 1.655 (4) | C102—Li2i | 2.558 (4) |
B1—C35 | 1.655 (4) | C103—C104 | 1.380 (4) |
B1—C17 | 1.657 (4) | C103—Li2i | 2.569 (4) |
B2—C41 | 1.648 (4) | C104—C105 | 1.379 (4) |
B2—C47 | 1.657 (4) | C104—Li2i | 2.540 (4) |
B2—C53 | 1.655 (4) | C105—Li2i | 2.5163 |
B2—C59 | 1.656 (4) | Li1—F62iii | 2.113 (3) |
C2—C3 | 1.378 (4) | Li1—F24ii | 2.165 (3) |
C3—C4 | 1.388 (4) | Li1—F25ii | 2.179 (3) |
C5—C10 | 1.389 (4) | Li1—Cliii | 2.338 (3) |
C5—C6 | 1.390 (4) | Li2—C100iii | 2.473 (4) |
C6—C7 | 1.376 (4) | Li2—C101iii | 2.494 (4) |
C7—C8 | 1.369 (4) | Li2—C105iii | 2.5163 |
C8—C9 | 1.377 (4) | Li2—C104iii | 2.540 (4) |
C9—C10 | 1.380 (4) | Li2—C102iii | 2.558 (4) |
C11—C16 | 1.382 (4) | Li2—C103iii | 2.569 (4) |
N1—Al—N2 | 97.79 (10) | F45—C45—C46 | 120.2 (3) |
N1—Al—C1 | 113.96 (11) | C44—C45—C46 | 120.0 (3) |
N2—Al—C1 | 115.94 (12) | F46—C46—C45 | 114.5 (2) |
N1—Al—Cl | 106.90 (8) | F46—C46—C41 | 121.2 (2) |
N2—Al—Cl | 106.44 (8) | C45—C46—C41 | 124.3 (3) |
C1—Al—Cl | 114.22 (10) | C52—C47—C48 | 112.1 (2) |
Al—Cl—Li1i | 130.96 (7) | C52—C47—B2 | 119.7 (2) |
C21—F21—Li2 | 106.51 (15) | C48—C47—B2 | 127.6 (2) |
C22—F22—Li2 | 125.60 (16) | F48—C48—C49 | 114.6 (2) |
C24—F24—Li1ii | 118.02 (16) | F48—C48—C47 | 120.6 (2) |
C25—F25—Li1ii | 115.09 (16) | C49—C48—C47 | 124.8 (3) |
C36—F36—Li1 | 119.49 (16) | F49—C49—C50 | 119.7 (3) |
C37—F37—Li1 | 111.95 (15) | F49—C49—C48 | 120.6 (3) |
C57—F57—Li2 | 106.91 (16) | C50—C49—C48 | 119.7 (3) |
C58—F58—Li2 | 128.14 (17) | F50—C50—C49 | 120.5 (3) |
C62—F62—Li1i | 143.5 (2) | F50—C50—C51 | 121.2 (3) |
C2—N1—C5 | 118.3 (2) | C49—C50—C51 | 118.3 (3) |
C2—N1—Al | 121.5 (2) | F51—C51—C52 | 120.3 (3) |
C5—N1—Al | 120.09 (17) | F51—C51—C50 | 119.6 (3) |
C4—N2—C11 | 118.2 (2) | C52—C51—C50 | 120.1 (3) |
C4—N2—Al | 121.75 (19) | C51—C52—F52 | 116.4 (3) |
C11—N2—Al | 119.95 (17) | C51—C52—C47 | 125.0 (3) |
C23—B1—C29 | 114.7 (2) | F52—C52—C47 | 118.6 (2) |
C23—B1—C35 | 112.7 (2) | C58—C53—C54 | 111.6 (2) |
C29—B1—C35 | 102.3 (2) | C58—C53—B2 | 128.0 (2) |
C23—B1—C17 | 101.3 (2) | C54—C53—B2 | 120.1 (2) |
C29—B1—C17 | 112.3 (2) | F54—C54—C55 | 116.5 (2) |
C35—B1—C17 | 114.1 (2) | F54—C54—C53 | 118.6 (2) |
C41—B2—C47 | 101.4 (2) | C55—C54—C53 | 124.9 (3) |
C41—B2—C53 | 113.3 (2) | F55—C55—C56 | 119.5 (3) |
C47—B2—C53 | 113.3 (2) | F55—C55—C54 | 120.6 (3) |
C41—B2—C59 | 113.7 (2) | C56—C55—C54 | 119.8 (3) |
C47—B2—C59 | 112.9 (2) | F56—C56—C57 | 121.3 (3) |
C53—B2—C59 | 102.7 (2) | F56—C56—C55 | 120.7 (3) |
N1—C2—C3 | 125.9 (3) | C57—C56—C55 | 117.9 (3) |
C4—C3—C2 | 125.0 (3) | F57—C57—C56 | 121.2 (3) |
N2—C4—C3 | 125.3 (3) | F57—C57—C58 | 119.0 (3) |
C10—C5—C6 | 119.1 (3) | C56—C57—C58 | 119.8 (3) |
C10—C5—N1 | 119.8 (3) | C57—C58—C53 | 125.9 (3) |
C6—C5—N1 | 121.0 (3) | C57—C58—F58 | 113.5 (2) |
C7—C6—C5 | 120.0 (3) | C53—C58—F58 | 120.6 (2) |
C8—C7—C6 | 120.6 (3) | C64—C59—C60 | 112.7 (2) |
C7—C8—C9 | 120.0 (3) | C64—C59—B2 | 127.1 (2) |
C8—C9—C10 | 120.1 (3) | C60—C59—B2 | 120.1 (2) |
C9—C10—C5 | 120.1 (3) | F60—C60—C61 | 115.7 (3) |
C16—C11—C12 | 119.4 (3) | F60—C60—C59 | 119.0 (2) |
C16—C11—N2 | 121.9 (2) | C61—C60—C59 | 125.3 (3) |
C12—C11—N2 | 118.7 (2) | F61—C61—C62 | 120.6 (3) |
C13—C12—C11 | 120.3 (3) | F61—C61—C60 | 121.4 (3) |
C12—C13—C14 | 120.2 (3) | C62—C61—C60 | 118.0 (3) |
C15—C14—C13 | 119.6 (3) | C63—C62—C61 | 120.2 (3) |
C14—C15—C16 | 120.9 (3) | C63—C62—F62 | 120.1 (3) |
C15—C16—C11 | 119.6 (3) | C61—C62—F62 | 119.7 (3) |
C22—C17—C18 | 111.0 (2) | F63—C63—C62 | 119.6 (3) |
C22—C17—B1 | 128.1 (2) | F63—C63—C64 | 121.2 (3) |
C18—C17—B1 | 120.4 (2) | C62—C63—C64 | 119.2 (3) |
F18—C18—C19 | 116.5 (2) | F64—C64—C59 | 121.0 (2) |
F18—C18—C17 | 117.9 (2) | F64—C64—C63 | 114.6 (3) |
C19—C18—C17 | 125.6 (2) | C59—C64—C63 | 124.4 (3) |
F19—C19—C18 | 120.9 (2) | C105—C100—C101 | 120.2 (3) |
F19—C19—C20 | 119.4 (2) | C105—C100—Li2i | 75.84 (17) |
C18—C19—C20 | 119.7 (2) | C101—C100—Li2i | 74.5 (2) |
F20—C20—C19 | 121.7 (2) | C102—C101—C100 | 120.1 (3) |
F20—C20—C21 | 120.5 (2) | C102—C101—Li2i | 76.8 (2) |
C19—C20—C21 | 117.8 (2) | C100—C101—Li2i | 72.9 (2) |
C22—C21—F21 | 119.9 (2) | C103—C102—C101 | 119.4 (3) |
C22—C21—C20 | 120.0 (2) | C103—C102—Li2i | 74.96 (19) |
F21—C21—C20 | 120.1 (2) | C101—C102—Li2i | 71.7 (2) |
C21—C22—F22 | 113.5 (2) | C102—C103—C104 | 120.4 (3) |
C21—C22—C17 | 125.9 (2) | C102—C103—Li2i | 74.09 (19) |
F22—C22—C17 | 120.6 (2) | C104—C103—Li2i | 73.20 (19) |
C24—C23—C28 | 112.0 (2) | C105—C104—C103 | 120.6 (3) |
C24—C23—B1 | 128.5 (2) | C105—C104—Li2i | 73.21 (16) |
C28—C23—B1 | 119.0 (2) | C103—C104—Li2i | 75.46 (19) |
C25—C24—F24 | 113.8 (2) | C100—C105—C104 | 119.2 (3) |
C25—C24—C23 | 124.8 (3) | C100—C105—Li2i | 72.39 (17) |
F24—C24—C23 | 121.4 (2) | C104—C105—Li2i | 75.14 (17) |
F25—C25—C24 | 119.0 (2) | F36—Li1—F62iii | 97.83 (12) |
F25—C25—C26 | 120.4 (2) | F36—Li1—F24ii | 99.97 (11) |
C24—C25—C26 | 120.7 (3) | F62iii—Li1—F24ii | 148.36 (14) |
F26—C26—C25 | 120.8 (3) | F36—Li1—F25ii | 147.14 (14) |
F26—C26—C27 | 121.1 (3) | F62iii—Li1—F25ii | 77.63 (10) |
C25—C26—C27 | 118.1 (3) | F24ii—Li1—F25ii | 73.21 (9) |
F27—C27—C26 | 120.7 (3) | F36—Li1—F37 | 72.75 (10) |
F27—C27—C28 | 120.0 (3) | F62iii—Li1—F37 | 79.71 (10) |
C26—C27—C28 | 119.3 (3) | F24ii—Li1—F37 | 80.89 (10) |
F28—C28—C27 | 116.1 (2) | F25ii—Li1—F37 | 74.42 (9) |
F28—C28—C23 | 118.7 (2) | F36—Li1—Cliii | 96.96 (10) |
C27—C28—C23 | 125.2 (3) | F62iii—Li1—Cliii | 111.47 (11) |
C34—C29—C30 | 112.9 (2) | F24ii—Li1—Cliii | 92.10 (10) |
C34—C29—B1 | 128.3 (2) | F25ii—Li1—Cliii | 115.13 (12) |
C30—C29—B1 | 118.8 (2) | F37—Li1—Cliii | 166.15 (13) |
F30—C30—C31 | 115.9 (2) | F58—Li2—F22 | 98.64 (12) |
F30—C30—C29 | 119.1 (2) | F58—Li2—F21 | 79.32 (10) |
C31—C30—C29 | 125.0 (3) | F22—Li2—F21 | 71.43 (9) |
F31—C31—C30 | 120.7 (2) | F58—Li2—F57 | 72.17 (10) |
F31—C31—C32 | 120.4 (2) | F22—Li2—F57 | 82.43 (10) |
C30—C31—C32 | 118.9 (3) | F21—Li2—F57 | 137.61 (12) |
F32—C32—C33 | 121.5 (3) | F58—Li2—C100iii | 139.96 (14) |
F32—C32—C31 | 119.0 (3) | F22—Li2—C100iii | 109.01 (14) |
C33—C32—C31 | 119.5 (3) | F21—Li2—C100iii | 136.39 (13) |
F33—C33—C32 | 120.2 (2) | F57—Li2—C100iii | 83.16 (11) |
F33—C33—C34 | 120.4 (3) | F58—Li2—C101iii | 110.84 (14) |
C32—C33—C34 | 119.5 (3) | F22—Li2—C101iii | 140.03 (17) |
F34—C34—C29 | 120.6 (2) | F21—Li2—C101iii | 138.78 (15) |
F34—C34—C33 | 115.1 (2) | F57—Li2—C101iii | 81.67 (12) |
C29—C34—C33 | 124.2 (3) | C100iii—Li2—C101iii | 32.65 (11) |
C36—C35—C40 | 112.3 (2) | F58—Li2—C105iii | 166.29 (8) |
C36—C35—B1 | 127.8 (2) | F22—Li2—C105iii | 95.07 (8) |
C40—C35—B1 | 119.2 (2) | F21—Li2—C105iii | 105.35 (7) |
F36—C36—C37 | 113.6 (2) | F57—Li2—C105iii | 109.78 (7) |
F36—C36—C35 | 122.0 (2) | C100iii—Li2—C105iii | 31.77 (9) |
C37—C36—C35 | 124.4 (2) | C101iii—Li2—C105iii | 57.11 (10) |
F37—C37—C38 | 120.5 (2) | F58—Li2—C104iii | 141.10 (14) |
F37—C37—C36 | 118.8 (2) | F22—Li2—C104iii | 106.50 (13) |
C38—C37—C36 | 120.7 (2) | F21—Li2—C104iii | 81.14 (11) |
F38—C38—C37 | 120.1 (2) | F57—Li2—C104iii | 139.42 (13) |
F38—C38—C39 | 121.4 (2) | C100iii—Li2—C104iii | 56.36 (12) |
C37—C38—C39 | 118.5 (2) | C101iii—Li2—C104iii | 66.02 (13) |
F39—C39—C38 | 120.1 (2) | C105iii—Li2—C104iii | 31.64 (9) |
F39—C39—C40 | 120.9 (2) | F58—Li2—C102iii | 100.05 (13) |
C38—C39—C40 | 119.0 (2) | F22—Li2—C102iii | 161.01 (15) |
F40—C40—C39 | 116.2 (2) | F21—Li2—C102iii | 108.85 (13) |
F40—C40—C35 | 118.8 (2) | F57—Li2—C102iii | 106.54 (13) |
C39—C40—C35 | 125.0 (2) | C100iii—Li2—C102iii | 57.00 (13) |
C46—C41—C42 | 112.6 (2) | C101iii—Li2—C102iii | 31.57 (11) |
C46—C41—B2 | 127.5 (2) | C105iii—Li2—C102iii | 66.28 (10) |
C42—C41—B2 | 119.6 (2) | C104iii—Li2—C102iii | 55.79 (11) |
F42—C42—C43 | 116.4 (2) | F58—Li2—C103iii | 112.60 (14) |
F42—C42—C41 | 118.4 (2) | F22—Li2—C103iii | 135.07 (15) |
C43—C42—C41 | 125.3 (2) | F21—Li2—C103iii | 83.18 (11) |
F43—C43—C42 | 120.7 (2) | F57—Li2—C103iii | 136.61 (13) |
F43—C43—C44 | 120.2 (3) | C100iii—Li2—C103iii | 66.03 (12) |
C42—C43—C44 | 119.1 (3) | C101iii—Li2—C103iii | 55.78 (12) |
F44—C44—C43 | 120.0 (3) | C105iii—Li2—C103iii | 56.22 (9) |
F44—C44—C45 | 121.2 (3) | C104iii—Li2—C103iii | 31.35 (10) |
C43—C44—C45 | 118.7 (3) | C102iii—Li2—C103iii | 30.95 (10) |
F45—C45—C44 | 119.8 (3) |
Symmetry codes: (i) x+1, y, z; (ii) −x, −y, −z+1; (iii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [AlCl(CH3)(C15H13N2)][Li(C24BF20)]2·C6H6 |
Mr | 1748.83 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 12.2522 (9), 13.8727 (10), 22.2931 (16) |
α, β, γ (°) | 79.743 (1), 80.829 (1), 64.077 (1) |
V (Å3) | 3339.2 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.23 |
Crystal size (mm) | 0.50 × 0.34 × 0.25 |
Data collection | |
Diffractometer | Bruker CCD 1000 diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Blessing, 1995) |
Tmin, Tmax | 0.894, 0.945 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17369, 12479, 7428 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.094, 0.93 |
No. of reflections | 12479 |
No. of parameters | 1058 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −0.29 |
Computer programs: SMART (Bruker, 1997), SMART, SHELXTL (Sheldrick, 1998), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL.
Al—N1 | 1.882 (2) | F37—Li1 | 2.246 (3) |
Al—N2 | 1.885 (2) | F57—Li2 | 2.436 (3) |
Al—C1 | 1.924 (3) | F58—Li2 | 1.895 (3) |
Al—Cl | 2.2136 (11) | F62—Li1i | 2.113 (3) |
Cl—Li1i | 2.338 (3) | C100—Li2i | 2.473 (4) |
F21—Li2 | 2.436 (3) | C101—Li2i | 2.494 (4) |
F22—Li2 | 1.956 (3) | C102—Li2i | 2.558 (4) |
F24—Li1ii | 2.165 (3) | C103—Li2i | 2.569 (4) |
F25—Li1ii | 2.179 (3) | C104—Li2i | 2.540 (4) |
F36—Li1 | 2.100 (3) | C105—Li2i | 2.5163 |
Symmetry codes: (i) x+1, y, z; (ii) −x, −y, −z+1. |
In recent reports, we have described the syntheses and structures of [HC{CMeN(2,6-iPr2Ph)}2]AlR2 and [HC{CMeN(2,6-iPr2Ph)}2]AlR+ complexes based on β-diketiminate ligands incorporating bulky N-aryl substituents (Radzewich et al., 1998, 1999). The cationic species undergo unusual cycloaddition reactions with alkenes and alkynes. During efforts to extend this chemistry to the parent [HC(CHNPh)2]AlMe+ system, we isolated the novel compound [HC(CHNPh)2]AlMeCl.2[Li{B(C6F5)4}].benzene, (I), the structure of which is described here.
The asymmetric unit consists of one neutral [HC(CHNPh)2]AlMeCl complex, two B(C6F5)4- anions, two Li+ cations and a benzene solvate molecule. These moieties all participate in long-distance intermolecular interactions to form a three-dimensional framework of coordination bonds (Fig. 1). Important bond distances are listed in Table 1.
The Al atom possesses a distorted tetrahedral coordination sphere comprised of a methyl group, a Cl atom and the two N atoms of the chelating diketiminate ligand. The angles about the metal center range from 97.79 (10) (N1—Al—N2) to 115.94 (12)° (N2—Al—C1). Due to the coordination of the Cl atom to the Li1 cation (see below), the Al—Cl distance [2.2136 (11) Å] is somewhat longer than a typical Al—Cl bond distance [2.12 (2) Å]. The latter value was obtained by averaging the distances of 794 A l—Cl bonds found in compounds listed in the Cambridge Structural Database (CSD; Allen & Kennard, 1993). The Al—C distance [1.924 (3) Å] is shorter than a typical Al—Me bond distance [1.959 (19) Å; 1024 CSD entries], but is very similar to the Al—C distance in [HC{CMeN(p-tolyl)}2]AlMe(OSO2CF3) [1.928 (6) Å; Qian et al., 1998]. The Al—N bond distances [average 1.884 (2) Å] fall in the same range as observed for related aluminium diketiminate complexes, e.g. [HC{CMeN(p-tolyl)}2]AlCl2 [1.850 (2) Å], [HC{CMeN(p-tolyl)}2]AlMe(OSO2CF3) [1.875 (4) and 1.873 (4) Å], [HC{CMeN(p-tolyl)}2]AlMe2 [1.905 (3) and 1.907 (3) Å] and [HC(CHNPh)2]AlMe2 [1.913 (4) Å; Radzewich et al., 1998, 1999; Qian et al., 1998]. Atoms N1, C2, C3, C4 and N2 of the diketiminate ligand are planar within 0.0316 (3) Å, and the Al atom is displaced by -0.32 Å out of this plane. The ipso-C atoms C5 and C11 of the phenyl ringsare displaced by 0.324 (4) and 0.225 (4) Å, respectively, on the other side of this plane. The dihedral angles between the phenyl-ring planes and the N—C—C—C—N plane are 45.03 (11) and 43.67 (8)°.
This structure presents the first example of an Li+ cation coordinated to six organohalogen atoms. Moreover, while six-coordinate Li+ usually adopts an octahedral geometry (LiF and LiSbF6), in (I), Li1 exhibits a distorted trigonal antiprismatic coordination sphere. Atom Li1 interacts with the Cl atom, atoms F36 and F37 of one of the B(C6F5)4- anions, atoms F24 and F25 of another B(C6F5)4- anion at (-x, -y, 1 - z), and atom F62 of a third B(C6F5)4- anion at (x - 1, y, z). Atoms F36 and F24 are ortho, F37 and F25 are meta, and F62 is a para substituent on the corresponding phenyl rings (Fig. 2). Although the Li1—Cl interaction results in an elongation of the Al—Cl bond, the Li1—Cl bond distance falls in the middle of the wide range of previously reported Li—Cl distances (2.169–2.792 Å, 162 CSD entries). The Li1—F bond distances vary in the range 2.100 (3)–2.246 (3) Å, with no apparent dependency on the F-atom position on the phenyl group. A CSD search showed that for 58 complexes, the Li—F distances vary in the range 1.771–2.355 Å. For comparison, the Li—F distance in crystalline LiF is 2.009 Å (Wells, 1984), the sum of the ionic radii for Li+ (0.60 Å) and F- (1.36 Å) according to Pauling (1960) is 1.96 Å, while the sum of van der Waals radii for lithium (1.82 Å) and fluorine (1.47 Å) is 3.29 Å (Porterfield, 1998).
Atom Li2 is coordinated to atoms F21 and F22 of one B(C6F5)4- anion, atoms F57 and F58 of the other B(C6F5)4- anion and the solvate benzene molecule at (x - 1, y, z) in a η6 fashion (Fig. 3). The Li2—F distances differ considerably, the ortho-F atom of each anion is coordinated more strongly [1.895 (3) Å for Li2—F22 and 1.956 (3) Å for Li2—F58] than the meta-F atoms [2.436 (3) Å each]. In fact, the Li2—F22 and Li2—F58 distances are the shortest Li—F(C) interactions reported to date. The shortest distance previously reported was 1.984 (9) Å in LiAl[OC(Ph)(CF3)2]4 (Barbarich et al., 1996). Conversely, the lengths of the Li2—F21 and Li2—F57 interactions exceed all other reported values for Li—F bond distances, regardless of whether fluorine is bound to another atom or not. Incidentally, the Li—F—C bond angles around F22 and F58 are 125.60 (16) and 128.14 (17)°, respectively, while the corresponding values for atoms F21 and F57 are 106.51 (15) and 106.91 (16)°, respectively. A review of the coordination chemistry of the F(C) unit with respect to lithium can be found in a paper by Plenio (1997). The Li2—C distances [average 2.53 (4) Å] are appreciably longer than the corresponding distances in other compounds with η6-coordinated Li+ cations, e.g. 2.38 (5) Å in [Li[{Al(iBu)2(NMes)}{Al(N[C6H2(CH3)2CH2])}]2 (Mes = 2,4,6-Me3C6H2; Horchler et al., 1997), 2.32 (4) Å in [Li(2,4,6-iPr3C6H2]4 (Ruhklandt-Senge et al., 1993), 2.34 (3) and 2.35 (7) Å in [Li(nBu)]2(LiMes*)2 (Mes* = 2,4,6-tBu3C6H2; Ruhklandt-Senge et al., 1993), 2.37 (9) Å in [Li(nBu)]2(LiMes*)2.Mes*Br (Ruhklandt-Senge et al., 1993), and 2.32 (1)–2.54 (1) Å in Li4[P(Me){CH(C6H4)}2].2tmeda (tmeda is N,N,N',N'-tetramethylethylenediamine; Winkler et al., 1994). The extended lengths of the Li—C bonds in (I) is likely a consequence of the strong coordination of Li2 to F22 and F58.
The B1 B(C6F5)4- anion coordinates to three Li atoms through two adjacent F atoms in each case. The coordinated atoms are Li1, Li1(-x, -y, 1 - z) and Li2. The B2 B(C6F5)4- anion interacts with two Li atoms, i.e. through a pair of vicinal F atoms to Li1 and with a para-F atom F62 to Li1(1 + x, y, z). The different coordination environments of the anions do not result in variations of the geometries about the B atoms. The average C—F distance for the F atoms coordinated to Li+ atoms is somewhat lengthened [1.372 (11) Å] compared with the other C—F bond distances in (I) [average 1.350 (8) Å], however, statistically, these average distances are not significantly different.