Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103018365/sq1023sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103018365/sq1023Isup2.hkl |
CCDC reference: 224495
A valved NMR tube was charged with (Me2bipy)PdCl2 (5.0 mg, 0.016 mmol) and [Li(Et2O)2.4][B(C6F5)4] (13.5 mg, 0.016 mmol), and CD2Cl2 (0.5 ml) was added by vacuum transfer. The NMR tube was briefly warmed to 296 K, vigorously shaken to form a pale yellow slurry and then heated in a 333 K bath to form a clear pale- yellow solution. The mixture was cooled to 296 K and pale-yellow plate-shaped crystals formed overnight.
Direct methods were used to locate the Pd atom and many of the C, Cl and F atoms from the E map. Repeated difference Fourier maps allowed the recognition of all expected C, Cl, F, B, Li and N atoms. All H atoms were placed at idealized positions and were allowed to ride on the parent atoms. On the basis of large thermal parameters, the CD2Cl2 molecules were considered to be partially occupied. Thus the occupancy of the atoms was taken to be equal for each molecule, and this occupancy was refined as a free variable. The resulting occupancies are 0.559 and 0.637. The B(C6F5)4− anion occupies a position such that there are two half anions in the asymmetric cell. Some elongated ellipsoids exist in the structure of this anion, which indicates that either it is thermally mobile or it has small positional disorder. However, the Li-bridged dinuclear monocation does not show elongated ellipsoids, which suggests that the elongation? is a feature of the anion and not a feature of the overall structure. Moreover, the B(C6F5)4− anion does not play significant part in the discussion of the overall structure?. Therefore, the anion was treated not as a rigid body but in the same way as the rest of the structure.
Data collection: SMART (Bruker,2001); cell refinement: SAINT-Plus (Bruker,1999); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker,1998); software used to prepare material for publication: SHELXTL.
Fig. 1. A view of the cation of complex (I), with displacement ellipsoids shown at the 50% probability level. H atoms have been omitted for clarity. |
[LiPd2Cl4(C12H12N2)2](C24F20B)·1.196CD2Cl2 | F(000) = 2952.528 |
Mr = 1513.06 | Dx = 1.806 Mg m−3 |
Monoclinic, P2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yc | Cell parameters from 27015 reflections |
a = 22.361 (6) Å | θ = 1.7–25.0° |
b = 7.939 (2) Å | µ = 1.06 mm−1 |
c = 31.754 (9) Å | T = 100 K |
β = 98.621 (5)° | Plate, pale yellow |
V = 5573 (3) Å3 | 0.40 × 0.16 × 0.10 mm |
Z = 4 |
Bruker SMART CCD diffractometer | 9813 independent reflections |
Radiation source: fine-focus sealed tube | 8967 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
ω scan | θmax = 25.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −19→26 |
Tmin = 0.676, Tmax = 0.901 | k = −9→9 |
27015 measured reflections | l = −37→36 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.076 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.182 | w = 1/[σ2(Fo2) + (0.0574P)2 + 46.4907P] where P = (Fo2 + 2Fc2)/3 |
S = 1.25 | (Δ/σ)max = 0.005 |
9813 reflections | Δρmax = 1.82 e Å−3 |
782 parameters | Δρmin = −1.38 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0 |
[LiPd2Cl4(C12H12N2)2](C24F20B)·1.196CD2Cl2 | V = 5573 (3) Å3 |
Mr = 1513.06 | Z = 4 |
Monoclinic, P2/c | Mo Kα radiation |
a = 22.361 (6) Å | µ = 1.06 mm−1 |
b = 7.939 (2) Å | T = 100 K |
c = 31.754 (9) Å | 0.40 × 0.16 × 0.10 mm |
β = 98.621 (5)° |
Bruker SMART CCD diffractometer | 9813 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 8967 reflections with I > 2σ(I) |
Tmin = 0.676, Tmax = 0.901 | Rint = 0.048 |
27015 measured reflections |
R[F2 > 2σ(F2)] = 0.076 | 0 restraints |
wR(F2) = 0.182 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.25 | w = 1/[σ2(Fo2) + (0.0574P)2 + 46.4907P] where P = (Fo2 + 2Fc2)/3 |
9813 reflections | Δρmax = 1.82 e Å−3 |
782 parameters | Δρmin = −1.38 e Å−3 |
Experimental. Absorption corrections were applied using SADABS based on redundant diffractions. |
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) | |
B1 | 0.5000 | 0.470 (2) | 0.2500 | 0.021 (3) | |
B2 | 1.0000 | 0.278 (2) | 0.7500 | 0.044 (4) | |
C1 | 0.2575 (3) | 1.395 (1) | 0.3940 (3) | 0.026 (2) | |
H1 | 0.2309 | 1.3041 | 0.3975 | 0.031* | |
C2 | 0.2341 (4) | 1.538 (1) | 0.3727 (3) | 0.030 (2) | |
H2 | 0.1923 | 1.5439 | 0.3614 | 0.036* | |
C3 | 0.2716 (4) | 1.674 (1) | 0.3677 (3) | 0.026 (2) | |
C4 | 0.3325 (3) | 1.656 (1) | 0.3840 (2) | 0.024 (2) | |
H4 | 0.3600 | 1.7446 | 0.3810 | 0.029* | |
C5 | 0.3535 (3) | 1.5079 (9) | 0.4048 (2) | 0.020 (2) | |
C6 | 0.4181 (3) | 1.4782 (9) | 0.4216 (3) | 0.023 (2) | |
C7 | 0.4639 (3) | 1.596 (1) | 0.4217 (2) | 0.023 (2) | |
H7 | 0.4545 | 1.7047 | 0.4101 | 0.028* | |
C8 | 0.5227 (3) | 1.557 (1) | 0.4384 (3) | 0.024 (2) | |
C9 | 0.5340 (4) | 1.394 (1) | 0.4545 (3) | 0.028 (2) | |
H9 | 0.5741 | 1.3612 | 0.4657 | 0.034* | |
C10 | 0.4872 (3) | 1.2809 (10) | 0.4542 (3) | 0.024 (2) | |
H10 | 0.4957 | 1.1710 | 0.4653 | 0.029* | |
C11 | 0.2463 (4) | 1.830 (1) | 0.3458 (3) | 0.035 (2) | |
H11A | 0.2128 | 1.8001 | 0.3234 | 0.053* | |
H11B | 0.2779 | 1.8877 | 0.3330 | 0.053* | |
H11C | 0.2314 | 1.9048 | 0.3665 | 0.053* | |
C12 | 0.5722 (4) | 1.686 (1) | 0.4399 (3) | 0.033 (2) | |
H12A | 0.5626 | 1.7643 | 0.4160 | 0.049* | |
H12B | 0.6105 | 1.6291 | 0.4378 | 0.049* | |
H12C | 0.5757 | 1.7483 | 0.4668 | 0.049* | |
C13 | 0.2162 (3) | 0.3125 (9) | 0.6021 (3) | 0.025 (2) | |
C14 | 0.1857 (3) | 0.159 (1) | 0.6050 (3) | 0.030 (2) | |
H14 | 0.1742 | 0.1277 | 0.6315 | 0.036* | |
C15 | 0.1722 (4) | 0.054 (1) | 0.5709 (3) | 0.034 (2) | |
C16 | 0.1879 (4) | 0.108 (1) | 0.5320 (3) | 0.041 (2) | |
H16 | 0.1785 | 0.0410 | 0.5072 | 0.049* | |
C17 | 0.2175 (4) | 0.263 (1) | 0.5301 (3) | 0.035 (2) | |
H17 | 0.2283 | 0.2991 | 0.5037 | 0.042* | |
C18 | 0.2816 (3) | 0.6798 (9) | 0.6583 (2) | 0.023 (2) | |
H18 | 0.2999 | 0.7816 | 0.6511 | 0.027* | |
C19 | 0.2763 (3) | 0.650 (1) | 0.7010 (3) | 0.024 (2) | |
H19 | 0.2912 | 0.7302 | 0.7222 | 0.029* | |
C20 | 0.2490 (3) | 0.502 (1) | 0.7123 (3) | 0.025 (2) | |
C21 | 0.2275 (3) | 0.392 (1) | 0.6794 (3) | 0.026 (2) | |
H21 | 0.2076 | 0.2912 | 0.6858 | 0.031* | |
C22 | 0.2343 (3) | 0.4245 (9) | 0.6378 (3) | 0.023 (2) | |
C23 | 0.1399 (4) | −0.110 (1) | 0.5742 (3) | 0.040 (2) | |
H23A | 0.1482 | −0.1519 | 0.6035 | 0.060* | |
H23B | 0.1542 | −0.1929 | 0.5550 | 0.060* | |
H23C | 0.0963 | −0.0935 | 0.5661 | 0.060* | |
C24 | 0.2450 (3) | 0.458 (1) | 0.7574 (3) | 0.026 (2) | |
H24A | 0.2668 | 0.5425 | 0.7764 | 0.039* | |
H24B | 0.2632 | 0.3470 | 0.7640 | 0.039* | |
H24C | 0.2025 | 0.4557 | 0.7616 | 0.039* | |
C25 | 0.4442 (3) | 0.6002 (9) | 0.2323 (2) | 0.020 (2) | |
C26 | 0.4187 (3) | 0.6282 (9) | 0.1901 (3) | 0.022 (2) | |
C27 | 0.3731 (3) | 0.7428 (9) | 0.1770 (3) | 0.024 (2) | |
C28 | 0.3518 (3) | 0.8419 (9) | 0.2075 (3) | 0.024 (2) | |
C29 | 0.3762 (3) | 0.8242 (9) | 0.2491 (3) | 0.026 (2) | |
C30 | 0.4217 (3) | 0.7067 (9) | 0.2607 (3) | 0.022 (2) | |
C31 | 0.4823 (3) | 0.3390 (9) | 0.2872 (2) | 0.020 (2) | |
C32 | 0.4260 (3) | 0.3129 (9) | 0.2990 (3) | 0.022 (2) | |
C33 | 0.4141 (3) | 0.1967 (9) | 0.3292 (2) | 0.022 (2) | |
C34 | 0.4599 (4) | 0.0979 (9) | 0.3485 (3) | 0.026 (2) | |
C35 | 0.5172 (4) | 0.115 (1) | 0.3375 (3) | 0.024 (2) | |
C36 | 0.5260 (3) | 0.2316 (9) | 0.3075 (3) | 0.021 (2) | |
C37 | 1.0018 (4) | 0.408 (1) | 0.7098 (4) | 0.044 (3) | |
C38 | 0.9569 (4) | 0.439 (1) | 0.6755 (4) | 0.049 (3) | |
C39 | 0.9594 (4) | 0.557 (1) | 0.6444 (4) | 0.054 (3) | |
C40 | 1.0117 (5) | 0.652 (1) | 0.6463 (5) | 0.064 (4) | |
C41 | 1.0582 (4) | 0.631 (1) | 0.6784 (4) | 0.056 (3) | |
C42 | 1.0520 (4) | 0.512 (1) | 0.7095 (4) | 0.051 (3) | |
C43 | 0.9417 (3) | 0.146 (1) | 0.7428 (3) | 0.034 (2) | |
C44 | 0.8992 (3) | 0.117 (1) | 0.7694 (3) | 0.034 (2) | |
C45 | 0.8517 (4) | 0.007 (1) | 0.7603 (4) | 0.042 (3) | |
C46 | 0.8446 (4) | −0.087 (1) | 0.7235 (4) | 0.041 (3) | |
C47 | 0.8867 (4) | −0.068 (1) | 0.6962 (3) | 0.038 (2) | |
C48 | 0.9338 (4) | 0.043 (1) | 0.7060 (3) | 0.036 (2) | |
C49 | 0.025 (1) | 0.379 (6) | 0.5524 (9) | 0.16 (2) | 0.559 (8) |
H49A | 0.0142 | 0.2948 | 0.5295 | 0.187* | 0.559 (8) |
H49B | −0.0109 | 0.4524 | 0.5526 | 0.187* | 0.559 (8) |
C50 | 0.909 (1) | 0.023 (3) | 0.5747 (6) | 0.080 (7) | 0.637 (7) |
H50A | 0.8806 | −0.0660 | 0.5801 | 0.097* | 0.637 (7) |
H50B | 0.9376 | 0.0425 | 0.6015 | 0.097* | 0.637 (7) |
Cl1 | 0.26644 (8) | 1.0402 (2) | 0.44567 (6) | 0.0262 (4) | |
Cl2 | 0.40746 (8) | 0.9547 (2) | 0.47591 (6) | 0.0255 (4) | |
Cl3 | 0.2858 (1) | 0.5817 (3) | 0.49552 (7) | 0.0345 (5) | |
Cl4 | 0.31960 (9) | 0.8464 (2) | 0.57232 (7) | 0.0300 (4) | |
Cl5 | 0.0392 (2) | 0.2660 (7) | 0.6040 (2) | 0.062 (2) | 0.559 (8) |
Cl6 | 0.0763 (3) | 0.4875 (7) | 0.5408 (2) | 0.078 (2) | 0.559 (8) |
Cl7 | 0.8694 (2) | 0.2104 (5) | 0.5599 (2) | 0.055 (2) | 0.637 (7) |
Cl8 | 0.9509 (2) | −0.0433 (8) | 0.5340 (2) | 0.074 (2) | 0.637 (7) |
F1 | 0.4373 (2) | 0.5397 (5) | 0.1577 (1) | 0.026 (1) | |
F2 | 0.3497 (2) | 0.7603 (6) | 0.1360 (2) | 0.029 (1) | |
F3 | 0.3075 (2) | 0.9537 (6) | 0.1954 (2) | 0.033 (1) | |
F4 | 0.3544 (2) | 0.9180 (6) | 0.2788 (2) | 0.032 (1) | |
F5 | 0.4432 (2) | 0.6960 (5) | 0.3030 (1) | 0.027 (1) | |
F6 | 0.3768 (2) | 0.4015 (5) | 0.2804 (1) | 0.025 (1) | |
F7 | 0.3575 (2) | 0.1791 (6) | 0.3380 (2) | 0.030 (1) | |
F8 | 0.4489 (2) | −0.0169 (6) | 0.3778 (2) | 0.034 (1) | |
F9 | 0.5623 (2) | 0.0159 (6) | 0.3572 (2) | 0.033 (1) | |
F10 | 0.5838 (2) | 0.2397 (5) | 0.2982 (2) | 0.025 (1) | |
F11 | 0.9031 (2) | 0.3541 (7) | 0.6718 (2) | 0.051 (2) | |
F12 | 0.9145 (2) | 0.5759 (8) | 0.6120 (2) | 0.062 (2) | |
F13 | 1.0162 (3) | 0.7672 (8) | 0.6152 (3) | 0.076 (2) | |
F14 | 1.1089 (2) | 0.7219 (7) | 0.6804 (3) | 0.068 (2) | |
F15 | 1.0987 (2) | 0.4992 (7) | 0.7416 (2) | 0.054 (2) | |
F16 | 0.9019 (2) | 0.1996 (6) | 0.8068 (2) | 0.049 (2) | |
F17 | 0.8113 (2) | −0.0129 (6) | 0.7877 (2) | 0.052 (2) | |
F18 | 0.7978 (2) | −0.1917 (6) | 0.7132 (2) | 0.050 (2) | |
F19 | 0.8799 (2) | −0.1555 (7) | 0.6593 (2) | 0.046 (1) | |
F20 | 0.9731 (2) | 0.0567 (7) | 0.6780 (2) | 0.043 (1) | |
Li1 | 0.3175 (7) | 0.864 (2) | 0.4987 (5) | 0.036 (3) | |
N1 | 0.3162 (3) | 1.3790 (8) | 0.4100 (2) | 0.020 (1) | |
N2 | 0.4297 (3) | 1.3223 (8) | 0.4386 (2) | 0.022 (1) | |
N3 | 0.2308 (3) | 0.3606 (8) | 0.5641 (2) | 0.027 (1) | |
N4 | 0.2619 (3) | 0.5701 (8) | 0.6273 (2) | 0.022 (1) | |
Pd1 | 0.35577 (2) | 1.17940 (7) | 0.44125 (2) | 0.0193 (2) | |
Pd2 | 0.27325 (3) | 0.58627 (7) | 0.56585 (2) | 0.0220 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
B1 | 0.013 (6) | 0.018 (6) | 0.033 (7) | 0.000 | 0.007 (5) | 0.000 |
B2 | 0.016 (7) | 0.015 (7) | 0.10 (1) | 0.000 | 0.011 (7) | 0.000 |
C1 | 0.020 (4) | 0.023 (4) | 0.034 (4) | 0.000 (3) | 0.004 (3) | −0.002 (3) |
C2 | 0.020 (4) | 0.031 (5) | 0.041 (5) | 0.004 (3) | 0.006 (4) | 0.003 (4) |
C3 | 0.028 (4) | 0.021 (4) | 0.030 (4) | 0.006 (3) | 0.009 (3) | 0.002 (3) |
C4 | 0.025 (4) | 0.016 (4) | 0.031 (4) | 0.003 (3) | 0.009 (3) | 0.000 (3) |
C5 | 0.018 (4) | 0.014 (4) | 0.029 (4) | 0.000 (3) | 0.009 (3) | −0.003 (3) |
C6 | 0.021 (4) | 0.013 (4) | 0.035 (4) | 0.000 (3) | 0.007 (3) | −0.004 (3) |
C7 | 0.026 (4) | 0.014 (4) | 0.032 (4) | 0.001 (3) | 0.012 (3) | 0.005 (3) |
C8 | 0.022 (4) | 0.017 (4) | 0.036 (4) | −0.001 (3) | 0.013 (3) | −0.002 (3) |
C9 | 0.019 (4) | 0.022 (4) | 0.044 (5) | 0.000 (3) | 0.008 (3) | 0.007 (4) |
C10 | 0.019 (4) | 0.014 (4) | 0.042 (5) | 0.005 (3) | 0.009 (3) | 0.007 (3) |
C11 | 0.034 (5) | 0.031 (5) | 0.041 (5) | 0.005 (4) | 0.009 (4) | 0.005 (4) |
C12 | 0.029 (5) | 0.025 (4) | 0.044 (5) | −0.006 (4) | 0.002 (4) | 0.001 (4) |
C13 | 0.019 (4) | 0.012 (4) | 0.046 (5) | −0.005 (3) | 0.013 (3) | 0.003 (3) |
C14 | 0.019 (4) | 0.021 (4) | 0.055 (5) | −0.003 (3) | 0.018 (4) | −0.002 (4) |
C15 | 0.027 (4) | 0.021 (4) | 0.058 (6) | −0.009 (4) | 0.021 (4) | −0.004 (4) |
C16 | 0.042 (5) | 0.023 (5) | 0.063 (6) | −0.011 (4) | 0.030 (5) | −0.015 (4) |
C17 | 0.033 (5) | 0.026 (5) | 0.049 (5) | −0.011 (4) | 0.017 (4) | −0.003 (4) |
C18 | 0.023 (4) | 0.012 (4) | 0.034 (4) | −0.002 (3) | 0.006 (3) | 0.004 (3) |
C19 | 0.015 (4) | 0.019 (4) | 0.039 (5) | 0.002 (3) | 0.009 (3) | −0.002 (3) |
C20 | 0.018 (4) | 0.020 (4) | 0.040 (5) | 0.007 (3) | 0.012 (3) | −0.002 (3) |
C21 | 0.017 (4) | 0.017 (4) | 0.046 (5) | 0.002 (3) | 0.014 (3) | 0.001 (4) |
C22 | 0.019 (4) | 0.013 (4) | 0.040 (5) | 0.002 (3) | 0.013 (3) | 0.007 (3) |
C23 | 0.033 (5) | 0.033 (5) | 0.058 (6) | −0.010 (4) | 0.021 (4) | −0.008 (4) |
C24 | 0.019 (4) | 0.018 (4) | 0.041 (5) | 0.001 (3) | 0.006 (3) | 0.002 (3) |
C25 | 0.019 (4) | 0.007 (3) | 0.036 (4) | −0.003 (3) | 0.012 (3) | 0.002 (3) |
C26 | 0.019 (4) | 0.012 (4) | 0.037 (4) | −0.002 (3) | 0.007 (3) | −0.002 (3) |
C27 | 0.017 (4) | 0.011 (4) | 0.043 (5) | −0.003 (3) | 0.007 (3) | 0.006 (3) |
C28 | 0.014 (4) | 0.010 (4) | 0.049 (5) | −0.001 (3) | 0.010 (3) | 0.002 (3) |
C29 | 0.020 (4) | 0.013 (4) | 0.048 (5) | −0.004 (3) | 0.018 (4) | −0.003 (3) |
C30 | 0.017 (4) | 0.012 (4) | 0.039 (5) | −0.008 (3) | 0.006 (3) | −0.003 (3) |
C31 | 0.019 (4) | 0.008 (3) | 0.036 (4) | −0.002 (3) | 0.009 (3) | −0.004 (3) |
C32 | 0.018 (4) | 0.011 (4) | 0.038 (4) | −0.001 (3) | 0.006 (3) | −0.005 (3) |
C33 | 0.018 (4) | 0.017 (4) | 0.034 (4) | −0.002 (3) | 0.012 (3) | −0.003 (3) |
C34 | 0.038 (5) | 0.011 (4) | 0.034 (4) | −0.005 (3) | 0.016 (4) | −0.002 (3) |
C35 | 0.026 (4) | 0.016 (4) | 0.031 (4) | 0.004 (3) | 0.005 (3) | −0.002 (3) |
C36 | 0.015 (4) | 0.014 (4) | 0.037 (4) | 0.000 (3) | 0.009 (3) | −0.009 (3) |
C37 | 0.015 (4) | 0.015 (4) | 0.103 (8) | 0.005 (3) | 0.013 (5) | 0.007 (5) |
C38 | 0.013 (4) | 0.026 (5) | 0.110 (9) | 0.004 (4) | 0.014 (5) | 0.020 (5) |
C39 | 0.023 (5) | 0.033 (6) | 0.107 (9) | 0.006 (4) | 0.009 (5) | 0.024 (6) |
C40 | 0.034 (6) | 0.028 (5) | 0.14 (1) | 0.004 (4) | 0.031 (7) | 0.033 (6) |
C41 | 0.022 (5) | 0.019 (5) | 0.13 (1) | −0.005 (4) | 0.023 (6) | 0.012 (6) |
C42 | 0.013 (4) | 0.023 (5) | 0.12 (1) | 0.005 (4) | 0.009 (5) | 0.011 (5) |
C43 | 0.014 (4) | 0.013 (4) | 0.073 (6) | 0.004 (3) | 0.006 (4) | −0.002 (4) |
C44 | 0.013 (4) | 0.015 (4) | 0.077 (7) | 0.003 (3) | 0.012 (4) | −0.002 (4) |
C45 | 0.014 (4) | 0.018 (4) | 0.096 (8) | 0.002 (3) | 0.016 (5) | 0.010 (5) |
C46 | 0.014 (4) | 0.011 (4) | 0.100 (8) | −0.006 (3) | 0.013 (5) | −0.001 (5) |
C47 | 0.021 (4) | 0.019 (4) | 0.072 (7) | 0.003 (3) | −0.001 (4) | 0.004 (4) |
C48 | 0.015 (4) | 0.024 (5) | 0.068 (6) | 0.005 (3) | 0.005 (4) | 0.018 (4) |
C49 | 0.08 (2) | 0.30 (6) | 0.08 (2) | 0.03 (3) | −0.02 (2) | −0.11 (3) |
C50 | 0.08 (1) | 0.12 (2) | 0.05 (1) | 0.02 (1) | 0.02 (1) | 0.00 (1) |
Cl1 | 0.0210 (9) | 0.0207 (9) | 0.038 (1) | −0.0050 (7) | 0.0087 (8) | 0.0021 (8) |
Cl2 | 0.0226 (9) | 0.0136 (9) | 0.042 (1) | 0.0011 (7) | 0.0103 (8) | 0.0071 (8) |
Cl3 | 0.046 (1) | 0.022 (1) | 0.038 (1) | −0.0126 (9) | 0.017 (1) | −0.0023 (9) |
Cl4 | 0.036 (1) | 0.0164 (9) | 0.039 (1) | −0.0091 (8) | 0.0098 (9) | 0.0021 (8) |
Cl5 | 0.035 (3) | 0.069 (4) | 0.081 (4) | 0.009 (2) | 0.010 (2) | −0.014 (3) |
Cl6 | 0.047 (3) | 0.044 (3) | 0.139 (6) | −0.006 (2) | 0.006 (3) | 0.005 (3) |
Cl7 | 0.043 (2) | 0.043 (2) | 0.084 (3) | −0.019 (2) | 0.024 (2) | −0.029 (2) |
Cl8 | 0.059 (3) | 0.093 (4) | 0.072 (3) | 0.016 (3) | 0.015 (2) | −0.009 (3) |
F1 | 0.026 (2) | 0.020 (2) | 0.032 (2) | 0.009 (2) | 0.009 (2) | 0.000 (2) |
F2 | 0.022 (2) | 0.017 (2) | 0.047 (3) | 0.004 (2) | 0.008 (2) | 0.009 (2) |
F3 | 0.022 (2) | 0.016 (2) | 0.063 (3) | 0.010 (2) | 0.013 (2) | 0.006 (2) |
F4 | 0.026 (2) | 0.017 (2) | 0.055 (3) | 0.003 (2) | 0.017 (2) | −0.011 (2) |
F5 | 0.026 (2) | 0.021 (2) | 0.036 (3) | −0.002 (2) | 0.010 (2) | −0.007 (2) |
F6 | 0.012 (2) | 0.022 (2) | 0.043 (3) | −0.000 (2) | 0.010 (2) | 0.003 (2) |
F7 | 0.025 (2) | 0.022 (2) | 0.048 (3) | −0.007 (2) | 0.020 (2) | 0.000 (2) |
F8 | 0.048 (3) | 0.014 (2) | 0.046 (3) | 0.002 (2) | 0.024 (2) | 0.008 (2) |
F9 | 0.033 (3) | 0.018 (2) | 0.049 (3) | 0.009 (2) | 0.009 (2) | 0.008 (2) |
F10 | 0.014 (2) | 0.019 (2) | 0.045 (3) | 0.006 (2) | 0.010 (2) | 0.003 (2) |
F11 | 0.013 (2) | 0.032 (3) | 0.106 (5) | −0.001 (2) | 0.004 (3) | 0.026 (3) |
F12 | 0.027 (3) | 0.050 (4) | 0.108 (5) | 0.004 (3) | 0.010 (3) | 0.040 (4) |
F13 | 0.041 (3) | 0.042 (4) | 0.148 (7) | 0.000 (3) | 0.028 (4) | 0.044 (4) |
F14 | 0.029 (3) | 0.025 (3) | 0.155 (7) | −0.009 (2) | 0.027 (4) | 0.013 (4) |
F15 | 0.017 (3) | 0.025 (3) | 0.121 (5) | −0.004 (2) | 0.007 (3) | 0.001 (3) |
F16 | 0.024 (3) | 0.026 (3) | 0.102 (5) | −0.007 (2) | 0.024 (3) | −0.022 (3) |
F17 | 0.027 (3) | 0.024 (3) | 0.111 (5) | −0.005 (2) | 0.034 (3) | −0.015 (3) |
F18 | 0.026 (3) | 0.023 (3) | 0.101 (5) | −0.014 (2) | 0.013 (3) | −0.005 (3) |
F19 | 0.028 (3) | 0.035 (3) | 0.071 (4) | −0.008 (2) | −0.002 (3) | 0.006 (3) |
F20 | 0.022 (3) | 0.033 (3) | 0.072 (4) | −0.007 (2) | 0.007 (2) | 0.008 (3) |
Li1 | 0.035 (8) | 0.038 (9) | 0.037 (8) | 0.003 (7) | 0.013 (6) | 0.000 (7) |
N1 | 0.016 (3) | 0.013 (3) | 0.031 (3) | 0.000 (2) | 0.006 (3) | −0.004 (3) |
N2 | 0.020 (3) | 0.012 (3) | 0.035 (4) | −0.001 (3) | 0.007 (3) | 0.005 (3) |
N3 | 0.026 (4) | 0.016 (3) | 0.041 (4) | −0.006 (3) | 0.014 (3) | −0.004 (3) |
N4 | 0.020 (3) | 0.017 (3) | 0.032 (4) | 0.001 (3) | 0.013 (3) | 0.003 (3) |
Pd1 | 0.0163 (3) | 0.0106 (3) | 0.0326 (3) | 0.0000 (2) | 0.0087 (2) | 0.0015 (2) |
Pd2 | 0.0220 (3) | 0.0119 (3) | 0.0343 (3) | −0.0041 (2) | 0.0108 (2) | −0.0003 (2) |
B1—C25i | 1.66 (1) | C37—C42 | 1.39 (1) |
B1—C25 | 1.66 (1) | C38—F11 | 1.37 (1) |
B1—C31i | 1.66 (1) | C38—C39 | 1.37 (1) |
B1—C31 | 1.66 (1) | C39—F12 | 1.33 (1) |
B2—C37 | 1.64 (1) | C39—C40 | 1.38 (1) |
B2—C37ii | 1.64 (1) | C40—C41 | 1.35 (2) |
B2—C43 | 1.66 (1) | C40—F13 | 1.36 (1) |
B2—C43ii | 1.66 (1) | C41—F14 | 1.34 (1) |
C1—N1 | 1.34 (1) | C41—C42 | 1.39 (2) |
C1—C2 | 1.39 (1) | C42—F15 | 1.35 (1) |
C1—H1 | 0.9500 | C43—C44 | 1.38 (1) |
C2—C3 | 1.39 (1) | C43—C48 | 1.42 (1) |
C2—H2 | 0.9500 | C44—F16 | 1.35 (1) |
C3—C4 | 1.39 (1) | C44—C45 | 1.37 (1) |
C3—C11 | 1.49 (1) | C45—F17 | 1.36 (1) |
C4—C5 | 1.39 (1) | C45—C46 | 1.37 (2) |
C5—N1 | 1.345 (9) | C46—F18 | 1.340 (9) |
C5—C6 | 1.48 (1) | C46—C47 | 1.38 (1) |
C6—N2 | 1.36 (1) | C47—F19 | 1.35 (1) |
C6—C7 | 1.38 (1) | C47—C48 | 1.37 (1) |
C7—C8 | 1.38 (1) | C48—F20 | 1.35 (1) |
C8—C9 | 1.40 (1) | C49—Cl6 | 1.53 (4) |
C8—C12 | 1.50 (1) | C49—Cl5 | 1.85 (4) |
C9—C10 | 1.38 (1) | C50—Cl7 | 1.76 (2) |
C10—N2 | 1.35 (1) | C50—Cl8 | 1.78 (2) |
C13—N3 | 1.35 (1) | Cl1—Pd1 | 2.306 (2) |
C13—C14 | 1.40 (1) | Cl2—Pd1 | 2.313 (2) |
C13—C22 | 1.45 (1) | Cl3—Pd2 | 2.292 (2) |
C14—C15 | 1.36 (1) | Cl4—Pd2 | 2.306 (2) |
C15—C16 | 1.40 (1) | Cl1—Li1 | 2.35 (2) |
C15—C23 | 1.50 (1) | Cl2—Li1 | 2.35 (2) |
C16—C17 | 1.40 (1) | Cl3—Li1 | 2.35 (2) |
C17—N3 | 1.33 (1) | Cl4—Li1 | 2.34 (2) |
C18—N4 | 1.34 (1) | N1—Pd1 | 2.004 (6) |
C18—C19 | 1.40 (1) | N2—Pd1 | 2.018 (6) |
C19—C20 | 1.39 (1) | N3—Pd2 | 2.024 (6) |
C20—C21 | 1.40 (1) | N4—Pd2 | 2.010 (6) |
C20—C24 | 1.49 (1) | C4—H4 | 0.9500 |
C21—C22 | 1.38 (1) | C7—H7 | 0.9500 |
C22—N4 | 1.374 (9) | C9—H9 | 0.9500 |
C25—C30 | 1.39 (1) | C10—H10 | 0.9500 |
C25—C26 | 1.39 (1) | C11—H11A | 0.9800 |
C26—F1 | 1.361 (9) | C11—H11B | 0.9800 |
C26—C27 | 1.38 (1) | C11—H11C | 0.9800 |
C27—F2 | 1.334 (9) | C12—H12A | 0.9800 |
C27—C28 | 1.39 (1) | C12—H12B | 0.9800 |
C28—F3 | 1.342 (8) | C12—H12C | 0.9800 |
C28—C29 | 1.36 (1) | C16—H16 | 0.9500 |
C29—F4 | 1.351 (9) | C17—H17 | 0.9500 |
C29—C30 | 1.39 (1) | C18—H18 | 0.9500 |
C30—F5 | 1.361 (9) | C19—H19 | 0.9500 |
C31—C36 | 1.38 (1) | C21—H21 | 0.9500 |
C31—C32 | 1.38 (1) | C23—H23A | 0.9800 |
C32—F6 | 1.363 (9) | C23—H23B | 0.9800 |
C32—C33 | 1.38 (1) | C23—H23C | 0.9800 |
C33—F7 | 1.343 (8) | C24—H24A | 0.9800 |
C33—C34 | 1.36 (1) | C24—H24B | 0.9800 |
C34—F8 | 1.352 (9) | C24—H24C | 0.9800 |
C34—C35 | 1.38 (1) | C49—H49A | 0.9900 |
C35—F9 | 1.354 (9) | C49—H49B | 0.9900 |
C35—C36 | 1.36 (1) | C50—H50A | 0.9900 |
C36—F10 | 1.371 (8) | C50—H50B | 0.9900 |
C37—C38 | 1.39 (2) | ||
C25i—B1—C25 | 102.3 (8) | C45—C44—C43 | 123.9 (9) |
C25i—B1—C31i | 112.6 (3) | F17—C45—C46 | 118.8 (8) |
C25—B1—C31i | 113.3 (4) | F17—C45—C44 | 120 (1) |
C25i—B1—C31 | 113.3 (4) | C46—C45—C44 | 120.8 (9) |
C25—B1—C31 | 112.6 (3) | F18—C46—C45 | 122.0 (8) |
C31i—B1—C31 | 103.0 (8) | F18—C46—C47 | 119.7 (9) |
C37—B2—C37ii | 103 (1) | C45—C46—C47 | 118.3 (8) |
C37—B2—C43 | 113.5 (5) | F19—C47—C48 | 120.5 (9) |
C37ii—B2—C43 | 113.1 (4) | F19—C47—C46 | 119.5 (8) |
C37—B2—C43ii | 113.1 (4) | C48—C47—C46 | 120 (1) |
C37ii—B2—C43ii | 113.5 (5) | F20—C48—C47 | 117.2 (9) |
C43—B2—C43ii | 101.5 (9) | F20—C48—C43 | 119.0 (7) |
N1—C1—C2 | 122.4 (7) | C47—C48—C43 | 123.7 (9) |
C1—C2—C3 | 120.2 (8) | Cl6—C49—Cl5 | 117 (2) |
C2—C3—C4 | 116.8 (7) | Cl7—C50—Cl8 | 111 (1) |
C2—C3—C11 | 120.2 (7) | Pd1—Cl1—Li1 | 89.8 (4) |
C4—C3—C11 | 123.0 (8) | Pd1—Cl2—Li1 | 89.6 (4) |
C3—C4—C5 | 120.5 (7) | Pd2—Cl3—Li1 | 91.3 (4) |
N1—C5—C4 | 121.8 (7) | Pd2—Cl4—Li1 | 91.3 (4) |
N1—C5—C6 | 115.1 (6) | Cl4—Li1—Cl3 | 87.0 (5) |
C4—C5—C6 | 123.1 (7) | Cl4—Li1—Cl2 | 115.9 (6) |
N2—C6—C7 | 121.0 (7) | Cl3—Li1—Cl2 | 123.1 (6) |
N2—C6—C5 | 113.9 (6) | Cl4—Li1—Cl1 | 133.4 (7) |
C7—C6—C5 | 125.0 (7) | Cl3—Li1—Cl1 | 115.2 (6) |
C8—C7—C6 | 121.0 (7) | Cl2—Li1—Cl1 | 86.8 (5) |
C7—C8—C9 | 117.0 (7) | C1—N1—C5 | 118.3 (7) |
C7—C8—C12 | 121.2 (7) | C1—N1—Pd1 | 126.5 (5) |
C9—C8—C12 | 121.8 (7) | C5—N1—Pd1 | 115.2 (5) |
C10—C9—C8 | 120.3 (7) | C10—N2—C6 | 118.9 (6) |
N2—C10—C9 | 121.7 (7) | C10—N2—Pd1 | 126.2 (5) |
N3—C13—C14 | 119.1 (8) | C6—N2—Pd1 | 114.8 (5) |
N3—C13—C22 | 116.7 (6) | C17—N3—C13 | 120.5 (7) |
C14—C13—C22 | 124.2 (7) | C17—N3—Pd2 | 125.9 (6) |
C15—C14—C13 | 122.1 (8) | C13—N3—Pd2 | 113.6 (5) |
C14—C15—C16 | 117.0 (8) | C18—N4—C22 | 118.6 (6) |
C14—C15—C23 | 122.0 (8) | C18—N4—Pd2 | 126.7 (5) |
C16—C15—C23 | 121.0 (8) | C22—N4—Pd2 | 114.6 (5) |
C17—C16—C15 | 119.4 (9) | N1—Pd1—N2 | 80.7 (2) |
N3—C17—C16 | 121.8 (8) | N3—Pd2—N4 | 81.0 (3) |
N4—C18—C19 | 122.4 (7) | N1—Pd1—Cl1 | 95.0 (2) |
C20—C19—C18 | 119.7 (8) | N2—Pd1—Cl1 | 174.4 (2) |
C19—C20—C21 | 116.9 (7) | N1—Pd1—Cl2 | 176.1 (2) |
C19—C20—C24 | 122.5 (8) | N2—Pd1—Cl2 | 95.7 (2) |
C21—C20—C24 | 120.5 (7) | N3—Pd2—Cl3 | 94.8 (2) |
C22—C21—C20 | 121.6 (7) | N4—Pd2—Cl3 | 175.4 (2) |
N4—C22—C21 | 120.7 (7) | N4—Pd2—Cl4 | 95.2 (2) |
N4—C22—C13 | 114.1 (7) | Cl1—Pd1—Cl2 | 88.69 (7) |
C21—C22—C13 | 125.1 (7) | Cl3—Pd2—Cl4 | 88.97 (7) |
C30—C25—C26 | 113.1 (7) | N1—C1—H1 | 118.8 |
C30—C25—B1 | 119.4 (6) | C2—C1—H1 | 118.8 |
C26—C25—B1 | 127.4 (6) | C1—C2—H2 | 119.9 |
F1—C26—C27 | 114.1 (7) | C3—C2—H2 | 119.9 |
F1—C26—C25 | 121.0 (6) | C3—C4—H4 | 119.8 |
C27—C26—C25 | 124.9 (7) | C5—C4—H4 | 119.8 |
F2—C27—C26 | 121.7 (7) | C8—C7—H7 | 119.5 |
F2—C27—C28 | 119.8 (7) | C6—C7—H7 | 119.5 |
C26—C27—C28 | 118.5 (7) | C10—C9—H9 | 119.8 |
F3—C28—C29 | 121.4 (7) | C8—C9—H9 | 119.8 |
F3—C28—C27 | 119.3 (7) | N2—C10—H10 | 119.1 |
C29—C28—C27 | 119.3 (7) | C9—C10—H10 | 119.1 |
F4—C29—C28 | 119.1 (7) | C3—C11—H11A | 109.5 |
F4—C29—C30 | 120.8 (8) | C3—C11—H11B | 109.5 |
C28—C29—C30 | 120.0 (7) | H11A—C11—H11B | 109.5 |
F5—C30—C25 | 119.7 (7) | C3—C11—H11C | 109.5 |
F5—C30—C29 | 116.2 (7) | H11A—C11—H11C | 109.5 |
C25—C30—C29 | 124.1 (8) | H11B—C11—H11C | 109.5 |
C36—C31—C32 | 112.9 (7) | C8—C12—H12A | 109.5 |
C36—C31—B1 | 119.3 (6) | C8—C12—H12B | 109.5 |
C32—C31—B1 | 127.6 (6) | H12A—C12—H12B | 109.5 |
F6—C32—C31 | 120.9 (7) | C8—C12—H12C | 109.5 |
F6—C32—C33 | 114.7 (6) | H12A—C12—H12C | 109.5 |
C31—C32—C33 | 124.4 (7) | H12B—C12—H12C | 109.5 |
F7—C33—C34 | 121.0 (7) | C15—C14—H14 | 118.9 |
F7—C33—C32 | 119.9 (7) | C13—C14—H14 | 118.9 |
C34—C33—C32 | 119.1 (7) | C17—C16—H16 | 120.3 |
F8—C34—C33 | 119.8 (7) | C15—C16—H16 | 120.3 |
F8—C34—C35 | 120.6 (7) | N3—C17—H17 | 119.1 |
C33—C34—C35 | 119.6 (7) | C16—C17—H17 | 119.1 |
F9—C35—C36 | 122.7 (7) | N4—C18—H18 | 118.8 |
F9—C35—C34 | 118.8 (7) | C19—C18—H18 | 118.8 |
C36—C35—C34 | 118.5 (7) | C20—C19—H19 | 120.2 |
C35—C36—F10 | 115.0 (6) | C18—C19—H19 | 120.2 |
C35—C36—C31 | 125.4 (7) | C22—C21—H21 | 119.2 |
F10—C36—C31 | 119.6 (7) | C20—C21—H21 | 119.2 |
C38—C37—C42 | 112.3 (9) | C15—C23—H23A | 109.5 |
C38—C37—B2 | 128.4 (7) | C15—C23—H23B | 109.5 |
C42—C37—B2 | 119.1 (9) | H23A—C23—H23B | 109.5 |
F11—C38—C39 | 114.0 (9) | C15—C23—H23C | 109.5 |
F11—C38—C37 | 120.1 (9) | H23A—C23—H23C | 109.5 |
C39—C38—C37 | 125.7 (9) | H23B—C23—H23C | 109.5 |
F12—C39—C38 | 121.6 (9) | C20—C24—H24A | 109.5 |
F12—C39—C40 | 120 (1) | C20—C24—H24B | 109.5 |
C38—C39—C40 | 118 (1) | H24A—C24—H24B | 109.5 |
C41—C40—F13 | 120.0 (9) | C20—C24—H24C | 109.5 |
C41—C40—C39 | 121 (1) | H24A—C24—H24C | 109.5 |
F13—C40—C39 | 119 (1) | H24B—C24—H24C | 109.5 |
F14—C41—C40 | 121 (1) | Cl6—C49—H49A | 108.1 |
F14—C41—C42 | 120 (1) | Cl5—C49—H49A | 108.1 |
C40—C41—C42 | 118.4 (9) | Cl6—C49—H49B | 108.1 |
F15—C42—C41 | 116.1 (8) | Cl5—C49—H49B | 108.1 |
F15—C42—C37 | 119.1 (9) | H49A—C49—H49B | 107.3 |
C41—C42—C37 | 125 (1) | Cl7—C50—H50A | 109.5 |
C44—C43—C48 | 113.3 (8) | Cl8—C50—H50A | 109.5 |
C44—C43—B2 | 128.1 (8) | Cl7—C50—H50B | 109.5 |
C48—C43—B2 | 118.5 (7) | Cl8—C50—H50B | 109.5 |
F16—C44—C45 | 115.2 (8) | H50A—C50—H50B | 108.1 |
F16—C44—C43 | 120.9 (7) | ||
N1—C1—C2—C3 | −1 (1) | F13—C40—C41—F14 | 0 (2) |
C1—C2—C3—C4 | 2 (1) | C39—C40—C41—F14 | 180 (1) |
C1—C2—C3—C11 | −178.5 (8) | F13—C40—C41—C42 | −180 (1) |
C2—C3—C4—C5 | −1 (1) | C39—C40—C41—C42 | −0 (2) |
C11—C3—C4—C5 | 179.0 (7) | F14—C41—C42—F15 | 2 (2) |
C3—C4—C5—N1 | −0 (1) | C40—C41—C42—F15 | −178 (1) |
C3—C4—C5—C6 | 177.8 (7) | F14—C41—C42—C37 | −179 (1) |
N1—C5—C6—N2 | 2 (1) | C40—C41—C42—C37 | 2 (2) |
C4—C5—C6—N2 | −176.4 (7) | C38—C37—C42—F15 | 178.1 (9) |
N1—C5—C6—C7 | −176.6 (7) | B2—C37—C42—F15 | 2 (1) |
C4—C5—C6—C7 | 5 (1) | C38—C37—C42—C41 | −1 (2) |
N2—C6—C7—C8 | 1 (1) | B2—C37—C42—C41 | −177 (1) |
C5—C6—C7—C8 | 179.3 (7) | C37—B2—C43—C44 | −126.6 (9) |
C6—C7—C8—C9 | 1 (1) | C37ii—B2—C43—C44 | −10 (1) |
C6—C7—C8—C12 | −178.1 (7) | C43ii—B2—C43—C44 | 112 (1) |
C7—C8—C9—C10 | −2 (1) | C37—B2—C43—C48 | 56 (1) |
C12—C8—C9—C10 | 177.4 (8) | C37ii—B2—C43—C48 | 172.0 (7) |
C8—C9—C10—N2 | 0 (1) | C43ii—B2—C43—C48 | −66.1 (6) |
N3—C13—C14—C15 | 2 (1) | C48—C43—C44—F16 | 177.0 (7) |
C22—C13—C14—C15 | −176.7 (8) | B2—C43—C44—F16 | −1 (1) |
C13—C14—C15—C16 | −2 (1) | C48—C43—C44—C45 | −3 (1) |
C13—C14—C15—C23 | 179.7 (8) | B2—C43—C44—C45 | 178.8 (8) |
C14—C15—C16—C17 | 2 (1) | F16—C44—C45—F17 | 0 (1) |
C23—C15—C16—C17 | 179.4 (9) | C43—C44—C45—F17 | −179.0 (8) |
C15—C16—C17—N3 | −0 (1) | F16—C44—C45—C46 | −179.0 (8) |
N4—C18—C19—C20 | −1 (1) | C43—C44—C45—C46 | 1 (1) |
C18—C19—C20—C21 | −1 (1) | F17—C45—C46—F18 | 2 (1) |
C18—C19—C20—C24 | 176.4 (7) | C44—C45—C46—F18 | −178.0 (8) |
C19—C20—C21—C22 | 2 (1) | F17—C45—C46—C47 | −178.8 (8) |
C24—C20—C21—C22 | −175.6 (7) | C44—C45—C46—C47 | 1 (1) |
C20—C21—C22—N4 | −1 (1) | F18—C46—C47—F19 | 0 (1) |
C20—C21—C22—C13 | 176.6 (7) | C45—C46—C47—F19 | −178.5 (8) |
N3—C13—C22—N4 | 3 (1) | F18—C46—C47—C48 | 178.2 (8) |
C14—C13—C22—N4 | −178.1 (7) | C45—C46—C47—C48 | −1 (1) |
N3—C13—C22—C21 | −175.0 (7) | F19—C47—C48—F20 | −2 (1) |
C14—C13—C22—C21 | 4 (1) | C46—C47—C48—F20 | −179.3 (8) |
C25i—B1—C25—C30 | −63.5 (6) | F19—C47—C48—C43 | 176.1 (8) |
C31i—B1—C25—C30 | 174.9 (6) | C46—C47—C48—C43 | −2 (1) |
C31—B1—C25—C30 | 58.5 (9) | C44—C43—C48—F20 | −178.9 (7) |
C25i—B1—C25—C26 | 110.9 (8) | B2—C43—C48—F20 | −1 (1) |
C31i—B1—C25—C26 | −11 (1) | C44—C43—C48—C47 | 4 (1) |
C31—B1—C25—C26 | −127.1 (7) | B2—C43—C48—C47 | −178.3 (8) |
C30—C25—C26—F1 | 177.3 (6) | Pd2—Cl4—Li1—Cl3 | −8.9 (4) |
B1—C25—C26—F1 | 3 (1) | Pd2—Cl4—Li1—Cl2 | −134.6 (6) |
C30—C25—C26—C27 | −3 (1) | Pd2—Cl4—Li1—Cl1 | 113.5 (9) |
B1—C25—C26—C27 | −178.1 (7) | Pd2—Cl3—Li1—Cl4 | 9.0 (4) |
F1—C26—C27—F2 | 1 (1) | Pd2—Cl3—Li1—Cl2 | 128.2 (7) |
C25—C26—C27—F2 | −178.3 (7) | Pd2—Cl3—Li1—Cl1 | −128.4 (5) |
F1—C26—C27—C28 | −178.7 (6) | Pd1—Cl2—Li1—Cl4 | −120.7 (6) |
C25—C26—C27—C28 | 2 (1) | Pd1—Cl2—Li1—Cl3 | 135.1 (7) |
F2—C27—C28—F3 | 0 (1) | Pd1—Cl2—Li1—Cl1 | 16.9 (4) |
C26—C27—C28—F3 | −179.9 (6) | Pd1—Cl1—Li1—Cl4 | 106.4 (9) |
F2—C27—C28—C29 | −179.5 (6) | Pd1—Cl1—Li1—Cl3 | −142.3 (5) |
C26—C27—C28—C29 | 0 (1) | Pd1—Cl1—Li1—Cl2 | −16.9 (4) |
F3—C28—C29—F4 | 2 (1) | C2—C1—N1—C5 | −0 (1) |
C27—C28—C29—F4 | −178.4 (6) | C2—C1—N1—Pd1 | −179.9 (6) |
F3—C28—C29—C30 | 179.5 (6) | C4—C5—N1—C1 | 1 (1) |
C27—C28—C29—C30 | −1 (1) | C6—C5—N1—C1 | −177.4 (7) |
C26—C25—C30—F5 | −178.8 (6) | C4—C5—N1—Pd1 | −179.5 (6) |
B1—C25—C30—F5 | −4 (1) | C6—C5—N1—Pd1 | 2.4 (8) |
C26—C25—C30—C29 | 3 (1) | C9—C10—N2—C6 | 2 (1) |
B1—C25—C30—C29 | 178.1 (7) | C9—C10—N2—Pd1 | −173.6 (6) |
F4—C29—C30—F5 | −2 (1) | C7—C6—N2—C10 | −3 (1) |
C28—C29—C30—F5 | −179.4 (6) | C5—C6—N2—C10 | 179.0 (7) |
F4—C29—C30—C25 | 176.7 (6) | C7—C6—N2—Pd1 | 173.4 (6) |
C28—C29—C30—C25 | −1 (1) | C5—C6—N2—Pd1 | −4.9 (8) |
C25i—B1—C31—C36 | −59.2 (9) | C16—C17—N3—C13 | 0 (1) |
C25—B1—C31—C36 | −174.8 (6) | C16—C17—N3—Pd2 | −179.9 (7) |
C31i—B1—C31—C36 | 62.7 (6) | C14—C13—N3—C17 | −1 (1) |
C25i—B1—C31—C32 | 126.3 (7) | C22—C13—N3—C17 | 178.0 (7) |
C25—B1—C31—C32 | 11 (1) | C14—C13—N3—Pd2 | 179.1 (6) |
C31i—B1—C31—C32 | −111.7 (8) | C22—C13—N3—Pd2 | −1.8 (9) |
C36—C31—C32—F6 | −176.4 (6) | C19—C18—N4—C22 | 1 (1) |
B1—C31—C32—F6 | −2 (1) | C19—C18—N4—Pd2 | −174.0 (5) |
C36—C31—C32—C33 | 2 (1) | C21—C22—N4—C18 | −0 (1) |
B1—C31—C32—C33 | 177.2 (7) | C13—C22—N4—C18 | −178.4 (7) |
F6—C32—C33—F7 | 0 (1) | C21—C22—N4—Pd2 | 175.5 (5) |
C31—C32—C33—F7 | −179.0 (7) | C13—C22—N4—Pd2 | −2.5 (8) |
F6—C32—C33—C34 | 177.7 (7) | C1—N1—Pd1—N2 | 175.8 (7) |
C31—C32—C33—C34 | −1 (1) | C5—N1—Pd1—N2 | −4.0 (5) |
F7—C33—C34—F8 | −2 (1) | C1—N1—Pd1—Cl1 | −7.8 (6) |
C32—C33—C34—F8 | −179.5 (7) | C5—N1—Pd1—Cl1 | 172.4 (5) |
F7—C33—C34—C35 | 177.5 (7) | C1—N1—Pd1—Cl2 | 155 (2) |
C32—C33—C34—C35 | −0 (1) | C5—N1—Pd1—Cl2 | −25 (3) |
F8—C34—C35—F9 | −1 (1) | C10—N2—Pd1—N1 | −179.4 (7) |
C33—C34—C35—F9 | 179.6 (7) | C6—N2—Pd1—N1 | 4.9 (5) |
F8—C34—C35—C36 | 179.6 (7) | C10—N2—Pd1—Cl1 | 140 (2) |
C33—C34—C35—C36 | 0 (1) | C6—N2—Pd1—Cl1 | −36 (2) |
F9—C35—C36—F10 | 1 (1) | C10—N2—Pd1—Cl2 | −0.8 (7) |
C34—C35—C36—F10 | −179.6 (7) | C6—N2—Pd1—Cl2 | −176.5 (5) |
F9—C35—C36—C31 | −178.1 (7) | Li1—Cl1—Pd1—N1 | −164.0 (4) |
C34—C35—C36—C31 | 1 (1) | Li1—Cl1—Pd1—N2 | −124 (2) |
C32—C31—C36—C35 | −2 (1) | Li1—Cl1—Pd1—Cl2 | 17.2 (4) |
B1—C31—C36—C35 | −177.7 (7) | Li1—Cl2—Pd1—N1 | −180 (100) |
C32—C31—C36—F10 | 178.3 (6) | Li1—Cl2—Pd1—N2 | 159.2 (4) |
B1—C31—C36—F10 | 3 (1) | Li1—Cl2—Pd1—Cl1 | −17.2 (4) |
C37ii—B2—C37—C38 | −110 (1) | C18—N4—Pd2—N3 | 176.7 (7) |
C43—B2—C37—C38 | 12 (1) | C22—N4—Pd2—N3 | 1.2 (5) |
C43ii—B2—C37—C38 | 127.1 (9) | C18—N4—Pd2—Cl3 | 153 (2) |
C37ii—B2—C37—C42 | 65.3 (8) | C22—N4—Pd2—Cl3 | −23 (3) |
C43—B2—C37—C42 | −172.3 (8) | C18—N4—Pd2—Cl4 | −4.2 (6) |
C43ii—B2—C37—C42 | −57 (1) | C22—N4—Pd2—Cl4 | −179.7 (5) |
C42—C37—C38—F11 | −176.8 (9) | C17—N3—Pd2—N4 | −179.5 (7) |
B2—C37—C38—F11 | −1 (2) | C13—N3—Pd2—N4 | 0.4 (5) |
C42—C37—C38—C39 | −1 (2) | C17—N3—Pd2—Cl3 | −1.3 (7) |
B2—C37—C38—C39 | 175 (1) | C13—N3—Pd2—Cl3 | 178.5 (5) |
F11—C38—C39—F12 | −5 (2) | C17—N3—Pd2—Cl4 | 167 (3) |
C37—C38—C39—F12 | 179 (1) | C13—N3—Pd2—Cl4 | −14 (3) |
F11—C38—C39—C40 | 178 (1) | Li1—Cl3—Pd2—N4 | −166 (2) |
C37—C38—C39—C40 | 2 (2) | Li1—Cl3—Pd2—N3 | 170.1 (4) |
F12—C39—C40—C41 | −178 (1) | Li1—Cl3—Pd2—Cl4 | −9.1 (4) |
C38—C39—C40—C41 | −1 (2) | Li1—Cl4—Pd2—N4 | −172.7 (4) |
F12—C39—C40—F13 | 1 (2) | Li1—Cl4—Pd2—N3 | −159 (3) |
C38—C39—C40—F13 | 178 (1) | Li1—Cl4—Pd2—Cl3 | 9.1 (4) |
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+2, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [LiPd2Cl4(C12H12N2)2](C24F20B)·1.196CD2Cl2 |
Mr | 1513.06 |
Crystal system, space group | Monoclinic, P2/c |
Temperature (K) | 100 |
a, b, c (Å) | 22.361 (6), 7.939 (2), 31.754 (9) |
β (°) | 98.621 (5) |
V (Å3) | 5573 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.06 |
Crystal size (mm) | 0.40 × 0.16 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.676, 0.901 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 27015, 9813, 8967 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.076, 0.182, 1.25 |
No. of reflections | 9813 |
No. of parameters | 782 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
w = 1/[σ2(Fo2) + (0.0574P)2 + 46.4907P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.82, −1.38 |
Computer programs: SMART (Bruker,2001), SAINT-Plus (Bruker,1999), SAINT-Plus, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker,1998), SHELXTL.
Cl1—Pd1 | 2.306 (2) | Cl3—Li1 | 2.35 (2) |
Cl2—Pd1 | 2.313 (2) | Cl4—Li1 | 2.34 (2) |
Cl3—Pd2 | 2.292 (2) | N1—Pd1 | 2.004 (6) |
Cl4—Pd2 | 2.306 (2) | N2—Pd1 | 2.018 (6) |
Cl1—Li1 | 2.35 (2) | N3—Pd2 | 2.024 (6) |
Cl2—Li1 | 2.35 (2) | N4—Pd2 | 2.010 (6) |
Cl4—Li1—Cl3 | 87.0 (5) | N2—Pd1—Cl2 | 95.7 (2) |
Cl2—Li1—Cl1 | 86.8 (5) | N3—Pd2—Cl3 | 94.8 (2) |
N1—Pd1—N2 | 80.7 (2) | N4—Pd2—Cl3 | 175.4 (2) |
N3—Pd2—N4 | 81.0 (3) | N4—Pd2—Cl4 | 95.2 (2) |
N1—Pd1—Cl1 | 95.0 (2) | Cl1—Pd1—Cl2 | 88.69 (7) |
N2—Pd1—Cl1 | 174.4 (2) | Cl3—Pd2—Cl4 | 88.97 (7) |
N1—Pd1—Cl2 | 176.1 (2) |
The reaction of (Me2bipy)Pd(Me)Cl (Me2bipy is 4,4'-Me2-2,2'-bipyridine) with [Li(Et2O)2.4][B(C6F5)4] (0.5 equivalent) in CD2Cl2 solution (296 K) quantitatively yields the dinuclear monocationic complex [{(Me2bipy)PdMe}2(µ-Cl)][B(C6F5)4]. This cation forms by initial Cl− abstraction from (Me2bipy)Pd(Me)Cl to yield (Me2bipy)PdMe+, which is trapped by the remaining (Me2bipy)Pd(Me)Cl by Cl bridging (Shen et al., 2003). LiCl is also formed. In an effort to generate the analogous (Me2bipy)PdCl+ and {(Me2bipy)PdCl}2(µ-Cl)+ cations, (Me2bipy)PdCl2 was treated with [Li(Et2O)2.4][B(C6F5)4] (1 equivalent) in CD2Cl2. Surprisingly, this reaction produced {(Me2bipy)PdCl2}2(µ-Li)+B(C6F5)4−, (I), which crystallized from the reaction mixture as a CD2Cl2 solvate. The molecular structure of (I) has been determined by X-ray crystallography. There are no significant cation/anion or ion/solvent interactions present in the unit cell. The {(Me2bipy)PdCl2}2(µ-Li)+ cation is shown in Fig. 1; the B(C6F5)4− anion and CD2Cl2 molecules are normal and are not shown.
The cation comprises an Li+ ion stabilized by complexation of two (Me2bipy)PdCl2 units, with each (Me2bipy)PdCl2 unit adopting a square-planar geometry. The sums of the angles about atoms Pd1 and Pd2 are 360.1 (s.u.value?) and 360.0 (s.u.)°, respectively. The Me2bipy ligands are slightly twisted around the C5—C6 and C13—C22 bonds, such that the N1—C5—C6—N2 and N3—C13—C22—N4 angles are 2(1) and 3(1)°, respectively. The average Pd—Cl bond distances [2.304 (2) Å], average Cl—Pd—Cl bond angles [88.83 (7)°] and other geometric bond parameters in (I) are very similar to those in the neutral complex (bipy)PdCl2 [Pd—Cl = 2.277 (3) and 2.317 (3) Å, and Cl—Pd—Cl = 89.89 (1)°; bipy is 2,2'-bipyridine; Canty et al., 1992), which shows that Li+ does not significantly perturb the structure of (Me2bipy)PdCl2 units.
The geometry at the Li+ cation is distorted tetrahedral. The Cl—Li—Cl angles associated with the four-membered LiCl2Pd rings are acute [Cl1—Li1—Cl2 = 86.8 (5)° and Cl3—Li1—Cl4 = 87.0 (5)°] and the other Cl—Li—Cl angles are correspondingly larger [115.2 (6)–133.4 (7)°]. The angle between the Li—Cl1—Cl2 and Li—Cl3—Cl4 planes is 79.04 (8)°. The Li—Cl distances are nearly equal [mean 2.35 (2) Å] and are approximately equal to the sum of the ionic radii of Li and Cl (0.60 and 1.81 Å, respectively; Huheey et al., 1993). These data indicate that Li—Cl interactions are quite weak.
Numerous examples of LmMCl2LiL'n complexes are known, in which LmMCl2 units (L,L' = ancillary ligands) coordinate in a bidentate fashion to Li+ via the Cl ligands, and many have been structurally characterized. However, most examples contain early transition metals, f block metals or anionic LnMCl2− units. Notable examples include {(Me3Si)2C5H3}2YbCl2Li(THF)2 (Chan et al., 2000; Hitchcock et al., 2000), (C5Me5)(C4H4BNiPr2)ZrCl.LiCl(Et2O)2 (Quan et al., 1994), {Me2N(indenyl)}2TiCl.LiCl(THF)2 (Greidanus et al., 2001) and {2,4-bis(2,6-diisopropylphenylimido)pentanate}FeCl2Li(THF)2 (Smith et al., 2001). Complex (I) is a rare example of a complex in which a neutral late-transition-metal L2MCl2 unit coordinates to Li+.
Compound (I) is also a rare example of a complex that exhibits an arrested Cl− abstraction. The higher electrophilic character of (Me2bipy)PdCl+ versus (Me2bipy)PdMe+ prohibits complete Cl− abstraction by Li+.