Positional disorder manifested as compositional in a pseudo-C₂-symmetrical Pd complex

The title compound {2-[3,5-bis­(trifluoro­meth­yl)-1H-pyrazol-1-ylmeth­yl]-6-(3,5-dimethyl-1H-pyrazol-1-ylmeth­yl)­pyridine}­meth­yl­palladium(II) tetra­kis[3,5-bis­(trifluoro­meth­yl)phen­yl]­borate, [Pd(C₁₈H₁₈F₆N₅)][B(C₈H₃F₆)₄], crystallizes as discrete cations and anions. The cation possesses a pseudo-twofold axis about which positional disorder of the tridentate ligand is exhibited. The four substituents on the two pyrazole rings exhibit CH₃/CF₃ disorder, while all other atoms are ordered. Thus, this disorder can be conveniently described `locally' as compositional, while `globally' for the entire tridentate ligand it is positional. The anion also exhibits typical rotational positional disorder in three of the CF₃ groups. All disordered CF₃ groups were modeled with idealized C_3v geometry.

S1. Comment

Cationic palladium(II) complexes of symmetrical α-diimine ligands with bulky aryl substituents on the N atoms are known to efficiently catalyze α-olefin oligomerization and polymerization reactions (Brookhart et al., 1995; Ittel et al., 2000; Gibson & Spitzmesser, 2003). These cationic α-diimine palladium complexes are often prepared by direct halide abstraction using silver or alkali metal salts of weakly coordinating ligands. The weakly coordinating ligands do not compete with an incoming monomer for the vacant coordination site of an active catalyst (Mecking, 2000; Mecking et al., 1998; Bianchini et al., 2006). The role of the weakly coordinating ligands is therefore only to stabilize the active catalysts. In our attempts to utilize bis(pyrazol-1-ylmethyl)pyridine palladium chloromethyl complexes to catalyze olefin reactions we found that such complexes yielded inactive cationic species when the Cl atom in the precursor complexes was abstracted (Ojwach et al., 2007). We were able to establish by X-ray crystallography that the cationic species formed after chloride abstraction had both pyrazolyl units strongly bound to palladium. This is in contrast to the chloromethyl precursor complex composition where only one pyrazolyl unit binds to palladium (Ojwach et al., 2007). The strong binding of the pyrazolyl units to palladium in the cationic species was believed to be responsible for the inability of the cationic species to catalyze α -olefin reactions.

During our studies of the factors that render cationic palladium complexes with strongly coordinated bis(pyrazol-1-ylmethyl)pyridine ligands inactive for α -olefin oligomerization and polymerization reactions, we replaced the CH₃ groups on one of the pyrazolyl units in the bis(3,5-dimethylpyrazol-1-ylmethyl)pyridine ligand with CF₃ groups. We aimed to synthesize a hemi-labile ligand, which upon complexation with palladium would allow olefin coordination to the metal centre (Jeffrey & Rauchfuss, 1979; Shi et al., 2002). We succeeded in preparing the desired palladium precursor complexes and the expected cationic palladium species (Scheme 1). Unfortunately, the cationic species showed no catalytic activity in olefin reactions. Spectroscopic data for the cation indicate that the tridentate ligand forms strong Pd—N bonds, whereas the CF₃ substituents do not make pyrazolyl unit labile. We confirmed the coordination of the ligand by X-ray crystallography and report here the structure of this complex, (I) (Scheme 2).

Ionic compound (I) crystallizes as discrete anions and cations. The Pd center in the cationic complex bears a large µ³-ligand and a methyl group. Both the cation and the tetrakis(1,3-bis-trifluoromethylphenyl)borate anion exhibit rotational positional disorder.

The most interesting aspect of the cationic structure is the disorder. The complex contains a pseudo-twofold axis passing along the Pd—C1 vector and exhibits rotation positional disorder about it. A 180° rotation about the axis superimposes the two pyrazolate rings to make the CH₃ and CF₃ groups appear disordered, whereas all other non-H atoms remain ordered. Since there is no ambiguity as to the composition of the µ³-ligand, the CH₃/CF₃ disorder is positional; however, it is manifested as compositional and was modeled as such. The CH₃/CF₃ disorder ratio is 86.5 (3):13.5 (3)%. This disorder can be thought of as positional in a `global' molecular sense and compositional in a `local' substituent sense. The geometries of the disordered CF₃ groups were modeled with a C_3v idealized arrangement based on a density functional theory (DFT) computation for 3-trifluoromethyl-1H-pyrazole.

The overall geometry of the Pd cation cannot be higher than C₁, and even with a symmetrical substitution pattern of the pyrazolate rings it cannot exceed C_s because of the ligated methyl group. The Pd1 coordination polygon defined by atoms C1, N1, N3 and N5 is irregular and slightly distorted from a number of possible geometries, such as D_2d and D_4h. The four ligating atoms are coplanar within 0.07 Å. The eccentricity of atom Pd1 is 0.078 (3) Å and it is displaced by 0.0139 (14) Å from the least-squares planes of the ligated atoms. The geometry about the Pd atom is typical and can be summarized as follows: the Pd atom has a distorted square-planar geometry with angles around the central Pd atom ranging from 85.75</span>(11) to 93.66<span style=" font-weight:600;">(12)° [85.77 (10) to 93.62 (12) according to CIF/Table 1; please check any other values that may need updating] with an average value of 90 (3)°. Atoms Pd1, N1, N3, N5, and C1 are coplanar within 0.06 Å. The average Pd—N(pz) distance and N(pz)—Pd—N(py) angle in (I) are statistically similar to the averages for the nine relevant compounds (Table 2) in the Cambridge Structural Database (CSD; Version 1.10; Allen, 2002); however, the Pd—N(py) distance in (I) is significantly longer than the average for the similar compounds in the CSD. This difference can be attributed to the trans influence of the methyl group. In seven of the nine related compounds, the ligand trans to the pyridine ring is a Cl atom, in one it is another pyridine group, and in [2,6-bis(3,5-dimethylpyrazolylmethyl)pyridine]methylpalladium(II) tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, compound (II), a methyl group. The Pd—N(py) distance in compound (I) is similar to the distance of 2.128 (2) Å in (II). The metal complex in the latter differs from the cation in compound (I) only in that it has all methyl groups substituted on the pyrazole moieties (Ojwach et al., 2007).

The dihedral angles between the best fitting least-squares planes defined by the ring pyrazolate atoms, ring pyridine atoms and four ligating atoms are tabulated in Table 3. These angles are similar to those for other compounds with the same tridentate pyrazolylmethyl pyridine ligands; thus a pseudo-C₂ geometry of the ligand is preferred to a pseudo-C_s-geometry.

The bond distances and angles in the tetrakis[3,5-bis(trifluoromethyl)phenyl]borate anion (Fig. 2) are typical, as confirmed by a Mogul structural check (Bruno et al., 2004). The geometry around the B atom is slightly distorted tetrahedral. The average angle around atom B1 is 109.5 (11)°, but the angles range from 107.8 (2) to 110.6 (2)°. The F atoms on three of the CF₃ groups in the anion show rotational positional disorder over three positions each. The F atoms attached to atom C26 are disordered in a 42.0 (4):29.2 (3):28.8 (3)% ratio, those attached to C42 are disordered in a 52.3 (3):33.3 (5):14.3 (4)% ratio, and those attached to atom C50 are disordered in a 54.0 (3):38.3 (4):7.7 (3)% ratio. All of these disordered F atoms in the anion were refined isotropically, and the CF₃ groups were refined with restraints. The geometries of the disordered CF₃ groups were modeled with a C_3v idealized arrangement based on a DFT computation for PhCF₃. It is quite common for the tetrakis[3,5-bis(trifluoromethyl)phenyl]borate anion in crystal structures to contain some disorder. Our data mining of the CSD revealed that in 295 out of 512 instances of this anion in the CSD there was some disorder in the anion.

Related literature

For related literature, see: Allen (2002); Bianchini et al. (2006); Brookhart et al. (1995); Gibson & Spitzmesser (2003); Ittel et al. (2000); Jeffrey & Rauchfuss (1979); Mecking (2000); Mecking et al. (1998); Ojwach et al. (2007); Shi et al. (2002).

S2. Experimental

To a J-Young NMR tube containing a solution of the palladium precursor complex (Scheme 2) (4.00 mg, 0.007 mmol) in CDCl₃ (0.2 ml) was added a solution of NaBAr₄ (6.00 mg, 0.007 mmol) in CDCl₃ (0.2 ml), and the ¹H NMR spectrum was acquired after vigorous shaking. The solution was left to stand at room temperature for several days to afford colourless single crystals of (I) suitable for X-ray analysis. ¹H NMR (CDCl₃): δ 1.27 (s, 3H, CH₃, Pd—Me), 2.17 (s, 3H, CH_3, pz), 2.33 (s, 3H, CH_3, pz), 5.16 (d, 2H, CH₂, ²J_HH = 15.6 Hz), 5.63 (s, 1H, pz), 5.98 (s, 1H, pz), 6.20 (d, 2H, CH₂, ²J_HH = 17.4 Hz), 6.71 (d, 1H, py, ³J_HH = 8.2 Hz), 7.23 (d, 2H, py, ³J_HH = 8.6 Hz), 7.34 (t, 1H, py, ³J_HH = 8.3 Hz), 7.48 (s, 4H, BAr₄^-), 7.66 (s, 8H, BAr₄^-).¹⁹F{¹H} NMR (CDCl₃): δ 62.6 (s, BAr₄^-), -60.2 (s, CF₃, pz), -56.0 (s, CF₃, pz). ¹³C{¹H} NMR (CDCl₃): δ 5.7, 11.5, 15.0, 52.1, 55.8, 109.2, 117.5, 122.6, 124.7, 134.7, 142.0, 48.8, 152.2, 162.6.

S3. Refinement

All H atoms were placed in idealized locations and refined as riding, with appropriate displacement parameters [U_iso(H) = 1.5U_eq(C) for methyl H atoms and U_iso(H) = 1.2U_eq(C) for all other H atoms. Default effective C—H distances were adopted [Csp³—secondary H = 0.99 Å, Csp³—primary H = 0.98 Å and Csp²—tertiary H = 0.95 Å].

The geometry of all disordered CF₃ groups was modeled on the basis of pbepbe/6–311++G(df,pd) DFT computations to conform to C_3v symmetry. This was achieved with the following restraints: the C—F distances were allowed to refine as one free variable FVAR2; the F···F separations were restrained to 1.607 (3) times FVAR2; the C_ipso···F separations were restrained to 1.746 (11) times FVAR2. This was achieved with DFIX commands in SHELTXL (Sheldrick, 2008). Attempts to conduct the refinement with SAME instructions did not result in computationally stable refinements. All disordered F atoms except F1, F2 and F3 were refined isotropically.

There were two large peaks (~2 e Å^-3) in the final difference map in the vicinity of the disordered group at C50, which may represent additional positions of the F atoms. No attempt to refine this CF₃ groups as disordered over four positions was made.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2008) and modiCIFer (Guzei, 2007).

Figures

	Fig. 1. The molecular structure of the cation of compound (I). Displacement ellipsoids are shown at the 50% probability level. All H atoms and all minor components of disordered atoms have been omitted for clarity.
	Fig. 2. The molecular structure of the anion of (I). Displacement ellipsoids are shown at the 50% probability level. All H atoms and all minor components of disordered atoms have been omitted for clarity. The disordered F atoms in the anion that were refined iostropically are shown with cross-hatched circles.

{2-[3,5-bis(trifluoromethyl)-1H-pyrazol-1-ylmethyl]-6-(3,5-dimethyl-1H-pyrazol- 1-ylmethyl)pyridine}methylpalladium(II) tetrakis[3,5-bis(trifluoromethyl)phenyl]borate

Crystal data

[Pd(C18H18F6N5)](C32H12BF24)	F(000) = 2744
Mr = 1388.00	Dx = 1.737 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 999 reflections
a = 10.9194 (4) Å	θ = 1.9–29.1°
b = 18.0256 (7) Å	µ = 0.50 mm^−1
c = 27.1635 (11) Å	T = 105 K
β = 96.865 (1)°	Block, colourless
V = 5308.2 (4) Å^3	0.36 × 0.31 × 0.26 mm
Z = 4

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	14211 independent reflections
Radiation source: fine-focus sealed tube	12423 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
0.30° ω scans	θmax = 29.1°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −14→14
Tmin = 0.841, Tmax = 0.882	k = −24→24
92342 measured reflections	l = −36→37

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.154	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0761P)^2 + 17.6386P] where P = (Fo^2 + 2Fc^2)/3
14211 reflections	(Δ/σ)max = 0.002
823 parameters	Δρmax = 2.16 e Å^−3
109 restraints	Δρmin = −1.63 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Pd1	0.82360 (2)	0.231916 (12)	0.695226 (8)	0.02061 (8)
N1	0.6820 (3)	0.29097 (15)	0.65737 (10)	0.0232 (5)
N2	0.7131 (3)	0.35531 (15)	0.63610 (10)	0.0243 (5)
N3	0.9230 (2)	0.25670 (15)	0.63454 (9)	0.0214 (5)
N4	1.0293 (2)	0.12993 (15)	0.69146 (10)	0.0244 (5)
N5	0.9709 (2)	0.17074 (15)	0.72426 (10)	0.0234 (5)
B1	0.9170 (3)	0.21064 (18)	0.37765 (11)	0.0172 (5)
C1	0.7297 (3)	0.21656 (18)	0.75589 (11)	0.0247 (6)
H1A	0.7490	0.1674	0.7701	0.037*
H1B	0.6408	0.2203	0.7456	0.037*
H1C	0.7547	0.2547	0.7808	0.037*
C3	0.5646 (3)	0.27789 (18)	0.63913 (12)	0.0237 (6)
C4	0.5189 (3)	0.3342 (2)	0.60658 (12)	0.0281 (7)
H4	0.4384	0.3385	0.5893	0.034*
C5	0.6165 (3)	0.38182 (18)	0.60529 (12)	0.0276 (6)
C7	0.8423 (3)	0.37912 (18)	0.64239 (12)	0.0270 (6)
H7A	0.8732	0.3810	0.6781	0.032*
H7B	0.8487	0.4295	0.6285	0.032*
C8	0.9197 (3)	0.32598 (18)	0.61642 (11)	0.0238 (6)
C9	0.9838 (3)	0.3458 (2)	0.57733 (12)	0.0294 (7)
H9	0.9800	0.3949	0.5647	0.035*
C10	1.0535 (3)	0.2919 (2)	0.55721 (13)	0.0339 (8)
H10	1.0983	0.3038	0.5304	0.041*
C11	1.0575 (3)	0.2207 (2)	0.57635 (13)	0.0316 (7)
H11	1.1056	0.1835	0.5630	0.038*
C12	0.9902 (3)	0.20439 (19)	0.61530 (11)	0.0246 (6)
C13	0.9835 (3)	0.12867 (18)	0.63873 (12)	0.0260 (6)
H13A	0.8968	0.1114	0.6345	0.031*
H13B	1.0328	0.0931	0.6216	0.031*
C15	1.1310 (3)	0.09649 (19)	0.71495 (13)	0.0286 (7)
C16	1.1396 (3)	0.1168 (2)	0.76359 (13)	0.0317 (7)
H16	1.2020	0.1022	0.7892	0.038*
C17	1.0388 (3)	0.16317 (19)	0.76869 (12)	0.0282 (6)
C2	0.4983 (3)	0.20831 (19)	0.65086 (12)	0.0263 (6)	0.865 (3)
F1	0.4038 (3)	0.19790 (16)	0.61644 (10)	0.0336 (6)	0.865 (3)
F2	0.4542 (2)	0.21236 (14)	0.69477 (9)	0.0288 (5)	0.865 (3)
F3	0.5713 (2)	0.14867 (13)	0.65236 (9)	0.0270 (5)	0.865 (3)
C2A	0.4983 (3)	0.20831 (19)	0.65086 (12)	0.0263 (6)	0.135 (3)
H2A1	0.5531	0.1656	0.6491	0.039*	0.135 (3)
H2A2	0.4247	0.2020	0.6268	0.039*	0.135 (3)
H2A3	0.4737	0.2119	0.6843	0.039*	0.135 (3)
C6	0.6243 (4)	0.4514 (2)	0.57596 (14)	0.0359 (8)	0.865 (3)
F4	0.7243 (3)	0.44958 (18)	0.55056 (11)	0.0443 (7)	0.865 (3)
F5	0.6395 (5)	0.51065 (14)	0.60537 (11)	0.0495 (8)	0.865 (3)
F6	0.5264 (3)	0.45876 (16)	0.54433 (10)	0.0403 (7)	0.865 (3)
C6A	0.6243 (4)	0.4514 (2)	0.57596 (14)	0.0359 (8)	0.135 (3)
H6A1	0.6448	0.4931	0.5986	0.054*	0.135 (3)
H6A2	0.5448	0.4607	0.5561	0.054*	0.135 (3)
H6A3	0.6886	0.4459	0.5539	0.054*	0.135 (3)
C14	1.2130 (3)	0.0485 (2)	0.68851 (15)	0.0375 (8)	0.865 (3)
H14A	1.1643	0.0086	0.6712	0.056*	0.865 (3)
H14B	1.2774	0.0270	0.7125	0.056*	0.865 (3)
H14C	1.2513	0.0784	0.6644	0.056*	0.865 (3)
C14A	1.2130 (3)	0.0485 (2)	0.68851 (15)	0.0375 (8)	0.135 (3)
F4A	1.1479 (10)	−0.0007 (8)	0.6619 (6)	0.057 (3)*	0.135 (3)
F5A	1.2925 (14)	0.0158 (10)	0.7209 (4)	0.057 (3)*	0.135 (3)
F6A	1.2714 (16)	0.0902 (6)	0.6594 (6)	0.057 (3)*	0.135 (3)
C18	1.0073 (3)	0.2000 (2)	0.81444 (12)	0.0385 (8)	0.865 (3)
H18A	0.9526	0.2422	0.8054	0.058*	0.865 (3)
H18B	1.0829	0.2176	0.8340	0.058*	0.865 (3)
H18C	0.9655	0.1646	0.8341	0.058*	0.865 (3)
C18A	1.0073 (3)	0.2000 (2)	0.81444 (12)	0.0385 (8)	0.135 (3)
F1A	0.9744 (14)	0.2695 (5)	0.8058 (4)	0.057 (3)*	0.135 (3)
F2A	1.0950 (10)	0.1970 (8)	0.8506 (4)	0.057 (3)*	0.135 (3)
F3A	0.9085 (11)	0.1672 (7)	0.8292 (5)	0.057 (3)*	0.135 (3)
F7	0.57197 (19)	0.16428 (14)	0.54352 (7)	0.0360 (5)
F8	0.7643 (2)	0.13812 (13)	0.55785 (7)	0.0350 (5)
F9	0.7085 (2)	0.25001 (12)	0.54043 (8)	0.0338 (5)
F10	0.3865 (3)	0.0887 (3)	0.3785 (2)	0.0427 (6)*	0.420 (4)
F11	0.5008 (5)	0.0771 (3)	0.31884 (11)	0.0427 (6)*	0.420 (4)
F12	0.5120 (5)	−0.00418 (18)	0.3775 (2)	0.0427 (6)*	0.420 (4)
F10A	0.3979 (4)	0.1151 (3)	0.3586 (3)	0.0427 (6)*	0.292 (3)
F11A	0.5257 (6)	0.0447 (4)	0.32468 (17)	0.0427 (6)*	0.292 (3)
F12A	0.4576 (6)	0.0122 (3)	0.3933 (2)	0.0427 (6)*	0.292 (3)
F10B	0.4616 (6)	0.1066 (4)	0.32482 (18)	0.0427 (6)*	0.288 (3)
F11B	0.5381 (6)	0.0031 (3)	0.3531 (3)	0.0427 (6)*	0.288 (3)
F12B	0.3993 (4)	0.0577 (4)	0.3905 (2)	0.0427 (6)*	0.288 (3)
F13	0.6272 (2)	0.14221 (19)	0.20765 (11)	0.0622 (9)
F14	0.7530 (3)	0.14536 (18)	0.15369 (9)	0.0616 (9)
F15	0.7127 (2)	0.24324 (11)	0.19243 (9)	0.0344 (5)
F16	1.22958 (19)	0.08148 (12)	0.25141 (9)	0.0372 (5)
F17	1.1627 (2)	−0.00426 (13)	0.29542 (9)	0.0428 (6)
F18	1.1053 (2)	−0.00028 (15)	0.21752 (10)	0.0481 (7)
F19	1.1242 (2)	−0.00917 (12)	0.47880 (11)	0.0448 (6)
F20	1.3140 (2)	0.02079 (14)	0.49695 (12)	0.0543 (7)
F21	1.1795 (3)	0.04912 (15)	0.54564 (10)	0.0617 (8)
F22	1.4494 (3)	0.2789 (2)	0.4844 (2)	0.0340 (5)*	0.523 (3)
F23	1.3002 (4)	0.3547 (2)	0.49272 (19)	0.0340 (5)*	0.523 (3)
F24	1.3562 (5)	0.3355 (3)	0.42029 (11)	0.0340 (5)*	0.523 (3)
F22A	1.4308 (4)	0.2859 (3)	0.49868 (19)	0.0340 (5)*	0.333 (5)
F23A	1.2886 (4)	0.3661 (2)	0.4739 (3)	0.0340 (5)*	0.333 (5)
F24A	1.3915 (5)	0.3126 (3)	0.42072 (15)	0.0340 (5)*	0.333 (5)
F22B	1.3373 (10)	0.3316 (6)	0.5084 (2)	0.0340 (5)*	0.143 (4)
F23B	1.4543 (4)	0.2777 (4)	0.4603 (5)	0.0340 (5)*	0.143 (4)
F24B	1.3158 (9)	0.3567 (4)	0.4301 (4)	0.0340 (5)*	0.143 (4)
F46	0.7831 (3)	0.5283 (2)	0.43697 (17)	0.0354 (5)*	0.540 (3)
F47	0.6375 (3)	0.4942 (3)	0.38154 (12)	0.0354 (5)*	0.540 (3)
F48	0.6768 (4)	0.4298 (2)	0.44904 (14)	0.0354 (5)*	0.540 (3)
F46A	0.8035 (4)	0.5041 (3)	0.45402 (17)	0.0354 (5)*	0.383 (4)
F47A	0.6692 (5)	0.5199 (3)	0.39002 (18)	0.0354 (5)*	0.383 (4)
F48A	0.6542 (4)	0.4262 (3)	0.43950 (18)	0.0354 (5)*	0.383 (4)
F46B	0.7560 (14)	0.5403 (2)	0.4160 (7)	0.0354 (5)*	0.077 (3)
F47B	0.7327 (16)	0.4457 (9)	0.4635 (3)	0.0354 (5)*	0.077 (3)
F48B	0.6136 (4)	0.4593 (10)	0.3947 (5)	0.0354 (5)*	0.077 (3)
F43	0.9962 (2)	0.52048 (10)	0.28150 (8)	0.0311 (4)
F44	1.15148 (18)	0.45304 (12)	0.30951 (9)	0.0342 (5)
F45	1.0224 (2)	0.41414 (11)	0.24889 (7)	0.0344 (5)
C19	0.7993 (3)	0.17581 (15)	0.40236 (10)	0.0173 (5)
C20	0.7878 (3)	0.18767 (15)	0.45285 (10)	0.0189 (5)
H20	0.8520	0.2132	0.4727	0.023*
C21	0.6864 (3)	0.16349 (16)	0.47479 (10)	0.0185 (5)
C22	0.5911 (3)	0.12503 (16)	0.44761 (11)	0.0206 (5)
H22	0.5217	0.1085	0.4626	0.025*
C23	0.6002 (2)	0.11153 (15)	0.39795 (10)	0.0228 (6)
C24	0.7016 (3)	0.13619 (16)	0.37627 (11)	0.0206 (5)
H24	0.7050	0.1258	0.3422	0.025*
C25	0.6818 (3)	0.17873 (19)	0.52867 (11)	0.0235 (6)
C26	0.4988 (2)	0.06988 (15)	0.36791 (9)	0.0370 (8)
C27	0.9276 (3)	0.17202 (15)	0.32375 (10)	0.0176 (5)
C28	0.8371 (3)	0.18715 (15)	0.28358 (10)	0.0186 (5)
H28	0.7739	0.2219	0.2881	0.022*
C29	0.8368 (3)	0.15330 (16)	0.23770 (11)	0.0197 (5)
C30	0.9297 (3)	0.10425 (16)	0.22890 (11)	0.0211 (5)
H30	0.9295	0.0808	0.1976	0.025*
C31	1.0227 (3)	0.09050 (16)	0.26708 (11)	0.0206 (5)
C32	1.0215 (3)	0.12340 (16)	0.31370 (11)	0.0194 (5)
H32	1.0863	0.1124	0.3392	0.023*
C33	0.7332 (3)	0.17095 (17)	0.19817 (11)	0.0236 (6)
C34	1.1297 (3)	0.04183 (18)	0.25804 (12)	0.0247 (6)
C35	1.0443 (3)	0.19791 (16)	0.41523 (10)	0.0185 (5)
C36	1.0681 (3)	0.13004 (16)	0.44036 (11)	0.0203 (5)
H36	1.0082	0.0917	0.4359	0.024*
C37	1.1766 (3)	0.11758 (17)	0.47152 (11)	0.0226 (6)
C38	1.2665 (3)	0.17223 (18)	0.47961 (11)	0.0231 (6)
H38	1.3400	0.1637	0.5013	0.028*
C39	1.2461 (2)	0.23958 (14)	0.45523 (10)	0.0215 (6)
C40	1.1370 (3)	0.25147 (16)	0.42367 (10)	0.0194 (5)
H40	1.1253	0.2979	0.4073	0.023*
C41	1.1982 (3)	0.0448 (2)	0.49786 (14)	0.0315 (7)
C42	1.3381 (2)	0.30101 (13)	0.46283 (8)	0.0277 (6)
C43	0.8976 (3)	0.30043 (16)	0.36859 (10)	0.0174 (5)
C44	0.9621 (3)	0.33788 (15)	0.33446 (10)	0.0182 (5)
H44	1.0115	0.3099	0.3147	0.022*
C45	0.9564 (3)	0.41476 (16)	0.32841 (10)	0.0183 (5)
C46	0.8850 (3)	0.45768 (17)	0.35614 (12)	0.0234 (6)
H46	0.8824	0.5101	0.3527	0.028*
C47	0.8175 (3)	0.42191 (15)	0.38914 (11)	0.0252 (6)
C48	0.8245 (3)	0.34537 (16)	0.39557 (11)	0.0224 (6)
H48	0.7783	0.3228	0.4190	0.027*
C49	1.0309 (3)	0.45037 (17)	0.29200 (12)	0.0237 (6)
C50	0.7320 (2)	0.46738 (13)	0.41592 (10)	0.0446 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.02401 (13)	0.01908 (12)	0.01921 (12)	−0.00295 (8)	0.00459 (8)	−0.00037 (8)
N1	0.0297 (13)	0.0194 (11)	0.0218 (12)	−0.0005 (10)	0.0083 (10)	−0.0014 (9)
N2	0.0320 (14)	0.0199 (12)	0.0220 (12)	0.0004 (10)	0.0079 (10)	−0.0002 (10)
N3	0.0207 (12)	0.0252 (12)	0.0180 (11)	−0.0041 (10)	0.0007 (9)	−0.0025 (9)
N4	0.0234 (12)	0.0246 (12)	0.0241 (12)	−0.0018 (10)	−0.0015 (10)	0.0001 (10)
N5	0.0246 (12)	0.0225 (12)	0.0226 (12)	−0.0013 (10)	0.0004 (10)	0.0009 (10)
B1	0.0182 (14)	0.0171 (13)	0.0161 (13)	0.0008 (11)	0.0017 (10)	−0.0005 (11)
C1	0.0306 (16)	0.0251 (14)	0.0197 (13)	−0.0018 (12)	0.0086 (11)	0.0045 (11)
C3	0.0243 (14)	0.0252 (14)	0.0226 (14)	0.0053 (11)	0.0070 (11)	−0.0016 (11)
C4	0.0298 (16)	0.0326 (16)	0.0230 (14)	0.0096 (13)	0.0069 (12)	−0.0004 (12)
C5	0.0366 (17)	0.0255 (15)	0.0221 (14)	0.0072 (13)	0.0089 (12)	−0.0002 (12)
C7	0.0352 (17)	0.0214 (14)	0.0252 (15)	−0.0062 (12)	0.0072 (12)	−0.0020 (11)
C8	0.0254 (14)	0.0262 (15)	0.0196 (13)	−0.0071 (12)	0.0025 (11)	−0.0018 (11)
C9	0.0316 (16)	0.0333 (17)	0.0235 (15)	−0.0098 (13)	0.0048 (12)	0.0016 (13)
C10	0.0320 (17)	0.048 (2)	0.0235 (15)	−0.0066 (15)	0.0084 (13)	0.0015 (14)
C11	0.0275 (16)	0.0426 (19)	0.0252 (15)	0.0013 (14)	0.0053 (13)	−0.0052 (14)
C12	0.0218 (14)	0.0318 (16)	0.0197 (13)	−0.0027 (12)	−0.0003 (11)	−0.0046 (12)
C13	0.0267 (15)	0.0264 (15)	0.0241 (14)	0.0005 (12)	−0.0003 (12)	−0.0047 (12)
C15	0.0235 (15)	0.0265 (15)	0.0342 (17)	−0.0036 (12)	−0.0034 (12)	0.0045 (13)
C16	0.0303 (17)	0.0315 (17)	0.0311 (17)	−0.0010 (13)	−0.0056 (13)	0.0086 (13)
C17	0.0311 (16)	0.0280 (15)	0.0246 (15)	−0.0055 (13)	−0.0005 (12)	0.0037 (12)
C2	0.0231 (14)	0.0294 (16)	0.0269 (15)	0.0026 (12)	0.0057 (12)	−0.0005 (12)
F1	0.0221 (12)	0.0429 (14)	0.0347 (13)	−0.0055 (10)	−0.0010 (9)	−0.0005 (11)
F2	0.0259 (11)	0.0324 (12)	0.0304 (12)	0.0031 (9)	0.0125 (9)	0.0029 (9)
F3	0.0252 (11)	0.0227 (10)	0.0345 (12)	0.0011 (9)	0.0089 (9)	−0.0024 (9)
C2A	0.0231 (14)	0.0294 (16)	0.0269 (15)	0.0026 (12)	0.0057 (12)	−0.0005 (12)
C6	0.045 (2)	0.0330 (18)	0.0305 (17)	0.0070 (16)	0.0096 (16)	0.0079 (14)
F4	0.0408 (15)	0.0575 (18)	0.0365 (14)	0.0074 (13)	0.0126 (11)	0.0237 (13)
F5	0.084 (2)	0.0215 (12)	0.0426 (15)	0.0065 (14)	0.0058 (15)	0.0063 (11)
F6	0.0422 (15)	0.0470 (15)	0.0314 (13)	0.0167 (12)	0.0031 (11)	0.0170 (12)
C6A	0.045 (2)	0.0330 (18)	0.0305 (17)	0.0070 (16)	0.0096 (16)	0.0079 (14)
C14	0.0286 (17)	0.0378 (19)	0.045 (2)	0.0045 (15)	−0.0006 (15)	0.0030 (16)
C14A	0.0286 (17)	0.0378 (19)	0.045 (2)	0.0045 (15)	−0.0006 (15)	0.0030 (16)
C18	0.044 (2)	0.048 (2)	0.0221 (15)	−0.0003 (17)	−0.0032 (14)	−0.0021 (15)
C18A	0.044 (2)	0.048 (2)	0.0221 (15)	−0.0003 (17)	−0.0032 (14)	−0.0021 (15)
F7	0.0260 (10)	0.0623 (15)	0.0210 (9)	−0.0063 (10)	0.0079 (7)	−0.0038 (9)
F8	0.0374 (11)	0.0449 (12)	0.0205 (9)	0.0076 (9)	−0.0062 (8)	0.0019 (8)
F9	0.0451 (12)	0.0325 (10)	0.0250 (10)	−0.0016 (9)	0.0093 (9)	−0.0116 (8)
F13	0.0343 (13)	0.083 (2)	0.0627 (17)	−0.0332 (13)	−0.0205 (12)	0.0376 (16)
F14	0.0772 (19)	0.081 (2)	0.0219 (11)	0.0473 (17)	−0.0143 (11)	−0.0179 (12)
F15	0.0297 (10)	0.0240 (9)	0.0453 (12)	0.0032 (8)	−0.0124 (9)	0.0012 (9)
F16	0.0246 (10)	0.0316 (11)	0.0585 (14)	0.0009 (8)	0.0182 (9)	0.0012 (10)
F17	0.0492 (14)	0.0330 (11)	0.0506 (13)	0.0218 (10)	0.0235 (11)	0.0149 (10)
F18	0.0354 (12)	0.0562 (15)	0.0524 (14)	0.0131 (11)	0.0040 (10)	−0.0332 (12)
F19	0.0415 (13)	0.0239 (10)	0.0669 (16)	0.0027 (9)	−0.0017 (11)	0.0119 (10)
F20	0.0300 (12)	0.0387 (13)	0.093 (2)	0.0150 (10)	0.0034 (13)	0.0255 (14)
F21	0.111 (3)	0.0414 (14)	0.0348 (13)	0.0190 (15)	0.0160 (14)	0.0180 (11)
F43	0.0411 (11)	0.0175 (8)	0.0362 (11)	−0.0006 (8)	0.0110 (9)	0.0038 (8)
F44	0.0210 (9)	0.0335 (11)	0.0491 (13)	−0.0053 (8)	0.0088 (9)	0.0007 (9)
F45	0.0568 (14)	0.0253 (10)	0.0235 (9)	−0.0058 (9)	0.0150 (9)	−0.0031 (8)
C19	0.0184 (12)	0.0153 (12)	0.0181 (12)	0.0024 (9)	0.0023 (10)	0.0002 (9)
C20	0.0202 (13)	0.0175 (12)	0.0187 (12)	0.0014 (10)	0.0008 (10)	−0.0012 (10)
C21	0.0188 (12)	0.0193 (12)	0.0173 (12)	0.0036 (10)	0.0018 (10)	0.0006 (10)
C22	0.0190 (13)	0.0215 (13)	0.0218 (13)	−0.0002 (10)	0.0043 (10)	−0.0015 (11)
C23	0.0218 (14)	0.0221 (14)	0.0248 (14)	−0.0040 (11)	0.0032 (11)	−0.0068 (11)
C24	0.0224 (13)	0.0211 (13)	0.0185 (12)	−0.0008 (11)	0.0039 (10)	−0.0036 (10)
C25	0.0197 (13)	0.0322 (16)	0.0187 (13)	0.0007 (11)	0.0026 (10)	−0.0009 (11)
C26	0.0314 (18)	0.048 (2)	0.0326 (17)	−0.0170 (16)	0.0084 (14)	−0.0161 (16)
C27	0.0197 (12)	0.0157 (12)	0.0179 (12)	−0.0005 (10)	0.0039 (10)	−0.0003 (9)
C28	0.0199 (13)	0.0164 (12)	0.0196 (12)	0.0002 (10)	0.0029 (10)	−0.0003 (10)
C29	0.0229 (13)	0.0174 (12)	0.0188 (12)	−0.0026 (10)	0.0024 (10)	−0.0002 (10)
C30	0.0263 (14)	0.0185 (13)	0.0197 (13)	−0.0021 (11)	0.0073 (11)	−0.0035 (10)
C31	0.0208 (13)	0.0187 (13)	0.0237 (13)	0.0007 (10)	0.0088 (11)	−0.0011 (10)
C32	0.0201 (13)	0.0186 (12)	0.0198 (13)	0.0003 (10)	0.0036 (10)	0.0001 (10)
C33	0.0276 (15)	0.0222 (14)	0.0201 (13)	−0.0015 (11)	−0.0002 (11)	−0.0034 (11)
C34	0.0249 (14)	0.0233 (14)	0.0273 (15)	0.0017 (11)	0.0084 (12)	−0.0040 (12)
C35	0.0186 (12)	0.0192 (12)	0.0181 (12)	0.0034 (10)	0.0037 (10)	−0.0010 (10)
C36	0.0221 (13)	0.0179 (12)	0.0211 (13)	0.0024 (10)	0.0036 (10)	−0.0003 (10)
C37	0.0232 (14)	0.0218 (14)	0.0234 (14)	0.0073 (11)	0.0052 (11)	0.0035 (11)
C38	0.0193 (13)	0.0293 (15)	0.0207 (13)	0.0059 (11)	0.0025 (10)	0.0014 (11)
C39	0.0180 (13)	0.0251 (14)	0.0212 (13)	0.0006 (11)	0.0020 (10)	−0.0014 (11)
C40	0.0205 (13)	0.0187 (12)	0.0192 (12)	0.0023 (10)	0.0035 (10)	0.0005 (10)
C41	0.0310 (17)	0.0277 (16)	0.0355 (18)	0.0089 (13)	0.0036 (14)	0.0083 (14)
C42	0.0227 (14)	0.0297 (16)	0.0296 (16)	−0.0026 (12)	−0.0010 (12)	0.0003 (13)
C43	0.0168 (12)	0.0175 (12)	0.0174 (12)	0.0017 (10)	−0.0007 (9)	−0.0007 (10)
C44	0.0174 (12)	0.0175 (12)	0.0195 (12)	0.0011 (10)	0.0013 (10)	−0.0020 (10)
C45	0.0172 (12)	0.0187 (12)	0.0185 (12)	−0.0011 (10)	−0.0003 (10)	−0.0006 (10)
C46	0.0262 (15)	0.0167 (13)	0.0271 (14)	0.0014 (11)	0.0030 (12)	−0.0015 (11)
C47	0.0303 (16)	0.0189 (13)	0.0284 (15)	0.0044 (12)	0.0118 (12)	−0.0032 (11)
C48	0.0240 (14)	0.0212 (14)	0.0229 (13)	0.0014 (11)	0.0068 (11)	−0.0007 (11)
C49	0.0257 (14)	0.0182 (13)	0.0279 (15)	−0.0025 (11)	0.0058 (12)	−0.0021 (11)
C50	0.063 (3)	0.0215 (16)	0.056 (2)	0.0089 (17)	0.036 (2)	0.0011 (16)

Geometric parameters (Å, º)

Pd1—N5	2.030 (3)	F16—C34	1.334 (4)
Pd1—N1	2.049 (3)	F17—C34	1.328 (4)
Pd1—C1	2.061 (3)	F18—C34	1.337 (4)
Pd1—N3	2.127 (3)	F19—C41	1.330 (5)
N1—C3	1.339 (4)	F20—C41	1.339 (4)
N1—N2	1.357 (4)	F21—C41	1.340 (4)
N2—C5	1.353 (4)	F22—C42	1.345 (3)
N2—C7	1.464 (4)	F23—C42	1.359 (3)
N3—C12	1.339 (4)	F24—C42	1.347 (3)
N3—C8	1.341 (4)	F22A—C42	1.346 (3)
N4—C15	1.354 (4)	F23A—C42	1.340 (3)
N4—N5	1.370 (4)	F24A—C42	1.361 (3)
N4—C13	1.460 (4)	F22B—C42	1.357 (3)
N5—C17	1.346 (4)	F23B—C42	1.346 (3)
B1—C27	1.638 (4)	F24B—C42	1.344 (3)
B1—C35	1.640 (4)	F46—C50	1.330 (3)
B1—C19	1.644 (4)	F47—C50	1.393 (3)
B1—C43	1.647 (4)	F48—C50	1.327 (3)
C1—H1A	0.9800	F46A—C50	1.388 (3)
C1—H1B	0.9800	F47A—C50	1.321 (3)
C1—H1C	0.9800	F48A—C50	1.346 (3)
C3—C4	1.398 (5)	F46B—C50	1.340 (3)
C3—C2	1.502 (5)	F47B—C50	1.348 (3)
C4—C5	1.372 (5)	F48B—C50	1.359 (3)
C4—H4	0.9500	F43—C49	1.340 (4)
C5—C6	1.493 (5)	F44—C49	1.346 (4)
C7—C8	1.507 (5)	F45—C49	1.334 (4)
C7—H7A	0.9900	C19—C24	1.403 (4)
C7—H7B	0.9900	C19—C20	1.408 (4)
C8—C9	1.386 (4)	C20—C21	1.389 (4)
C9—C10	1.385 (5)	C20—H20	0.9500
C9—H9	0.9500	C21—C22	1.388 (4)
C10—C11	1.383 (6)	C21—C25	1.496 (4)
C10—H10	0.9500	C22—C23	1.386 (4)
C11—C12	1.390 (5)	C22—H22	0.9500
C11—H11	0.9500	C23—C24	1.388 (4)
C12—C13	1.512 (5)	C23—C26	1.497 (3)
C13—H13A	0.9900	C24—H24	0.9500
C13—H13B	0.9900	C27—C32	1.401 (4)
C15—C16	1.364 (5)	C27—C28	1.408 (4)
C15—C14	1.489 (5)	C28—C29	1.387 (4)
C16—C17	1.402 (5)	C28—H28	0.9500
C16—H16	0.9500	C29—C30	1.388 (4)
C17—C18	1.486 (5)	C29—C33	1.498 (4)
C2—F1	1.320 (4)	C30—C31	1.384 (4)
C2—F3	1.336 (4)	C30—H30	0.9500
C2—F2	1.340 (4)	C31—C32	1.400 (4)
C6—F6	1.296 (5)	C31—C34	1.504 (4)
C6—F5	1.333 (5)	C32—H32	0.9500
C6—F4	1.359 (5)	C35—C40	1.397 (4)
C14—H14A	0.9800	C35—C36	1.410 (4)
C14—H14B	0.9800	C36—C37	1.390 (4)
C14—H14C	0.9800	C36—H36	0.9500
C18—H18A	0.9800	C37—C38	1.389 (5)
C18—H18B	0.9800	C37—C41	1.499 (4)
C18—H18C	0.9800	C38—C39	1.388 (4)
F7—C25	1.335 (4)	C38—H38	0.9500
F8—C25	1.344 (4)	C39—C40	1.399 (4)
F9—C25	1.348 (4)	C39—C42	1.493 (3)
F10—C26	1.336 (3)	C40—H40	0.9500
F11—C26	1.342 (3)	C43—C44	1.402 (4)
F12—C26	1.365 (3)	C43—C48	1.403 (4)
F10A—C26	1.369 (3)	C44—C45	1.396 (4)
F11A—C26	1.324 (3)	C44—H44	0.9500
F12A—C26	1.353 (3)	C45—C46	1.383 (4)
F10B—C26	1.364 (3)	C45—C49	1.498 (4)
F11B—C26	1.355 (3)	C46—C47	1.386 (4)
F12B—C26	1.329 (3)	C46—H46	0.9500
F13—C33	1.321 (4)	C47—C48	1.392 (4)
F14—C33	1.335 (4)	C47—C50	1.495 (3)
F15—C33	1.328 (4)	C48—H48	0.9500
N5—Pd1—N1	172.77 (10)	F11—C26—F12	105.7 (3)
N5—Pd1—C1	93.62 (12)	F11A—C26—F10A	107.4 (3)
N1—Pd1—C1	93.07 (11)	F12A—C26—F10A	104.1 (3)
N5—Pd1—N3	87.76 (11)	F11A—C26—C23	115.3 (3)
N1—Pd1—N3	85.77 (10)	F12B—C26—C23	115.0 (3)
C1—Pd1—N3	175.40 (12)	F10—C26—C23	113.2 (3)
C3—N1—N2	105.7 (3)	F11—C26—C23	113.2 (3)
C3—N1—Pd1	136.5 (2)	F12A—C26—C23	112.1 (3)
N2—N1—Pd1	116.5 (2)	F11B—C26—C23	111.5 (3)
C5—N2—N1	110.4 (3)	F10B—C26—C23	110.4 (3)
C5—N2—C7	129.6 (3)	F12—C26—C23	109.4 (3)
N1—N2—C7	119.2 (3)	F10A—C26—C23	109.2 (3)
C12—N3—C8	120.3 (3)	C32—C27—C28	115.6 (3)
C12—N3—Pd1	120.6 (2)	C32—C27—B1	124.9 (3)
C8—N3—Pd1	119.1 (2)	C28—C27—B1	119.5 (2)
C15—N4—N5	110.6 (3)	C29—C28—C27	122.5 (3)
C15—N4—C13	128.4 (3)	C29—C28—H28	118.8
N5—N4—C13	120.9 (3)	C27—C28—H28	118.8
C17—N5—N4	106.2 (3)	C28—C29—C30	120.8 (3)
C17—N5—Pd1	136.8 (2)	C28—C29—C33	118.1 (3)
N4—N5—Pd1	116.61 (19)	C30—C29—C33	121.1 (3)
C27—B1—C35	110.6 (2)	C31—C30—C29	118.1 (3)
C27—B1—C19	110.2 (2)	C31—C30—H30	121.0
C35—B1—C19	109.8 (2)	C29—C30—H30	121.0
C27—B1—C43	107.8 (2)	C30—C31—C32	121.1 (3)
C35—B1—C43	108.4 (2)	C30—C31—C34	119.8 (3)
C19—B1—C43	110.1 (2)	C32—C31—C34	119.0 (3)
Pd1—C1—H1A	109.5	C31—C32—C27	121.8 (3)
Pd1—C1—H1B	109.5	C31—C32—H32	119.1
H1A—C1—H1B	109.5	C27—C32—H32	119.1
Pd1—C1—H1C	109.5	F13—C33—F15	105.5 (3)
H1A—C1—H1C	109.5	F13—C33—F14	106.3 (3)
H1B—C1—H1C	109.5	F15—C33—F14	106.0 (3)
N1—C3—C4	111.1 (3)	F13—C33—C29	112.4 (3)
N1—C3—C2	122.2 (3)	F15—C33—C29	113.3 (2)
C4—C3—C2	126.6 (3)	F14—C33—C29	112.7 (3)
C5—C4—C3	104.5 (3)	F17—C34—F16	106.6 (3)
C5—C4—H4	127.7	F17—C34—F18	106.5 (3)
C3—C4—H4	127.7	F16—C34—F18	106.2 (3)
N2—C5—C4	108.3 (3)	F17—C34—C31	112.7 (3)
N2—C5—C6	122.4 (3)	F16—C34—C31	111.9 (3)
C4—C5—C6	129.3 (3)	F18—C34—C31	112.5 (3)
N2—C7—C8	110.2 (3)	C40—C35—C36	115.6 (3)
N2—C7—H7A	109.6	C40—C35—B1	123.3 (3)
C8—C7—H7A	109.6	C36—C35—B1	121.1 (3)
N2—C7—H7B	109.6	C37—C36—C35	122.0 (3)
C8—C7—H7B	109.6	C37—C36—H36	119.0
H7A—C7—H7B	108.1	C35—C36—H36	119.0
N3—C8—C9	121.8 (3)	C38—C37—C36	121.1 (3)
N3—C8—C7	114.3 (3)	C38—C37—C41	118.5 (3)
C9—C8—C7	123.9 (3)	C36—C37—C41	120.4 (3)
C10—C9—C8	118.3 (3)	C39—C38—C37	118.3 (3)
C10—C9—H9	120.9	C39—C38—H38	120.8
C8—C9—H9	120.9	C37—C38—H38	120.8
C11—C10—C9	119.7 (3)	C38—C39—C40	120.2 (2)
C11—C10—H10	120.2	C38—C39—C42	121.0 (2)
C9—C10—H10	120.2	C40—C39—C42	118.8 (2)
C10—C11—C12	119.2 (3)	C35—C40—C39	122.8 (3)
C10—C11—H11	120.4	C35—C40—H40	118.6
C12—C11—H11	120.4	C39—C40—H40	118.6
N3—C12—C11	120.8 (3)	F19—C41—F20	106.7 (3)
N3—C12—C13	114.5 (3)	F19—C41—F21	105.3 (3)
C11—C12—C13	124.7 (3)	F20—C41—F21	106.9 (3)
N4—C13—C12	111.8 (3)	F19—C41—C37	113.6 (3)
N4—C13—H13A	109.3	F20—C41—C37	111.7 (3)
C12—C13—H13A	109.3	F21—C41—C37	112.2 (3)
N4—C13—H13B	109.3	F23A—C42—F22A	107.7 (3)
C12—C13—H13B	109.3	F24B—C42—F23B	107.3 (3)
H13A—C13—H13B	107.9	F22—C42—F24	107.0 (2)
N4—C15—C16	107.1 (3)	F24B—C42—F22B	106.3 (3)
N4—C15—C14	122.5 (3)	F23B—C42—F22B	106.4 (3)
C16—C15—C14	130.4 (3)	F22—C42—F23	106.0 (2)
C15—C16—C17	107.0 (3)	F24—C42—F23	105.7 (2)
C15—C16—H16	126.5	F23A—C42—F24A	106.2 (3)
C17—C16—H16	126.5	F22A—C42—F24A	106.1 (3)
N5—C17—C16	109.1 (3)	F23A—C42—C39	113.4 (2)
N5—C17—C18	123.1 (3)	F24B—C42—C39	113.3 (3)
C16—C17—C18	127.8 (3)	F22—C42—C39	113.5 (2)
F1—C2—F3	108.7 (3)	F22A—C42—C39	112.7 (3)
F1—C2—F2	107.7 (3)	F23B—C42—C39	112.6 (3)
F3—C2—F2	107.1 (3)	F24—C42—C39	112.9 (2)
F1—C2—C3	108.9 (3)	F22B—C42—C39	110.5 (3)
F3—C2—C3	112.2 (3)	F23—C42—C39	111.3 (2)
F2—C2—C3	112.2 (3)	F24A—C42—C39	110.3 (2)
F6—C6—F5	110.4 (4)	C44—C43—C48	115.4 (3)
F6—C6—F4	108.4 (3)	C44—C43—B1	120.4 (2)
F5—C6—F4	105.9 (4)	C48—C43—B1	124.1 (3)
F6—C6—C5	110.1 (4)	C45—C44—C43	122.5 (3)
F5—C6—C5	111.4 (3)	C45—C44—H44	118.8
F4—C6—C5	110.6 (3)	C43—C44—H44	118.8
C15—C14—H14A	109.5	C46—C45—C44	120.7 (3)
C15—C14—H14B	109.5	C46—C45—C49	120.4 (3)
C15—C14—H14C	109.5	C44—C45—C49	118.9 (3)
C17—C18—H18A	109.5	C45—C46—C47	118.0 (3)
C17—C18—H18B	109.5	C45—C46—H46	121.0
C17—C18—H18C	109.5	C47—C46—H46	121.0
C24—C19—C20	114.7 (3)	C46—C47—C48	121.1 (2)
C24—C19—B1	124.9 (2)	C46—C47—C50	118.1 (2)
C20—C19—B1	120.3 (2)	C48—C47—C50	120.7 (2)
C21—C20—C19	122.6 (3)	C47—C48—C43	122.2 (3)
C21—C20—H20	118.7	C47—C48—H48	118.9
C19—C20—H20	118.7	C43—C48—H48	118.9
C22—C21—C20	121.0 (3)	F45—C49—F43	106.7 (3)
C22—C21—C25	120.0 (3)	F45—C49—F44	106.9 (3)
C20—C21—C25	119.0 (3)	F43—C49—F44	106.3 (2)
C23—C22—C21	118.0 (3)	F45—C49—C45	112.5 (2)
C23—C22—H22	121.0	F43—C49—C45	112.5 (3)
C21—C22—H22	121.0	F44—C49—C45	111.6 (3)
C22—C23—C24	120.7 (2)	F48—C50—F46	109.3 (3)
C22—C23—C26	119.0 (2)	F47A—C50—F48A	109.4 (3)
C24—C23—C26	120.4 (2)	F46B—C50—F47B	107.7 (3)
C23—C24—C19	123.1 (3)	F46B—C50—F48B	106.4 (3)
C23—C24—H24	118.5	F47B—C50—F48B	105.7 (3)
C19—C24—H24	118.5	F47A—C50—F46A	105.4 (3)
F7—C25—F8	106.2 (3)	F48A—C50—F46A	103.8 (3)
F7—C25—F9	107.0 (3)	F48—C50—F47	105.7 (2)
F8—C25—F9	105.6 (3)	F46—C50—F47	104.0 (2)
F7—C25—C21	113.4 (3)	F47A—C50—C47	116.6 (3)
F8—C25—C21	112.2 (3)	F48—C50—C47	114.3 (3)
F9—C25—C21	112.0 (3)	F46—C50—C47	114.1 (2)
F10—C26—F11	108.3 (3)	F46B—C50—C47	113.9 (4)
F11A—C26—F12A	108.1 (3)	F48A—C50—C47	113.3 (3)
F12B—C26—F11B	107.2 (3)	F47B—C50—C47	112.0 (4)
F12B—C26—F10B	107.6 (3)	F48B—C50—C47	110.6 (4)
F11B—C26—F10B	104.4 (3)	F46A—C50—C47	107.2 (3)
F10—C26—F12	106.7 (3)	F47—C50—C47	108.6 (2)
C1—Pd1—N1—C3	−62.9 (3)	C24—C23—C26—F12	101.0 (4)
N3—Pd1—N1—C3	121.5 (3)	C22—C23—C26—F10A	73.6 (4)
C1—Pd1—N1—N2	132.6 (2)	C24—C23—C26—F10A	−106.3 (4)
N3—Pd1—N1—N2	−42.9 (2)	C35—B1—C27—C32	11.0 (4)
C3—N1—N2—C5	0.2 (3)	C19—B1—C27—C32	−110.5 (3)
Pd1—N1—N2—C5	169.1 (2)	C43—B1—C27—C32	129.3 (3)
C3—N1—N2—C7	−170.5 (3)	C35—B1—C27—C28	−169.2 (2)
Pd1—N1—N2—C7	−1.6 (3)	C19—B1—C27—C28	69.2 (3)
N5—Pd1—N3—C12	40.2 (2)	C43—B1—C27—C28	−50.9 (3)
N1—Pd1—N3—C12	−136.5 (2)	C32—C27—C28—C29	3.3 (4)
N5—Pd1—N3—C8	−138.4 (2)	B1—C27—C28—C29	−176.5 (3)
N1—Pd1—N3—C8	44.9 (2)	C27—C28—C29—C30	−2.3 (4)
C15—N4—N5—C17	0.9 (3)	C27—C28—C29—C33	177.4 (3)
C13—N4—N5—C17	−177.0 (3)	C28—C29—C30—C31	−0.3 (4)
C15—N4—N5—Pd1	175.3 (2)	C33—C29—C30—C31	180.0 (3)
C13—N4—N5—Pd1	−2.5 (4)	C29—C30—C31—C32	1.8 (4)
C1—Pd1—N5—C17	−42.5 (3)	C29—C30—C31—C34	−175.8 (3)
N3—Pd1—N5—C17	133.1 (3)	C30—C31—C32—C27	−0.6 (4)
C1—Pd1—N5—N4	145.4 (2)	C34—C31—C32—C27	176.9 (3)
N3—Pd1—N5—N4	−39.0 (2)	C28—C27—C32—C31	−1.9 (4)
N2—N1—C3—C4	−0.8 (3)	B1—C27—C32—C31	177.9 (3)
Pd1—N1—C3—C4	−166.4 (2)	C28—C29—C33—F13	−70.4 (4)
N2—N1—C3—C2	175.5 (3)	C30—C29—C33—F13	109.4 (4)
Pd1—N1—C3—C2	9.9 (5)	C28—C29—C33—F15	49.1 (4)
N1—C3—C4—C5	1.1 (4)	C30—C29—C33—F15	−131.1 (3)
C2—C3—C4—C5	−175.0 (3)	C28—C29—C33—F14	169.5 (3)
N1—N2—C5—C4	0.5 (4)	C30—C29—C33—F14	−10.8 (4)
C7—N2—C5—C4	170.0 (3)	C30—C31—C34—F17	−138.7 (3)
N1—N2—C5—C6	−178.9 (3)	C32—C31—C34—F17	43.7 (4)
C7—N2—C5—C6	−9.4 (5)	C30—C31—C34—F16	101.2 (3)
C3—C4—C5—N2	−1.0 (4)	C32—C31—C34—F16	−76.4 (4)
C3—C4—C5—C6	178.3 (3)	C30—C31—C34—F18	−18.3 (4)
C5—N2—C7—C8	−102.3 (4)	C32—C31—C34—F18	164.1 (3)
N1—N2—C7—C8	66.3 (4)	C27—B1—C35—C40	98.8 (3)
C12—N3—C8—C9	0.6 (5)	C19—B1—C35—C40	−139.4 (3)
Pd1—N3—C8—C9	179.2 (2)	C43—B1—C35—C40	−19.1 (4)
C12—N3—C8—C7	−178.9 (3)	C27—B1—C35—C36	−79.5 (3)
Pd1—N3—C8—C7	−0.3 (3)	C19—B1—C35—C36	42.3 (3)
N2—C7—C8—N3	−63.0 (4)	C43—B1—C35—C36	162.5 (2)
N2—C7—C8—C9	117.6 (3)	C40—C35—C36—C37	0.1 (4)
N3—C8—C9—C10	−0.5 (5)	B1—C35—C36—C37	178.6 (3)
C7—C8—C9—C10	178.9 (3)	C35—C36—C37—C38	0.6 (5)
C8—C9—C10—C11	−0.1 (5)	C35—C36—C37—C41	179.6 (3)
C9—C10—C11—C12	0.6 (5)	C36—C37—C38—C39	−0.9 (4)
C8—N3—C12—C11	0.0 (5)	C41—C37—C38—C39	−179.9 (3)
Pd1—N3—C12—C11	−178.6 (2)	C37—C38—C39—C40	0.4 (4)
C8—N3—C12—C13	−178.9 (3)	C37—C38—C39—C42	179.2 (2)
Pd1—N3—C12—C13	2.5 (3)	C36—C35—C40—C39	−0.6 (4)
C10—C11—C12—N3	−0.6 (5)	B1—C35—C40—C39	−179.0 (3)
C10—C11—C12—C13	178.2 (3)	C38—C39—C40—C35	0.3 (4)
C15—N4—C13—C12	−113.6 (4)	C42—C39—C40—C35	−178.5 (2)
N5—N4—C13—C12	63.8 (4)	C38—C37—C41—F19	−164.1 (3)
N3—C12—C13—N4	−61.1 (4)	C36—C37—C41—F19	16.9 (5)
C11—C12—C13—N4	120.0 (3)	C38—C37—C41—F20	−43.3 (4)
N5—N4—C15—C16	−0.8 (4)	C36—C37—C41—F20	137.6 (3)
C13—N4—C15—C16	176.8 (3)	C38—C37—C41—F21	76.7 (4)
N5—N4—C15—C14	−179.9 (3)	C36—C37—C41—F21	−102.4 (4)
C13—N4—C15—C14	−2.3 (5)	C38—C39—C42—F23A	−129.4 (4)
N4—C15—C16—C17	0.5 (4)	C40—C39—C42—F23A	49.3 (4)
C14—C15—C16—C17	179.4 (3)	C38—C39—C42—F24B	168.4 (7)
N4—N5—C17—C16	−0.5 (4)	C40—C39—C42—F24B	−12.8 (7)
Pd1—N5—C17—C16	−173.2 (3)	C38—C39—C42—F22	15.4 (4)
N4—N5—C17—C18	179.1 (3)	C40—C39—C42—F22	−165.9 (3)
Pd1—N5—C17—C18	6.5 (5)	C38—C39—C42—F22A	−6.8 (4)
C15—C16—C17—N5	0.0 (4)	C40—C39—C42—F22A	171.9 (4)
C15—C16—C17—C18	−179.6 (3)	C38—C39—C42—F23B	46.4 (7)
N1—C3—C2—F1	−158.9 (3)	C40—C39—C42—F23B	−134.8 (7)
C4—C3—C2—F1	16.8 (5)	C38—C39—C42—F24	137.4 (4)
N1—C3—C2—F3	−38.6 (4)	C40—C39—C42—F24	−43.9 (4)
C4—C3—C2—F3	137.1 (3)	C38—C39—C42—F22B	−72.4 (7)
N1—C3—C2—F2	81.9 (4)	C40—C39—C42—F22B	106.3 (7)
C4—C3—C2—F2	−102.4 (4)	C38—C39—C42—F23	−104.0 (4)
N2—C5—C6—F6	170.8 (3)	C40—C39—C42—F23	74.7 (4)
C4—C5—C6—F6	−8.5 (5)	C38—C39—C42—F24A	111.6 (4)
N2—C5—C6—F5	−66.4 (5)	C40—C39—C42—F24A	−69.6 (4)
C4—C5—C6—F5	114.3 (5)	C27—B1—C43—C44	−39.3 (3)
N2—C5—C6—F4	51.0 (5)	C35—B1—C43—C44	80.5 (3)
C4—C5—C6—F4	−128.2 (4)	C19—B1—C43—C44	−159.5 (2)
C27—B1—C19—C24	−17.4 (4)	C27—B1—C43—C48	145.0 (3)
C35—B1—C19—C24	−139.4 (3)	C35—B1—C43—C48	−95.2 (3)
C43—B1—C19—C24	101.4 (3)	C19—B1—C43—C48	24.8 (4)
C27—B1—C19—C20	165.6 (2)	C48—C43—C44—C45	1.4 (4)
C35—B1—C19—C20	43.6 (3)	B1—C43—C44—C45	−174.7 (2)
C43—B1—C19—C20	−75.6 (3)	C43—C44—C45—C46	−0.4 (4)
C24—C19—C20—C21	−1.4 (4)	C43—C44—C45—C49	178.4 (3)
B1—C19—C20—C21	175.9 (3)	C44—C45—C46—C47	−1.5 (4)
C19—C20—C21—C22	0.9 (4)	C49—C45—C46—C47	179.7 (3)
C19—C20—C21—C25	−179.8 (3)	C45—C46—C47—C48	2.3 (5)
C20—C21—C22—C23	0.0 (4)	C45—C46—C47—C50	−174.8 (3)
C25—C21—C22—C23	−179.3 (3)	C46—C47—C48—C43	−1.3 (5)
C21—C22—C23—C24	−0.3 (4)	C50—C47—C48—C43	175.7 (3)
C21—C22—C23—C26	179.8 (2)	C44—C43—C48—C47	−0.5 (4)
C22—C23—C24—C19	−0.3 (5)	B1—C43—C48—C47	175.4 (3)
C26—C23—C24—C19	179.7 (3)	C46—C45—C49—F45	−136.0 (3)
C20—C19—C24—C23	1.1 (4)	C44—C45—C49—F45	45.2 (4)
B1—C19—C24—C23	−176.0 (3)	C46—C45—C49—F43	−15.5 (4)
C22—C21—C25—F7	−11.4 (4)	C44—C45—C49—F43	165.7 (3)
C20—C21—C25—F7	169.3 (3)	C46—C45—C49—F44	103.9 (3)
C22—C21—C25—F8	108.9 (3)	C44—C45—C49—F44	−75.0 (3)
C20—C21—C25—F8	−70.4 (4)	C46—C47—C50—F47A	39.7 (4)
C22—C21—C25—F9	−132.5 (3)	C48—C47—C50—F47A	−137.4 (4)
C20—C21—C25—F9	48.2 (4)	C46—C47—C50—F48	−176.0 (3)
C22—C23—C26—F11A	−165.4 (4)	C48—C47—C50—F48	6.9 (4)
C24—C23—C26—F11A	14.6 (5)	C46—C47—C50—F46	−49.2 (4)
C22—C23—C26—F12B	8.5 (5)	C48—C47—C50—F46	133.7 (4)
C24—C23—C26—F12B	−171.4 (4)	C46—C47—C50—F46B	−18.4 (10)
C22—C23—C26—F10	39.7 (4)	C48—C47—C50—F46B	164.5 (10)
C24—C23—C26—F10	−140.3 (4)	C46—C47—C50—F48A	168.0 (3)
C22—C23—C26—F11	163.4 (4)	C48—C47—C50—F48A	−9.1 (4)
C24—C23—C26—F11	−16.6 (4)	C46—C47—C50—F47B	−140.9 (10)
C22—C23—C26—F12A	−41.2 (4)	C48—C47—C50—F47B	42.0 (10)
C24—C23—C26—F12A	138.8 (4)	C46—C47—C50—F48B	101.4 (10)
C22—C23—C26—F11B	−113.9 (4)	C48—C47—C50—F48B	−75.7 (10)
C24—C23—C26—F11B	66.2 (4)	C46—C47—C50—F46A	−78.0 (4)
C22—C23—C26—F10B	130.5 (4)	C48—C47—C50—F46A	104.9 (4)
C24—C23—C26—F10B	−49.5 (4)	C46—C47—C50—F47	66.3 (4)
C22—C23—C26—F12	−79.1 (4)	C48—C47—C50—F47	−110.8 (4)