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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 C3v geometry.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108002503/sk3199sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108002503/sk3199Isup2.hkl
Contains datablock I

CCDC reference: 682791

Comment top

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 C3v 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 Cs 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 D2d and D4h. 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-Cs-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 C3v 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 top

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).

Experimental top

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, CH3, pz), 2.33 (s, 3H, CH3, pz), 5.16 (d, 2H, CH2, 2JHH = 15.6 Hz), 5.63 (s, 1H, pz), 5.98 (s, 1H, pz), 6.20 (d, 2H, CH2, 2JHH = 17.4 Hz), 6.71 (d, 1H, py, 3JHH = 8.2 Hz), 7.23 (d, 2H, py, 3JHH = 8.6 Hz), 7.34 (t, 1H, py, 3JHH = 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.

Refinement top

All H atoms were placed in idealized locations and refined as riding, with appropriate displacement parameters [Uiso(H) = 1.5Ueq(C) for methyl H atoms and Uiso(H) = 1.2Ueq(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 C3v 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 Cipso···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 top

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 top
[Figure 1] 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.
[Figure 2] 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 top
Crystal data top
[Pd(C18H18F6N5)](C32H12BF24)F(000) = 2744
Mr = 1388.00Dx = 1.737 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 999 reflections
a = 10.9194 (4) Åθ = 1.9–29.1°
b = 18.0256 (7) ŵ = 0.50 mm1
c = 27.1635 (11) ÅT = 105 K
β = 96.865 (1)°Block, colourless
V = 5308.2 (4) Å30.36 × 0.31 × 0.26 mm
Z = 4
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer
14211 independent reflections
Radiation source: fine-focus sealed tube12423 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
0.30° ω scansθmax = 29.1°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
h = 1414
Tmin = 0.841, Tmax = 0.882k = 2424
92342 measured reflectionsl = 3637
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.154H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0761P)2 + 17.6386P]
where P = (Fo2 + 2Fc2)/3
14211 reflections(Δ/σ)max = 0.002
823 parametersΔρmax = 2.16 e Å3
109 restraintsΔρmin = 1.63 e Å3
Crystal data top
[Pd(C18H18F6N5)](C32H12BF24)V = 5308.2 (4) Å3
Mr = 1388.00Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.9194 (4) ŵ = 0.50 mm1
b = 18.0256 (7) ÅT = 105 K
c = 27.1635 (11) Å0.36 × 0.31 × 0.26 mm
β = 96.865 (1)°
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer
14211 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
12423 reflections with I > 2σ(I)
Tmin = 0.841, Tmax = 0.882Rint = 0.030
92342 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.058109 restraints
wR(F2) = 0.154H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0761P)2 + 17.6386P]
where P = (Fo2 + 2Fc2)/3
14211 reflectionsΔρmax = 2.16 e Å3
823 parametersΔρmin = 1.63 e Å3
Special details top

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 (Å2) top
xyzUiso*/UeqOcc. (<1)
Pd10.82360 (2)0.231916 (12)0.695226 (8)0.02061 (8)
N10.6820 (3)0.29097 (15)0.65737 (10)0.0232 (5)
N20.7131 (3)0.35531 (15)0.63610 (10)0.0243 (5)
N30.9230 (2)0.25670 (15)0.63454 (9)0.0214 (5)
N41.0293 (2)0.12993 (15)0.69146 (10)0.0244 (5)
N50.9709 (2)0.17074 (15)0.72426 (10)0.0234 (5)
B10.9170 (3)0.21064 (18)0.37765 (11)0.0172 (5)
C10.7297 (3)0.21656 (18)0.75589 (11)0.0247 (6)
H1A0.74900.16740.77010.037*
H1B0.64080.22030.74560.037*
H1C0.75470.25470.78080.037*
C30.5646 (3)0.27789 (18)0.63913 (12)0.0237 (6)
C40.5189 (3)0.3342 (2)0.60658 (12)0.0281 (7)
H40.43840.33850.58930.034*
C50.6165 (3)0.38182 (18)0.60529 (12)0.0276 (6)
C70.8423 (3)0.37912 (18)0.64239 (12)0.0270 (6)
H7A0.87320.38100.67810.032*
H7B0.84870.42950.62850.032*
C80.9197 (3)0.32598 (18)0.61642 (11)0.0238 (6)
C90.9838 (3)0.3458 (2)0.57733 (12)0.0294 (7)
H90.98000.39490.56470.035*
C101.0535 (3)0.2919 (2)0.55721 (13)0.0339 (8)
H101.09830.30380.53040.041*
C111.0575 (3)0.2207 (2)0.57635 (13)0.0316 (7)
H111.10560.18350.56300.038*
C120.9902 (3)0.20439 (19)0.61530 (11)0.0246 (6)
C130.9835 (3)0.12867 (18)0.63873 (12)0.0260 (6)
H13A0.89680.11140.63450.031*
H13B1.03280.09310.62160.031*
C151.1310 (3)0.09649 (19)0.71495 (13)0.0286 (7)
C161.1396 (3)0.1168 (2)0.76359 (13)0.0317 (7)
H161.20200.10220.78920.038*
C171.0388 (3)0.16317 (19)0.76869 (12)0.0282 (6)
C20.4983 (3)0.20831 (19)0.65086 (12)0.0263 (6)0.865 (3)
F10.4038 (3)0.19790 (16)0.61644 (10)0.0336 (6)0.865 (3)
F20.4542 (2)0.21236 (14)0.69477 (9)0.0288 (5)0.865 (3)
F30.5713 (2)0.14867 (13)0.65236 (9)0.0270 (5)0.865 (3)
C2A0.4983 (3)0.20831 (19)0.65086 (12)0.0263 (6)0.135 (3)
H2A10.55310.16560.64910.039*0.135 (3)
H2A20.42470.20200.62680.039*0.135 (3)
H2A30.47370.21190.68430.039*0.135 (3)
C60.6243 (4)0.4514 (2)0.57596 (14)0.0359 (8)0.865 (3)
F40.7243 (3)0.44958 (18)0.55056 (11)0.0443 (7)0.865 (3)
F50.6395 (5)0.51065 (14)0.60537 (11)0.0495 (8)0.865 (3)
F60.5264 (3)0.45876 (16)0.54433 (10)0.0403 (7)0.865 (3)
C6A0.6243 (4)0.4514 (2)0.57596 (14)0.0359 (8)0.135 (3)
H6A10.64480.49310.59860.054*0.135 (3)
H6A20.54480.46070.55610.054*0.135 (3)
H6A30.68860.44590.55390.054*0.135 (3)
C141.2130 (3)0.0485 (2)0.68851 (15)0.0375 (8)0.865 (3)
H14A1.16430.00860.67120.056*0.865 (3)
H14B1.27740.02700.71250.056*0.865 (3)
H14C1.25130.07840.66440.056*0.865 (3)
C14A1.2130 (3)0.0485 (2)0.68851 (15)0.0375 (8)0.135 (3)
F4A1.1479 (10)0.0007 (8)0.6619 (6)0.057 (3)*0.135 (3)
F5A1.2925 (14)0.0158 (10)0.7209 (4)0.057 (3)*0.135 (3)
F6A1.2714 (16)0.0902 (6)0.6594 (6)0.057 (3)*0.135 (3)
C181.0073 (3)0.2000 (2)0.81444 (12)0.0385 (8)0.865 (3)
H18A0.95260.24220.80540.058*0.865 (3)
H18B1.08290.21760.83400.058*0.865 (3)
H18C0.96550.16460.83410.058*0.865 (3)
C18A1.0073 (3)0.2000 (2)0.81444 (12)0.0385 (8)0.135 (3)
F1A0.9744 (14)0.2695 (5)0.8058 (4)0.057 (3)*0.135 (3)
F2A1.0950 (10)0.1970 (8)0.8506 (4)0.057 (3)*0.135 (3)
F3A0.9085 (11)0.1672 (7)0.8292 (5)0.057 (3)*0.135 (3)
F70.57197 (19)0.16428 (14)0.54352 (7)0.0360 (5)
F80.7643 (2)0.13812 (13)0.55785 (7)0.0350 (5)
F90.7085 (2)0.25001 (12)0.54043 (8)0.0338 (5)
F100.3865 (3)0.0887 (3)0.3785 (2)0.0427 (6)*0.420 (4)
F110.5008 (5)0.0771 (3)0.31884 (11)0.0427 (6)*0.420 (4)
F120.5120 (5)0.00418 (18)0.3775 (2)0.0427 (6)*0.420 (4)
F10A0.3979 (4)0.1151 (3)0.3586 (3)0.0427 (6)*0.292 (3)
F11A0.5257 (6)0.0447 (4)0.32468 (17)0.0427 (6)*0.292 (3)
F12A0.4576 (6)0.0122 (3)0.3933 (2)0.0427 (6)*0.292 (3)
F10B0.4616 (6)0.1066 (4)0.32482 (18)0.0427 (6)*0.288 (3)
F11B0.5381 (6)0.0031 (3)0.3531 (3)0.0427 (6)*0.288 (3)
F12B0.3993 (4)0.0577 (4)0.3905 (2)0.0427 (6)*0.288 (3)
F130.6272 (2)0.14221 (19)0.20765 (11)0.0622 (9)
F140.7530 (3)0.14536 (18)0.15369 (9)0.0616 (9)
F150.7127 (2)0.24324 (11)0.19243 (9)0.0344 (5)
F161.22958 (19)0.08148 (12)0.25141 (9)0.0372 (5)
F171.1627 (2)0.00426 (13)0.29542 (9)0.0428 (6)
F181.1053 (2)0.00028 (15)0.21752 (10)0.0481 (7)
F191.1242 (2)0.00917 (12)0.47880 (11)0.0448 (6)
F201.3140 (2)0.02079 (14)0.49695 (12)0.0543 (7)
F211.1795 (3)0.04912 (15)0.54564 (10)0.0617 (8)
F221.4494 (3)0.2789 (2)0.4844 (2)0.0340 (5)*0.523 (3)
F231.3002 (4)0.3547 (2)0.49272 (19)0.0340 (5)*0.523 (3)
F241.3562 (5)0.3355 (3)0.42029 (11)0.0340 (5)*0.523 (3)
F22A1.4308 (4)0.2859 (3)0.49868 (19)0.0340 (5)*0.333 (5)
F23A1.2886 (4)0.3661 (2)0.4739 (3)0.0340 (5)*0.333 (5)
F24A1.3915 (5)0.3126 (3)0.42072 (15)0.0340 (5)*0.333 (5)
F22B1.3373 (10)0.3316 (6)0.5084 (2)0.0340 (5)*0.143 (4)
F23B1.4543 (4)0.2777 (4)0.4603 (5)0.0340 (5)*0.143 (4)
F24B1.3158 (9)0.3567 (4)0.4301 (4)0.0340 (5)*0.143 (4)
F460.7831 (3)0.5283 (2)0.43697 (17)0.0354 (5)*0.540 (3)
F470.6375 (3)0.4942 (3)0.38154 (12)0.0354 (5)*0.540 (3)
F480.6768 (4)0.4298 (2)0.44904 (14)0.0354 (5)*0.540 (3)
F46A0.8035 (4)0.5041 (3)0.45402 (17)0.0354 (5)*0.383 (4)
F47A0.6692 (5)0.5199 (3)0.39002 (18)0.0354 (5)*0.383 (4)
F48A0.6542 (4)0.4262 (3)0.43950 (18)0.0354 (5)*0.383 (4)
F46B0.7560 (14)0.5403 (2)0.4160 (7)0.0354 (5)*0.077 (3)
F47B0.7327 (16)0.4457 (9)0.4635 (3)0.0354 (5)*0.077 (3)
F48B0.6136 (4)0.4593 (10)0.3947 (5)0.0354 (5)*0.077 (3)
F430.9962 (2)0.52048 (10)0.28150 (8)0.0311 (4)
F441.15148 (18)0.45304 (12)0.30951 (9)0.0342 (5)
F451.0224 (2)0.41414 (11)0.24889 (7)0.0344 (5)
C190.7993 (3)0.17581 (15)0.40236 (10)0.0173 (5)
C200.7878 (3)0.18767 (15)0.45285 (10)0.0189 (5)
H200.85200.21320.47270.023*
C210.6864 (3)0.16349 (16)0.47479 (10)0.0185 (5)
C220.5911 (3)0.12503 (16)0.44761 (11)0.0206 (5)
H220.52170.10850.46260.025*
C230.6002 (2)0.11153 (15)0.39795 (10)0.0228 (6)
C240.7016 (3)0.13619 (16)0.37627 (11)0.0206 (5)
H240.70500.12580.34220.025*
C250.6818 (3)0.17873 (19)0.52867 (11)0.0235 (6)
C260.4988 (2)0.06988 (15)0.36791 (9)0.0370 (8)
C270.9276 (3)0.17202 (15)0.32375 (10)0.0176 (5)
C280.8371 (3)0.18715 (15)0.28358 (10)0.0186 (5)
H280.77390.22190.28810.022*
C290.8368 (3)0.15330 (16)0.23770 (11)0.0197 (5)
C300.9297 (3)0.10425 (16)0.22890 (11)0.0211 (5)
H300.92950.08080.19760.025*
C311.0227 (3)0.09050 (16)0.26708 (11)0.0206 (5)
C321.0215 (3)0.12340 (16)0.31370 (11)0.0194 (5)
H321.08630.11240.33920.023*
C330.7332 (3)0.17095 (17)0.19817 (11)0.0236 (6)
C341.1297 (3)0.04183 (18)0.25804 (12)0.0247 (6)
C351.0443 (3)0.19791 (16)0.41523 (10)0.0185 (5)
C361.0681 (3)0.13004 (16)0.44036 (11)0.0203 (5)
H361.00820.09170.43590.024*
C371.1766 (3)0.11758 (17)0.47152 (11)0.0226 (6)
C381.2665 (3)0.17223 (18)0.47961 (11)0.0231 (6)
H381.34000.16370.50130.028*
C391.2461 (2)0.23958 (14)0.45523 (10)0.0215 (6)
C401.1370 (3)0.25147 (16)0.42367 (10)0.0194 (5)
H401.12530.29790.40730.023*
C411.1982 (3)0.0448 (2)0.49786 (14)0.0315 (7)
C421.3381 (2)0.30101 (13)0.46283 (8)0.0277 (6)
C430.8976 (3)0.30043 (16)0.36859 (10)0.0174 (5)
C440.9621 (3)0.33788 (15)0.33446 (10)0.0182 (5)
H441.01150.30990.31470.022*
C450.9564 (3)0.41476 (16)0.32841 (10)0.0183 (5)
C460.8850 (3)0.45768 (17)0.35614 (12)0.0234 (6)
H460.88240.51010.35270.028*
C470.8175 (3)0.42191 (15)0.38914 (11)0.0252 (6)
C480.8245 (3)0.34537 (16)0.39557 (11)0.0224 (6)
H480.77830.32280.41900.027*
C491.0309 (3)0.45037 (17)0.29200 (12)0.0237 (6)
C500.7320 (2)0.46738 (13)0.41592 (10)0.0446 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.02401 (13)0.01908 (12)0.01921 (12)0.00295 (8)0.00459 (8)0.00037 (8)
N10.0297 (13)0.0194 (11)0.0218 (12)0.0005 (10)0.0083 (10)0.0014 (9)
N20.0320 (14)0.0199 (12)0.0220 (12)0.0004 (10)0.0079 (10)0.0002 (10)
N30.0207 (12)0.0252 (12)0.0180 (11)0.0041 (10)0.0007 (9)0.0025 (9)
N40.0234 (12)0.0246 (12)0.0241 (12)0.0018 (10)0.0015 (10)0.0001 (10)
N50.0246 (12)0.0225 (12)0.0226 (12)0.0013 (10)0.0004 (10)0.0009 (10)
B10.0182 (14)0.0171 (13)0.0161 (13)0.0008 (11)0.0017 (10)0.0005 (11)
C10.0306 (16)0.0251 (14)0.0197 (13)0.0018 (12)0.0086 (11)0.0045 (11)
C30.0243 (14)0.0252 (14)0.0226 (14)0.0053 (11)0.0070 (11)0.0016 (11)
C40.0298 (16)0.0326 (16)0.0230 (14)0.0096 (13)0.0069 (12)0.0004 (12)
C50.0366 (17)0.0255 (15)0.0221 (14)0.0072 (13)0.0089 (12)0.0002 (12)
C70.0352 (17)0.0214 (14)0.0252 (15)0.0062 (12)0.0072 (12)0.0020 (11)
C80.0254 (14)0.0262 (15)0.0196 (13)0.0071 (12)0.0025 (11)0.0018 (11)
C90.0316 (16)0.0333 (17)0.0235 (15)0.0098 (13)0.0048 (12)0.0016 (13)
C100.0320 (17)0.048 (2)0.0235 (15)0.0066 (15)0.0084 (13)0.0015 (14)
C110.0275 (16)0.0426 (19)0.0252 (15)0.0013 (14)0.0053 (13)0.0052 (14)
C120.0218 (14)0.0318 (16)0.0197 (13)0.0027 (12)0.0003 (11)0.0046 (12)
C130.0267 (15)0.0264 (15)0.0241 (14)0.0005 (12)0.0003 (12)0.0047 (12)
C150.0235 (15)0.0265 (15)0.0342 (17)0.0036 (12)0.0034 (12)0.0045 (13)
C160.0303 (17)0.0315 (17)0.0311 (17)0.0010 (13)0.0056 (13)0.0086 (13)
C170.0311 (16)0.0280 (15)0.0246 (15)0.0055 (13)0.0005 (12)0.0037 (12)
C20.0231 (14)0.0294 (16)0.0269 (15)0.0026 (12)0.0057 (12)0.0005 (12)
F10.0221 (12)0.0429 (14)0.0347 (13)0.0055 (10)0.0010 (9)0.0005 (11)
F20.0259 (11)0.0324 (12)0.0304 (12)0.0031 (9)0.0125 (9)0.0029 (9)
F30.0252 (11)0.0227 (10)0.0345 (12)0.0011 (9)0.0089 (9)0.0024 (9)
C2A0.0231 (14)0.0294 (16)0.0269 (15)0.0026 (12)0.0057 (12)0.0005 (12)
C60.045 (2)0.0330 (18)0.0305 (17)0.0070 (16)0.0096 (16)0.0079 (14)
F40.0408 (15)0.0575 (18)0.0365 (14)0.0074 (13)0.0126 (11)0.0237 (13)
F50.084 (2)0.0215 (12)0.0426 (15)0.0065 (14)0.0058 (15)0.0063 (11)
F60.0422 (15)0.0470 (15)0.0314 (13)0.0167 (12)0.0031 (11)0.0170 (12)
C6A0.045 (2)0.0330 (18)0.0305 (17)0.0070 (16)0.0096 (16)0.0079 (14)
C140.0286 (17)0.0378 (19)0.045 (2)0.0045 (15)0.0006 (15)0.0030 (16)
C14A0.0286 (17)0.0378 (19)0.045 (2)0.0045 (15)0.0006 (15)0.0030 (16)
C180.044 (2)0.048 (2)0.0221 (15)0.0003 (17)0.0032 (14)0.0021 (15)
C18A0.044 (2)0.048 (2)0.0221 (15)0.0003 (17)0.0032 (14)0.0021 (15)
F70.0260 (10)0.0623 (15)0.0210 (9)0.0063 (10)0.0079 (7)0.0038 (9)
F80.0374 (11)0.0449 (12)0.0205 (9)0.0076 (9)0.0062 (8)0.0019 (8)
F90.0451 (12)0.0325 (10)0.0250 (10)0.0016 (9)0.0093 (9)0.0116 (8)
F130.0343 (13)0.083 (2)0.0627 (17)0.0332 (13)0.0205 (12)0.0376 (16)
F140.0772 (19)0.081 (2)0.0219 (11)0.0473 (17)0.0143 (11)0.0179 (12)
F150.0297 (10)0.0240 (9)0.0453 (12)0.0032 (8)0.0124 (9)0.0012 (9)
F160.0246 (10)0.0316 (11)0.0585 (14)0.0009 (8)0.0182 (9)0.0012 (10)
F170.0492 (14)0.0330 (11)0.0506 (13)0.0218 (10)0.0235 (11)0.0149 (10)
F180.0354 (12)0.0562 (15)0.0524 (14)0.0131 (11)0.0040 (10)0.0332 (12)
F190.0415 (13)0.0239 (10)0.0669 (16)0.0027 (9)0.0017 (11)0.0119 (10)
F200.0300 (12)0.0387 (13)0.093 (2)0.0150 (10)0.0034 (13)0.0255 (14)
F210.111 (3)0.0414 (14)0.0348 (13)0.0190 (15)0.0160 (14)0.0180 (11)
F430.0411 (11)0.0175 (8)0.0362 (11)0.0006 (8)0.0110 (9)0.0038 (8)
F440.0210 (9)0.0335 (11)0.0491 (13)0.0053 (8)0.0088 (9)0.0007 (9)
F450.0568 (14)0.0253 (10)0.0235 (9)0.0058 (9)0.0150 (9)0.0031 (8)
C190.0184 (12)0.0153 (12)0.0181 (12)0.0024 (9)0.0023 (10)0.0002 (9)
C200.0202 (13)0.0175 (12)0.0187 (12)0.0014 (10)0.0008 (10)0.0012 (10)
C210.0188 (12)0.0193 (12)0.0173 (12)0.0036 (10)0.0018 (10)0.0006 (10)
C220.0190 (13)0.0215 (13)0.0218 (13)0.0002 (10)0.0043 (10)0.0015 (11)
C230.0218 (14)0.0221 (14)0.0248 (14)0.0040 (11)0.0032 (11)0.0068 (11)
C240.0224 (13)0.0211 (13)0.0185 (12)0.0008 (11)0.0039 (10)0.0036 (10)
C250.0197 (13)0.0322 (16)0.0187 (13)0.0007 (11)0.0026 (10)0.0009 (11)
C260.0314 (18)0.048 (2)0.0326 (17)0.0170 (16)0.0084 (14)0.0161 (16)
C270.0197 (12)0.0157 (12)0.0179 (12)0.0005 (10)0.0039 (10)0.0003 (9)
C280.0199 (13)0.0164 (12)0.0196 (12)0.0002 (10)0.0029 (10)0.0003 (10)
C290.0229 (13)0.0174 (12)0.0188 (12)0.0026 (10)0.0024 (10)0.0002 (10)
C300.0263 (14)0.0185 (13)0.0197 (13)0.0021 (11)0.0073 (11)0.0035 (10)
C310.0208 (13)0.0187 (13)0.0237 (13)0.0007 (10)0.0088 (11)0.0011 (10)
C320.0201 (13)0.0186 (12)0.0198 (13)0.0003 (10)0.0036 (10)0.0001 (10)
C330.0276 (15)0.0222 (14)0.0201 (13)0.0015 (11)0.0002 (11)0.0034 (11)
C340.0249 (14)0.0233 (14)0.0273 (15)0.0017 (11)0.0084 (12)0.0040 (12)
C350.0186 (12)0.0192 (12)0.0181 (12)0.0034 (10)0.0037 (10)0.0010 (10)
C360.0221 (13)0.0179 (12)0.0211 (13)0.0024 (10)0.0036 (10)0.0003 (10)
C370.0232 (14)0.0218 (14)0.0234 (14)0.0073 (11)0.0052 (11)0.0035 (11)
C380.0193 (13)0.0293 (15)0.0207 (13)0.0059 (11)0.0025 (10)0.0014 (11)
C390.0180 (13)0.0251 (14)0.0212 (13)0.0006 (11)0.0020 (10)0.0014 (11)
C400.0205 (13)0.0187 (12)0.0192 (12)0.0023 (10)0.0035 (10)0.0005 (10)
C410.0310 (17)0.0277 (16)0.0355 (18)0.0089 (13)0.0036 (14)0.0083 (14)
C420.0227 (14)0.0297 (16)0.0296 (16)0.0026 (12)0.0010 (12)0.0003 (13)
C430.0168 (12)0.0175 (12)0.0174 (12)0.0017 (10)0.0007 (9)0.0007 (10)
C440.0174 (12)0.0175 (12)0.0195 (12)0.0011 (10)0.0013 (10)0.0020 (10)
C450.0172 (12)0.0187 (12)0.0185 (12)0.0011 (10)0.0003 (10)0.0006 (10)
C460.0262 (15)0.0167 (13)0.0271 (14)0.0014 (11)0.0030 (12)0.0015 (11)
C470.0303 (16)0.0189 (13)0.0284 (15)0.0044 (12)0.0118 (12)0.0032 (11)
C480.0240 (14)0.0212 (14)0.0229 (13)0.0014 (11)0.0068 (11)0.0007 (11)
C490.0257 (14)0.0182 (13)0.0279 (15)0.0025 (11)0.0058 (12)0.0021 (11)
C500.063 (3)0.0215 (16)0.056 (2)0.0089 (17)0.036 (2)0.0011 (16)
Geometric parameters (Å, º) top
Pd1—N52.030 (3)F16—C341.334 (4)
Pd1—N12.049 (3)F17—C341.328 (4)
Pd1—C12.061 (3)F18—C341.337 (4)
Pd1—N32.127 (3)F19—C411.330 (5)
N1—C31.339 (4)F20—C411.339 (4)
N1—N21.357 (4)F21—C411.340 (4)
N2—C51.353 (4)F22—C421.345 (3)
N2—C71.464 (4)F23—C421.359 (3)
N3—C121.339 (4)F24—C421.347 (3)
N3—C81.341 (4)F22A—C421.346 (3)
N4—C151.354 (4)F23A—C421.340 (3)
N4—N51.370 (4)F24A—C421.361 (3)
N4—C131.460 (4)F22B—C421.357 (3)
N5—C171.346 (4)F23B—C421.346 (3)
B1—C271.638 (4)F24B—C421.344 (3)
B1—C351.640 (4)F46—C501.330 (3)
B1—C191.644 (4)F47—C501.393 (3)
B1—C431.647 (4)F48—C501.327 (3)
C1—H1A0.9800F46A—C501.388 (3)
C1—H1B0.9800F47A—C501.321 (3)
C1—H1C0.9800F48A—C501.346 (3)
C3—C41.398 (5)F46B—C501.340 (3)
C3—C21.502 (5)F47B—C501.348 (3)
C4—C51.372 (5)F48B—C501.359 (3)
C4—H40.9500F43—C491.340 (4)
C5—C61.493 (5)F44—C491.346 (4)
C7—C81.507 (5)F45—C491.334 (4)
C7—H7A0.9900C19—C241.403 (4)
C7—H7B0.9900C19—C201.408 (4)
C8—C91.386 (4)C20—C211.389 (4)
C9—C101.385 (5)C20—H200.9500
C9—H90.9500C21—C221.388 (4)
C10—C111.383 (6)C21—C251.496 (4)
C10—H100.9500C22—C231.386 (4)
C11—C121.390 (5)C22—H220.9500
C11—H110.9500C23—C241.388 (4)
C12—C131.512 (5)C23—C261.497 (3)
C13—H13A0.9900C24—H240.9500
C13—H13B0.9900C27—C321.401 (4)
C15—C161.364 (5)C27—C281.408 (4)
C15—C141.489 (5)C28—C291.387 (4)
C16—C171.402 (5)C28—H280.9500
C16—H160.9500C29—C301.388 (4)
C17—C181.486 (5)C29—C331.498 (4)
C2—F11.320 (4)C30—C311.384 (4)
C2—F31.336 (4)C30—H300.9500
C2—F21.340 (4)C31—C321.400 (4)
C6—F61.296 (5)C31—C341.504 (4)
C6—F51.333 (5)C32—H320.9500
C6—F41.359 (5)C35—C401.397 (4)
C14—H14A0.9800C35—C361.410 (4)
C14—H14B0.9800C36—C371.390 (4)
C14—H14C0.9800C36—H360.9500
C18—H18A0.9800C37—C381.389 (5)
C18—H18B0.9800C37—C411.499 (4)
C18—H18C0.9800C38—C391.388 (4)
F7—C251.335 (4)C38—H380.9500
F8—C251.344 (4)C39—C401.399 (4)
F9—C251.348 (4)C39—C421.493 (3)
F10—C261.336 (3)C40—H400.9500
F11—C261.342 (3)C43—C441.402 (4)
F12—C261.365 (3)C43—C481.403 (4)
F10A—C261.369 (3)C44—C451.396 (4)
F11A—C261.324 (3)C44—H440.9500
F12A—C261.353 (3)C45—C461.383 (4)
F10B—C261.364 (3)C45—C491.498 (4)
F11B—C261.355 (3)C46—C471.386 (4)
F12B—C261.329 (3)C46—H460.9500
F13—C331.321 (4)C47—C481.392 (4)
F14—C331.335 (4)C47—C501.495 (3)
F15—C331.328 (4)C48—H480.9500
N5—Pd1—N1172.77 (10)F11—C26—F12105.7 (3)
N5—Pd1—C193.62 (12)F11A—C26—F10A107.4 (3)
N1—Pd1—C193.07 (11)F12A—C26—F10A104.1 (3)
N5—Pd1—N387.76 (11)F11A—C26—C23115.3 (3)
N1—Pd1—N385.77 (10)F12B—C26—C23115.0 (3)
C1—Pd1—N3175.40 (12)F10—C26—C23113.2 (3)
C3—N1—N2105.7 (3)F11—C26—C23113.2 (3)
C3—N1—Pd1136.5 (2)F12A—C26—C23112.1 (3)
N2—N1—Pd1116.5 (2)F11B—C26—C23111.5 (3)
C5—N2—N1110.4 (3)F10B—C26—C23110.4 (3)
C5—N2—C7129.6 (3)F12—C26—C23109.4 (3)
N1—N2—C7119.2 (3)F10A—C26—C23109.2 (3)
C12—N3—C8120.3 (3)C32—C27—C28115.6 (3)
C12—N3—Pd1120.6 (2)C32—C27—B1124.9 (3)
C8—N3—Pd1119.1 (2)C28—C27—B1119.5 (2)
C15—N4—N5110.6 (3)C29—C28—C27122.5 (3)
C15—N4—C13128.4 (3)C29—C28—H28118.8
N5—N4—C13120.9 (3)C27—C28—H28118.8
C17—N5—N4106.2 (3)C28—C29—C30120.8 (3)
C17—N5—Pd1136.8 (2)C28—C29—C33118.1 (3)
N4—N5—Pd1116.61 (19)C30—C29—C33121.1 (3)
C27—B1—C35110.6 (2)C31—C30—C29118.1 (3)
C27—B1—C19110.2 (2)C31—C30—H30121.0
C35—B1—C19109.8 (2)C29—C30—H30121.0
C27—B1—C43107.8 (2)C30—C31—C32121.1 (3)
C35—B1—C43108.4 (2)C30—C31—C34119.8 (3)
C19—B1—C43110.1 (2)C32—C31—C34119.0 (3)
Pd1—C1—H1A109.5C31—C32—C27121.8 (3)
Pd1—C1—H1B109.5C31—C32—H32119.1
H1A—C1—H1B109.5C27—C32—H32119.1
Pd1—C1—H1C109.5F13—C33—F15105.5 (3)
H1A—C1—H1C109.5F13—C33—F14106.3 (3)
H1B—C1—H1C109.5F15—C33—F14106.0 (3)
N1—C3—C4111.1 (3)F13—C33—C29112.4 (3)
N1—C3—C2122.2 (3)F15—C33—C29113.3 (2)
C4—C3—C2126.6 (3)F14—C33—C29112.7 (3)
C5—C4—C3104.5 (3)F17—C34—F16106.6 (3)
C5—C4—H4127.7F17—C34—F18106.5 (3)
C3—C4—H4127.7F16—C34—F18106.2 (3)
N2—C5—C4108.3 (3)F17—C34—C31112.7 (3)
N2—C5—C6122.4 (3)F16—C34—C31111.9 (3)
C4—C5—C6129.3 (3)F18—C34—C31112.5 (3)
N2—C7—C8110.2 (3)C40—C35—C36115.6 (3)
N2—C7—H7A109.6C40—C35—B1123.3 (3)
C8—C7—H7A109.6C36—C35—B1121.1 (3)
N2—C7—H7B109.6C37—C36—C35122.0 (3)
C8—C7—H7B109.6C37—C36—H36119.0
H7A—C7—H7B108.1C35—C36—H36119.0
N3—C8—C9121.8 (3)C38—C37—C36121.1 (3)
N3—C8—C7114.3 (3)C38—C37—C41118.5 (3)
C9—C8—C7123.9 (3)C36—C37—C41120.4 (3)
C10—C9—C8118.3 (3)C39—C38—C37118.3 (3)
C10—C9—H9120.9C39—C38—H38120.8
C8—C9—H9120.9C37—C38—H38120.8
C11—C10—C9119.7 (3)C38—C39—C40120.2 (2)
C11—C10—H10120.2C38—C39—C42121.0 (2)
C9—C10—H10120.2C40—C39—C42118.8 (2)
C10—C11—C12119.2 (3)C35—C40—C39122.8 (3)
C10—C11—H11120.4C35—C40—H40118.6
C12—C11—H11120.4C39—C40—H40118.6
N3—C12—C11120.8 (3)F19—C41—F20106.7 (3)
N3—C12—C13114.5 (3)F19—C41—F21105.3 (3)
C11—C12—C13124.7 (3)F20—C41—F21106.9 (3)
N4—C13—C12111.8 (3)F19—C41—C37113.6 (3)
N4—C13—H13A109.3F20—C41—C37111.7 (3)
C12—C13—H13A109.3F21—C41—C37112.2 (3)
N4—C13—H13B109.3F23A—C42—F22A107.7 (3)
C12—C13—H13B109.3F24B—C42—F23B107.3 (3)
H13A—C13—H13B107.9F22—C42—F24107.0 (2)
N4—C15—C16107.1 (3)F24B—C42—F22B106.3 (3)
N4—C15—C14122.5 (3)F23B—C42—F22B106.4 (3)
C16—C15—C14130.4 (3)F22—C42—F23106.0 (2)
C15—C16—C17107.0 (3)F24—C42—F23105.7 (2)
C15—C16—H16126.5F23A—C42—F24A106.2 (3)
C17—C16—H16126.5F22A—C42—F24A106.1 (3)
N5—C17—C16109.1 (3)F23A—C42—C39113.4 (2)
N5—C17—C18123.1 (3)F24B—C42—C39113.3 (3)
C16—C17—C18127.8 (3)F22—C42—C39113.5 (2)
F1—C2—F3108.7 (3)F22A—C42—C39112.7 (3)
F1—C2—F2107.7 (3)F23B—C42—C39112.6 (3)
F3—C2—F2107.1 (3)F24—C42—C39112.9 (2)
F1—C2—C3108.9 (3)F22B—C42—C39110.5 (3)
F3—C2—C3112.2 (3)F23—C42—C39111.3 (2)
F2—C2—C3112.2 (3)F24A—C42—C39110.3 (2)
F6—C6—F5110.4 (4)C44—C43—C48115.4 (3)
F6—C6—F4108.4 (3)C44—C43—B1120.4 (2)
F5—C6—F4105.9 (4)C48—C43—B1124.1 (3)
F6—C6—C5110.1 (4)C45—C44—C43122.5 (3)
F5—C6—C5111.4 (3)C45—C44—H44118.8
F4—C6—C5110.6 (3)C43—C44—H44118.8
C15—C14—H14A109.5C46—C45—C44120.7 (3)
C15—C14—H14B109.5C46—C45—C49120.4 (3)
C15—C14—H14C109.5C44—C45—C49118.9 (3)
C17—C18—H18A109.5C45—C46—C47118.0 (3)
C17—C18—H18B109.5C45—C46—H46121.0
C17—C18—H18C109.5C47—C46—H46121.0
C24—C19—C20114.7 (3)C46—C47—C48121.1 (2)
C24—C19—B1124.9 (2)C46—C47—C50118.1 (2)
C20—C19—B1120.3 (2)C48—C47—C50120.7 (2)
C21—C20—C19122.6 (3)C47—C48—C43122.2 (3)
C21—C20—H20118.7C47—C48—H48118.9
C19—C20—H20118.7C43—C48—H48118.9
C22—C21—C20121.0 (3)F45—C49—F43106.7 (3)
C22—C21—C25120.0 (3)F45—C49—F44106.9 (3)
C20—C21—C25119.0 (3)F43—C49—F44106.3 (2)
C23—C22—C21118.0 (3)F45—C49—C45112.5 (2)
C23—C22—H22121.0F43—C49—C45112.5 (3)
C21—C22—H22121.0F44—C49—C45111.6 (3)
C22—C23—C24120.7 (2)F48—C50—F46109.3 (3)
C22—C23—C26119.0 (2)F47A—C50—F48A109.4 (3)
C24—C23—C26120.4 (2)F46B—C50—F47B107.7 (3)
C23—C24—C19123.1 (3)F46B—C50—F48B106.4 (3)
C23—C24—H24118.5F47B—C50—F48B105.7 (3)
C19—C24—H24118.5F47A—C50—F46A105.4 (3)
F7—C25—F8106.2 (3)F48A—C50—F46A103.8 (3)
F7—C25—F9107.0 (3)F48—C50—F47105.7 (2)
F8—C25—F9105.6 (3)F46—C50—F47104.0 (2)
F7—C25—C21113.4 (3)F47A—C50—C47116.6 (3)
F8—C25—C21112.2 (3)F48—C50—C47114.3 (3)
F9—C25—C21112.0 (3)F46—C50—C47114.1 (2)
F10—C26—F11108.3 (3)F46B—C50—C47113.9 (4)
F11A—C26—F12A108.1 (3)F48A—C50—C47113.3 (3)
F12B—C26—F11B107.2 (3)F47B—C50—C47112.0 (4)
F12B—C26—F10B107.6 (3)F48B—C50—C47110.6 (4)
F11B—C26—F10B104.4 (3)F46A—C50—C47107.2 (3)
F10—C26—F12106.7 (3)F47—C50—C47108.6 (2)
C1—Pd1—N1—C362.9 (3)C24—C23—C26—F12101.0 (4)
N3—Pd1—N1—C3121.5 (3)C22—C23—C26—F10A73.6 (4)
C1—Pd1—N1—N2132.6 (2)C24—C23—C26—F10A106.3 (4)
N3—Pd1—N1—N242.9 (2)C35—B1—C27—C3211.0 (4)
C3—N1—N2—C50.2 (3)C19—B1—C27—C32110.5 (3)
Pd1—N1—N2—C5169.1 (2)C43—B1—C27—C32129.3 (3)
C3—N1—N2—C7170.5 (3)C35—B1—C27—C28169.2 (2)
Pd1—N1—N2—C71.6 (3)C19—B1—C27—C2869.2 (3)
N5—Pd1—N3—C1240.2 (2)C43—B1—C27—C2850.9 (3)
N1—Pd1—N3—C12136.5 (2)C32—C27—C28—C293.3 (4)
N5—Pd1—N3—C8138.4 (2)B1—C27—C28—C29176.5 (3)
N1—Pd1—N3—C844.9 (2)C27—C28—C29—C302.3 (4)
C15—N4—N5—C170.9 (3)C27—C28—C29—C33177.4 (3)
C13—N4—N5—C17177.0 (3)C28—C29—C30—C310.3 (4)
C15—N4—N5—Pd1175.3 (2)C33—C29—C30—C31180.0 (3)
C13—N4—N5—Pd12.5 (4)C29—C30—C31—C321.8 (4)
C1—Pd1—N5—C1742.5 (3)C29—C30—C31—C34175.8 (3)
N3—Pd1—N5—C17133.1 (3)C30—C31—C32—C270.6 (4)
C1—Pd1—N5—N4145.4 (2)C34—C31—C32—C27176.9 (3)
N3—Pd1—N5—N439.0 (2)C28—C27—C32—C311.9 (4)
N2—N1—C3—C40.8 (3)B1—C27—C32—C31177.9 (3)
Pd1—N1—C3—C4166.4 (2)C28—C29—C33—F1370.4 (4)
N2—N1—C3—C2175.5 (3)C30—C29—C33—F13109.4 (4)
Pd1—N1—C3—C29.9 (5)C28—C29—C33—F1549.1 (4)
N1—C3—C4—C51.1 (4)C30—C29—C33—F15131.1 (3)
C2—C3—C4—C5175.0 (3)C28—C29—C33—F14169.5 (3)
N1—N2—C5—C40.5 (4)C30—C29—C33—F1410.8 (4)
C7—N2—C5—C4170.0 (3)C30—C31—C34—F17138.7 (3)
N1—N2—C5—C6178.9 (3)C32—C31—C34—F1743.7 (4)
C7—N2—C5—C69.4 (5)C30—C31—C34—F16101.2 (3)
C3—C4—C5—N21.0 (4)C32—C31—C34—F1676.4 (4)
C3—C4—C5—C6178.3 (3)C30—C31—C34—F1818.3 (4)
C5—N2—C7—C8102.3 (4)C32—C31—C34—F18164.1 (3)
N1—N2—C7—C866.3 (4)C27—B1—C35—C4098.8 (3)
C12—N3—C8—C90.6 (5)C19—B1—C35—C40139.4 (3)
Pd1—N3—C8—C9179.2 (2)C43—B1—C35—C4019.1 (4)
C12—N3—C8—C7178.9 (3)C27—B1—C35—C3679.5 (3)
Pd1—N3—C8—C70.3 (3)C19—B1—C35—C3642.3 (3)
N2—C7—C8—N363.0 (4)C43—B1—C35—C36162.5 (2)
N2—C7—C8—C9117.6 (3)C40—C35—C36—C370.1 (4)
N3—C8—C9—C100.5 (5)B1—C35—C36—C37178.6 (3)
C7—C8—C9—C10178.9 (3)C35—C36—C37—C380.6 (5)
C8—C9—C10—C110.1 (5)C35—C36—C37—C41179.6 (3)
C9—C10—C11—C120.6 (5)C36—C37—C38—C390.9 (4)
C8—N3—C12—C110.0 (5)C41—C37—C38—C39179.9 (3)
Pd1—N3—C12—C11178.6 (2)C37—C38—C39—C400.4 (4)
C8—N3—C12—C13178.9 (3)C37—C38—C39—C42179.2 (2)
Pd1—N3—C12—C132.5 (3)C36—C35—C40—C390.6 (4)
C10—C11—C12—N30.6 (5)B1—C35—C40—C39179.0 (3)
C10—C11—C12—C13178.2 (3)C38—C39—C40—C350.3 (4)
C15—N4—C13—C12113.6 (4)C42—C39—C40—C35178.5 (2)
N5—N4—C13—C1263.8 (4)C38—C37—C41—F19164.1 (3)
N3—C12—C13—N461.1 (4)C36—C37—C41—F1916.9 (5)
C11—C12—C13—N4120.0 (3)C38—C37—C41—F2043.3 (4)
N5—N4—C15—C160.8 (4)C36—C37—C41—F20137.6 (3)
C13—N4—C15—C16176.8 (3)C38—C37—C41—F2176.7 (4)
N5—N4—C15—C14179.9 (3)C36—C37—C41—F21102.4 (4)
C13—N4—C15—C142.3 (5)C38—C39—C42—F23A129.4 (4)
N4—C15—C16—C170.5 (4)C40—C39—C42—F23A49.3 (4)
C14—C15—C16—C17179.4 (3)C38—C39—C42—F24B168.4 (7)
N4—N5—C17—C160.5 (4)C40—C39—C42—F24B12.8 (7)
Pd1—N5—C17—C16173.2 (3)C38—C39—C42—F2215.4 (4)
N4—N5—C17—C18179.1 (3)C40—C39—C42—F22165.9 (3)
Pd1—N5—C17—C186.5 (5)C38—C39—C42—F22A6.8 (4)
C15—C16—C17—N50.0 (4)C40—C39—C42—F22A171.9 (4)
C15—C16—C17—C18179.6 (3)C38—C39—C42—F23B46.4 (7)
N1—C3—C2—F1158.9 (3)C40—C39—C42—F23B134.8 (7)
C4—C3—C2—F116.8 (5)C38—C39—C42—F24137.4 (4)
N1—C3—C2—F338.6 (4)C40—C39—C42—F2443.9 (4)
C4—C3—C2—F3137.1 (3)C38—C39—C42—F22B72.4 (7)
N1—C3—C2—F281.9 (4)C40—C39—C42—F22B106.3 (7)
C4—C3—C2—F2102.4 (4)C38—C39—C42—F23104.0 (4)
N2—C5—C6—F6170.8 (3)C40—C39—C42—F2374.7 (4)
C4—C5—C6—F68.5 (5)C38—C39—C42—F24A111.6 (4)
N2—C5—C6—F566.4 (5)C40—C39—C42—F24A69.6 (4)
C4—C5—C6—F5114.3 (5)C27—B1—C43—C4439.3 (3)
N2—C5—C6—F451.0 (5)C35—B1—C43—C4480.5 (3)
C4—C5—C6—F4128.2 (4)C19—B1—C43—C44159.5 (2)
C27—B1—C19—C2417.4 (4)C27—B1—C43—C48145.0 (3)
C35—B1—C19—C24139.4 (3)C35—B1—C43—C4895.2 (3)
C43—B1—C19—C24101.4 (3)C19—B1—C43—C4824.8 (4)
C27—B1—C19—C20165.6 (2)C48—C43—C44—C451.4 (4)
C35—B1—C19—C2043.6 (3)B1—C43—C44—C45174.7 (2)
C43—B1—C19—C2075.6 (3)C43—C44—C45—C460.4 (4)
C24—C19—C20—C211.4 (4)C43—C44—C45—C49178.4 (3)
B1—C19—C20—C21175.9 (3)C44—C45—C46—C471.5 (4)
C19—C20—C21—C220.9 (4)C49—C45—C46—C47179.7 (3)
C19—C20—C21—C25179.8 (3)C45—C46—C47—C482.3 (5)
C20—C21—C22—C230.0 (4)C45—C46—C47—C50174.8 (3)
C25—C21—C22—C23179.3 (3)C46—C47—C48—C431.3 (5)
C21—C22—C23—C240.3 (4)C50—C47—C48—C43175.7 (3)
C21—C22—C23—C26179.8 (2)C44—C43—C48—C470.5 (4)
C22—C23—C24—C190.3 (5)B1—C43—C48—C47175.4 (3)
C26—C23—C24—C19179.7 (3)C46—C45—C49—F45136.0 (3)
C20—C19—C24—C231.1 (4)C44—C45—C49—F4545.2 (4)
B1—C19—C24—C23176.0 (3)C46—C45—C49—F4315.5 (4)
C22—C21—C25—F711.4 (4)C44—C45—C49—F43165.7 (3)
C20—C21—C25—F7169.3 (3)C46—C45—C49—F44103.9 (3)
C22—C21—C25—F8108.9 (3)C44—C45—C49—F4475.0 (3)
C20—C21—C25—F870.4 (4)C46—C47—C50—F47A39.7 (4)
C22—C21—C25—F9132.5 (3)C48—C47—C50—F47A137.4 (4)
C20—C21—C25—F948.2 (4)C46—C47—C50—F48176.0 (3)
C22—C23—C26—F11A165.4 (4)C48—C47—C50—F486.9 (4)
C24—C23—C26—F11A14.6 (5)C46—C47—C50—F4649.2 (4)
C22—C23—C26—F12B8.5 (5)C48—C47—C50—F46133.7 (4)
C24—C23—C26—F12B171.4 (4)C46—C47—C50—F46B18.4 (10)
C22—C23—C26—F1039.7 (4)C48—C47—C50—F46B164.5 (10)
C24—C23—C26—F10140.3 (4)C46—C47—C50—F48A168.0 (3)
C22—C23—C26—F11163.4 (4)C48—C47—C50—F48A9.1 (4)
C24—C23—C26—F1116.6 (4)C46—C47—C50—F47B140.9 (10)
C22—C23—C26—F12A41.2 (4)C48—C47—C50—F47B42.0 (10)
C24—C23—C26—F12A138.8 (4)C46—C47—C50—F48B101.4 (10)
C22—C23—C26—F11B113.9 (4)C48—C47—C50—F48B75.7 (10)
C24—C23—C26—F11B66.2 (4)C46—C47—C50—F46A78.0 (4)
C22—C23—C26—F10B130.5 (4)C48—C47—C50—F46A104.9 (4)
C24—C23—C26—F10B49.5 (4)C46—C47—C50—F4766.3 (4)
C22—C23—C26—F1279.1 (4)C48—C47—C50—F47110.8 (4)

Experimental details

Crystal data
Chemical formula[Pd(C18H18F6N5)](C32H12BF24)
Mr1388.00
Crystal system, space groupMonoclinic, P21/n
Temperature (K)105
a, b, c (Å)10.9194 (4), 18.0256 (7), 27.1635 (11)
β (°) 96.865 (1)
V3)5308.2 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.50
Crystal size (mm)0.36 × 0.31 × 0.26
Data collection
DiffractometerBruker SMART 1000 CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2007)
Tmin, Tmax0.841, 0.882
No. of measured, independent and
observed [I > 2σ(I)] reflections
92342, 14211, 12423
Rint0.030
(sin θ/λ)max1)0.685
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.058, 0.154, 1.01
No. of reflections14211
No. of parameters823
No. of restraints109
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0761P)2 + 17.6386P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)2.16, 1.63

Computer programs: SMART (Bruker, 2000), SAINT-Plus (Bruker, 2007), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2008) and modiCIFer (Guzei, 2007).

Selected geometric parameters (Å, º) top
Pd1—N52.030 (3)Pd1—C12.061 (3)
Pd1—N12.049 (3)Pd1—N32.127 (3)
N5—Pd1—N1172.77 (10)N5—Pd1—N387.76 (11)
N5—Pd1—C193.62 (12)N1—Pd1—N385.77 (10)
N1—Pd1—C193.07 (11)C1—Pd1—N3175.40 (12)
Distances and angles (Å, °) in compound (I) compared to those for similar compounds in the CSD top
Compound (I)Average for nine similar compounds in the CSDa
Pd—N(pz) distance2.039 (13)2.03 (2)
Pd—N(py) distance2.127 (3)2.04 (4)
N(pz)—Pd—N(py) angle86.8 (14)86.4 (16)
(a) Cambridge Structural Database, Version 1.10 (Allen, 2002).
Dihedral angles (°) between least-squares planes in the cation top
Atoms defining least-squares planeN1,N2,C3,C4,C5N4,N5,C15,C16,C17N3,C8,C9,C10,C11,C12
C1,N1,N3,N551.14 (11)39.44 (11)42.48 (12)
N1,N2,C3,C4,C587.86 (12)70.32 (10)
N4,N5,C15,C16,C1761.06 (12)
 

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