Square [Pd₄(μ-CN)₄(C₆F₅)₄(PEt₃)₄]·2C₆H₅CH₃

The tetrameric title complex in the crystal of its toluene disolvate, i.e. tetra-μ-cyano-tetrakis­[(penta­fluoro­phenyl)(tri­ethyl­phosphine)­palladium(II)] toluene disolvate, [Pd₄(μ-CN)₄(C₆F₅)₄(PEt₃)₄]·2C₇H₈, occupies a special position on a crystallographic inversion centre and contains a square arrangement of four square-planar palladium centres.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.004 Å
• Disorder in main residue
• R factor = 0.025
• wR factor = 0.061
• Data-to-parameter ratio = 19.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



ABSTM_02  Alert C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
          Tmin and Tmax reported:      0.695     0.801
          Tmin' and Tmax expected:      0.710     0.717
          RR' =      0.876
          Please check that your absorption correction is appropriate.

PLAT_301  Alert C Main Residue Disorder ........................       9.00 Perc.

General Notes



ABSTM_02  When printed, the submitted absorption T values will be replaced
          by the scaled T values. Since the ratio of scaled T's is
          identical to the ratio of reported T values, the scaling does
          not imply a change to the absorption corrections used in the
          study.
          Ratio of Tmax expected/reported      0.895
          Tmax scaled      0.717 Tmin scaled      0.622


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 2 Alert Level C = Please check

---

S1. Comment

The construction of cyclic nanostructures using coordination chemistry is a topic of growing interest (Olenyuk et al., 1998; Fujita 1998; Navarro & Lippert, 1999). One of the most popular patterns is that of a molecular square where transition metal building blocks affording coordination sites at 90° are linked by bidentate ligands defining bonds at 180°. The latter are usually neutral symmetric N-donor ligands such as 4,4'-bipyridyl, 1,4-dicyanobenzene, 4,4'-dicyano-1,1'-diphenyl, linear bis(pyridyl)porphirines and the like (Stang et al., 1995, 1997; Fujita et al., 1994; Wu et al., 1998).

The two simplest bridging ligands making two linear bonds are C₂^2- and CN^-. While their short length does not afford a square hole useful to host anything inside, they both offer excellent electronic communication and might be used to constitute tetrametallic knots in a more sophisticated network containing other ligands. The CN^- bridge seems to offer two potential advantages over an acetylene bridge. Firstly, N—M bond formation is easily reversible, thus allowing rearrangements in solution towards favorable structures; this ability is usually needed for the self-assembly of nanostructures and cannot be easily achieved with the irreversible formation of acetylide–M bonds. Secondly, when coordinated to building blocks with different ligands, the asymmetric CN^- should be able, in principle, to discriminate between different trans ligands according to their different trans influences.

Different structural patterns based on CN^- bridges can be found in the structures of metallic cyanide complexes, ranging from chain structures (e.g. AgCN) to three-dimensional frameworks, e.g. Prussian Blue (Wells, 1984). The structures of [Rh₄(µ-CN)₄(C₂B₁₀H₁₁)₄(PPh₃)₄] (Kalb et al., 1982), [Ti₄(µ-CN)₄(C₅H₅)₈] (Schinnerling & Thewalt, 1992) and [Cu₄(µ-CN)₄(tmtch)₄] (tmtch = SC₁₀H₆, 3,3,6,6-tetramethyl-1-thia-cycloheptyne; Olbrich et al., 1993), have been determined. They all are folded to a greater or lesser extent towards a butterfly geometry, due to the lack of 90° bond angles at the metal. The structure of a box-shaped framework formed from squares of [{RhCl(C₅Me₅)}₂{Co(C₅H₅)(CN)}₂(µ-CN)₄] has also been reported (Klausmeyer et al., 1998). Surprisingly, the only structural determination of a complex with a metal ideally suited to produce 90° bond angles is that of [Au₄(µ-CN)₄(n-C₃H₇)₈] (Phillips & Powell, 1939); this molecule was structurally characterized as early as 1939, and the precision of the data is severely limited by the technology available at that time.

Some time ago, one of the authors reported a number of tetrameric and polymeric Pd complexes containing bridging cyano ligands. Vapour-pressure-based molecular-weight determinations on solutions of some of them suggested a tetranuclear structure [Pd₄(µ-CN)₄R₄L₄] (R = C₆F₅, C₆Cl₅; L = PEt₃, PPh₃, AsPh₃), but this proposal could not be supported by a single-crystal structure determination. Now we have succeeded in crystallizing and solving the structure of the compound with R = C₆F₅ and L = PEt₃.

As anticipated, the structure contains a square array of palladium centres linked by bridging cyanide ligands (Fig. 1). This perfectly flat arrangement allows the molecule to sit on an inversion centre: any deviation towards a tetrahedral arrangement of Pd atoms would break this symmetry. The asymmetric unit also contains a molecule of toluene solvent.

As mentioned in the Experimental section, disorder is observed in the positions of the C and N atoms of the bridging cyanide ligands. The ¹H and ¹⁹F NMR spectra show that a complicated mixture of isomers is present in solution. Solid-state IR shows a single sharp absorption at 2176 cm_-1 supporting a model with a symmetric arrangement of cyanide ligands and the `square' having virtual fourfold symmetry.

S2. Experimental

The title compound was prepared as reported in the literature (Usón et al., 1983). Colourless single crystals were grown on cooling a toluene solution of the complex at 253 K for several weeks.

S3. Refinement

Disorder is observed in the positions of the C and N atoms of the bridging cyanide ligands. The eventual strategy adopted to model this was to fix the occupancy of each atomic position with a C:N ratio of 1:1 and to constrain the coordinates and displacement parameters of the C and N atoms at each position to be equivalent. This constrains the Pd—N and Pd—C distances to be equivalent and these distances should thus be treated with caution. All H atoms were constrained to ideal geometries. Methyl H atoms were positioned with a rotating group refinement and isotropic displacement parameters 1.5 times that of their adjacent C atom. All other H atoms were assigned isotropic displacement parameters 1.2 times that of their adjacent C atom. The highest residual electron-density peak (1.01 e Å^-3) is found 0.84 Å from P1. All other residual electron-density peaks have values less than 1 e Å^-3.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Bruker, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. The molecular structure of the tetrameric Pd complex in the crystal of the title compound showing 50% probability displacement ellipsoids. The H atoms have been omitted for clarity. The second component atoms of the disordered part of the structure are shown in parentheses.

Palladium, tetrakis[µ-(cyano-C:N)]tetrakis(pentafluorophenyl) tetrakis(triethylphosphine)tetra-, cyclo (9CI), ditoluene

Crystal data

[Pd4(CN)4(C6F5)4(C6H15P)4]·2C7H8	F(000) = 1848
Mr = 1854.79	Dx = 1.625 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.8845 (10) Å	Cell parameters from 441 reflections
b = 14.8554 (18) Å	θ = 2–25°
c = 21.652 (3) Å	µ = 1.11 mm^−1
β = 97.372 (9)°	T = 173 K
V = 3791.0 (8) Å^3	Block, colourless
Z = 2	0.3 × 0.3 × 0.3 mm

Data collection

CCD area-detector diffractometer	8699 independent reflections
Radiation source: fine-focus sealed tube	6789 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
ω scans	θmax = 27.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −15→15
Tmin = 0.695, Tmax = 0.801	k = −19→19
38987 measured reflections	l = −27→28

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.061	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0336P)^2] where P = (Fo^2 + 2Fc^2)/3
8699 reflections	(Δ/σ)max = 0.001
449 parameters	Δρmax = 1.01 e Å^−3
0 restraints	Δρmin = −0.75 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	0.549498 (14)	−0.223794 (11)	0.065058 (8)	0.02383 (5)
Pd2	0.246938 (14)	0.025756 (11)	0.083650 (8)	0.02292 (5)
C1A	0.42579 (17)	−0.12888 (14)	0.06457 (10)	0.0278 (5)	0.50
C2A	0.30701 (18)	0.09898 (14)	0.01589 (10)	0.0301 (5)	0.50
N1A	0.35909 (18)	−0.07465 (14)	0.07015 (10)	0.0285 (5)	0.50
N2A	0.64715 (16)	−0.14097 (13)	0.01756 (10)	0.0237 (4)	0.50
N1B	0.42579 (17)	−0.12888 (14)	0.06457 (10)	0.0278 (5)	0.50
N2B	0.30701 (18)	0.09898 (14)	0.01589 (10)	0.0301 (5)	0.50
C1B	0.35909 (18)	−0.07465 (14)	0.07015 (10)	0.0285 (5)	0.50
C2B	0.64715 (16)	−0.14097 (13)	0.01756 (10)	0.0237 (4)	0.50
P1	0.43375 (6)	−0.31907 (4)	0.10737 (3)	0.03429 (15)
P2	0.11997 (5)	0.13484 (4)	0.10126 (3)	0.02513 (13)
C10	0.67556 (19)	−0.31656 (15)	0.07088 (11)	0.0270 (5)
C11	0.7011 (2)	−0.36491 (16)	0.02030 (12)	0.0339 (6)
F11	0.63377 (14)	−0.35788 (11)	−0.03497 (7)	0.0503 (4)
C12	0.7944 (2)	−0.42179 (17)	0.02241 (15)	0.0437 (7)
F12	0.81750 (15)	−0.46538 (11)	−0.02906 (9)	0.0643 (5)
C13	0.8634 (2)	−0.43295 (17)	0.07789 (17)	0.0479 (8)
F13	0.95275 (15)	−0.48974 (12)	0.08120 (11)	0.0752 (6)
C14	0.8396 (2)	−0.38786 (17)	0.12962 (14)	0.0416 (7)
F14	0.90451 (13)	−0.40133 (11)	0.18475 (9)	0.0600 (5)
C15	0.7478 (2)	−0.33019 (16)	0.12516 (12)	0.0327 (5)
F15	0.72855 (13)	−0.28742 (10)	0.17839 (7)	0.0439 (4)
C20	0.19911 (19)	−0.04493 (15)	0.15670 (11)	0.0265 (5)
C21	0.2478 (2)	−0.03018 (15)	0.21721 (12)	0.0325 (5)
F21	0.32964 (14)	0.03387 (10)	0.22920 (7)	0.0500 (4)
C22	0.2184 (2)	−0.07704 (18)	0.26800 (12)	0.0410 (6)
F22	0.27015 (18)	−0.05946 (12)	0.32598 (7)	0.0659 (5)
C23	0.1357 (2)	−0.14152 (18)	0.25910 (14)	0.0438 (7)
F23	0.10380 (17)	−0.18584 (12)	0.30849 (9)	0.0682 (6)
C24	0.0861 (2)	−0.16043 (17)	0.19995 (14)	0.0413 (7)
F24	0.00538 (15)	−0.22464 (11)	0.19080 (10)	0.0670 (5)
C25	0.1193 (2)	−0.11361 (16)	0.15038 (12)	0.0335 (5)
F25	0.06995 (14)	−0.13713 (11)	0.09261 (8)	0.0559 (5)
C30	0.3051 (2)	−0.33575 (19)	0.04913 (15)	0.0483 (7)
H30A	0.2551	−0.3809	0.0654	0.058*
H30B	0.2626	−0.2784	0.0437	0.058*
C31	0.3336 (3)	−0.3668 (3)	−0.01369 (16)	0.0711 (10)
H31A	0.3788	−0.3205	−0.0313	0.107*
H31B	0.2633	−0.3770	−0.0418	0.107*
H31C	0.3771	−0.4230	−0.0086	0.107*
C40	0.4880 (2)	−0.43085 (17)	0.12880 (13)	0.0400 (6)
H40A	0.5069	−0.4610	0.0906	0.048*
H40B	0.5597	−0.4238	0.1572	0.048*
C41	0.4104 (3)	−0.49317 (19)	0.16005 (14)	0.0493 (7)
H41A	0.3971	−0.4676	0.2002	0.074*
H41B	0.4464	−0.5523	0.1668	0.074*
H41C	0.3379	−0.4996	0.1333	0.074*
C50	0.3752 (2)	−0.27189 (19)	0.17340 (13)	0.0439 (7)
H50A	0.3308	−0.2174	0.1598	0.053*
H50B	0.3228	−0.3161	0.1885	0.053*
C51	0.4655 (3)	−0.2471 (3)	0.22655 (15)	0.0681 (10)
H51A	0.5133	−0.2996	0.2383	0.102*
H51B	0.4291	−0.2273	0.2624	0.102*
H51C	0.5124	−0.1982	0.2134	0.102*
C60	0.1715 (2)	0.20602 (17)	0.16768 (12)	0.0367 (6)
H60A	0.1131	0.2519	0.1732	0.044*
H60B	0.1821	0.1685	0.2057	0.044*
C61	0.2820 (2)	0.2532 (2)	0.16072 (14)	0.0523 (8)
H61A	0.3391	0.2086	0.1528	0.078*
H61B	0.3082	0.2862	0.1991	0.078*
H61C	0.2701	0.2955	0.1257	0.078*
C70	−0.01827 (19)	0.09583 (17)	0.11888 (12)	0.0334 (6)
H70A	−0.0064	0.0541	0.1548	0.040*
H70B	−0.0616	0.1482	0.1314	0.040*
C71	−0.0887 (2)	0.0482 (2)	0.06484 (14)	0.0458 (7)
H71A	−0.1108	0.0914	0.0313	0.069*
H71B	−0.1569	0.0226	0.0791	0.069*
H71C	−0.0437	−0.0002	0.0494	0.069*
C80	0.0884 (2)	0.21135 (16)	0.03553 (11)	0.0304 (5)
H80A	0.1598	0.2414	0.0280	0.036*
H80B	0.0617	0.1753	−0.0020	0.036*
C81	0.0001 (2)	0.28380 (19)	0.04288 (15)	0.0484 (7)
H81A	−0.0718	0.2552	0.0494	0.073*
H81B	−0.0114	0.3209	0.0052	0.073*
H81C	0.0266	0.3218	0.0788	0.073*
C90	0.4079 (3)	−0.4081 (3)	0.38117 (18)	0.0876 (13)
H90A	0.4827	−0.4230	0.3695	0.131*
H90B	0.3997	−0.4356	0.4215	0.131*
H90C	0.4005	−0.3426	0.3842	0.131*
C91	0.3177 (3)	−0.4434 (2)	0.33287 (14)	0.0549 (8)
C92	0.2981 (3)	−0.5363 (2)	0.32470 (16)	0.0613 (9)
H92	0.3435	−0.5781	0.3501	0.074*
C93	0.2134 (3)	−0.5675 (2)	0.27999 (17)	0.0627 (9)
H93	0.2006	−0.6304	0.2754	0.075*
C94	0.1490 (3)	−0.5096 (3)	0.24281 (17)	0.0616 (9)
H94	0.0912	−0.5316	0.2121	0.074*
C95	0.1669 (2)	−0.4188 (2)	0.24934 (16)	0.0564 (9)
H95	0.1221	−0.3782	0.2227	0.068*
C96	0.2488 (2)	−0.3858 (2)	0.29394 (14)	0.0458 (7)
H96	0.2587	−0.3226	0.2983	0.055*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.02402 (9)	0.02250 (9)	0.02620 (10)	0.00150 (7)	0.00799 (7)	0.00186 (7)
Pd2	0.02295 (9)	0.02252 (9)	0.02429 (9)	0.00100 (7)	0.00689 (7)	0.00197 (7)
C1A	0.0278 (11)	0.0279 (11)	0.0294 (12)	0.0017 (9)	0.0100 (9)	0.0047 (9)
C2A	0.0283 (11)	0.0280 (11)	0.0346 (13)	0.0062 (9)	0.0066 (10)	−0.0009 (9)
N1A	0.0290 (11)	0.0279 (11)	0.0300 (12)	0.0000 (9)	0.0087 (9)	0.0046 (9)
N2A	0.0238 (10)	0.0212 (10)	0.0278 (11)	0.0031 (8)	0.0095 (9)	0.0033 (8)
N1B	0.0278 (11)	0.0279 (11)	0.0294 (12)	0.0017 (9)	0.0100 (9)	0.0047 (9)
N2B	0.0283 (11)	0.0280 (11)	0.0346 (13)	0.0062 (9)	0.0066 (10)	−0.0009 (9)
C1B	0.0290 (11)	0.0279 (11)	0.0300 (12)	0.0000 (9)	0.0087 (9)	0.0046 (9)
C2B	0.0238 (10)	0.0212 (10)	0.0278 (11)	0.0031 (8)	0.0095 (9)	0.0033 (8)
P1	0.0366 (4)	0.0275 (3)	0.0418 (4)	−0.0042 (3)	0.0166 (3)	0.0006 (3)
P2	0.0246 (3)	0.0265 (3)	0.0250 (3)	0.0023 (2)	0.0061 (2)	−0.0008 (2)
C10	0.0253 (11)	0.0222 (11)	0.0351 (14)	0.0018 (9)	0.0103 (10)	0.0034 (10)
C11	0.0341 (13)	0.0290 (12)	0.0404 (15)	−0.0015 (11)	0.0120 (11)	0.0008 (11)
F11	0.0627 (11)	0.0529 (10)	0.0370 (9)	0.0052 (8)	0.0127 (8)	−0.0090 (8)
C12	0.0445 (16)	0.0264 (13)	0.066 (2)	−0.0002 (12)	0.0304 (15)	−0.0070 (13)
F12	0.0674 (12)	0.0477 (10)	0.0863 (14)	0.0028 (9)	0.0421 (11)	−0.0236 (9)
C13	0.0290 (14)	0.0266 (13)	0.090 (3)	0.0077 (11)	0.0159 (15)	0.0056 (15)
F13	0.0442 (10)	0.0461 (10)	0.137 (2)	0.0238 (8)	0.0192 (11)	0.0014 (11)
C14	0.0303 (13)	0.0305 (13)	0.062 (2)	0.0022 (11)	−0.0009 (13)	0.0094 (13)
F14	0.0413 (9)	0.0504 (10)	0.0821 (14)	0.0071 (8)	−0.0166 (9)	0.0142 (9)
C15	0.0308 (13)	0.0259 (12)	0.0423 (15)	0.0007 (10)	0.0084 (11)	0.0021 (11)
F15	0.0476 (9)	0.0447 (9)	0.0375 (9)	0.0047 (7)	−0.0012 (7)	0.0000 (7)
C20	0.0255 (11)	0.0261 (11)	0.0289 (13)	0.0026 (9)	0.0081 (10)	0.0032 (9)
C21	0.0397 (14)	0.0268 (12)	0.0309 (13)	0.0006 (11)	0.0046 (11)	0.0019 (10)
F21	0.0630 (10)	0.0422 (9)	0.0400 (9)	−0.0174 (8)	−0.0122 (8)	0.0039 (7)
C22	0.0627 (18)	0.0351 (14)	0.0265 (14)	0.0111 (14)	0.0103 (12)	0.0041 (11)
F22	0.1157 (16)	0.0535 (11)	0.0264 (9)	0.0065 (11)	0.0016 (9)	0.0049 (8)
C23	0.0562 (17)	0.0358 (14)	0.0450 (17)	0.0119 (13)	0.0282 (14)	0.0183 (12)
F23	0.0927 (14)	0.0564 (11)	0.0648 (12)	0.0111 (10)	0.0455 (11)	0.0326 (9)
C24	0.0339 (14)	0.0294 (13)	0.063 (2)	−0.0027 (11)	0.0155 (13)	0.0124 (13)
F24	0.0523 (10)	0.0486 (10)	0.1005 (16)	−0.0206 (9)	0.0109 (10)	0.0240 (10)
C25	0.0316 (13)	0.0307 (13)	0.0378 (15)	−0.0011 (11)	0.0032 (11)	0.0020 (11)
F25	0.0646 (11)	0.0455 (9)	0.0519 (11)	−0.0229 (8)	−0.0149 (8)	0.0033 (8)
C30	0.0361 (15)	0.0385 (15)	0.070 (2)	−0.0060 (12)	0.0064 (14)	0.0045 (14)
C31	0.074 (2)	0.083 (3)	0.052 (2)	−0.025 (2)	−0.0048 (18)	−0.0018 (19)
C40	0.0383 (14)	0.0344 (14)	0.0486 (17)	−0.0001 (12)	0.0102 (12)	0.0152 (12)
C41	0.0579 (19)	0.0395 (15)	0.0518 (19)	−0.0122 (14)	0.0124 (15)	0.0121 (13)
C50	0.0460 (16)	0.0426 (15)	0.0463 (17)	0.0001 (13)	0.0183 (13)	0.0061 (13)
C51	0.054 (2)	0.115 (3)	0.0368 (18)	−0.021 (2)	0.0110 (15)	−0.0038 (18)
C60	0.0423 (15)	0.0371 (14)	0.0304 (14)	0.0065 (12)	0.0037 (11)	−0.0075 (11)
C61	0.0505 (18)	0.0564 (18)	0.0478 (18)	−0.0141 (15)	−0.0014 (14)	−0.0162 (14)
C70	0.0282 (12)	0.0355 (13)	0.0397 (15)	0.0041 (10)	0.0167 (11)	0.0028 (11)
C71	0.0324 (14)	0.0542 (17)	0.0530 (18)	−0.0110 (13)	0.0141 (13)	−0.0049 (14)
C80	0.0288 (12)	0.0313 (13)	0.0317 (13)	0.0041 (10)	0.0060 (10)	0.0069 (10)
C81	0.0459 (16)	0.0442 (16)	0.0571 (19)	0.0184 (13)	0.0137 (14)	0.0152 (14)
C90	0.070 (2)	0.134 (4)	0.057 (2)	0.002 (3)	0.002 (2)	0.004 (2)
C91	0.0488 (18)	0.082 (2)	0.0376 (17)	0.0106 (17)	0.0179 (14)	0.0087 (16)
C92	0.072 (2)	0.065 (2)	0.050 (2)	0.0305 (18)	0.0223 (18)	0.0268 (17)
C93	0.077 (2)	0.0516 (19)	0.065 (2)	0.0111 (18)	0.030 (2)	0.0057 (17)
C94	0.0497 (19)	0.077 (2)	0.062 (2)	0.0007 (18)	0.0185 (17)	0.0057 (18)
C95	0.0393 (16)	0.066 (2)	0.068 (2)	0.0114 (15)	0.0213 (16)	0.0264 (17)
C96	0.0369 (15)	0.0482 (16)	0.0570 (19)	0.0057 (13)	0.0234 (14)	0.0107 (14)

Geometric parameters (Å, º)

Pd1—C1A	2.036 (2)	C14—C15	1.381 (3)
Pd1—N2A	2.0554 (19)	C15—F15	1.361 (3)
Pd1—P1	2.2490 (7)	C20—C21	1.380 (3)
Pd1—C10	2.028 (2)	C20—C25	1.388 (3)
Pd2—C2A	2.028 (2)	C21—F21	1.361 (3)
Pd2—N1A	2.046 (2)	C21—C22	1.384 (3)
Pd2—P2	2.2795 (6)	C22—F22	1.351 (3)
Pd2—C20	2.039 (2)	C22—C23	1.368 (4)
C1A—N1A	1.147 (3)	C23—F23	1.351 (3)
C2A—N2A^i	1.145 (3)	C23—C24	1.368 (4)
N2A—C2A^i	1.145 (3)	C24—F24	1.350 (3)
P1—C50	1.809 (3)	C24—C25	1.378 (4)
P1—C40	1.820 (3)	C25—F25	1.357 (3)
P1—C30	1.870 (3)	C30—C31	1.515 (4)
P2—C80	1.822 (2)	C40—C41	1.525 (3)
P2—C60	1.826 (3)	C50—C51	1.514 (4)
P2—C70	1.828 (2)	C60—C61	1.513 (4)
C10—C11	1.376 (3)	C70—C71	1.523 (4)
C10—C15	1.379 (3)	C80—C81	1.526 (3)
C11—F11	1.356 (3)	C90—C91	1.493 (5)
C11—C12	1.390 (3)	C91—C96	1.391 (4)
C12—F12	1.347 (3)	C91—C92	1.407 (5)
C12—C13	1.375 (4)	C92—C93	1.384 (5)
C13—F13	1.351 (3)	C93—C94	1.348 (5)
C13—C14	1.366 (4)	C94—C95	1.369 (5)
C14—F14	1.350 (3)	C95—C96	1.371 (4)
C1A—Pd1—N2A	92.09 (8)	C14—C13—C12	119.6 (2)
C1A—Pd1—P1	87.65 (6)	F14—C14—C13	119.8 (2)
N2A—Pd1—P1	174.08 (6)	F14—C14—C15	120.7 (3)
C10—Pd1—C1A	176.64 (9)	C13—C14—C15	119.5 (3)
C10—Pd1—N2A	88.73 (8)	F15—C15—C10	120.0 (2)
C10—Pd1—P1	91.87 (6)	F15—C15—C14	116.6 (2)
C2A—Pd2—N1A	89.51 (8)	C10—C15—C14	123.4 (2)
C2A—Pd2—P2	92.39 (6)	C21—C20—C25	114.1 (2)
C2A—Pd2—C20	175.01 (9)	C21—C20—Pd2	121.99 (17)
N1A—Pd2—P2	178.10 (6)	C25—C20—Pd2	123.86 (18)
C20—Pd2—N1A	89.25 (8)	F21—C21—C20	119.6 (2)
C20—Pd2—P2	88.85 (6)	F21—C21—C22	116.6 (2)
N1A—C1A—Pd1	173.6 (2)	C20—C21—C22	123.8 (2)
N2A^i—C2A—Pd2	171.7 (2)	F22—C22—C23	120.0 (2)
C1A—N1A—Pd2	176.7 (2)	F22—C22—C21	120.6 (3)
C2A^i—N2A—Pd1	170.9 (2)	C23—C22—C21	119.4 (3)
C50—P1—C40	108.15 (13)	F23—C23—C22	119.9 (3)
C50—P1—C30	102.73 (13)	F23—C23—C24	120.7 (3)
C40—P1—C30	106.47 (13)	C22—C23—C24	119.4 (2)
C50—P1—Pd1	113.28 (9)	F24—C24—C23	119.7 (2)
C40—P1—Pd1	117.56 (8)	F24—C24—C25	120.8 (3)
C30—P1—Pd1	107.38 (10)	C23—C24—C25	119.6 (2)
C80—P2—C60	105.57 (12)	F25—C25—C24	117.1 (2)
C80—P2—C70	105.09 (11)	F25—C25—C20	119.3 (2)
C60—P2—C70	103.80 (12)	C24—C25—C20	123.7 (2)
C80—P2—Pd2	112.77 (8)	C31—C30—P1	112.8 (2)
C60—P2—Pd2	112.41 (9)	C41—C40—P1	116.88 (19)
C70—P2—Pd2	116.20 (8)	C51—C50—P1	112.8 (2)
C11—C10—C15	115.1 (2)	C61—C60—P2	113.42 (19)
C11—C10—Pd1	122.84 (18)	C71—C70—P2	114.02 (17)
C15—C10—Pd1	121.82 (17)	C81—C80—P2	115.71 (18)
F11—C11—C10	119.8 (2)	C96—C91—C92	116.9 (3)
F11—C11—C12	117.0 (2)	C96—C91—C90	121.5 (3)
C10—C11—C12	123.2 (3)	C92—C91—C90	121.7 (3)
F12—C12—C13	120.2 (2)	C93—C92—C91	120.7 (3)
F12—C12—C11	120.8 (3)	C94—C93—C92	120.7 (3)
C13—C12—C11	119.1 (3)	C93—C94—C95	119.9 (4)
F13—C13—C14	120.5 (3)	C94—C95—C96	120.8 (3)
F13—C13—C12	119.9 (3)	C95—C96—C91	121.1 (3)
C10—Pd1—P1—C50	127.35 (13)	Pd2—C20—C21—C22	−179.56 (19)
C1A—Pd1—P1—C50	−49.32 (12)	F21—C21—C22—F22	−0.6 (4)
C10—Pd1—P1—C40	−0.03 (13)	C20—C21—C22—F22	179.6 (2)
C1A—Pd1—P1—C40	−176.70 (13)	F21—C21—C22—C23	179.2 (2)
C10—Pd1—P1—C30	−119.93 (12)	C20—C21—C22—C23	−0.6 (4)
C1A—Pd1—P1—C30	63.40 (12)	F22—C22—C23—F23	1.8 (4)
C2A—Pd2—P2—C80	21.14 (11)	C21—C22—C23—F23	−178.0 (2)
C20—Pd2—P2—C80	−163.69 (11)	F22—C22—C23—C24	−178.2 (2)
C2A—Pd2—P2—C60	−98.07 (11)	C21—C22—C23—C24	2.0 (4)
C20—Pd2—P2—C60	77.10 (12)	F23—C23—C24—F24	−0.7 (4)
C2A—Pd2—P2—C70	142.56 (11)	C22—C23—C24—F24	179.3 (2)
C20—Pd2—P2—C70	−42.27 (12)	F23—C23—C24—C25	179.3 (2)
N2A—Pd1—C10—C11	−71.23 (19)	C22—C23—C24—C25	−0.7 (4)
P1—Pd1—C10—C11	102.87 (19)	F24—C24—C25—F25	−2.1 (4)
N2A—Pd1—C10—C15	103.36 (19)	C23—C24—C25—F25	177.9 (2)
P1—Pd1—C10—C15	−82.53 (18)	F24—C24—C25—C20	177.9 (2)
C15—C10—C11—F11	178.5 (2)	C23—C24—C25—C20	−2.1 (4)
Pd1—C10—C11—F11	−6.6 (3)	C21—C20—C25—F25	−176.7 (2)
C15—C10—C11—C12	−1.7 (3)	Pd2—C20—C25—F25	0.9 (3)
Pd1—C10—C11—C12	173.22 (18)	C21—C20—C25—C24	3.3 (4)
F11—C11—C12—F12	1.9 (3)	Pd2—C20—C25—C24	−179.14 (19)
C10—C11—C12—F12	−177.9 (2)	C50—P1—C30—C31	174.4 (2)
F11—C11—C12—C13	−178.3 (2)	C40—P1—C30—C31	−72.1 (3)
C10—C11—C12—C13	1.9 (4)	Pd1—P1—C30—C31	54.7 (2)
F12—C12—C13—F13	−1.9 (4)	C50—P1—C40—C41	47.6 (3)
C11—C12—C13—F13	178.3 (2)	C30—P1—C40—C41	−62.2 (3)
F12—C12—C13—C14	179.5 (2)	Pd1—P1—C40—C41	177.38 (18)
C11—C12—C13—C14	−0.3 (4)	C40—P1—C50—C51	71.0 (3)
F13—C13—C14—F14	−1.2 (4)	C30—P1—C50—C51	−176.7 (2)
C12—C13—C14—F14	177.4 (2)	Pd1—P1—C50—C51	−61.2 (2)
F13—C13—C14—C15	−179.9 (2)	C80—P2—C60—C61	−64.6 (2)
C12—C13—C14—C15	−1.4 (4)	C70—P2—C60—C61	−174.9 (2)
C11—C10—C15—F15	−178.3 (2)	Pd2—P2—C60—C61	58.7 (2)
Pd1—C10—C15—F15	6.7 (3)	C80—P2—C70—C71	59.0 (2)
C11—C10—C15—C14	−0.1 (3)	C60—P2—C70—C71	169.67 (19)
Pd1—C10—C15—C14	−175.05 (18)	Pd2—P2—C70—C71	−66.4 (2)
F14—C14—C15—F15	1.2 (3)	C60—P2—C80—C81	−59.4 (2)
C13—C14—C15—F15	179.9 (2)	C70—P2—C80—C81	49.9 (2)
F14—C14—C15—C10	−177.2 (2)	Pd2—P2—C80—C81	177.46 (17)
C13—C14—C15—C10	1.6 (4)	C96—C91—C92—C93	−0.3 (4)
N1A—Pd2—C20—C21	93.8 (2)	C90—C91—C92—C93	179.4 (3)
P2—Pd2—C20—C21	−86.29 (19)	C91—C92—C93—C94	0.9 (5)
N1A—Pd2—C20—C25	−83.6 (2)	C92—C93—C94—C95	−0.2 (5)
P2—Pd2—C20—C25	96.32 (19)	C93—C94—C95—C96	−0.9 (5)
C25—C20—C21—F21	178.2 (2)	C94—C95—C96—C91	1.5 (4)
Pd2—C20—C21—F21	0.6 (3)	C92—C91—C96—C95	−0.8 (4)
C25—C20—C21—C22	−1.9 (3)	C90—C91—C96—C95	179.4 (3)

Symmetry code: (i) −x+1, −y, −z.