Bis(μ-4-benzyl-3,5-diphenyl­pyrazolato-κ²N:N′)bis­[(4,4′-dimethyl-2,2′-bipyridine-κ²N,N′)palladium(II)] bis­(hexa­fluoro­phosphate) diethyl ether monosolvate monohydrate

In the crystal structure of the title compound, [Pd₂(C₂₂H₁₇N₂)₂(C₁₂H₁₂N₂)₂](PF₆)₂·C₄H₁₀O·H₂O, two Pd(dmbpy) units (dmbpy is 4,4′-dimethyl-2,2′-bipyridine) are bridged by 4-benzyl-3,5-diphenyl­pyrazolate ligands in an exodentate fashion, which results in a clip-like cavity between the two Pd(dmbpy)Pd planes. A disordered hexa­fluorido­phosphate anion is held in the cavity by an anion–π inter­action [P—F...Cg1 = 3.435 (15) Å (Cg1 is the centroid of the Pd–dmbpy chelate ring system) and P—F...Cg2 = 3.187 (15) Å (Cg2 is the centroid of a pyridine ring)]. A crystallographic twofold rotation axis passes through an F atom of the disordered anion and the mid-point of the two Pd atoms. The P and two F atoms of the second anion also lie on a twofold rotation axis, as do the O atom of the diethyl ether and the water O atom. The crystal structure is stabilized by electrostatic forces between the cations and anions, and inter­molecular hydrogen bonds involving hexa­fluorido­phosphate anions (C—H...F), the solvent diethyl ether mol­ecules and water mol­ecules (C—H...O).

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.011 Å
• Disorder in solvent or counterion
• R factor = 0.045
• wR factor = 0.144
• Data-to-parameter ratio = 19.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT420_ALERT_2_B D-H Without Acceptor       O2     -   H2A    ...          ?

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.87 Ratio
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         P2
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         P1
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       3.20
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      17.00 Perc.
PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         11
PLAT432_ALERT_2_C Short Inter X...Y Contact  F9     ..  C36     ..       2.95 Ang.

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           28.29
           From the CIF: _reflns_number_total               9007
           Count of symmetry unique reflns         4867
           Completeness (_total/calc)            185.06%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      4140
           Fraction of Friedel pairs measured     0.851
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

In our previous publictions, we reported a 3,5-diphenylpyrazolate-bridged dinuclear Pd(II) complex having an inorganic anion as the charge-balancing species (Huang et al., 2005 and 2007). Recently, we reported a 4-benzyl substituted 3,5-diphenylpyrazole ligand (Huang et al., 2007). In the present paper, we report the crytal structure of a dinuclear palladium(II) complex based on 4,4'-dimethyl-2,2'-bipyridine (dmbpy) and 4-benzyl-3,5-diphenylpyrazolate (Fig. 1). In the cation, a crystallographic twofold rotation axis passes through F6 and the mid-point of the Pd1—Pd1ⁱ atoms (Fig. 1).The distance of two palladium atoms is 2.9989 (6) Å which are shorter than that of our previous dipalladium complexes (Table 1). The Pd^II center has a cis-square-planar geometry defined by a N,N'-bidentate pyrazolate ligand and a chelating 4,4'-dimethyl-2,2'-bipyridine ligand. This conformation creates an 'open book' disposition for the square-planar environment of the two Pd atoms. The dihedral angle between the two coordination planes around the Pd atoms is 61.0 (1)°. The two Pd(dmbpy)Pd planes form a cleft with a cavity of approximately 180 ų. An interesting feature of the structure is the presence of a disordered hexafluorophosphate anion in the clip-like cavity formed by the Pd(dmbpy)Pd1 and Pd(dmbpy)Pdⁱ planes. This disordered hexafluorophosphate anions is generated by a twofold rotation axis and held in the cavity by an anion–π interaction (P2—F8···Cg1 3.435 (15) Å, Cg1 is the centroid of the ring system Pd1, N1, C6, C7, N2; P2—F8···Cg2 3.187 (15) Å, Cg2 is the centroid of the ring system N1, C1, C2, C3, C5, C6). Atoms P1, F3 and F4 of the second anion lie also on a twofold rotation axis (Wyckoff letter a) and is located near the cation by C—H···F intermolecular hydrogen bonds. The compound packs by elestrostatic interactions, C—H···F intermolecular hydrogen bonds between the cations and anions, and C—H···O intermolecular hydrogen bonds between the solvent diethyl ether molecules and water molecules. The non-classical hydrogen bonds that connect cations and anions are detailed in Table 2.

Related literature

For related literature, see: Flack (1983); Huang et al. (2005); Huang, Wu, Liu & Song (2007); Huang, Wu, Liu & Sun (2007).

S2. Experimental

A mixture of [4,4'-dimethyl-2,2'-bipyridine]dinitratopalladium (83.0 mg, 0.20 mmol) and 4-benzyl-3,5-diphenylpyrazole (31.0 mg, 0.10 mmol) was dissolved in water (5 ml) and stirred 2 h resulting in a clear yellow solution. To the mixture was added a tenfold excess of potassium hexafluorophosphate, which resulted in the immediate deposition of yellow microcrystals.The crystals were filtered, washed with a minimum amount of cold water and dried under vacuum (quantative yield, of 129.6 mg). Crystals were obtained by the vapor diffusion of diethyl ether into a 1 mM solution of in acetonitrile. ¹H NMR (400 MHz, [D₃] acetonitrile): δ 2.45 (12H, s, dmbpy-CH₃), 4.09 (4H, s, CH₂), 6.82 (4H, m, Ph—H), 7.03 (6H, m, Ph—H), 7.20 (4H, d, J=5.9 Hz, dmbpy-H_5,5'), 7.26 (8H, t, J = 7.5 Hz, Ph—H), 7.33 (4H, t, J = 7.3 Hz, Ph—H), 7.53 (8H, d, J = 7.5 Hz, Ph—H), 7.77 (4H, d, J = 5.9 Hz, dmbpy-H_6,6'), 7.99 (4H, s, dmbpy-H_3,3') p.p.m.

S3. Refinement

The value -0.02 (3) of the Flack parameter (Flack, 1983) indicates the absolute structure of the measured crystal was correctly determined. The water O atoms were refined with anisotropic displacement parameters. The H atoms of water molecules were located in a difference Fourier map and refined as riding, with O—H distances of 0.97 Å and U_iso(H) = 1.2U_eq(O). The aromatic H atoms were constrained to an ideal geometry, with C—H distances of 0.93 Å and U_iso(H) = 1.2U_eq(C). The methyl H atoms were rotated to fit the electron density, with C—H distances of 0.96 Å and U_iso(H) = 1.5U_eq(C). The methylene H atoms were constrained to ideal geometry, with C—H distances of 0.97 Å and U_iso(H) = 1.2U_eq(C). Both PF₆^- anions and ether molecule were disordered about twofold rotation axis. The largest peak and deepest hole on the final difference Fourier map corresponds to 1.05 and -0.720 e Å^-3, and were located 1.15 and 0.16 Å from the F3 and C35 atoms, respectively.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A view of the title compound, showing 30% probability displacement ellipsoids and the atom numbering scheme.
	Fig. 2. Crystal packing of the title compound.

Bis(µ-4-benzyl-3,5-diphenylpyrazolato-κ²N:N')bis[(4,4'-δimethyl-2,2'-bipyridine-κ²N,N')palladium(II)] bis(hexafluoridophosphate) diethyl ether monosolvate monohydrate

Crystal data

[Pd2(C22H17N2)2(C12H12N2)2](PF6)2·C4H10O·H2O	Dx = 1.444 Mg m^−3
Mr = 1582.10	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3121	Cell parameters from 9974 reflections
Hall symbol: P 31 2"	θ = 2.4–27.9°
a = 22.1138 (3) Å	µ = 0.62 mm^−1
c = 12.8884 (2) Å	T = 291 K
V = 5458.29 (13) Å^3	Block, yellow
Z = 3	0.48 × 0.42 × 0.36 mm
F(000) = 2412

Data collection

Bruker SMART CCD area-detector diffractometer	9007 independent reflections
Radiation source: sealed tube	8156 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
φ and ω scans	θmax = 28.3°, θmin = 1.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −29→29
Tmin = 0.756, Tmax = 0.808	k = −29→29
47040 measured reflections	l = −16→16

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.045	H-atom parameters constrained
wR(F^2) = 0.144	w = 1/[σ^2(Fo^2) + (0.0859P)^2 + 2.0829P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max = 0.001
9007 reflections	Δρmax = 1.05 e Å^−3
466 parameters	Δρmin = −0.74 e Å^−3
0 restraints	Absolute structure: Flack (1983), with 4168 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (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)
C1	0.5436 (3)	0.8913 (3)	1.0360 (4)	0.0499 (10)
H1	0.5219	0.9138	1.0659	0.060*
C2	0.5767 (3)	0.8665 (3)	1.0993 (4)	0.0590 (13)
H2	0.5777	0.8732	1.1706	0.071*
C3	0.6080 (3)	0.8319 (3)	1.0572 (4)	0.0600 (13)
C4	0.6420 (5)	0.8022 (5)	1.1256 (6)	0.095 (3)
H4A	0.6909	0.8355	1.1322	0.142*
H4B	0.6362	0.7600	1.0952	0.142*
H4C	0.6206	0.7921	1.1929	0.142*
C5	0.6071 (3)	0.8259 (3)	0.9514 (5)	0.0577 (12)
H5	0.6284	0.8033	0.9208	0.069*
C6	0.5751 (2)	0.8527 (2)	0.8887 (4)	0.0439 (9)
C7	0.5768 (2)	0.8544 (2)	0.7752 (4)	0.0422 (9)
C8	0.6115 (3)	0.8291 (3)	0.7153 (4)	0.0525 (11)
H8	0.6319	0.8060	0.7471	0.063*
C9	0.6160 (3)	0.8379 (3)	0.6094 (4)	0.0580 (13)
C10	0.6557 (5)	0.8132 (5)	0.5452 (6)	0.089 (2)
H10A	0.6379	0.7643	0.5576	0.133*
H10B	0.7042	0.8389	0.5637	0.133*
H10C	0.6505	0.8204	0.4731	0.133*
C11	0.5847 (3)	0.8732 (3)	0.5659 (4)	0.0591 (13)
H11	0.5870	0.8809	0.4947	0.071*
C12	0.5500 (3)	0.8965 (3)	0.6292 (4)	0.0508 (11)
H12	0.5295	0.9201	0.5992	0.061*
C13	0.4209 (2)	0.9453 (2)	0.6460 (4)	0.0422 (9)
C14	0.3722 (2)	0.8706 (2)	0.6242 (4)	0.0468 (10)
C15	0.3780 (3)	0.8400 (3)	0.5326 (5)	0.0652 (14)
H15	0.4128	0.8663	0.4847	0.078*
C16	0.3309 (5)	0.7694 (4)	0.5139 (7)	0.084 (2)
H16	0.3354	0.7484	0.4542	0.101*
C17	0.2784 (5)	0.7310 (3)	0.5822 (7)	0.088 (2)
H17	0.2472	0.6841	0.5685	0.106*
C18	0.2716 (4)	0.7611 (4)	0.6711 (8)	0.086 (2)
H18	0.2352	0.7349	0.7169	0.103*
C19	0.3187 (3)	0.8307 (3)	0.6929 (5)	0.0620 (12)
H19	0.3143	0.8506	0.7539	0.074*
C20	0.4195 (2)	0.9389 (2)	1.0197 (4)	0.0403 (9)
C21	0.3762 (2)	0.8629 (2)	1.0408 (4)	0.0455 (10)
C22	0.3518 (3)	0.8147 (3)	0.9600 (5)	0.0589 (13)
H22	0.3615	0.8299	0.8916	0.071*
C23	0.3129 (3)	0.7436 (3)	0.9820 (6)	0.0715 (17)
H23	0.2971	0.7116	0.9278	0.086*
C24	0.2976 (3)	0.7204 (3)	1.0813 (7)	0.082 (2)
H24	0.2704	0.6728	1.0944	0.098*
C25	0.3214 (3)	0.7660 (4)	1.1609 (6)	0.0725 (18)
H25	0.3114	0.7495	1.2287	0.087*
C26	0.3609 (3)	0.8374 (3)	1.1428 (5)	0.0591 (13)
H26	0.3772	0.8683	1.1984	0.071*
C27	0.4274 (2)	1.0032 (3)	0.5939 (3)	0.0429 (8)
C28	0.3809 (3)	1.0019 (3)	0.5084 (4)	0.0528 (11)
H28A	0.3642	0.9587	0.4699	0.063*
H28B	0.4085	1.0401	0.4613	0.063*
C29	0.3190 (3)	1.0073 (2)	0.5424 (4)	0.0498 (11)
C30	0.2880 (3)	0.9856 (3)	0.6380 (5)	0.0644 (14)
H30	0.3081	0.9699	0.6865	0.077*
C31	0.2275 (4)	0.9864 (5)	0.6643 (9)	0.096 (3)
H31	0.2067	0.9696	0.7286	0.115*
C32	0.1984 (5)	1.0118 (6)	0.5953 (11)	0.117 (4)
H32	0.1591	1.0145	0.6138	0.140*
C33	0.2280 (5)	1.0335 (5)	0.4983 (11)	0.108 (4)
H33	0.2079	1.0494	0.4501	0.130*
C34	0.2877 (4)	1.0314 (3)	0.4731 (6)	0.0742 (19)
H34	0.3075	1.0466	0.4078	0.089*
C35	0.0657 (19)	0.0584 (18)	0.794 (3)	0.282 (17)
H35A	0.0256	0.0564	0.8277	0.338*
H35B	0.0548	0.0504	0.7204	0.338*
C36	0.1279 (17)	0.1337 (17)	0.806 (2)	0.267 (14)
H36A	0.1342	0.1462	0.8782	0.401*
H36B	0.1185	0.1654	0.7682	0.401*
H36C	0.1696	0.1359	0.7795	0.401*
F1	0.5517 (4)	1.0008 (4)	0.4557 (3)	0.1223 (19)
F2	0.5204 (7)	0.9199 (4)	0.3331 (6)	0.185 (4)
F3	0.4871 (6)	1.0000	0.3333	0.220 (9)
F4	0.6205 (7)	1.0000	0.3333	0.218 (7)
F5	0.8020 (4)	1.0593 (5)	0.8395 (10)	0.098 (3)	0.50
F6	0.8550 (5)	1.0000	0.8333	0.174 (5)
F7	0.7642 (6)	0.9347 (7)	0.9591 (14)	0.270 (7)
F8	0.7129 (6)	0.9957 (7)	0.9187 (15)	0.158 (6)	0.50
F9	0.8204 (7)	1.0540 (8)	0.9732 (17)	0.173 (7)	0.50
N1	0.5419 (2)	0.8839 (2)	0.9324 (3)	0.0409 (7)
N2	0.5449 (2)	0.8865 (2)	0.7307 (3)	0.0405 (7)
N3	0.46707 (19)	0.96654 (19)	0.7249 (3)	0.0386 (7)
N4	0.46601 (18)	0.96287 (19)	0.9408 (3)	0.0384 (7)
O1	0.0732 (17)	0.0000	0.8333	0.290 (15)
O2	0.2246 (11)	0.2246 (11)	1.0000	0.332 (17)
H2A	0.2470	0.2505	0.9373	0.398*
P1	0.55322 (12)	1.0000	0.3333	0.0683 (6)
P2	0.7837 (3)	0.9967 (3)	0.8965 (6)	0.122 (2)	0.50
Pd1	0.500203 (16)	0.921712 (16)	0.83157 (2)	0.03555 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.058 (3)	0.064 (3)	0.040 (2)	0.040 (2)	0.004 (2)	0.003 (2)
C2	0.067 (3)	0.078 (4)	0.046 (3)	0.047 (3)	0.000 (2)	0.009 (3)
C3	0.069 (3)	0.071 (4)	0.056 (3)	0.047 (3)	0.001 (3)	0.016 (3)
C4	0.129 (7)	0.135 (7)	0.072 (4)	0.105 (6)	0.011 (5)	0.035 (5)
C5	0.066 (3)	0.063 (3)	0.066 (3)	0.049 (3)	0.003 (3)	0.008 (3)
C6	0.042 (2)	0.041 (2)	0.052 (3)	0.0235 (17)	0.0037 (19)	0.0088 (19)
C7	0.043 (2)	0.042 (2)	0.047 (2)	0.0253 (17)	−0.0012 (19)	−0.0018 (18)
C8	0.055 (3)	0.057 (3)	0.058 (3)	0.038 (2)	0.000 (2)	−0.005 (2)
C9	0.056 (3)	0.068 (3)	0.060 (3)	0.038 (3)	0.000 (2)	−0.013 (2)
C10	0.104 (6)	0.130 (7)	0.071 (4)	0.088 (6)	−0.001 (4)	−0.027 (4)
C11	0.061 (3)	0.079 (4)	0.048 (3)	0.043 (3)	0.003 (2)	−0.006 (3)
C12	0.060 (3)	0.065 (3)	0.042 (2)	0.043 (3)	0.001 (2)	0.001 (2)
C13	0.0375 (19)	0.049 (2)	0.042 (2)	0.0227 (18)	−0.0035 (17)	−0.0047 (18)
C14	0.045 (2)	0.043 (2)	0.053 (3)	0.0231 (18)	−0.009 (2)	−0.0076 (19)
C15	0.069 (3)	0.066 (3)	0.061 (3)	0.035 (3)	−0.011 (3)	−0.020 (3)
C16	0.103 (5)	0.066 (4)	0.093 (5)	0.050 (4)	−0.031 (5)	−0.034 (4)
C17	0.086 (5)	0.048 (3)	0.125 (7)	0.029 (3)	−0.038 (5)	−0.016 (4)
C18	0.062 (4)	0.050 (3)	0.130 (7)	0.017 (3)	−0.003 (4)	0.006 (4)
C19	0.058 (3)	0.051 (3)	0.070 (3)	0.023 (2)	0.002 (3)	0.001 (3)
C20	0.0340 (19)	0.044 (2)	0.045 (2)	0.0209 (17)	0.0018 (17)	0.0033 (18)
C21	0.0374 (19)	0.048 (2)	0.056 (3)	0.0251 (19)	0.0064 (18)	0.008 (2)
C22	0.054 (3)	0.051 (3)	0.067 (3)	0.024 (2)	0.006 (3)	0.000 (2)
C23	0.060 (3)	0.046 (3)	0.102 (5)	0.022 (2)	0.007 (3)	−0.002 (3)
C24	0.054 (3)	0.051 (3)	0.135 (7)	0.022 (3)	0.015 (4)	0.024 (4)
C25	0.059 (3)	0.073 (4)	0.083 (5)	0.031 (3)	0.018 (3)	0.039 (4)
C26	0.051 (2)	0.058 (3)	0.061 (3)	0.023 (2)	0.006 (2)	0.017 (3)
C27	0.0407 (19)	0.049 (2)	0.041 (2)	0.0238 (18)	−0.0036 (17)	−0.0006 (19)
C28	0.050 (2)	0.058 (3)	0.044 (3)	0.022 (2)	−0.007 (2)	0.003 (2)
C29	0.048 (2)	0.0312 (18)	0.065 (3)	0.0159 (17)	−0.018 (2)	−0.0006 (19)
C30	0.060 (3)	0.062 (3)	0.080 (4)	0.037 (3)	−0.005 (3)	0.000 (3)
C31	0.064 (4)	0.087 (5)	0.141 (8)	0.040 (4)	0.008 (4)	−0.011 (5)
C32	0.080 (5)	0.103 (7)	0.196 (12)	0.068 (5)	−0.033 (7)	−0.033 (8)
C33	0.095 (6)	0.083 (5)	0.173 (10)	0.064 (5)	−0.070 (7)	−0.025 (6)
C34	0.078 (4)	0.046 (3)	0.098 (5)	0.031 (3)	−0.036 (4)	0.002 (3)
C35	0.28 (3)	0.27 (4)	0.29 (3)	0.13 (3)	0.15 (3)	0.00 (3)
C36	0.27 (3)	0.28 (3)	0.33 (3)	0.20 (3)	−0.01 (3)	−0.09 (3)
F1	0.160 (5)	0.157 (5)	0.047 (2)	0.077 (4)	−0.004 (3)	0.002 (3)
F2	0.282 (12)	0.118 (5)	0.138 (6)	0.087 (6)	0.020 (6)	0.015 (5)
F3	0.197 (9)	0.37 (3)	0.149 (10)	0.186 (14)	0.000 (6)	0.000 (12)
F4	0.188 (8)	0.30 (2)	0.200 (12)	0.152 (11)	0.013 (7)	0.026 (13)
F5	0.050 (4)	0.068 (5)	0.160 (10)	0.016 (4)	0.000 (5)	0.007 (5)
F6	0.110 (5)	0.099 (6)	0.309 (16)	0.049 (3)	0.009 (4)	0.018 (8)
F7	0.150 (8)	0.208 (11)	0.42 (2)	0.066 (9)	−0.013 (11)	0.086 (12)
F8	0.088 (7)	0.095 (8)	0.291 (19)	0.045 (6)	0.021 (9)	0.024 (10)
F9	0.097 (8)	0.120 (10)	0.28 (2)	0.040 (8)	0.038 (11)	0.061 (12)
N1	0.0424 (18)	0.0435 (18)	0.0425 (19)	0.0258 (15)	0.0024 (16)	0.0035 (16)
N2	0.0427 (18)	0.0451 (18)	0.0409 (19)	0.0273 (15)	0.0031 (15)	0.0001 (16)
N3	0.0353 (16)	0.0387 (17)	0.0426 (19)	0.0192 (14)	−0.0027 (14)	−0.0017 (15)
N4	0.0343 (16)	0.0369 (16)	0.046 (2)	0.0195 (13)	0.0048 (15)	0.0013 (15)
O1	0.29 (3)	0.30 (4)	0.28 (3)	0.15 (2)	0.025 (15)	0.05 (3)
O2	0.278 (18)	0.278 (18)	0.29 (3)	0.03 (3)	0.056 (16)	−0.056 (16)
P1	0.0776 (11)	0.0938 (17)	0.0389 (10)	0.0469 (8)	0.0025 (5)	0.0049 (10)
P2	0.061 (2)	0.078 (3)	0.219 (7)	0.029 (2)	0.013 (3)	0.010 (4)
Pd1	0.03531 (15)	0.03791 (16)	0.03836 (16)	0.02200 (12)	0.00096 (12)	0.00067 (12)

Geometric parameters (Å, º)

C1—N1	1.343 (6)	C24—H24	0.9300
C1—C2	1.378 (7)	C25—C26	1.390 (9)
C1—H1	0.9300	C25—H25	0.9300
C2—C3	1.375 (8)	C26—H26	0.9300
C2—H2	0.9300	C27—C20^i	1.409 (6)
C3—C5	1.370 (8)	C27—C28	1.497 (6)
C3—C4	1.506 (7)	C28—C29	1.499 (8)
C4—H4A	0.9600	C28—H28A	0.9700
C4—H4B	0.9600	C28—H28B	0.9700
C4—H4C	0.9600	C29—C30	1.375 (9)
C5—C6	1.388 (6)	C29—C34	1.389 (7)
C5—H5	0.9300	C30—C31	1.387 (9)
C6—N1	1.356 (6)	C30—H30	0.9300
C6—C7	1.464 (7)	C31—C32	1.373 (14)
C7—N2	1.355 (5)	C31—H31	0.9300
C7—C8	1.387 (6)	C32—C33	1.382 (16)
C8—C9	1.375 (8)	C32—H32	0.9300
C8—H8	0.9300	C33—C34	1.382 (13)
C9—C11	1.394 (8)	C33—H33	0.9300
C9—C10	1.495 (8)	C34—H34	0.9300
C10—H10A	0.9600	C35—O1	1.47 (4)
C10—H10B	0.9600	C35—C36	1.55 (4)
C10—H10C	0.9600	C35—H35A	0.9700
C11—C12	1.384 (7)	C35—H35B	0.9700
C11—H11	0.9300	C36—H36A	0.9600
C12—N2	1.321 (6)	C36—H36B	0.9600
C12—H12	0.9300	C36—H36C	0.9600
C13—N3	1.349 (6)	P1—F3	1.462 (15)
C13—C27	1.388 (7)	P1—F4	1.489 (15)
C13—C14	1.480 (6)	P1—F2	1.542 (8)
C14—C19	1.385 (8)	P1—F2^ii	1.542 (8)
C14—C15	1.397 (8)	P1—F1^ii	1.577 (4)
C15—C16	1.398 (10)	P1—F1	1.577 (4)
C15—H15	0.9300	P2—F5^i	1.425 (13)
C16—C17	1.362 (12)	P2—F5	1.436 (12)
C16—H16	0.9300	P2—F7	1.458 (13)
C17—C18	1.372 (12)	P2—F9	1.49 (2)
C17—H17	0.9300	P2—F8	1.582 (13)
C18—C19	1.389 (9)	P2—P2^i	1.634 (15)
C18—H18	0.9300	P2—F6	1.744 (11)
C19—H19	0.9300	F5—P2^i	1.425 (12)
C20—N4	1.352 (6)	F6—P2^i	1.744 (11)
C20—C27^i	1.409 (6)	N1—Pd1	2.002 (3)
C20—C21	1.484 (6)	N2—Pd1	2.010 (3)
C21—C22	1.392 (8)	N3—N4^i	1.352 (5)
C21—C26	1.403 (7)	N3—Pd1	2.033 (3)
C22—C23	1.392 (8)	N4—N3^i	1.352 (5)
C22—H22	0.9300	N4—Pd1	2.017 (3)
C23—C24	1.356 (11)	O1—C35^iii	1.47 (4)
C23—H23	0.9300	O2—H2A	0.9713
C24—C25	1.348 (12)	Pd1—Pd1^i	2.9989 (6)
N1—C1—C2	121.9 (4)	C30—C29—C34	116.9 (6)
N1—C1—H1	119.0	C30—C29—C28	123.3 (5)
C2—C1—H1	119.0	C34—C29—C28	119.6 (6)
C3—C2—C1	120.2 (5)	C29—C30—C31	122.0 (7)
C3—C2—H2	119.9	C29—C30—H30	119.0
C1—C2—H2	119.9	C31—C30—H30	119.0
C5—C3—C2	117.3 (5)	C32—C31—C30	120.0 (10)
C5—C3—C4	121.8 (5)	C32—C31—H31	120.0
C2—C3—C4	120.9 (6)	C30—C31—H31	120.0
C3—C4—H4A	109.5	C31—C32—C33	119.3 (8)
C3—C4—H4B	109.5	C31—C32—H32	120.4
H4A—C4—H4B	109.5	C33—C32—H32	120.4
C3—C4—H4C	109.5	C34—C33—C32	119.8 (7)
H4A—C4—H4C	109.5	C34—C33—H33	120.1
H4B—C4—H4C	109.5	C32—C33—H33	120.1
C3—C5—C6	121.6 (5)	C33—C34—C29	121.9 (8)
C3—C5—H5	119.2	C33—C34—H34	119.0
C6—C5—H5	119.2	C29—C34—H34	119.0
N1—C6—C5	119.8 (5)	O1—C35—C36	119 (4)
N1—C6—C7	114.6 (4)	O1—C35—H35A	107.7
C5—C6—C7	125.5 (4)	C36—C35—H35A	107.7
N2—C7—C8	121.0 (4)	O1—C35—H35B	107.7
N2—C7—C6	115.0 (4)	C36—C35—H35B	107.7
C8—C7—C6	124.0 (4)	H35A—C35—H35B	107.1
C9—C8—C7	120.7 (5)	C35—C36—H36A	109.5
C9—C8—H8	119.7	C35—C36—H36B	109.5
C7—C8—H8	119.7	H36A—C36—H36B	109.5
C8—C9—C11	117.2 (5)	C35—C36—H36C	109.5
C8—C9—C10	120.8 (6)	H36A—C36—H36C	109.5
C11—C9—C10	121.9 (6)	H36B—C36—H36C	109.5
C9—C10—H10A	109.5	F3—P1—F4	180.000 (4)
C9—C10—H10B	109.5	F3—P1—F2	95.9 (5)
H10A—C10—H10B	109.5	F4—P1—F2	84.1 (5)
C9—C10—H10C	109.5	F3—P1—F2^ii	95.9 (5)
H10A—C10—H10C	109.5	F4—P1—F2^ii	84.1 (5)
H10B—C10—H10C	109.5	F2—P1—F2^ii	168.1 (10)
C12—C11—C9	119.6 (5)	F3—P1—F1^ii	88.5 (3)
C12—C11—H11	120.2	F4—P1—F1^ii	91.5 (3)
C9—C11—H11	120.2	F2—P1—F1^ii	89.5 (4)
N2—C12—C11	122.6 (5)	F2^ii—P1—F1^ii	90.8 (4)
N2—C12—H12	118.7	F3—P1—F1	88.5 (3)
C11—C12—H12	118.7	F4—P1—F1	91.5 (3)
N3—C13—C27	109.4 (4)	F2—P1—F1	90.8 (4)
N3—C13—C14	122.2 (4)	F2^ii—P1—F1	89.5 (4)
C27—C13—C14	128.4 (4)	F1^ii—P1—F1	177.0 (6)
C19—C14—C15	119.2 (5)	F5^i—P2—F5	105.5 (7)
C19—C14—C13	120.1 (5)	F5^i—P2—F7	76.7 (8)
C15—C14—C13	120.6 (5)	F5—P2—F7	177.0 (10)
C14—C15—C16	119.2 (7)	F5^i—P2—F9	174.8 (8)
C14—C15—H15	120.4	F5—P2—F9	75.4 (8)
C16—C15—H15	120.4	F7—P2—F9	102.3 (11)
C17—C16—C15	120.8 (7)	F5^i—P2—F8	84.6 (8)
C17—C16—H16	119.6	F5—P2—F8	84.6 (7)
C15—C16—H16	119.6	F7—P2—F8	93.6 (8)
C16—C17—C18	120.2 (6)	F9—P2—F8	90.4 (9)
C16—C17—H17	119.9	F5^i—P2—P2^i	55.5 (6)
C18—C17—H17	119.9	F5—P2—P2^i	54.8 (6)
C17—C18—C19	120.2 (7)	F7—P2—P2^i	128.0 (10)
C17—C18—H18	119.9	F9—P2—P2^i	127.2 (8)
C19—C18—H18	119.9	F8—P2—P2^i	100.4 (7)
C14—C19—C18	120.3 (6)	F5^i—P2—F6	85.0 (5)
C14—C19—H19	119.9	F5—P2—F6	84.7 (5)
C18—C19—H19	119.9	F7—P2—F6	97.7 (7)
N4—C20—C27^i	108.2 (4)	F9—P2—F6	100.2 (6)
N4—C20—C21	121.0 (4)	F8—P2—F6	162.5 (9)
C27^i—C20—C21	130.7 (4)	P2^i—P2—F6	62.1 (3)
C22—C21—C26	117.9 (5)	P2^i—F5—P2	69.7 (7)
C22—C21—C20	120.9 (5)	P2^i—F6—P2	55.9 (6)
C26—C21—C20	121.1 (5)	C1—N1—C6	119.0 (4)
C21—C22—C23	119.8 (6)	C1—N1—Pd1	125.9 (3)
C21—C22—H22	120.1	C6—N1—Pd1	115.0 (3)
C23—C22—H22	120.1	C12—N2—C7	118.8 (4)
C24—C23—C22	121.0 (7)	C12—N2—Pd1	126.4 (3)
C24—C23—H23	119.5	C7—N2—Pd1	114.5 (3)
C22—C23—H23	119.5	C13—N3—N4^i	108.4 (3)
C25—C24—C23	120.4 (6)	C13—N3—Pd1	137.3 (3)
C25—C24—H24	119.8	N4^i—N3—Pd1	114.1 (3)
C23—C24—H24	119.8	N3^i—N4—C20	109.0 (3)
C24—C25—C26	120.6 (6)	N3^i—N4—Pd1	113.9 (3)
C24—C25—H25	119.7	C20—N4—Pd1	137.0 (3)
C26—C25—H25	119.7	C35—O1—C35^iii	113 (4)
C25—C26—C21	120.2 (6)	H2A—O2—H2A^iv	113.3 (1)
C25—C26—H26	119.9	N1—Pd1—N2	80.8 (1)
C21—C26—H26	119.9	N1—Pd1—N4	95.2 (1)
C13—C27—C20^i	105.0 (4)	N2—Pd1—N4	173.5 (2)
C13—C27—C28	125.7 (4)	N1—Pd1—N3	174.7 (2)
C20^i—C27—C28	129.0 (4)	N2—Pd1—N3	96.8 (1)
C27—C28—C29	115.5 (4)	N4—Pd1—N3	86.8 (1)
C27—C28—H28A	108.4	N1—Pd1—Pd1^i	110.59 (12)
C29—C28—H28A	108.4	N2—Pd1—Pd1^i	110.18 (11)
C27—C28—H28B	108.4	N4—Pd1—Pd1^i	66.34 (11)
C29—C28—H28B	108.4	N3—Pd1—Pd1^i	65.68 (11)
H28A—C28—H28B	107.5
N1—C1—C2—C3	−1.2 (10)	C30—C29—C34—C33	−0.2 (9)
C1—C2—C3—C5	2.4 (10)	C28—C29—C34—C33	176.0 (6)
C1—C2—C3—C4	−177.7 (7)	F5^i—P2—F5—P2^i	−23.9 (8)
C2—C3—C5—C6	−0.8 (9)	F9—P2—F5—P2^i	161.4 (7)
C4—C3—C5—C6	179.3 (7)	F8—P2—F5—P2^i	−106.8 (8)
C3—C5—C6—N1	−2.0 (9)	F6—P2—F5—P2^i	59.4 (4)
C3—C5—C6—C7	174.2 (6)	F5^i—P2—F6—P2^i	53.3 (5)
N1—C6—C7—N2	−0.3 (6)	F5—P2—F6—P2^i	−52.8 (5)
C5—C6—C7—N2	−176.6 (5)	F7—P2—F6—P2^i	129.1 (9)
N1—C6—C7—C8	176.2 (5)	F9—P2—F6—P2^i	−126.9 (8)
C5—C6—C7—C8	−0.2 (8)	F8—P2—F6—P2^i	−0.5 (18)
N2—C7—C8—C9	1.9 (8)	C2—C1—N1—C6	−1.7 (8)
C6—C7—C8—C9	−174.3 (5)	C2—C1—N1—Pd1	−176.6 (4)
C7—C8—C9—C11	0.2 (8)	C5—C6—N1—C1	3.3 (7)
C7—C8—C9—C10	177.6 (6)	C7—C6—N1—C1	−173.3 (4)
C8—C9—C11—C12	−1.0 (9)	C5—C6—N1—Pd1	178.7 (4)
C10—C9—C11—C12	−178.4 (6)	C7—C6—N1—Pd1	2.1 (5)
C9—C11—C12—N2	−0.3 (9)	C11—C12—N2—C7	2.4 (8)
N3—C13—C14—C19	68.4 (6)	C11—C12—N2—Pd1	176.8 (4)
C27—C13—C14—C19	−111.3 (6)	C8—C7—N2—C12	−3.2 (7)
N3—C13—C14—C15	−114.1 (6)	C6—C7—N2—C12	173.4 (4)
C27—C13—C14—C15	66.2 (7)	C8—C7—N2—Pd1	−178.3 (4)
C19—C14—C15—C16	−1.9 (9)	C6—C7—N2—Pd1	−1.7 (5)
C13—C14—C15—C16	−179.4 (6)	C27—C13—N3—N4^i	0.6 (5)
C14—C15—C16—C17	2.1 (11)	C14—C13—N3—N4^i	−179.1 (4)
C15—C16—C17—C18	−0.6 (12)	C27—C13—N3—Pd1	−173.7 (3)
C16—C17—C18—C19	−1.0 (12)	C14—C13—N3—Pd1	6.6 (7)
C15—C14—C19—C18	0.3 (9)	C27^i—C20—N4—N3^i	0.5 (5)
C13—C14—C19—C18	177.9 (6)	C21—C20—N4—N3^i	−177.2 (4)
C17—C18—C19—C14	1.2 (11)	C27^i—C20—N4—Pd1	175.6 (3)
N4—C20—C21—C22	−35.4 (7)	C21—C20—N4—Pd1	−2.0 (7)
C27^i—C20—C21—C22	147.6 (5)	C36—C35—O1—C35^iii	147 (3)
N4—C20—C21—C26	142.2 (5)	C1—N1—Pd1—N2	172.7 (5)
C27^i—C20—C21—C26	−34.9 (7)	C6—N1—Pd1—N2	−2.4 (3)
C26—C21—C22—C23	0.7 (8)	C1—N1—Pd1—N4	−2.1 (4)
C20—C21—C22—C23	178.3 (5)	C6—N1—Pd1—N4	−177.2 (3)
C21—C22—C23—C24	0.7 (9)	C1—N1—Pd1—Pd1^i	64.5 (4)
C22—C23—C24—C25	−1.7 (10)	C6—N1—Pd1—Pd1^i	−110.6 (3)
C23—C24—C25—C26	1.3 (10)	C12—N2—Pd1—N1	−172.4 (5)
C24—C25—C26—C21	0.1 (9)	C7—N2—Pd1—N1	2.2 (3)
C22—C21—C26—C25	−1.1 (8)	C12—N2—Pd1—N3	2.8 (5)
C20—C21—C26—C25	−178.7 (5)	C7—N2—Pd1—N3	177.4 (3)
N3—C13—C27—C20^i	−0.3 (5)	C12—N2—Pd1—Pd1^i	−63.7 (4)
C14—C13—C27—C20^i	179.4 (5)	C7—N2—Pd1—Pd1^i	110.9 (3)
N3—C13—C27—C28	−173.6 (4)	N3^i—N4—Pd1—N1	111.1 (3)
C14—C13—C27—C28	6.1 (8)	C20—N4—Pd1—N1	−63.9 (5)
C13—C27—C28—C29	90.3 (6)	N3^i—N4—Pd1—N3	−63.9 (3)
C20^i—C27—C28—C29	−81.4 (6)	C20—N4—Pd1—N3	121.1 (4)
C27—C28—C29—C30	−27.2 (7)	N3^i—N4—Pd1—Pd1^i	0.9 (2)
C27—C28—C29—C34	156.9 (5)	C20—N4—Pd1—Pd1^i	−174.1 (5)
C34—C29—C30—C31	1.1 (9)	C13—N3—Pd1—N2	65.8 (5)
C28—C29—C30—C31	−175.0 (6)	N4^i—N3—Pd1—N2	−108.3 (3)
C29—C30—C31—C32	−2.5 (12)	C13—N3—Pd1—N4	−119.6 (5)
C30—C31—C32—C33	3.0 (14)	N4^i—N3—Pd1—N4	66.3 (3)
C31—C32—C33—C34	−2.2 (14)	C13—N3—Pd1—Pd1^i	174.9 (5)
C32—C33—C34—C29	0.8 (12)	N4^i—N3—Pd1—Pd1^i	0.9 (2)

Symmetry codes: (i) x−y+1, −y+2, −z+5/3; (ii) x−y+1, −y+2, −z+2/3; (iii) x−y, −y, −z+5/3; (iv) y, x, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···F1^i	0.93	2.50	3.228 (8)	135
C12—H12···F1	0.93	2.44	3.200 (8)	139
C36—H36A···O2	0.96	2.45	3.25 (3)	141
C36—H36B···F7^v	0.96	2.31	3.04 (4)	133
C36—H36C···F9^v	0.96	2.19	2.95 (3)	135

Symmetry codes: (i) x−y+1, −y+2, −z+5/3; (v) −x+y, −x+1, z−1/3.