(3,8,9,14-Tetraethyl-2,4,13,15-tetramethyltripyrrinato)(trifluoroacetato)­palladium(II)

In the crystal structure, the title compound {systematic name: [2,5-bis­(4-ethyl-3,5-dimethyl-2H-pyrrol-2-ylidene­meth­yl)-1H-pyrrolato](trifluoroacetato)palladium(II)}, [Pd(C₂F₃O₂)(C₂₇H₃₄N₃)], forms chiral mol­ecules with a helical distortion of the tripyrrinate ligand backbone and an essentially planar PdN₃O core, with Pd-N distances ranging from 1.977 (3) to 2.045 (3) Å and a Pd-O distance of 2.051 (2) Å. This distortion of the organic ligand is considered as the conformational answer to the steric inter­action of the terminal methyl groups of the tripyrrinate ligand with the donor O atom of the trifluoro­acetate group.

S1. Comment

The structure of the title complex, (I), was determined as part of a continuing study (Bröring et al., 2001, 2002, 2003) of neutral palladium(II) complexes of tripyrrinate ligands, (trpy)PdX. Neutral palladium(II) complexes of such α,ω-dimethyltripyrrinate ligands are typically characterized by the steric repulsion that is present between the formally negatively charged coligand (in particular the donor atom of that coligand) and the two methyl groups C1 and C16 situated at the termini of the open-chain tripyrrole (methyl termini). The steric overcrowding at the open site of the linear tripyrrole which can be quantified by an analysis of the van der Waals radii of the involved methyl groups and ligand donor atom (Bröring et al., 2007) leads to strained, nonplanar structures for trifluoracetato(2,15-dimethyl-3,4,7,8,13,14-hexaethyltripyrrinato)palladium(II) and the azido, chlorido, bromido and iodido complexes of the same (trpy)Pd fragment (Bröring et al., 2001, 2002, 2003), and in the case of trifluoracetato(2,15-dimethyl-3,4,13,14-tetraethyltripyrrinato)palladium(II) even a fluxional behaviour has been observed, i.e. a dynamic interconversion process between two different non-planar conformations in solution (Scheme 2). These two limiting conformations have so far been the only ones observed for (trpy)PdX species, and they have been named pseudoplanar and helical in accordance with the respective tripyrrole conformations. In the pseudoplanar conformation (C_s symmetry of the tripyrrin ligand), the Pd^II centre is bound in an intermediate situation between distorted square-planar and distorted tetrahedral, while for the helical form (C₂ symmetry of the tripyrrin ligand) a planar coordination of the palladium(II) ion results. The pseudoplanar scenario is present in the majority of compounds, while the helical form has been observed in only two cases so far, both of which employ the trifluoracetate ligand.

(trpy)PdOAc^F, (I), crystallizes in the monoclinic system, space group P2₁/c, with Z = 4. The CF₃ group of the trifluoracetate ligand shows disorder and is refined in two orientations with occupancies of 60.0 (4) and 40.0 (4)%. The Pd^II atom is bound in an almost square-planar fashion with a deviation of the Pd atom from the mean PdN₃O plane of 0.0177 (3) Å and bond angles N2—Pd1—O1 and N1—Pd1—N3 of 178.79 (11) and 177.08 (11)°, respectively. Two long and one short Pd—N bond, the latter being the one to the central nitrogen donor N2, are present in the coordination unit. The alternating C—C bond lengths of the tripyrrolic ligand perimeter C2–C15 indicate an unequal charge distribution, and it can be proposed that the negative charge of the deprotonated trpy ligand is located mainly at the central C₄N unit. This interpretation would also be in agreement with the above mentioned finding of a short Pd1—N2 bond and with the differences in the C—N bond lengths of N1 and N3 that indicate the presence of imino-like substructures at these positions. In order to create a sufficiently large binding pocket for atom O1 of the trifluoracetate ligand within a square-planar coordination geometry, the positions of the terminal methyl groups C1H₃ and C16H₃ of (I) are characterized by displacements of 1.127 (4) and -1.364 (5) Å from the mean PdN₃O plane. These displacements are achieved by a pronounced helical twist and nonplanar structure of the trpy ligand similar to the ruffled conformation shown by a number of metalloporphyrins (Senge, 2000) which can be quantified by the dihedral angles between the mean planes of adjacent C₄N moieties of 35.4 (2) and 28.0 (2)° (Fig. 2). The overall twist as measured by the dihedral angle between the mean planes of the opposite C₄N rings is as large as 57.8 (2)°. These values are within the data ranges of 25.7 (2)–38.3 (2)° and 54.8 (2)–63.8 (2)°, respectively, found earlier for related compounds (Bröring et al., 2001, 2002).

The pronounced non-planarity of (I) in the crystal seems to be in contrast to the apparent planarity and C_2v symmetry observed by ambient temperature ¹H NMR spectroscopy. More explicitly, the protons of the methylene groups from the trpy ligands' ethyl groups do not split diastereotopically but give a simple quartett signal, and the F atoms produce a singlet in the ¹⁹F NMR spectrum. These data indicate a racemization process in addition to the rotation of the trifluoroacetate around the Pd1—O1 and the C27—C28 bonds in solution, all of which are fast on the NMR time scale. Obviously, the nonplanar structure is caused by the steric influence of the terminal methyl groups of the tripyrrin on the anionic coligand. Only through a severe twist of the tripyrrin system can the binding atom O1 of the trifluoracetate group find enough space to coordinate to the central Pd^II metal as part of a distorted square-planar geometry. The bound O atom of the trifluoracetate ligand is thereby located almost ideally amid the terminal methyl groups with distances C1···C16, C1···O1 and C16···O1 of 5.861 (6), 2.933 (5) and 2.935 (5) Å, respectively. These C_methyl—O values undercut the sum of the van der Waals values (Bondi, 1964) by as much as 17.2%, thus indicating significant intramolecular strain being stored in the compound. Owing to the helicity of the trpy ligand the complex is chiral in the solid state, and both enantiomers are found in the unit cell in a 1:1 ratio.

Related literature

For related literature, see: Bondi (1964); Bröring & Brandt (2001, 2002); Bröring et al. (2003, 2007); Senge (2000); Sheldrick (1997).

S2. Experimental

3,4-Diethyl-2,5-diformylpyrrole (175 mg, 1.4 mmol) and 3-ethyl-2,4-dimethylpyrrole (354 mg, 2.8 mmol) were dissolved in trifluoroacetic acid (10 ml) and heated to reflux for 10 h. After cooling to room temperature all volatiles were removed in vacuo, and the resulting dark residue was treated with a slurry of palladium(II) acetate (317 mg, 1.4 mmol) and sodium acetate (347 mg, 4.23 mmol) in dichloromethane (50 ml). After stirring at room temperature for 16 h, the mixture was again taken to dryness, then redissolved in dichloromethane and filtered. From the filtrate, the title compound can be isolated by chromatography on silica with dichloromethane (dark green fraction) and subsequent recrystallization from dichloromethane/hexane. The compound yields a green, air-stable powder. Yield 50%.

Combustion analysis: found C 54.94, H 5.67, N 6.62%; C₂₈H₃₄F₃N₃O₂Pd (608.01) requires C 55.31%, H 5.64%, N 6.91%. ¹H NMR (400 MHz, CD₂Cl₂, p.p.m.): δ 6.75 (s, 2H), 2.53 (q, J = 7.6 Hz, 4H), 2.31 (q, J = 7.6 Hz, 4H), 2.30 (s, 6H), 2.15 (s, 6H), 1.12 (t, J = 7.6 Hz, 6H), 1.01 (t, J = 7.6 Hz, 6H). ¹³C-NMR (100 MHz, CD₂Cl₂): δ p.p.m. 173.6, 142.1,140.6, 138.3, 137.8, 136.8, 119.6, 18.2, 17.8, 17.2, 13.9, 9.8. ¹⁹F-NMR (376 MHz, CD₂Cl₂): δ p.p.m. -74.2. UV/Vis (CH₂Cl₂): λ_max, nm (ε L mol^-1 cm^-1) = 270 (17000), 355 (42000), 446 (13000), 650 s h (32000), 679 nm (43000).

Suitable crystals for X-ray diffraction were grown by slow evaporation of a solution of (I) in dichloromethane/hexane.

S3. Refinement

H-atom refinement was performed as follows. The rotations of the idealized methyl H atoms around C1—C2, C4—C19, C13—C24, C15—C16, C17—C18, C20—C21, C22—C23 and C25—C26 were varied. All other H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å.

The disordered CF₃ group was refined with constrained equivalent anisotropic displacement parameters for both atom types C and F. Additionally the similarity restraint SAME (SHELXL97; Sheldrick, 1997) has been applied to the two parts of the disordered group.

Computing details

Data collection: WinXpose in X-AREA (Stoe & Cie, 2003); cell refinement: Wincell in X-AREA; data reduction: WinIntegrate in X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Mercury (Version 1.4.1; Macrae et al., 2006).

Figures

Scheme 1: Perspective representation of (I). Scheme 2: Conformational dynamics of (trpy)PdX complexes. Figure 1: A perspective drawing of the molecule of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Only the preferred orientation of the disordered CF3 group is shown.

Trifluoracetato-(1,3,12,14-tetramethyl-2,7,8,13- tetraethyltripyrrinato)palladium(II)

Crystal data

[Pd(CF3O)(C27H34N3O)]	F(000) = 1248
Mr = 608.17	Dx = 1.482 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8000 reflections
a = 8.9511 (6) Å	θ = 1.7–26.0°
b = 24.128 (2) Å	µ = 0.73 mm^−1
c = 12.6581 (9) Å	T = 193 K
β = 94.806 (8)°	Block, violet
V = 2724.2 (4) Å^3	0.34 × 0.20 × 0.13 mm
Z = 4

Data collection

Stoe IPDS-1 diffractometer	5284 independent reflections
Radiation source: fine-focus sealed tube	4084 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ϕ scans	θmax = 26.0°, θmin = 1.8°
Absorption correction: multi-scan (Blessing, 1995)	h = −11→10
Tmin = 0.886, Tmax = 0.906	k = −29→29
21198 measured reflections	l = −15→15

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.103	H-atom parameters constrained
S = 1.19	w = 1/[σ^2(Fo^2) + (0.0584P)^2] where P = (Fo^2 + 2Fc^2)/3
5284 reflections	(Δ/σ)max = 0.006
343 parameters	Δρmax = 1.18 e Å^−3
6 restraints	Δρmin = −0.84 e Å^−3

Special details

Experimental. ¹H NMR (400 MHz, CD₂Cl₂, p.p.m.): δ 6.75 (s, 2H), 2.53 (q, J = 7.6 Hz, 4H), 2.31 (q, J = 7.6 Hz, 4H), 2.30 (s, 6H), 2.15 (s, 6H), 1.12 (t, J = 7.6 Hz, 6H), 1.01 (t, J = 7.6 Hz, 6H). ¹³C-NMR (100 MHz, CD₂Cl₂): δ p.p.m. 173.6, 142.1,140.6, 138.3, 137.8, 136.8, 119.6, 18.2, 17.8, 17.2, 13.9, 9.8. ¹⁹F-NMR (376 MHz, CD₂Cl₂): δ p.p.m. -74.2. UV/Vis (CH₂Cl₂): λ_max, nm (ε L mol^-1 cm^-1) = 270 (17000), 355 (42000), 446 (13000), 650 s h (32000), 679 nm (43000).

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	−0.0193 (4)	0.87984 (16)	0.4485 (3)	0.0352 (9)
H1A	−0.0022	0.8746	0.5253	0.053*
H1B	−0.1257	0.8874	0.4296	0.053*
H1C	0.0409	0.9111	0.4268	0.053*
C2	0.0253 (4)	0.82847 (14)	0.3931 (3)	0.0229 (7)
C3	−0.0477 (4)	0.80908 (14)	0.2951 (3)	0.0257 (7)
C4	0.0166 (4)	0.75945 (15)	0.2731 (3)	0.0250 (7)
C5	0.1277 (4)	0.74840 (14)	0.3603 (3)	0.0232 (7)
C6	0.1983 (4)	0.69884 (14)	0.3823 (3)	0.0235 (7)
H6	0.1914	0.6718	0.3276	0.028*
C7	0.2801 (4)	0.68407 (13)	0.4783 (3)	0.0231 (7)
C8	0.3183 (4)	0.62926 (14)	0.5156 (3)	0.0243 (7)
C9	0.3758 (4)	0.63482 (14)	0.6200 (3)	0.0258 (7)
C10	0.3793 (3)	0.69254 (14)	0.6437 (3)	0.0236 (7)
C11	0.4495 (4)	0.71804 (14)	0.7352 (3)	0.0237 (7)
H11	0.4637	0.6959	0.7972	0.028*
C12	0.4986 (4)	0.77140 (14)	0.7430 (3)	0.0236 (7)
C13	0.6053 (4)	0.79441 (15)	0.8242 (3)	0.0267 (7)
C14	0.6555 (4)	0.84295 (15)	0.7838 (3)	0.0286 (8)
C15	0.5791 (4)	0.85018 (14)	0.6801 (3)	0.0271 (8)
C16	0.6151 (5)	0.89392 (18)	0.6037 (4)	0.0417 (10)
H16A	0.5798	0.9299	0.6277	0.063*
H16B	0.5654	0.8854	0.5336	0.063*
H16C	0.7238	0.8954	0.5993	0.063*
C17	−0.1722 (4)	0.83821 (17)	0.2302 (3)	0.0361 (9)
H17A	−0.2400	0.8556	0.2785	0.043*
H17B	−0.2311	0.8105	0.1865	0.043*
C18	−0.1161 (6)	0.8823 (2)	0.1582 (5)	0.0647 (16)
H18A	−0.0615	0.9107	0.2012	0.097*
H18B	−0.2015	0.8993	0.1169	0.097*
H18C	−0.0491	0.8653	0.1100	0.097*
C19	−0.0237 (4)	0.72260 (17)	0.1802 (3)	0.0344 (9)
H19A	−0.1314	0.7146	0.1758	0.052*
H19B	0.0327	0.6879	0.1888	0.052*
H19C	0.0011	0.7412	0.1151	0.052*
C20	0.2949 (4)	0.57734 (14)	0.4517 (3)	0.0302 (8)
H20A	0.3633	0.5484	0.4830	0.036*
H20B	0.3223	0.5846	0.3788	0.036*
C21	0.1347 (4)	0.55541 (17)	0.4460 (4)	0.0391 (10)
H21A	0.1063	0.5481	0.5178	0.059*
H21B	0.1282	0.5210	0.4047	0.059*
H21C	0.0665	0.5830	0.4116	0.059*
C22	0.4266 (4)	0.58932 (15)	0.6963 (3)	0.0315 (8)
H22A	0.4557	0.5566	0.6555	0.038*
H22B	0.5165	0.6020	0.7405	0.038*
C23	0.3085 (6)	0.5723 (2)	0.7675 (4)	0.0509 (12)
H23A	0.2746	0.6049	0.8050	0.076*
H23B	0.3505	0.5450	0.8191	0.076*
H23C	0.2233	0.5559	0.7248	0.076*
C24	0.6550 (4)	0.76770 (17)	0.9281 (3)	0.0344 (9)
H24A	0.6174	0.7892	0.9860	0.052*
H24B	0.7647	0.7666	0.9369	0.052*
H24C	0.6153	0.7299	0.9293	0.052*
C25	0.7705 (4)	0.88188 (17)	0.8349 (4)	0.0373 (9)
H25A	0.8347	0.8957	0.7806	0.045*
H25B	0.8352	0.8616	0.8891	0.045*
C26	0.6984 (5)	0.93064 (19)	0.8866 (4)	0.0512 (12)
H26A	0.6347	0.9171	0.9403	0.077*
H26B	0.6373	0.9516	0.8326	0.077*
H26C	0.7767	0.9547	0.9202	0.077*
C27	0.2464 (4)	0.91324 (16)	0.6146 (3)	0.0341 (8)
N1	0.1326 (3)	0.79369 (11)	0.4308 (2)	0.0228 (6)
N2	0.3204 (3)	0.72147 (12)	0.5569 (2)	0.0229 (6)
N3	0.4818 (3)	0.80893 (11)	0.6574 (2)	0.0252 (6)
C28	0.2449 (13)	0.9754 (6)	0.6095 (9)	0.0467 (15)	0.600 (4)
F1	0.2586 (10)	0.9951 (2)	0.5114 (6)	0.0886 (11)	0.600 (4)
F2	0.1168 (8)	0.9976 (2)	0.6327 (6)	0.0886 (11)	0.600 (4)
F3	0.3494 (9)	0.9972 (2)	0.6756 (6)	0.0886 (11)	0.600 (4)
C28'	0.2567 (19)	0.9770 (9)	0.5967 (12)	0.0467 (15)	0.400 (4)
F1'	0.3777 (12)	0.9935 (3)	0.5478 (9)	0.0886 (11)	0.400 (4)
F2'	0.1571 (13)	0.9960 (3)	0.5219 (10)	0.0886 (11)	0.400 (4)
F3'	0.2672 (14)	1.0066 (3)	0.6838 (9)	0.0886 (11)	0.400 (4)
Pd1	0.30518 (3)	0.803058 (10)	0.54596 (2)	0.02076 (10)
O1	0.2937 (3)	0.88782 (10)	0.5365 (2)	0.0298 (6)
O2	0.1972 (4)	0.89567 (12)	0.6943 (2)	0.0526 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.038 (2)	0.034 (2)	0.033 (2)	0.0109 (16)	−0.0044 (17)	−0.0029 (17)
C2	0.0228 (15)	0.0245 (16)	0.0212 (18)	0.0029 (13)	0.0017 (13)	0.0045 (14)
C3	0.0241 (16)	0.0294 (18)	0.0234 (19)	−0.0004 (13)	0.0009 (14)	0.0023 (15)
C4	0.0240 (16)	0.0308 (18)	0.0202 (19)	−0.0037 (13)	0.0025 (14)	0.0023 (14)
C5	0.0251 (16)	0.0264 (17)	0.0179 (18)	−0.0038 (13)	0.0009 (14)	−0.0008 (14)
C6	0.0255 (15)	0.0227 (16)	0.0224 (18)	−0.0030 (13)	0.0024 (13)	−0.0047 (14)
C7	0.0246 (16)	0.0204 (16)	0.0240 (19)	0.0003 (12)	0.0007 (14)	−0.0028 (13)
C8	0.0213 (15)	0.0214 (16)	0.030 (2)	−0.0006 (12)	−0.0006 (14)	−0.0008 (14)
C9	0.0212 (15)	0.0242 (17)	0.032 (2)	0.0040 (13)	0.0013 (14)	0.0032 (15)
C10	0.0221 (15)	0.0231 (16)	0.0252 (19)	−0.0001 (13)	0.0004 (13)	0.0004 (14)
C11	0.0231 (16)	0.0264 (17)	0.0211 (19)	0.0035 (13)	−0.0009 (13)	0.0027 (14)
C12	0.0218 (16)	0.0257 (17)	0.0231 (19)	0.0018 (13)	0.0002 (14)	−0.0006 (14)
C13	0.0213 (15)	0.0327 (19)	0.0257 (19)	0.0018 (13)	0.0004 (14)	−0.0035 (15)
C14	0.0234 (16)	0.0303 (18)	0.032 (2)	−0.0005 (13)	0.0006 (15)	−0.0060 (16)
C15	0.0230 (16)	0.0270 (17)	0.031 (2)	−0.0026 (13)	0.0007 (15)	−0.0048 (15)
C16	0.040 (2)	0.041 (2)	0.044 (3)	−0.0114 (17)	0.0015 (19)	0.0055 (19)
C17	0.0310 (19)	0.043 (2)	0.033 (2)	0.0048 (16)	−0.0084 (16)	0.0047 (18)
C18	0.058 (3)	0.069 (3)	0.062 (4)	−0.003 (3)	−0.020 (3)	0.040 (3)
C19	0.0343 (19)	0.043 (2)	0.025 (2)	−0.0032 (16)	−0.0017 (16)	−0.0035 (17)
C20	0.0318 (18)	0.0217 (17)	0.036 (2)	0.0020 (14)	−0.0009 (16)	−0.0028 (15)
C21	0.0325 (19)	0.031 (2)	0.052 (3)	−0.0031 (16)	−0.0054 (18)	−0.0066 (18)
C22	0.0323 (18)	0.0254 (17)	0.035 (2)	0.0033 (15)	−0.0074 (16)	0.0023 (16)
C23	0.063 (3)	0.049 (3)	0.041 (3)	0.006 (2)	0.009 (2)	0.017 (2)
C24	0.0338 (19)	0.041 (2)	0.027 (2)	−0.0008 (16)	−0.0040 (16)	0.0002 (17)
C25	0.0281 (18)	0.039 (2)	0.043 (3)	−0.0075 (16)	−0.0064 (17)	−0.0061 (18)
C26	0.046 (2)	0.042 (2)	0.062 (3)	0.0009 (19)	−0.018 (2)	−0.018 (2)
C27	0.046 (2)	0.0274 (19)	0.027 (2)	0.0013 (16)	−0.0083 (17)	0.0004 (16)
N1	0.0270 (14)	0.0203 (14)	0.0213 (15)	0.0023 (11)	0.0029 (12)	0.0000 (11)
N2	0.0225 (13)	0.0247 (14)	0.0209 (16)	0.0017 (11)	−0.0015 (12)	−0.0003 (12)
N3	0.0273 (14)	0.0229 (14)	0.0253 (16)	−0.0010 (11)	0.0021 (12)	−0.0010 (12)
C28	0.085 (4)	0.023 (2)	0.030 (3)	0.001 (2)	−0.006 (3)	−0.003 (2)
F1	0.114 (3)	0.0288 (11)	0.123 (3)	0.0115 (18)	0.009 (3)	0.0021 (14)
F2	0.114 (3)	0.0288 (11)	0.123 (3)	0.0115 (18)	0.009 (3)	0.0021 (14)
F3	0.114 (3)	0.0288 (11)	0.123 (3)	0.0115 (18)	0.009 (3)	0.0021 (14)
C28'	0.085 (4)	0.023 (2)	0.030 (3)	0.001 (2)	−0.006 (3)	−0.003 (2)
F1'	0.114 (3)	0.0288 (11)	0.123 (3)	0.0115 (18)	0.009 (3)	0.0021 (14)
F2'	0.114 (3)	0.0288 (11)	0.123 (3)	0.0115 (18)	0.009 (3)	0.0021 (14)
F3'	0.114 (3)	0.0288 (11)	0.123 (3)	0.0115 (18)	0.009 (3)	0.0021 (14)
Pd1	0.02466 (14)	0.01781 (14)	0.01931 (15)	0.00049 (10)	−0.00115 (9)	−0.00011 (11)
O1	0.0409 (14)	0.0227 (12)	0.0251 (14)	−0.0006 (10)	−0.0015 (11)	0.0001 (11)
O2	0.096 (3)	0.0341 (16)	0.0284 (17)	0.0068 (16)	0.0122 (17)	−0.0010 (13)

Geometric parameters (Å, º)

C1—C2	1.494 (5)	C18—H18C	0.98
C1—H1A	0.98	C19—H19A	0.98
C1—H1B	0.98	C19—H19B	0.98
C1—H1C	0.98	C19—H19C	0.98
C2—N1	1.333 (4)	C20—C21	1.525 (5)
C2—C3	1.432 (5)	C20—H20A	0.99
C3—C4	1.367 (5)	C20—H20B	0.99
C3—C17	1.503 (5)	C21—H21A	0.98
C4—C5	1.447 (5)	C21—H21B	0.98
C4—C19	1.494 (5)	C21—H21C	0.98
C5—C6	1.370 (5)	C22—C23	1.502 (6)
C5—N1	1.410 (4)	C22—H22A	0.99
C6—C7	1.411 (5)	C22—H22B	0.99
C6—H6	0.9500	C23—H23A	0.98
C7—N2	1.369 (4)	C23—H23B	0.98
C7—C8	1.436 (5)	C23—H23C	0.98
C8—C9	1.384 (5)	C24—H24A	0.98
C8—C20	1.496 (5)	C24—H24B	0.98
C9—C10	1.424 (5)	C24—H24C	0.98
C9—C22	1.507 (5)	C25—C26	1.516 (6)
C10—N2	1.369 (5)	C25—H25A	0.99
C10—C11	1.412 (5)	C25—H25B	0.99
C11—C12	1.361 (5)	C26—H26A	0.98
C11—H11	0.9500	C26—H26B	0.98
C12—N3	1.410 (5)	C26—H26C	0.98
C12—C13	1.453 (5)	C27—O2	1.212 (5)
C13—C14	1.369 (5)	C27—O1	1.266 (5)
C13—C24	1.498 (5)	C27—C28	1.501 (15)
C14—C15	1.439 (6)	C27—C28'	1.56 (2)
C14—C25	1.500 (5)	N1—Pd1	2.045 (3)
C15—N3	1.338 (4)	N2—Pd1	1.977 (3)
C15—C16	1.485 (5)	N3—Pd1	2.033 (3)
C16—H16A	0.98	C28—F1	1.344 (11)
C16—H16B	0.98	C28—F3	1.311 (11)
C16—H16C	0.98	C28—F2	1.321 (13)
C17—C18	1.513 (6)	C28'—F3'	1.312 (16)
C17—H17A	0.99	C28'—F2'	1.327 (16)
C17—H17B	0.99	C28'—F1'	1.352 (16)
C18—H18A	0.98	Pd1—O1	2.051 (2)
C18—H18B	0.98
C2—C1—H1A	109.5	C21—C20—H20A	108.8
C2—C1—H1B	109.5	C8—C20—H20B	108.8
H1A—C1—H1B	109.5	C21—C20—H20B	108.8
C2—C1—H1C	109.5	H20A—C20—H20B	107.7
H1A—C1—H1C	109.5	C20—C21—H21A	109.5
H1B—C1—H1C	109.5	C20—C21—H21B	109.5
N1—C2—C3	111.6 (3)	H21A—C21—H21B	109.5
N1—C2—C1	124.5 (3)	C20—C21—H21C	109.5
C3—C2—C1	123.9 (3)	H21A—C21—H21C	109.5
C4—C3—C2	107.0 (3)	H21B—C21—H21C	109.5
C4—C3—C17	127.2 (3)	C23—C22—C9	113.2 (3)
C2—C3—C17	125.8 (3)	C23—C22—H22A	108.9
C3—C4—C5	106.3 (3)	C9—C22—H22A	108.9
C3—C4—C19	127.1 (3)	C23—C22—H22B	108.9
C5—C4—C19	126.6 (3)	C9—C22—H22B	108.9
C6—C5—N1	123.9 (3)	H22A—C22—H22B	107.8
C6—C5—C4	126.3 (3)	C22—C23—H23A	109.5
N1—C5—C4	108.9 (3)	C22—C23—H23B	109.5
C5—C6—C7	126.4 (3)	H23A—C23—H23B	109.5
C5—C6—H6	116.8	C22—C23—H23C	109.5
C7—C6—H6	116.8	H23A—C23—H23C	109.5
N2—C7—C6	123.0 (3)	H23B—C23—H23C	109.5
N2—C7—C8	109.1 (3)	C13—C24—H24A	109.5
C6—C7—C8	127.4 (3)	C13—C24—H24B	109.5
C9—C8—C7	106.5 (3)	H24A—C24—H24B	109.5
C9—C8—C20	128.4 (3)	C13—C24—H24C	109.5
C7—C8—C20	125.1 (3)	H24A—C24—H24C	109.5
C8—C9—C10	107.2 (3)	H24B—C24—H24C	109.5
C8—C9—C22	127.6 (3)	C14—C25—C26	111.8 (3)
C10—C9—C22	125.3 (3)	C14—C25—H25A	109.3
N2—C10—C11	123.4 (3)	C26—C25—H25A	109.3
N2—C10—C9	109.3 (3)	C14—C25—H25B	109.3
C11—C10—C9	126.8 (3)	C26—C25—H25B	109.3
C12—C11—C10	126.2 (3)	H25A—C25—H25B	107.9
C12—C11—H11	116.9	C25—C26—H26A	109.5
C10—C11—H11	116.9	C25—C26—H26B	109.5
C11—C12—N3	122.6 (3)	H26A—C26—H26B	109.5
C11—C12—C13	127.0 (3)	C25—C26—H26C	109.5
N3—C12—C13	108.7 (3)	H26A—C26—H26C	109.5
C14—C13—C12	106.2 (3)	H26B—C26—H26C	109.5
C14—C13—C24	127.9 (3)	O2—C27—O1	130.5 (4)
C12—C13—C24	125.9 (3)	O2—C27—C28	112.5 (5)
C13—C14—C15	107.4 (3)	O1—C27—C28	116.9 (5)
C13—C14—C25	127.5 (4)	O2—C27—C28'	119.8 (7)
C15—C14—C25	125.0 (3)	O1—C27—C28'	109.7 (7)
N3—C15—C14	110.9 (3)	C28—C27—C28'	7.4 (10)
N3—C15—C16	124.2 (4)	C2—N1—C5	106.1 (3)
C14—C15—C16	124.6 (3)	C2—N1—Pd1	131.6 (2)
C15—C16—H16A	109.5	C5—N1—Pd1	121.2 (2)
C15—C16—H16B	109.5	C7—N2—C10	107.9 (3)
H16A—C16—H16B	109.5	C7—N2—Pd1	126.4 (2)
C15—C16—H16C	109.5	C10—N2—Pd1	125.7 (2)
H16A—C16—H16C	109.5	C15—N3—C12	106.7 (3)
H16B—C16—H16C	109.5	C15—N3—Pd1	130.9 (3)
C3—C17—C18	112.9 (3)	C12—N3—Pd1	121.0 (2)
C3—C17—H17A	109.0	F1—C28—F3	109.4 (11)
C18—C17—H17A	109.0	F1—C28—F2	102.1 (10)
C3—C17—H17B	109.0	F3—C28—F2	106.4 (10)
C18—C17—H17B	109.0	F1—C28—C27	113.0 (9)
H17A—C17—H17B	107.8	F3—C28—C27	111.7 (9)
C17—C18—H18A	109.5	F2—C28—C27	113.6 (9)
C17—C18—H18B	109.5	F3'—C28'—F2'	114.1 (17)
H18A—C18—H18B	109.5	F3'—C28'—F1'	102.7 (14)
C17—C18—H18C	109.5	F2'—C28'—F1'	95.1 (12)
H18A—C18—H18C	109.5	F3'—C28'—C27	114.7 (12)
H18B—C18—H18C	109.5	F2'—C28'—C27	113.6 (13)
C4—C19—H19A	109.5	F1'—C28'—C27	114.6 (14)
C4—C19—H19B	109.5	N2—Pd1—N3	88.62 (11)
H19A—C19—H19B	109.5	N2—Pd1—N1	89.04 (11)
C4—C19—H19C	109.5	N3—Pd1—N1	177.10 (11)
H19A—C19—H19C	109.5	N2—Pd1—O1	178.79 (11)
H19B—C19—H19C	109.5	N3—Pd1—O1	90.19 (11)
C8—C20—C21	113.9 (3)	N1—Pd1—O1	92.14 (10)
C8—C20—H20A	108.8	C27—O1—Pd1	117.1 (2)
N1—C2—C3—C4	1.2 (4)	C4—C5—N1—Pd1	−166.0 (2)
C1—C2—C3—C4	−175.9 (3)	C6—C7—N2—C10	171.7 (3)
N1—C2—C3—C17	−179.3 (3)	C8—C7—N2—C10	−1.5 (4)
C1—C2—C3—C17	3.6 (6)	C6—C7—N2—Pd1	−10.8 (5)
C2—C3—C4—C5	1.1 (4)	C8—C7—N2—Pd1	176.0 (2)
C17—C3—C4—C5	−178.4 (3)	C11—C10—N2—C7	172.0 (3)
C2—C3—C4—C19	178.7 (3)	C9—C10—N2—C7	−0.4 (4)
C17—C3—C4—C19	−0.8 (6)	C11—C10—N2—Pd1	−5.5 (4)
C3—C4—C5—C6	166.3 (3)	C9—C10—N2—Pd1	−177.9 (2)
C19—C4—C5—C6	−11.3 (6)	C14—C15—N3—C12	−3.8 (4)
C3—C4—C5—N1	−2.9 (4)	C16—C15—N3—C12	170.0 (3)
C19—C4—C5—N1	179.4 (3)	C14—C15—N3—Pd1	162.5 (2)
N1—C5—C6—C7	2.9 (5)	C16—C15—N3—Pd1	−23.8 (5)
C4—C5—C6—C7	−164.8 (3)	C11—C12—N3—C15	−161.4 (3)
C5—C6—C7—N2	−11.2 (5)	C13—C12—N3—C15	4.3 (4)
C5—C6—C7—C8	160.7 (3)	C11—C12—N3—Pd1	30.7 (4)
N2—C7—C8—C9	2.8 (4)	C13—C12—N3—Pd1	−163.6 (2)
C6—C7—C8—C9	−170.0 (3)	O2—C27—C28—F1	−162.6 (8)
N2—C7—C8—C20	−178.6 (3)	O1—C27—C28—F1	15.8 (11)
C6—C7—C8—C20	8.6 (5)	C28'—C27—C28—F1	26 (7)
C7—C8—C9—C10	−2.9 (4)	O2—C27—C28—F3	73.5 (10)
C20—C8—C9—C10	178.5 (3)	O1—C27—C28—F3	−108.1 (8)
C7—C8—C9—C22	177.3 (3)	C28'—C27—C28—F3	−98 (8)
C20—C8—C9—C22	−1.2 (6)	O2—C27—C28—F2	−46.8 (10)
C8—C9—C10—N2	2.1 (4)	O1—C27—C28—F2	131.6 (7)
C22—C9—C10—N2	−178.1 (3)	C28'—C27—C28—F2	142 (8)
C8—C9—C10—C11	−169.9 (3)	O2—C27—C28'—F3'	25.5 (16)
C22—C9—C10—C11	9.9 (5)	O1—C27—C28'—F3'	−154.9 (11)
N2—C10—C11—C12	−15.6 (5)	C28—C27—C28'—F3'	35 (7)
C9—C10—C11—C12	155.4 (4)	O2—C27—C28'—F2'	−108.1 (12)
C10—C11—C12—N3	1.2 (5)	O1—C27—C28'—F2'	71.4 (14)
C10—C11—C12—C13	−161.8 (3)	C28—C27—C28'—F2'	−99 (8)
C11—C12—C13—C14	161.7 (3)	O2—C27—C28'—F1'	144.0 (10)
N3—C12—C13—C14	−3.2 (4)	O1—C27—C28'—F1'	−36.5 (13)
C11—C12—C13—C24	−15.0 (6)	C28—C27—C28'—F1'	153 (8)
N3—C12—C13—C24	−180.0 (3)	C7—N2—Pd1—N3	−151.4 (3)
C12—C13—C14—C15	0.9 (4)	C10—N2—Pd1—N3	25.7 (3)
C24—C13—C14—C15	177.6 (3)	C7—N2—Pd1—N1	26.9 (3)
C12—C13—C14—C25	−178.1 (3)	C10—N2—Pd1—N1	−156.1 (3)
C24—C13—C14—C25	−1.4 (6)	C7—N2—Pd1—O1	−141 (5)
C13—C14—C15—N3	1.8 (4)	C10—N2—Pd1—O1	36 (5)
C25—C14—C15—N3	−179.2 (3)	C15—N3—Pd1—N2	158.3 (3)
C13—C14—C15—C16	−171.9 (4)	C12—N3—Pd1—N2	−37.2 (3)
C25—C14—C15—C16	7.1 (6)	C15—N3—Pd1—N1	122 (2)
C4—C3—C17—C18	−97.2 (5)	C12—N3—Pd1—N1	−74 (2)
C2—C3—C17—C18	83.4 (5)	C15—N3—Pd1—O1	−21.5 (3)
C9—C8—C20—C21	98.0 (4)	C12—N3—Pd1—O1	143.1 (3)
C7—C8—C20—C21	−80.3 (5)	C2—N1—Pd1—N2	160.8 (3)
C8—C9—C22—C23	−96.5 (5)	C5—N1—Pd1—N2	−32.6 (3)
C10—C9—C22—C23	83.8 (5)	C2—N1—Pd1—N3	−163 (2)
C13—C14—C25—C26	−98.7 (5)	C5—N1—Pd1—N3	4 (2)
C15—C14—C25—C26	82.4 (5)	C2—N1—Pd1—O1	−19.5 (3)
C3—C2—N1—C5	−3.0 (4)	C5—N1—Pd1—O1	147.2 (2)
C1—C2—N1—C5	174.1 (3)	O2—C27—O1—Pd1	−4.7 (6)
C3—C2—N1—Pd1	165.1 (2)	C28—C27—O1—Pd1	177.2 (5)
C1—C2—N1—Pd1	−17.8 (5)	C28'—C27—O1—Pd1	175.8 (7)
C6—C5—N1—C2	−165.9 (3)	N2—Pd1—O1—C27	−82 (5)
C4—C5—N1—C2	3.6 (4)	N3—Pd1—O1—C27	−71.3 (3)
C6—C5—N1—Pd1	24.4 (4)	N1—Pd1—O1—C27	110.4 (3)