Crystal structure of μ-carbonyl-1:2κ2C:C-carbonyl-1κC-(1η5-cyclo­penta­dien­yl)iodido-2κI-[μ-2-(pyridin-2-yl)ethene-1,1-diyl-1κC1:2κ2N,C1]ironpalladium(Fe—Pd) benzene monosolvate

Verpekin, V.V.; Kreindlin, A.Z.; Semeikin, O.V.; Smol'yakov, A.F.; Dolgushin, F.M.; Chudin, O.S.; Ustynyuk, N.A.

doi:10.1107/S2056989016019915

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ISSN: 2056-9890

Volume 73| Part 1| January 2017| Pages 68-71

https://doi.org/10.1107/S2056989016019915

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Crystal structure of μ-carbonyl-1:2κ²C:C-carbonyl-1κC-(1η⁵-cyclopentadienyl)iodido-2κI-[μ-2-(pyridin-2-yl)ethene-1,1-diyl-1κC¹:2κ²N,C¹]ironpalladium(Fe—Pd) benzene monosolvate

Victor V. Verpekin,^a Arkadii Z. Kreindlin,^b Oleg V. Semeikin,^b Alexander F. Smol'yakov,^b Fedor M. Dolgushin,^b ^* Oleg S. Chudin ^a and Nikolai A. Ustynyuk ^b

^aInstitute of Chemistry and Chemical Technology, Krasnoyarsk Research Center, Siberian Branch of the Russian Academy of Sciences, Akademgorodok 50-24, Krasnoyarsk, 660036, Russian Federation, and ^bA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow 119991, Russian Federation
^*Correspondence e-mail: fedya@ineos.ac.ru

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 2 December 2016; accepted 14 December 2016; online 1 January 2017)

The reaction of Cp(CO)₂FeI with 2-ethynylpyridine under Sonogashira conditions [5% PdCl₂(PPh₃)₂, 10% CuI, THF–NEt₃ (2:1)] afforded the title binuclear μ-pyridylvinylidene FePd complex (FePd1) as a benzene solvate, [FePd(C₅H₅)(C₇H₅N)I(CO)₂]·C₆H₆, in a very low yield rather than the expected iron o-pyridylethynyl complex Cp(CO)₂Fe—C≡C-(2-C₅H₄N). The Fe and Pd atoms in FePd1 are bridged by carbonyl and pyridylvinylidene ligands, the pyridyl N atom being bonded to the palladium atom. The use of equimolar amounts of PdCl₂ increases the yield of FePd1 to 12%. The reaction pathway leading to FePd1 is proposed.

Keywords: crystal structure; μ-pyridylvinylidene; binuclear complex; iron; palladium.

CCDC reference: 1523136

1. Chemical context

Transition metal σ-pyridylethynyl complexes attract considerable research interest since they can act as precursors for pyridylvinylidene complexes (Chou et al., 2008 ) and as buildings blocks for supramolecular assemblies in molecular electronics (Le Stang et al., 1999 ), as well as materials for non-linear optics (Wu et al., 1997 ).

Since the presence of two Lewis base centres (C_β and N atoms) makes pyridylethynyl complexes potential catalysts for electrochemical proton reduction (Valyaev et al., 2007 ), we decided to study the CV behavior of the o-pyridylethynyl iron complex Cp(CO)₂Fe-C≡C-(2-C₅H₄N) in acidified solutions. The efficient preparation of iron arylethynyls Cp(CO)₂Fe-C≡C-Ar by Pd/Cu-catalyzed Sonogashira coupling of Cp(CO)₂FeI (FpI) with terminal arylacetylenes HC≡C-Ar (Nakaya et al., 2009 ) inspired us to study the reaction of Cp(CO)₂FeI with o-pyridylacetylene HC≡C-(2-C₅H₄N) under the same conditions (5% PdCl₂(PPh₃)₂, 10% CuI, THF:NEt₃ (2:1), 333 K). This reaction was found to afford no target complex. Instead, the binuclear FePd μ₂-pyridylvinylidene complex (FePd1) was isolated in a yield of 2%. The yield increases to 12% using PdCl₂ as an educt instead of (Ph₃P)₂PdCl₂ and pure diisopropylamine as the solvent. The structure of FePd1, which crystallized as a benzene solvate [FePd(C₅H₅)(C₇H₅N)I(CO)₂]·C₆H₆, was determined by X-ray diffraction.

Thus, while the alkynylation of FpI with terminal arylacetylens HC≡C-Ar proceeds along the typical Sonogashira pathway to afford FpC≡C-Ar in reasonable yields (Nakaya et al., 2009), the same reaction of o-pyridylacetylene did not result in the Sonogashira alkynylation product, but afforded the binuclear complex FePd1 where the metal atoms are bridged through the carbonyl and pyridylvinylidene ligands, the pyridyl nitrogen atom being bound to the palladium atom. Although additional experimental and probably theoretical studies are needed to reveal the true reaction pathway, one can assume the formation of FePd1 to be caused by the following successive steps in the palladium coordination sphere: (i) the oxidation addition of FpI at the Fe—I bond, (ii) the acetylene–vinylidene rearrangement of the π-pyridylacetylene ligand followed by (iii) insertion of the Cp(CO)₂Fe-fragment into the Pd=C bond and accompanied by (iv) formation of the bridging carbonyl group and the Pd—N bond (Fig. 1, pathway A). Presumably, it is the Pd—N bond that efficiently stabilizes FePd1, thereby favoring pathway A. This stabilization cannot occur in the case of reactions of arylacetylenes, and the typical Sonogashira reaction proceeds via the formation of a pyridylethynyl complex followed by the Fe—C-reductive elimination (Sonogashira, 1998 ) (Fig. 1, pathway B).

Figure 1
The reaction pathway.

Figure 2
The molecular structure of complex FePd1 with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The benzene solvent molecule is omitted.

2. Structural commentary

The molecular structure of the title compound is shown in Fig. 2. The iron atom is coordinated by the cyclopentadienyl ligand [the Fe—C distances lie between 2.075 (3) and 2.128 (3) Å and the Fe—Cp centroid distance is 1.731 (1) Å] and to two carbonyl ligands, one of which is terminal [the Fe1—C1—O1 angle is 177.6 (3)°] and the second one is bridging to the palladium atom [the Fe1—C2—O2 and O2—C2—Pd1 angles are 141.7 (2) and 137.0 (2)°, respectively, and the Fe1—C2 and Pd1—C2 distances are 1.942 (3) Å and 2.012 (3) Å, respectively]. In addition, the iron and palladium atoms are linked through the bridging pyridylvinylidene fragment coordinated by the C3 atom. The four-membered ring Fe1–C2–Pd1–C3 thereby formed is folded slightly by 11.61 (14)° along the Fe1⋯Pd1 line with a short metal–metal distance of 2.5779 (4) Å [for comparison the values of the covalent radii for these metals are r(Fe) = 1.32, r(Pd) = 1.39 Å; Cordero et al., 2008 ]. The Fe1—C3 distance of 1.836 (3) Å is noticeably longer compared to the analogous distances in mononuclear iron vinylidene complexes: for example, 1.744 (4) Å in (η⁵-C₅H₅)Fe(SnPh₃)(CO)(=C=CHPh) (Adams et al., 1999 ) and 1.744 (9) Å in (η⁵-C₅Me₅)Fe(CO)(TMS)(=C=C(TMS)Ph) (Kalman et al., 2014 ), and the Fe1—C3—C4 angle of 156.9 (2)° is noticeably deviated from linearity. At the same time, the Pd1—C3—C4 angle is 118.58 (19)°, which suggests an unsymmetrical coordination of the C3 atom to the iron and palladium atoms. This asymmetry can be explained by the η²-coordination of the Fe=C double bond to the palladium atom. It is noteworthy that in Fe–M-type binuclear μ₂-vinylidene complexes, the coordination to the metal atoms is characterized by approximately equal values for the Fe—C—C and M—C—C angles [131.8–145.3° according to a CCDC (Groom et al., 2016 ) search]. The C3—C4 distance of 1.328 (4) Å in the vinylidene fragment corresponds with typical C=C double-bond lengths in olefins. Besides coordination to C3, the palladium atom binds to the pyridylvinylidene fragment via the nitrogen atom of the pyridine ring to a five-membered chelating ring (the ring is almost planar and the maximum deviation from the mean plane is 0.02 Å for atoms C3 and C4). The iodine atom completes the coordination sphere of the 16-electron palladium atom, which corresponds to a slightly distorted square-planar geometry [the dihedral angle between the N1/Pd1/C3 and I1/Pd/C2 planes is 3.2 (1)°].

3. Supramolecular features

In the crystal, the complexes form centrosymmetrical dimers (Fig. 3) due to π-stacking interactions between the pyridylvinylidene fragments with an interplanar distance of 3.36 Å and a shortest interatomic C5⋯C9(1 − x, −y, −z) distance of 3.339 (4) Å. The outer plane of the pyridylvinylidene fragment in the dimer is additionally shielded by the solvating benzene molecule, which is oriented by one of its C—H groups to the centroid a of the five-membered chelating palladacycle [the C6S—H6SA⋯Cg1 distance is 2.67 Å; Cg1 is the centroid of the five-membered ring, the angle between the Cg1⋯H6SA vector and the ring normal is 9.7°, and the C6S—H6SA⋯Cg1 angle is 160°].

Figure 3
Centrosymmetric stacked dimer in the crystal packing. Atoms labelled with the suffix A are generated by the symmetry operation (1 − x, −y, −z).

4. Synthesis and crystallization

A mixture of Cp(CO)₂FeI (127.3 mg, 0.419 mmol) and PdCl₂ (76 mg, 0.429 mmol) in diisopropyl amine (4 ml) was heated to 315 K and H—C≡C(2-C₅H₄N) (0.3 ml) was added. The mixture was stirred for 16 h at 333 K and the diisopropyl amine was removed under reduced pressure. The crude mixture was extracted with dichloromethane, the extract was filtered through celite, and the solvent was evaporated to dryness. The residue was dissolved in a dichloromethane–hexane (1:1) mixture and chromatographed on a silica column (9.5 × 1 cm). A dark-yellow band was eluted with dichloromethane and the eluate was evaporated to yield Cp(CO)₂Fe(μ-C=CH(2-C₅H₄N)PdI (FePd1) (29 mg, 12%) as a brown solid. Red–brown crystals of the complex suitable for X-ray diffraction analysis were obtained after recrystallization from a dichloromethane–benzene solvent mixture. IR (CH₂Cl₂, ν/cm⁻¹): 2028s, 1880s (ν_CO), 1600m, 1584m, 1548m, 1468m (ν_C=C and ν_C=N).

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. Atom H4 of the vinyl group was located in a difference Fourier map and refined freely. All other H atoms were fixed geometrically and refined using a riding model with U_iso(H) = 1.2U_eq(C).

Table 1
Experimental details

Crystal data
Chemical formula	[FePd(C₅H₅)(C₇H₅N)I(CO)₂]·C₆H₆
M_r	591.49
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	14.3058 (8), 9.0983 (5), 14.7315 (8)
β (°)	100.553 (1)
V (Å³)	1885.00 (18)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	3.38
Crystal size (mm)	0.24 × 0.18 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.578, 0.774
No. of measured, independent and observed [I > 2σ(I)] reflections	23041, 5501, 5075
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.066, 1.15
No. of reflections	5501
No. of parameters	239
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.74, −0.81
Computer programs: APEX2 and SAINT (Bruker, 2004), SHELXS97 and SHELXTL (Sheldrick, 2008 ) and SHELXL2014 (Sheldrick, 2015 ).

Supporting information

CCDC reference: 1523136

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989016019915/hb7640sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016019915/hb7640Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

µ-Carbonyl-1:2κ²C:C-carbonyl-1κC-(1η⁵-cyclopentadienyl)iodido-2κI-[µ-2-(pyridin-2-yl)ethene-1,1-diyl-1κC¹:2κ²N,C¹]ironpalladium(Fe—Pd) benzene monosolvate top

Crystal data top

[FePd(C₅H₅)(C₇H₅N)I(CO)₂]·C₆H₆	F(000) = 1136
M_r = 591.49	D_x = 2.084 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.3058 (8) Å	Cell parameters from 9930 reflections
b = 9.0983 (5) Å	θ = 2.6–33.2°
c = 14.7315 (8) Å	µ = 3.38 mm⁻¹
β = 100.553 (1)°	T = 100 K
V = 1885.00 (18) Å³	Prism, red-brown
Z = 4	0.24 × 0.18 × 0.08 mm

Data collection top

Bruker APEXII CCD diffractometer	5075 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.023
Absorption correction: multi-scan (SADABS; Bruker, 2004)	θ_max = 30.0°, θ_min = 1.5°
T_min = 0.578, T_max = 0.774	h = −20→20
23041 measured reflections	k = −12→12
5501 independent reflections	l = −20→20

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.066	w = 1/[σ²(F_o²) + (0.0294P)² + 3.6027P] where P = (F_o² + 2F_c²)/3
S = 1.15	(Δ/σ)_max < 0.001
5501 reflections	Δρ_max = 1.74 e Å⁻³
239 parameters	Δρ_min = −0.81 e Å⁻³

Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Pd1	0.30724 (2)	0.14951 (2)	0.06141 (2)	0.01181 (5)
Fe1	0.25581 (3)	0.41750 (4)	0.02367 (3)	0.01291 (7)
I1	0.29779 (2)	−0.05920 (2)	0.18779 (2)	0.01770 (5)
O1	0.43529 (15)	0.5582 (2)	0.10253 (15)	0.0230 (4)
O2	0.23406 (14)	0.3136 (2)	0.20723 (14)	0.0190 (4)
N1	0.37283 (15)	0.0155 (2)	−0.03060 (15)	0.0140 (4)
C1	0.36439 (19)	0.5038 (3)	0.07341 (18)	0.0162 (5)
C2	0.25372 (17)	0.3042 (3)	0.13501 (18)	0.0149 (4)
C3	0.32265 (18)	0.2919 (3)	−0.03820 (17)	0.0145 (4)
C4	0.36562 (18)	0.2467 (3)	−0.10583 (17)	0.0154 (5)
H4	0.376 (3)	0.311 (4)	−0.156 (3)	0.020 (9)*
C5	0.39136 (18)	0.0925 (3)	−0.10481 (17)	0.0148 (4)
C6	0.43071 (19)	0.0223 (3)	−0.17359 (18)	0.0178 (5)
H6A	0.4448	0.0770	−0.2244	0.021*
C7	0.44904 (19)	−0.1271 (3)	−0.16727 (19)	0.0196 (5)
H7A	0.4746	−0.1763	−0.2141	0.024*
C8	0.42948 (19)	−0.2043 (3)	−0.09119 (19)	0.0192 (5)
H8A	0.4414	−0.3069	−0.0853	0.023*
C9	0.39229 (19)	−0.1283 (3)	−0.02432 (19)	0.0169 (5)
H9A	0.3801	−0.1805	0.0281	0.020*
C10	0.11143 (19)	0.3898 (3)	−0.0416 (2)	0.0211 (5)
H10A	0.0767	0.2940	−0.0511	0.025*
C11	0.1632 (2)	0.4550 (3)	−0.1039 (2)	0.0213 (5)
H11A	0.1706	0.4153	−0.1654	0.026*
C12	0.2014 (2)	0.5884 (3)	−0.0635 (2)	0.0222 (6)
H12A	0.2398	0.6603	−0.0925	0.027*
C13	0.1717 (2)	0.6070 (3)	0.0232 (2)	0.0248 (6)
H13A	0.1859	0.6933	0.0655	0.030*
C14	0.1163 (2)	0.4836 (3)	0.0370 (2)	0.0230 (6)
H14A	0.0853	0.4656	0.0915	0.028*
C1S	−0.1486 (2)	0.1192 (3)	0.2145 (2)	0.0238 (6)
H1SA	−0.2048	0.1147	0.2400	0.029*
C2S	−0.0785 (2)	0.2217 (3)	0.2473 (2)	0.0237 (6)
H2SA	−0.0870	0.2876	0.2951	0.028*
C3S	0.0040 (2)	0.2276 (3)	0.2099 (2)	0.0245 (6)
H3SA	0.0518	0.2980	0.2321	0.029*
C4S	0.0165 (2)	0.1307 (4)	0.1402 (2)	0.0261 (6)
H4SA	0.0733	0.1334	0.1155	0.031*
C5S	−0.0544 (2)	0.0301 (4)	0.1070 (2)	0.0272 (6)
H5SA	−0.0469	−0.0347	0.0583	0.033*
C6S	−0.1363 (2)	0.0238 (3)	0.1447 (2)	0.0242 (6)
H6SA	−0.1842	−0.0464	0.1224	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.01461 (9)	0.00833 (8)	0.01273 (9)	0.00015 (6)	0.00316 (6)	0.00055 (6)
Fe1	0.01464 (16)	0.00873 (15)	0.01475 (16)	0.00053 (12)	0.00109 (13)	0.00039 (12)
I1	0.02540 (9)	0.01143 (8)	0.01803 (9)	−0.00009 (6)	0.00861 (6)	0.00256 (6)
O1	0.0235 (10)	0.0192 (10)	0.0246 (10)	−0.0048 (8)	−0.0001 (8)	0.0015 (8)
O2	0.0224 (9)	0.0154 (9)	0.0191 (9)	0.0037 (7)	0.0035 (7)	−0.0003 (7)
N1	0.0162 (9)	0.0120 (9)	0.0140 (9)	0.0002 (8)	0.0033 (7)	−0.0005 (7)
C1	0.0212 (12)	0.0108 (11)	0.0165 (11)	0.0006 (9)	0.0033 (9)	0.0024 (9)
C2	0.0140 (10)	0.0106 (10)	0.0195 (11)	−0.0002 (8)	0.0014 (9)	−0.0010 (9)
C3	0.0162 (11)	0.0103 (10)	0.0161 (11)	−0.0004 (8)	0.0004 (9)	0.0027 (9)
C4	0.0182 (11)	0.0147 (11)	0.0133 (11)	−0.0015 (9)	0.0030 (9)	0.0025 (9)
C5	0.0152 (11)	0.0157 (11)	0.0133 (11)	−0.0021 (9)	0.0019 (9)	−0.0002 (9)
C6	0.0191 (11)	0.0185 (12)	0.0160 (11)	−0.0005 (10)	0.0038 (9)	−0.0003 (9)
C7	0.0201 (12)	0.0192 (12)	0.0201 (12)	0.0020 (10)	0.0048 (10)	−0.0056 (10)
C8	0.0207 (12)	0.0141 (12)	0.0224 (13)	0.0023 (9)	0.0030 (10)	−0.0033 (10)
C9	0.0188 (11)	0.0126 (11)	0.0195 (12)	0.0000 (9)	0.0044 (9)	0.0003 (9)
C10	0.0171 (12)	0.0157 (12)	0.0280 (14)	−0.0008 (9)	−0.0029 (10)	0.0020 (10)
C11	0.0205 (12)	0.0232 (13)	0.0178 (12)	0.0037 (10)	−0.0027 (10)	0.0022 (10)
C12	0.0230 (13)	0.0136 (12)	0.0273 (14)	0.0019 (10)	−0.0027 (11)	0.0092 (10)
C13	0.0246 (13)	0.0135 (12)	0.0327 (15)	0.0083 (10)	−0.0042 (11)	−0.0032 (11)
C14	0.0177 (12)	0.0275 (14)	0.0233 (13)	0.0080 (11)	0.0026 (10)	0.0002 (11)
C1S	0.0204 (13)	0.0207 (13)	0.0311 (15)	0.0027 (10)	0.0065 (11)	0.0073 (11)
C2S	0.0275 (14)	0.0209 (13)	0.0229 (13)	0.0016 (11)	0.0046 (11)	0.0003 (11)
C3S	0.0231 (13)	0.0216 (13)	0.0278 (14)	−0.0055 (11)	0.0023 (11)	−0.0022 (11)
C4S	0.0245 (14)	0.0274 (15)	0.0283 (15)	−0.0056 (11)	0.0100 (11)	−0.0025 (12)
C5S	0.0352 (16)	0.0223 (14)	0.0255 (14)	−0.0081 (12)	0.0094 (12)	−0.0041 (11)
C6S	0.0227 (13)	0.0206 (13)	0.0280 (14)	−0.0041 (11)	0.0008 (11)	0.0045 (11)

Geometric parameters (Å, º) top

Pd1—C3	1.999 (2)	C8—C9	1.387 (4)
Pd1—C2	2.012 (3)	C8—H8A	0.9500
Pd1—N1	2.161 (2)	C9—H9A	0.9500
Pd1—Fe1	2.5779 (4)	C10—C11	1.411 (4)
Pd1—I1	2.6800 (3)	C10—C14	1.430 (4)
Fe1—C1	1.775 (3)	C10—H10A	1.0000
Fe1—C3	1.836 (3)	C11—C12	1.416 (4)
Fe1—C2	1.942 (3)	C11—H11A	1.0000
Fe1—C12	2.075 (3)	C12—C13	1.428 (5)
Fe1—C13	2.102 (3)	C12—H12A	1.0000
Fe1—C11	2.119 (3)	C13—C14	1.410 (4)
Fe1—C14	2.128 (3)	C13—H13A	1.0000
Fe1—C10	2.128 (3)	C14—H14A	1.0000
O1—C1	1.140 (3)	C1S—C6S	1.381 (5)
O2—C2	1.152 (3)	C1S—C2S	1.389 (4)
N1—C9	1.337 (3)	C1S—H1SA	0.9500
N1—C5	1.365 (3)	C2S—C3S	1.392 (4)
C3—C4	1.328 (4)	C2S—H2SA	0.9500
C4—C5	1.449 (4)	C3S—C4S	1.389 (4)
C4—H4	0.97 (4)	C3S—H3SA	0.9500
C5—C6	1.400 (4)	C4S—C5S	1.388 (4)
C6—C7	1.384 (4)	C4S—H4SA	0.9500
C6—H6A	0.9500	C5S—C6S	1.386 (4)
C7—C8	1.394 (4)	C5S—H5SA	0.9500
C7—H7A	0.9500	C6S—H6SA	0.9500

C3—Pd1—C2	92.66 (10)	C6—C5—C4	124.7 (2)
C3—Pd1—N1	77.66 (9)	C7—C6—C5	119.7 (3)
C2—Pd1—N1	169.95 (9)	C7—C6—H6A	120.1
C3—Pd1—Fe1	45.13 (7)	C5—C6—H6A	120.1
C2—Pd1—Fe1	48.15 (7)	C6—C7—C8	119.0 (2)
N1—Pd1—Fe1	122.54 (6)	C6—C7—H7A	120.5
C3—Pd1—I1	174.36 (7)	C8—C7—H7A	120.5
C2—Pd1—I1	92.79 (7)	C9—C8—C7	118.6 (2)
N1—Pd1—I1	96.83 (6)	C9—C8—H8A	120.7
Fe1—Pd1—I1	140.469 (12)	C7—C8—H8A	120.7
C1—Fe1—C3	89.11 (12)	N1—C9—C8	122.7 (2)
C1—Fe1—C2	91.94 (11)	N1—C9—H9A	118.6
C3—Fe1—C2	100.29 (11)	C8—C9—H9A	118.6
C1—Fe1—C12	97.17 (12)	C11—C10—C14	108.8 (3)
C3—Fe1—C12	109.26 (12)	C11—C10—Fe1	70.25 (15)
C2—Fe1—C12	149.12 (12)	C14—C10—Fe1	70.36 (15)
C1—Fe1—C13	95.50 (12)	C11—C10—H10A	125.6
C3—Fe1—C13	149.20 (12)	C14—C10—H10A	125.6
C2—Fe1—C13	109.93 (12)	Fe1—C10—H10A	125.6
C12—Fe1—C13	39.97 (13)	C10—C11—C12	107.2 (3)
C1—Fe1—C11	130.76 (12)	C10—C11—Fe1	70.95 (16)
C3—Fe1—C11	87.59 (11)	C12—C11—Fe1	68.61 (15)
C2—Fe1—C11	136.91 (11)	C10—C11—H11A	126.4
C12—Fe1—C11	39.46 (11)	C12—C11—H11A	126.4
C13—Fe1—C11	66.44 (12)	Fe1—C11—H11A	126.4
C1—Fe1—C14	126.99 (12)	C11—C12—C13	108.8 (3)
C3—Fe1—C14	143.55 (12)	C11—C12—Fe1	71.93 (16)
C2—Fe1—C14	84.98 (11)	C13—C12—Fe1	71.03 (16)
C12—Fe1—C14	66.00 (12)	C11—C12—H12A	125.6
C13—Fe1—C14	38.94 (12)	C13—C12—H12A	125.6
C11—Fe1—C14	65.88 (11)	Fe1—C12—H12A	125.6
C1—Fe1—C10	160.54 (11)	C14—C13—C12	107.5 (3)
C3—Fe1—C10	104.63 (11)	C14—C13—Fe1	71.51 (16)
C2—Fe1—C10	98.91 (11)	C12—C13—Fe1	68.99 (16)
C12—Fe1—C10	65.54 (11)	C14—C13—H13A	126.2
C13—Fe1—C10	65.65 (11)	C12—C13—H13A	126.2
C11—Fe1—C10	38.80 (11)	Fe1—C13—H13A	126.2
C14—Fe1—C10	39.26 (11)	C13—C14—C10	107.7 (3)
C1—Fe1—Pd1	97.81 (8)	C13—C14—Fe1	69.55 (16)
C3—Fe1—Pd1	50.52 (8)	C10—C14—Fe1	70.37 (16)
C2—Fe1—Pd1	50.48 (7)	C13—C14—H14A	126.1
C12—Fe1—Pd1	154.42 (9)	C10—C14—H14A	126.1
C13—Fe1—Pd1	156.51 (10)	Fe1—C14—H14A	126.1
C11—Fe1—Pd1	116.79 (8)	C6S—C1S—C2S	120.0 (3)
C14—Fe1—Pd1	118.88 (9)	C6S—C1S—H1SA	120.0
C10—Fe1—Pd1	101.57 (8)	C2S—C1S—H1SA	120.0
C9—N1—C5	119.3 (2)	C1S—C2S—C3S	119.9 (3)
C9—N1—Pd1	128.13 (18)	C1S—C2S—H2SA	120.1
C5—N1—Pd1	112.53 (17)	C3S—C2S—H2SA	120.1
O1—C1—Fe1	177.6 (3)	C4S—C3S—C2S	120.1 (3)
O2—C2—Fe1	141.7 (2)	C4S—C3S—H3SA	120.0
O2—C2—Pd1	137.0 (2)	C2S—C3S—H3SA	120.0
Fe1—C2—Pd1	81.37 (10)	C5S—C4S—C3S	119.6 (3)
C4—C3—Fe1	156.9 (2)	C5S—C4S—H4SA	120.2
C4—C3—Pd1	118.58 (19)	C3S—C4S—H4SA	120.2
Fe1—C3—Pd1	84.35 (10)	C6S—C5S—C4S	120.2 (3)
C3—C4—C5	116.3 (2)	C6S—C5S—H5SA	119.9
C3—C4—H4	122 (2)	C4S—C5S—H5SA	119.9
C5—C4—H4	121 (2)	C1S—C6S—C5S	120.2 (3)
N1—C5—C6	120.5 (2)	C1S—C6S—H6SA	119.9
N1—C5—C4	114.8 (2)	C5S—C6S—H6SA	119.9

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