Bis(tetra-n-butylammonium) di-μ-chloro-bis[(tetramethyl buta-1,3-diene-1,2,3,4-tetracarboxylato-κ²C¹,C⁴)palladium]

The anionic complex in the title compound, (C₁₆H₃₆N)₂[Pd₂(C₁₂H₁₂O₈)₂Cl₂], lies on a centre of inversion, so that the {Pd₂(μ-Cl)₂} core is planar, which is the most frequent conformation found for complexes containing this moiety in the Cambridge Structural Database [October 2001 Release; Allen & Kennard (1993). Chem. Des. Autom. News, 8, 1, 31–37]. This dinuclear complex has a Pd...Pd distance of 3.5119 (4) Å. The bite angle of the chelating ligand [79.79 (8)°] distorts the square-planar coordination around the metal atom.

S1. Comment

The chemistry of metallacycles has been of increasing interest during recent years, as a result of their involvement in catalytic processes and their application in organic syntheses (Ojima et al., 1996). The cycloaddition of two unsaturated fragments to a metal unit is one of the most useful methods of metallacycle synthesis, since it gives access to relatively complex structures starting from small unsaturated molecules (Cámpora et al., 1999). In particular, the oxidative cycloaddition of acetylenic esters such as dimethyl acetylenedicarboxylate (dmad) to Ni, Pd and Pt has received much attention, due in part to its involvement in different oligomerization and co-oligomerization catalytic reactions, and also because of the interesting behaviour of the compounds formed as precursors in organometallic chemistry. Thus, the polymer complex, palladacyclopentadiene, [Pd(C₄R₄)]_n (R is COOMe), formed in the reaction of dmad with Pd(dba)₂ (dba is dibenzylidene acetone), reacts with a wide range of donor ligands to give discrete soluble molecules (tom Dieck et al., 1990). Other aspects recently studied are the use of these compounds as catalysts in the metathesis of enynes (Trost et al., 1993), dimerization of allenyl ketones (Hashmi, 1995), conversion of alkynes to conjugated dienes (van Belzen et al., 1998, and references therein) and co-cyclotrimerizations of acetylenes with other acetylenes, alkenes and allenes (Munz et al., 1991). With this background, we present here the crystal structure of one such dinuclear metallacycle, the title compound, (I). \sch

In complex (I) (Fig. 1), the coordination around the Pd^II atoms is approximately planar, the largest deviation from the plane defined by the metallacycle ring and the Cl atoms (r.m.s. deviation 0.0478 Å) being 0.0792 (14) Å for atom C2. The bond angles around the Pd atom deviate from ideal square-planar values (Table 1); the largest deviation is the C1—Pd1—C4 angle of 79.79 (8)°. This value is within the range found for related complexes in the Cambridge Structural Database (CSD; October 2001 release; Allen & Kennard, 1993), where the C—Pd—C angle for the tetraalkyl buta-1,3-diene-1,2,3,4-tetracarboxylate Pd^II fragment in the CSD (7 hits) ranges from 79.18 to 80.38°. The –CO₂ groups of the ester functions bound to the C atoms trans to Cl are nearly perpendicular to the palladacycle ring, as indicated by the Pd1—C1—C5—O2 and Pd1—C4—C8—O8 torsion angles. The angle between the other two carboxylate groups and the palladacycle plane is smaller (Table 1). The Pd—Cl distances are typical for µ-Cl dinuclear complexes of Pd. The Pd—C distances are similar to those found in other complexes containing this ligand (Sánchez et al., 2002).

The molecule of (I) lies on a centre of inversion, so the [Pd₂(µ-Cl)₂] moiety is strictly planar. The CSD contains 151 entries for dinuclear complexes of Pd^II bridged by two Cl atoms, in which the [Pd₂(µ-Cl)₂] moiety is either planar or bent. A statistical analysis of the dihedral angle of the [Pd₂(µ-Cl)₂] unit along the Cl···Cl axis reveals that the most frequent conformation is planar (Fig. 2): 39.7% of the hits are strictly planar. In the title complex, the Pd1···Pd1ⁱ distance [symmetry code: (i) 1 - x, 1 - y, 1 - z] is 3.5119 (4) Å, which is within the most frequently occupied region of the range found in dinuclear complexes containing the [Pd₂(µ-Cl)₂] core (Fig. 3); 28% of the structures exhibit a distance of between 3.50 and 3.55 Å.

The anionic complex in (I) is sandwiched between two [NBu₄]⁺ cations. The N atoms from the cations lie on the perpendicular to the [Pd₂(µ-Cl)₂] core, over the Pd^II atoms [N1—Pd1—Pd1ⁱ 89.91 (2)°]. The distances from Pd1 to the two nearest N atoms are 4.4650 (15) and 5.6764 (16) Å. The next nearest N atom to Pd1 is 6.1776 (16) Å away. The structure does not present hydrogen bonds.

The structure of the analogous iodo complex has been reported by Rheingold et al. (1989), the cation being methyltriphenylphosphonium. The iodo complex is also centrosymmetric and the Pd···Pd distance is 3.912 Å, which is larger than that found in the chloro complex, (I), due to the larger radius of the bridging I atom. The geometrical features of the palladacycle fragment are similar in both compounds. The mean Pd—C distance is 2.017 (3) Å in the iodo complex, which is larger than that found in (I) (Table 1), due to a stronger trans influence from I^- than from Cl^-. The –CO₂ groups of the ester functions nearest to the Pd atom are approximately perpendicular to the palladacycle ring (Pd—C—C═O torsion angles of 100.3° and 82.3°), as in (I) (Table 1). The tilt of the other carboxylate groups from the palladacycle plane is also smaller (torsion angles of -163.7° and 56.2°). The anionic iodo complex is sandwiched between two [PMe(Ph)₃]⁺ cations and the P atoms in the cations are placed on the perpendicular to the Pd···Pd axis (P—Pd—Pd 106.4°), with the shortest P—Pd distance being 5.064 Å.

The conformation found for the methoxycarbonyl groups in the above complexes suggests that, as the methoxycarbonyl groups at the α position relative to Pd become more perpendicular to the palladacycle ring, the adjacent methoxycarbonyl groups at the β position become more parallel to the ring. This is confirmed by the scatter plot of these angles for the tetramethyl buta-1,3-diene-1,2,3,4-tetracarboxylate Pd^II fragments in the CSD (Fig. 4), the angle between the planes defined by two adjacent methoxycarbonyl groups ranging from 42.4 to 74.7°.

S2. Experimental

The title complex was prepared according to following method: a stochiometric amount of tetrabutylammonium chloride (molar ratio 1:1) was added to a dichloromethane solution (10 ml) of the precursor [Pd{C₄(COOMe)₄}]_n (0.07 g, 0.18 mmol) (see Scheme). The reaction solution was stirred at room temperature for 30 min, and then the solvent was partially evaporated under reduced pressure. The addition of diethyl ether caused the formation of a pale-yellow solid, which was filtered off, washed with diethyl ether and air dried. Crystals of (I) were obtained by recrystallization from dichloromethane-diethyl ether (yield 84%). Analysis found: C 50.5, H 7.4, N 1.9%; calculated for C₅₆H₉₆N₂Cl₂O₁₆Pd₂: C 50.3, H 7.2, N 2.1%. IR (cm^-1): 1712, 1694 (C═O, str); ¹H NMR (CDCl₃, δ, p.p.m.): 3.57 (s, 6H, COOMe), 3,62 (s, 6H, COOMe), 3.40 (t, 16H, NBu₄), 1.74 (m, 16H, NBu₄), 1.53 (m, 16H, NBu₄), 1.00 (t, 24H, NBu₄). The palladacyclopentadiene precursor was prepared by the published method of Moseley & Maitlis (1974). The tetrabutylammonium chloride was purchased from Aldrich and used without further purification. CHN analyses were carried out with a Perkin-Elmer 240 C microanalyser. The IR spectra were recorded on a Perkin-Elmer spectrophotometer 16 F PC FT—IR, using Nujol mulls between polyethylene sheets. The NMR data were recorded on a Bruker AC 200E (¹H) spectrometer.

S3. Refinement

H atoms were placed in calculated positions, with C—H distances of 0.99 and 0.98 Å for methylene and methyl groups, respectively, and were refined as riding, with U_iso(H) = 1.2U_eq(C) for the methylene groups and U_iso(H) = 1.5U_eq(C) for the methyl groups.

Computing details

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997).

Figures

	Fig. 1. A perspective view of the complex anion in (I). H atoms have been omitted for clarity and displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A histogram showing the dihedral angles of the [Pd2(µ-Cl)2] core along the Cl···Cl line among the structures found in the CSD search.
	Fig. 3. A histogram showing the distribution of Pd···Pd distances among the structures found in the CSD search containing the [Pd2(µ-Cl)2] core.
	Fig. 4. A scatter plot for the angle between the palladacycle ring and the methoxy carbonyl groups in the α position (angle 1) and the β position (angle 2).

Bis(tetra-n-butylammonium) di-µ-chloro-bis[(tetramethyl buta-1,3-diene-1,2,3,4-tetracarboxylato-κ²C¹,C⁴)palladium(0)]

Crystal data

(C16H36N)2[Pd2(C12H12O8)2Cl2]	Z = 1
Mr = 1337.05	F(000) = 700
Triclinic, P1	Dx = 1.381 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5024 (6) Å	Cell parameters from 61 reflections
b = 12.6678 (7) Å	θ = 9.8–24.7°
c = 14.637 (1) Å	µ = 0.71 mm^−1
α = 95.929 (5)°	T = 173 K
β = 106.777 (5)°	Block, yellow
γ = 104.100 (5)°	0.40 × 0.35 × 0.28 mm
V = 1607.25 (19) Å^3

Data collection

Siemens P4 four-circle diffractometer	Rint = 0.020
Graphite monochromator	θmax = 25°, θmin = 3.1°
ω scans	h = −10→11
Absorption correction: ψ scan (North et al., 1968)	k = −14→14
Tmin = 0.787, Tmax = 0.821	l = −17→17
11249 measured reflections	3 standard reflections every 247 reflections
5644 independent reflections	intensity decay: 4.3%
5057 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Primary atom site location: Patterson
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.055	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0286P)^2 + 0.2945P] where P = (Fo^2 + 2Fc^2)/3
5644 reflections	(Δ/σ)max = 0.001
352 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.30 e Å^−3

Special details

Geometry. Mean-plane data from final SHELXL refinement run:-

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

- 8.4969 (0.0014) x + 7.0902 (0.0041) y + 6.6545 (0.0049) z = 2.6524 (0.0019)

* 0.0612 (0.0004) Pd1 * -0.0014 (0.0007) Cl1 * -0.0556 (0.0007) Cl1_$2 * 0.0237 (0.0013) C1 * -0.0792 (0.0014) C2 * 0.0036 (0.0014) C3 * 0.0477 (0.0014) C4

Rms deviation of fitted atoms = 0.0478

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
Pd1	0.341355 (17)	0.409571 (12)	0.407262 (10)	0.02387 (6)
Cl1	0.47927 (6)	0.40997 (4)	0.57353 (3)	0.03337 (12)
C4	0.2249 (2)	0.39908 (16)	0.26774 (13)	0.0262 (4)
C1	0.1965 (2)	0.25730 (16)	0.37886 (13)	0.0263 (4)
O4	−0.04187 (16)	0.03752 (12)	0.28919 (11)	0.0382 (3)
O2	0.28426 (16)	0.11963 (12)	0.46152 (10)	0.0334 (3)
O7	0.38614 (17)	0.49555 (12)	0.19327 (10)	0.0370 (3)
O6	−0.13533 (17)	0.23134 (15)	0.10813 (12)	0.0516 (4)
O3	0.03675 (18)	0.06776 (12)	0.16151 (10)	0.0424 (4)
O8	0.20414 (19)	0.56965 (13)	0.21534 (11)	0.0466 (4)
O5	0.04985 (17)	0.34095 (13)	0.06528 (10)	0.0401 (4)
N1	0.35422 (17)	0.77880 (13)	0.66800 (11)	0.0268 (3)
O1	0.13103 (18)	0.20452 (14)	0.51231 (11)	0.0444 (4)
C15	0.6339 (2)	0.75879 (19)	0.91192 (15)	0.0359 (5)
H15A	0.7029	0.73	0.8834	0.043*
H15B	0.6779	0.8402	0.9319	0.043*
C8	0.2641 (2)	0.49638 (17)	0.22220 (13)	0.0313 (5)
C13	0.4952 (2)	0.76333 (17)	0.74026 (14)	0.0288 (4)
H13A	0.5797	0.8329	0.7561	0.035*
H13B	0.5269	0.7046	0.7083	0.035*
C2	0.1042 (2)	0.21948 (17)	0.28586 (13)	0.0274 (4)
C25	0.3234 (2)	0.88474 (17)	0.70531 (15)	0.0336 (5)
H25A	0.2219	0.8865	0.6633	0.04*
H25B	0.3177	0.8823	0.7716	0.04*
C17	0.2130 (2)	0.68430 (16)	0.65572 (15)	0.0308 (4)
H17A	0.1228	0.6991	0.6108	0.037*
H17B	0.1965	0.6831	0.7194	0.037*
C5	0.2101 (2)	0.18497 (16)	0.45257 (14)	0.0275 (4)
C6	0.0226 (2)	0.10055 (17)	0.24800 (14)	0.0303 (4)
C14	0.4768 (2)	0.73279 (17)	0.83506 (14)	0.0315 (4)
H14A	0.4144	0.7753	0.8575	0.038*
H14B	0.4228	0.6529	0.8244	0.038*
C21	0.3865 (2)	0.78435 (18)	0.57259 (14)	0.0314 (4)
H21A	0.4018	0.713	0.5497	0.038*
H21B	0.4839	0.8429	0.585	0.038*
C3	0.1154 (2)	0.30316 (16)	0.22352 (13)	0.0269 (4)
C18	0.2208 (3)	0.57063 (18)	0.61710 (18)	0.0426 (5)
H18A	0.3221	0.5617	0.6517	0.051*
H18B	0.2091	0.5638	0.5471	0.051*
C16	0.6269 (3)	0.7086 (2)	1.00071 (16)	0.0484 (6)
H16A	0.7303	0.7278	1.0481	0.073*
H16B	0.5859	0.6278	0.9816	0.073*
H16C	0.56	0.7377	1.0299	0.073*
C22	0.2624 (2)	0.80773 (18)	0.49135 (15)	0.0339 (5)
H22A	0.1647	0.7486	0.476	0.041*
H22B	0.2457	0.8791	0.5125	0.041*
C28	0.5450 (4)	1.0611 (3)	0.8907 (2)	0.0803 (10)
H28A	0.5543	1.1213	0.9418	0.12*
H28B	0.6475	1.0574	0.8925	0.12*
H28C	0.4873	0.9907	0.9014	0.12*
C7	−0.0037 (2)	0.28567 (18)	0.12742 (14)	0.0331 (5)
C10	−0.0446 (3)	−0.0460 (2)	0.11606 (18)	0.0578 (7)
H10A	−0.0273	−0.0621	0.0539	0.087*
H10B	−0.1546	−0.0581	0.1047	0.087*
H10C	−0.0072	−0.095	0.1586	0.087*
C24	0.1999 (3)	0.8415 (2)	0.31834 (16)	0.0420 (5)
H24A	0.2382	0.8432	0.263	0.063*
H24B	0.1891	0.9145	0.3387	0.063*
H24C	0.0998	0.7857	0.2993	0.063*
C23	0.3119 (3)	0.8125 (2)	0.40169 (16)	0.0487 (6)
H23A	0.4132	0.8682	0.4193	0.058*
H23B	0.3241	0.7396	0.3799	0.058*
C26	0.4422 (3)	0.99147 (18)	0.70878 (18)	0.0449 (6)
H26A	0.4106	1.0176	0.6466	0.054*
H26B	0.5421	0.9765	0.7164	0.054*
C12	0.4497 (3)	0.5932 (2)	0.1603 (2)	0.0619 (8)
H12A	0.5374	0.5847	0.1409	0.093*
H12B	0.4839	0.6576	0.2129	0.093*
H12C	0.3715	0.6041	0.1046	0.093*
C27	0.4613 (3)	1.08237 (19)	0.79257 (18)	0.0523 (6)
H27A	0.5189	1.1543	0.7828	0.063*
H27B	0.3587	1.0876	0.7918	0.063*
C11	−0.0626 (3)	0.3390 (2)	−0.02681 (17)	0.0588 (7)
H11A	−0.0115	0.3816	−0.0663	0.088*
H11B	−0.1405	0.3718	−0.0149	0.088*
H11C	−0.1118	0.2622	−0.0614	0.088*
C9	0.1492 (3)	0.1469 (3)	0.59282 (19)	0.0667 (9)
H9A	0.0881	0.1661	0.6322	0.1*
H9B	0.2576	0.1686	0.6328	0.1*
H9C	0.1142	0.0668	0.5683	0.1*
C20	0.1277 (3)	0.4606 (2)	0.7351 (2)	0.0731 (9)
H20A	0.0423	0.4019	0.7395	0.11*
H20B	0.1403	0.5291	0.7784	0.11*
H20C	0.2222	0.4383	0.7545	0.11*
C19	0.0938 (3)	0.4798 (2)	0.6315 (2)	0.0607 (8)
H19A	−0.0033	0.5002	0.6119	0.073*
H19B	0.079	0.4097	0.5882	0.073*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.02789 (9)	0.02605 (9)	0.01788 (8)	0.01227 (6)	0.00402 (6)	0.00403 (5)
Cl1	0.0420 (3)	0.0286 (3)	0.0225 (2)	0.0111 (2)	0.0001 (2)	0.00252 (19)
C4	0.0269 (10)	0.0319 (11)	0.0224 (9)	0.0143 (9)	0.0066 (8)	0.0063 (8)
C1	0.0249 (10)	0.0340 (11)	0.0258 (10)	0.0141 (8)	0.0112 (8)	0.0077 (8)
O4	0.0283 (7)	0.0413 (9)	0.0444 (9)	0.0034 (7)	0.0138 (7)	0.0157 (7)
O2	0.0314 (7)	0.0350 (8)	0.0388 (8)	0.0140 (6)	0.0123 (6)	0.0149 (6)
O7	0.0413 (8)	0.0318 (8)	0.0380 (8)	0.0070 (7)	0.0126 (7)	0.0157 (6)
O6	0.0281 (9)	0.0695 (12)	0.0425 (9)	0.0031 (8)	−0.0014 (7)	0.0103 (8)
O3	0.0535 (10)	0.0333 (8)	0.0323 (8)	−0.0012 (7)	0.0153 (7)	0.0006 (6)
O8	0.0584 (10)	0.0403 (9)	0.0440 (9)	0.0279 (8)	0.0067 (8)	0.0160 (7)
O5	0.0401 (8)	0.0496 (9)	0.0233 (7)	0.0110 (7)	−0.0017 (6)	0.0140 (7)
N1	0.0249 (8)	0.0283 (9)	0.0293 (8)	0.0091 (7)	0.0113 (7)	0.0027 (7)
O1	0.0516 (9)	0.0676 (11)	0.0381 (8)	0.0346 (9)	0.0292 (8)	0.0292 (8)
C15	0.0360 (11)	0.0387 (12)	0.0294 (11)	0.0070 (10)	0.0087 (9)	0.0060 (9)
C8	0.0365 (11)	0.0299 (11)	0.0197 (9)	0.0099 (9)	−0.0024 (8)	0.0033 (8)
C13	0.0234 (10)	0.0327 (11)	0.0286 (10)	0.0061 (8)	0.0081 (8)	0.0036 (8)
C2	0.0231 (9)	0.0364 (11)	0.0264 (10)	0.0112 (8)	0.0102 (8)	0.0093 (8)
C25	0.0423 (12)	0.0293 (11)	0.0364 (11)	0.0156 (9)	0.0197 (10)	0.0047 (9)
C17	0.0219 (10)	0.0325 (11)	0.0365 (11)	0.0059 (8)	0.0092 (8)	0.0055 (9)
C5	0.0221 (9)	0.0325 (11)	0.0271 (10)	0.0053 (8)	0.0081 (8)	0.0078 (8)
C6	0.0188 (9)	0.0387 (12)	0.0313 (10)	0.0075 (9)	0.0041 (8)	0.0106 (9)
C14	0.0319 (11)	0.0318 (11)	0.0322 (11)	0.0074 (9)	0.0142 (9)	0.0059 (9)
C21	0.0307 (11)	0.0387 (12)	0.0285 (10)	0.0125 (9)	0.0137 (9)	0.0048 (9)
C3	0.0252 (10)	0.0345 (11)	0.0225 (9)	0.0125 (9)	0.0063 (8)	0.0068 (8)
C18	0.0383 (12)	0.0318 (12)	0.0486 (13)	0.0065 (10)	0.0072 (10)	−0.0034 (10)
C16	0.0615 (16)	0.0496 (15)	0.0338 (12)	0.0164 (12)	0.0132 (11)	0.0116 (11)
C22	0.0299 (11)	0.0393 (12)	0.0323 (11)	0.0112 (9)	0.0089 (9)	0.0059 (9)
C28	0.110 (3)	0.0524 (18)	0.0557 (18)	0.0230 (18)	−0.0012 (18)	−0.0088 (14)
C7	0.0327 (12)	0.0371 (12)	0.0273 (10)	0.0137 (10)	0.0035 (9)	0.0052 (9)
C10	0.0768 (19)	0.0382 (14)	0.0392 (13)	−0.0024 (13)	0.0084 (13)	−0.0002 (11)
C24	0.0437 (13)	0.0473 (13)	0.0333 (12)	0.0140 (11)	0.0089 (10)	0.0080 (10)
C23	0.0493 (14)	0.0732 (18)	0.0339 (12)	0.0307 (13)	0.0158 (11)	0.0160 (12)
C26	0.0575 (15)	0.0298 (12)	0.0492 (14)	0.0086 (11)	0.0239 (12)	0.0058 (10)
C12	0.0603 (17)	0.0532 (16)	0.0726 (18)	0.0067 (13)	0.0202 (14)	0.0411 (15)
C27	0.0684 (17)	0.0298 (12)	0.0530 (15)	0.0131 (12)	0.0143 (13)	0.0010 (11)
C11	0.0643 (17)	0.0678 (18)	0.0306 (12)	0.0222 (14)	−0.0106 (12)	0.0173 (12)
C9	0.078 (2)	0.108 (2)	0.0519 (16)	0.0525 (19)	0.0427 (15)	0.0542 (17)
C20	0.0536 (17)	0.0507 (17)	0.106 (3)	0.0001 (14)	0.0194 (17)	0.0307 (17)
C19	0.0403 (14)	0.0339 (14)	0.088 (2)	−0.0007 (11)	0.0033 (14)	0.0014 (13)

Geometric parameters (Å, º)

Pd1—Cl1	2.4070 (5)	C21—H21A	0.99
Pd1—Cl1^i	2.4295 (6)	C21—H21B	0.99
Pd1—C1	2.000 (2)	C3—C7	1.484 (3)
Pd1—C4	1.9950 (18)	C18—C19	1.531 (3)
Pd1—Pd1^i	3.5119 (4)	C18—H18A	0.99
Pd1—N1^i	4.4650 (15)	C18—H18B	0.99
Pd1—N1	5.6764 (16)	C16—H16A	0.98
Pd1—N1^ii	6.1776 (16)	C16—H16B	0.98
C4—C3	1.346 (3)	C16—H16C	0.98
C4—C8	1.481 (3)	C22—C23	1.518 (3)
C1—C2	1.350 (3)	C22—H22A	0.99
C1—C5	1.484 (3)	C22—H22B	0.99
O4—C6	1.204 (2)	C28—C27	1.515 (4)
O2—C5	1.205 (2)	C28—H28A	0.98
O7—C8	1.346 (3)	C28—H28B	0.98
O7—C12	1.434 (3)	C28—H28C	0.98
O6—C7	1.206 (3)	C10—H10A	0.98
O3—C6	1.345 (2)	C10—H10B	0.98
O3—C10	1.442 (3)	C10—H10C	0.98
O8—C8	1.200 (2)	C24—C23	1.513 (3)
O5—C7	1.342 (3)	C24—H24A	0.98
O5—C11	1.452 (3)	C24—H24B	0.98
N1—C17	1.517 (2)	C24—H24C	0.98
N1—C13	1.518 (2)	C23—H23A	0.99
N1—C21	1.519 (2)	C23—H23B	0.99
N1—C25	1.522 (2)	C26—C27	1.530 (3)
O1—C5	1.347 (2)	C26—H26A	0.99
O1—C9	1.440 (3)	C26—H26B	0.99
C15—C16	1.516 (3)	C12—H12A	0.98
C15—C14	1.523 (3)	C12—H12B	0.98
C15—H15A	0.99	C12—H12C	0.98
C15—H15B	0.99	C27—H27A	0.99
C13—C14	1.525 (3)	C27—H27B	0.99
C13—H13A	0.99	C11—H11A	0.98
C13—H13B	0.99	C11—H11B	0.98
C2—C3	1.473 (3)	C11—H11C	0.98
C2—C6	1.479 (3)	C9—H9A	0.98
C25—C26	1.521 (3)	C9—H9B	0.98
C25—H25A	0.99	C9—H9C	0.98
C25—H25B	0.99	C20—C19	1.516 (4)
C17—C18	1.519 (3)	C20—H20A	0.98
C17—H17A	0.99	C20—H20B	0.98
C17—H17B	0.99	C20—H20C	0.98
C14—H14A	0.99	C19—H19A	0.99
C14—H14B	0.99	C19—H19B	0.99
C21—C22	1.525 (3)
Cl1—Pd1—Cl1^i	86.875 (19)	C15—C16—H16A	109.5
C1—Pd1—C4	79.79 (8)	C15—C16—H16B	109.5
C1—Pd1—Cl1	97.15 (6)	H16A—C16—H16B	109.5
C1—Pd1—Cl1^i	174.38 (5)	C15—C16—H16C	109.5
C4—Pd1—Cl1	176.44 (6)	H16A—C16—H16C	109.5
C4—Pd1—Cl1^i	96.06 (6)	H16B—C16—H16C	109.5
Pd1^i—Pd1—N1^i	89.91 (2)	C23—C22—C21	109.43 (17)
Pd1^i—Pd1—N1^ii	137.035 (16)	C23—C22—H22A	109.8
Pd1—Cl1—Pd1^i	93.125 (19)	C21—C22—H22A	109.8
C3—C4—C8	125.72 (17)	C23—C22—H22B	109.8
C3—C4—Pd1	116.27 (14)	C21—C22—H22B	109.8
C8—C4—Pd1	118.01 (14)	H22A—C22—H22B	108.2
C2—C1—C5	122.46 (18)	C27—C28—H28A	109.5
C2—C1—Pd1	116.07 (14)	C27—C28—H28B	109.5
C5—C1—Pd1	120.68 (13)	H28A—C28—H28B	109.5
C8—O7—C12	115.57 (18)	C27—C28—H28C	109.5
C6—O3—C10	115.40 (17)	H28A—C28—H28C	109.5
C7—O5—C11	116.28 (18)	H28B—C28—H28C	109.5
C17—N1—C13	110.88 (15)	O6—C7—O5	123.53 (18)
C17—N1—C21	111.09 (15)	O6—C7—C3	124.0 (2)
C13—N1—C21	107.10 (14)	O5—C7—C3	112.40 (17)
C17—N1—C25	106.87 (14)	O3—C10—H10A	109.5
C13—N1—C25	109.91 (15)	O3—C10—H10B	109.5
C21—N1—C25	111.03 (15)	H10A—C10—H10B	109.5
C5—O1—C9	115.14 (17)	O3—C10—H10C	109.5
C16—C15—C14	112.44 (19)	H10A—C10—H10C	109.5
C16—C15—H15A	109.1	H10B—C10—H10C	109.5
C14—C15—H15A	109.1	C23—C24—H24A	109.5
C16—C15—H15B	109.1	C23—C24—H24B	109.5
C14—C15—H15B	109.1	H24A—C24—H24B	109.5
H15A—C15—H15B	107.8	C23—C24—H24C	109.5
O8—C8—O7	123.3 (2)	H24A—C24—H24C	109.5
O8—C8—C4	126.8 (2)	H24B—C24—H24C	109.5
O7—C8—C4	109.82 (16)	C24—C23—C22	113.49 (19)
N1—C13—C14	115.96 (15)	C24—C23—H23A	108.9
N1—C13—H13A	108.3	C22—C23—H23A	108.9
C14—C13—H13A	108.3	C24—C23—H23B	108.9
N1—C13—H13B	108.3	C22—C23—H23B	108.9
C14—C13—H13B	108.3	H23A—C23—H23B	107.7
H13A—C13—H13B	107.4	C25—C26—C27	111.89 (19)
C1—C2—C3	113.54 (18)	C25—C26—H26A	109.2
C1—C2—C6	122.04 (18)	C27—C26—H26A	109.2
C3—C2—C6	123.53 (17)	C25—C26—H26B	109.2
C26—C25—N1	115.11 (17)	C27—C26—H26B	109.2
C26—C25—H25A	108.5	H26A—C26—H26B	107.9
N1—C25—H25A	108.5	O7—C12—H12A	109.5
C26—C25—H25B	108.5	O7—C12—H12B	109.5
N1—C25—H25B	108.5	H12A—C12—H12B	109.5
H25A—C25—H25B	107.5	O7—C12—H12C	109.5
N1—C17—C18	114.75 (16)	H12A—C12—H12C	109.5
N1—C17—H17A	108.6	H12B—C12—H12C	109.5
C18—C17—H17A	108.6	C28—C27—C26	112.6 (2)
N1—C17—H17B	108.6	C28—C27—H27A	109.1
C18—C17—H17B	108.6	C26—C27—H27A	109.1
H17A—C17—H17B	107.6	C28—C27—H27B	109.1
O2—C5—O1	123.32 (18)	C26—C27—H27B	109.1
O2—C5—C1	126.14 (17)	H27A—C27—H27B	107.8
O1—C5—C1	110.51 (16)	O5—C11—H11A	109.5
O4—C6—O3	122.71 (19)	O5—C11—H11B	109.5
O4—C6—C2	126.24 (19)	H11A—C11—H11B	109.5
O3—C6—C2	110.94 (17)	O5—C11—H11C	109.5
C15—C14—C13	109.72 (16)	H11A—C11—H11C	109.5
C15—C14—H14A	109.7	H11B—C11—H11C	109.5
C13—C14—H14A	109.7	O1—C9—H9A	109.5
C15—C14—H14B	109.7	O1—C9—H9B	109.5
C13—C14—H14B	109.7	H9A—C9—H9B	109.5
H14A—C14—H14B	108.2	O1—C9—H9C	109.5
N1—C21—C22	115.59 (16)	H9A—C9—H9C	109.5
N1—C21—H21A	108.4	H9B—C9—H9C	109.5
C22—C21—H21A	108.4	C19—C20—H20A	109.5
N1—C21—H21B	108.4	C19—C20—H20B	109.5
C22—C21—H21B	108.4	H20A—C20—H20B	109.5
H21A—C21—H21B	107.4	C19—C20—H20C	109.5
C4—C3—C2	114.01 (17)	H20A—C20—H20C	109.5
C4—C3—C7	124.83 (18)	H20B—C20—H20C	109.5
C2—C3—C7	120.34 (18)	C20—C19—C18	113.5 (2)
C17—C18—C19	110.3 (2)	C20—C19—H19A	108.9
C17—C18—H18A	109.6	C18—C19—H19A	108.9
C19—C18—H18A	109.6	C20—C19—H19B	108.9
C17—C18—H18B	109.6	C18—C19—H19B	108.9
C19—C18—H18B	109.6	H19A—C19—H19B	107.7
H18A—C18—H18B	108.1
C1—Pd1—Cl1—Pd1^i	176.05 (5)	C2—C1—C5—O1	−103.6 (2)
Cl1^i—Pd1—Cl1—Pd1^i	0.02 (10)	Pd1—C1—C5—O1	86.92 (18)
C1—Pd1—C4—C3	−0.88 (14)	C10—O3—C6—O4	6.4 (3)
Cl1^i—Pd1—C4—C3	175.28 (14)	C10—O3—C6—C2	−177.33 (19)
C1—Pd1—C4—C8	178.46 (16)	C1—C2—C6—O4	42.2 (3)
Cl1^i—Pd1—C4—C8	−5.38 (15)	C4—C3—C7—O6	−140.9 (2)
C4—Pd1—C1—C2	4.14 (14)	C3—C2—C6—O4	−149.3 (2)
Cl1—Pd1—C1—C2	−174.02 (14)	C1—C2—C6—O3	−133.95 (19)
C4—Pd1—C1—C5	174.24 (16)	C3—C2—C6—O3	34.6 (2)
Cl1—Pd1—C1—C5	−3.93 (15)	C16—C15—C14—C13	−167.83 (18)
C12—O7—C8—O8	4.9 (3)	N1—C13—C14—C15	−160.52 (16)
C12—O7—C8—C4	−171.59 (19)	C17—N1—C21—C22	62.8 (2)
C3—C4—C8—O8	86.0 (3)	C13—N1—C21—C22	−176.00 (17)
Pd1—C4—C8—O8	−93.3 (2)	C25—N1—C21—C22	−56.0 (2)
C3—C4—C8—O7	−97.7 (2)	C8—C4—C3—C2	178.52 (17)
Pd1—C1—C5—O2	−90.9 (2)	Pd1—C4—C3—C2	−2.2 (2)
Pd1—C4—C8—O7	83.06 (17)	C8—C4—C3—C7	−11.9 (3)
C17—N1—C13—C14	−47.0 (2)	Pd1—C4—C3—C7	167.37 (15)
C21—N1—C13—C14	−168.32 (16)	C1—C2—C3—C4	5.6 (2)
C25—N1—C13—C14	71.0 (2)	C6—C2—C3—C4	−163.82 (18)
C5—C1—C2—C3	−176.29 (16)	C1—C2—C3—C7	−164.52 (17)
Pd1—C1—C2—C3	−6.4 (2)	C6—C2—C3—C7	26.1 (3)
C5—C1—C2—C6	−6.7 (3)	N1—C17—C18—C19	165.76 (18)
Pd1—C1—C2—C6	163.18 (14)	N1—C21—C22—C23	179.16 (18)
C17—N1—C25—C26	−171.60 (18)	C11—O5—C7—O6	4.2 (3)
C13—N1—C25—C26	68.0 (2)	C11—O5—C7—C3	−173.27 (19)
C21—N1—C25—C26	−50.3 (2)	C2—C3—C7—O6	28.0 (3)
C13—N1—C17—C18	−61.2 (2)	C4—C3—C7—O5	36.5 (3)
C21—N1—C17—C18	57.8 (2)	C2—C3—C7—O5	−154.55 (17)
C25—N1—C17—C18	179.07 (17)	C21—C22—C23—C24	−176.9 (2)
C9—O1—C5—O2	4.0 (3)	N1—C25—C26—C27	−147.8 (2)
C9—O1—C5—C1	−173.9 (2)	C25—C26—C27—C28	72.6 (3)
C2—C1—C5—O2	78.5 (3)	C17—C18—C19—C20	−76.7 (3)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1.