A chloro-bridged dinuclear phosphinitopalladium complex, di-μ-chloro-bis­[(diphenoxy­phosphinite-κP)(diphenoxy­phosphinito-κP)palladium(II)]

The title compound, [Pd₂(C₁₂H₁₀O₃P)₂Cl₂(C₁₂H₁₁O₃P)₂], consists of a dinuclear μ-chloro-bridged palladium unit with two diphenoxy­phosphinite groups per Pd atom, linked together by a hydrogen bond. The asymmetric unit contains one half of the mol­ecule, with the other half generated by an inversion centre. The geometry around the P atoms may be described as distorted tetra­hedral. Adjacent mol­ecules of the complex are linked by weak C—H...O and C—H...Cl hydrogen bonds. The structure is additionally stabilized by π–π stacking inter­actions between the aryl rings. These inter­actions form a herring-bone pattern in the crystal structure.

S1. Comment

Carbon–carbon bond-forming reactions are important fundamental processes in synthetic chemistry. Among such reactions the most commonly recognized are: carbonylation, which, depending on the conditions, enables the synthesis of carboxylic acids, esters or amides in a one-step process (Mägerlein et al., 2000); olefination of aryl halides, the so-called Heck reaction (Beletskaya & Cheprakov, 2000); and the Suzuki process, which leads to the formation of biphenyl derivatives (Miyaura & Suzuki, 1995). Palladium compounds with phosphine ligands are frequently used as catalyst precursors in the above-mentioned reactions. Phosphinites, however, represent an interesting alternative to phosphines as ligands for metal ions employed as catalysts in organic synthesis. Such complexes have proved to be air-stable and highly active in methoxycarbonylation or the Heck reaction (Pryjomska et al., 2006) and also in Suzuki cross-coupling of aryl halides (Li, 2002). In this paper, we report the synthesis and crystallization of the title dimeric phosphinitopalladium complex, (I), which may be successfully used as an efficient catalyst precursor.

The molecule of the compound (I) (Fig. 1) contains a dimetallocyclic Pd₂Cl₂ core, with a crystallographic centre of inversion at the mid-point of the Pd···Pdⁱ vector [symmetry code: (i) −x + 1, −y + 1, −z + 1]. The positive charge of each Pd atom is balanced by the O⁻ atoms. There is clearly no Pd—Pd bond in the dimer, the Pd···Pdⁱ distance of 3.4830 (9) Å being too long to consider any metal–metal interaction. The Pd atoms are four-coordinated in a square-planar geometry. The angles between adjacent ligands deviate only slightly from the expected value of 90° (Table 1). As a result of the presence of the inversion centre, the Pd/Cl/Pdⁱ/Clⁱ ring is strictly planar. The Pd—Cl and Pd—Clⁱ bond lengths are quite similar [2.4139 (8) and 2.4002 (8) Å, respectively]. These distances appear to be somewhat large compared with the range reported for typical four-coordinate palladium complexes (2.298–2.354 Å; Orpen et al., 1989). However, such long bond distances are normally observed for analogous dinuclear µ-chloro-bridged palladium compounds and might be justified by the trans effect of the phosphorus ligands.

The geometric parameters around the four-coordinate atoms P1 and P2 indicate a noticeable deformation of the ideal tetrahedron towards a trigonal pyramid. The O3—P1—Pd and O6—P2—Pd angles differ considerably from the ideal value of 109.5° and approach 120°, while the O1—P1—O2 and O4—P2–O5 angles are very close to 90° (Table 1). Such large distortions of these angles might be explained by the steric effects of the different substituents or bond types, and are commonly observed for palladium complexes with diphenylphosphane ligands (Stockland et al., 2004). The bond lengths P1—O1, P1—O2, P2—O4 and P2—O5 are typical (Allen et al., 1987). In contrast, the nearly equal distances P1—O3 and P2—O6 fall between the values expected for single and double P—O bonds. As a result, the OH group on each side of the molecule forms a nearly symmetric intramolecular hydrogen bond with O⁻ (Table 2). The existence of this type of hydrogen-bond interaction was also confirmed by ¹H NMR spectroscopy (CDCl₃), which revealed a broad signal at 10 p.p.m. This O3—H3···O6 interaction generates an S(6) motif (Bernstein et al., 1995) in the crystal structure.

Several µ-chloro-bridged dinuclear phosphinitopalladium complexes have previously been structurally characterized. The intramolecular hydrogen-bond geometries of such compounds are compared with that of (I) in Table 3. The O3—H3 distance of 1.08 (2) Å may at first appear to be rather large, especially when it is contrasted with the value observed for a typical hydroxy group. However, this bond length is comparable with the O—H distances found in the other characterized structures. Furthermore, there are also numerous complexes with longer O—H bond lengths, and in those cases the hydrogen-bond geometry becomes almost ideally symmetric. Finally, it is worth noting that the O···O distance observed for (I) is slightly longer than in all other palladium complexes described.

The molecules of (I) are linked by a few weak hydrogen-bond interactions of C—H···Cl and C—H···O types (Desiraju & Steiner, 1999). The aryl atoms C14, C43 and C45 act as hydrogen-bond donors (Table 2). As a consequence, a three-dimensional network of hydrogen-bond interactions is formed in the crystal structure (Fig. 2). Even though the H···Cl distance may at first appear to be fairly long compared with the expected value (Aullón et al., 1998), the presence of C—H···Cl hydrogen bonds was confirmed spectroscopically for a complex with H···Cl spacings even greater than 3 Å, where Cl was bonded to Pd (Fábry et al., 2004).

Additionally, the C21–C26 and C51–C56 phenyl rings are engaged in π–π stacking contacts (Fig. 3), which further assist in the stabilization of the crystal structure by assembling chains running parallel to the [010] direction. The observed distance between the centroids and the offset of the aryl rings (Table 4) are standard for energetically favourable non-bonded aromatic interactions (McGaughey et al., 1998). The phenyl rings in neighbouring stacks are arranged perpendicularly, thus forming a herring-bone pattern in the crystal structure.

S2. Experimental

PdCl₂(cod) (cod is cyclooctadiene) (0.072 g, 0.3 mmol) was dissolved in benzene (1 ml) and then diphenylphosphite (0.12 ml, 0.6 mmol) was added. A white precipitate was formed immediately. The mixture was stirred for 1 h. After that time, the product was filtered off, washed with diethyl ether and dried in vacuo. Finally, the product was recrystallized from chloroform. Analysis, calculated: C 47.32, H 3.47%; found: C 47.18, H 3.29%. Spectroscopic analysis: IR (KBr, ν, cm⁻¹): 1600 (s), 1480 (vs), 1200 (vs), 900 (vs), 750 (m), 700 (m), 500 (m); IR (Nujol, ν, cm⁻¹): 381.7, 338.0 [m(Pd—Cl); ¹H NMR (CDCl₃, δ, p.p.m.): 7.15 (m, Ph), 10.0 (br, OH); ³¹P NMR (CDCl₃, δ, p.p.m.): 65.5.

S3. Refinement

Carbon-bound H atoms were positioned geometrically and refined using a riding model, with aromatic C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C). The position of H3 was obtained from a difference Fourier map and refined, with U_iso(H) = 1.5U_eq(O). The highest residual peak and the deepest hole in the final difference map are located 2.17 Å from Cl and 0.72 Å from Pd, respectively.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Unlabelled atoms are symmetrically dependent via an inversion centre. [Symmetry code: (i) −x + 1, −y + 1, −z + 1.]
	Fig. 2. Part of the crystal structure of (I), viewed in an oblique direction. Weak intermolecular hydrogen bonds are represented by dashed lines. For clarity, H atoms not involved in the interactions discussed have been omitted. [Symmetry codes: (ii) x − 1/2, −y + 1/2, z − 1/2; (iii) x + 1/2, −y + 3/2, z + 1/2; (iv) −x + 1/2, y + 1/2, −z + 3/2.]
	Fig. 3. The arrangement of the molecules in the crystal structure of (I), viewed along the a axis. The π–π stacking interactions are represented by dashed lines. Cg1 and Cg2 denote the centroids of the C21–C26 and C51–C56 phenyl rings, respectively. All H atoms have been omitted. [Symmetry codes: (v) x, y + 1, z; (vi) x, y − 1, z.]

di-µ-chloro-bis[(diphenoxyphosphinite-κP)(diphenoxyphosphinito- κP)palladium(II)]

Crystal data

[Pd2(C12H10O3P)2Cl2(C12H11O3P)2]	F(000) = 1224
Mr = 1218.40	Dx = 1.676 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 28302 reflections
a = 12.268 (3) Å	θ = 4.5–37.5°
b = 10.514 (2) Å	µ = 1.05 mm^−1
c = 19.549 (4) Å	T = 110 K
β = 106.78 (3)°	Plate, colourless
V = 2414.2 (10) Å^3	0.20 × 0.13 × 0.06 mm
Z = 2

Data collection

Kuma KM-4 CCD area-detector diffractometer	12649 independent reflections
Radiation source: fine-focus sealed tube	8606 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
ϕ and ω scans	θmax = 37.5°, θmin = 4.5°
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2003)	h = −20→20
Tmin = 0.837, Tmax = 0.933	k = −17→18
57621 measured reflections	l = −33→31

Refinement

Refinement on F^2	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	w = 1/[σ^2(Fo^2) + (0.0362P)^2 + 0.8428P] where P = (Fo^2 + 2Fc^2)/3
12649 reflections	(Δ/σ)max = 0.001
310 parameters	Δρmax = 1.04 e Å^−3
0 restraints	Δρmin = −0.75 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Pd	0.36101 (2)	0.51004 (2)	0.50536 (1)	0.01297 (5)
Cl	0.53346 (5)	0.40069 (6)	0.56905 (3)	0.01974 (12)
P1	0.20802 (5)	0.61886 (6)	0.44481 (3)	0.01690 (12)
P2	0.27013 (5)	0.42196 (6)	0.57661 (3)	0.01622 (12)
O1	0.18286 (15)	0.60351 (17)	0.36057 (9)	0.0211 (4)
C11	0.1461 (2)	0.4904 (2)	0.32201 (12)	0.0186 (5)
C12	0.2026 (2)	0.4578 (3)	0.27290 (13)	0.0246 (5)
H12	0.2659	0.5063	0.2690	0.030*
C13	0.1654 (3)	0.3524 (3)	0.22916 (14)	0.0295 (6)
H13	0.2030	0.3289	0.1949	0.035*
C14	0.0738 (3)	0.2823 (3)	0.23568 (15)	0.0312 (6)
H14	0.0483	0.2108	0.2056	0.037*
C15	0.0187 (3)	0.3156 (3)	0.28578 (14)	0.0282 (6)
H15	−0.0439	0.2662	0.2900	0.034*
C16	0.0544 (2)	0.4210 (3)	0.33014 (13)	0.0232 (5)
H16	0.0172	0.4443	0.3647	0.028*
O2	0.23974 (16)	0.76624 (17)	0.44511 (9)	0.0224 (4)
C21	0.2879 (2)	0.8261 (2)	0.51191 (14)	0.0239 (5)
C22	0.3934 (3)	0.8793 (3)	0.52435 (17)	0.0352 (7)
H22	0.4345	0.8727	0.4901	0.042*
C23	0.4391 (3)	0.9434 (3)	0.58876 (18)	0.0416 (8)
H23	0.5120	0.9820	0.5981	0.050*
C24	0.3812 (3)	0.9517 (3)	0.63853 (16)	0.0393 (8)
H24	0.4137	0.9949	0.6824	0.047*
C25	0.2753 (4)	0.8970 (4)	0.62459 (19)	0.0512 (10)
H25	0.2344	0.9026	0.6590	0.061*
C26	0.2277 (3)	0.8340 (3)	0.56106 (17)	0.0418 (8)
H26	0.1544	0.7965	0.5515	0.050*
O3	0.09909 (15)	0.60156 (19)	0.46543 (9)	0.0248 (4)
H3	0.1181 (16)	0.5258 (18)	0.5040 (12)	0.037*
O4	0.34453 (15)	0.42536 (16)	0.65826 (8)	0.0193 (3)
C41	0.3641 (2)	0.5369 (2)	0.69983 (12)	0.0181 (5)
C42	0.4644 (2)	0.6021 (2)	0.70876 (13)	0.0222 (5)
H42	0.5160	0.5781	0.6830	0.027*
C43	0.4890 (2)	0.7041 (3)	0.75632 (15)	0.0290 (6)
H43	0.5579	0.7502	0.7631	0.035*
C44	0.4135 (3)	0.7384 (3)	0.79359 (15)	0.0308 (6)
H44	0.4315	0.8064	0.8270	0.037*
C45	0.3113 (3)	0.6736 (3)	0.78221 (15)	0.0326 (7)
H45	0.2587	0.6985	0.8071	0.039*
C46	0.2856 (2)	0.5723 (3)	0.73453 (14)	0.0265 (6)
H46	0.2153	0.5283	0.7260	0.032*
O5	0.27312 (16)	0.27112 (16)	0.57155 (9)	0.0229 (4)
C51	0.2216 (2)	0.2066 (2)	0.50654 (13)	0.0241 (5)
C52	0.2834 (3)	0.1883 (3)	0.45890 (14)	0.0302 (6)
H52	0.3575	0.2235	0.4676	0.036*
C53	0.2349 (3)	0.1171 (3)	0.39751 (16)	0.0407 (8)
H53	0.2756	0.1051	0.3634	0.049*
C54	0.1292 (3)	0.0644 (3)	0.38610 (16)	0.0403 (8)
H54	0.0976	0.0137	0.3449	0.048*
C55	0.0685 (3)	0.0851 (3)	0.43460 (17)	0.0465 (9)
H55	−0.0052	0.0492	0.4262	0.056*
C56	0.1143 (3)	0.1579 (3)	0.49557 (16)	0.0396 (8)
H56	0.0724	0.1733	0.5287	0.048*
O6	0.15064 (15)	0.46728 (19)	0.57140 (10)	0.0259 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd	0.01199 (8)	0.01610 (9)	0.01137 (7)	0.00122 (6)	0.00426 (5)	0.00195 (6)
Cl	0.0171 (3)	0.0259 (3)	0.0183 (3)	0.0067 (2)	0.0084 (2)	0.0115 (2)
P1	0.0145 (3)	0.0206 (3)	0.0135 (3)	0.0040 (2)	0.0005 (2)	−0.0025 (2)
P2	0.0176 (3)	0.0191 (3)	0.0133 (3)	−0.0052 (2)	0.0067 (2)	−0.0025 (2)
O1	0.0241 (9)	0.0228 (9)	0.0130 (7)	0.0022 (7)	0.0000 (7)	−0.0027 (7)
C11	0.0203 (11)	0.0193 (11)	0.0124 (9)	0.0061 (9)	−0.0015 (8)	−0.0013 (8)
C12	0.0239 (13)	0.0296 (14)	0.0190 (12)	0.0047 (11)	0.0040 (10)	−0.0007 (10)
C13	0.0361 (16)	0.0316 (15)	0.0189 (12)	0.0080 (12)	0.0051 (12)	−0.0048 (11)
C14	0.0413 (17)	0.0231 (14)	0.0230 (13)	0.0039 (12)	−0.0006 (12)	−0.0049 (10)
C15	0.0309 (15)	0.0257 (14)	0.0242 (13)	0.0001 (11)	0.0019 (12)	−0.0007 (11)
C16	0.0238 (13)	0.0266 (13)	0.0160 (11)	0.0036 (10)	0.0009 (10)	−0.0012 (10)
O2	0.0286 (10)	0.0184 (9)	0.0156 (8)	0.0064 (7)	−0.0010 (7)	−0.0027 (7)
C21	0.0297 (14)	0.0176 (12)	0.0206 (12)	0.0073 (10)	0.0013 (11)	−0.0009 (9)
C22	0.0376 (17)	0.0316 (16)	0.0338 (16)	−0.0044 (13)	0.0065 (13)	−0.0068 (12)
C23	0.0386 (18)	0.0347 (18)	0.0428 (19)	−0.0080 (14)	−0.0019 (15)	−0.0080 (14)
C24	0.057 (2)	0.0294 (16)	0.0242 (14)	−0.0015 (15)	−0.0003 (15)	−0.0051 (12)
C25	0.070 (3)	0.051 (2)	0.0384 (19)	−0.0171 (19)	0.0239 (19)	−0.0233 (16)
C26	0.0399 (19)	0.054 (2)	0.0323 (16)	−0.0114 (16)	0.0124 (14)	−0.0195 (15)
O3	0.0152 (8)	0.0365 (11)	0.0208 (9)	0.0050 (7)	0.0023 (7)	−0.0047 (8)
O4	0.0253 (9)	0.0197 (9)	0.0139 (8)	−0.0035 (7)	0.0071 (7)	−0.0011 (6)
C41	0.0218 (12)	0.0201 (12)	0.0112 (9)	−0.0021 (9)	0.0031 (9)	−0.0022 (8)
C42	0.0209 (12)	0.0228 (13)	0.0218 (12)	−0.0004 (10)	0.0044 (10)	0.0002 (10)
C43	0.0256 (14)	0.0255 (14)	0.0308 (14)	−0.0047 (11)	0.0002 (12)	−0.0052 (11)
C44	0.0411 (17)	0.0245 (14)	0.0228 (13)	−0.0009 (12)	0.0031 (12)	−0.0087 (11)
C45	0.0403 (17)	0.0372 (17)	0.0252 (14)	0.0015 (13)	0.0172 (13)	−0.0083 (12)
C46	0.0298 (14)	0.0308 (15)	0.0214 (12)	−0.0060 (11)	0.0116 (11)	−0.0068 (11)
O5	0.0354 (11)	0.0182 (9)	0.0158 (8)	−0.0108 (7)	0.0083 (8)	−0.0029 (6)
C51	0.0361 (16)	0.0167 (12)	0.0177 (12)	−0.0044 (10)	0.0051 (11)	−0.0005 (9)
C52	0.0319 (16)	0.0311 (15)	0.0245 (13)	0.0036 (12)	0.0032 (12)	−0.0102 (11)
C53	0.050 (2)	0.0432 (19)	0.0239 (14)	0.0151 (16)	0.0033 (14)	−0.0099 (13)
C54	0.062 (2)	0.0238 (15)	0.0221 (14)	0.0034 (14)	−0.0094 (15)	−0.0054 (11)
C55	0.056 (2)	0.0410 (19)	0.0332 (17)	−0.0271 (17)	−0.0020 (16)	−0.0025 (14)
C56	0.049 (2)	0.0430 (19)	0.0277 (15)	−0.0263 (15)	0.0125 (15)	−0.0053 (13)
O6	0.0166 (9)	0.0403 (11)	0.0238 (9)	−0.0055 (8)	0.0105 (7)	−0.0020 (8)

Geometric parameters (Å, º)

Pd—Cl	2.4139 (8)	C24—C25	1.375 (4)
Pd—Cl^i	2.4002 (8)	C24—H24	0.9500
Cl—Pd^i	2.4002 (8)	C25—C26	1.380 (4)
Pd—P1	2.2248 (8)	C25—H25	0.9500
Pd—P2	2.2220 (8)	C26—H26	0.9500
P1—O1	1.594 (2)	O3—H3	1.08 (2)
P1—O2	1.597 (2)	O4—C41	1.407 (3)
P1—O3	1.514 (2)	C41—C42	1.375 (4)
P2—O4	1.594 (2)	C41—C46	1.379 (4)
P2—O5	1.590 (2)	C42—C43	1.394 (4)
P2—O6	1.517 (2)	C42—H42	0.9500
O1—C11	1.410 (3)	C43—C44	1.382 (4)
C11—C12	1.380 (4)	C43—H43	0.9500
C11—C16	1.389 (4)	C44—C45	1.387 (4)
C12—C13	1.393 (4)	C44—H44	0.9500
C12—H12	0.9500	C45—C46	1.390 (4)
C13—C14	1.380 (4)	C45—H45	0.9500
C13—H13	0.9500	C46—H46	0.9500
C14—C15	1.385 (4)	O5—C51	1.418 (3)
C14—H14	0.9500	C51—C56	1.371 (4)
C15—C16	1.397 (4)	C51—C52	1.373 (4)
C15—H15	0.9500	C52—C53	1.394 (4)
C16—H16	0.9500	C52—H52	0.9500
O2—C21	1.416 (3)	C53—C54	1.368 (4)
C21—C22	1.366 (4)	C53—H53	0.9500
C21—C26	1.372 (4)	C54—C55	1.381 (4)
C22—C23	1.395 (4)	C54—H54	0.9500
C22—H22	0.9500	C55—C56	1.391 (4)
C23—C24	1.363 (4)	C55—H55	0.9500
C23—H23	0.9500	C56—H56	0.9500
P1—Pd—P2	92.81 (3)	C23—C24—C25	119.3 (3)
P1—Pd—Cl	176.81 (2)	C23—C24—H24	120.3
P1—Pd—Cl^i	89.78 (3)	C25—C24—H24	120.3
P2—Pd—Cl	90.10 (3)	C24—C25—C26	120.6 (3)
P2—Pd—Cl^i	177.40 (2)	C24—C25—H25	119.7
Cl—Pd—Cl^i	87.31 (3)	C26—C25—H25	119.7
Pd—Cl—Pd^i	92.69 (3)	C21—C26—C25	119.1 (3)
O1—P1—Pd	112.32 (7)	C21—C26—H26	120.5
O2—P1—Pd	109.25 (7)	C25—C26—H26	120.5
O3—P1—Pd	118.06 (8)	P1—O3—H3	104.2 (8)
O1—P1—O2	94.38 (9)	P2—O4—C41	123.4 (2)
O1—P1—O3	109.9 (1)	C42—C41—C46	122.0 (2)
O2—P1—O3	110.4 (1)	C42—C41—O4	119.1 (2)
O4—P2—Pd	111.87 (7)	C46—C41—O4	118.8 (2)
O5—P2—Pd	110.60 (7)	C41—C42—C43	118.8 (2)
O6—P2—Pd	118.50 (8)	C41—C42—H42	120.6
O4—P2—O5	93.89 (9)	C43—C42—H42	120.6
O4—P2—O6	108.9 (1)	C44—C43—C42	120.2 (3)
O5—P2—O6	110.4 (1)	C44—C43—H43	119.9
P1—O1—C11	125.1 (2)	C42—C43—H43	119.9
C12—C11—C16	122.4 (2)	C43—C44—C45	120.0 (3)
C12—C11—O1	115.7 (2)	C43—C44—H44	120.0
C16—C11—O1	121.8 (2)	C45—C44—H44	120.0
C11—C12—C13	118.9 (3)	C44—C45—C46	120.3 (3)
C11—C12—H12	120.6	C44—C45—H45	119.9
C13—C12—H12	120.6	C46—C45—H45	119.9
C14—C13—C12	120.0 (3)	C41—C46—C45	118.7 (3)
C14—C13—H13	120.0	C41—C46—H46	120.6
C12—C13—H13	120.0	C45—C46—H46	120.6
C13—C14—C15	120.4 (3)	P2—O5—C51	121.4 (2)
C13—C14—H14	119.8	C56—C51—C52	122.3 (2)
C15—C14—H14	119.8	C56—C51—O5	118.6 (2)
C14—C15—C16	120.6 (3)	C52—C51—O5	119.0 (2)
C14—C15—H15	119.7	C51—C52—C53	118.5 (3)
C16—C15—H15	119.7	C51—C52—H52	120.7
C11—C16—C15	117.7 (2)	C53—C52—H52	120.7
C11—C16—H16	121.2	C54—C53—C52	120.4 (3)
C15—C16—H16	121.2	C54—C53—H53	119.8
P1—O2—C21	118.1 (2)	C52—C53—H53	119.8
C22—C21—C26	121.6 (2)	C53—C54—C55	119.8 (3)
C22—C21—O2	117.9 (2)	C53—C54—H54	120.1
C26—C21—O2	120.4 (2)	C55—C54—H54	120.1
C21—C22—C23	118.1 (3)	C54—C55—C56	120.7 (3)
C21—C22—H22	120.9	C54—C55—H55	119.7
C23—C22—H22	120.9	C56—C55—H55	119.7
C24—C23—C22	121.2 (3)	C51—C56—C55	118.2 (3)
C24—C23—H23	119.4	C51—C56—H56	120.9
C22—C23—H23	119.4	C55—C56—H56	120.9
P2—Pd—Cl—Pd^i	179.72 (2)	O2—C21—C26—C25	−177.6 (3)
Cl^i—Pd—Cl—Pd^i	0.0	C26—C21—C22—C23	−0.5 (5)
P2—Pd—P1—O1	−130.85 (8)	C21—C22—C23—C24	0.9 (5)
Cl^i—Pd—P1—O1	48.93 (8)	C22—C23—C24—C25	−0.7 (5)
P2—Pd—P1—O2	125.80 (8)	C23—C24—C25—C26	0.1 (5)
Cl^i—Pd—P1—O2	−54.42 (8)	C24—C25—C26—C21	0.2 (5)
P2—Pd—P1—O3	−1.37 (9)	C25—C26—C21—C22	−0.1 (5)
Cl^i—Pd—P1—O3	178.41 (9)	Pd—P2—O4—C41	73.3 (2)
P1—Pd—P2—O4	−134.89 (8)	O5—P2—O4—C41	−172.7 (2)
Cl—Pd—P2—O4	43.81 (8)	O6—P2—O4—C41	−59.6 (2)
P1—Pd—P2—O5	121.87 (8)	P2—O4—C41—C42	−98.2 (2)
Cl—Pd—P2—O5	−59.43 (8)	P2—O4—C41—C46	86.4 (2)
P1—Pd—P2—O6	−7.01 (9)	O4—C41—C42—C43	−172.9 (2)
Cl—Pd—P2—O6	171.69 (9)	O4—C41—C46—C45	172.4 (2)
Pd—P1—O1—C11	68.6 (2)	C46—C41—C42—C43	2.4 (4)
O2—P1—O1—C11	−178.6 (2)	C41—C42—C43—C44	0.0 (4)
O3—P1—O1—C11	−65.0 (2)	C42—C43—C44—C45	−1.8 (4)
P1—O1—C11—C12	−133.6 (2)	C43—C44—C45—C46	1.4 (5)
P1—O1—C11—C16	50.1 (2)	C44—C45—C46—C41	0.9 (4)
O1—C11—C12—C13	−175.3 (2)	C45—C46—C45—C44	−2.8 (4)
O1—C11—C16—C15	175.2 (2)	Pd—P2—O5—C51	−62.3 (2)
C16—C11—C12—C13	0.9 (4)	O4—P2—O5—C51	−177.4 (2)
C11—C12—C13—C14	−0.4 (4)	O6—P2—O5—C51	70.8 (2)
C12—C13—C14—C15	−0.3 (4)	P2—O5—C51—C52	86.7 (3)
C13—C14—C15—C16	0.5 (4)	P2—O5—C51—C56	−97.3 (3)
C14—C15—C16—C11	0.1 (4)	O5—C51—C52—C53	175.5 (3)
C15—C16—C11—C12	−0.8 (4)	O5—C51—C56—C55	−174.4 (3)
Pd—P1—O2—C21	−54.8 (2)	C56—C51—C52—C53	−0.3 (5)
O1—P1—O2—C21	−170.2 (2)	C51—C52—C53—C54	−1.5 (5)
O3—P1—O2—C21	76.7 (2)	C52—C53—C54—C55	2.0 (5)
P1—O2—C21—C22	120.4 (3)	C53—C54—C55—C56	−0.8 (5)
P1—O2—C21—C26	−61.9 (3)	C54—C55—C56—C51	−0.9 (5)
O2—C21—C22—C23	177.2 (3)	C55—C56—C51—C52	1.5 (5)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O6	1.08 (2)	1.40 (2)	2.435 (2)	158 (2)
C14—H14···Cl^ii	0.95	2.87	3.692 (3)	145
C43—H43···O1^iii	0.95	2.58	3.332 (3)	136
C45—H45···O5^iv	0.95	2.63	3.466 (3)	147

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