New palladium complexes with phosphino- and phosphinitopyridine ligands

Three new palladium complexes containing a difunctional P,N-chelate, namely tris­(chloro­{[1-methyl-1-(6-methyl-2-pyridyl)ethoxy]diphenylphospine-κ²N,P}methyl­palladium(II)chloro­form solvate, 3[Pd(CH₃)Cl(C₂₁H₂₂NOP)]·CHCl₃, (III), dichloro­[2-(2,6-dimethyl­phen­yl)-6-(diphenyl­phosphinometh­yl)­pyridine-κ²N,P]palladium(II), [PdCl₂(C₂₆H₂₄NP)], (IV), and chloro­[2-(2,6-dimethyl­phen­yl)-6-(diphenyl­phos­phino­meth­yl)pyridine-κ²N,P]methyl­palladium(II), [Pd(CH₃)Cl(C₂₆H₂₄NP)], (V), are reported. Geometric data and the conformations of the ligands around the metal centers, as well as slight distortions of the Pd coordination environments from idealized square-planar geometry, are discussed and compared with the situations in related compounds. Non-conventional hydrogen-bond inter­actions (C—H...Cl) have been found in all three complexes. Compound (III) is the first six-membered chloro–meth­yl–phosphinite P,N-type Pd^II complex to be structurally characterized.

S1. Comment

Ligands containing at least two chemically different donor functions and able to chelate a metal center are of considerable interest since they provide a way to influence selectively the bonding and/or reactivity of the other ligands, in particular those in trans positions (Braunstein & Naud, 2001). This concept as been successfully applied to ligands containing a P,O or a P,N donor set (Braunstein & Naud, 2001; Slone et al., 1999).

Phosphinite- and phosphinopyridine ligands find widespread applications in the coordination chemistry of the transition metals (Newcome or Newkome, 1993, and references therein; Chen et al., 2003a) and in homogeneous catalysis (Agbossou et al., 1998, and references therein; Espinet & Soulantica, 1999, and references therein; Bianchini & Meli, 2002, and references therein; Chen et al., 2003b; Braunstein, 2004, and references therein; Speiser et al., 2004a,b; Speiser et al., 2004). We have recently reported the synthesis of the ligands 2-ethyl-6-methyl-[1'-methyl-1'-oxy(diphenylphosphino)]pyridine, (I) (Speiser et al., 2004), and 2-(2,6-dimethylphenyl)-6-[(diphenylphosphanyl)methyl]pyridine, (II) (Speiser et al., 2004a), and investigated the catalytic properties of their [NiCl₂(P,N)] complexes for ethylene oligomerization. Owing to the paramagnetism of these Ni^II compounds, it was felt desirable to prepare analogous Pd^II complexes amenable to NMR studies in solution. For comparison, we have selected complexes of the type [PdCl₂(P,N)] for which the Pd—Cl distances should provide direct evidence of the respective trans influences of the P and N donor functions, and of the type [PdCl(CH₃)(P,N)], since the stoichiometric or catalytic insertion of small molecules (such as CO or olefins) into the Pd—CH₃ σ bond is very much influenced by the nature of the donor group situated in the trans position. The new Pd complexes (III)–(V) have been synthesized, and their structural features are analyzed and, in the case of (III), compared with the Ni analog (Speiser et al., 2004).

Despite the relevance of Pd complexes featuring these types of P,N ligands in the catalytic alternating copolymerization of olefins and CO as well as in other C—C coupling reactions, (III) is the first six-membered chloromethyl–phosphinite P,N-type palladium(II) complex to be structurally characterized. Other groups have reported six-membered chloromethyl–Pd complexes with iminophosphine (van den Beuken et al., 1998; Song et al., 2002; Reddy et al., 2002; Spek, 2003) and l-(dimethylamino)-8(diphenylphosphino)naphthalene ligands (Dekker et al., 1992). Recently, Chen et al. (2003b) reported the first structurally characterized five-membered chloromethyl–phosphinopyridine-based Pd^II complex. Other five-membered chloromethyl complexes containing 2-(2-pyridyl)phosphaalkenes (van der Sluis et al., 1997), 2-(2-pyridyl)phospholes (Sauthier et al., 2002), iminophosphines (Coleman et al., 2001; Reddy et al., 2001, 2002; Doherty et al., 2002; Daugulis & Brookhart, 2002) and phosphino-oxazoline (Apfelbacher et al., 2003) P,N ligands have also been reported.

The structure of (III) shows that the asymmetric unit contains three very similar but crystallographically different molecules (A–C), with a chloroform molecule. Although the geometric data are as expected for the three molecules (Table 1), examination reveals (Fig. 1) that the P,N chelate in molecules A and C has approximately the same conformation, whereas in B the pyridine ring has a different orientation with respect to the Pd—N axis. This is confirmed by the torsion-angle values, which are similar for A and C [Cl1—Pd1—N1—C9 = −55.9 (3)° and Cl3—Pd3—N3—C53 = −61.6 (3)°, respectively], whereas for B the Cl2—Pd2—N2—C31 angle is 51.3 (3)°. The symmetry-equivalent asymmetric units contain enantiomers of A, B and C with opposite torsion angles.

Analysis of molecule A shows a folding of the ligand along the Pd1···C2 hinge, creating a roof-like conformation, which generates a niche limited by a phenyl group (Fig. 2). This conformation is similar to the [NiCl₂(P,N)] analog (Speiser et al., 2004) for which the Ni coordination geometry was slightly distorted square-planar. The Pd atom is almost in the mean plane passing through atoms Cl1, C1, N1 and P1 [the deviation of Pd is 0.0390 (3) Å] and the sum of the bond angles around the Pd atom is 360.56°. Although the distance from the metal to the corresponding plane in the analogous Ni complex [0.03 (1) Å] is similar to that for Pd, the sum of the bond angles around the Ni center is larger (365.22°), indicating a slight distortion toward tetrahedral for the Ni coordination (Speiser et al., 2004). Molecules B and C are almost identical to A and therefore will not be discussed further.

Within the ligands of complexes (IV) (Fig. 3) and (V) (Fig. 4) the geometric data (Tables 2 and 3) are similar and in the expected ranges; the only marked difference between these two structures concerns the Pd—N distance, which is larger in (V) [2.286 (3) Å] than in (IV) [2.098 (2) Å]. The aromatic substituent at the 6-position is oriented nearly perpendicularly to the pyridine ring, as evidenced by the torsion angle N1—C6—C7—C12 [70.3 (3)° for (IV) and 78.9 (4)° for (V)].

In (IV), the Pd—Cl bond distance trans to the P atom is longer than that trans to N, which is consistent with the respective trans influences of the P and N donor atoms (Hartley, 1973). The methyl group in (III) and (V) is cis to the P atom, which is in agreement with the fact that the donor groups with the largest trans influence avoid being mutually trans to one another. This is consistent with complexes of the type [PdCl(CH₃)(P,N)] (Apfelbacher et al., 2003; Chen et al., 2003b; Coleman et al., 2001; Daugulis & Brookhart, 2002).

The P,N chelate bite angle [81.74 (6)° for (IV) and 78.91 (8)° for (V)] is in accordance with that of other five-membered P,N chelates [82.5 (2)°; Perera et al., 1995]. As expected on increasing in size from this five-membered ring chelate to a six-membered ring as in (III), the chelate bite angle increases by 4–5° [84.0 (1)° for A in (III)].

Although no classical intermolecular hydrogen bonds were detected in (III)–(V), significant non-conventional C—H···Cl hydrogen bonds are present. They constitute structure directing elements. Compound (III) has an interaction involving the Cl atom on the Pd metal center of molecule A and a phenyl H atom of a neighboring A molecule (C13—H13···Cl1ⁱ; symmetry codes as in Table 4; Fig. 5). Another interaction of this type is observed between the H atom of the chloroform solvent molecule and a Cl atom from the palladium metal center of molecule B (C67—H67···Cl2ⁱⁱ). Furthermore, molecules A and C have an intramolecular interaction between a phenyl H atom and the O atom adjacent to the P atom (C22—H22···O1 and C66—H66···O3), and finally in molecule B an interaction involves the H atoms of the pyridine methyl group and the Pd-bound Cl atom (C32—H32···Cl2). In (IV), an interaction exists between a Pd-bound Cl atom and a pyridine H atom (C4—H4···Cl2ⁱⁱ) (Fig. 6). A similar interaction occurs in (V) involving a phenyl H atom (C23—H23···Cl1ⁱⁱ; Fig. 7). In both cases, these interactions result in infinite one-dimensional chains of molecules along (100).

From a packing viewpoint, the crystal structure of (III) can be described in term of pseudo-slabs stacked along (001). These slabs, interconnected by van der Waals contacts, are constituted by a succession of A, B and C moieties, as defined above (Fig. 1) with molecules of CHCl₃ located between these slabs (Fig. 8). For (IV) and (V), the bc and ac projections show that the molecular moieties are placed along pseudo-slabs, with these slabs connected via van der Waals contacts, but specifically through the organic part of the corresponding molecules (see Fig. 8).

S2. Experimental

All solvents were dried and distilled under N₂ using common techniques unless otherwise stated. [PdCl(CH₃)(COD)] and [PdCl₂(COD)] (COD is 1,5-cyclo-octadiene, C₈H₁₂) were prepared according to the literature methods (Rulke et al., 1993; Ladipo & Anderson, 1994; Chatt et al., 1957). The ¹H and ³¹P{H} NMR spectra were recorded at 300.13 and 76.0 MHz, respectively, on an FT Bruker AC300, Avance 300 instrument. Ligands (I) and (II) were prepared according to reported procedures (Speiser et al., 2004) and (Speiser et al., 2004a). Compound (III) was synthesized by addition of solid [PdCl(CH₃)(COD)] (0.391 g, 1.475 mmol) to a solution of (I) (0.545 g, 1.623 mmol) in CH₂Cl₂ (20 ml), and the yellow mixture was stirred for 2 h at room temperature. The solvent was evaporated under reduced pressure and the white residue was washed with diethyl ether (2 × 10 ml) and pentane (1 × 10 ml). The product was dried under vacuum overnight, and (III) was obtained as a white solid. Crystals of (III) suitable for X-ray diffraction were obtained by slow diffusion of pentane into a CHCl₃ solution of (III) (yield 0.442 g, 0.897 mmol, 61%). Compound (IV) was obtained using a procedure similar to that described above for (III), using (II) (0.615 g, 1.612 mmol) and [PdCl₂(COD)] (0.460 g, 1.612 mmol), and was obtained as a yellow–white solid. Crystals of (IV) suitable for X-ray diffraction were obtained by slow diffusion of pentane into a CH₂Cl₂ solution of (IV) (yield 0.595 g, 1.064 mmol, 66%). Compound (V) was obtained using a procedure similar to that described above for (III), using (II) (0.588 g, 1.541 mmol) and [PdCl(CH₃)(COD)] (0.408 g, 1.541 mmol), and was obtained as a yellow–white solid. Crystals of (V) suitable for X-ray diffraction were obtained by slow diffusion of pentane into a CH₂Cl₂ solution of this complex (yield 0.463 g, 0.859 mmol, 56%).

S3. Refinement

The rotational orientations of the methyl groups were refined by the circular Fourier method available in SHELXL97 (Sheldrick, 1997). All H atoms were treated as riding with C—H and N—H distances ranging from 0.95 to 1.00 Å and U_iso(H) values equal to 1.5 (methyl H atoms) or 1.2 (all other H atoms) times U_eq of the parent atom.

Computing details

For all compounds, data collection: Collect (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON 98 (Spek, 1998); software used to prepare material for publication: SHELXL97.

Figures

Figure 1 The P,N chelate conformations of molecules A–C in (III), with the atomic labelling. Displacement ellipsoids are drawn at the 50% probability level. H atoms and CH groups from phenyl rings have been omitted for clarity. Figure 2 A view of the roof-like conformation, formed by the ligand folding along the Pd1···C2 hinge, in the structure of molecule A of (III). Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. Figure 3 A view of (IV), with the atomic labeling. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. Figure 4 A view of (V), with the atomic labeling. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. Figure 5 Part of the crystal structure of (III), showing the C—H···Cl interactions (view down the a axis). [Symmetry code as in Table 4.] Figure 6 Part of the crystal structure of (IV), showing the C—H···Cl interactions (view down the c axis). [Symmetry code as in Table 4.] Figure 7 Part of the crystal structure of (V), showing the C—H···Cl interaction (view down the c axis). [Symmetry code as in Table 4.] Figure 8 A view of the packing for complexes (III) (view down the a axis), (IV) (view down the a axis) and (V) (view down the b axis).

(III) tris{chloro[6-(1-diphenylphosphinoxy-1-methylethyl)-2- ethylpyridine-κ²N,P]methylpalladium(II)} chloroform solvate

Crystal data

3[Pd(CH3)Cl(C21H22NOP)]·CHCl3	F(000) = 3232
Mr = 1596.12	Dx = 1.526 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 53191 reflections
a = 14.628 (1) Å	θ = 1.0–30.0°
b = 28.573 (5) Å	µ = 1.11 mm^−1
c = 17.324 (2) Å	T = 173 K
β = 106.39 (5)°	Prism, yellow
V = 6947 (2) Å^3	0.13 × 0.10 × 0.08 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	13997 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.067
Graphite monochromator	θmax = 30.0°, θmin = 1.4°
ϕ or ω scans?	h = −20→20
58356 measured reflections	k = −40→37
20304 independent reflections	l = −20→24

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.123	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.05P)^2] where P = (Fo^2 + 2Fc^2)/3
20304 reflections	(Δ/σ)max < 0.001
766 parameters	Δρmax = 0.69 e Å^−3
0 restraints	Δρmin = −0.88 e Å^−3

Special details

Experimental. The ¹H and ³¹P{H} NMR spectra were recorded at 300.13 and 76.0 MHz, respectively, on an FT Bruker AC300, Avance 300 instrument.

Complex (III) 1H NMR (CDCl3) d: 0.88 (s, 3H, Pd—CH3), 2.35 (s, 6H, C(CH3)2), 3.15 (s, 3H, py-CH3), 7.08–7.94 (13H, aromatics); 31P{1H} NMR (CDCl3) d: 115.1 (s).

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
Pd1	0.669851 (18)	0.147149 (9)	0.524282 (15)	0.02158 (7)
Pd2	0.160306 (19)	0.174448 (9)	0.461121 (15)	0.02309 (7)
Pd3	0.58016 (2)	0.065989 (9)	−0.119917 (15)	0.02473 (7)
Cl1	0.64261 (7)	0.17960 (3)	0.64262 (6)	0.0374 (2)
Cl2	0.17972 (7)	0.14661 (3)	0.33570 (5)	0.0341 (2)
Cl3	0.41905 (7)	0.09301 (4)	−0.16601 (7)	0.0485 (3)
Cl4	1.00402 (9)	0.04814 (5)	0.17843 (7)	0.0642 (4)
Cl5	0.96332 (8)	0.02422 (4)	0.32661 (6)	0.0426 (3)
Cl6	1.14485 (9)	−0.00041 (5)	0.30325 (8)	0.0662 (4)
P1	0.67942 (6)	0.12422 (3)	0.40771 (5)	0.02135 (19)
P2	0.15468 (7)	0.19846 (3)	0.57863 (5)	0.0235 (2)
P3	0.71737 (7)	0.03546 (3)	−0.05830 (5)	0.0236 (2)
O1	0.57421 (17)	0.12312 (8)	0.34547 (13)	0.0262 (5)
O2	0.25818 (16)	0.21736 (8)	0.62816 (13)	0.0257 (5)
O3	0.73630 (18)	0.04390 (9)	0.03721 (13)	0.0300 (6)
N1	0.5488 (2)	0.09807 (10)	0.50089 (16)	0.0251 (7)
N2	0.2492 (2)	0.23671 (10)	0.46537 (17)	0.0275 (7)
N3	0.6284 (2)	0.12531 (10)	−0.03750 (16)	0.0246 (6)
C1	0.7897 (3)	0.18681 (14)	0.5415 (2)	0.0343 (9)
H1A	0.8333	0.1718	0.5153	0.051*
H1B	0.8211	0.1898	0.5993	0.051*
H1C	0.7725	0.2180	0.5183	0.051*
C2	0.4832 (2)	0.13152 (12)	0.3646 (2)	0.0252 (8)
C3	0.4746 (3)	0.18301 (13)	0.3861 (2)	0.0338 (9)
H3A	0.4806	0.2028	0.3416	0.051*
H3B	0.5253	0.1908	0.4349	0.051*
H3C	0.4125	0.1883	0.3955	0.051*
C4	0.4107 (3)	0.12050 (14)	0.2845 (2)	0.0376 (10)
H4A	0.4197	0.1420	0.2432	0.056*
H4B	0.3461	0.1242	0.2898	0.056*
H4C	0.4196	0.0882	0.2689	0.056*
C5	0.4738 (2)	0.10003 (12)	0.4325 (2)	0.0260 (8)
C6	0.3919 (3)	0.07466 (14)	0.4272 (2)	0.0357 (9)
H6	0.3397	0.0766	0.3800	0.043*
C7	0.3860 (3)	0.04652 (15)	0.4901 (3)	0.0428 (11)
H7	0.3288	0.0301	0.4877	0.051*
C8	0.4639 (3)	0.04248 (14)	0.5564 (2)	0.0394 (10)
H8	0.4618	0.0223	0.5995	0.047*
C9	0.5452 (3)	0.06797 (13)	0.5598 (2)	0.0325 (9)
C10	0.6331 (3)	0.06242 (14)	0.6298 (2)	0.0432 (11)
H10A	0.6893	0.0716	0.6133	0.065*
H10B	0.6393	0.0297	0.6473	0.065*
H10C	0.6278	0.0824	0.6743	0.065*
C11	0.7440 (2)	0.15791 (12)	0.35142 (19)	0.0231 (7)
C12	0.7086 (3)	0.20129 (13)	0.3198 (2)	0.0370 (10)
H12	0.6487	0.2117	0.3245	0.044*
C13	0.7596 (3)	0.22929 (14)	0.2816 (2)	0.0427 (11)
H13	0.7344	0.2587	0.2602	0.051*
C14	0.8459 (3)	0.21504 (14)	0.2745 (2)	0.0399 (10)
H14	0.8808	0.2345	0.2484	0.048*
C15	0.8820 (3)	0.17246 (15)	0.3053 (2)	0.0406 (10)
H15	0.9419	0.1623	0.3004	0.049*
C16	0.8313 (3)	0.14426 (13)	0.3434 (2)	0.0334 (9)
H16	0.8571	0.1149	0.3646	0.040*
C17	0.7232 (2)	0.06530 (11)	0.40657 (19)	0.0208 (7)
C18	0.8035 (3)	0.05100 (12)	0.4664 (2)	0.0275 (8)
H18	0.8328	0.0718	0.5090	0.033*
C19	0.8411 (3)	0.00687 (13)	0.4643 (2)	0.0330 (9)
H19	0.8965	−0.0025	0.5050	0.040*
C20	0.7977 (3)	−0.02372 (13)	0.4028 (2)	0.0343 (9)
H20	0.8236	−0.0541	0.4014	0.041*
C21	0.7173 (3)	−0.01034 (12)	0.3437 (2)	0.0313 (9)
H21	0.6877	−0.0316	0.3019	0.038*
C22	0.6796 (3)	0.03414 (13)	0.3450 (2)	0.0277 (8)
H22	0.6243	0.0434	0.3041	0.033*
C23	0.0773 (3)	0.11694 (12)	0.4633 (2)	0.0332 (9)
H23A	0.0707	0.1128	0.5177	0.050*
H23B	0.1073	0.0891	0.4482	0.050*
H23C	0.0142	0.1214	0.4252	0.050*
C24	0.3461 (2)	0.21441 (13)	0.6022 (2)	0.0276 (8)
C25	0.4183 (3)	0.23693 (15)	0.6731 (2)	0.0384 (10)
H25A	0.4242	0.2181	0.7215	0.058*
H25B	0.3969	0.2685	0.6815	0.058*
H25C	0.4803	0.2387	0.6620	0.058*
C26	0.3735 (3)	0.16361 (13)	0.5931 (2)	0.0335 (9)
H26A	0.3809	0.1470	0.6440	0.050*
H26B	0.4338	0.1627	0.5789	0.050*
H26C	0.3235	0.1485	0.5505	0.050*
C27	0.3331 (3)	0.24196 (12)	0.5246 (2)	0.0277 (8)
C28	0.4029 (3)	0.27177 (14)	0.5142 (2)	0.0371 (10)
H28	0.4618	0.2745	0.5549	0.045*
C29	0.3868 (3)	0.29739 (14)	0.4449 (3)	0.0427 (10)
H29	0.4357	0.3168	0.4362	0.051*
C30	0.3002 (3)	0.29498 (13)	0.3882 (2)	0.0391 (10)
H30	0.2877	0.3137	0.3410	0.047*
C31	0.2304 (3)	0.26503 (12)	0.4000 (2)	0.0313 (9)
C32	0.1315 (3)	0.26434 (14)	0.3442 (2)	0.0386 (10)
H32A	0.1222	0.2357	0.3119	0.058*
H32B	0.1221	0.2917	0.3087	0.058*
H32C	0.0853	0.2652	0.3757	0.058*
C33	0.0759 (2)	0.24791 (12)	0.5744 (2)	0.0244 (8)
C34	−0.0061 (3)	0.25169 (13)	0.5103 (2)	0.0327 (9)
H34	−0.0177	0.2297	0.4675	0.039*
C35	−0.0708 (3)	0.28730 (14)	0.5082 (3)	0.0421 (11)
H35	−0.1272	0.2894	0.4647	0.050*
C36	−0.0529 (3)	0.31979 (14)	0.5699 (3)	0.0422 (11)
H36	−0.0970	0.3444	0.5684	0.051*
C37	0.0283 (3)	0.31664 (14)	0.6333 (2)	0.0387 (10)
H37	0.0401	0.3391	0.6753	0.046*
C38	0.0930 (3)	0.28090 (13)	0.6361 (2)	0.0304 (8)
H38	0.1489	0.2788	0.6801	0.036*
C39	0.1252 (3)	0.15918 (12)	0.6501 (2)	0.0253 (8)
C40	0.0298 (3)	0.15232 (15)	0.6459 (2)	0.0401 (10)
H40	−0.0181	0.1703	0.6096	0.048*
C41	0.0047 (3)	0.11922 (16)	0.6947 (3)	0.0466 (11)
H41	−0.0605	0.1144	0.6915	0.056*
C42	0.0749 (3)	0.09299 (14)	0.7483 (2)	0.0384 (10)
H42	0.0574	0.0697	0.7807	0.046*
C43	0.1685 (3)	0.10067 (13)	0.7543 (2)	0.0333 (9)
H43	0.2163	0.0836	0.7924	0.040*
C44	0.1948 (3)	0.13350 (12)	0.7048 (2)	0.0269 (8)
H44	0.2602	0.1383	0.7086	0.032*
C45	0.5484 (3)	0.01136 (14)	−0.1983 (2)	0.0355 (9)
H45A	0.6074	−0.0019	−0.2051	0.053*
H45B	0.5082	0.0224	−0.2504	0.053*
H45C	0.5142	−0.0127	−0.1771	0.053*
C46	0.6743 (3)	0.06986 (13)	0.0756 (2)	0.0298 (8)
C47	0.5794 (3)	0.04549 (15)	0.0638 (2)	0.0424 (10)
H47A	0.5902	0.0136	0.0851	0.064*
H47B	0.5456	0.0443	0.0063	0.064*
H47C	0.5411	0.0628	0.0923	0.064*
C48	0.7323 (3)	0.06774 (15)	0.1645 (2)	0.0437 (11)
H48A	0.7391	0.0351	0.1825	0.066*
H48B	0.6992	0.0855	0.1970	0.066*
H48C	0.7955	0.0813	0.1709	0.066*
C49	0.6616 (2)	0.11980 (12)	0.0439 (2)	0.0262 (8)
C50	0.6819 (3)	0.15768 (14)	0.0951 (2)	0.0378 (10)
H50	0.7031	0.1531	0.1516	0.045*
C51	0.6713 (3)	0.20253 (14)	0.0634 (2)	0.0409 (10)
H51	0.6838	0.2290	0.0979	0.049*
C52	0.6426 (3)	0.20805 (13)	−0.0183 (3)	0.0389 (10)
H52	0.6366	0.2386	−0.0410	0.047*
C53	0.6223 (3)	0.16917 (13)	−0.0681 (2)	0.0315 (9)
C54	0.5930 (3)	0.17481 (14)	−0.1579 (2)	0.0451 (11)
H54A	0.6165	0.1482	−0.1825	0.068*
H54B	0.6201	0.2038	−0.1721	0.068*
H54C	0.5233	0.1761	−0.1779	0.068*
C55	0.8198 (3)	0.06234 (12)	−0.0785 (2)	0.0269 (8)
C56	0.9115 (3)	0.05170 (14)	−0.0320 (2)	0.0376 (10)
H56	0.9210	0.0275	0.0070	0.045*
C57	0.9892 (3)	0.07626 (17)	−0.0422 (3)	0.0498 (12)
H57	1.0516	0.0692	−0.0094	0.060*
C58	0.9760 (4)	0.11042 (17)	−0.0990 (3)	0.0545 (13)
H58	1.0293	0.1273	−0.1056	0.065*
C59	0.8860 (4)	0.12073 (15)	−0.1471 (3)	0.0516 (12)
H59	0.8774	0.1444	−0.1870	0.062*
C60	0.8078 (3)	0.09651 (15)	−0.1374 (2)	0.0389 (10)
H60	0.7458	0.1034	−0.1712	0.047*
C61	0.7396 (3)	−0.02683 (12)	−0.0594 (2)	0.0286 (8)
C62	0.7709 (3)	−0.04660 (13)	−0.1206 (2)	0.0335 (9)
H62	0.7843	−0.0271	−0.1604	0.040*
C63	0.7829 (3)	−0.09470 (15)	−0.1240 (3)	0.0432 (11)
H63	0.8031	−0.1081	−0.1666	0.052*
C64	0.7652 (4)	−0.12272 (15)	−0.0655 (3)	0.0546 (13)
H64	0.7746	−0.1556	−0.0670	0.066*
C65	0.7341 (3)	−0.10359 (15)	−0.0053 (3)	0.0619 (13)
H65	0.7216	−0.1233	0.0347	0.074*
C66	0.7204 (4)	−0.05535 (14)	−0.0017 (3)	0.0485 (12)
H66	0.6982	−0.0423	0.0401	0.058*
C67	1.0524 (3)	0.04118 (15)	0.2833 (2)	0.0385 (11)
H67	1.0792	0.0719	0.3070	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.01955 (14)	0.02291 (14)	0.02108 (14)	−0.00107 (11)	0.00377 (11)	−0.00322 (11)
Pd2	0.02425 (15)	0.02233 (14)	0.02036 (13)	−0.00058 (11)	0.00249 (11)	−0.00078 (11)
Pd3	0.02399 (15)	0.02674 (15)	0.02130 (14)	−0.00009 (11)	0.00290 (11)	−0.00193 (11)
Cl1	0.0417 (6)	0.0413 (6)	0.0319 (5)	−0.0090 (4)	0.0146 (4)	−0.0156 (4)
Cl2	0.0357 (5)	0.0381 (5)	0.0279 (5)	0.0011 (4)	0.0081 (4)	−0.0071 (4)
Cl3	0.0286 (5)	0.0515 (7)	0.0559 (7)	0.0089 (5)	−0.0037 (5)	−0.0118 (5)
Cl4	0.0532 (8)	0.1012 (10)	0.0359 (6)	−0.0019 (7)	0.0088 (6)	0.0100 (6)
Cl5	0.0411 (6)	0.0445 (6)	0.0452 (6)	−0.0085 (5)	0.0170 (5)	−0.0061 (5)
Cl6	0.0509 (8)	0.0742 (9)	0.0791 (9)	0.0201 (7)	0.0273 (7)	0.0254 (7)
P1	0.0205 (5)	0.0218 (4)	0.0206 (4)	0.0017 (4)	0.0038 (4)	0.0000 (4)
P2	0.0206 (5)	0.0272 (5)	0.0213 (4)	−0.0002 (4)	0.0038 (4)	0.0005 (4)
P3	0.0266 (5)	0.0247 (5)	0.0188 (4)	0.0014 (4)	0.0053 (4)	0.0004 (4)
O1	0.0224 (13)	0.0324 (14)	0.0216 (12)	0.0043 (11)	0.0027 (10)	−0.0027 (10)
O2	0.0191 (13)	0.0341 (14)	0.0235 (12)	−0.0016 (10)	0.0053 (10)	−0.0044 (10)
O3	0.0362 (15)	0.0360 (15)	0.0169 (12)	0.0094 (12)	0.0062 (11)	0.0016 (11)
N1	0.0270 (16)	0.0231 (15)	0.0249 (15)	−0.0020 (13)	0.0069 (13)	−0.0048 (12)
N2	0.0324 (18)	0.0249 (16)	0.0272 (16)	−0.0018 (13)	0.0115 (14)	−0.0002 (13)
N3	0.0228 (15)	0.0241 (16)	0.0251 (15)	−0.0002 (12)	0.0035 (13)	−0.0003 (12)
C1	0.0198 (19)	0.040 (2)	0.040 (2)	−0.0044 (17)	0.0034 (17)	−0.0034 (18)
C2	0.0184 (18)	0.0293 (19)	0.0248 (18)	0.0021 (15)	0.0011 (15)	−0.0038 (15)
C3	0.030 (2)	0.029 (2)	0.039 (2)	0.0072 (16)	0.0043 (18)	−0.0052 (17)
C4	0.024 (2)	0.047 (2)	0.035 (2)	0.0029 (18)	−0.0039 (17)	−0.0101 (19)
C5	0.0224 (18)	0.0223 (18)	0.035 (2)	0.0020 (14)	0.0101 (16)	−0.0102 (15)
C6	0.024 (2)	0.037 (2)	0.045 (2)	−0.0058 (17)	0.0075 (18)	−0.0101 (19)
C7	0.032 (2)	0.042 (2)	0.059 (3)	−0.0127 (19)	0.021 (2)	−0.008 (2)
C8	0.044 (3)	0.035 (2)	0.045 (2)	−0.0097 (19)	0.021 (2)	0.0027 (19)
C9	0.039 (2)	0.028 (2)	0.034 (2)	−0.0008 (17)	0.0166 (18)	−0.0006 (17)
C10	0.048 (3)	0.042 (2)	0.034 (2)	−0.006 (2)	0.004 (2)	0.0118 (19)
C11	0.0259 (19)	0.0225 (18)	0.0194 (16)	−0.0006 (14)	0.0038 (15)	−0.0008 (14)
C12	0.042 (2)	0.030 (2)	0.042 (2)	0.0096 (18)	0.016 (2)	0.0053 (18)
C13	0.063 (3)	0.029 (2)	0.038 (2)	0.006 (2)	0.017 (2)	0.0107 (18)
C14	0.043 (3)	0.044 (2)	0.031 (2)	−0.009 (2)	0.0083 (19)	0.0109 (19)
C15	0.031 (2)	0.048 (3)	0.044 (2)	−0.0003 (19)	0.013 (2)	0.016 (2)
C16	0.030 (2)	0.031 (2)	0.038 (2)	0.0035 (17)	0.0080 (18)	0.0114 (17)
C17	0.0250 (18)	0.0191 (17)	0.0198 (16)	−0.0003 (14)	0.0085 (14)	−0.0006 (13)
C18	0.028 (2)	0.0283 (19)	0.0241 (18)	0.0041 (16)	0.0030 (16)	−0.0008 (15)
C19	0.035 (2)	0.035 (2)	0.0279 (19)	0.0079 (18)	0.0072 (17)	0.0086 (17)
C20	0.045 (3)	0.0242 (19)	0.037 (2)	0.0067 (18)	0.017 (2)	0.0029 (17)
C21	0.041 (2)	0.0239 (19)	0.030 (2)	0.0017 (17)	0.0125 (18)	−0.0040 (16)
C22	0.029 (2)	0.031 (2)	0.0255 (18)	−0.0010 (16)	0.0122 (16)	0.0025 (16)
C23	0.041 (2)	0.0228 (19)	0.029 (2)	−0.0079 (17)	−0.0010 (18)	0.0015 (15)
C24	0.0193 (18)	0.034 (2)	0.0292 (19)	−0.0014 (15)	0.0058 (16)	−0.0022 (16)
C25	0.024 (2)	0.052 (3)	0.036 (2)	−0.0061 (18)	0.0038 (18)	−0.0083 (19)
C26	0.029 (2)	0.033 (2)	0.036 (2)	0.0051 (17)	0.0057 (18)	0.0007 (17)
C27	0.0243 (19)	0.0262 (19)	0.034 (2)	0.0037 (15)	0.0100 (17)	−0.0042 (16)
C28	0.032 (2)	0.036 (2)	0.047 (2)	−0.0053 (18)	0.0161 (19)	0.0014 (19)
C29	0.041 (3)	0.037 (2)	0.060 (3)	−0.0057 (19)	0.029 (2)	0.002 (2)
C30	0.056 (3)	0.025 (2)	0.045 (2)	0.0046 (19)	0.028 (2)	0.0066 (18)
C31	0.043 (2)	0.0253 (19)	0.0284 (19)	0.0065 (17)	0.0144 (18)	−0.0008 (16)
C32	0.048 (3)	0.036 (2)	0.030 (2)	0.0042 (19)	0.0088 (19)	0.0086 (18)
C33	0.0207 (18)	0.0251 (18)	0.0283 (18)	−0.0009 (14)	0.0083 (15)	0.0037 (15)
C34	0.028 (2)	0.034 (2)	0.033 (2)	−0.0007 (17)	0.0034 (17)	0.0003 (17)
C35	0.031 (2)	0.038 (2)	0.052 (3)	0.0023 (19)	0.002 (2)	0.012 (2)
C36	0.039 (3)	0.028 (2)	0.063 (3)	0.0099 (18)	0.022 (2)	0.005 (2)
C37	0.042 (3)	0.032 (2)	0.045 (2)	−0.0019 (19)	0.017 (2)	−0.0085 (18)
C38	0.029 (2)	0.033 (2)	0.0288 (19)	−0.0007 (17)	0.0080 (17)	−0.0001 (16)
C39	0.0232 (19)	0.0290 (19)	0.0222 (17)	0.0011 (15)	0.0039 (15)	−0.0004 (15)
C40	0.026 (2)	0.054 (3)	0.037 (2)	−0.0035 (19)	0.0038 (18)	0.011 (2)
C41	0.032 (2)	0.062 (3)	0.046 (3)	−0.010 (2)	0.013 (2)	0.008 (2)
C42	0.052 (3)	0.035 (2)	0.033 (2)	−0.007 (2)	0.019 (2)	0.0008 (18)
C43	0.041 (2)	0.029 (2)	0.0278 (19)	0.0070 (18)	0.0071 (18)	0.0024 (16)
C44	0.030 (2)	0.0231 (18)	0.0272 (18)	0.0016 (15)	0.0080 (16)	−0.0006 (15)
C45	0.035 (2)	0.040 (2)	0.028 (2)	−0.0079 (18)	0.0018 (17)	−0.0091 (17)
C46	0.038 (2)	0.032 (2)	0.0215 (18)	−0.0024 (17)	0.0119 (17)	−0.0028 (15)
C47	0.053 (3)	0.041 (2)	0.042 (2)	−0.008 (2)	0.028 (2)	−0.0014 (19)
C48	0.068 (3)	0.046 (3)	0.0184 (18)	0.007 (2)	0.014 (2)	0.0000 (17)
C49	0.0235 (19)	0.029 (2)	0.0273 (18)	−0.0012 (15)	0.0100 (16)	−0.0011 (15)
C50	0.041 (2)	0.040 (2)	0.030 (2)	0.0011 (19)	0.0050 (19)	−0.0084 (18)
C51	0.041 (2)	0.029 (2)	0.047 (3)	−0.0010 (18)	0.003 (2)	−0.0138 (19)
C52	0.036 (2)	0.022 (2)	0.051 (3)	0.0028 (17)	0.001 (2)	−0.0031 (18)
C53	0.024 (2)	0.032 (2)	0.036 (2)	0.0043 (16)	0.0047 (17)	0.0020 (17)
C54	0.063 (3)	0.031 (2)	0.036 (2)	0.005 (2)	0.005 (2)	0.0092 (18)
C55	0.027 (2)	0.0276 (19)	0.0269 (19)	−0.0029 (16)	0.0091 (16)	−0.0043 (15)
C56	0.033 (2)	0.041 (2)	0.035 (2)	−0.0049 (19)	0.0040 (19)	−0.0078 (18)
C57	0.036 (3)	0.058 (3)	0.053 (3)	−0.010 (2)	0.010 (2)	−0.019 (2)
C58	0.050 (3)	0.052 (3)	0.075 (3)	−0.022 (2)	0.038 (3)	−0.022 (3)
C59	0.067 (3)	0.040 (3)	0.062 (3)	−0.005 (2)	0.042 (3)	0.004 (2)
C60	0.037 (2)	0.046 (3)	0.036 (2)	0.004 (2)	0.0149 (19)	0.0037 (19)
C61	0.028 (2)	0.0235 (19)	0.031 (2)	0.0019 (15)	0.0039 (17)	−0.0015 (16)
C62	0.029 (2)	0.034 (2)	0.033 (2)	0.0036 (17)	0.0001 (17)	−0.0036 (17)
C63	0.031 (2)	0.044 (3)	0.047 (2)	0.006 (2)	0.000 (2)	−0.016 (2)
C64	0.048 (3)	0.031 (2)	0.080 (4)	−0.001 (2)	0.011 (3)	−0.009 (2)
C65	0.076 (3)	0.033 (2)	0.086 (4)	0.000 (2)	0.038 (3)	0.015 (2)
C66	0.068 (3)	0.029 (2)	0.055 (3)	0.003 (2)	0.027 (3)	0.007 (2)
C67	0.039 (3)	0.040 (2)	0.033 (2)	−0.003 (2)	0.006 (2)	−0.0019 (19)

Geometric parameters (Å, º)

Pd1—Cl1	2.3838 (10)	C25—H25B	0.9800
Pd1—P1	2.1650 (9)	C25—H25C	0.9801
Pd1—N1	2.205 (3)	C26—H26A	0.9801
Pd1—C1	2.038 (4)	C26—H26B	0.9801
Pd2—Cl2	2.4047 (10)	C26—H26C	0.9800
Pd2—P2	2.1717 (10)	C27—C28	1.380 (5)
Pd2—N2	2.193 (3)	C28—C29	1.369 (6)
Pd2—C23	2.050 (4)	C28—H28	0.9502
Pd3—Cl3	2.3929 (12)	C29—C30	1.369 (6)
Pd3—P3	2.1725 (13)	C29—H29	0.9500
Pd3—N3	2.200 (3)	C30—C31	1.390 (6)
Pd3—C45	2.034 (4)	C30—H30	0.9500
Cl4—C67	1.765 (4)	C31—C32	1.497 (6)
Cl5—C67	1.745 (5)	C32—H32A	0.9800
Cl6—C67	1.760 (5)	C32—H32B	0.9800
P1—O1	1.611 (2)	C32—H32C	0.9799
P1—C17	1.803 (3)	C33—C34	1.390 (5)
P1—C11	1.814 (4)	C33—C38	1.394 (5)
P2—O2	1.608 (2)	C34—C35	1.384 (5)
P2—C33	1.811 (4)	C34—H34	0.9500
P2—C39	1.812 (4)	C35—C36	1.383 (6)
P3—O3	1.617 (2)	C35—H35	0.9500
P3—C55	1.804 (4)	C36—C37	1.375 (6)
P3—C61	1.810 (4)	C36—H36	0.9499
O1—C2	1.479 (4)	C37—C38	1.383 (5)
O2—C24	1.480 (4)	C37—H37	0.9501
O3—C46	1.468 (4)	C38—H38	0.9502
N1—C9	1.347 (4)	C39—C44	1.389 (5)
N1—C5	1.369 (4)	C39—C40	1.391 (5)
N2—C31	1.355 (4)	C40—C41	1.384 (6)
N2—C27	1.368 (4)	C40—H40	0.9502
N3—C53	1.354 (4)	C41—C42	1.393 (6)
N3—C49	1.364 (4)	C41—H41	0.9502
C1—H1A	0.9800	C42—C43	1.363 (6)
C1—H1B	0.9798	C42—H42	0.9501
C1—H1C	0.9801	C43—C44	1.395 (5)
C2—C5	1.518 (5)	C43—H43	0.9501
C2—C4	1.524 (5)	C44—H44	0.9501
C2—C3	1.531 (5)	C45—H45A	0.9798
C3—H3A	0.9797	C45—H45B	0.9802
C3—H3B	0.9801	C45—H45C	0.9801
C3—H3C	0.9801	C46—C47	1.514 (6)
C4—H4A	0.9798	C46—C49	1.522 (5)
C4—H4B	0.9799	C46—C48	1.536 (5)
C4—H4C	0.9802	C47—H47A	0.9800
C5—C6	1.381 (5)	C47—H47B	0.9802
C6—C7	1.377 (6)	C47—H47C	0.9800
C6—H6	0.9500	C48—H48A	0.9801
C7—C8	1.376 (6)	C48—H48B	0.9800
C7—H7	0.9499	C48—H48C	0.9804
C8—C9	1.382 (5)	C49—C50	1.378 (5)
C8—H8	0.9500	C50—C51	1.385 (6)
C9—C10	1.507 (5)	C50—H50	0.9501
C10—H10A	0.9800	C51—C52	1.367 (6)
C10—H10B	0.9800	C51—H51	0.9503
C10—H10C	0.9799	C52—C53	1.387 (5)
C11—C16	1.378 (5)	C52—H52	0.9501
C11—C12	1.395 (5)	C53—C54	1.501 (5)
C12—C13	1.384 (6)	C54—H54A	0.9800
C12—H12	0.9502	C54—H54B	0.9799
C13—C14	1.365 (6)	C54—H54C	0.9802
C13—H13	0.9500	C55—C60	1.387 (5)
C14—C15	1.373 (5)	C55—C56	1.388 (5)
C14—H14	0.9500	C56—C57	1.389 (6)
C15—C16	1.383 (5)	C56—H56	0.9501
C15—H15	0.9501	C57—C58	1.362 (7)
C16—H16	0.9500	C57—H57	0.9501
C17—C18	1.391 (5)	C58—C59	1.377 (7)
C17—C22	1.398 (5)	C58—H58	0.9500
C18—C19	1.380 (5)	C59—C60	1.387 (6)
C18—H18	0.9501	C59—H59	0.9501
C19—C20	1.386 (5)	C60—H60	0.9500
C19—H19	0.9499	C61—C66	1.378 (5)
C20—C21	1.378 (5)	C61—C62	1.387 (5)
C20—H20	0.9501	C62—C63	1.389 (5)
C21—C22	1.388 (5)	C62—H62	0.9502
C21—H21	0.9499	C63—C64	1.372 (7)
C22—H22	0.9502	C63—H63	0.9502
C23—H23A	0.9798	C64—C65	1.365 (7)
C23—H23B	0.9802	C64—H64	0.9500
C23—H23C	0.9800	C65—C66	1.397 (6)
C24—C25	1.518 (5)	C65—H65	0.9516
C24—C27	1.523 (5)	C66—H66	0.9500
C24—C26	1.526 (5)	C67—H67	0.9999
C25—H25A	0.9799
C1—Pd1—P1	91.45 (12)	H26A—C26—H26B	109.5
C1—Pd1—N1	173.65 (14)	C24—C26—H26C	109.5
P1—Pd1—N1	84.03 (8)	H26A—C26—H26C	109.5
C1—Pd1—Cl1	90.20 (12)	H26B—C26—H26C	109.5
P1—Pd1—Cl1	172.09 (4)	N2—C27—C28	120.7 (3)
N1—Pd1—Cl1	94.87 (8)	N2—C27—C24	117.9 (3)
C23—Pd2—P2	93.23 (12)	C28—C27—C24	121.4 (3)
C23—Pd2—N2	176.97 (13)	C29—C28—C27	119.6 (4)
P2—Pd2—N2	83.76 (8)	C29—C28—H28	120.2
C23—Pd2—Cl2	88.48 (12)	C27—C28—H28	120.2
P2—Pd2—Cl2	175.46 (4)	C28—C29—C30	119.9 (4)
N2—Pd2—Cl2	94.50 (8)	C28—C29—H29	120.0
C45—Pd3—P3	91.45 (12)	C30—C29—H29	120.1
C45—Pd3—N3	174.34 (14)	C29—C30—C31	119.6 (4)
P3—Pd3—N3	84.71 (8)	C29—C30—H30	120.2
C45—Pd3—Cl3	90.38 (12)	C31—C30—H30	120.2
P3—Pd3—Cl3	168.49 (4)	N2—C31—C30	120.5 (4)
N3—Pd3—Cl3	94.21 (9)	N2—C31—C32	117.6 (3)
O1—P1—C17	104.46 (14)	C30—C31—C32	121.9 (3)
O1—P1—C11	101.24 (14)	C31—C32—H32A	109.5
C17—P1—C11	104.41 (16)	C31—C32—H32B	109.5
O1—P1—Pd1	109.22 (10)	H32A—C32—H32B	109.5
C17—P1—Pd1	114.16 (11)	C31—C32—H32C	109.5
C11—P1—Pd1	121.43 (11)	H32A—C32—H32C	109.5
O2—P2—C33	104.59 (14)	H32B—C32—H32C	109.5
O2—P2—C39	102.30 (14)	C34—C33—C38	119.2 (3)
C33—P2—C39	103.87 (17)	C34—C33—P2	119.2 (3)
O2—P2—Pd2	109.10 (10)	C38—C33—P2	121.5 (3)
C33—P2—Pd2	113.59 (12)	C35—C34—C33	120.5 (4)
C39—P2—Pd2	121.64 (12)	C35—C34—H34	119.8
O3—P3—C55	102.91 (15)	C33—C34—H34	119.8
O3—P3—C61	100.27 (15)	C36—C35—C34	119.7 (4)
C55—P3—C61	104.76 (17)	C36—C35—H35	120.2
O3—P3—Pd3	108.10 (11)	C34—C35—H35	120.1
C55—P3—Pd3	115.89 (12)	C37—C36—C35	120.3 (4)
C61—P3—Pd3	122.23 (12)	C37—C36—H36	119.8
C2—O1—P1	126.6 (2)	C35—C36—H36	119.8
C24—O2—P2	125.9 (2)	C36—C37—C38	120.3 (4)
C46—O3—P3	126.1 (2)	C36—C37—H37	119.8
C9—N1—C5	119.2 (3)	C38—C37—H37	119.8
C9—N1—Pd1	117.9 (2)	C37—C38—C33	120.0 (3)
C5—N1—Pd1	122.6 (2)	C37—C38—H38	120.0
C31—N2—C27	119.2 (3)	C33—C38—H38	120.0
C31—N2—Pd2	118.6 (2)	C44—C39—C40	119.6 (3)
C27—N2—Pd2	120.8 (2)	C44—C39—P2	121.6 (3)
C53—N3—C49	118.5 (3)	C40—C39—P2	118.7 (3)
C53—N3—Pd3	119.0 (2)	C41—C40—C39	119.9 (4)
C49—N3—Pd3	122.5 (2)	C41—C40—H40	120.1
Pd1—C1—H1A	109.5	C39—C40—H40	120.0
Pd1—C1—H1B	109.5	C40—C41—C42	120.1 (4)
H1A—C1—H1B	109.5	C40—C41—H41	119.9
Pd1—C1—H1C	109.5	C42—C41—H41	119.9
H1A—C1—H1C	109.5	C43—C42—C41	120.0 (4)
H1B—C1—H1C	109.5	C43—C42—H42	120.0
O1—C2—C5	111.2 (3)	C41—C42—H42	120.0
O1—C2—C4	101.6 (3)	C42—C43—C44	120.5 (4)
C5—C2—C4	113.1 (3)	C42—C43—H43	119.8
O1—C2—C3	110.6 (3)	C44—C43—H43	119.8
C5—C2—C3	110.5 (3)	C39—C44—C43	119.9 (4)
C4—C2—C3	109.6 (3)	C39—C44—H44	120.1
C2—C3—H3A	109.5	C43—C44—H44	120.1
C2—C3—H3B	109.5	Pd3—C45—H45A	109.5
H3A—C3—H3B	109.5	Pd3—C45—H45B	109.5
C2—C3—H3C	109.5	H45A—C45—H45B	109.5
H3A—C3—H3C	109.5	Pd3—C45—H45C	109.5
H3B—C3—H3C	109.5	H45A—C45—H45C	109.5
C2—C4—H4A	109.5	H45B—C45—H45C	109.4
C2—C4—H4B	109.5	O3—C46—C47	111.5 (3)
H4A—C4—H4B	109.5	O3—C46—C49	109.8 (3)
C2—C4—H4C	109.4	C47—C46—C49	111.7 (3)
H4A—C4—H4C	109.5	O3—C46—C48	101.4 (3)
H4B—C4—H4C	109.5	C47—C46—C48	110.1 (3)
N1—C5—C6	120.3 (3)	C49—C46—C48	112.1 (3)
N1—C5—C2	118.0 (3)	C46—C47—H47A	109.5
C6—C5—C2	121.7 (3)	C46—C47—H47B	109.5
C7—C6—C5	120.0 (4)	H47A—C47—H47B	109.5
C7—C6—H6	120.0	C46—C47—H47C	109.5
C5—C6—H6	120.0	H47A—C47—H47C	109.5
C8—C7—C6	119.2 (4)	H47B—C47—H47C	109.5
C8—C7—H7	120.4	C46—C48—H48A	109.5
C6—C7—H7	120.4	C46—C48—H48B	109.5
C7—C8—C9	119.4 (4)	H48A—C48—H48B	109.5
C7—C8—H8	120.3	C46—C48—H48C	109.5
C9—C8—H8	120.3	H48A—C48—H48C	109.4
N1—C9—C8	121.5 (4)	H48B—C48—H48C	109.4
N1—C9—C10	118.0 (3)	N3—C49—C50	121.6 (3)
C8—C9—C10	120.5 (4)	N3—C49—C46	116.9 (3)
C9—C10—H10A	109.5	C50—C49—C46	121.5 (3)
C9—C10—H10B	109.5	C49—C50—C51	119.5 (4)
H10A—C10—H10B	109.5	C49—C50—H50	120.3
C9—C10—H10C	109.5	C51—C50—H50	120.3
H10A—C10—H10C	109.5	C52—C51—C50	119.0 (3)
H10B—C10—H10C	109.5	C52—C51—H51	120.5
C16—C11—C12	117.7 (3)	C50—C51—H51	120.5
C16—C11—P1	122.8 (3)	C51—C52—C53	120.1 (4)
C12—C11—P1	119.3 (3)	C51—C52—H52	120.0
C13—C12—C11	120.7 (4)	C53—C52—H52	120.0
C13—C12—H12	119.7	N3—C53—C52	121.2 (3)
C11—C12—H12	119.6	N3—C53—C54	118.3 (3)
C14—C13—C12	120.6 (4)	C52—C53—C54	120.5 (3)
C14—C13—H13	119.7	C53—C54—H54A	109.5
C12—C13—H13	119.7	C53—C54—H54B	109.5
C13—C14—C15	119.5 (4)	H54A—C54—H54B	109.5
C13—C14—H14	120.3	C53—C54—H54C	109.5
C15—C14—H14	120.2	H54A—C54—H54C	109.5
C14—C15—C16	120.2 (4)	H54B—C54—H54C	109.5
C14—C15—H15	119.9	C60—C55—C56	118.8 (4)
C16—C15—H15	119.9	C60—C55—P3	120.1 (3)
C11—C16—C15	121.3 (3)	C56—C55—P3	120.9 (3)
C11—C16—H16	119.3	C55—C56—C57	120.5 (4)
C15—C16—H16	119.4	C55—C56—H56	119.8
C18—C17—C22	119.3 (3)	C57—C56—H56	119.8
C18—C17—P1	119.6 (2)	C58—C57—C56	120.0 (4)
C22—C17—P1	121.1 (3)	C58—C57—H57	120.0
C19—C18—C17	120.5 (3)	C56—C57—H57	120.0
C19—C18—H18	119.7	C57—C58—C59	120.5 (4)
C17—C18—H18	119.7	C57—C58—H58	119.8
C18—C19—C20	119.8 (3)	C59—C58—H58	119.7
C18—C19—H19	120.1	C58—C59—C60	120.0 (4)
C20—C19—H19	120.1	C58—C59—H59	120.0
C21—C20—C19	120.4 (3)	C60—C59—H59	120.0
C21—C20—H20	119.8	C55—C60—C59	120.1 (4)
C19—C20—H20	119.8	C55—C60—H60	119.9
C20—C21—C22	120.1 (3)	C59—C60—H60	119.9
C20—C21—H21	119.9	C66—C61—C62	119.4 (3)
C22—C21—H21	119.9	C66—C61—P3	120.0 (3)
C21—C22—C17	119.8 (3)	C62—C61—P3	120.5 (3)
C21—C22—H22	120.1	C61—C62—C63	120.6 (4)
C17—C22—H22	120.1	C61—C62—H62	119.7
Pd2—C23—H23A	109.5	C63—C62—H62	119.7
Pd2—C23—H23B	109.5	C64—C63—C62	119.5 (4)
H23A—C23—H23B	109.5	C64—C63—H63	120.2
Pd2—C23—H23C	109.5	C62—C63—H63	120.2
H23A—C23—H23C	109.5	C65—C64—C63	120.3 (4)
H23B—C23—H23C	109.5	C65—C64—H64	119.8
O2—C24—C25	101.3 (3)	C63—C64—H64	119.9
O2—C24—C27	109.6 (3)	C64—C65—C66	120.8 (4)
C25—C24—C27	112.3 (3)	C64—C65—H65	119.6
O2—C24—C26	111.2 (3)	C66—C65—H65	119.6
C25—C24—C26	110.1 (3)	C61—C66—C65	119.4 (4)
C27—C24—C26	111.8 (3)	C61—C66—H66	120.3
C24—C25—H25A	109.5	C65—C66—H66	120.3
C24—C25—H25B	109.5	Cl5—C67—Cl6	110.7 (2)
H25A—C25—H25B	109.5	Cl5—C67—Cl4	110.1 (2)
C24—C25—H25C	109.5	Cl6—C67—Cl4	109.9 (2)
H25A—C25—H25C	109.5	Cl5—C67—H67	108.7
H25B—C25—H25C	109.5	Cl6—C67—H67	108.7
C24—C26—H26A	109.5	Cl4—C67—H67	108.7
C24—C26—H26B	109.5

(IV) dichloro[2-(2,6-dimethylphenyl)-6-(diphenylphosphanomethyl)pyridine- κ²N,P]palladium(II)

Crystal data

C26H24Cl2NPPd	Z = 2
Mr = 558.73	F(000) = 564
Triclinic, P1	Dx = 1.566 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 10.151 (1) Å	Cell parameters from 7840 reflections
b = 11.461 (1) Å	θ = 1.0–27.9°
c = 12.106 (2) Å	µ = 1.09 mm^−1
α = 95.40 (5)°	T = 173 K
β = 109.93 (5)°	Prism, yellow–orange
γ = 112.23 (5)°	0.13 × 0.10 × 0.08 mm
V = 1184.7 (9) Å^3

Data collection

Nonius KappaCCD diffractometer	4878 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.033
Graphite monochromator	θmax = 27.8°, θmin = 1.9°
ϕ or ω scans?	h = −13→13
14956 measured reflections	k = −14→15
5587 independent 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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.078	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0331P)^2 + 0.3488P] where P = (Fo^2 + 2Fc^2)/3
5587 reflections	(Δ/σ)max = 0.001
280 parameters	Δρmax = 0.49 e Å^−3
0 restraints	Δρmin = −0.80 e Å^−3

Special details

Experimental. The ¹H and ³¹P{H} NMR spectra were recorded at 300.13 and 76.0 MHz, respectively, on an FT Bruker AC300, Avance 300 instrument.

Complex (IV) 1H NMR (CDCl3) d: 2.01 (s, 6H, Ph(CH3)2), 4.27 (d, 2H, PCH2, 2JPH = 13.7 Hz), 7.03–7.88 (16H, aromatics); 31P{1H} NMR (CDCl3) d: 46.1 (s).

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
Pd1	0.194666 (18)	−0.044011 (15)	0.279218 (15)	0.02745 (7)
Cl1	0.09907 (8)	−0.27189 (5)	0.26100 (6)	0.04143 (16)
Cl2	−0.03851 (7)	−0.04876 (6)	0.25935 (7)	0.04838 (17)
P1	0.30688 (7)	0.17127 (5)	0.33743 (5)	0.02879 (14)
N1	0.4199 (2)	−0.01187 (17)	0.29826 (16)	0.0270 (4)
C1	0.4896 (3)	0.1836 (2)	0.4487 (2)	0.0336 (5)
H1A	0.5711	0.2748	0.4758	0.040*
H1B	0.4749	0.1565	0.5205	0.040*
C2	0.5374 (3)	0.0955 (2)	0.3882 (2)	0.0301 (5)
C3	0.6920 (3)	0.1252 (2)	0.4180 (2)	0.0391 (6)
H3	0.7716	0.1993	0.4818	0.047*
C4	0.7299 (3)	0.0469 (3)	0.3548 (2)	0.0445 (6)
H4	0.8359	0.0645	0.3757	0.053*
C5	0.6123 (3)	−0.0581 (2)	0.2603 (2)	0.0391 (6)
H5	0.6378	−0.1118	0.2149	0.047*
C6	0.4565 (3)	−0.0860 (2)	0.2308 (2)	0.0297 (5)
C7	0.3342 (3)	−0.1896 (2)	0.1182 (2)	0.0311 (5)
C8	0.3001 (3)	−0.3211 (2)	0.1115 (2)	0.0380 (6)
C9	0.1895 (3)	−0.4132 (2)	0.0021 (3)	0.0482 (7)
H9	0.1623	−0.5032	−0.0034	0.058*
C10	0.1196 (3)	−0.3756 (3)	−0.0973 (3)	0.0533 (8)
H10	0.0436	−0.4397	−0.1705	0.064*
C11	0.1589 (3)	−0.2464 (3)	−0.0915 (2)	0.0479 (7)
H11	0.1126	−0.2216	−0.1620	0.057*
C12	0.2653 (3)	−0.1508 (2)	0.0157 (2)	0.0368 (5)
C13	0.3741 (4)	−0.3664 (3)	0.2176 (3)	0.0534 (7)
H13A	0.3389	−0.3514	0.2812	0.080*
H13B	0.4878	−0.3177	0.2496	0.080*
H13C	0.3439	−0.4597	0.1913	0.080*
C14	0.3075 (4)	−0.0112 (3)	0.0163 (3)	0.0551 (8)
H14A	0.2941	−0.0006	−0.0657	0.083*
H14B	0.4164	0.0425	0.0730	0.083*
H14C	0.2397	0.0163	0.0418	0.083*
C15	0.2380 (3)	0.2622 (2)	0.4158 (2)	0.0323 (5)
C16	0.2256 (3)	0.3718 (2)	0.3845 (2)	0.0431 (6)
H16	0.2537	0.4006	0.3212	0.052*
C17	0.1720 (4)	0.4398 (3)	0.4452 (3)	0.0520 (7)
H17	0.1624	0.5145	0.4230	0.062*
C18	0.1328 (3)	0.3988 (3)	0.5378 (3)	0.0516 (7)
H18	0.0963	0.4454	0.5794	0.062*
C19	0.1462 (3)	0.2907 (3)	0.5704 (3)	0.0500 (7)
H19	0.1207	0.2638	0.6352	0.060*
C20	0.1967 (3)	0.2210 (2)	0.5088 (2)	0.0404 (6)
H20	0.2032	0.1450	0.5299	0.049*
C21	0.3442 (3)	0.2497 (2)	0.2223 (2)	0.0333 (5)
C22	0.4934 (3)	0.3177 (3)	0.2287 (3)	0.0516 (7)
H22	0.5819	0.3328	0.2996	0.062*
C23	0.5120 (5)	0.3636 (3)	0.1300 (4)	0.0724 (10)
H23	0.6139	0.4099	0.1337	0.087*
C24	0.3865 (5)	0.3430 (3)	0.0286 (3)	0.0689 (10)
H24	0.4013	0.3731	−0.0386	0.083*
C25	0.2390 (4)	0.2793 (3)	0.0223 (3)	0.0601 (9)
H25	0.1518	0.2681	−0.0480	0.072*
C26	0.2166 (3)	0.2311 (2)	0.1187 (2)	0.0434 (6)
H26	0.1140	0.1854	0.1138	0.052*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.02733 (11)	0.02842 (11)	0.03118 (11)	0.01414 (8)	0.01488 (8)	0.00781 (7)
Cl1	0.0495 (4)	0.0299 (3)	0.0511 (4)	0.0157 (3)	0.0298 (3)	0.0088 (3)
Cl2	0.0309 (3)	0.0489 (4)	0.0659 (4)	0.0194 (3)	0.0210 (3)	0.0036 (3)
P1	0.0308 (3)	0.0292 (3)	0.0320 (3)	0.0158 (2)	0.0159 (3)	0.0089 (2)
N1	0.0282 (9)	0.0318 (9)	0.0266 (9)	0.0161 (8)	0.0132 (8)	0.0108 (7)
C1	0.0343 (12)	0.0377 (12)	0.0290 (12)	0.0175 (10)	0.0116 (10)	0.0062 (9)
C2	0.0317 (12)	0.0356 (12)	0.0274 (11)	0.0177 (10)	0.0129 (10)	0.0107 (9)
C3	0.0316 (13)	0.0453 (14)	0.0369 (14)	0.0185 (11)	0.0089 (11)	0.0083 (11)
C4	0.0297 (13)	0.0578 (16)	0.0505 (16)	0.0243 (12)	0.0160 (12)	0.0127 (13)
C5	0.0384 (13)	0.0480 (14)	0.0442 (15)	0.0277 (12)	0.0215 (12)	0.0141 (11)
C6	0.0352 (12)	0.0334 (12)	0.0299 (12)	0.0208 (10)	0.0164 (10)	0.0127 (9)
C7	0.0338 (12)	0.0359 (12)	0.0333 (12)	0.0201 (10)	0.0190 (10)	0.0102 (9)
C8	0.0467 (15)	0.0393 (13)	0.0429 (14)	0.0246 (12)	0.0279 (12)	0.0133 (11)
C9	0.0539 (17)	0.0340 (13)	0.0587 (18)	0.0175 (12)	0.0294 (15)	0.0031 (12)
C10	0.0455 (16)	0.0523 (17)	0.0482 (17)	0.0186 (14)	0.0113 (14)	−0.0044 (13)
C11	0.0477 (16)	0.0582 (17)	0.0370 (14)	0.0295 (14)	0.0110 (12)	0.0060 (12)
C12	0.0408 (13)	0.0453 (14)	0.0349 (13)	0.0265 (11)	0.0187 (11)	0.0103 (10)
C13	0.080 (2)	0.0410 (14)	0.0565 (18)	0.0357 (15)	0.0343 (16)	0.0195 (13)
C14	0.087 (2)	0.0520 (16)	0.0400 (16)	0.0449 (16)	0.0226 (15)	0.0184 (12)
C15	0.0317 (12)	0.0320 (12)	0.0367 (13)	0.0155 (10)	0.0167 (10)	0.0063 (9)
C16	0.0544 (16)	0.0374 (13)	0.0514 (16)	0.0253 (12)	0.0307 (14)	0.0153 (11)
C17	0.0635 (19)	0.0392 (14)	0.0659 (19)	0.0306 (14)	0.0318 (16)	0.0116 (13)
C18	0.0482 (16)	0.0520 (16)	0.0624 (19)	0.0266 (13)	0.0293 (15)	0.0024 (14)
C19	0.0531 (17)	0.0602 (17)	0.0511 (17)	0.0279 (14)	0.0344 (14)	0.0135 (13)
C20	0.0478 (15)	0.0429 (14)	0.0430 (14)	0.0252 (12)	0.0250 (12)	0.0160 (11)
C21	0.0420 (13)	0.0310 (12)	0.0350 (13)	0.0200 (10)	0.0200 (11)	0.0106 (9)
C22	0.0498 (16)	0.0553 (17)	0.0595 (18)	0.0231 (14)	0.0305 (15)	0.0258 (14)
C23	0.084 (3)	0.070 (2)	0.092 (3)	0.0325 (19)	0.064 (2)	0.044 (2)
C24	0.121 (3)	0.0566 (19)	0.058 (2)	0.046 (2)	0.057 (2)	0.0331 (16)
C25	0.101 (3)	0.0445 (16)	0.0341 (15)	0.0411 (17)	0.0170 (16)	0.0113 (12)
C26	0.0503 (15)	0.0391 (13)	0.0399 (14)	0.0228 (12)	0.0142 (12)	0.0082 (11)

Geometric parameters (Å, º)

Pd1—Cl1	2.3747 (12)	C12—C14	1.490 (4)
Pd1—Cl2	2.2749 (13)	C13—H13A	0.9800
Pd1—P1	2.2093 (11)	C13—H13B	0.9800
Pd1—N1	2.098 (2)	C13—H13C	0.9800
P1—C21	1.798 (2)	C14—H14A	0.9800
P1—C15	1.814 (2)	C14—H14B	0.9800
P1—C1	1.826 (3)	C14—H14C	0.9800
N1—C6	1.357 (3)	C15—C16	1.383 (3)
N1—C2	1.369 (3)	C15—C20	1.392 (3)
C1—C2	1.506 (3)	C16—C17	1.390 (4)
C1—H1A	0.9900	C16—H16	0.9500
C1—H1B	0.9900	C17—C18	1.377 (4)
C2—C3	1.378 (3)	C17—H17	0.9500
C3—C4	1.368 (4)	C18—C19	1.375 (4)
C3—H3	0.9500	C18—H18	0.9500
C4—C5	1.380 (3)	C19—C20	1.384 (4)
C4—H4	0.9500	C19—H19	0.9500
C5—C6	1.393 (3)	C20—H20	0.9500
C5—H5	0.9500	C21—C22	1.387 (4)
C6—C7	1.496 (3)	C21—C26	1.389 (4)
C7—C8	1.400 (3)	C22—C23	1.392 (4)
C7—C12	1.405 (3)	C22—H22	0.9500
C8—C9	1.398 (4)	C23—C24	1.355 (5)
C8—C13	1.499 (4)	C23—H23	0.9500
C9—C10	1.373 (4)	C24—C25	1.366 (5)
C9—H9	0.9500	C24—H24	0.9500
C10—C11	1.368 (4)	C25—C26	1.388 (4)
C10—H10	0.9500	C25—H25	0.9500
C11—C12	1.391 (4)	C26—H26	0.9500
C11—H11	0.9500
N1—Pd1—P1	81.74 (5)	C11—C12—C7	118.4 (2)
N1—Pd1—Cl2	171.99 (5)	C11—C12—C14	119.0 (2)
P1—Pd1—Cl2	90.52 (3)	C7—C12—C14	122.5 (2)
N1—Pd1—Cl1	96.05 (5)	C8—C13—H13A	109.5
P1—Pd1—Cl1	167.92 (2)	C8—C13—H13B	109.5
Cl2—Pd1—Cl1	91.95 (3)	H13A—C13—H13B	109.5
C21—P1—C15	107.09 (11)	C8—C13—H13C	109.5
C21—P1—C1	109.32 (11)	H13A—C13—H13C	109.5
C15—P1—C1	107.36 (11)	H13B—C13—H13C	109.5
C21—P1—Pd1	114.41 (8)	C12—C14—H14A	109.5
C15—P1—Pd1	122.56 (8)	C12—C14—H14B	109.5
C1—P1—Pd1	94.68 (8)	H14A—C14—H14B	109.5
C6—N1—C2	119.13 (19)	C12—C14—H14C	109.5
C6—N1—Pd1	126.31 (15)	H14A—C14—H14C	109.5
C2—N1—Pd1	114.56 (14)	H14B—C14—H14C	109.5
C2—C1—P1	107.59 (15)	C16—C15—C20	119.4 (2)
C2—C1—H1A	110.2	C16—C15—P1	121.09 (18)
P1—C1—H1A	110.2	C20—C15—P1	119.53 (19)
C2—C1—H1B	110.2	C15—C16—C17	120.2 (2)
P1—C1—H1B	110.2	C15—C16—H16	119.9
H1A—C1—H1B	108.5	C17—C16—H16	119.9
N1—C2—C3	121.8 (2)	C18—C17—C16	119.8 (3)
N1—C2—C1	116.7 (2)	C18—C17—H17	120.1
C3—C2—C1	121.4 (2)	C16—C17—H17	120.1
C4—C3—C2	119.3 (2)	C19—C18—C17	120.4 (2)
C4—C3—H3	120.3	C19—C18—H18	119.8
C2—C3—H3	120.3	C17—C18—H18	119.8
C3—C4—C5	119.2 (2)	C18—C19—C20	120.1 (3)
C3—C4—H4	120.4	C18—C19—H19	120.0
C5—C4—H4	120.4	C20—C19—H19	120.0
C4—C5—C6	120.7 (2)	C19—C20—C15	120.1 (2)
C4—C5—H5	119.7	C19—C20—H20	120.0
C6—C5—H5	119.7	C15—C20—H20	120.0
N1—C6—C5	119.7 (2)	C22—C21—C26	119.4 (2)
N1—C6—C7	121.3 (2)	C22—C21—P1	122.7 (2)
C5—C6—C7	118.7 (2)	C26—C21—P1	117.74 (18)
C8—C7—C12	120.8 (2)	C21—C22—C23	119.2 (3)
C8—C7—C6	120.7 (2)	C21—C22—H22	120.4
C12—C7—C6	118.2 (2)	C23—C22—H22	120.4
C9—C8—C7	118.2 (2)	C24—C23—C22	120.8 (3)
C9—C8—C13	119.2 (2)	C24—C23—H23	119.6
C7—C8—C13	122.6 (2)	C22—C23—H23	119.6
C10—C9—C8	121.0 (2)	C23—C24—C25	120.7 (3)
C10—C9—H9	119.5	C23—C24—H24	119.7
C8—C9—H9	119.5	C25—C24—H24	119.7
C11—C10—C9	120.3 (2)	C24—C25—C26	119.8 (3)
C11—C10—H10	119.8	C24—C25—H25	120.1
C9—C10—H10	119.8	C26—C25—H25	120.1
C10—C11—C12	121.2 (3)	C25—C26—C21	120.0 (3)
C10—C11—H11	119.4	C25—C26—H26	120.0
C12—C11—H11	119.4	C21—C26—H26	120.0

(V) chloro[2-(2,6-dimethylphenyl)-6-(diphenylphosphanomethyl)pyridine- κ²N,P]methylpalladium(II)

Crystal data

[Pd(CH3)Cl(C26H24NP)]	F(000) = 1096
Mr = 538.32	Dx = 1.502 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2yn	Cell parameters from 23164 reflections
a = 11.507 (1) Å	θ = 1.0–30.0°
b = 12.011 (2) Å	µ = 0.97 mm^−1
c = 17.490 (2) Å	T = 173 K
β = 99.92 (5)°	Prism, yellow
V = 2381.2 (6) Å^3	0.10 × 0.08 × 0.06 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	4250 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.045
Graphite monochromator	θmax = 30.0°, θmin = 2.3°
ϕ or ω scans?	h = −16→15
6838 measured reflections	k = 0→16
6837 independent reflections	l = 0→24

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.112	H-atom parameters constrained
S = 0.91	w = 1/[σ^2(Fo^2)] where P = (Fo^2 + 2Fc^2)/3
6837 reflections	(Δ/σ)max < 0.001
280 parameters	Δρmax = 0.72 e Å^−3
0 restraints	Δρmin = −0.63 e Å^−3

Special details

Experimental. The ¹H and ³¹P{H} NMR spectra were recorded at 300.13 and 76.0 MHz, respectively, on an FT Bruker AC300, Avance 300 instrument.

Complex (V) 1H NMR (CDCl3) d: 0.80 (s, 3H, Pd—CH3), 2.01 (s, 6H, Ph(CH3)2), 4.19 (d, 2H, PCH2, 2JPH = 11.4 Hz), 7.09–7.90 (16H, aromatics); 31P{1H} NMR (CDCl3) d: 42.6 (s).

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
Pd1	0.11677 (2)	0.25415 (2)	0.110714 (16)	0.02959 (9)
Cl1	0.30199 (8)	0.21959 (8)	0.07376 (6)	0.0466 (3)
P1	−0.05236 (7)	0.26689 (7)	0.15132 (5)	0.0289 (2)
N1	0.1737 (2)	0.3362 (2)	0.22921 (16)	0.0304 (6)
C1	−0.0014 (3)	0.2373 (3)	0.2539 (2)	0.0343 (8)
H1A	−0.0650	0.2530	0.2840	0.041*
H1B	0.0209	0.1578	0.2610	0.041*
C2	0.1041 (3)	0.3104 (3)	0.2818 (2)	0.0319 (8)
C3	0.1238 (3)	0.3526 (3)	0.3561 (2)	0.0400 (9)
H3	0.0733	0.3322	0.3915	0.048*
C4	0.2163 (4)	0.4239 (4)	0.3791 (2)	0.0522 (11)
H4	0.2318	0.4526	0.4305	0.063*
C5	0.2862 (3)	0.4528 (4)	0.3255 (2)	0.0485 (11)
H5	0.3505	0.5025	0.3397	0.058*
C6	0.2630 (3)	0.4097 (3)	0.2515 (2)	0.0357 (8)
C7	0.3319 (3)	0.4532 (3)	0.1927 (2)	0.0355 (8)
C8	0.4477 (3)	0.4154 (3)	0.1920 (2)	0.0444 (10)
C9	0.5104 (4)	0.4645 (4)	0.1405 (3)	0.0541 (12)
H9	0.5891	0.4412	0.1399	0.065*
C10	0.4619 (4)	0.5462 (4)	0.0901 (3)	0.0566 (12)
H10	0.5065	0.5777	0.0546	0.068*
C11	0.3488 (4)	0.5827 (3)	0.0909 (2)	0.0498 (11)
H11	0.3156	0.6390	0.0557	0.060*
C12	0.2828 (3)	0.5378 (3)	0.1429 (2)	0.0421 (9)
C13	0.5009 (4)	0.3232 (4)	0.2433 (3)	0.0615 (13)
H13A	0.5806	0.3079	0.2335	0.092*
H13B	0.4522	0.2562	0.2326	0.092*
H13C	0.5046	0.3449	0.2977	0.092*
C14	0.1617 (4)	0.5839 (4)	0.1473 (3)	0.0592 (13)
H14A	0.1472	0.6503	0.1144	0.089*
H14B	0.1578	0.6039	0.2011	0.089*
H14C	0.1018	0.5275	0.1291	0.089*
C15	−0.1158 (3)	0.4055 (3)	0.1463 (2)	0.0319 (8)
C16	−0.1352 (4)	0.4576 (3)	0.0750 (2)	0.0459 (10)
H16	−0.1145	0.4208	0.0312	0.055*
C17	−0.1848 (4)	0.5631 (4)	0.0666 (3)	0.0554 (12)
H17	−0.2013	0.5969	0.0168	0.066*
C18	−0.2100 (4)	0.6184 (3)	0.1303 (3)	0.0571 (12)
H18	−0.2421	0.6914	0.1249	0.068*
C19	−0.1891 (4)	0.5691 (4)	0.2010 (3)	0.0582 (12)
H19	−0.2060	0.6082	0.2450	0.070*
C20	−0.1434 (3)	0.4622 (3)	0.2097 (2)	0.0445 (10)
H20	−0.1310	0.4278	0.2593	0.053*
C21	−0.1750 (3)	0.1727 (3)	0.1214 (2)	0.0302 (8)
C22	−0.2912 (3)	0.2097 (3)	0.1009 (2)	0.0393 (9)
H22	−0.3076	0.2872	0.1012	0.047*
C23	−0.3827 (3)	0.1353 (4)	0.0803 (3)	0.0532 (11)
H23	−0.4616	0.1615	0.0678	0.064*
C24	−0.3590 (4)	0.0219 (4)	0.0778 (2)	0.0507 (11)
H24	−0.4213	−0.0298	0.0632	0.061*
C25	−0.2444 (4)	−0.0144 (3)	0.0968 (3)	0.0501 (11)
H25	−0.2281	−0.0918	0.0951	0.060*
C26	−0.1528 (3)	0.0590 (3)	0.1182 (2)	0.0402 (9)
H26	−0.0743	0.0320	0.1309	0.048*
C27	0.0382 (3)	0.1836 (3)	0.0086 (2)	0.0436 (10)
H27A	0.0528	0.1032	0.0104	0.065*
H27B	0.0711	0.2163	−0.0344	0.065*
H27C	−0.0469	0.1975	0.0007	0.065*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.02577 (13)	0.02849 (15)	0.03430 (15)	−0.00068 (11)	0.00460 (9)	−0.00135 (11)
Cl1	0.0313 (5)	0.0468 (6)	0.0628 (7)	0.0032 (4)	0.0111 (4)	−0.0096 (5)
P1	0.0255 (4)	0.0290 (5)	0.0315 (5)	−0.0008 (4)	0.0027 (3)	0.0004 (4)
N1	0.0267 (14)	0.0289 (16)	0.0340 (16)	0.0015 (12)	0.0014 (12)	−0.0023 (12)
C1	0.0330 (17)	0.035 (2)	0.035 (2)	0.0013 (16)	0.0047 (15)	0.0082 (16)
C2	0.0295 (17)	0.0290 (19)	0.035 (2)	0.0049 (14)	0.0009 (15)	0.0030 (15)
C3	0.046 (2)	0.041 (2)	0.034 (2)	0.0016 (18)	0.0081 (17)	−0.0040 (17)
C4	0.060 (3)	0.061 (3)	0.034 (2)	−0.007 (2)	0.003 (2)	−0.018 (2)
C5	0.040 (2)	0.054 (3)	0.050 (3)	−0.0154 (19)	0.005 (2)	−0.019 (2)
C6	0.0314 (19)	0.033 (2)	0.042 (2)	0.0033 (15)	0.0043 (16)	−0.0025 (16)
C7	0.0322 (19)	0.031 (2)	0.042 (2)	−0.0078 (15)	0.0045 (16)	−0.0099 (16)
C8	0.038 (2)	0.039 (2)	0.057 (3)	−0.0065 (17)	0.0104 (19)	−0.0167 (19)
C9	0.040 (2)	0.053 (3)	0.075 (3)	−0.009 (2)	0.025 (2)	−0.021 (2)
C10	0.065 (3)	0.056 (3)	0.056 (3)	−0.022 (2)	0.029 (2)	−0.018 (2)
C11	0.061 (3)	0.047 (3)	0.040 (2)	−0.019 (2)	0.005 (2)	−0.0055 (19)
C12	0.041 (2)	0.039 (2)	0.045 (2)	−0.0116 (18)	0.0027 (18)	−0.0113 (18)
C13	0.042 (2)	0.054 (3)	0.086 (4)	0.008 (2)	0.004 (2)	−0.006 (3)
C14	0.046 (3)	0.056 (3)	0.071 (3)	0.006 (2)	−0.001 (2)	0.010 (2)
C15	0.0271 (17)	0.0275 (18)	0.040 (2)	−0.0042 (14)	0.0012 (15)	0.0008 (15)
C16	0.058 (3)	0.041 (2)	0.037 (2)	−0.001 (2)	0.0011 (19)	−0.0003 (18)
C17	0.059 (3)	0.041 (3)	0.061 (3)	−0.002 (2)	−0.004 (2)	0.018 (2)
C18	0.051 (3)	0.030 (2)	0.088 (4)	0.0035 (19)	0.005 (3)	0.005 (2)
C19	0.066 (3)	0.043 (3)	0.068 (3)	0.007 (2)	0.019 (3)	−0.012 (2)
C20	0.050 (2)	0.042 (2)	0.043 (2)	0.0051 (19)	0.0115 (19)	−0.0023 (18)
C21	0.0254 (17)	0.034 (2)	0.0317 (19)	−0.0034 (14)	0.0073 (14)	−0.0016 (15)
C22	0.0314 (19)	0.045 (2)	0.042 (2)	0.0045 (16)	0.0077 (16)	−0.0030 (17)
C23	0.025 (2)	0.075 (3)	0.059 (3)	−0.003 (2)	0.0046 (19)	−0.004 (2)
C24	0.043 (2)	0.063 (3)	0.046 (3)	−0.025 (2)	0.009 (2)	−0.005 (2)
C25	0.059 (3)	0.036 (2)	0.057 (3)	−0.012 (2)	0.017 (2)	−0.006 (2)
C26	0.032 (2)	0.035 (2)	0.054 (3)	−0.0023 (16)	0.0092 (18)	−0.0020 (18)
C27	0.039 (2)	0.054 (3)	0.039 (2)	−0.0073 (19)	0.0093 (18)	−0.0139 (19)

Geometric parameters (Å, º)

Pd1—Cl1	2.3681 (14)	C13—H13A	0.9800
Pd1—P1	2.189 (2)	C13—H13B	0.9800
Pd1—N1	2.286 (3)	C13—H13C	0.9800
Pd1—C27	2.042 (4)	C14—H14A	0.9800
P1—C15	1.814 (4)	C14—H14B	0.9800
P1—C21	1.815 (3)	C14—H14C	0.9800
P1—C1	1.823 (4)	C15—C16	1.378 (5)
N1—C2	1.356 (4)	C15—C20	1.384 (5)
N1—C6	1.360 (4)	C16—C17	1.387 (6)
C1—C2	1.510 (5)	C16—H16	0.9500
C1—H1A	0.9900	C17—C18	1.370 (6)
C1—H1B	0.9900	C17—H17	0.9500
C2—C3	1.377 (5)	C18—C19	1.354 (7)
C3—C4	1.372 (5)	C18—H18	0.9500
C3—H3	0.9500	C19—C20	1.385 (6)
C4—C5	1.381 (5)	C19—H19	0.9500
C4—H4	0.9500	C20—H20	0.9500
C5—C6	1.376 (5)	C21—C26	1.392 (5)
C5—H5	0.9500	C21—C22	1.396 (5)
C6—C7	1.497 (5)	C22—C23	1.380 (5)
C7—C12	1.394 (5)	C22—H22	0.9500
C7—C8	1.411 (5)	C23—C24	1.391 (6)
C8—C9	1.379 (6)	C23—H23	0.9500
C8—C13	1.489 (6)	C24—C25	1.375 (6)
C9—C10	1.372 (7)	C24—H24	0.9500
C9—H9	0.9500	C25—C26	1.375 (5)
C10—C11	1.375 (6)	C25—H25	0.9500
C10—H10	0.9500	C26—H26	0.9500
C11—C12	1.390 (5)	C27—H27A	0.9800
C11—H11	0.9500	C27—H27B	0.9800
C12—C14	1.513 (5)	C27—H27C	0.9800
C27—Pd1—P1	91.64 (11)	C8—C13—H13A	109.5
C27—Pd1—N1	170.52 (11)	C8—C13—H13B	109.5
P1—Pd1—N1	78.92 (8)	H13A—C13—H13B	109.5
C27—Pd1—Cl1	88.40 (11)	C8—C13—H13C	109.5
P1—Pd1—Cl1	173.30 (4)	H13A—C13—H13C	109.5
N1—Pd1—Cl1	101.07 (8)	H13B—C13—H13C	109.5
C15—P1—C21	105.80 (15)	C12—C14—H14A	109.5
C15—P1—C1	106.57 (17)	C12—C14—H14B	109.5
C21—P1—C1	105.33 (16)	H14A—C14—H14B	109.5
C15—P1—Pd1	114.90 (11)	C12—C14—H14C	109.5
C21—P1—Pd1	123.61 (11)	H14A—C14—H14C	109.5
C1—P1—Pd1	98.77 (12)	H14B—C14—H14C	109.5
C2—N1—C6	117.3 (3)	C16—C15—C20	118.5 (3)
C2—N1—Pd1	114.0 (2)	C16—C15—P1	117.5 (3)
C6—N1—Pd1	128.6 (2)	C20—C15—P1	124.0 (3)
C2—C1—P1	108.0 (2)	C15—C16—C17	120.7 (4)
C2—C1—H1A	110.1	C15—C16—H16	119.7
P1—C1—H1A	110.1	C17—C16—H16	119.7
C2—C1—H1B	110.1	C18—C17—C16	119.8 (4)
P1—C1—H1B	110.1	C18—C17—H17	120.1
H1A—C1—H1B	108.4	C16—C17—H17	120.1
N1—C2—C3	122.4 (3)	C19—C18—C17	120.1 (4)
N1—C2—C1	116.7 (3)	C19—C18—H18	120.0
C3—C2—C1	120.8 (3)	C17—C18—H18	120.0
C4—C3—C2	120.0 (4)	C18—C19—C20	120.6 (4)
C4—C3—H3	120.0	C18—C19—H19	119.7
C2—C3—H3	120.0	C20—C19—H19	119.7
C3—C4—C5	118.1 (4)	C15—C20—C19	120.2 (4)
C3—C4—H4	120.9	C15—C20—H20	119.9
C5—C4—H4	120.9	C19—C20—H20	119.9
C6—C5—C4	120.2 (4)	C26—C21—C22	118.5 (3)
C6—C5—H5	119.9	C26—C21—P1	119.0 (3)
C4—C5—H5	119.9	C22—C21—P1	122.6 (3)
N1—C6—C5	121.9 (3)	C23—C22—C21	121.0 (4)
N1—C6—C7	119.5 (3)	C23—C22—H22	119.5
C5—C6—C7	118.4 (3)	C21—C22—H22	119.5
C12—C7—C8	120.7 (4)	C22—C23—C24	119.8 (4)
C12—C7—C6	118.6 (3)	C22—C23—H23	120.1
C8—C7—C6	120.5 (4)	C24—C23—H23	120.1
C9—C8—C7	118.0 (4)	C25—C24—C23	119.2 (4)
C9—C8—C13	120.4 (4)	C25—C24—H24	120.4
C7—C8—C13	121.6 (4)	C23—C24—H24	120.4
C10—C9—C8	121.6 (4)	C24—C25—C26	121.4 (4)
C10—C9—H9	119.2	C24—C25—H25	119.3
C8—C9—H9	119.2	C26—C25—H25	119.3
C9—C10—C11	120.2 (4)	C25—C26—C21	120.2 (4)
C9—C10—H10	119.9	C25—C26—H26	119.9
C11—C10—H10	119.9	C21—C26—H26	119.9
C10—C11—C12	120.5 (4)	Pd1—C27—H27A	109.5
C10—C11—H11	119.7	Pd1—C27—H27B	109.5
C12—C11—H11	119.7	H27A—C27—H27B	109.5
C11—C12—C7	118.9 (4)	Pd1—C27—H27C	109.5
C11—C12—C14	120.2 (4)	H27A—C27—H27C	109.5
C7—C12—C14	120.9 (4)	H27B—C27—H27C	109.5