Dichlorido{N-[2-(diphenyl­phos­phanyl)benzyl­idene]-2-methyl­aniline}palladium(II) acetonitrile monosolvate

The title imino-phosphine compound, [PdCl₂(C₂₆H₂₂NP)]·CH₃CN, was prepared by reaction of N-[2-(diphenyl­phos­phan­yl)benzyl­idene]-2-methyl­aniline with dichlorido(cyclo­­octa-1,5-diene)palladium(II) in dry CH₂Cl₂. The Pd^II cation is coordinated by the P and N atoms of the bidentate chelating ligand and by two chloride anions, generating a distorted square-planar coordination geometry. There is a detectable trans influence for the chloride ligands. The methyl group present in this structure has an influence on the crystal packing.

S1. Comment

Imino–phosphine complexes have been studied since the early 1990s (Newkome, 1993; Ghilardi et al., 1992). Their preparation is versatile because a wide range of amines and aldehydes of varying steric bulk are either available commercially or can be easily synthesized (Mogorosi et al. 2011; Nobre & Monteiro, 2009; Pellagati et al., 2005; Newkome, 1993; Ghilardi et al., 1992; Vaughan et al., 2011; Puri et al., 2011; Doherty et al., 2002; Onani et al., 2010; Motswainyana et al., 2012). The soft P atom coordinates strongly to soft metals, while the hard N atom is weakly coordinated and therefore more easily displaced, thus allowing hemilability. The hemilability of these ligands provides a unique reversible protection of coordination, an important property of ligands which leads to improved catalytic reactions (Ojwach et al., 2007).

Phosphine-based complexes have been less well explored for their potential to inhibit tumour growth, possibly due to their susceptibility to oxidation, which makes them very difficult to handle in air. In our attempt to prepare new imino–phosphine palladium(II) complexes, which could induce apoptosis in tumour cells, we synthesized and crystallized the title compound, (I).

Compound (I) proved to possess remarkable antiproliferative activities against the human breast (MCF-7) and human colon (HT-29) cancer cell lines compared with the reference drug cisplatin. The recorded cytotoxic activities could be attributed to the higher aqueous solubility of this palladium(II) complex, which makes it easier to dissociate in solution, thereby making the compound bio-available (Gao et al., 2009). The imino–phosphine ligand N-[2-(diphenylphosphanyl)benzylidene]-2-methylaniline forms a six-membered ring around the metal centre, which stabilizes the complex during biological investigations, probably resulting in the observed antitumour profiles (Bacchi et al., 2000).

The Pd^II cation in (I) (Fig. 1) is coordinated by the P and N atoms of the imino–phosphine ligand and two chloride anions, generating a distorted square-planar coordination geometry around the metal centre. The bond angles around Pd1 (Table 1) describe the observed distorted square-planar geometry, while also indicating some ring strain induced by the chelating nature of the bidentate ligand. The Pd—C1 bond lengths (Table 1) are in good agreement with the average Pd—Cl bond length of 2.298 (15) Å for known palladium(II) complexes (Allen, 2002; Chiririwa & Muller, 2012). The average Pd—N and Pd—P bond lengths (Table 1) also compare well with literature values (Chiririwa & Muller, 2012; Motswainyana et al., 2012). There is a detectable trans influence for the chloride anions, since the Pd1—Cl1 bond is significantly longer than Pd1—Cl2, thus reflecting the stronger trans influence of the diphenylphosphanyl group compared with an amine (Doherty et al., 2002). The Pd^II cation deviates by 0.0026 (3) Å from the best least-squares plane through atoms P1, N1, Cl1 and Cl2. This plane makes an angle of 46.57 (11)° with the best least-squares plane through the C2–C7 ring. The Pd-containing six-membered ring has a screw-boat conformation, with atoms Pd1 and P1 deviating from the plane through the other four atoms.

Despite the presence of several phenyl groups, no π–π interactions are present in the crystal packing of (I); only a number of weaker C—H···π contacts are observed [C23—H23···Cg1ⁱ = 2.84 Å and C26—H26A···Cg2ⁱⁱ = 2.93 Å; Cg1 and Cg2 are the centroids of the C2–C7 and C14–C19 rings, respectively; symmetry codes: (i) -x + 3/2, y - 1/2, -z + 3/2; (ii) -x + 3/2, y + 1/2, -z + 3/2].

The asymmetric unit of (I) contains one solvent molecule of acetonitrile, which was essential during the crystallization experiments to obtain good quality crystals. Two acetonitrile molecules occupy relatively large voids of 233 ų, and there are four such voids in the unit cell. In the packing, the position of the acetonitrile is fixed on one side by a C27—H27C···Cl2 interaction [H27C···Cl2ⁱⁱⁱ = 2.700 Å; symmetry code: (iii) -x + 1, -y + 2, -z + 1] and by a weak π-interaction (C27—H27B···Cg2 = 3.29 Å) (Fig. 2). Furthermore, atom N2 interacts with atoms H11, H16 and H22 of neighbouring molecules [N2···H11^iv = 2.756 Å, N2···H16^v = 2.652 Å and N2···H22^vi = 2.775 Å; symmetry codes: (iv) x, y - 1, z; (v) -x + 1, y, -z + 1/2; (vi) -x + 1, -y + 1, -z + 1]. Despite these interactions, the acetonitrile molecules show a slight disorder, as indicated by the difference electron-density map (e.g. peaks of 0.63, 0.46 and -0.52 e Å^-3 close to acetonitrile).

The shortest interactions for both Cl atoms are C—H···Cl interactions (Fig. 3) [Cl1···H13ⁱⁱⁱ = 2.86 Å, Cl1···H17^vii = 2.75 Å, Cl2···H1ⁱⁱ = 2.60 Å, Cl2···H5^viii = 2.83 Å and Cl2···H27Cⁱⁱⁱ = 2.700 Å; symmetry codes: (vii) x, y + 1, z; (viii) x, -y + 2, z + 1/2].

The Cambridge Structural Database (CSD, Version 5.34; Allen, 2002) contains 18 structures containing a dichlorido{[2-(diphenylphosphanyl)benzylidene]amine}palladium(II) group. The angles between the best planes through the benzene ring and the PdCl₂NP group range between 27.6 and 62.5°. The structure with refcode XUWHUG (Koprowski et al., 2002) is almost identical to (I), only missing the ortho-methyl group, but crystallizes in the space group P1. A fit of the two structures results in an r.m.s. deviation of 0.263 Å. As in (I), both Cl atoms attached to Pd also interact with H—C bonds. However, the interaction of the Cl atom equivalent to Cl2 in (I) with the H atom attached to the C atom equivalent to C25 in (I) is not possible, due to the presence of the methyl group. Instead, atom Cl2 interacts with atom Cl3 of the dichloromethane present in the packing, and a different crystal packing is observed for XUWHUG which also contains π–π interactions.

Related literature

For related literature, see: Allen (2002); Bacchi et al. (2000); Chiririwa & Muller (2012); Doherty et al. (2002); Gao et al. (2009); Ghilardi et al. (1992); Koprowski et al. (2002); Mogorosi et al. (2011); Motswainyana et al. (2012); Newkome (1993); Nobre & Monteiro (2009); Ojwach et al. (2007); Onani et al. (2010); Pellagati et al. (2005); Puri et al. (2011); Vaughan et al. (2011).

S2. Experimental

All reactions were carried out under a nitrogen atmosphere using a dual vacuum/nitrogen line and standard Schlenk techniques. Solvents were dried and purified by heating under reflux and under a nitrogen atmosphere in the presence of a suitable drying agent.

For the preparation of N-[2-(diphenylphosphanyl)benzylidene]-2-methylaniline, 2-methylaniline (0.1030 g, 0.961 mmol) was added dropwise to a solution of 2-(diphenylphosphanyl)benzaldehyde (0.2790 g, 0.961 mmol) in dry CH₂Cl₂ (10 ml). Anhydrous magnesium sulfate (~0.5 g) was added to the solution, after which the reaction was stirred at room temperature for 20 h. The resulting yellow mixture was filtered to obtain a yellow solution, which gave a yellow oil upon evaporation of the solvent (yield 0.2990 g, 82%). Spectroscopic analysis: IR (Nujol, ν, cm^-1): 1622 (C═N imine), 1593, 1585, 1505 (C═C phenyl), 1435 (P—Ph). Analysis, calculated for C₂₆H₂₂NP: C 82.30, H 5.84, N 3.69%; found: C 82.04, H 5.93, N 3.55%.

The preparation of (I) followed the synthetic protocol of Koprowski et al. (2002), with minor modifications at the precipitation stage of the product. Crystals of (I) suitable for X-ray crystallographic analysis were grown by slow evaporation of an acetonitrile solution of the complex (yield 0.0697 g, 75%). Spectroscopic analysis: IR (Nujol, ν, cm^-1): 1614 (C═N imine), 1585, 1560, 1502 (C═C phenyl). Analysis, calculated for C₂₆H₂₂Cl₂NPPd: C 56.09, H 3.98, N 2.52%; found: C 55.83, H 4.22, N 2.77%.

S3. Refinement

All H atoms were placed in idealized positions and refined in riding mode, with C—H = 0.93 (aromatic) or 0.96 Å (methyl), and with U_iso(H) = 1.2 or 1.5U_eq(C).

Computing details

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The interaction of the acetonitrile solvent molecules with neighbouring complex molecules in (I). Dashed lines indicate the various interactions. The centroid of the C14–C19 ring is indicated by a solid dot (yellow in the electronic version of the paper). For clarity, only the H atoms involved in the interactions are shown. [Symmetry codes: (iii) -x + 1, -y + 2, -z + 1; (iv) x, y - 1, z; (v) -x + 1, y, -z + 1/2; (vi) -x + 1, -y + 1, -z + 1.]
	Fig. 3. C—H···Cl interations (dashed lines) in the crystal packing of (I). For clarity, only the H atoms involved in the interactions are shown. [Symmetry codes: (ii) -x + 3/2, y + 1/2, -z + 3/2; (iii) -x + 1, -y + 2, -z + 1; (vii) x, y + 1, z; (viii) x, -y + 2, z + 1/2.]

Dichlorido{N-[2-(diphenylphosphanyl)benzylidene]-2-methylaniline}palladium(II) acetonitrile monosolvate

Crystal data

[PdCl2(C26H22NP)]·C2H3N	F(000) = 2416
Mr = 597.77	Dx = 1.501 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 32.350 (3) Å	Cell parameters from 5198 reflections
b = 9.9963 (3) Å	θ = 2.9–26.3°
c = 20.8851 (16) Å	µ = 0.98 mm^−1
β = 128.423 (13)°	T = 100 K
V = 5291.3 (12) Å^3	Block, yellow
Z = 8	0.2 × 0.2 × 0.2 mm

Data collection

Agilent SuperNova diffractometer (single source at offset, Eos detector)	5391 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	4721 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.025
Detector resolution: 15.9631 pixels mm^-1	θmax = 26.4°, θmin = 2.9°
ω scans	h = −40→34
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −12→10
Tmin = 0.983, Tmax = 1.000	l = −26→25
10592 measured reflections

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.075	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0255P)^2 + 11.5559P] where P = (Fo^2 + 2Fc^2)/3
5391 reflections	(Δ/σ)max = 0.003
309 parameters	Δρmax = 0.75 e Å^−3
0 restraints	Δρmin = −0.52 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
Pd1	0.637890 (8)	1.06809 (2)	0.634944 (12)	0.01449 (7)
Cl1	0.57031 (3)	1.21650 (7)	0.58060 (4)	0.02303 (16)
Cl2	0.67864 (3)	1.15859 (7)	0.76645 (4)	0.02010 (15)
P1	0.60233 (3)	0.98303 (7)	0.51296 (4)	0.01688 (15)
N1	0.69700 (9)	0.9302 (2)	0.68102 (13)	0.0183 (5)
N2	0.38905 (17)	0.4779 (4)	0.1631 (3)	0.0693 (11)
C1	0.71814 (11)	0.8903 (3)	0.64898 (17)	0.0209 (6)
H1	0.7460	0.8304	0.6799	0.025*
C2	0.70380 (11)	0.9276 (3)	0.56977 (17)	0.0201 (6)
C3	0.65416 (11)	0.9765 (3)	0.50325 (16)	0.0182 (6)
C4	0.64503 (12)	1.0060 (3)	0.43027 (17)	0.0222 (6)
H4	0.6121	1.0377	0.3860	0.027*
C5	0.68440 (12)	0.9886 (3)	0.42290 (18)	0.0266 (7)
H5	0.6781	1.0107	0.3743	0.032*
C6	0.73281 (13)	0.9387 (3)	0.4874 (2)	0.0282 (7)
H6	0.7591	0.9268	0.4822	0.034*
C7	0.74248 (12)	0.9062 (3)	0.56015 (19)	0.0251 (7)
H7	0.7749	0.8700	0.6029	0.030*
C8	0.54572 (11)	1.0641 (3)	0.42268 (16)	0.0198 (6)
C9	0.54967 (12)	1.1958 (3)	0.40363 (17)	0.0243 (6)
H9	0.5818	1.2404	0.4357	0.029*
C10	0.50546 (12)	1.2584 (3)	0.33696 (18)	0.0285 (7)
H10	0.5082	1.3451	0.3237	0.034*
C11	0.45714 (12)	1.1941 (3)	0.28948 (18)	0.0302 (7)
H11	0.4276	1.2377	0.2449	0.036*
C12	0.45293 (13)	1.0648 (3)	0.30838 (18)	0.0304 (7)
H12	0.4205	1.0214	0.2765	0.036*
C13	0.49723 (11)	0.9997 (3)	0.37519 (17)	0.0250 (6)
H13	0.4943	0.9128	0.3880	0.030*
C14	0.58476 (10)	0.8086 (3)	0.50583 (16)	0.0190 (6)
C15	0.59009 (12)	0.7175 (3)	0.46123 (18)	0.0266 (7)
H15	0.6022	0.7464	0.4332	0.032*
C16	0.57752 (12)	0.5837 (3)	0.4580 (2)	0.0305 (7)
H16	0.5813	0.5231	0.4282	0.037*
C17	0.55932 (11)	0.5412 (3)	0.4995 (2)	0.0300 (7)
H17	0.5509	0.4516	0.4977	0.036*
C18	0.55362 (11)	0.6306 (3)	0.54345 (19)	0.0272 (7)
H18	0.5415	0.6011	0.5713	0.033*
C19	0.56584 (10)	0.7646 (3)	0.54659 (17)	0.0225 (6)
H19	0.5614	0.8249	0.5758	0.027*
C20	0.71923 (12)	0.8740 (3)	0.76071 (17)	0.0239 (6)
C21	0.68644 (14)	0.7899 (3)	0.7662 (2)	0.0311 (7)
H21	0.6518	0.7735	0.7203	0.037*
C22	0.70622 (14)	0.7324 (3)	0.8402 (2)	0.0330 (8)
H22	0.6857	0.6743	0.8447	0.040*
C23	0.75659 (14)	0.7626 (3)	0.9067 (2)	0.0333 (8)
H23	0.7698	0.7247	0.9568	0.040*
C24	0.78840 (13)	0.8462 (3)	0.9028 (2)	0.0347 (8)
H24	0.8224	0.8643	0.9497	0.042*
C25	0.76964 (13)	0.9056 (3)	0.82715 (19)	0.0299 (7)
C26	0.80273 (13)	0.9990 (4)	0.8220 (2)	0.0422 (9)
H26A	0.8274	1.0419	0.8740	0.063*
H26B	0.7807	1.0654	0.7811	0.063*
H26C	0.8216	0.9506	0.8077	0.063*
C27	0.43269 (18)	0.6835 (6)	0.2598 (3)	0.0827 (17)
H27A	0.4461	0.7419	0.2401	0.124*
H27B	0.4612	0.6549	0.3143	0.124*
H27C	0.4069	0.7302	0.2602	0.124*
C28	0.40812 (17)	0.5665 (5)	0.2063 (3)	0.0509 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.01842 (11)	0.01280 (11)	0.01271 (11)	−0.00138 (8)	0.00990 (9)	0.00025 (8)
Cl1	0.0241 (3)	0.0242 (4)	0.0199 (3)	0.0057 (3)	0.0132 (3)	0.0033 (3)
Cl2	0.0244 (3)	0.0203 (3)	0.0149 (3)	−0.0019 (3)	0.0119 (3)	−0.0026 (3)
P1	0.0232 (4)	0.0133 (3)	0.0138 (3)	−0.0027 (3)	0.0113 (3)	−0.0001 (3)
N1	0.0247 (12)	0.0167 (12)	0.0152 (11)	0.0030 (10)	0.0132 (10)	0.0034 (10)
N2	0.085 (3)	0.047 (2)	0.088 (3)	−0.005 (2)	0.059 (3)	0.010 (2)
C1	0.0255 (15)	0.0170 (14)	0.0201 (14)	0.0008 (12)	0.0141 (12)	0.0020 (12)
C2	0.0300 (15)	0.0140 (13)	0.0219 (14)	0.0000 (12)	0.0188 (13)	0.0007 (12)
C3	0.0270 (14)	0.0127 (13)	0.0183 (13)	−0.0046 (12)	0.0158 (12)	−0.0032 (11)
C4	0.0319 (16)	0.0167 (14)	0.0188 (14)	−0.0067 (13)	0.0161 (13)	−0.0030 (12)
C5	0.0443 (18)	0.0191 (15)	0.0255 (15)	−0.0054 (14)	0.0262 (15)	−0.0023 (13)
C6	0.0436 (18)	0.0222 (16)	0.0367 (18)	−0.0007 (15)	0.0337 (16)	−0.0014 (14)
C7	0.0315 (16)	0.0209 (15)	0.0278 (16)	0.0005 (13)	0.0208 (14)	−0.0009 (13)
C8	0.0250 (14)	0.0198 (14)	0.0142 (13)	0.0004 (13)	0.0121 (12)	−0.0005 (12)
C9	0.0327 (16)	0.0181 (14)	0.0183 (14)	−0.0020 (13)	0.0139 (13)	−0.0010 (12)
C10	0.0425 (18)	0.0190 (15)	0.0212 (15)	0.0021 (14)	0.0184 (14)	0.0041 (13)
C11	0.0360 (17)	0.0286 (17)	0.0190 (15)	0.0066 (15)	0.0136 (14)	0.0056 (14)
C12	0.0297 (16)	0.0340 (18)	0.0190 (15)	−0.0027 (15)	0.0110 (13)	0.0000 (14)
C13	0.0292 (15)	0.0239 (16)	0.0178 (14)	−0.0033 (14)	0.0126 (13)	0.0024 (13)
C14	0.0215 (14)	0.0148 (13)	0.0149 (13)	−0.0029 (12)	0.0084 (11)	0.0012 (11)
C15	0.0365 (17)	0.0215 (16)	0.0249 (15)	−0.0097 (14)	0.0206 (14)	−0.0053 (13)
C16	0.0365 (18)	0.0190 (16)	0.0305 (17)	−0.0061 (14)	0.0182 (15)	−0.0060 (13)
C17	0.0239 (15)	0.0174 (15)	0.0356 (18)	−0.0053 (13)	0.0119 (14)	0.0033 (14)
C18	0.0222 (15)	0.0258 (16)	0.0325 (17)	−0.0045 (13)	0.0165 (14)	0.0077 (14)
C19	0.0187 (14)	0.0234 (15)	0.0237 (15)	−0.0009 (12)	0.0123 (12)	0.0024 (13)
C20	0.0359 (16)	0.0209 (15)	0.0209 (14)	0.0131 (14)	0.0207 (14)	0.0075 (13)
C21	0.057 (2)	0.0197 (15)	0.0364 (18)	0.0144 (16)	0.0385 (17)	0.0108 (14)
C22	0.047 (2)	0.0278 (17)	0.0385 (19)	0.0070 (16)	0.0337 (17)	0.0076 (15)
C23	0.050 (2)	0.0295 (18)	0.0346 (18)	0.0129 (16)	0.0332 (17)	0.0081 (15)
C24	0.0313 (17)	0.0335 (19)	0.0304 (17)	0.0083 (16)	0.0147 (15)	−0.0006 (15)
C25	0.0364 (17)	0.0268 (17)	0.0262 (16)	0.0079 (15)	0.0192 (15)	0.0049 (14)
C26	0.0329 (18)	0.052 (2)	0.0304 (18)	0.0002 (18)	0.0141 (15)	0.0054 (18)
C27	0.060 (3)	0.119 (5)	0.056 (3)	0.019 (3)	0.030 (2)	−0.028 (3)
C28	0.056 (3)	0.063 (3)	0.044 (2)	0.019 (2)	0.036 (2)	0.015 (2)

Geometric parameters (Å, º)

Pd1—Cl1	2.2770 (7)	C12—C13	1.393 (4)
Pd1—Cl2	2.3664 (7)	C13—H13	0.9300
Pd1—P1	2.2122 (8)	C14—C15	1.388 (4)
Pd1—N1	2.049 (2)	C14—C19	1.393 (4)
P1—C3	1.811 (3)	C15—H15	0.9300
P1—C8	1.809 (3)	C15—C16	1.387 (4)
P1—C14	1.811 (3)	C16—H16	0.9300
N1—C1	1.282 (3)	C16—C17	1.383 (4)
N1—C20	1.454 (3)	C17—H17	0.9300
N2—C28	1.134 (5)	C17—C18	1.373 (5)
C1—H1	0.9300	C18—H18	0.9300
C1—C2	1.462 (4)	C18—C19	1.386 (4)
C2—C3	1.405 (4)	C19—H19	0.9300
C2—C7	1.402 (4)	C20—C21	1.413 (4)
C3—C4	1.392 (4)	C20—C25	1.368 (4)
C4—H4	0.9300	C21—H21	0.9300
C4—C5	1.385 (4)	C21—C22	1.378 (4)
C5—H5	0.9300	C22—H22	0.9300
C5—C6	1.376 (4)	C22—C23	1.365 (5)
C6—H6	0.9300	C23—H23	0.9300
C6—C7	1.386 (4)	C23—C24	1.367 (5)
C7—H7	0.9300	C24—H24	0.9300
C8—C9	1.404 (4)	C24—C25	1.422 (4)
C8—C13	1.387 (4)	C25—C26	1.474 (5)
C9—H9	0.9300	C26—H26A	0.9600
C9—C10	1.379 (4)	C26—H26B	0.9600
C10—H10	0.9300	C26—H26C	0.9600
C10—C11	1.383 (4)	C27—H27A	0.9600
C11—H11	0.9300	C27—H27B	0.9600
C11—C12	1.382 (4)	C27—H27C	0.9600
C12—H12	0.9300	C27—C28	1.464 (7)
Cl1—Pd1—Cl2	89.95 (3)	C11—C12—C13	120.0 (3)
P1—Pd1—Cl1	91.45 (3)	C13—C12—H12	120.0
P1—Pd1—Cl2	178.15 (3)	C8—C13—C12	120.1 (3)
N1—Pd1—Cl1	178.15 (7)	C8—C13—H13	120.0
N1—Pd1—Cl2	91.61 (7)	C12—C13—H13	120.0
N1—Pd1—P1	87.01 (7)	C15—C14—P1	121.6 (2)
C3—P1—Pd1	106.73 (9)	C15—C14—C19	119.2 (3)
C3—P1—C14	102.78 (13)	C19—C14—P1	119.2 (2)
C8—P1—Pd1	119.56 (9)	C14—C15—H15	119.7
C8—P1—C3	107.90 (13)	C16—C15—C14	120.7 (3)
C8—P1—C14	106.41 (13)	C16—C15—H15	119.7
C14—P1—Pd1	112.13 (9)	C15—C16—H16	120.3
C1—N1—Pd1	127.53 (19)	C17—C16—C15	119.5 (3)
C1—N1—C20	115.6 (2)	C17—C16—H16	120.3
C20—N1—Pd1	116.78 (17)	C16—C17—H17	119.8
N1—C1—H1	116.0	C18—C17—C16	120.3 (3)
N1—C1—C2	127.9 (3)	C18—C17—H17	119.8
C2—C1—H1	116.0	C17—C18—H18	119.7
C3—C2—C1	124.9 (3)	C17—C18—C19	120.5 (3)
C7—C2—C1	116.1 (3)	C19—C18—H18	119.7
C7—C2—C3	119.0 (3)	C14—C19—H19	120.1
C2—C3—P1	118.1 (2)	C18—C19—C14	119.8 (3)
C4—C3—P1	122.3 (2)	C18—C19—H19	120.1
C4—C3—C2	119.4 (3)	C21—C20—N1	117.4 (3)
C3—C4—H4	119.6	C25—C20—N1	120.1 (3)
C5—C4—C3	120.7 (3)	C25—C20—C21	122.5 (3)
C5—C4—H4	119.6	C20—C21—H21	120.3
C4—C5—H5	119.9	C22—C21—C20	119.3 (3)
C6—C5—C4	120.1 (3)	C22—C21—H21	120.3
C6—C5—H5	119.9	C21—C22—H22	120.7
C5—C6—H6	119.9	C23—C22—C21	118.5 (3)
C5—C6—C7	120.1 (3)	C23—C22—H22	120.7
C7—C6—H6	119.9	C22—C23—H23	118.6
C2—C7—H7	119.7	C22—C23—C24	122.8 (3)
C6—C7—C2	120.5 (3)	C24—C23—H23	118.6
C6—C7—H7	119.7	C23—C24—H24	119.9
C9—C8—P1	120.2 (2)	C23—C24—C25	120.3 (3)
C13—C8—P1	120.0 (2)	C25—C24—H24	119.9
C13—C8—C9	119.6 (3)	C20—C25—C24	116.6 (3)
C8—C9—H9	120.3	C20—C25—C26	122.3 (3)
C10—C9—C8	119.5 (3)	C24—C25—C26	121.1 (3)
C10—C9—H9	120.3	H27A—C27—H27B	109.5
C9—C10—H10	119.5	H27A—C27—H27C	109.5
C9—C10—C11	120.9 (3)	H27B—C27—H27C	109.5
C11—C10—H10	119.5	C28—C27—H27A	109.5
C10—C11—H11	120.1	C28—C27—H27B	109.5
C12—C11—C10	119.8 (3)	C28—C27—H27C	109.5
C12—C11—H11	120.1	N2—C28—C27	178.0 (5)
C11—C12—H12	120.0
Pd1—P1—C3—C2	45.0 (2)	C3—P1—C14—C15	−29.3 (3)
Pd1—P1—C3—C4	−141.1 (2)	C3—P1—C14—C19	150.1 (2)
Pd1—P1—C8—C9	61.7 (3)	C3—C2—C7—C6	3.0 (4)
Pd1—P1—C8—C13	−113.7 (2)	C3—C4—C5—C6	1.5 (4)
Pd1—P1—C14—C15	−143.6 (2)	C4—C5—C6—C7	−0.3 (5)
Pd1—P1—C14—C19	35.9 (2)	C5—C6—C7—C2	−2.0 (5)
Pd1—N1—C1—C2	−3.4 (4)	C7—C2—C3—P1	172.3 (2)
Pd1—N1—C20—C21	68.0 (3)	C7—C2—C3—C4	−1.8 (4)
Pd1—N1—C20—C25	−110.6 (3)	C8—P1—C3—C2	174.7 (2)
Cl1—Pd1—P1—C3	131.11 (10)	C8—P1—C3—C4	−11.4 (3)
Cl1—Pd1—P1—C8	8.46 (11)	C8—P1—C14—C15	84.0 (3)
Cl1—Pd1—P1—C14	−117.09 (10)	C8—P1—C14—C19	−96.6 (2)
Cl2—Pd1—N1—C1	−140.8 (2)	C8—C9—C10—C11	1.1 (5)
Cl2—Pd1—N1—C20	36.6 (2)	C9—C8—C13—C12	0.9 (4)
P1—Pd1—N1—C1	37.9 (2)	C9—C10—C11—C12	−0.6 (5)
P1—Pd1—N1—C20	−144.6 (2)	C10—C11—C12—C13	0.1 (5)
P1—C3—C4—C5	−174.3 (2)	C11—C12—C13—C8	−0.3 (5)
P1—C8—C9—C10	−176.7 (2)	C13—C8—C9—C10	−1.3 (4)
P1—C8—C13—C12	176.3 (2)	C14—P1—C3—C2	−73.1 (2)
P1—C14—C15—C16	178.6 (2)	C14—P1—C3—C4	100.7 (2)
P1—C14—C19—C18	−178.2 (2)	C14—P1—C8—C9	−170.1 (2)
N1—Pd1—P1—C3	−49.93 (11)	C14—P1—C8—C13	14.5 (3)
N1—Pd1—P1—C8	−172.58 (13)	C14—C15—C16—C17	0.2 (5)
N1—Pd1—P1—C14	61.88 (12)	C15—C14—C19—C18	1.2 (4)
N1—C1—C2—C3	−23.0 (5)	C15—C16—C17—C18	0.1 (5)
N1—C1—C2—C7	159.9 (3)	C16—C17—C18—C19	0.2 (5)
N1—C20—C21—C22	178.7 (3)	C17—C18—C19—C14	−0.9 (4)
N1—C20—C25—C24	−179.9 (3)	C19—C14—C15—C16	−0.9 (4)
N1—C20—C25—C26	1.8 (5)	C20—N1—C1—C2	179.1 (3)
C1—N1—C20—C21	−114.3 (3)	C20—C21—C22—C23	2.2 (5)
C1—N1—C20—C25	67.2 (4)	C21—C20—C25—C24	1.7 (5)
C1—C2—C3—P1	−4.7 (4)	C21—C20—C25—C26	−176.7 (3)
C1—C2—C3—C4	−178.7 (3)	C21—C22—C23—C24	−0.8 (5)
C1—C2—C7—C6	−179.8 (3)	C22—C23—C24—C25	−0.3 (5)
C2—C3—C4—C5	−0.5 (4)	C23—C24—C25—C20	−0.1 (5)
C3—P1—C8—C9	−60.4 (3)	C23—C24—C25—C26	178.2 (3)
C3—P1—C8—C13	124.2 (2)	C25—C20—C21—C22	−2.7 (5)