cis-Di­chloro­(di­methyl­aminomethyl­ene)­(tri­phenyl­phosphine)palladium(II) acetone solvate

The synthesis and X-ray structural analysis of the title compound, [PdCl₂(C₃H₇N)(C₁₈H₁₅P)]·C₃H₆O, are described. The crystal structure contains discrete monomeric mol­ecules of the carbene complex and solvent mol­ecules separated by normal van der Waals distances. The Pd atom is four-coordinate in an essentially square-planar environment, with the chlorine ligands mutually cis; Pd-P = 2.2495 (7), Pd-Cl = 2.3508 (7) and 2.3600 (7), Pd-C 1.948 (2) and N-C(carbene) 1.274 (3) Å.

S1. Comment

The reaction of the Vilsmeier salt, chloromethylenedimethylammonium chloride, with formally low-valent nucleophilic transition metal species has been used for the synthesis of a range of transition metal dimethyaminomethylene complexes (Cucciolito et al., 1999; Hartshorn et al., 1978; Rendina et al., 1995).

We have now used this reaction to prepare the title palladium complex, (I), according to the following sequence (dba = dibenzylidene acetone):

1/2Pd₂(dba)₃·CHCl₃ + PPh₃ + [ClCH=NMe₂]⁺Cl^- → cis-[(Ph₃P)Pd(CHNMe₂)Cl₂] + 3/2dba + 1/2 CHCl₃

Complex (I) was required for comparison with the platinum analogue, cis-[(Ph₃P)Pt(CHNMe₂)Cl₂], (II), which has been obtained by two different routes (Barefield et al., 1982; Ferguson et al., 1999), and for which an X-ray crystallographic study has been reported (Barefield et al., 1982).

The crystal structure of (I) contains discrete monomeric molecules of the carbene complex and solvent molecules separated by normal van der Waals distances. Principal dimensions are collected in Table 1 and mean-plane data are in the CIF. The Pd atom is four-coordinate in an essentially square-planar environment with the chlorine ligands mutually cis. The framework atoms of the carbene ligand (C1/N1/C2/C3) are close to being coplanar, and the dihedral angle between this plane and the coordination plane (Pd1/P1/Cl1/Cl2/C1) is 72.30 (10)° [cf. 84° for the Pt analogue (II)].

The interatomic distances in (I) are very similar to those reported (Barefield et al., 1982) for (II), except that the M—P bond length is somewhat greater for M = Pd [2.2495 (7) Å] than for M = Pt [2.220 (2) Å]. Similar differences have been found for other pairs of Pd and Pt complexes containing phosphine ligands (McCrindle et al., 1995). The Pd1—C1 [1.948 (2) Å] and C1—N1 [1.274 (3) Å] bonds are relatively short, consistent with π-bonding within the metal–carbene moiety comparable with those observed in other Pd–carbene complexes (Dixon et al., 1995).

S2. Experimental

A solution of Pd₂(dba)₃·CHCl₃ (517.5 mg, 0.500 mmol) and PPh₃ (262.3 mg, 1.00 mmol) in dry CH₂Cl₂ (20 ml) was added dropwise to a cooled (263 K) suspension of [ClHC═CNMe₂]Cl [generated in situ from dimethylformamide (80 mg, 1.1 mmol) and oxalyl chloride (127 mg, 1.00 mmol) in CH₂Cl₂ (3 ml) with stirring under nitrogen. The temperature of the reaction mixture was allowed to rise to ambient and stirring was continued for 16 h. The solvent was then removed in vacuo, the residue was washed with benzene to remove dibenzylideneacetone, and the insoluble fraction was crystallized from CH₂Cl₂ /pentane to give cis-[(Ph₃P)Pd(CHNMe₂)Cl₂] as very fine white needles (194.5 mg, 39.1% yield). Analysis calculated for C₂₁H₂₂Cl₂NPPd: C 50.78, H 4.46, N 2.82%; found: C 50.90, H 4.32, N 2.79%. NMR (CDCl₃): ¹H δ 9.25 (1H, d, ³J_PH = 7.6 Hz), 7.65 - 7.75 (6H, m), 7.35–7.48 (9H, m), 3.59 (3H,s), 2.85 (3H, s); ¹³C δ 221.2, 134.2 (d, ²J_PC = 11 Hz), 131.4 (d, ⁴J_PC = 2.5 Hz), 129.6 (d, ¹J_PC = 54 Hz), 128.8 (d, ³J_PC = 11 Hz), 51.48, 49.71; ³¹P δ 25.6. Recrystallization of the material from acetone gave well formed colourless blocks, one of which was selected for X-ray crystallographic examination.

S3. Refinement

The title compound crystallized in the triclinic system; space group P1 was assumed and confirmed by the analysis. All H atoms of the Pd complex were resolved in difference maps and were treated as riding atoms (C—H 0.93–0.96 Å) during refinement. The H atoms of the acetone solvate molecule were not at all clearly resolved and these were allowed for in the final calculations by placing six 0.5 occupancy H atoms around the C5 and C6 atoms with appropriate geometry constraints and C—H = 0.96 Å. Examination of the structure with PLATON (Spek, 2000) showed that there were no solvent-accessible voids in the crystal lattice. The acetone of solvation fills what would otherwise have been a void in the crystal lattice.

Computing details

Data collection: CAD-4-PC Software (Enraf-Nonius, 1992); cell refinement: SET4 and CELDIM in CAD-4-PC Software (Enraf-Nonius, 1992); data reduction: DATRD2 in NRCVAX96 (Gabe et al., 1989); program(s) used to solve structure: NRCVAX96 via Patterson heavy-atom method; program(s) used to refine structure: NRCVAX96 and SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: NRCVAX96, SHELXL97 and WORDPERFECT macro PREP8 (Ferguson, 1998).

cis-Dichloro(dimethylaminomethylene)(triphenylphosphine)palladium(II)

Crystal data

[PdCl2(C3H7N)(C18H15P)]·C3H6O	F(000) = 564
Mr = 554.74	? #Insert any comments here.
Triclinic, P1	Dx = 1.465 Mg m^−3
a = 8.9821 (14) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.8560 (18) Å	Cell parameters from 25 reflections
c = 14.3002 (19) Å	θ = 9.4–10.7°
α = 91.279 (16)°	µ = 1.03 mm^−1
β = 107.901 (16)°	T = 294 K
γ = 107.173 (15)°	Lath, colourless
V = 1257.9 (3) Å^3	0.40 × 0.25 × 0.14 mm
Z = 2

Data collection

Enraf-Nonius CAD-4 diffractometer	4660 reflections with I > 2σ(I)
Radiation source: X-ray tube	Rint = 0.000
Graphite monochromator	θmax = 27.5°, θmin = 2.3°
θ/2θ scans	h = −11→10
Absorption correction: gaussian (ABSO in NRCVAX; Gabe et al., 1989)	k = 0→14
Tmin = 0.810, Tmax = 0.907	l = −18→18
5768 measured reflections	3 standard reflections every 120 min
5768 independent reflections	intensity decay: 0.8%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.028	H-atom parameters constrained
wR(F^2) = 0.063	w = 1/[σ^2(Fo^2) + (0.0275P)^2 + 0.3092P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
5768 reflections	Δρmax = 0.38 e Å^−3
274 parameters	Δρmin = −0.32 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: heavy-atom	Extinction coefficient: 0.0132 (5)

Special details

Experimental. ? #Insert any special details here.

Geometry. Details of mean-plane calculations from last SHELXL97 refinement cycle

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

7.4569 (0.0023) x + 0.6581 (0.0047) y + 1.9729 (0.0059) z = 1.7662 (0.0013)

* 0.0416 (0.0006) Pd1 * -0.0649 (0.0009) C1 * -0.0532 (0.0007) Cl1 * 0.0373 (0.0006) Cl2 * 0.0392 (0.0006) P1

Rms deviation of fitted atoms = 0.0484

- 2.4299 (0.0153) x + 7.9261 (0.0143) y + 9.2309 (0.0197) z = 1.2544 (0.0043)

Angle to previous plane (with approximate e.s.d.) = 72.30(0.10)

* 0.0026 (0.0008) C1 * -0.0068 (0.0021) N1 * 0.0021 (0.0006) C2 * 0.0021 (0.0006) C3 - 0.0860 (0.0049) Pd1

Rms deviation of fitted atoms = 0.0039

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Pd1	0.19865 (2)	0.025504 (16)	0.156965 (13)	0.03523 (7)
Cl1	0.17092 (10)	−0.13179 (6)	0.26622 (5)	0.06020 (18)
Cl2	0.23976 (8)	−0.11594 (6)	0.04660 (5)	0.04989 (15)
P1	0.15889 (7)	0.16225 (6)	0.26042 (4)	0.03746 (13)
C11	0.3210 (3)	0.2124 (2)	0.38025 (17)	0.0426 (5)
C12	0.4386 (3)	0.1508 (3)	0.41061 (19)	0.0545 (6)
C13	0.5589 (4)	0.1878 (3)	0.5029 (2)	0.0652 (8)
C14	0.5640 (4)	0.2861 (3)	0.5652 (2)	0.0621 (7)
C15	0.4488 (4)	0.3496 (3)	0.5362 (2)	0.0701 (8)
C16	0.3286 (4)	0.3135 (3)	0.4441 (2)	0.0621 (7)
C21	−0.0337 (3)	0.0878 (2)	0.28403 (17)	0.0417 (5)
C22	−0.0459 (4)	0.0841 (3)	0.3782 (2)	0.0593 (7)
C23	−0.1967 (4)	0.0231 (3)	0.3905 (3)	0.0754 (9)
C24	−0.3350 (4)	−0.0326 (3)	0.3098 (3)	0.0750 (10)
C25	−0.3238 (3)	−0.0288 (3)	0.2166 (3)	0.0670 (8)
C26	−0.1744 (3)	0.0295 (3)	0.2035 (2)	0.0555 (7)
C31	0.1483 (3)	0.3163 (2)	0.21586 (17)	0.0429 (5)
C32	0.2931 (4)	0.4070 (2)	0.2149 (2)	0.0574 (7)
C33	0.2918 (5)	0.5234 (3)	0.1780 (2)	0.0703 (9)
C34	0.1460 (5)	0.5502 (3)	0.1418 (2)	0.0803 (10)
C35	0.0018 (5)	0.4604 (3)	0.1413 (3)	0.0825 (10)
C36	0.0019 (4)	0.3437 (3)	0.1782 (2)	0.0619 (7)
C1	0.1990 (3)	0.1492 (2)	0.06041 (16)	0.0420 (5)
N1	0.3162 (3)	0.2167 (2)	0.03235 (15)	0.0500 (5)
C2	0.4865 (4)	0.2176 (3)	0.0774 (3)	0.0749 (9)
C3	0.2898 (5)	0.3012 (3)	−0.0462 (2)	0.0842 (11)
O1	0.3101 (4)	0.4881 (3)	0.7721 (3)	0.1148 (10)
C4	0.2122 (6)	0.4707 (5)	0.6910 (4)	0.1034 (14)
C5	0.1936 (8)	0.5828 (7)	0.6379 (4)	0.183 (3)
C6	0.1122 (8)	0.3395 (6)	0.6430 (4)	0.207 (4)
H12	0.4370	0.0835	0.3686	0.065*
H13	0.6369	0.1449	0.5224	0.078*
H14	0.6450	0.3104	0.6272	0.074*
H15	0.4519	0.4171	0.5787	0.084*
H16	0.2518	0.3576	0.4248	0.074*
H22	0.0469	0.1226	0.4332	0.071*
H23	−0.2041	0.0198	0.4539	0.090*
H24	−0.4359	−0.0726	0.3184	0.090*
H25	−0.4175	−0.0658	0.1619	0.080*
H26	−0.1677	0.0298	0.1399	0.067*
H32	0.3923	0.3894	0.2394	0.069*
H33	0.3898	0.5837	0.1778	0.084*
H34	0.1450	0.6289	0.1176	0.096*
H35	−0.0972	0.4781	0.1159	0.099*
H36	−0.0967	0.2836	0.1777	0.074*
H1	0.0974	0.1610	0.0299	0.050*
H2A	0.4913	0.1594	0.1270	0.112*
H2B	0.5554	0.3039	0.1074	0.112*
H2C	0.5247	0.1899	0.0273	0.112*
H3A	0.1738	0.2873	−0.0759	0.126*
H3B	0.3338	0.2810	−0.0957	0.126*
H3C	0.3447	0.3904	−0.0182	0.126*
H5A	0.2669	0.6617	0.6793	0.275*	0.50
H5B	0.0819	0.5832	0.6217	0.275*	0.50
H5C	0.2201	0.5766	0.5782	0.275*	0.50
H5D	0.1123	0.5527	0.5735	0.275*	0.50
H5E	0.2973	0.6311	0.6311	0.275*	0.50
H5F	0.1591	0.6378	0.6746	0.275*	0.50
H6A	0.1386	0.2777	0.6870	0.310*	0.50
H6B	0.1349	0.3235	0.5833	0.310*	0.50
H6C	−0.0025	0.3309	0.6273	0.310*	0.50
H6D	0.0421	0.3437	0.5781	0.310*	0.50
H6E	0.0457	0.2979	0.6817	0.310*	0.50
H6F	0.1832	0.2905	0.6378	0.310*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.03555 (10)	0.03347 (10)	0.03702 (10)	0.01274 (7)	0.01051 (7)	0.00692 (6)
Cl1	0.0799 (5)	0.0460 (4)	0.0609 (4)	0.0229 (3)	0.0278 (4)	0.0229 (3)
Cl2	0.0541 (4)	0.0482 (3)	0.0502 (3)	0.0209 (3)	0.0169 (3)	0.0000 (3)
P1	0.0396 (3)	0.0368 (3)	0.0372 (3)	0.0147 (3)	0.0115 (2)	0.0074 (2)
C11	0.0428 (13)	0.0418 (12)	0.0405 (12)	0.0116 (10)	0.0116 (10)	0.0083 (10)
C12	0.0595 (16)	0.0561 (16)	0.0474 (14)	0.0268 (13)	0.0091 (12)	0.0028 (12)
C13	0.0625 (18)	0.075 (2)	0.0527 (16)	0.0327 (16)	0.0012 (14)	0.0062 (14)
C14	0.0627 (18)	0.0618 (18)	0.0444 (15)	0.0108 (14)	0.0021 (13)	0.0065 (13)
C15	0.081 (2)	0.0606 (18)	0.0556 (17)	0.0234 (16)	0.0045 (15)	−0.0122 (14)
C16	0.0675 (18)	0.0560 (16)	0.0574 (17)	0.0293 (14)	0.0049 (14)	−0.0072 (13)
C21	0.0426 (13)	0.0427 (12)	0.0462 (13)	0.0197 (10)	0.0174 (11)	0.0119 (10)
C22	0.0595 (17)	0.077 (2)	0.0519 (16)	0.0300 (15)	0.0241 (13)	0.0158 (14)
C23	0.079 (2)	0.100 (3)	0.075 (2)	0.043 (2)	0.0488 (19)	0.0361 (19)
C24	0.0545 (18)	0.071 (2)	0.120 (3)	0.0268 (16)	0.049 (2)	0.036 (2)
C25	0.0437 (16)	0.0676 (19)	0.087 (2)	0.0174 (14)	0.0171 (15)	0.0131 (16)
C26	0.0469 (15)	0.0643 (17)	0.0524 (15)	0.0171 (13)	0.0128 (12)	0.0092 (13)
C31	0.0546 (14)	0.0375 (12)	0.0388 (12)	0.0194 (11)	0.0137 (11)	0.0055 (10)
C32	0.0643 (17)	0.0460 (15)	0.0602 (17)	0.0157 (13)	0.0198 (14)	0.0090 (12)
C33	0.098 (3)	0.0414 (15)	0.070 (2)	0.0107 (16)	0.0357 (18)	0.0109 (14)
C34	0.133 (3)	0.0449 (17)	0.073 (2)	0.043 (2)	0.034 (2)	0.0212 (15)
C35	0.097 (3)	0.068 (2)	0.098 (3)	0.051 (2)	0.028 (2)	0.0330 (19)
C36	0.0661 (18)	0.0506 (16)	0.0735 (19)	0.0284 (14)	0.0190 (15)	0.0174 (14)
C1	0.0450 (13)	0.0429 (13)	0.0400 (12)	0.0181 (11)	0.0125 (10)	0.0072 (10)
N1	0.0603 (14)	0.0434 (11)	0.0517 (12)	0.0170 (10)	0.0251 (11)	0.0119 (9)
C2	0.0545 (18)	0.070 (2)	0.103 (3)	0.0111 (15)	0.0392 (18)	0.0130 (18)
C3	0.124 (3)	0.068 (2)	0.075 (2)	0.032 (2)	0.050 (2)	0.0380 (17)
O1	0.096 (2)	0.121 (2)	0.116 (2)	0.0253 (18)	0.0280 (19)	0.018 (2)
C4	0.087 (3)	0.143 (4)	0.086 (3)	0.024 (3)	0.048 (2)	0.020 (3)
C5	0.228 (8)	0.212 (7)	0.139 (5)	0.110 (6)	0.059 (5)	0.060 (5)
C6	0.200 (6)	0.193 (6)	0.136 (5)	−0.100 (5)	0.087 (5)	−0.021 (4)

Geometric parameters (Å, º)

Pd1—P1	2.2495 (7)	C33—C34	1.372 (5)
Pd1—Cl1	2.3508 (7)	C33—H33	0.93
Pd1—Cl2	2.3600 (7)	C34—C35	1.370 (5)
Pd1—C1	1.948 (2)	C34—H34	0.93
P1—C11	1.819 (2)	C35—C36	1.383 (4)
P1—C21	1.818 (2)	C35—H35	0.93
P1—C31	1.821 (2)	C36—H36	0.93
C11—C12	1.378 (3)	C1—N1	1.274 (3)
C11—C16	1.384 (3)	C1—H1	0.93
C12—C13	1.384 (4)	N1—C2	1.463 (4)
C12—H12	0.93	N1—C3	1.473 (3)
C13—C14	1.355 (4)	C2—H2A	0.96
C13—H13	0.93	C2—H2B	0.96
C14—C15	1.373 (4)	C2—H2C	0.96
C14—H14	0.93	C3—H3A	0.96
C15—C16	1.381 (4)	C3—H3B	0.96
C15—H15	0.93	C3—H3C	0.96
C16—H16	0.93	O1—C4	1.191 (5)
C21—C22	1.385 (3)	C4—C6	1.459 (7)
C21—C26	1.387 (3)	C4—C5	1.472 (7)
C22—C23	1.387 (4)	C5—H5A	0.96
C22—H22	0.93	C5—H5B	0.96
C23—C24	1.372 (5)	C5—H5C	0.96
C23—H23	0.93	C5—H5D	0.96
C24—C25	1.367 (4)	C5—H5E	0.96
C24—H24	0.93	C5—H5F	0.96
C25—C26	1.377 (4)	C6—H6A	0.96
C25—H25	0.93	C6—H6B	0.96
C26—H26	0.93	C6—H6C	0.96
C31—C36	1.382 (4)	C6—H6D	0.96
C31—C32	1.384 (4)	C6—H6E	0.96
C32—C33	1.382 (4)	C6—H6F	0.96
C32—H32	0.93
Cl1—Pd1—Cl2	91.73 (3)	C35—C36—H36	119.9
Cl1—Pd1—P1	89.09 (3)	Pd1—C1—N1	130.27 (19)
Cl1—Pd1—C1	174.55 (7)	Pd1—C1—H1	114.9
Cl2—Pd1—P1	179.16 (2)	N1—C1—H1	114.9
Cl2—Pd1—C1	88.37 (7)	C1—N1—C2	122.3 (2)
P1—Pd1—C1	90.80 (7)	C1—N1—C3	122.2 (2)
C11—P1—C21	107.02 (11)	C2—N1—C3	115.5 (2)
C11—P1—C31	102.99 (11)	N1—C2—H2A	109.5
C21—P1—C31	106.19 (11)	N1—C2—H2B	109.5
Pd1—P1—C11	114.45 (8)	H2A—C2—H2B	109.5
Pd1—P1—C21	110.47 (8)	N1—C2—H2C	109.5
Pd1—P1—C31	115.00 (8)	H2A—C2—H2C	109.5
P1—C11—C12	121.37 (19)	H2B—C2—H2C	109.5
P1—C11—C16	120.57 (19)	N1—C3—H3A	109.5
C12—C11—C16	118.1 (2)	N1—C3—H3B	109.5
C11—C12—C13	120.8 (3)	H3A—C3—H3B	109.5
C11—C12—H12	119.6	N1—C3—H3C	109.5
C13—C12—H12	119.6	H3A—C3—H3C	109.5
C14—C13—C12	120.6 (3)	H3B—C3—H3C	109.5
C14—C13—H13	119.7	O1—C4—C6	120.7 (5)
C12—C13—H13	119.7	O1—C4—C5	119.7 (5)
C13—C14—C15	119.6 (3)	C6—C4—C5	119.6 (5)
C13—C14—H14	120.2	C4—C5—H5A	109.5
C15—C14—H14	120.2	C4—C5—H5B	109.5
C14—C15—C16	120.2 (3)	H5A—C5—H5B	109.5
C14—C15—H15	119.9	C4—C5—H5C	109.5
C16—C15—H15	119.9	H5A—C5—H5C	109.5
C15—C16—C11	120.7 (3)	H5B—C5—H5C	109.5
C15—C16—H16	119.6	C4—C5—H5D	109.5
C11—C16—H16	119.6	H5A—C5—H5D	141.1
P1—C21—C22	123.3 (2)	H5B—C5—H5D	56.3
P1—C21—C26	118.07 (19)	H5C—C5—H5D	56.3
C22—C21—C26	118.6 (2)	C4—C5—H5E	109.5
C21—C22—C23	120.0 (3)	H5A—C5—H5E	56.3
C21—C22—H22	120.0	H5B—C5—H5E	141.1
C23—C22—H22	120.0	H5C—C5—H5E	56.3
C24—C23—C22	120.5 (3)	H5D—C5—H5E	109.5
C24—C23—H23	119.7	C4—C5—H5F	109.5
C22—C23—H23	119.7	H5A—C5—H5F	56.3
C25—C24—C23	119.7 (3)	H5B—C5—H5F	56.3
C25—C24—H24	120.1	H5C—C5—H5F	141.1
C23—C24—H24	120.1	H5D—C5—H5F	109.5
C24—C25—C26	120.3 (3)	H5E—C5—H5F	109.5
C24—C25—H25	119.8	C4—C6—H6A	109.5
C26—C25—H25	119.8	C4—C6—H6B	109.5
C25—C26—C21	120.8 (3)	H6A—C6—H6B	109.5
C25—C26—H26	119.6	C4—C6—H6C	109.5
C21—C26—H26	119.6	H6A—C6—H6C	109.5
P1—C31—C36	123.1 (2)	H6B—C6—H6C	109.5
P1—C31—C32	118.04 (19)	C4—C6—H6D	109.5
C32—C31—C36	118.8 (2)	H6A—C6—H6D	141.1
C33—C32—C31	120.7 (3)	H6B—C6—H6D	56.3
C33—C32—H32	119.6	H6C—C6—H6D	56.3
C31—C32—H32	119.6	C4—C6—H6E	109.5
C34—C33—C32	120.1 (3)	H6A—C6—H6E	56.3
C34—C33—H33	120.0	H6B—C6—H6E	141.1
C32—C33—H33	120.0	H6C—C6—H6E	56.3
C35—C34—C33	119.7 (3)	H6D—C6—H6E	109.5
C35—C34—H34	120.2	C4—C6—H6F	109.5
C33—C34—H34	120.2	H6A—C6—H6F	56.3
C34—C35—C36	120.7 (3)	H6B—C6—H6F	56.3
C34—C35—H35	119.6	H6C—C6—H6F	141.1
C36—C35—H35	119.6	H6D—C6—H6F	109.5
C31—C36—C35	120.1 (3)	H6E—C6—H6F	109.5
C31—C36—H36	119.9
C1—Pd1—P1—C21	119.28 (11)	Pd1—P1—C21—C26	−48.4 (2)
Cl1—Pd1—P1—C21	−55.28 (8)	C26—C21—C22—C23	0.0 (4)
Cl2—Pd1—P1—C21	111.1 (17)	P1—C21—C22—C23	−178.6 (2)
C1—Pd1—P1—C11	−119.86 (11)	C21—C22—C23—C24	−0.9 (5)
Cl1—Pd1—P1—C11	65.58 (9)	C22—C23—C24—C25	0.6 (5)
Cl2—Pd1—P1—C11	−128.1 (17)	C23—C24—C25—C26	0.5 (5)
C1—Pd1—P1—C31	−0.89 (11)	C24—C25—C26—C21	−1.5 (4)
Cl1—Pd1—P1—C31	−175.44 (9)	C22—C21—C26—C25	1.2 (4)
Cl2—Pd1—P1—C31	−9.1 (17)	P1—C21—C26—C25	179.8 (2)
C21—P1—C11—C12	110.4 (2)	C21—P1—C31—C36	−19.0 (3)
C31—P1—C11—C12	−137.9 (2)	C11—P1—C31—C36	−131.3 (2)
Pd1—P1—C11—C12	−12.3 (2)	Pd1—P1—C31—C36	103.5 (2)
C21—P1—C11—C16	−69.0 (2)	C21—P1—C31—C32	164.6 (2)
C31—P1—C11—C16	42.7 (2)	C11—P1—C31—C32	52.3 (2)
Pd1—P1—C11—C16	168.3 (2)	Pd1—P1—C31—C32	−72.9 (2)
C16—C11—C12—C13	1.0 (4)	C36—C31—C32—C33	0.7 (4)
P1—C11—C12—C13	−178.4 (2)	P1—C31—C32—C33	177.2 (2)
C11—C12—C13—C14	−0.4 (5)	C31—C32—C33—C34	0.0 (5)
C12—C13—C14—C15	−0.2 (5)	C32—C33—C34—C35	−0.7 (5)
C13—C14—C15—C16	0.0 (5)	C33—C34—C35—C36	0.8 (5)
C14—C15—C16—C11	0.7 (5)	C32—C31—C36—C35	−0.6 (4)
C12—C11—C16—C15	−1.1 (4)	P1—C31—C36—C35	−176.9 (2)
P1—C11—C16—C15	178.3 (2)	C34—C35—C36—C31	−0.2 (5)
C11—P1—C21—C22	5.0 (2)	P1—Pd1—C1—N1	110.8 (2)
C31—P1—C21—C22	−104.5 (2)	Cl1—Pd1—C1—N1	−160.4 (6)
Pd1—P1—C21—C22	130.2 (2)	Cl2—Pd1—C1—N1	−69.4 (2)
C11—P1—C21—C26	−173.61 (19)	Pd1—C1—N1—C2	−4.5 (4)
C31—P1—C21—C26	76.9 (2)	Pd1—C1—N1—C3	176.9 (2)