(R)-Di-[mu]-acetato-[kappa]²O:O'-bis{[2-(1-aminoethyl)phenyl-[kappa]²C¹,N]palladium(II)}, (R)-di-[mu]-chloro-bis{[2-(1-aminoethyl)phenyl-[kappa]²C¹,N]palladium(II)} and [SP-4-4]-(R)-[2-(1-aminoethyl)phenyl-[kappa]²C¹,N]chloro(pyridine-[kappa]N)palladium(II)

The title complexes, [Pd₂(C₈H₁₀N)₂(C₂H₃O₂)₂], (I), [Pd₂(C₈H₁₀N)₂Cl₂], (II), and [Pd(C₈H₁₀N)Cl(C₅H₅N)], (III), respectively, have been prepared as intermediates and the final product of a cyclo­palladation reaction sequence, and their structures studied by single-crystal X-ray diffraction. Complexes (I) and (II) represent the first structurally characterized dinuclear cyclo­palladation products of primary amines. For (I) and (III), pseudosymmetry relates two independent mol­ecules in the asymmetric unit.

S1. Comment

We are interested in the cyclopalladation products of primary amines as building blocks for molecular crystals. Since the discovery of cyclopalladation by Cope & Friedrich (1968), preparative efforts and structural investigations have been focused on complexes derived from tertiary amines. The work of Lewis et al. (1973), Dunina et al. (1984), Fuchita & Tsuchiya (1993), Fuchita et al., (1995, 1997) and Vicente et al. (1993, 1997) has shown that the reaction can, in principle, be extended to primary and secondary amines when appropriate reaction conditions and Pd^II sources are utilized.

For primary amines, no complete structural study of the cyclopalladation pathway has been carried out to date. We decided to characterize both of the intermediates and the final product of the reaction sequence shown in Scheme 1, using single-crystal diffraction. \sch

Starting from palladium(II) acetate and (R)-(1-phenyl)ethylamine, according to the method of Fuchita et al. (1997), steps (a) and (b) gave the dinuclear products (I) and (II), respectively. Bridging acetato and chloro ligands induce different overall conformations in these complexes. In (I), the planes of coordination around the Pd centres are stacked (Fig. 1), with a relatively short Pd···Pd distance of 2.9059 (14) Å. Based on spectroscopic results, Fuchita and coworkers had correctly assigned the anti configuration to this acetato-bridged dimer.

In contrast with the rather compact molecular shape of (I), the chloro complex, (II), is essentially flat (Fig. 2). The best planes through the two Pd centres and their coordinating atoms subtend a dihedral angle of 5.9 (2)°. Complexes (I) and (II) represent the first examples of structurally characterized dinuclear intermediates in the cyclopalladation of primary amines.

For the final reaction product, (III) (Fig. 3), five X-ray structure determinations involving cyclopalladated complexes of primary amines have been published to date (Dunina et al., 1999; Vicente et al., 1993; Fedorov et al., 1997; Fuchita et al., 1997). The groups of Vicente and Jones (Vicente et al., 1993) have described both a neutral compound and a cationic complex derived from the same chiral ligand, (1-phenyl)ethylamine, used in our preparations.

S2. Experimental

We prepared the series of compounds (I)-(III) according to the procedure of Fuchita et al. (1997). (R)-(+)-(1-phenyl)ethylamine was reacted with palladium(II) acetate to give the acetato-bridged dinuclear cyclopalladated complex (I) (Scheme 1), which was converted into the corresponding chloro-bridged analogue, (II), by reaction with sodium chloride. The chloro-bridged dinuclear complex was then cleaved with pyridine to give the mononuclear cyclopalladated complex, (III). Yields of up to 90% for the dinuclear intermediates, (I) and (II), and of 75% for the mononuclear complex, (III), have been obtained. Complexes (II) and (III) crystallize as elongated plates and needles, respectively.

S3. Refinement

Complexes (I) and (III) crystallize with two molecules in the asymmetric unit. In both cases, the independent moieties are related by pseudosymmetry. We can exclude centrosymmetric space groups because enantiomerically pure ligands of known chirality were used for the synthesis and the absolute configuration of the ligands is reliably reproduced by the diffraction experiment. We note that, despite several systematic absence violations, the structure of (III) can apparently be solved in space group I4₁/a. Tentative refinement in this centrosymmetric supergroup results in an unreasonably anisotropic displacement parameter for the methyl C atom attached to the chiral centre, an artificially shortened C—C separation (ca 1.1 Å) associated with this group, and significantly higher residual electron density close to the methyl group (0.84 Å). Fig. 4 shows the pseudosymmetry between the independent molecules in (III). This model, although obviously inappropriate for (III), might well represent the hitherto-unknown structure of the racemate. In the refinement of (I)-(III), all H atoms were introduced in idealized positions, with C—H = 0.98 Å and N—H = 0.95 Å Please clarify - 0.98 Å given in CIF data for N—H in (I), and included as riding with U_iso(H) = 1.3U_eq(C, N).

Computing details

For all compounds, data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1990); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of the two symmetrically independent molecules in (I). Displacement ellipsoids are at the 30% probability level and H atoms have been omitted for clarity.
	Fig. 2. A view of the molecule of (II). Displacement ellipsoids are at the 30% probability level and H atoms have been omitted for clarity.
	Fig. 3. A view of the two symmetrically independent molecules in (III). Displacement ellipsoids are at the 30% probability level and H atoms have been omitted for clarity.
	Fig. 4. The pseudo-glide plane in (III). The pseudo reflection is in the view direction, the pseudo translation to the right.

(I) (R)-di-µ-acetato-κ²O:O'-bis{[2-(1-aminoethyl)phenyl- κ²C¹,N]palladium(II)}

Crystal data

[Pd2(C8H10N)2(C2H3O2)2]	F(000) = 1136
Mr = 571.23	Dx = 1.716 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 30754 reflections
a = 10.423 (4) Å	θ = 1.3–28.7°
b = 13.398 (5) Å	µ = 1.65 mm^−1
c = 15.861 (5) Å	T = 295 K
β = 93.429 (9)°	Parallelepiped, yellow
V = 2210.9 (13) Å^3	0.12 × 0.05 × 0.05 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	11234 independent reflections
Radiation source: fine-focus sealed tube	7251 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.092
ω scans	θmax = 28.7°, θmin = 1.3°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −13→14
Tmin = 0.826, Tmax = 0.922	k = −18→18
30720 measured reflections	l = −21→21

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)] = 0.065	H-atom parameters constrained
wR(F^2) = 0.177	w = 1/[σ^2(Fo^2) + (0.0546P)^2 + 1.0577P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.028
11234 reflections	Δρmax = 0.70 e Å^−3
513 parameters	Δρmin = −1.27 e Å^−3
1 restraint	Absolute structure: Flack (1983); 5274 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (7)

Special details

Experimental. The values of Tmin and Tmax are 0.757793 and 1.000000 from SADABS.

To ensure sufficient diffraction intensity in the case of (III), a relatively long needle (1.05 × 0.08 × 0.03 mm) was selected for data collection.

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	0.85407 (8)	0.84420 (6)	0.47109 (5)	0.0449 (2)
Pd2	1.06517 (8)	0.72032 (7)	0.53806 (6)	0.0510 (3)
Pd3	0.63183 (8)	0.93673 (6)	0.03734 (5)	0.0464 (2)
Pd4	0.42956 (8)	1.05594 (7)	−0.05130 (6)	0.0483 (2)
O11	0.7520 (8)	0.7442 (8)	0.5407 (5)	0.060 (2)
C123	0.7894 (12)	0.6610 (12)	0.5657 (7)	0.057 (3)
C124	0.6899 (17)	0.6017 (14)	0.6065 (10)	0.092 (6)
H12A	0.7274	0.5386	0.6273	0.120*
H12B	0.6184	0.5878	0.5652	0.120*
H12C	0.6583	0.6396	0.6539	0.120*
O21	0.8998 (8)	0.6235 (7)	0.5582 (6)	0.061 (2)
O12	0.9087 (10)	0.9227 (7)	0.5876 (5)	0.064 (2)
C121	0.9693 (12)	0.8788 (11)	0.6502 (7)	0.054 (3)
C122	0.9691 (16)	0.9290 (12)	0.7339 (8)	0.086 (5)
H12D	0.9621	0.8786	0.7782	0.111*
H12E	0.8959	0.9748	0.7344	0.111*
H12F	1.0493	0.9665	0.7442	0.111*
O22	1.0286 (9)	0.8005 (8)	0.6488 (6)	0.066 (3)
O31	0.5885 (8)	0.8497 (7)	−0.0782 (5)	0.058 (2)
C341	0.5391 (12)	0.8868 (10)	−0.1456 (9)	0.058 (3)
C342	0.5546 (15)	0.8273 (12)	−0.2284 (7)	0.081 (5)
H34A	0.4893	0.8491	−0.2715	0.105*
H34B	0.5440	0.7558	−0.2175	0.105*
H34C	0.6404	0.8393	−0.2485	0.105*
O41	0.4797 (8)	0.9699 (8)	−0.1530 (5)	0.060 (2)
O32	0.7417 (8)	1.0295 (7)	−0.0318 (5)	0.055 (2)
C343	0.7076 (12)	1.1114 (11)	−0.0695 (8)	0.053 (3)
C344	0.8142 (14)	1.1628 (14)	−0.1157 (9)	0.083 (5)
H34D	0.7962	1.1566	−0.1768	0.108*
H34E	0.8968	1.1311	−0.0996	0.108*
H34F	0.8178	1.2336	−0.1001	0.108*
O42	0.5983 (8)	1.1486 (7)	−0.0720 (5)	0.061 (2)
C11	0.8252 (11)	0.7707 (10)	0.3647 (7)	0.052 (3)
C12	0.7396 (12)	0.6904 (9)	0.3474 (8)	0.055 (3)
H12	0.6803	0.6699	0.3898	0.072*
C13	0.7393 (13)	0.6399 (9)	0.2698 (8)	0.061 (3)
H13	0.6827	0.5822	0.2596	0.080*
C14	0.8184 (15)	0.6708 (12)	0.2071 (9)	0.073 (4)
H14	0.8166	0.6356	0.1529	0.095*
C15	0.8988 (13)	0.7505 (12)	0.2216 (7)	0.063 (4)
H15	0.9532	0.7732	0.1771	0.082*
C16	0.9039 (11)	0.7998 (9)	0.2995 (7)	0.048 (3)
C17	0.9968 (12)	0.8879 (9)	0.3223 (7)	0.051 (3)
H17	1.0796	0.8602	0.3435	0.066*
C18	1.0218 (14)	0.9634 (11)	0.2497 (7)	0.075 (4)
H18A	0.9394	0.9870	0.2240	0.098*
H18B	1.0703	0.9302	0.2067	0.098*
H18C	1.0713	1.0203	0.2729	0.098*
N1	0.9370 (10)	0.9449 (9)	0.3954 (6)	0.061 (3)
H1A	0.8723	0.9923	0.3725	0.080*
H1B	1.0038	0.9823	0.4280	0.080*
C21	1.2265 (12)	0.7920 (10)	0.5214 (8)	0.058 (3)
C22	1.2798 (13)	0.8719 (14)	0.5772 (9)	0.080 (5)
H22	1.2300	0.8983	0.6227	0.104*
C23	1.3980 (14)	0.9084 (14)	0.5648 (11)	0.094 (6)
H23	1.4320	0.9616	0.6022	0.123*
C24	1.4714 (16)	0.8752 (16)	0.5036 (12)	0.091 (6)
H24	1.5583	0.9018	0.4989	0.118*
C25	1.4226 (13)	0.8020 (11)	0.4463 (10)	0.076 (4)
H25	1.4727	0.7796	0.3995	0.098*
C26	1.2997 (12)	0.7617 (9)	0.4583 (8)	0.061 (3)
C27	1.2479 (13)	0.6714 (11)	0.4032 (10)	0.075 (4)
H27	1.2372	0.6965	0.3452	0.098*
C28	1.326 (2)	0.5727 (17)	0.398 (2)	0.212 (16)
H28A	1.3385	0.5438	0.4550	0.276*
H28B	1.4092	0.5867	0.3758	0.276*
H28C	1.2780	0.5254	0.3611	0.276*
N2	1.1104 (10)	0.6481 (8)	0.4305 (6)	0.060 (3)
H2A	1.1026	0.5760	0.4393	0.078*
H2B	1.0480	0.6670	0.3845	0.078*
C31	0.6661 (11)	1.0124 (9)	0.1434 (6)	0.044 (3)
C32	0.7279 (14)	1.1060 (11)	0.1532 (9)	0.070 (4)
H32	0.7653	1.1354	0.1037	0.091*
C33	0.7393 (14)	1.1606 (14)	0.2313 (10)	0.085 (5)
H33	0.7795	1.2266	0.2353	0.111*
C34	0.6895 (16)	1.1138 (13)	0.3012 (10)	0.083 (5)
H34	0.7021	1.1457	0.3567	0.108*
C35	0.6203 (13)	1.0205 (10)	0.2946 (8)	0.062 (4)
H35	0.5819	0.9924	0.3443	0.081*
C36	0.6083 (12)	0.9703 (9)	0.2169 (8)	0.053 (3)
C37	0.5324 (11)	0.8724 (10)	0.2024 (7)	0.053 (3)
H37	0.5588	0.8239	0.2463	0.070*
C38	0.3866 (12)	0.8922 (11)	0.2040 (10)	0.088 (5)
H38A	0.3585	0.9339	0.1556	0.115*
H38B	0.3687	0.9268	0.2565	0.115*
H38C	0.3402	0.8286	0.2010	0.115*
N3	0.5616 (11)	0.8329 (9)	0.1185 (6)	0.061 (3)
H3A	0.4831	0.8038	0.0919	0.079*
H3B	0.6248	0.7791	0.1266	0.079*
C41	0.2682 (12)	0.9842 (10)	−0.0357 (7)	0.050 (3)
C42	0.2365 (13)	0.8934 (10)	−0.0680 (8)	0.059 (3)
H42	0.2988	0.8567	−0.0999	0.077*
C43	0.1136 (14)	0.8504 (12)	−0.0561 (9)	0.074 (4)
H43	0.0930	0.7837	−0.0784	0.096*
C44	0.0240 (14)	0.9026 (12)	−0.0132 (12)	0.080 (5)
H44	−0.0609	0.8737	−0.0055	0.105*
C45	0.0555 (12)	0.9975 (10)	0.0192 (9)	0.065 (4)
H45	−0.0088	1.0363	0.0478	0.084*
C46	0.1775 (11)	1.0364 (8)	0.0110 (6)	0.045 (2)
C47	0.2205 (11)	1.1392 (8)	0.0461 (8)	0.053 (3)
H47	0.1909	1.1892	0.0043	0.068*
C48	0.1709 (12)	1.1712 (9)	0.1306 (7)	0.060 (3)
H48A	0.2037	1.1254	0.1750	0.078*
H48B	0.0767	1.1696	0.1270	0.078*
H48C	0.2004	1.2391	0.1440	0.078*
N4	0.3658 (9)	1.1390 (7)	0.0486 (6)	0.052 (2)
H4A	0.4001	1.1105	0.1022	0.068*
H4B	0.3973	1.2077	0.0450	0.068*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.0510 (5)	0.0385 (5)	0.0454 (4)	0.0045 (4)	0.0029 (3)	0.0006 (4)
Pd2	0.0481 (5)	0.0418 (6)	0.0628 (5)	0.0018 (4)	0.0012 (4)	0.0073 (4)
Pd3	0.0520 (5)	0.0374 (5)	0.0498 (5)	0.0031 (4)	0.0034 (4)	0.0017 (4)
Pd4	0.0473 (5)	0.0384 (5)	0.0591 (5)	0.0048 (4)	0.0020 (4)	0.0040 (4)
O11	0.058 (5)	0.064 (7)	0.060 (5)	−0.001 (5)	0.010 (4)	0.019 (5)
C123	0.056 (7)	0.068 (10)	0.046 (6)	−0.010 (7)	0.005 (5)	0.000 (6)
C124	0.094 (12)	0.079 (12)	0.106 (12)	−0.003 (10)	0.026 (10)	0.046 (10)
O21	0.052 (5)	0.043 (5)	0.087 (6)	−0.001 (4)	−0.001 (4)	0.014 (4)
O12	0.094 (6)	0.044 (6)	0.054 (5)	0.011 (5)	−0.005 (4)	0.000 (4)
C121	0.064 (8)	0.055 (8)	0.042 (6)	−0.003 (6)	−0.009 (5)	−0.001 (5)
C122	0.135 (13)	0.069 (10)	0.050 (7)	0.011 (10)	−0.019 (8)	−0.010 (7)
O22	0.071 (6)	0.059 (7)	0.066 (5)	0.008 (5)	−0.006 (5)	0.004 (5)
O31	0.077 (6)	0.038 (5)	0.058 (5)	0.013 (5)	−0.005 (4)	−0.002 (4)
C341	0.052 (7)	0.034 (7)	0.086 (9)	0.000 (5)	0.001 (6)	−0.004 (6)
C342	0.119 (12)	0.073 (10)	0.050 (7)	0.035 (9)	−0.005 (7)	−0.006 (7)
O41	0.061 (5)	0.068 (7)	0.052 (5)	0.010 (5)	0.011 (4)	0.008 (4)
O32	0.056 (5)	0.044 (6)	0.067 (5)	0.011 (4)	0.009 (4)	0.013 (4)
C343	0.052 (7)	0.044 (8)	0.062 (7)	−0.010 (6)	0.004 (6)	0.007 (6)
C344	0.074 (10)	0.088 (12)	0.088 (10)	−0.015 (9)	0.016 (8)	0.039 (9)
O42	0.054 (5)	0.044 (6)	0.085 (6)	0.000 (4)	0.010 (4)	0.015 (5)
C11	0.041 (6)	0.053 (8)	0.061 (7)	0.006 (6)	−0.006 (5)	0.003 (6)
C12	0.061 (7)	0.041 (7)	0.062 (7)	0.001 (5)	−0.007 (6)	0.000 (5)
C13	0.078 (8)	0.023 (6)	0.080 (8)	−0.006 (5)	−0.024 (7)	−0.005 (6)
C14	0.083 (10)	0.054 (10)	0.079 (9)	−0.004 (8)	−0.015 (8)	−0.020 (7)
C15	0.068 (8)	0.071 (9)	0.049 (6)	0.019 (7)	−0.004 (6)	0.004 (6)
C16	0.051 (6)	0.046 (7)	0.046 (6)	0.013 (5)	−0.009 (5)	−0.009 (5)
C17	0.059 (7)	0.050 (7)	0.044 (6)	−0.001 (5)	0.002 (5)	0.005 (5)
C18	0.094 (10)	0.082 (10)	0.052 (7)	−0.017 (8)	0.012 (6)	0.013 (7)
N1	0.065 (6)	0.048 (7)	0.072 (6)	−0.003 (6)	0.011 (5)	−0.025 (6)
C21	0.061 (8)	0.037 (7)	0.073 (8)	−0.002 (6)	−0.010 (6)	0.015 (6)
C22	0.061 (8)	0.103 (14)	0.077 (9)	−0.017 (8)	0.006 (7)	0.015 (9)
C23	0.069 (9)	0.098 (15)	0.115 (13)	−0.017 (9)	−0.002 (9)	0.016 (11)
C24	0.066 (10)	0.096 (16)	0.109 (13)	−0.006 (10)	0.002 (9)	0.014 (11)
C25	0.067 (9)	0.055 (9)	0.108 (12)	0.023 (7)	0.031 (8)	0.025 (8)
C26	0.055 (7)	0.044 (7)	0.082 (9)	0.002 (5)	−0.003 (6)	0.033 (6)
C27	0.080 (9)	0.056 (8)	0.095 (10)	0.012 (7)	0.033 (8)	0.009 (7)
C28	0.103 (16)	0.105 (18)	0.44 (5)	0.059 (14)	0.10 (2)	0.03 (2)
N2	0.065 (6)	0.044 (6)	0.071 (7)	0.009 (5)	0.006 (5)	0.009 (5)
C31	0.059 (6)	0.036 (7)	0.035 (5)	0.004 (5)	−0.005 (5)	0.005 (4)
C32	0.080 (9)	0.048 (8)	0.078 (9)	−0.018 (7)	−0.021 (7)	0.003 (7)
C33	0.083 (11)	0.082 (12)	0.089 (11)	0.005 (9)	−0.014 (9)	0.001 (9)
C34	0.099 (11)	0.064 (11)	0.082 (10)	0.007 (9)	−0.042 (9)	−0.031 (8)
C35	0.085 (9)	0.045 (8)	0.055 (7)	0.016 (6)	−0.012 (6)	−0.005 (6)
C36	0.064 (7)	0.028 (6)	0.065 (7)	0.003 (5)	−0.005 (6)	0.005 (5)
C37	0.063 (7)	0.044 (6)	0.053 (6)	0.006 (5)	−0.001 (5)	0.007 (5)
C38	0.067 (8)	0.078 (10)	0.121 (12)	−0.018 (7)	0.021 (8)	−0.047 (9)
N3	0.089 (8)	0.040 (6)	0.054 (5)	−0.020 (6)	0.008 (5)	−0.012 (5)
C41	0.058 (7)	0.049 (8)	0.042 (6)	0.003 (6)	0.003 (5)	0.009 (5)
C42	0.061 (7)	0.042 (7)	0.074 (8)	−0.009 (6)	0.001 (6)	−0.010 (6)
C43	0.081 (9)	0.048 (8)	0.088 (9)	0.003 (7)	−0.031 (7)	−0.014 (7)
C44	0.057 (9)	0.059 (11)	0.126 (14)	−0.018 (8)	0.011 (8)	0.007 (9)
C45	0.054 (7)	0.049 (8)	0.092 (10)	−0.007 (6)	−0.001 (6)	0.016 (7)
C46	0.058 (6)	0.029 (5)	0.045 (5)	0.012 (5)	−0.008 (5)	0.007 (4)
C47	0.062 (7)	0.028 (5)	0.068 (7)	0.006 (5)	0.010 (6)	0.011 (5)
C48	0.067 (8)	0.048 (7)	0.067 (7)	0.001 (6)	0.017 (6)	−0.002 (6)
N4	0.057 (5)	0.029 (5)	0.071 (6)	−0.008 (4)	0.004 (5)	0.002 (4)

Geometric parameters (Å, º)

Pd1—Pd2	2.9059 (14)	N1—H1A	0.9800
Pd1—O11	2.071 (9)	N1—H1B	0.9800
Pd1—O12	2.172 (9)	C21—C26	1.356 (18)
Pd1—N1	2.033 (12)	C21—C22	1.48 (2)
Pd1—C11	1.962 (13)	C22—C23	1.35 (2)
Pd2—O21	2.196 (9)	C22—H22	0.9800
Pd2—O22	2.112 (10)	C23—C24	1.35 (2)
Pd2—N2	2.041 (10)	C23—H23	0.9800
Pd2—C21	1.968 (13)	C24—C25	1.41 (2)
Pd3—Pd4	2.9355 (14)	C24—H24	0.9800
Pd3—O31	2.196 (9)	C25—C26	1.414 (18)
Pd3—O32	2.052 (8)	C25—H25	0.9800
Pd3—N3	2.059 (10)	C26—C27	1.57 (2)
Pd3—C31	1.979 (11)	C27—N2	1.553 (16)
Pd4—O41	2.074 (9)	C27—C28	1.55 (2)
Pd4—O42	2.193 (9)	C27—H27	0.9800
Pd4—N4	2.078 (10)	C28—H28A	0.9801
Pd4—C41	1.966 (13)	C28—H28B	0.9801
O11—C123	1.238 (18)	C28—H28C	0.9801
C123—O21	1.268 (16)	N2—H2A	0.9800
C123—C124	1.484 (19)	N2—H2B	0.9800
C124—H12A	0.9801	C31—C32	1.414 (17)
C124—H12B	0.9801	C31—C36	1.457 (16)
C124—H12C	0.9801	C32—C33	1.44 (2)
O12—C121	1.287 (15)	C32—H32	0.9800
C121—O22	1.218 (16)	C33—C34	1.40 (2)
C121—C122	1.488 (17)	C33—H33	0.9800
C122—H12D	0.9801	C34—C35	1.44 (2)
C122—H12E	0.9801	C34—H34	0.9800
C122—H12F	0.9801	C35—C36	1.404 (17)
O31—C341	1.260 (16)	C35—H35	0.9800
C341—O41	1.277 (16)	C36—C37	1.542 (17)
C341—C342	1.553 (18)	C37—N3	1.480 (14)
C342—H34A	0.9801	C37—C38	1.544 (17)
C342—H34B	0.9801	C37—H37	0.9800
C342—H34C	0.9801	C38—H38A	0.9801
O32—C343	1.290 (15)	C38—H38B	0.9801
C343—O42	1.242 (15)	C38—H38C	0.9801
C343—C344	1.530 (17)	N3—H3A	0.9800
C344—H34D	0.9801	N3—H3B	0.9800
C344—H34E	0.9801	C41—C42	1.352 (18)
C344—H34F	0.9801	C41—C46	1.420 (16)
C11—C16	1.413 (16)	C42—C43	1.428 (19)
C11—C12	1.413 (17)	C42—H42	0.9800
C12—C13	1.404 (17)	C43—C44	1.38 (2)
C12—H12	0.9800	C43—H43	0.9800
C13—C14	1.39 (2)	C44—C45	1.40 (2)
C13—H13	0.9800	C44—H44	0.9800
C14—C15	1.37 (2)	C45—C46	1.388 (16)
C14—H14	0.9800	C45—H45	0.9800
C15—C16	1.399 (16)	C46—C47	1.541 (15)
C15—H15	0.9800	C47—N4	1.512 (14)
C16—C17	1.555 (17)	C47—C48	1.526 (15)
C17—N1	1.550 (14)	C47—H47	0.9800
C17—C18	1.566 (16)	C48—H48A	0.9801
C17—H17	0.9800	C48—H48B	0.9801
C18—H18A	0.9801	C48—H48C	0.9801
C18—H18B	0.9801	N4—H4A	0.9800
C18—H18C	0.9801	N4—H4B	0.9800
O11—Pd1—O12	88.7 (4)	C17—N1—Pd1	108.6 (8)
N1—Pd1—O11	174.0 (4)	C17—N1—H1A	110.0
N1—Pd1—O12	94.7 (4)	Pd1—N1—H1A	110.0
C11—Pd1—O11	94.4 (5)	C17—N1—H1B	110.0
C11—Pd1—O12	173.6 (4)	Pd1—N1—H1B	110.0
C11—Pd1—N1	82.7 (5)	H1A—N1—H1B	108.3
C11—Pd1—Pd2	95.8 (3)	C26—C21—C22	116.8 (12)
N1—Pd1—Pd2	104.8 (3)	C26—C21—Pd2	118.4 (10)
O11—Pd1—Pd2	80.6 (3)	C22—C21—Pd2	124.6 (10)
O12—Pd1—Pd2	79.1 (3)	C23—C22—C21	119.3 (16)
O22—Pd2—O21	89.9 (4)	C23—C22—H22	120.3
N2—Pd2—O21	93.7 (4)	C21—C22—H22	120.4
N2—Pd2—O22	176.5 (4)	C24—C23—C22	123.2 (19)
C21—Pd2—O21	172.9 (5)	C24—C23—H23	118.4
C21—Pd2—O22	93.5 (5)	C22—C23—H23	118.4
C21—Pd2—N2	82.9 (5)	C23—C24—C25	119.7 (16)
C21—Pd2—Pd1	107.8 (4)	C23—C24—H24	120.1
N2—Pd2—Pd1	99.9 (3)	C25—C24—H24	120.1
O22—Pd2—Pd1	81.0 (2)	C24—C25—C26	118.2 (14)
O21—Pd2—Pd1	78.9 (2)	C24—C25—H25	120.9
O32—Pd3—O31	88.3 (4)	C26—C25—H25	120.9
N3—Pd3—O31	95.8 (4)	C21—C26—C25	122.6 (14)
N3—Pd3—O32	166.9 (4)	C21—C26—C27	116.9 (11)
C31—Pd3—O31	178.0 (4)	C25—C26—C27	120.2 (13)
C31—Pd3—O32	93.8 (4)	N2—C27—C28	109.6 (13)
C31—Pd3—N3	82.4 (4)	N2—C27—C26	107.0 (10)
C31—Pd3—Pd4	102.5 (3)	C28—C27—C26	121.4 (16)
O32—Pd3—Pd4	79.8 (2)	N2—C27—H27	106.0
N3—Pd3—Pd4	113.3 (3)	C28—C27—H27	106.0
O31—Pd3—Pd4	77.5 (2)	C26—C27—H27	106.0
O41—Pd4—O42	87.5 (4)	C27—C28—H28A	109.5
N4—Pd4—O41	175.9 (4)	C27—C28—H28B	109.5
N4—Pd4—O42	96.1 (3)	H28A—C28—H28B	109.5
C41—Pd4—O41	94.8 (4)	C27—C28—H28C	109.5
C41—Pd4—O42	174.5 (4)	H28A—C28—H28C	109.5
C41—Pd4—N4	81.4 (4)	H28B—C28—H28C	109.5
C41—Pd4—Pd3	105.6 (3)	C27—N2—Pd2	113.6 (9)
O41—Pd4—Pd3	82.1 (2)	C27—N2—H2A	108.8
N4—Pd4—Pd3	100.3 (3)	Pd2—N2—H2A	108.8
O42—Pd4—Pd3	79.7 (2)	C27—N2—H2B	108.8
C123—O11—Pd1	126.2 (9)	Pd2—N2—H2B	108.8
O11—C123—O21	126.7 (13)	H2A—N2—H2B	107.7
O11—C123—C124	114.0 (13)	C32—C31—C36	117.6 (11)
O21—C123—C124	119.4 (14)	C32—C31—Pd3	127.2 (9)
C123—C124—H12A	109.5	C36—C31—Pd3	114.8 (9)
C123—C124—H12B	109.5	C31—C32—C33	124.0 (14)
H12A—C124—H12B	109.5	C31—C32—H32	118.0
C123—C124—H12C	109.5	C33—C32—H32	118.0
H12A—C124—H12C	109.5	C34—C33—C32	116.1 (16)
H12B—C124—H12C	109.5	C34—C33—H33	122.0
C123—O21—Pd2	120.3 (9)	C32—C33—H33	122.0
C121—O12—Pd1	121.8 (9)	C33—C34—C35	122.5 (14)
O22—C121—O12	127.3 (12)	C33—C34—H34	118.7
O22—C121—C122	115.7 (12)	C35—C34—H34	118.7
O12—C121—C122	117.1 (13)	C36—C35—C34	119.8 (14)
C121—C122—H12D	109.5	C36—C35—H35	120.1
C121—C122—H12E	109.5	C34—C35—H35	120.1
H12D—C122—H12E	109.5	C35—C36—C31	119.8 (12)
C121—C122—H12F	109.5	C35—C36—C37	123.9 (12)
H12D—C122—H12F	109.5	C31—C36—C37	116.3 (10)
H12E—C122—H12F	109.5	N3—C37—C36	107.8 (10)
C121—O22—Pd2	124.7 (9)	N3—C37—C38	109.4 (10)
C341—O31—Pd3	123.5 (9)	C36—C37—C38	110.3 (11)
O31—C341—O41	126.4 (13)	N3—C37—H37	109.7
O31—C341—C342	117.2 (12)	C36—C37—H37	109.7
O41—C341—C342	116.4 (12)	C38—C37—H37	109.7
C341—C342—H34A	109.5	C37—C38—H38A	109.5
C341—C342—H34B	109.5	C37—C38—H38B	109.5
H34A—C342—H34B	109.5	H38A—C38—H38B	109.5
C341—C342—H34C	109.5	C37—C38—H38C	109.5
H34A—C342—H34C	109.5	H38A—C38—H38C	109.5
H34B—C342—H34C	109.5	H38B—C38—H38C	109.5
C341—O41—Pd4	123.8 (9)	C37—N3—Pd3	114.9 (8)
C343—O32—Pd3	128.0 (8)	C37—N3—H3A	108.5
O42—C343—O32	125.7 (11)	Pd3—N3—H3A	108.5
O42—C343—C344	119.7 (12)	C37—N3—H3B	108.5
O32—C343—C344	114.6 (12)	Pd3—N3—H3B	108.5
C343—C344—H34D	109.5	H3A—N3—H3B	107.5
C343—C344—H34E	109.5	C42—C41—C46	119.1 (12)
H34D—C344—H34E	109.5	C42—C41—Pd4	125.7 (10)
C343—C344—H34F	109.5	C46—C41—Pd4	115.2 (9)
H34D—C344—H34F	109.5	C41—C42—C43	120.9 (13)
H34E—C344—H34F	109.5	C41—C42—H42	119.5
C343—O42—Pd4	120.7 (9)	C43—C42—H42	119.6
C16—C11—C12	117.1 (12)	C44—C43—C42	120.0 (14)
C16—C11—Pd1	115.1 (9)	C44—C43—H43	120.0
C12—C11—Pd1	127.7 (9)	C42—C43—H43	120.0
C13—C12—C11	120.4 (12)	C43—C44—C45	119.3 (14)
C13—C12—H12	119.8	C43—C44—H44	120.3
C11—C12—H12	119.8	C45—C44—H44	120.3
C14—C13—C12	120.8 (12)	C46—C45—C44	120.1 (14)
C14—C13—H13	119.6	C46—C45—H45	119.9
C12—C13—H13	119.6	C44—C45—H45	119.9
C15—C14—C13	119.7 (13)	C45—C46—C41	120.4 (11)
C15—C14—H14	120.2	C45—C46—C47	123.4 (11)
C13—C14—H14	120.2	C41—C46—C47	116.2 (10)
C14—C15—C16	120.5 (13)	N4—C47—C48	111.6 (10)
C14—C15—H15	119.8	N4—C47—C46	106.1 (9)
C16—C15—H15	119.8	C48—C47—C46	117.5 (9)
C15—C16—C11	121.5 (13)	N4—C47—H47	107.0
C15—C16—C17	123.6 (11)	C48—C47—H47	107.0
C11—C16—C17	114.9 (10)	C46—C47—H47	107.0
N1—C17—C16	105.9 (9)	C47—C48—H48A	109.5
N1—C17—C18	108.9 (10)	C47—C48—H48B	109.5
C16—C17—C18	116.6 (10)	H48A—C48—H48B	109.5
N1—C17—H17	108.4	C47—C48—H48C	109.5
C16—C17—H17	108.4	H48A—C48—H48C	109.5
C18—C17—H17	108.4	H48B—C48—H48C	109.5
C17—C18—H18A	109.5	C47—N4—Pd4	110.2 (7)
C17—C18—H18B	109.5	C47—N4—H4A	109.6
H18A—C18—H18B	109.5	Pd4—N4—H4A	109.6
C17—C18—H18C	109.5	C47—N4—H4B	109.6
H18A—C18—H18C	109.5	Pd4—N4—H4B	109.6
H18B—C18—H18C	109.5	H4A—N4—H4B	108.1

(II) (R)-di-µ-chloro-bis{[2-(1-aminoethyl)phenyl-κ²C¹,N]palladium(II)}

Crystal data

[Pd2(C8H10N)2Cl2]	F(000) = 1024
Mr = 524.04	Dx = 1.955 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 24302 reflections
a = 7.330 (3) Å	θ = 1.8–28.2°
b = 10.819 (4) Å	µ = 2.32 mm^−1
c = 22.453 (8) Å	T = 293 K
V = 1780.4 (11) Å^3	Elongated plate, light yellow
Z = 4	1.00 × 0.45 × 0.02 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	4390 independent reflections
Radiation source: fine-focus sealed tube	3782 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.088
ω scans	θmax = 28.2°, θmin = 1.8°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.205, Tmax = 0.955	k = −14→14
24210 measured reflections	l = −29→29

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)] = 0.049	H-atom parameters constrained
wR(F^2) = 0.109	w = 1/[σ^2(Fo^2) + (0.048P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
4390 reflections	Δρmax = 0.77 e Å^−3
201 parameters	Δρmin = −0.88 e Å^−3
0 restraints	Absolute structure: Flack (1983); 1864 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (6)

Special details

Experimental. The values of Tmin and Tmax are 0.757793 and 1.000000 from SADABS.

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	0.31461 (7)	0.90027 (5)	0.03219 (2)	0.03502 (14)
Pd2	0.10607 (7)	0.73789 (5)	0.14796 (2)	0.03421 (14)
Cl1	0.0137 (2)	0.85650 (19)	0.05849 (8)	0.0438 (5)
Cl2	0.4042 (3)	0.79497 (19)	0.12412 (9)	0.0500 (5)
C11	0.2580 (10)	0.9937 (7)	−0.0395 (3)	0.0381 (16)
C12	0.0897 (11)	0.9983 (7)	−0.0692 (3)	0.0424 (17)
H12	−0.0148	0.9510	−0.0543	0.055*
C13	0.0732 (12)	1.0699 (8)	−0.1196 (4)	0.051 (2)
H13	−0.0451	1.0759	−0.1397	0.066*
C14	0.2180 (14)	1.1323 (9)	−0.1418 (4)	0.064 (3)
H14	0.2024	1.1826	−0.1777	0.084*
C15	0.3818 (14)	1.1269 (8)	−0.1159 (4)	0.058 (2)
H15	0.4856	1.1708	−0.1335	0.076*
C16	0.4048 (11)	1.0581 (7)	−0.0633 (3)	0.0445 (17)
C17	0.5817 (11)	1.0477 (8)	−0.0316 (4)	0.053 (2)
H17	0.6803	1.0414	−0.0609	0.069*
C18	0.6211 (19)	1.1525 (9)	0.0095 (6)	0.111 (5)
H18A	0.5134	1.1692	0.0341	0.145*
H18B	0.6515	1.2263	−0.0138	0.145*
H18C	0.7243	1.1309	0.0353	0.145*
N1	0.5715 (8)	0.9303 (7)	0.0030 (3)	0.0504 (17)
H1A	0.6521	0.9345	0.0360	0.066*
H1B	0.6088	0.8634	−0.0216	0.066*
C21	0.1680 (10)	0.6466 (6)	0.2198 (3)	0.0343 (15)
C22	0.3435 (9)	0.6108 (7)	0.2366 (3)	0.0391 (16)
H22	0.4484	0.6272	0.2107	0.051*
C23	0.3660 (12)	0.5502 (8)	0.2918 (4)	0.055 (2)
H23	0.4887	0.5280	0.3053	0.072*
C24	0.2221 (12)	0.5230 (7)	0.3257 (4)	0.051 (2)
H24	0.2418	0.4794	0.3634	0.066*
C25	0.0485 (10)	0.5537 (7)	0.3095 (4)	0.0433 (18)
H25	−0.0553	0.5340	0.3354	0.056*
C26	0.0232 (9)	0.6133 (7)	0.2558 (3)	0.0357 (15)
C27	−0.1652 (10)	0.6525 (7)	0.2357 (3)	0.0383 (16)
H27	−0.2493	0.5826	0.2402	0.050*
C28	−0.2377 (10)	0.7610 (8)	0.2700 (4)	0.0497 (19)
H28A	−0.2503	0.7385	0.3121	0.065*
H28B	−0.3572	0.7847	0.2540	0.065*
H28C	−0.1530	0.8307	0.2662	0.065*
N2	−0.1484 (7)	0.6841 (6)	0.1707 (3)	0.0377 (14)
H2A	−0.2316	0.7486	0.1614	0.049*
H2B	−0.1811	0.6139	0.1476	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.0289 (2)	0.0425 (3)	0.0337 (3)	−0.0004 (2)	−0.0008 (2)	0.0020 (2)
Pd2	0.0279 (2)	0.0431 (3)	0.0316 (2)	−0.0021 (2)	−0.0006 (2)	0.0011 (2)
Cl1	0.0301 (9)	0.0649 (13)	0.0363 (9)	0.0027 (8)	0.0016 (7)	0.0083 (8)
Cl2	0.0334 (9)	0.0677 (13)	0.0489 (10)	−0.0066 (9)	−0.0038 (8)	0.0173 (9)
C11	0.037 (4)	0.042 (4)	0.035 (4)	0.002 (3)	−0.001 (3)	−0.005 (3)
C12	0.040 (4)	0.050 (4)	0.037 (4)	0.007 (4)	0.002 (3)	0.004 (3)
C13	0.047 (5)	0.065 (5)	0.040 (4)	−0.001 (4)	−0.017 (4)	0.002 (4)
C14	0.068 (6)	0.073 (6)	0.052 (5)	0.013 (5)	−0.011 (5)	0.019 (5)
C15	0.059 (5)	0.064 (6)	0.052 (5)	0.001 (5)	0.014 (5)	0.018 (4)
C16	0.042 (4)	0.053 (4)	0.039 (4)	−0.005 (4)	0.008 (4)	0.002 (3)
C17	0.043 (4)	0.061 (5)	0.056 (5)	−0.016 (4)	−0.004 (4)	0.007 (4)
C18	0.137 (12)	0.056 (6)	0.141 (12)	−0.022 (7)	−0.053 (11)	−0.006 (7)
N1	0.027 (3)	0.069 (5)	0.055 (4)	0.005 (3)	−0.004 (3)	0.006 (3)
C21	0.033 (4)	0.037 (3)	0.034 (3)	0.000 (3)	−0.001 (3)	0.004 (3)
C22	0.032 (4)	0.047 (4)	0.038 (4)	−0.002 (3)	0.005 (3)	0.004 (3)
C23	0.046 (5)	0.064 (5)	0.056 (5)	0.007 (4)	−0.002 (4)	0.015 (4)
C24	0.055 (5)	0.043 (4)	0.054 (5)	0.010 (4)	0.004 (4)	0.007 (4)
C25	0.034 (4)	0.048 (4)	0.048 (4)	−0.001 (3)	0.006 (3)	−0.001 (3)
C26	0.025 (3)	0.046 (4)	0.036 (3)	−0.002 (3)	−0.002 (3)	−0.003 (3)
C27	0.030 (4)	0.045 (4)	0.040 (4)	−0.005 (3)	0.000 (3)	0.000 (3)
C28	0.038 (4)	0.061 (5)	0.049 (4)	−0.003 (4)	0.006 (3)	−0.001 (4)
N2	0.021 (3)	0.060 (4)	0.032 (3)	−0.004 (2)	−0.001 (2)	0.000 (3)

Geometric parameters (Å, º)

Pd1—Cl1	2.332 (2)	C18—H18B	0.9801
Pd1—Cl2	2.447 (2)	C18—H18C	0.9801
Pd1—N1	2.020 (6)	N1—H1A	0.9500
Pd1—C11	1.946 (8)	N1—H1B	0.9500
Pd2—Cl1	2.4781 (19)	C21—C26	1.381 (10)
Pd2—Cl2	2.333 (2)	C21—C22	1.395 (10)
Pd2—N2	2.019 (5)	C22—C23	1.411 (11)
Pd2—C21	1.946 (7)	C22—H22	0.9800
C11—C16	1.388 (10)	C23—C24	1.333 (12)
C11—C12	1.404 (11)	C23—H23	0.9800
C12—C13	1.377 (10)	C24—C25	1.364 (11)
C12—H12	0.9800	C24—H24	0.9800
C13—C14	1.352 (12)	C25—C26	1.381 (10)
C13—H13	0.9800	C25—H25	0.9800
C14—C15	1.335 (13)	C26—C27	1.513 (10)
C14—H14	0.9800	C27—C28	1.501 (11)
C15—C16	1.406 (11)	C27—N2	1.505 (9)
C15—H15	0.9800	C27—H27	0.9800
C16—C17	1.484 (11)	C28—H28A	0.9801
C17—C18	1.489 (13)	C28—H28B	0.9801
C17—N1	1.490 (10)	C28—H28C	0.9801
C17—H17	0.9800	N2—H2A	0.9500
C18—H18A	0.9801	N2—H2B	0.9500
Cl1—Pd1—Cl2	86.90 (7)	H18B—C18—H18C	109.5
N1—Pd1—Cl1	175.2 (2)	C17—N1—Pd1	110.7 (5)
N1—Pd1—Cl2	95.67 (19)	C17—N1—H1A	109.5
C11—Pd1—N1	81.2 (3)	Pd1—N1—H1A	109.5
C11—Pd1—Cl1	96.5 (2)	C17—N1—H1B	109.5
C11—Pd1—Cl2	175.5 (2)	Pd1—N1—H1B	109.5
Cl2—Pd2—Cl1	86.15 (7)	H1A—N1—H1B	108.1
N2—Pd2—Cl1	95.82 (17)	C26—C21—C22	118.6 (6)
N2—Pd2—Cl2	177.97 (18)	C26—C21—Pd2	116.0 (5)
C21—Pd2—N2	81.9 (3)	C22—C21—Pd2	125.4 (5)
C21—Pd2—Cl1	177.4 (2)	C21—C22—C23	118.2 (7)
C21—Pd2—Cl2	96.1 (2)	C21—C22—H22	120.9
Pd1—Cl1—Pd2	92.98 (7)	C23—C22—H22	120.9
Pd2—Cl2—Pd1	93.74 (7)	C24—C23—C22	120.8 (8)
C16—C11—C12	118.7 (7)	C24—C23—H23	119.6
C16—C11—Pd1	114.5 (6)	C22—C23—H23	119.6
C12—C11—Pd1	126.8 (6)	C23—C24—C25	122.2 (8)
C13—C12—C11	119.2 (8)	C23—C24—H24	118.9
C13—C12—H12	120.4	C25—C24—H24	118.9
C11—C12—H12	120.4	C24—C25—C26	118.1 (7)
C14—C13—C12	121.0 (8)	C24—C25—H25	120.9
C14—C13—H13	119.5	C26—C25—H25	120.9
C12—C13—H13	119.5	C25—C26—C21	122.0 (6)
C15—C14—C13	121.6 (8)	C25—C26—C27	120.9 (6)
C15—C14—H14	119.2	C21—C26—C27	117.0 (6)
C13—C14—H14	119.2	C28—C27—N2	110.4 (6)
C14—C15—C16	119.7 (8)	C28—C27—C26	112.9 (6)
C14—C15—H15	120.1	N2—C27—C26	106.2 (6)
C16—C15—H15	120.1	C28—C27—H27	109.1
C11—C16—C15	119.7 (8)	N2—C27—H27	109.1
C11—C16—C17	117.0 (7)	C26—C27—H27	109.1
C15—C16—C17	123.2 (8)	C27—C28—H28A	109.5
C16—C17—C18	114.2 (9)	C27—C28—H28B	109.5
C16—C17—N1	105.7 (6)	H28A—C28—H28B	109.5
C18—C17—N1	109.7 (8)	C27—C28—H28C	109.5
C16—C17—H17	109.1	H28A—C28—H28C	109.5
C18—C17—H17	109.1	H28B—C28—H28C	109.5
N1—C17—H17	109.1	C27—N2—Pd2	112.7 (4)
C17—C18—H18A	109.5	C27—N2—H2A	109.0
C17—C18—H18B	109.5	Pd2—N2—H2A	109.0
H18A—C18—H18B	109.5	C27—N2—H2B	109.0
C17—C18—H18C	109.5	Pd2—N2—H2B	109.0
H18A—C18—H18C	109.5	H2A—N2—H2B	107.8

(III) [SP-4–4]-(R)-[2-(1-aminoethyl)phenyl-κ²C¹,N]chloro(pyridine- κN)palladium(II)

Crystal data

[Pd(C8H10N)Cl(C5H5N)]	Dx = 1.685 Mg m^−3
Mr = 341.12	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41	Cell parameters from 37267 reflections
Hall symbol: I 4bw	θ = 1.6–28.5°
a = 18.511 (5) Å	µ = 1.56 mm^−1
c = 15.698 (6) Å	T = 293 K
V = 5379 (3) Å^3	Needle, coluorless
Z = 16	1.05 × 0.08 × 0.03 mm
F(000) = 2720

Data collection

Bruker SMART APEX CCD area-detector diffractometer	6731 independent reflections
Radiation source: fine-focus sealed tube	5005 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.098
ω scans	θmax = 28.5°, θmin = 1.6°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −24→24
Tmin = 0.292, Tmax = 0.955	k = −24→24
37248 measured reflections	l = −20→20

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)] = 0.046	H-atom parameters constrained
wR(F^2) = 0.110	w = 1/[σ^2(Fo^2) + (0.0375P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
6731 reflections	Δρmax = 0.54 e Å^−3
309 parameters	Δρmin = −0.54 e Å^−3
1 restraint	Absolute structure: Flack (1983); 3192 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (6)

Special details

Experimental. The values of Tmin and Tmax are 0.757793 and 1.000000 from SADABS.

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	0.49331 (3)	0.39613 (3)	0.24549 (3)	0.03910 (18)
Cl1	0.40499 (12)	0.39478 (13)	0.35822 (18)	0.0545 (6)
N12	0.4158 (3)	0.3628 (3)	0.1619 (6)	0.0408 (18)
C9	0.3589 (4)	0.4045 (4)	0.1446 (7)	0.050 (2)
H9	0.3584	0.4538	0.1674	0.065*
C10	0.3033 (4)	0.3831 (5)	0.0987 (7)	0.055 (2)
H10	0.2612	0.4147	0.0922	0.072*
C11	0.3041 (5)	0.3152 (5)	0.0591 (8)	0.069 (3)
H11	0.2653	0.3000	0.0207	0.090*
C12	0.3613 (5)	0.2713 (4)	0.0762 (8)	0.063 (3)
H12	0.3629	0.2219	0.0540	0.081*
C13	0.4169 (5)	0.2978 (5)	0.1255 (8)	0.059 (3)
H13	0.4595	0.2673	0.1343	0.077*
N11	0.5772 (3)	0.4231 (3)	0.3253 (5)	0.0434 (18)
H11A	0.5795	0.4741	0.3312	0.056*
H11B	0.5690	0.4028	0.3800	0.056*
C1	0.7101 (4)	0.4313 (5)	0.3306 (5)	0.070 (2)
H1A	0.7078	0.4835	0.3199	0.091*
H1B	0.7548	0.4118	0.3064	0.091*
H1C	0.7093	0.4224	0.3921	0.091*
C2	0.6471 (4)	0.3954 (4)	0.2902 (5)	0.0410 (17)
H2	0.6501	0.3438	0.3034	0.053*
C3	0.6410 (4)	0.4028 (4)	0.1946 (6)	0.0376 (18)
C4	0.7003 (5)	0.4120 (4)	0.1414 (7)	0.053 (2)
H4	0.7492	0.4109	0.1654	0.069*
C5	0.6912 (6)	0.4225 (5)	0.0565 (8)	0.063 (3)
H5	0.7339	0.4287	0.0203	0.082*
C6	0.6230 (5)	0.4247 (5)	0.0193 (9)	0.063 (3)
H6	0.6177	0.4325	−0.0421	0.082*
C7	0.5628 (5)	0.4156 (5)	0.0704 (7)	0.053 (2)
H7	0.5146	0.4169	0.0446	0.069*
C8	0.5698 (4)	0.4043 (4)	0.1609 (7)	0.042 (2)
Pd2	0.10564 (3)	−0.00190 (3)	0.14678 (3)	0.03857 (18)
Cl2	0.10783 (12)	−0.08972 (12)	0.03174 (19)	0.0538 (6)
N22	0.1433 (4)	−0.0787 (3)	0.2290 (6)	0.044 (2)
C29	0.2082 (4)	−0.0762 (5)	0.2635 (8)	0.061 (3)
H29	0.2388	−0.0343	0.2516	0.080*
C30	0.2348 (5)	−0.1295 (5)	0.3152 (10)	0.085 (4)
H30	0.2819	−0.1236	0.3429	0.110*
C31	0.1960 (5)	−0.1901 (6)	0.3279 (7)	0.073 (3)
H31	0.2179	−0.2316	0.3567	0.095*
C32	0.1302 (5)	−0.1932 (5)	0.3022 (9)	0.086 (4)
H32	0.0984	−0.2329	0.3196	0.112*
C33	0.1048 (5)	−0.1365 (5)	0.2469 (10)	0.086 (4)
H33	0.0567	−0.1413	0.2214	0.112*
N21	0.0712 (3)	0.0791 (3)	0.0715 (5)	0.0436 (19)
H21A	0.0968	0.0772	0.0191	0.057*
H21B	0.0214	0.0720	0.0594	0.057*
C21	0.1474 (4)	0.1892 (4)	0.0755 (5)	0.061 (2)
H21C	0.1504	0.2384	0.0985	0.080*
H21D	0.1445	0.1913	0.0133	0.080*
H21E	0.1904	0.1619	0.0923	0.080*
C22	0.0810 (4)	0.1525 (4)	0.1102 (7)	0.049 (2)
H22	0.0389	0.1819	0.0951	0.063*
C23	0.0807 (4)	0.1422 (5)	0.2037 (6)	0.0397 (19)
C24	0.0696 (4)	0.2000 (5)	0.2595 (8)	0.063 (3)
H24	0.0626	0.2488	0.2369	0.082*
C25	0.0683 (5)	0.1880 (7)	0.3482 (9)	0.070 (3)
H25	0.0619	0.2279	0.3886	0.091*
C26	0.0763 (5)	0.1189 (6)	0.3751 (8)	0.072 (3)
H26	0.0728	0.1091	0.4364	0.094*
C27	0.0891 (5)	0.0615 (6)	0.3211 (8)	0.067 (3)
H27	0.0958	0.0126	0.3438	0.087*
C28	0.0925 (4)	0.0739 (5)	0.2357 (7)	0.045 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.0382 (3)	0.0410 (3)	0.0381 (5)	−0.0041 (2)	−0.0042 (3)	−0.0026 (3)
Cl1	0.0554 (12)	0.0656 (14)	0.0425 (17)	−0.0121 (11)	0.0016 (11)	0.0020 (12)
N12	0.047 (4)	0.035 (3)	0.040 (5)	−0.001 (3)	−0.007 (3)	−0.005 (3)
C9	0.046 (4)	0.047 (4)	0.057 (6)	0.006 (3)	−0.008 (4)	−0.007 (4)
C10	0.046 (4)	0.065 (5)	0.056 (6)	0.006 (4)	−0.007 (4)	−0.017 (4)
C11	0.053 (5)	0.077 (6)	0.077 (8)	−0.031 (4)	−0.018 (5)	0.026 (6)
C12	0.083 (6)	0.048 (5)	0.057 (7)	−0.016 (4)	−0.013 (5)	−0.012 (4)
C13	0.053 (5)	0.053 (5)	0.071 (8)	0.001 (4)	0.004 (5)	−0.001 (5)
N11	0.043 (4)	0.045 (3)	0.042 (5)	−0.004 (3)	0.006 (3)	−0.006 (3)
C1	0.041 (4)	0.108 (7)	0.061 (5)	−0.010 (4)	−0.005 (4)	−0.011 (5)
C2	0.042 (4)	0.044 (4)	0.037 (4)	−0.008 (3)	−0.001 (3)	0.000 (3)
C3	0.044 (4)	0.027 (3)	0.042 (5)	0.000 (3)	−0.002 (3)	0.005 (3)
C4	0.056 (4)	0.042 (4)	0.060 (6)	0.006 (3)	−0.001 (4)	−0.005 (4)
C5	0.074 (6)	0.058 (5)	0.058 (8)	0.020 (4)	0.018 (5)	0.005 (5)
C6	0.064 (6)	0.075 (6)	0.049 (8)	0.006 (5)	0.008 (5)	0.005 (6)
C7	0.050 (5)	0.069 (6)	0.039 (7)	0.003 (4)	−0.002 (4)	−0.001 (5)
C8	0.041 (4)	0.041 (4)	0.043 (7)	−0.008 (3)	−0.003 (4)	−0.001 (4)
Pd2	0.0377 (3)	0.0407 (3)	0.0374 (5)	−0.0029 (2)	−0.0021 (3)	0.0030 (3)
Cl2	0.0570 (13)	0.0550 (12)	0.0495 (18)	0.0044 (10)	−0.0004 (12)	−0.0083 (12)
N22	0.050 (4)	0.042 (4)	0.041 (6)	−0.005 (3)	−0.007 (3)	−0.003 (3)
C29	0.044 (4)	0.080 (6)	0.060 (7)	−0.020 (4)	−0.024 (4)	0.040 (5)
C30	0.047 (5)	0.104 (8)	0.104 (11)	−0.017 (5)	−0.016 (6)	0.051 (7)
C31	0.069 (6)	0.096 (7)	0.056 (7)	0.014 (5)	−0.018 (5)	0.033 (6)
C32	0.073 (6)	0.063 (6)	0.123 (11)	−0.023 (5)	−0.037 (7)	0.049 (6)
C33	0.058 (5)	0.074 (6)	0.126 (11)	−0.023 (5)	−0.030 (7)	0.039 (7)
N21	0.052 (4)	0.049 (4)	0.030 (4)	0.000 (3)	0.003 (3)	0.011 (3)
C21	0.065 (5)	0.042 (4)	0.077 (6)	−0.014 (3)	0.011 (4)	0.001 (4)
C22	0.037 (4)	0.039 (4)	0.070 (6)	0.008 (3)	0.007 (4)	0.002 (4)
C23	0.030 (3)	0.050 (4)	0.039 (4)	−0.006 (3)	0.006 (3)	−0.007 (3)
C24	0.050 (4)	0.056 (5)	0.084 (8)	−0.011 (4)	0.001 (5)	−0.026 (5)
C25	0.071 (6)	0.089 (7)	0.052 (7)	−0.003 (5)	0.011 (5)	−0.029 (6)
C26	0.064 (6)	0.115 (9)	0.038 (8)	−0.025 (6)	0.014 (5)	−0.015 (6)
C27	0.070 (6)	0.082 (7)	0.049 (9)	−0.021 (5)	0.018 (6)	0.009 (6)
C28	0.034 (4)	0.060 (5)	0.040 (6)	−0.016 (3)	0.001 (4)	−0.009 (5)

Geometric parameters (Å, º)

Pd1—Cl1	2.409 (3)	Pd2—Cl2	2.430 (3)
Pd1—N11	2.056 (7)	Pd2—N21	2.012 (7)
Pd1—N12	2.040 (7)	Pd2—N22	2.042 (8)
Pd1—C8	1.947 (10)	Pd2—C28	1.994 (10)
N12—C13	1.331 (12)	N22—C33	1.317 (10)
N12—C9	1.335 (10)	N22—C29	1.318 (11)
C9—C10	1.318 (12)	C29—C30	1.369 (14)
C9—H9	0.9800	C29—H29	0.9800
C10—C11	1.402 (13)	C30—C31	1.346 (13)
C10—H10	0.9800	C30—H30	0.9800
C11—C12	1.361 (13)	C31—C32	1.283 (11)
C11—H11	0.9800	C31—H31	0.9800
C12—C13	1.377 (13)	C32—C33	1.441 (14)
C12—H12	0.9800	C32—H32	0.9800
C13—H13	0.9800	C33—H33	0.9800
N11—C2	1.498 (10)	N21—C22	1.499 (11)
N11—H11A	0.9500	N21—H21A	0.9500
N11—H11B	0.9500	N21—H21B	0.9500
C1—C2	1.484 (10)	C21—C22	1.507 (9)
C1—H1A	0.9801	C21—H21C	0.9801
C1—H1B	0.9801	C21—H21D	0.9801
C1—H1C	0.9801	C21—H21E	0.9801
C2—C3	1.511 (12)	C22—C23	1.480 (14)
C2—H2	0.9800	C22—H22	0.9800
C3—C4	1.390 (13)	C23—C28	1.378 (13)
C3—C8	1.421 (12)	C23—C24	1.397 (13)
C4—C5	1.358 (16)	C24—C25	1.410 (18)
C4—H4	0.9800	C24—H24	0.9800
C5—C6	1.392 (15)	C25—C26	1.356 (15)
C5—H5	0.9800	C25—H25	0.9800
C6—C7	1.382 (14)	C26—C27	1.380 (15)
C6—H6	0.9800	C26—H26	0.9800
C7—C8	1.442 (15)	C27—C28	1.361 (16)
C7—H7	0.9800	C27—H27	0.9800
N11—Pd1—Cl1	93.9 (2)	N21—Pd2—Cl2	93.9 (2)
N12—Pd1—Cl1	89.6 (2)	N22—Pd2—Cl2	89.9 (2)
C8—Pd1—Cl1	174.4 (3)	C28—Pd2—Cl2	173.1 (3)
N12—Pd1—N11	175.0 (3)	N21—Pd2—N22	175.9 (3)
C8—Pd1—N11	81.2 (3)	C28—Pd2—N21	81.3 (4)
C8—Pd1—N12	95.5 (4)	C28—Pd2—N22	95.1 (4)
C13—N12—C9	116.5 (8)	C33—N22—C29	115.7 (8)
C13—N12—Pd1	122.6 (6)	C33—N22—Pd2	121.1 (7)
C9—N12—Pd1	120.7 (6)	C29—N22—Pd2	123.2 (6)
C10—C9—N12	123.7 (8)	N22—C29—C30	123.2 (8)
C10—C9—H9	118.2	N22—C29—H29	118.4
N12—C9—H9	118.2	C30—C29—H29	118.4
C9—C10—C11	120.2 (8)	C31—C30—C29	119.7 (9)
C9—C10—H10	119.9	C31—C30—H30	120.2
C11—C10—H10	119.9	C29—C30—H30	120.2
C12—C11—C10	117.2 (9)	C32—C31—C30	119.9 (9)
C12—C11—H11	121.4	C32—C31—H31	120.1
C10—C11—H11	121.4	C30—C31—H31	120.1
C11—C12—C13	118.6 (8)	C31—C32—C33	117.7 (9)
C11—C12—H12	120.7	C31—C32—H32	121.1
C13—C12—H12	120.7	C33—C32—H32	121.1
N12—C13—C12	123.5 (8)	N22—C33—C32	123.0 (9)
N12—C13—H13	118.2	N22—C33—H33	118.5
C12—C13—H13	118.2	C32—C33—H33	118.5
C2—N11—Pd1	110.2 (6)	C22—N21—Pd2	113.5 (6)
C2—N11—H11A	109.6	C22—N21—H21A	108.9
Pd1—N11—H11A	109.6	Pd2—N21—H21A	108.9
C2—N11—H11B	109.6	C22—N21—H21B	108.9
Pd1—N11—H11B	109.6	Pd2—N21—H21B	108.9
H11A—N11—H11B	108.1	H21A—N21—H21B	107.7
C2—C1—H1A	109.5	C22—C21—H21C	109.5
C2—C1—H1B	109.5	C22—C21—H21D	109.5
H1A—C1—H1B	109.5	H21C—C21—H21D	109.5
C2—C1—H1C	109.5	C22—C21—H21E	109.5
H1A—C1—H1C	109.5	H21C—C21—H21E	109.5
H1B—C1—H1C	109.5	H21D—C21—H21E	109.5
C1—C2—N11	111.7 (7)	C23—C22—N21	106.6 (7)
C1—C2—C3	116.3 (7)	C23—C22—C21	114.7 (8)
N11—C2—C3	105.7 (7)	N21—C22—C21	111.2 (7)
C1—C2—H2	107.6	C23—C22—H22	108.0
N11—C2—H2	107.6	N21—C22—H22	108.0
C3—C2—H2	107.6	C21—C22—H22	108.0
C4—C3—C8	120.5 (9)	C28—C23—C24	119.9 (11)
C4—C3—C2	123.3 (8)	C28—C23—C22	118.5 (9)
C8—C3—C2	116.2 (8)	C24—C23—C22	121.6 (9)
C5—C4—C3	120.6 (10)	C23—C24—C25	120.1 (11)
C5—C4—H4	119.7	C23—C24—H24	120.0
C3—C4—H4	119.7	C25—C24—H24	120.0
C4—C5—C6	121.9 (11)	C26—C25—C24	117.0 (11)
C4—C5—H5	119.0	C26—C25—H25	121.5
C6—C5—H5	119.0	C24—C25—H25	121.5
C7—C6—C5	119.0 (12)	C25—C26—C27	123.6 (12)
C7—C6—H6	120.5	C25—C26—H26	118.2
C5—C6—H6	120.5	C27—C26—H26	118.2
C6—C7—C8	121.1 (9)	C28—C27—C26	119.0 (10)
C6—C7—H7	119.4	C28—C27—H27	120.5
C8—C7—H7	119.4	C26—C27—H27	120.5
C3—C8—C7	116.9 (8)	C27—C28—C23	120.4 (10)
C3—C8—Pd1	114.8 (8)	C27—C28—Pd2	125.2 (8)
C7—C8—Pd1	128.2 (7)	C23—C28—Pd2	114.3 (8)