trans-Chlorido[6-chloro-4-(4-methoxy­benz­yl)-3-oxo-3,4-dihydro­pyrazin-2-yl]­bis­(triphenyl­phosphine)palladium(II)

Robeyns, K.; Alen, J.; De Borggraeve, W.M.; Compernolle, F.; Van Meervelt, L.

doi:10.1107/S1600536807063441

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page m93

https://doi.org/10.1107/S1600536807063441

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trans-Chlorido[6-chloro-4-(4-methoxybenzyl)-3-oxo-3,4-dihydropyrazin-2-yl]bis(triphenylphosphine)palladium(II)

Koen Robeyns,^a Jo Alen,^b Wim M. De Borggraeve,^b Frans Compernolle ^b and Luc Van Meervelt ^a ^*

^aBiomolecular Architecture, Katholieke Universiteit Leuven, Department of Chemistry, Celestijnenlaan 200F, B-3001 Leuven (Heverlee), Belgium, and ^bMolecular Design and Synthesis, Katholieke Universiteit Leuven, Department of Chemistry, Celestijnenlaan 200F, B-3001 Leuven (Heverlee), Belgium
^*Correspondence e-mail: luc.vanmeervelt@chem.kuleuven.be

(Received 19 November 2007; accepted 26 November 2007; online 6 December 2007)

The title compound, [Pd(C₁₂H₁₀ClN₂O₂)Cl(C₁₈H₁₅P)₂], is the intermediate of the reduction of a 3,5-dichloropyrazinone [Loosen, Tutonda, Khorasani, Compernolle & Hoornaert (1991 ). Tetrahedron, 47, 9259–9268]. This species is formed by oxidative addition of coordinatively unsaturated Pd⁰ to the reactive 3-position of the heterocycle. The coordination around the Pd atom is square planar, with two trans PPh₃ ligands. π–π interactions are observed between the centroid of the pyrazinone ring and planes of two adjacent phenyl rings, one from each PPh₃ group (3.25 and 3.078 Å), stabilizing the intermediate structure. This could explain the reduced reactivity towards substitution of the Cl atom by the formate anion, resulting in poor yield of the reduced compound. 3-Substituted pyrazinones are important precursors in the synthesis of 5-aminopiperidinone-2-carboxylate (APC) systems.

Related literature

For related literature on the reduction of 3,5-dichloropyrazinones, see: Loosen et al. (1991). For related literature on 3,5-dichloropyrazinones, see: Pawar & De Borggraeve (2006 ). For related literature on APC systems, see: De Borggraeve et al. (2004 ); Alen et al. (2007 ). For the Cambridge Structural Database (Version 5.28), see: Allen (2002 ).

Experimental

Crystal data

[Pd(C₁₂H₁₀ClN₂O₂)Cl(C₁₈H₁₅P)₂]
M_r = 916.06
Triclinic, $[P \overline 1]$
a = 10.7544 (1) Å
b = 13.1526 (1) Å
c = 16.9967 (1) Å
α = 91.811 (1)°
β = 94.39 (1)°
γ = 98.451 (1)°
V = 2368.83 (3) Å³
Z = 2
Cu Kα radiation
μ = 5.13 mm⁻¹
T = 100 (2) K
0.5 × 0.24 × 0.24 mm

Data collection

Bruker SMART 6000 diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.175, T_max = 0.292
23121 measured reflections
8422 independent reflections
7879 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.073
S = 1.08
8422 reflections
515 parameters
318 restraints
H-atom parameters constrained
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ) and ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807063441/dn2294sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807063441/dn2294Isup2.hkl

checkCIF report

Comment top

The target structure 5-chloro-1-(4-methoxybenzyl)-2(1H)-pyrazinone) was synthesized as a starting product for the synthesis of dipeptide mimics (Alen et al., 2007; De Borggraeve et al., 2004). This compound can be formed by reduction of a 3,5-dichloropyrazinone with sodium formate using Pd(PPh₃)₄ as a catalyst. Surprisingly, the title compound (I) was isolated as an intermediate (Scheme 1, Fig. 1). This means that substitution of the chlorine atom with sodium formate and subsequent proton shift leading to the desired compound, did not occur. In similar reactions the yields are high and no traces of the intermediate substance are found. However, the presence of a hydrogen atom para to the palladium atom and a para-methoxybenzyl substituent on the N-1 nitrogen atom of the pyrazinone scaffold, seem to increase the stability of the intermediate. This stability might arise from the π–π interactions between the pyrazinone and two phenyl rings of the PPh₃ groups. The centroid of the pyrazinone makes a distance of 3.25 Å and 3.078 Å with the planes formed by the two adjacent phenyl rings. Searches in the CSD database (Version 5.28) (Allen, 2002) for similar structures (59 hits in 50 crystal structures) revealed that the angle between the pyrazinone ring and an adjacent phenyl ring is on average 27.6° (range 13.0° - 65.2°). As fragment for the CSD search a Pd atom with only four substituents (2 PPh₃ groups, any halogen and an aromatic ring consisting of any atom type) was used. In the represented structure the angles are 15.4° and 13.9°, resulting in almost parallel pyrazinone and adjacent phenyl rings.

Related literature top

For related literature on the reduction of 3,5-dichloropyrazinones, see: Loosen et al. (1991). For related literature on 3,5-dichloropyrazinones, see: Pawar & De Borggraeve (2006). For related literature on APC systems, see: De Borggraeve et al. (2004); Alen et al. (2007). For the Cambridge Structural Database, see: Allen (2002).

Experimental top

To a solution of 570 mg (2 mmol) 3,5-dichloropyrazinone in 20 ml DMF, 204 mg (3 mmol) sodium formate and 115 mg Pd(PPh₃)₄ are added. The solution is stirred for 4 h at 110 °C under inert atmosphere. After removal of the solvent, the residue is treated with 50 ml of water and extracted with 3x 50 ml dichloromethane. After drying over magnesium sulfate and evaporation of the solvent, the product was chromatographically purified (Heptane/EtOAc 50:50). The title compound was formed as a by-product with a yield of 45% and spontaneously crystallized from the Heptane/EtOAc mixture.

Structure description top

For related literature on the reduction of 3,5-dichloropyrazinones, see: Loosen et al. (1991). For related literature on 3,5-dichloropyrazinones, see: Pawar & De Borggraeve (2006). For related literature on APC systems, see: De Borggraeve et al. (2004); Alen et al. (2007). For the Cambridge Structural Database, see: Allen (2002).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of the title compound (I), showing the atom-labeling scheme with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity.
	Fig. 2. The title compound (I) is the stable intermediate in the synthesis of 5-chloro-1-(4-methoxybenzyl)-2(1H)-pyrazinone.

trans-Chlorido[6-chloro-4-(4-methoxybenzyl)-3-oxo-3,4-dihydropyrazin-2- yl]bis(triphenylphosphine)palladium(II) top

Crystal data top

[Pd(C₁₂H₁₀ClN₂O₂)Cl(C₁₈H₁₅P)₂]	Z = 2
M_r = 916.06	F(000) = 936
Triclinic, P1	D_x = 1.284 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54178 Å
a = 10.7544 (1) Å	Cell parameters from 6414 reflections
b = 13.1526 (1) Å	θ = 2.6–70.6°
c = 16.9967 (1) Å	µ = 5.13 mm⁻¹
α = 91.811 (1)°	T = 100 K
β = 94.39 (1)°	Block, transparent
γ = 98.451 (1)°	0.5 × 0.24 × 0.24 mm
V = 2368.83 (3) Å³

Data collection top

Bruker SMART 6000 diffractometer	8422 independent reflections
Radiation source: fine-focus sealed tube	7879 reflections with I > 2σ(I)
Crossed Goebel mirrors monochromator	R_int = 0.041
ω and φ scans	θ_max = 68.8°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −12→12
T_min = 0.175, T_max = 0.292	k = −15→15
23121 measured reflections	l = −20→20

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0381P)² + 0.3456P] where P = (F_o² + 2F_c²)/3
8422 reflections	(Δ/σ)_max = 0.002
515 parameters	Δρ_max = 0.58 e Å⁻³
318 restraints	Δρ_min = −0.58 e Å⁻³

Crystal data top

[Pd(C₁₂H₁₀ClN₂O₂)Cl(C₁₈H₁₅P)₂]	γ = 98.451 (1)°
M_r = 916.06	V = 2368.83 (3) Å³
Triclinic, P1	Z = 2
a = 10.7544 (1) Å	Cu Kα radiation
b = 13.1526 (1) Å	µ = 5.13 mm⁻¹
c = 16.9967 (1) Å	T = 100 K
α = 91.811 (1)°	0.5 × 0.24 × 0.24 mm
β = 94.39 (1)°

Data collection top

Bruker SMART 6000 diffractometer	8422 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	7879 reflections with I > 2σ(I)
T_min = 0.175, T_max = 0.292	R_int = 0.041
23121 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	318 restraints
wR(F²) = 0.073	H-atom parameters constrained
S = 1.08	Δρ_max = 0.58 e Å⁻³
8422 reflections	Δρ_min = −0.58 e Å⁻³
515 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Pd1	0.882642 (11)	0.283301 (9)	0.798987 (7)	0.00908 (6)
P2	0.83318 (4)	0.22202 (3)	0.92192 (2)	0.00951 (10)
C3	0.84174 (17)	0.08526 (14)	0.92756 (11)	0.0124 (3)
C4	0.83393 (19)	0.02691 (15)	0.85665 (11)	0.0177 (4)
H4	0.8301	0.0594	0.8076	0.021*
C5	0.8318 (2)	−0.07905 (15)	0.85853 (12)	0.0221 (4)
H5	0.8258	−0.1189	0.8104	0.027*
C6	0.83855 (19)	−0.12702 (15)	0.93000 (13)	0.0210 (4)
H6	0.8377	−0.1993	0.9308	0.025*
C7	0.84646 (18)	−0.06874 (15)	1.00047 (12)	0.0184 (4)
H7	0.8512	−0.1013	1.0495	0.022*
C8	0.84748 (17)	0.03648 (15)	0.99934 (11)	0.0152 (4)
H8	0.8521	0.0758	1.0476	0.018*
C9	0.93153 (18)	0.28969 (14)	1.00503 (11)	0.0141 (4)
C10	0.8973 (2)	0.28020 (16)	1.08230 (12)	0.0196 (4)
H10	0.8211	0.2379	1.0921	0.023*
C11	0.9737 (2)	0.33190 (17)	1.14494 (12)	0.0255 (4)
H11	0.9503	0.3243	1.1974	0.031*
C12	1.0844 (2)	0.39479 (16)	1.13073 (13)	0.0272 (5)
H12	1.1367	0.4303	1.1736	0.033*
C13	1.1187 (2)	0.40580 (15)	1.05453 (14)	0.0252 (5)
H13	1.1943	0.4493	1.0452	0.030*
C14	1.0431 (2)	0.35355 (14)	0.99098 (12)	0.0188 (4)
H14	1.0672	0.3613	0.9386	0.023*
C15	0.67328 (18)	0.23049 (15)	0.94789 (10)	0.0139 (4)
C16	0.6417 (2)	0.32462 (15)	0.97354 (12)	0.0196 (4)
H16	0.7061	0.3821	0.9845	0.023*
C17	0.5173 (2)	0.33501 (17)	0.98318 (13)	0.0265 (5)
H17	0.4970	0.3993	1.0010	0.032*
C18	0.4222 (2)	0.25182 (18)	0.96699 (13)	0.0264 (5)
H18	0.3368	0.2594	0.9725	0.032*
C19	0.4529 (2)	0.15776 (17)	0.94274 (13)	0.0238 (4)
H19	0.3883	0.1003	0.9326	0.029*
C20	0.5775 (2)	0.14669 (16)	0.93306 (11)	0.0186 (4)
H20	0.5975	0.0819	0.9163	0.022*
P21	0.90967 (4)	0.34277 (3)	0.67295 (2)	0.00962 (10)
C22	1.06025 (17)	0.42371 (13)	0.66477 (11)	0.0123 (3)
O22	0.63099 (13)	0.14734 (10)	0.74606 (8)	0.0164 (3)
C23	1.11981 (18)	0.47685 (15)	0.73317 (11)	0.0162 (4)
H23	1.0858	0.4651	0.7826	0.019*
C24	1.2293 (2)	0.54722 (16)	0.72865 (13)	0.0234 (4)
H24	1.2687	0.5846	0.7749	0.028*
C25	1.2805 (2)	0.56260 (17)	0.65720 (14)	0.0265 (5)
H25	1.3551	0.6105	0.6544	0.032*
C26	1.2236 (2)	0.50845 (17)	0.58949 (13)	0.0242 (4)
H26	1.2601	0.5182	0.5406	0.029*
C27	1.1130 (2)	0.43986 (15)	0.59306 (11)	0.0187 (4)
H27	1.0732	0.4038	0.5464	0.022*
C28	0.89390 (18)	0.23888 (15)	0.59781 (11)	0.0155 (4)
C29	0.9105 (2)	0.14114 (15)	0.62008 (12)	0.0191 (4)
H29	0.9347	0.1297	0.6736	0.023*
C30	0.8916 (2)	0.05938 (17)	0.56403 (14)	0.0278 (5)
H30	0.9043	−0.0074	0.5793	0.033*
C31	0.8544 (2)	0.07548 (17)	0.48620 (14)	0.0293 (5)
H31	0.8393	0.0193	0.4485	0.035*
C32	0.8392 (2)	0.17322 (19)	0.46310 (13)	0.0295 (5)
H32	0.8152	0.1842	0.4094	0.035*
C33	0.8591 (2)	0.25544 (17)	0.51857 (12)	0.0226 (4)
H33	0.8491	0.3226	0.5027	0.027*
C34	0.79522 (19)	0.42356 (15)	0.63620 (10)	0.0153 (4)
C35	0.8235 (2)	0.53018 (15)	0.64354 (11)	0.0192 (4)
H35	0.9064	0.5619	0.6616	0.023*
C36	0.7301 (2)	0.59064 (18)	0.62441 (12)	0.0274 (5)
H36	0.7494	0.6635	0.6294	0.033*
C37	0.6096 (2)	0.5446 (2)	0.59829 (13)	0.0304 (5)
H37	0.5464	0.5860	0.5850	0.037*
C38	0.5802 (2)	0.4381 (2)	0.59132 (12)	0.0274 (5)
H38	0.4969	0.4067	0.5738	0.033*
C39	0.67304 (19)	0.37767 (17)	0.61004 (11)	0.0197 (4)
H39	0.6533	0.3048	0.6050	0.024*
Cl40	1.08823 (4)	0.23058 (3)	0.81045 (3)	0.01784 (10)
C41	0.71073 (17)	0.32121 (14)	0.78835 (10)	0.0112 (3)
N42	0.68875 (15)	0.41388 (12)	0.80409 (9)	0.0134 (3)
C43	0.56729 (19)	0.43210 (15)	0.79552 (11)	0.0155 (4)
Cl45	0.54465 (5)	0.55731 (4)	0.82009 (3)	0.02764 (12)
C46	0.46835 (18)	0.36031 (15)	0.77103 (10)	0.0156 (4)
H46	0.3853	0.3772	0.7655	0.019*
N47	0.49052 (15)	0.26179 (12)	0.75423 (9)	0.0136 (3)
C48	0.61075 (17)	0.23561 (14)	0.76109 (10)	0.0122 (3)
C49	0.38425 (18)	0.18064 (15)	0.72664 (11)	0.0168 (4)
H49A	0.3067	0.1955	0.7497	0.020*
H49B	0.4025	0.1135	0.7456	0.020*
C50	0.36165 (18)	0.17346 (14)	0.63773 (12)	0.0157 (4)
C51	0.25756 (19)	0.20966 (15)	0.60036 (12)	0.0185 (4)
H51	0.2003	0.2384	0.6312	0.022*
C52	0.2369 (2)	0.20408 (15)	0.51874 (12)	0.0222 (4)
H52	0.1656	0.2287	0.4939	0.027*
C53	0.3206 (2)	0.16237 (14)	0.47317 (12)	0.0188 (4)
C54	0.4253 (2)	0.12637 (16)	0.50919 (12)	0.0216 (4)
H54	0.4831	0.0986	0.4782	0.026*
C55	0.44411 (19)	0.13164 (16)	0.59098 (12)	0.0203 (4)
H55	0.5148	0.1062	0.6157	0.024*
O56	0.29196 (16)	0.15893 (12)	0.39257 (9)	0.0268 (3)
C57	0.3688 (3)	0.1064 (3)	0.34498 (15)	0.0500 (8)
H57A	0.4568	0.1394	0.3539	0.075*
H57B	0.3399	0.1095	0.2891	0.075*
H57C	0.3623	0.0344	0.3594	0.075*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.00829 (8)	0.01200 (8)	0.00741 (8)	0.00311 (5)	−0.00019 (5)	0.00213 (5)
P2	0.0098 (2)	0.0118 (2)	0.0068 (2)	0.00126 (16)	−0.00014 (16)	0.00116 (15)
C3	0.0102 (8)	0.0130 (8)	0.0138 (8)	0.0015 (6)	−0.0006 (7)	0.0018 (6)
C4	0.0197 (10)	0.0199 (9)	0.0136 (9)	0.0042 (8)	−0.0006 (7)	−0.0001 (7)
C5	0.0253 (11)	0.0175 (9)	0.0228 (10)	0.0045 (8)	−0.0016 (8)	−0.0062 (8)
C6	0.0152 (10)	0.0148 (9)	0.0331 (11)	0.0028 (7)	0.0002 (8)	0.0028 (8)
C7	0.0127 (9)	0.0197 (9)	0.0240 (10)	0.0034 (7)	0.0024 (7)	0.0111 (8)
C8	0.0119 (9)	0.0201 (9)	0.0140 (9)	0.0030 (7)	0.0020 (7)	0.0034 (7)
C9	0.0169 (9)	0.0120 (8)	0.0130 (8)	0.0033 (7)	−0.0029 (7)	−0.0008 (6)
C10	0.0210 (10)	0.0233 (10)	0.0141 (9)	0.0049 (8)	−0.0014 (8)	−0.0048 (7)
C11	0.0313 (12)	0.0287 (11)	0.0164 (9)	0.0097 (9)	−0.0030 (8)	−0.0093 (8)
C12	0.0332 (12)	0.0202 (10)	0.0261 (11)	0.0063 (9)	−0.0110 (9)	−0.0099 (8)
C13	0.0246 (11)	0.0121 (9)	0.0351 (12)	−0.0028 (8)	−0.0104 (9)	0.0000 (8)
C14	0.0210 (10)	0.0130 (9)	0.0214 (9)	0.0010 (7)	−0.0030 (8)	0.0026 (7)
C15	0.0134 (9)	0.0203 (9)	0.0085 (8)	0.0034 (7)	0.0021 (7)	0.0026 (7)
C16	0.0204 (10)	0.0184 (9)	0.0212 (10)	0.0038 (8)	0.0068 (8)	0.0043 (7)
C17	0.0295 (12)	0.0243 (10)	0.0305 (11)	0.0142 (9)	0.0121 (9)	0.0066 (9)
C18	0.0175 (10)	0.0363 (12)	0.0292 (11)	0.0101 (9)	0.0110 (8)	0.0110 (9)
C19	0.0159 (10)	0.0311 (11)	0.0235 (10)	0.0000 (8)	0.0033 (8)	0.0020 (8)
C20	0.0186 (10)	0.0222 (10)	0.0149 (9)	0.0026 (8)	0.0021 (7)	−0.0007 (7)
P21	0.0116 (2)	0.0115 (2)	0.0060 (2)	0.00296 (16)	0.00008 (15)	0.00123 (15)
C22	0.0127 (9)	0.0123 (8)	0.0132 (8)	0.0056 (7)	0.0013 (7)	0.0035 (6)
O22	0.0156 (7)	0.0142 (6)	0.0195 (7)	0.0057 (5)	−0.0031 (5)	−0.0020 (5)
C23	0.0150 (9)	0.0175 (9)	0.0166 (9)	0.0036 (7)	0.0022 (7)	0.0000 (7)
C24	0.0184 (10)	0.0245 (10)	0.0260 (10)	0.0012 (8)	−0.0012 (8)	−0.0028 (8)
C25	0.0173 (10)	0.0242 (10)	0.0378 (12)	−0.0003 (8)	0.0061 (9)	0.0037 (9)
C26	0.0244 (11)	0.0248 (10)	0.0264 (10)	0.0058 (8)	0.0133 (8)	0.0086 (8)
C27	0.0238 (10)	0.0193 (9)	0.0147 (9)	0.0074 (8)	0.0046 (8)	0.0021 (7)
C28	0.0149 (9)	0.0177 (9)	0.0131 (9)	0.0014 (7)	−0.0012 (7)	−0.0030 (7)
C29	0.0220 (10)	0.0165 (9)	0.0182 (9)	0.0018 (8)	0.0010 (8)	−0.0001 (7)
C30	0.0356 (13)	0.0178 (10)	0.0287 (11)	0.0012 (9)	0.0024 (9)	−0.0059 (8)
C31	0.0334 (12)	0.0241 (11)	0.0271 (11)	−0.0026 (9)	0.0006 (9)	−0.0140 (9)
C32	0.0353 (13)	0.0362 (12)	0.0164 (10)	0.0093 (10)	−0.0047 (9)	−0.0081 (9)
C33	0.0300 (11)	0.0242 (10)	0.0139 (9)	0.0084 (9)	−0.0033 (8)	−0.0028 (8)
C34	0.0176 (9)	0.0231 (9)	0.0071 (8)	0.0078 (7)	0.0019 (7)	0.0044 (7)
C35	0.0248 (11)	0.0214 (10)	0.0141 (9)	0.0106 (8)	0.0032 (8)	0.0055 (7)
C36	0.0380 (13)	0.0315 (11)	0.0195 (10)	0.0230 (10)	0.0087 (9)	0.0100 (8)
C37	0.0315 (12)	0.0505 (14)	0.0181 (10)	0.0291 (11)	0.0081 (9)	0.0154 (9)
C38	0.0177 (10)	0.0545 (14)	0.0128 (9)	0.0131 (10)	0.0009 (8)	0.0125 (9)
C39	0.0162 (10)	0.0343 (11)	0.0094 (8)	0.0045 (8)	0.0014 (7)	0.0074 (7)
Cl40	0.0125 (2)	0.0251 (2)	0.0184 (2)	0.00943 (17)	0.00230 (16)	0.00715 (17)
C41	0.0136 (9)	0.0156 (8)	0.0045 (7)	0.0024 (7)	0.0010 (6)	0.0010 (6)
N42	0.0158 (8)	0.0163 (7)	0.0084 (7)	0.0048 (6)	−0.0007 (6)	−0.0007 (5)
C43	0.0191 (10)	0.0169 (9)	0.0119 (8)	0.0091 (7)	−0.0011 (7)	−0.0025 (7)
Cl45	0.0266 (3)	0.0223 (2)	0.0346 (3)	0.01454 (19)	−0.0088 (2)	−0.0137 (2)
C46	0.0155 (9)	0.0230 (9)	0.0102 (8)	0.0104 (7)	0.0004 (7)	−0.0016 (7)
N47	0.0116 (8)	0.0176 (7)	0.0113 (7)	0.0026 (6)	−0.0003 (6)	−0.0008 (6)
C48	0.0134 (9)	0.0166 (9)	0.0069 (8)	0.0038 (7)	−0.0010 (6)	0.0015 (6)
C49	0.0108 (9)	0.0197 (9)	0.0190 (9)	0.0002 (7)	0.0004 (7)	0.0008 (7)
C50	0.0133 (9)	0.0126 (8)	0.0200 (9)	−0.0002 (7)	−0.0013 (7)	0.0011 (7)
C51	0.0166 (10)	0.0176 (9)	0.0213 (10)	0.0046 (7)	−0.0013 (8)	−0.0006 (7)
C52	0.0257 (11)	0.0180 (9)	0.0230 (10)	0.0090 (8)	−0.0087 (8)	0.0016 (8)
C53	0.0254 (10)	0.0131 (8)	0.0163 (9)	0.0009 (7)	−0.0040 (8)	−0.0005 (7)
C54	0.0220 (10)	0.0233 (10)	0.0196 (10)	0.0055 (8)	0.0003 (8)	−0.0052 (8)
C55	0.0172 (10)	0.0227 (10)	0.0211 (10)	0.0080 (8)	−0.0056 (8)	−0.0018 (8)
O56	0.0393 (9)	0.0273 (8)	0.0151 (7)	0.0131 (7)	−0.0047 (6)	−0.0004 (6)
C57	0.0578 (19)	0.084 (2)	0.0150 (11)	0.0361 (17)	−0.0002 (11)	−0.0048 (12)

Geometric parameters (Å, º) top

Pd1—C41	1.9812 (19)	C26—C27	1.389 (3)
Pd1—P21	2.3280 (4)	C26—H26	0.9500
Pd1—P2	2.3343 (4)	C27—H27	0.9500
Pd1—Cl40	2.4084 (4)	C28—C29	1.384 (3)
P2—C3	1.8198 (18)	C28—C33	1.402 (3)
P2—C9	1.8225 (18)	C29—C30	1.395 (3)
P2—C15	1.8259 (19)	C29—H29	0.9500
C3—C4	1.398 (3)	C30—C31	1.384 (3)
C3—C8	1.398 (3)	C30—H30	0.9500
C4—C5	1.392 (3)	C31—C32	1.385 (4)
C4—H4	0.9500	C31—H31	0.9500
C5—C6	1.388 (3)	C32—C33	1.393 (3)
C5—H5	0.9500	C32—H32	0.9500
C6—C7	1.392 (3)	C33—H33	0.9500
C6—H6	0.9500	C34—C35	1.390 (3)
C7—C8	1.383 (3)	C34—C39	1.396 (3)
C7—H7	0.9500	C35—C36	1.396 (3)
C8—H8	0.9500	C35—H35	0.9500
C9—C10	1.395 (3)	C36—C37	1.381 (4)
C9—C14	1.401 (3)	C36—H36	0.9500
C10—C11	1.388 (3)	C37—C38	1.390 (4)
C10—H10	0.9500	C37—H37	0.9500
C11—C12	1.388 (4)	C38—C39	1.390 (3)
C11—H11	0.9500	C38—H38	0.9500
C12—C13	1.380 (4)	C39—H39	0.9500
C12—H12	0.9500	C41—N42	1.299 (2)
C13—C14	1.398 (3)	C41—C48	1.474 (3)
C13—H13	0.9500	N42—C43	1.360 (3)
C14—H14	0.9500	C43—C46	1.345 (3)
C15—C20	1.396 (3)	C43—Cl45	1.7423 (19)
C15—C16	1.396 (3)	C46—N47	1.377 (2)
C16—C17	1.387 (3)	C46—H46	0.9500
C16—H16	0.9500	N47—C48	1.384 (2)
C17—C18	1.388 (3)	N47—C49	1.481 (2)
C17—H17	0.9500	C49—C50	1.510 (3)
C18—C19	1.385 (3)	C49—H49A	0.9900
C18—H18	0.9500	C49—H49B	0.9900
C19—C20	1.391 (3)	C50—C55	1.394 (3)
C19—H19	0.9500	C50—C51	1.397 (3)
C20—H20	0.9500	C51—C52	1.386 (3)
P21—C22	1.8199 (19)	C51—H51	0.9500
P21—C28	1.8208 (19)	C52—C53	1.392 (3)
P21—C34	1.8283 (19)	C52—H52	0.9500
C22—C27	1.393 (3)	C53—O56	1.379 (2)
C22—C23	1.398 (3)	C53—C54	1.391 (3)
O22—C48	1.235 (2)	C54—C55	1.387 (3)
C23—C24	1.395 (3)	C54—H54	0.9500
C23—H23	0.9500	C55—H55	0.9500
C24—C25	1.380 (3)	O56—C57	1.432 (3)
C24—H24	0.9500	C57—H57A	0.9800
C25—C26	1.385 (3)	C57—H57B	0.9800
C25—H25	0.9500	C57—H57C	0.9800

C41—Pd1—P21	87.89 (5)	C26—C27—C22	120.32 (18)
C41—Pd1—P2	86.59 (5)	C26—C27—H27	119.8
P21—Pd1—P2	174.088 (16)	C22—C27—H27	119.8
C41—Pd1—Cl40	177.83 (5)	C29—C28—C33	119.68 (18)
P21—Pd1—Cl40	92.403 (15)	C29—C28—P21	119.31 (15)
P2—Pd1—Cl40	93.033 (15)	C33—C28—P21	120.94 (15)
C3—P2—C9	108.29 (8)	C28—C29—C30	120.10 (19)
C3—P2—C15	102.83 (9)	C28—C29—H29	119.9
C9—P2—C15	103.12 (9)	C30—C29—H29	119.9
C3—P2—Pd1	111.86 (6)	C31—C30—C29	120.1 (2)
C9—P2—Pd1	114.02 (6)	C31—C30—H30	120.0
C15—P2—Pd1	115.72 (6)	C29—C30—H30	120.0
C4—C3—C8	119.60 (17)	C32—C31—C30	120.24 (19)
C4—C3—P2	117.83 (14)	C32—C31—H31	119.9
C8—C3—P2	122.43 (14)	C30—C31—H31	119.9
C5—C4—C3	119.52 (18)	C31—C32—C33	120.0 (2)
C5—C4—H4	120.2	C31—C32—H32	120.0
C3—C4—H4	120.2	C33—C32—H32	120.0
C6—C5—C4	120.65 (19)	C32—C33—C28	119.9 (2)
C6—C5—H5	119.7	C32—C33—H33	120.1
C4—C5—H5	119.7	C28—C33—H33	120.1
C5—C6—C7	119.69 (18)	C35—C34—C39	119.60 (18)
C5—C6—H6	120.2	C35—C34—P21	120.60 (15)
C7—C6—H6	120.2	C39—C34—P21	119.27 (15)
C8—C7—C6	120.18 (18)	C34—C35—C36	120.0 (2)
C8—C7—H7	119.9	C34—C35—H35	120.0
C6—C7—H7	119.9	C36—C35—H35	120.0
C7—C8—C3	120.35 (18)	C37—C36—C35	120.0 (2)
C7—C8—H8	119.8	C37—C36—H36	120.0
C3—C8—H8	119.8	C35—C36—H36	120.0
C10—C9—C14	119.27 (17)	C36—C37—C38	120.4 (2)
C10—C9—P2	121.40 (15)	C36—C37—H37	119.8
C14—C9—P2	119.33 (15)	C38—C37—H37	119.8
C11—C10—C9	120.6 (2)	C37—C38—C39	119.7 (2)
C11—C10—H10	119.7	C37—C38—H38	120.2
C9—C10—H10	119.7	C39—C38—H38	120.2
C12—C11—C10	119.9 (2)	C38—C39—C34	120.3 (2)
C12—C11—H11	120.1	C38—C39—H39	119.9
C10—C11—H11	120.1	C34—C39—H39	119.9
C13—C12—C11	120.12 (19)	N42—C41—C48	123.17 (17)
C13—C12—H12	119.9	N42—C41—Pd1	122.49 (13)
C11—C12—H12	119.9	C48—C41—Pd1	114.33 (13)
C12—C13—C14	120.6 (2)	C41—N42—C43	118.09 (16)
C12—C13—H13	119.7	C46—C43—N42	124.11 (17)
C14—C13—H13	119.7	C46—C43—Cl45	120.40 (15)
C13—C14—C9	119.5 (2)	N42—C43—Cl45	115.49 (14)
C13—C14—H14	120.2	C43—C46—N47	118.31 (17)
C9—C14—H14	120.2	C43—C46—H46	120.8
C20—C15—C16	118.82 (18)	N47—C46—H46	120.8
C20—C15—P2	120.50 (15)	C46—N47—C48	121.92 (16)
C16—C15—P2	120.19 (15)	C46—N47—C49	119.99 (16)
C17—C16—C15	120.59 (19)	C48—N47—C49	118.08 (15)
C17—C16—H16	119.7	O22—C48—N47	122.10 (17)
C15—C16—H16	119.7	O22—C48—C41	123.50 (17)
C16—C17—C18	120.3 (2)	N47—C48—C41	114.40 (16)
C16—C17—H17	119.9	N47—C49—C50	112.06 (15)
C18—C17—H17	119.9	N47—C49—H49A	109.2
C19—C18—C17	119.5 (2)	C50—C49—H49A	109.2
C19—C18—H18	120.3	N47—C49—H49B	109.2
C17—C18—H18	120.3	C50—C49—H49B	109.2
C18—C19—C20	120.6 (2)	H49A—C49—H49B	107.9
C18—C19—H19	119.7	C55—C50—C51	118.42 (18)
C20—C19—H19	119.7	C55—C50—C49	121.16 (18)
C19—C20—C15	120.24 (19)	C51—C50—C49	120.43 (18)
C19—C20—H20	119.9	C52—C51—C50	120.69 (19)
C15—C20—H20	119.9	C52—C51—H51	119.7
C22—P21—C28	107.68 (9)	C50—C51—H51	119.7
C22—P21—C34	102.95 (9)	C51—C52—C53	119.96 (19)
C28—P21—C34	103.53 (9)	C51—C52—H52	120.0
C22—P21—Pd1	113.86 (6)	C53—C52—H52	120.0
C28—P21—Pd1	112.69 (6)	O56—C53—C54	123.74 (19)
C34—P21—Pd1	115.12 (6)	O56—C53—C52	115.97 (18)
C27—C22—C23	119.38 (18)	C54—C53—C52	120.28 (18)
C27—C22—P21	122.84 (14)	C55—C54—C53	119.10 (19)
C23—C22—P21	117.63 (14)	C55—C54—H54	120.5
C24—C23—C22	119.85 (18)	C53—C54—H54	120.5
C24—C23—H23	120.1	C54—C55—C50	121.55 (19)
C22—C23—H23	120.1	C54—C55—H55	119.2
C25—C24—C23	120.17 (19)	C50—C55—H55	119.2
C25—C24—H24	119.9	C53—O56—C57	116.97 (18)
C23—C24—H24	119.9	O56—C57—H57A	109.5
C24—C25—C26	120.3 (2)	O56—C57—H57B	109.5
C24—C25—H25	119.9	H57A—C57—H57B	109.5
C26—C25—H25	119.9	O56—C57—H57C	109.5
C25—C26—C27	120.0 (2)	H57A—C57—H57C	109.5
C25—C26—H26	120.0	H57B—C57—H57C	109.5
C27—C26—H26	120.0

Experimental details

Crystal data
Chemical formula	[Pd(C₁₂H₁₀ClN₂O₂)Cl(C₁₈H₁₅P)₂]
M_r	916.06
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	10.7544 (1), 13.1526 (1), 16.9967 (1)
α, β, γ (°)	91.811 (1), 94.39 (1), 98.451 (1)
V (Å³)	2368.83 (3)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	5.13
Crystal size (mm)	0.5 × 0.24 × 0.24

Data collection
Diffractometer	Bruker SMART 6000
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.175, 0.292
No. of measured, independent and observed [I > 2σ(I)] reflections	23121, 8422, 7879
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.605

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.073, 1.08
No. of reflections	8422
No. of parameters	515
No. of restraints	318
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.58

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997), PLATON (Spek, 2003).

Acknowledgements

The Katholieke Universiteit Leuven is gratefully acknowledged for financial support. The authors thank the FWO [Fund for Scientific Research–Flanders (Belgium)] for financial support. JA and WMDB (Postdoctoral Fellows of the FWO–Flanders) thank the FWO for Fellowships received. WMDB also thanks the FWO for a `Krediet aan Navorsers'.

References

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