Enhanced π-back-donation resulting in the trans labilization of a pyridine ligand in an N-heterocyclic carbene (NHC) Pd^II precatalyst: a case study

The mol­ecular structure of the benzimidazol-2-yl­idene–PdCl₂–pyridine-type PEPPSI (pyridine-enhanced precatalyst, preparation, stabilization and initiation) complex {1,3-bis­[2-(diiso­propyl­amino)­eth­yl]benzimidazol-2-yl­idene-κC²}di­chlorido­(pyridine-κN)palladium(II), [PdCl₂(C₅H₅N)(C₂₃H₄₀N₄)], has been characterized by elemental analysis, IR and NMR spectroscopy, and natural bond orbital (NBO) and charge decomposition analysis (CDA). Cambridge Structural Database (CSD) searches were used to understand the structural characteristics of the PEPPSI complexes in comparison with the usual N-heterocyclic carbene (NHC) complexes. The presence of weak C—H...Cl-type hydrogen-bond and π–π stacking inter­actions between benzene rings were verified using NCI plots and Hirshfeld surface analysis. The preferred method in the CDA of PEPPSI complexes is to separate their geometries into only two fragments, i.e. the bulky NHC ligand and the remaining fragment. In this study, the geometry of the PEPPSI complex is separated into five fragments, namely benzimidazol-2-yl­idene (Bimy), two chlorides, pyridine (Py) and the Pd^II ion. Thus, the individual roles of the Pd atom and the Py ligand in the donation and back-donation mechanisms have been clearly revealed. The NHC ligand in the PEPPSI complex in this study acts as a strong σ-donor with a considerable amount of π-back-donation from Pd to C_carbene. The electron-poor character of Pd^II is supported by π-back-donation from the Pd centre and the weakness of the Pd—N(Py) bond. According to CSD searches, Bimy ligands in PEPPSI complexes have a stronger σ-donating ability than imidazol-2-yl­idene ligands in PEPPSI complexes.

Computing details

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

[1,3-Bis(2-diisopropylaminoethyl)benzimidazol-2-ylidene-κC²]dichlorido(pyridine-κN)palladium(II)

Crystal data

[PdCl2(C5H5N)(C23H40N4)]	F(000) = 1312
Mr = 628.99	Dx = 1.362 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.1029 (4) Å	Cell parameters from 4189 reflections
b = 15.9363 (5) Å	θ = 3.7–28.3°
c = 19.3855 (8) Å	µ = 0.80 mm^−1
β = 100.640 (4)°	T = 297 K
V = 3067.5 (2) Å^3	Block, yellow
Z = 4	0.47 × 0.4 × 0.32 mm

Data collection

Rigaku OD Xcalibur Eos diffractometer	4563 reflections with I > 2σ(I)
Detector resolution: 8.0667 pixels mm^-1	Rint = 0.021
ω scan	θmax = 25.7°, θmin = 3.2°
Absorption correction: analytical [CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by Clark & Reid (1995)]	h = −7→12
	k = −9→19
9525 measured reflections	l = −22→23
5780 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.074	w = 1/[σ^2(Fo^2) + (0.0247P)^2 + 1.050P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.002
5780 reflections	Δρmax = 0.27 e Å^−3
337 parameters	Δρmin = −0.29 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. The data collection, cell refinement, data reduction and analytical absorption correction were performed using the CrysAlisPro 1.171.38.41 software (Rigaku Oxford Diffraction, 2015). Structure solution was performed using ShelXT (Sheldrick, 2015a) embedded in the Olex2 (Dolomanov et al., 2009) program. The refinement was carried out by full-matrix least-squares method on the positional and anisotropic temperature parameters using ShelXL (Sheldrick, 2015b). All non-hydrogen atoms were refined anisotropically.

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

	x	y	z	Uiso*/Ueq
Pd1	0.48736 (2)	0.20588 (2)	0.63296 (2)	0.03711 (8)
Cl1	0.59726 (10)	0.21385 (5)	0.74738 (4)	0.0681 (2)
Cl2	0.38340 (8)	0.20336 (5)	0.51726 (4)	0.0552 (2)
N1	0.4467 (2)	0.07782 (14)	0.64450 (12)	0.0432 (6)
N2	0.8978 (2)	0.23799 (14)	0.53019 (12)	0.0412 (6)
N3	0.6419 (2)	0.35671 (13)	0.60868 (11)	0.0379 (5)
N4	0.4381 (2)	0.38898 (13)	0.61886 (11)	0.0357 (5)
N5	0.1585 (2)	0.38502 (14)	0.72316 (12)	0.0404 (5)
C1	0.5243 (3)	0.32400 (17)	0.61999 (13)	0.0374 (6)
C2	0.6293 (3)	0.44333 (16)	0.59833 (14)	0.0389 (6)
C3	0.7183 (3)	0.50379 (18)	0.58319 (16)	0.0501 (8)
H3	0.805289	0.490027	0.577780	0.060*
C4	0.6722 (3)	0.58488 (19)	0.57654 (17)	0.0571 (9)
H4	0.729087	0.626856	0.565805	0.068*
C5	0.5435 (3)	0.60601 (18)	0.58535 (16)	0.0551 (8)
H5	0.516548	0.661865	0.581237	0.066*
C6	0.4546 (3)	0.54613 (17)	0.60008 (16)	0.0473 (7)
H6	0.368112	0.560269	0.606008	0.057*
C7	0.4994 (3)	0.46417 (16)	0.60565 (14)	0.0363 (6)
C8	0.4704 (3)	0.02199 (19)	0.59731 (17)	0.0577 (9)
H8	0.504899	0.041334	0.558965	0.069*
C9	0.4471 (4)	−0.0619 (2)	0.60177 (19)	0.0684 (10)
H9	0.467021	−0.098720	0.567851	0.082*
C10	0.3941 (4)	−0.0908 (2)	0.6571 (2)	0.0649 (10)
C11	0.3681 (3)	−0.0350 (2)	0.70592 (18)	0.0591 (9)
H11	0.331030	−0.053254	0.743768	0.071*
C12	0.3970 (3)	0.04863 (19)	0.69905 (16)	0.0500 (7)
H12	0.381389	0.086022	0.733510	0.060*
C13	0.7636 (3)	0.30782 (17)	0.60559 (14)	0.0422 (7)
H13A	0.768747	0.260996	0.637950	0.051*
H13B	0.842118	0.342874	0.620493	0.051*
C14	0.7655 (3)	0.27466 (18)	0.53249 (15)	0.0421 (7)
H14A	0.696068	0.232401	0.520214	0.051*
H14B	0.747196	0.320019	0.498706	0.051*
C15	0.9645 (3)	0.2797 (2)	0.47750 (17)	0.0544 (8)
H15	1.054896	0.255340	0.482716	0.065*
C16	0.9838 (3)	0.3730 (2)	0.4941 (2)	0.0718 (10)
H16A	0.899551	0.401766	0.480201	0.108*
H16B	1.049040	0.395800	0.469033	0.108*
H16C	1.014830	0.380267	0.543648	0.108*
C17	0.8968 (4)	0.2652 (3)	0.40183 (18)	0.0814 (12)
H17A	0.892167	0.206105	0.392254	0.122*
H17B	0.947934	0.292289	0.371086	0.122*
H17C	0.807404	0.288170	0.394269	0.122*
C18	0.8989 (3)	0.14547 (19)	0.52649 (18)	0.0567 (8)
H18	0.846742	0.127984	0.481016	0.068*
C19	1.0432 (3)	0.1132 (2)	0.5326 (2)	0.0868 (13)
H19A	1.074790	0.124646	0.489811	0.130*
H19B	1.044981	0.053750	0.540885	0.130*
H19C	1.100271	0.140836	0.570954	0.130*
C20	0.8367 (4)	0.1072 (2)	0.5836 (2)	0.0835 (12)
H20A	0.888870	0.122163	0.628506	0.125*
H20B	0.835007	0.047260	0.578747	0.125*
H20C	0.746377	0.127746	0.580271	0.125*
C21	0.2998 (2)	0.38237 (18)	0.63191 (14)	0.0392 (6)
H21A	0.261561	0.328899	0.614513	0.047*
H21B	0.245054	0.426598	0.606758	0.047*
C22	0.2976 (2)	0.38952 (18)	0.70980 (14)	0.0413 (6)
H22A	0.350616	0.344471	0.734772	0.050*
H22B	0.337962	0.442370	0.727404	0.050*
C23	0.1352 (3)	0.30857 (19)	0.76190 (17)	0.0551 (8)
H23	0.040751	0.310057	0.767388	0.066*
C24	0.2195 (4)	0.3027 (3)	0.83564 (19)	0.0890 (13)
H24A	0.312762	0.296600	0.832623	0.134*
H24B	0.191007	0.255008	0.859397	0.134*
H24C	0.207651	0.352830	0.861296	0.134*
C25	0.1508 (4)	0.2323 (2)	0.7180 (2)	0.0848 (13)
H25A	0.098201	0.239367	0.671834	0.127*
H25B	0.120214	0.183442	0.739518	0.127*
H25C	0.243877	0.225406	0.714844	0.127*
C26	0.1193 (3)	0.46378 (19)	0.75438 (16)	0.0507 (8)
H26	0.184350	0.475295	0.797470	0.061*
C27	0.1214 (4)	0.5361 (2)	0.7041 (2)	0.0817 (12)
H27A	0.211627	0.544516	0.696356	0.123*
H27B	0.090572	0.586162	0.723734	0.123*
H27C	0.063340	0.523632	0.660263	0.123*
C28	−0.0205 (3)	0.4572 (2)	0.7726 (2)	0.0720 (10)
H28A	−0.083356	0.438882	0.732075	0.108*
H28B	−0.047455	0.511154	0.787217	0.108*
H28C	−0.018873	0.417520	0.809977	0.108*
H10	0.376 (3)	−0.147 (2)	0.6612 (16)	0.065 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.04446 (13)	0.03198 (12)	0.03714 (12)	−0.00141 (11)	0.01341 (9)	−0.00090 (10)
Cl1	0.0996 (7)	0.0532 (5)	0.0440 (4)	0.0016 (5)	−0.0062 (4)	−0.0045 (4)
Cl2	0.0704 (5)	0.0511 (4)	0.0417 (4)	−0.0111 (4)	0.0037 (4)	0.0012 (4)
N1	0.0523 (14)	0.0365 (12)	0.0428 (14)	−0.0022 (12)	0.0136 (12)	0.0012 (11)
N2	0.0341 (12)	0.0414 (13)	0.0509 (14)	0.0033 (11)	0.0152 (11)	−0.0009 (11)
N3	0.0358 (12)	0.0363 (12)	0.0440 (13)	−0.0015 (11)	0.0139 (11)	−0.0049 (10)
N4	0.0376 (11)	0.0319 (11)	0.0406 (13)	−0.0026 (11)	0.0152 (10)	0.0005 (10)
N5	0.0320 (11)	0.0458 (13)	0.0461 (13)	0.0008 (11)	0.0137 (10)	0.0021 (11)
C1	0.0367 (14)	0.0410 (15)	0.0353 (15)	−0.0023 (13)	0.0086 (12)	0.0000 (12)
C2	0.0436 (15)	0.0362 (15)	0.0388 (15)	−0.0043 (13)	0.0123 (13)	−0.0053 (12)
C3	0.0495 (17)	0.0464 (17)	0.0578 (19)	−0.0095 (16)	0.0188 (16)	−0.0062 (15)
C4	0.064 (2)	0.0410 (17)	0.069 (2)	−0.0181 (17)	0.0214 (18)	−0.0038 (16)
C5	0.070 (2)	0.0315 (15)	0.064 (2)	−0.0043 (16)	0.0152 (18)	0.0000 (15)
C6	0.0501 (17)	0.0384 (16)	0.0551 (18)	0.0031 (14)	0.0138 (15)	0.0007 (14)
C7	0.0392 (15)	0.0360 (14)	0.0353 (14)	−0.0025 (13)	0.0106 (12)	−0.0014 (12)
C8	0.085 (2)	0.0429 (17)	0.0506 (19)	−0.0082 (18)	0.0271 (18)	−0.0040 (15)
C9	0.103 (3)	0.0387 (17)	0.063 (2)	−0.007 (2)	0.015 (2)	−0.0053 (17)
C10	0.067 (2)	0.0419 (19)	0.080 (3)	−0.0110 (18)	−0.003 (2)	0.0137 (19)
C11	0.0479 (18)	0.063 (2)	0.067 (2)	−0.0064 (17)	0.0123 (17)	0.0280 (19)
C12	0.0529 (17)	0.0520 (18)	0.0476 (17)	0.0064 (16)	0.0163 (15)	0.0087 (15)
C13	0.0358 (14)	0.0441 (16)	0.0481 (17)	0.0028 (13)	0.0110 (13)	−0.0049 (14)
C14	0.0363 (14)	0.0444 (16)	0.0471 (17)	−0.0001 (13)	0.0117 (13)	−0.0018 (13)
C15	0.0414 (16)	0.064 (2)	0.064 (2)	0.0070 (16)	0.0247 (16)	0.0075 (17)
C16	0.0537 (19)	0.066 (2)	0.100 (3)	−0.0135 (19)	0.023 (2)	0.013 (2)
C17	0.099 (3)	0.096 (3)	0.058 (2)	0.008 (3)	0.037 (2)	0.001 (2)
C18	0.0546 (19)	0.0493 (18)	0.070 (2)	−0.0011 (17)	0.0199 (17)	−0.0086 (17)
C19	0.070 (2)	0.057 (2)	0.139 (4)	0.020 (2)	0.034 (3)	−0.008 (2)
C20	0.096 (3)	0.052 (2)	0.112 (3)	0.005 (2)	0.044 (3)	0.017 (2)
C21	0.0312 (13)	0.0393 (15)	0.0476 (16)	−0.0033 (13)	0.0089 (12)	−0.0017 (13)
C22	0.0330 (14)	0.0462 (16)	0.0457 (16)	−0.0004 (14)	0.0097 (12)	−0.0003 (14)
C23	0.0458 (17)	0.0543 (19)	0.071 (2)	0.0009 (16)	0.0254 (17)	0.0125 (17)
C24	0.087 (3)	0.112 (3)	0.071 (3)	0.011 (3)	0.021 (2)	0.044 (2)
C25	0.084 (3)	0.0446 (19)	0.136 (4)	−0.008 (2)	0.046 (3)	0.006 (2)
C26	0.0454 (16)	0.0544 (18)	0.0547 (19)	0.0025 (16)	0.0160 (15)	−0.0073 (16)
C27	0.097 (3)	0.049 (2)	0.110 (3)	0.013 (2)	0.046 (3)	0.005 (2)
C28	0.0555 (19)	0.077 (2)	0.091 (3)	0.011 (2)	0.033 (2)	−0.011 (2)

Geometric parameters (Å, º)

Pd1—Cl1	2.2934 (8)	C15—H15	0.9800
Pd1—Cl2	2.2947 (8)	C15—C16	1.527 (4)
Pd1—N1	2.102 (2)	C15—C17	1.518 (5)
Pd1—C1	1.944 (3)	C16—H16A	0.9600
N1—C8	1.329 (3)	C16—H16B	0.9600
N1—C12	1.335 (3)	C16—H16C	0.9600
N2—C14	1.467 (3)	C17—H17A	0.9600
N2—C15	1.482 (3)	C17—H17B	0.9600
N2—C18	1.476 (4)	C17—H17C	0.9600
N3—C1	1.351 (3)	C18—H18	0.9800
N3—C2	1.397 (3)	C18—C19	1.530 (4)
N3—C13	1.466 (3)	C18—C20	1.500 (4)
N4—C1	1.351 (3)	C19—H19A	0.9600
N4—C7	1.394 (3)	C19—H19B	0.9600
N4—C21	1.469 (3)	C19—H19C	0.9600
N5—C22	1.477 (3)	C20—H20A	0.9600
N5—C23	1.473 (4)	C20—H20B	0.9600
N5—C26	1.479 (3)	C20—H20C	0.9600
C2—C3	1.386 (4)	C21—H21A	0.9700
C2—C7	1.386 (3)	C21—H21B	0.9700
C3—H3	0.9300	C21—C22	1.519 (3)
C3—C4	1.371 (4)	C22—H22A	0.9700
C4—H4	0.9300	C22—H22B	0.9700
C4—C5	1.384 (4)	C23—H23	0.9800
C5—H5	0.9300	C23—C24	1.526 (5)
C5—C6	1.376 (4)	C23—C25	1.509 (5)
C6—H6	0.9300	C24—H24A	0.9600
C6—C7	1.380 (4)	C24—H24B	0.9600
C8—H8	0.9300	C24—H24C	0.9600
C8—C9	1.364 (4)	C25—H25A	0.9600
C9—H9	0.9300	C25—H25B	0.9600
C9—C10	1.364 (5)	C25—H25C	0.9600
C10—C11	1.359 (5)	C26—H26	0.9800
C10—H10	0.93 (3)	C26—C27	1.512 (4)
C11—H11	0.9300	C26—C28	1.522 (4)
C11—C12	1.376 (4)	C27—H27A	0.9600
C12—H12	0.9300	C27—H27B	0.9600
C13—H13A	0.9700	C27—H27C	0.9600
C13—H13B	0.9700	C28—H28A	0.9600
C13—C14	1.516 (4)	C28—H28B	0.9600
C14—H14A	0.9700	C28—H28C	0.9600
C14—H14B	0.9700
Cl1—Pd1—Cl2	177.23 (3)	C15—C16—H16C	109.5
N1—Pd1—Cl1	91.15 (7)	H16A—C16—H16B	109.5
N1—Pd1—Cl2	91.37 (7)	H16A—C16—H16C	109.5
C1—Pd1—Cl1	90.07 (8)	H16B—C16—H16C	109.5
C1—Pd1—Cl2	87.41 (8)	C15—C17—H17A	109.5
C1—Pd1—N1	178.70 (10)	C15—C17—H17B	109.5
C8—N1—Pd1	120.87 (19)	C15—C17—H17C	109.5
C8—N1—C12	117.0 (3)	H17A—C17—H17B	109.5
C12—N1—Pd1	122.14 (19)	H17A—C17—H17C	109.5
C14—N2—C15	112.1 (2)	H17B—C17—H17C	109.5
C14—N2—C18	114.5 (2)	N2—C18—H18	108.7
C18—N2—C15	114.0 (2)	N2—C18—C19	110.3 (3)
C1—N3—C2	110.2 (2)	N2—C18—C20	111.2 (3)
C1—N3—C13	124.8 (2)	C19—C18—H18	108.7
C2—N3—C13	125.0 (2)	C20—C18—H18	108.7
C1—N4—C7	110.8 (2)	C20—C18—C19	109.2 (3)
C1—N4—C21	125.0 (2)	C18—C19—H19A	109.5
C7—N4—C21	124.2 (2)	C18—C19—H19B	109.5
C22—N5—C26	111.5 (2)	C18—C19—H19C	109.5
C23—N5—C22	112.1 (2)	H19A—C19—H19B	109.5
C23—N5—C26	114.4 (2)	H19A—C19—H19C	109.5
N3—C1—Pd1	126.2 (2)	H19B—C19—H19C	109.5
N4—C1—Pd1	127.26 (18)	C18—C20—H20A	109.5
N4—C1—N3	106.6 (2)	C18—C20—H20B	109.5
C3—C2—N3	132.2 (3)	C18—C20—H20C	109.5
C3—C2—C7	121.2 (3)	H20A—C20—H20B	109.5
C7—C2—N3	106.5 (2)	H20A—C20—H20C	109.5
C2—C3—H3	121.5	H20B—C20—H20C	109.5
C4—C3—C2	116.9 (3)	N4—C21—H21A	109.5
C4—C3—H3	121.5	N4—C21—H21B	109.5
C3—C4—H4	119.1	N4—C21—C22	110.8 (2)
C3—C4—C5	121.9 (3)	H21A—C21—H21B	108.1
C5—C4—H4	119.1	C22—C21—H21A	109.5
C4—C5—H5	119.3	C22—C21—H21B	109.5
C6—C5—C4	121.4 (3)	N5—C22—C21	111.1 (2)
C6—C5—H5	119.3	N5—C22—H22A	109.4
C5—C6—H6	121.5	N5—C22—H22B	109.4
C5—C6—C7	117.1 (3)	C21—C22—H22A	109.4
C7—C6—H6	121.5	C21—C22—H22B	109.4
C2—C7—N4	105.9 (2)	H22A—C22—H22B	108.0
C6—C7—N4	132.6 (2)	N5—C23—H23	106.6
C6—C7—C2	121.5 (2)	N5—C23—C24	114.5 (3)
N1—C8—H8	118.0	N5—C23—C25	109.7 (3)
N1—C8—C9	123.9 (3)	C24—C23—H23	106.6
C9—C8—H8	118.0	C25—C23—H23	106.6
C8—C9—H9	120.7	C25—C23—C24	112.4 (3)
C8—C9—C10	118.5 (3)	C23—C24—H24A	109.5
C10—C9—H9	120.7	C23—C24—H24B	109.5
C9—C10—H10	120 (2)	C23—C24—H24C	109.5
C11—C10—C9	118.8 (3)	H24A—C24—H24B	109.5
C11—C10—H10	121 (2)	H24A—C24—H24C	109.5
C10—C11—H11	120.2	H24B—C24—H24C	109.5
C10—C11—C12	119.6 (3)	C23—C25—H25A	109.5
C12—C11—H11	120.2	C23—C25—H25B	109.5
N1—C12—C11	122.1 (3)	C23—C25—H25C	109.5
N1—C12—H12	118.9	H25A—C25—H25B	109.5
C11—C12—H12	118.9	H25A—C25—H25C	109.5
N3—C13—H13A	109.1	H25B—C25—H25C	109.5
N3—C13—H13B	109.1	N5—C26—H26	108.7
N3—C13—C14	112.3 (2)	N5—C26—C27	110.3 (2)
H13A—C13—H13B	107.9	N5—C26—C28	111.5 (2)
C14—C13—H13A	109.1	C27—C26—H26	108.7
C14—C13—H13B	109.1	C27—C26—C28	109.0 (3)
N2—C14—C13	109.7 (2)	C28—C26—H26	108.7
N2—C14—H14A	109.7	C26—C27—H27A	109.5
N2—C14—H14B	109.7	C26—C27—H27B	109.5
C13—C14—H14A	109.7	C26—C27—H27C	109.5
C13—C14—H14B	109.7	H27A—C27—H27B	109.5
H14A—C14—H14B	108.2	H27A—C27—H27C	109.5
N2—C15—H15	106.5	H27B—C27—H27C	109.5
N2—C15—C16	110.4 (2)	C26—C28—H28A	109.5
N2—C15—C17	114.6 (3)	C26—C28—H28B	109.5
C16—C15—H15	106.5	C26—C28—H28C	109.5
C17—C15—H15	106.5	H28A—C28—H28B	109.5
C17—C15—C16	111.7 (3)	H28A—C28—H28C	109.5
C15—C16—H16A	109.5	H28B—C28—H28C	109.5
C15—C16—H16B	109.5
Pd1—N1—C8—C9	179.6 (3)	C10—C11—C12—N1	1.9 (5)
Pd1—N1—C12—C11	178.8 (2)	C12—N1—C8—C9	−0.1 (5)
N1—C8—C9—C10	1.3 (6)	C13—N3—C1—Pd1	−1.2 (4)
N3—C2—C3—C4	−179.8 (3)	C13—N3—C1—N4	−179.9 (2)
N3—C2—C7—N4	−1.0 (3)	C13—N3—C2—C3	0.3 (5)
N3—C2—C7—C6	178.5 (3)	C13—N3—C2—C7	179.9 (2)
N3—C13—C14—N2	171.2 (2)	C14—N2—C15—C16	59.3 (3)
N4—C21—C22—N5	178.6 (2)	C14—N2—C15—C17	−67.9 (3)
C1—N3—C2—C3	−177.9 (3)	C14—N2—C18—C19	−173.7 (3)
C1—N3—C2—C7	1.7 (3)	C14—N2—C18—C20	−52.3 (4)
C1—N3—C13—C14	87.3 (3)	C15—N2—C14—C13	−120.9 (3)
C1—N4—C7—C2	0.1 (3)	C15—N2—C18—C19	55.5 (4)
C1—N4—C7—C6	−179.4 (3)	C15—N2—C18—C20	176.8 (3)
C1—N4—C21—C22	87.4 (3)	C18—N2—C14—C13	107.4 (3)
C2—N3—C1—Pd1	177.05 (19)	C18—N2—C15—C16	−168.7 (3)
C2—N3—C1—N4	−1.6 (3)	C18—N2—C15—C17	64.1 (4)
C2—N3—C13—C14	−90.7 (3)	C21—N4—C1—Pd1	4.1 (4)
C2—C3—C4—C5	0.8 (5)	C21—N4—C1—N3	−177.3 (2)
C3—C2—C7—N4	178.6 (3)	C21—N4—C7—C2	178.3 (2)
C3—C2—C7—C6	−1.8 (4)	C21—N4—C7—C6	−1.2 (5)
C3—C4—C5—C6	−1.1 (5)	C22—N5—C23—C24	63.7 (3)
C4—C5—C6—C7	0.0 (5)	C22—N5—C23—C25	−63.6 (3)
C5—C6—C7—N4	−179.1 (3)	C22—N5—C26—C27	62.5 (3)
C5—C6—C7—C2	1.4 (4)	C22—N5—C26—C28	−176.3 (2)
C7—N4—C1—Pd1	−177.71 (19)	C23—N5—C22—C21	113.4 (3)
C7—N4—C1—N3	0.9 (3)	C23—N5—C26—C27	−169.0 (3)
C7—N4—C21—C22	−90.5 (3)	C23—N5—C26—C28	−47.8 (3)
C7—C2—C3—C4	0.6 (4)	C26—N5—C22—C21	−116.9 (3)
C8—N1—C12—C11	−1.5 (4)	C26—N5—C23—C24	−64.4 (3)
C8—C9—C10—C11	−0.8 (6)	C26—N5—C23—C25	168.2 (3)
C9—C10—C11—C12	−0.7 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···Cl1^i	0.93 (3)	2.82 (3)	3.615 (4)	145 (3)

Symmetry code: (i) −x+1, y−1/2, −z+3/2.