Two orthopalladated chromophores

The title compounds, {5-(di­methyl­amino)-2-[N-(4-methoxy­phenyl)­imino­methyl]­phenyl}[N-(4-methoxy­phenyl)-4-nitro­salicyl­aldiminato]­palladium(II), [Pd(C₁₄H₁₁N₂O₄)(C₁₆H₁₇N₂O)], (I), and [4-(diethyl­amino)-N-(4-methoxy­phenyl)­sali­cyl­aldiminato]{2-[N-(4-methoxy­phenyl)­imino­methyl]-5-nitrophenyl}palladium(II) di­chloro­methane hemisolvate, [Pd(C₁₄H₁₁N₂O₃)(C₁₈H₂₁N₂O₂)]·0.5CH₂Cl₂, (II), both contain push-pull chromophores coordinated to Pd in a square-planar arrangement. In both compounds, the five-membered orthopalladated ring is essentially planar, while the coordinated six-membered ring is not. Deviations from a coplanar arrangement of the phenyl­ene rings of the coordinated Schiff bases are observed in both (I) and (II) as a result of intramolecular steric interactions.

S1. Comment

Organometallic complexes containing metallic centres bonded to organic π-electron conjugated systems are materials under investigation for applications in second-order non-linear optics (NLO). In comparison with all organic compounds, they show additional chemical variables (the nature of the metal, its oxidation state, coordination geometry etc.) that may lead, in principle, to enhanced NLO properties. Some interesting results have been reported for organometallic fragments attached at the end of organic conjugated systems and acting as electron donor or acceptor groups (Whittall et al., 1998).

A less investigated possibility is the use of metallic centres acting as conjugation bridges along push–pull systems (Buey et al., 1998). In this case, conjugation should involve π interactions between the metal and the organic ligands. This obviously poses some limitations on the nature of the metal, since its coordination geometry should allow, in the optimal case, a coplanar arrangement of the metal coordination sphere and of the organic conjugated ligands. Cyclometallated compounds (e.g. cyclometallated Schiff bases) seem a suitable choice since, in these compounds, a coplanar arrangement of metallated and ortho-aromatic rings must occur (Dehand & Pfeffer, 1976; Churchill et al., 1980); furthermore, aromatic imines may be easily functionalized with electron donor or acceptor groups, resulting in fairly highly NLO active compounds (Morley, 1995).

We have recently started a systematic investigation on the synthesis and structure of orthopalladated aromatic imines as precursors of fragments to be incorporated in polymers, and in the two complexes reported here, (I) and (II), a Pd atom is coordinated to two aromatic Schiff bases.

In both title compounds, the imines are functionalized with strong electron donor–acceptor groups. In particular, one imine is of the push–pull type and contains methoxy donor and nitro acceptor groups, while the second coordinated imine is of the electron-rich type as it contains only electron-donor groups (i.e. methoxy and dialkylamino). The two complexes substantially differ in the nature of the cyclometallated imine which is the push–pull group in the case of (I) and the electron-rich group in the case of (II). Furthermore, in both (I) and (II), the strongest electron-donor group (i.e. dialkylamino) and the nitro acceptor group are placed in opposite directions with respect to the Pd atom, so as to favour a charge transfer possibly involving the metal.

Both compounds show a strong absorption band in the UV-vis region which should correspond to the HOMO–LUMO transition (HOMO is highest occupied molecular orbital and LUMO is lowest unoccupied molecular orbital). A positive solvatochromic effect is observed for this band (see Experimental), as generally found in second-order NLO active compounds. The effect, though rather small, is comparable with values reported in the literature for other organometallic compounds (Di Bella et al., 1994). The NLO activity of the compounds has been tested by EFISH measurements in chloroform solution at λ = 1907 nm (Levine & Bethea, 1975). The values obtained, i.e. µβ = 120 × 10 ^-48 e.s.u. for (I) and µβ = 75 × 10 ^-48 e.s.u. for (II), indicate a moderate activity (Dalton et al., 1999) (esu = ?).

The coordination around the Pd atom is substantially square planar in both complexes, showing standard values for the distances from metal to coordinated atoms (O'Keefe & Steel, 2000). Of the two rings to which the metal atom belongs, the cyclopalladated (five-membered) ring is substantially planar, while the salicylaldiminate (six-membered) ring is not, mainly as a result of metal atom being out of the mean plane defined by the remaining five atoms. A planar-trigonal geometry is observed around the N atom of the amino group [N1 in (I) and N3 in (II)]. The sp² hybridization of this atom should favour electron donation to the adjacent phenyl ring. This is consistent with the observed shortening of N1—C3 for (I) and N3—C19 for (II) (Allen et al., 1987) and with some distortions of bond lenghts observed in the phenyl ring attached to the dialkylamino group.

Deviations from coplanarity of the phenyl rings are observed in coordinated imines of both compounds through torsions around the bonds not constrained by coordination [i.e. N2—C10 and N3—C21 in (I), and N4—C26 and N1—C5 in (II)]. These deviations seem to be due to internal steric repulsions [C9···C11 2.95 (1) Å and C22···C24 2.916 (9) Å for (I); C4···C8 2.871 (9) Å and C25···C27 2.902 (9) Å for (II)], but also to short contacts involving atoms of different ligands [C8···C20 3.44 (1) Å, C8···C21 3.237 (9) Å and O3···C15 2.929 (9) Å for (I); C13···C26 3.12 (1) Å and C13···C31 3.44 (1) Å for (II)]. These contacts, in particular those involving atoms of different ligands, probably also play a role in determining the non-planar conformation of the six-membered ring containing the Pd atom.

In the case of (II), solvent molecules (dichloromethane) in special positions (binary axis) are also present in the crystals. Although the C and Cl atoms of the solvent molecule have high anisotropic displacement parameters, no evidence of static disorder was found.

S2. Experimental

Compound (I) was prepared by reaction of di-µ-acetato-bis({5-(dimethylamino)- 2-[N-(4-methoxyphenyl)iminomethyl]phenyl}palladium(II)) with N-(4-methoxyphenyl)-4-nitrosalicylaldimine and compound (II) was prepared by reaction of di-µ-acetato-bis({2-[N-(4-methoxyphenyliminomethyl)-5-nitrophenyl}- palladium(II)) with N-(4-methoxyphenyl)-4-(diethylamino)salicylaldimine. In both cases, a molar ratio of 2:1 of imine and dinuclear complex was used. Reactions were performed at room temperature for 1 h in CH₂Cl₂/ethanol solvent. Melting points: 568 K (decomposition) for (I) and 584 K (decomposition) for (II). Analysis for (I): Pd 16.9% calculated, 16.6% found; for (II): Pd 16.1% calculated, 15.9% found. UV-vis λ_max/nm: 421 in ethyl acetate (µ = 1.78 D) and 425 in dimethylformamide (DMF) (µ = 3.82 D) for (I); 358 in ethyl acetate and 362 in DMF for (II). Crystals suitable for single-crystal X-ray diffraction analysis were obtained by slow evaporation from chloroform for (I) and from dichloromethane–hexane for (II).

S3. Refinement

All H atoms were stereochemically positioned. For all H atoms were refined as riding, with U_iso equal to U_eq of the carrier atom, and C—H distances in the range 0.93–0.97 Å. For (I), symmetry-equivalent reflections were not merged. The total of 8378 reflections includes 3634 Friedel pairs. The Flack (1983) parameter was refined with TWIN and BASF instructions (and MERG 0) according to the SHELX97 manual. For (II), systematically absent reflections corresponding to lattice centering were not collected.

Computing details

For both compounds, data collection: MACH3 Software (Nonius, 1996); cell refinement: CELLDIM (Nonius, 1996); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1999).

Figures

	Fig. 1. The molecule of (I) with displacement ellipsoids at the 50% probability level.
	Fig. 2. The molecule of (II) with displacement ellipsoids at the 50% probability level. The solvent molecule is not shown.

(I) {5-(dimethylamino)-2-[N-(4-methoxyphenyl)iminomethyl]phenyl}[N-(4- methoxyphenyl)-4-nitrosalicylaldiminato]palladium(II)

Crystal data

C30H28N4O5Pd	Dx = 1.554 Mg m^−3
Mr = 630.96	Mo Kα radiation, λ = 0.71069 Å
Orthorhombic, Pca21	Cell parameters from 24 reflections
a = 24.41 (2) Å	θ = 8.2–9.5°
b = 14.479 (6) Å	µ = 0.74 mm^−1
c = 7.630 (4) Å	T = 293 K
V = 2697 (3) Å^3	Prism, orange
Z = 4	0.5 × 0.1 × 0.04 mm
F(000) = 1288

Data collection

Enraf Nonius MACH 3 diffractometer	4033 reflections with I > 2σ(I)
Radiation source: Enraf Nonius FR590	Rint = 0.054
Graphite monochromator	θmax = 30.0°, θmin = 2.2°
ω/θ scans	h = −34→34
Absorption correction: ψ scan (North et al., 1968)	k = −20→20
Tmin = 0.939, Tmax = 1.000	l = −10→10
8378 measured reflections	2 standard reflections every 120 min
7823 independent reflections	intensity decay: 2%

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)] = 0.055	H-atom parameters constrained
wR(F^2) = 0.124	w = 1/[σ^2(Fo^2) + (0.0375P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.96	(Δ/σ)max = 0.002
7823 reflections	Δρmax = 0.51 e Å^−3
361 parameters	Δρmin = −0.51 e Å^−3
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.11 (5)

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. A refinement against 4189 reflections obtained after merging symmetry equivalent as well as Friedel pairs gave R1=0.044 and wR2=0.1026.

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

	x	y	z	Uiso*/Ueq
Pd1	0.616634 (15)	0.11843 (3)	0.96592 (8)	0.03391 (10)
N1	0.5971 (2)	−0.2610 (4)	0.9101 (7)	0.0427 (15)
N2	0.5503 (2)	0.1601 (4)	0.8246 (7)	0.0372 (13)
N3	0.6830 (2)	0.0804 (3)	1.1150 (7)	0.0352 (13)
N4	0.7755 (3)	0.4763 (4)	0.8129 (10)	0.0589 (18)
O1	0.4959 (2)	0.5209 (4)	0.6418 (8)	0.0567 (15)
O2	0.6597 (2)	−0.2247 (4)	1.5478 (7)	0.0699 (17)
O3	0.64339 (17)	0.2523 (3)	0.9993 (8)	0.0435 (15)
O4	0.7377 (3)	0.5254 (4)	0.7743 (12)	0.098 (3)
O5	0.8229 (3)	0.4973 (4)	0.8010 (11)	0.092 (2)
C1	0.6467 (3)	−0.2767 (5)	1.0032 (13)	0.063 (3)
H1A	0.6538	−0.3419	1.0089	0.063*
H1B	0.6435	−0.2524	1.1198	0.063*
H1C	0.6764	−0.2465	0.9437	0.063*
C2	0.5711 (3)	−0.3411 (5)	0.8309 (11)	0.059 (2)
H2A	0.5906	−0.3959	0.8642	0.059*
H2B	0.5717	−0.3349	0.7057	0.059*
H2C	0.5339	−0.3453	0.8706	0.059*
C3	0.5768 (3)	−0.1744 (4)	0.8809 (9)	0.0359 (15)
C4	0.5275 (3)	−0.1625 (5)	0.7908 (10)	0.0465 (18)
H4	0.5079	−0.2140	0.7539	0.046*
C5	0.5080 (3)	−0.0773 (5)	0.7566 (10)	0.0421 (17)
H5	0.4753	−0.0711	0.6952	0.042*
C6	0.5357 (2)	0.0017 (5)	0.8114 (9)	0.0369 (15)
C7	0.5855 (2)	−0.0066 (4)	0.9073 (8)	0.0349 (15)
C8	0.6045 (2)	−0.0956 (4)	0.9397 (11)	0.0353 (18)
H8	0.6368	−0.1030	1.0028	0.035*
C9	0.5194 (3)	0.0930 (5)	0.7731 (10)	0.0459 (19)
H9	0.4872	0.1045	0.7120	0.046*
C10	0.5350 (3)	0.2520 (5)	0.7830 (9)	0.0402 (16)
C11	0.4829 (3)	0.2853 (5)	0.8182 (9)	0.0399 (16)
H11	0.4576	0.2468	0.8727	0.040*
C12	0.4674 (3)	0.3744 (5)	0.7747 (9)	0.0423 (16)
H12	0.4322	0.3953	0.7983	0.042*
C13	0.5060 (3)	0.4326 (5)	0.6940 (10)	0.0430 (17)
C14	0.5587 (3)	0.4010 (5)	0.6648 (9)	0.0454 (18)
H14	0.5846	0.4398	0.6140	0.045*
C15	0.5728 (3)	0.3127 (5)	0.7107 (10)	0.0478 (18)
H15	0.6087	0.2928	0.6929	0.048*
C16	0.4435 (3)	0.5578 (5)	0.6581 (12)	0.060 (2)
H16A	0.4433	0.6199	0.6143	0.060*
H16B	0.4329	0.5578	0.7793	0.060*
H16C	0.4181	0.5210	0.5920	0.060*
C17	0.6924 (3)	−0.3035 (5)	1.5296 (12)	0.071 (3)
H17A	0.6803	−0.3500	1.6106	0.071*
H17B	0.7298	−0.2879	1.5536	0.071*
H17C	0.6893	−0.3266	1.4121	0.071*
C18	0.6700 (3)	−0.1506 (5)	1.4428 (11)	0.0394 (17)
C19	0.6321 (2)	−0.0802 (4)	1.4508 (16)	0.0448 (16)
H19	0.6030	−0.0837	1.5293	0.045*
C20	0.6373 (3)	−0.0054 (5)	1.3437 (9)	0.0393 (15)
H20	0.6108	0.0407	1.3465	0.039*
C21	0.6812 (2)	0.0028 (4)	1.2311 (8)	0.0334 (14)
C22	0.7210 (3)	−0.0645 (4)	1.2281 (9)	0.0389 (16)
H22	0.7514	−0.0584	1.1555	0.039*
C23	0.7150 (3)	−0.1425 (5)	1.3362 (9)	0.0426 (17)
H23	0.7415	−0.1885	1.3356	0.043*
C24	0.7292 (3)	0.1255 (4)	1.1039 (8)	0.0350 (14)
H24	0.7593	0.0993	1.1599	0.035*
C25	0.7386 (2)	0.2120 (4)	1.0135 (8)	0.0350 (16)
C26	0.6947 (2)	0.2730 (4)	0.9774 (15)	0.0367 (13)
C27	0.7097 (3)	0.3618 (4)	0.9140 (8)	0.0422 (18)
H27	0.6827	0.4055	0.8925	0.042*
C28	0.7624 (3)	0.3833 (5)	0.8848 (9)	0.0456 (16)
C29	0.8052 (3)	0.3229 (5)	0.9187 (8)	0.048 (2)
H29	0.8414	0.3393	0.8962	0.048*
C30	0.7925 (2)	0.2395 (4)	0.9852 (14)	0.0441 (18)
H30	0.8207	0.1989	1.0133	0.044*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.02889 (16)	0.03758 (19)	0.03525 (19)	−0.0010 (2)	−0.0037 (4)	0.0009 (5)
N1	0.054 (3)	0.040 (3)	0.035 (4)	−0.011 (3)	−0.009 (3)	0.003 (2)
N2	0.034 (3)	0.043 (3)	0.035 (3)	0.004 (3)	−0.007 (2)	0.005 (3)
N3	0.034 (3)	0.030 (3)	0.042 (3)	0.000 (2)	0.000 (3)	−0.002 (2)
N4	0.072 (5)	0.038 (4)	0.067 (5)	−0.012 (3)	0.003 (4)	−0.001 (4)
O1	0.056 (3)	0.042 (3)	0.072 (4)	0.002 (3)	−0.010 (3)	0.006 (3)
O2	0.095 (4)	0.052 (3)	0.063 (4)	0.011 (3)	0.019 (3)	0.020 (3)
O3	0.038 (2)	0.037 (2)	0.055 (5)	−0.0030 (18)	−0.005 (3)	−0.008 (3)
O4	0.089 (6)	0.050 (3)	0.155 (8)	−0.003 (4)	−0.026 (5)	0.036 (5)
O5	0.083 (4)	0.054 (3)	0.139 (7)	−0.020 (3)	0.032 (5)	0.010 (4)
C1	0.059 (5)	0.050 (4)	0.079 (9)	−0.005 (4)	−0.006 (5)	−0.003 (5)
C2	0.085 (6)	0.043 (4)	0.049 (5)	−0.017 (4)	−0.002 (4)	0.006 (4)
C3	0.036 (3)	0.039 (4)	0.032 (3)	−0.006 (3)	0.008 (3)	0.004 (3)
C4	0.049 (4)	0.050 (4)	0.040 (4)	−0.008 (4)	−0.010 (4)	−0.010 (4)
C5	0.033 (3)	0.059 (5)	0.034 (4)	−0.004 (3)	−0.004 (3)	−0.007 (4)
C6	0.033 (3)	0.051 (4)	0.026 (3)	0.002 (3)	0.000 (3)	−0.004 (3)
C7	0.029 (3)	0.041 (4)	0.034 (4)	−0.001 (3)	0.000 (2)	−0.001 (3)
C8	0.035 (3)	0.047 (3)	0.023 (5)	−0.009 (2)	−0.005 (3)	0.006 (3)
C9	0.033 (4)	0.067 (5)	0.038 (4)	0.002 (3)	−0.010 (3)	0.001 (4)
C10	0.036 (4)	0.047 (4)	0.038 (4)	−0.004 (3)	−0.008 (3)	0.004 (3)
C11	0.034 (3)	0.048 (4)	0.038 (4)	−0.004 (3)	0.002 (3)	0.007 (3)
C12	0.032 (3)	0.050 (4)	0.045 (4)	0.002 (3)	0.001 (3)	−0.001 (4)
C13	0.048 (4)	0.044 (4)	0.038 (4)	0.001 (4)	−0.007 (3)	0.004 (4)
C14	0.040 (4)	0.056 (5)	0.040 (4)	−0.012 (3)	0.006 (3)	0.014 (4)
C15	0.032 (3)	0.066 (5)	0.046 (4)	0.004 (3)	0.001 (3)	0.009 (4)
C16	0.078 (6)	0.047 (5)	0.056 (5)	0.013 (4)	−0.007 (5)	−0.006 (4)
C17	0.101 (7)	0.054 (5)	0.058 (6)	−0.003 (5)	−0.003 (5)	0.013 (4)
C18	0.049 (3)	0.048 (3)	0.020 (5)	0.001 (3)	−0.001 (3)	0.007 (3)
C19	0.046 (3)	0.058 (3)	0.030 (4)	−0.002 (3)	0.007 (4)	0.000 (5)
C20	0.038 (3)	0.040 (4)	0.039 (4)	0.004 (3)	0.002 (3)	0.001 (4)
C21	0.030 (3)	0.037 (3)	0.034 (4)	−0.005 (3)	−0.007 (3)	−0.006 (3)
C22	0.039 (4)	0.049 (4)	0.029 (4)	−0.004 (3)	0.003 (3)	−0.001 (3)
C23	0.041 (4)	0.045 (4)	0.041 (4)	0.006 (3)	−0.006 (3)	−0.003 (3)
C24	0.040 (3)	0.031 (3)	0.034 (3)	0.007 (3)	−0.005 (3)	−0.008 (3)
C25	0.035 (3)	0.040 (3)	0.030 (4)	−0.003 (3)	−0.007 (2)	−0.004 (3)
C26	0.037 (3)	0.037 (3)	0.036 (4)	−0.007 (2)	0.002 (5)	−0.004 (5)
C27	0.055 (4)	0.033 (4)	0.039 (4)	0.001 (3)	−0.013 (3)	−0.003 (3)
C28	0.058 (4)	0.038 (3)	0.041 (4)	−0.016 (4)	−0.006 (3)	0.002 (4)
C29	0.037 (3)	0.062 (5)	0.045 (5)	−0.010 (3)	0.006 (3)	0.007 (4)
C30	0.035 (3)	0.050 (3)	0.048 (5)	0.000 (3)	−0.003 (4)	0.009 (5)

Geometric parameters (Å, º)

Pd1—C7	2.014 (6)	C10—C15	1.389 (9)
Pd1—N2	2.037 (5)	C11—C12	1.384 (9)
Pd1—N3	2.055 (5)	C11—H11	0.9300
Pd1—O3	2.062 (4)	C12—C13	1.407 (10)
N1—C3	1.366 (8)	C12—H12	0.9300
N1—C1	1.423 (8)	C13—C14	1.383 (10)
N1—C2	1.453 (8)	C14—C15	1.371 (9)
N2—C9	1.291 (8)	C14—H14	0.9300
N2—C10	1.417 (8)	C15—H15	0.9300
N3—C24	1.306 (8)	C16—H16A	0.9600
N3—C21	1.431 (8)	C16—H16B	0.9600
N4—O5	1.200 (8)	C16—H16C	0.9600
N4—O4	1.202 (9)	C17—H17A	0.9600
N4—C28	1.489 (9)	C17—H17B	0.9600
O1—C13	1.362 (8)	C17—H17C	0.9600
O1—C16	1.393 (9)	C18—C23	1.372 (9)
O2—C18	1.362 (8)	C18—C19	1.377 (8)
O2—C17	1.399 (9)	C19—C20	1.362 (10)
O3—C26	1.298 (6)	C19—H19	0.9300
C1—H1A	0.9600	C20—C21	1.379 (8)
C1—H1B	0.9600	C20—H20	0.9300
C1—H1C	0.9600	C21—C22	1.376 (8)
C2—H2A	0.9600	C22—C23	1.407 (9)
C2—H2B	0.9600	C22—H22	0.9300
C2—H2C	0.9600	C23—H23	0.9300
C3—C4	1.396 (9)	C24—C25	1.447 (8)
C3—C8	1.400 (8)	C24—H24	0.9300
C4—C5	1.348 (9)	C25—C30	1.392 (8)
C4—H4	0.9300	C25—C26	1.416 (8)
C5—C6	1.393 (9)	C26—C27	1.421 (9)
C5—H5	0.9300	C27—C28	1.342 (9)
C6—C9	1.411 (9)	C27—H27	0.9300
C6—C7	1.424 (8)	C28—C29	1.388 (9)
C7—C8	1.392 (8)	C29—C30	1.346 (9)
C8—H8	0.9300	C29—H29	0.9300
C9—H9	0.9300	C30—H30	0.9300
C10—C11	1.386 (9)
C7—Pd1—N2	81.3 (2)	C13—C12—H12	120.6
C7—Pd1—N3	100.3 (2)	O1—C13—C14	115.6 (6)
N2—Pd1—N3	177.8 (2)	O1—C13—C12	124.7 (7)
C7—Pd1—O3	173.0 (2)	C14—C13—C12	119.7 (7)
N2—Pd1—O3	92.2 (2)	C15—C14—C13	120.1 (6)
N3—Pd1—O3	86.2 (2)	C15—C14—H14	120.0
C3—N1—C1	122.4 (6)	C13—C14—H14	120.0
C3—N1—C2	120.4 (6)	C14—C15—C10	121.6 (6)
C1—N1—C2	116.8 (6)	C14—C15—H15	119.2
C9—N2—C10	119.0 (6)	C10—C15—H15	119.2
C9—N2—Pd1	113.7 (5)	O1—C16—H16A	109.5
C10—N2—Pd1	127.3 (4)	O1—C16—H16B	109.5
C24—N3—C21	117.4 (5)	H16A—C16—H16B	109.5
C24—N3—Pd1	120.7 (4)	O1—C16—H16C	109.5
C21—N3—Pd1	121.9 (4)	H16A—C16—H16C	109.5
O5—N4—O4	124.9 (7)	H16B—C16—H16C	109.5
O5—N4—C28	117.7 (7)	O2—C17—H17A	109.5
O4—N4—C28	117.4 (7)	O2—C17—H17B	109.5
C13—O1—C16	120.0 (6)	H17A—C17—H17B	109.5
C18—O2—C17	118.6 (6)	O2—C17—H17C	109.5
C26—O3—Pd1	120.5 (4)	H17A—C17—H17C	109.5
N1—C1—H1A	109.5	H17B—C17—H17C	109.5
N1—C1—H1B	109.5	O2—C18—C23	124.3 (6)
H1A—C1—H1B	109.5	O2—C18—C19	115.6 (7)
N1—C1—H1C	109.5	C23—C18—C19	120.0 (7)
H1A—C1—H1C	109.5	C20—C19—C18	120.0 (8)
H1B—C1—H1C	109.5	C20—C19—H19	120.0
N1—C2—H2A	109.5	C18—C19—H19	120.0
N1—C2—H2B	109.5	C19—C20—C21	121.0 (6)
H2A—C2—H2B	109.5	C19—C20—H20	119.5
N1—C2—H2C	109.5	C21—C20—H20	119.5
H2A—C2—H2C	109.5	C22—C21—C20	119.9 (6)
H2B—C2—H2C	109.5	C22—C21—N3	121.5 (6)
N1—C3—C4	120.4 (6)	C20—C21—N3	118.5 (6)
N1—C3—C8	121.4 (6)	C21—C22—C23	119.0 (6)
C4—C3—C8	118.2 (6)	C21—C22—H22	120.5
C5—C4—C3	121.0 (6)	C23—C22—H22	120.5
C5—C4—H4	119.5	C18—C23—C22	120.0 (6)
C3—C4—H4	119.5	C18—C23—H23	120.0
C4—C5—C6	121.3 (6)	C22—C23—H23	120.0
C4—C5—H5	119.3	N3—C24—C25	126.8 (6)
C6—C5—H5	119.3	N3—C24—H24	116.6
C5—C6—C9	124.7 (6)	C25—C24—H24	116.6
C5—C6—C7	120.0 (6)	C30—C25—C26	120.4 (6)
C9—C6—C7	115.2 (6)	C30—C25—C24	118.1 (6)
C8—C7—C6	117.0 (6)	C26—C25—C24	120.9 (6)
C8—C7—Pd1	131.8 (4)	O3—C26—C25	124.1 (6)
C6—C7—Pd1	111.1 (5)	O3—C26—C27	120.1 (6)
C7—C8—C3	122.4 (6)	C25—C26—C27	115.8 (5)
C7—C8—H8	118.8	C28—C27—C26	121.0 (6)
C3—C8—H8	118.8	C28—C27—H27	119.5
N2—C9—C6	118.6 (6)	C26—C27—H27	119.5
N2—C9—H9	120.7	C27—C28—C29	123.0 (6)
C6—C9—H9	120.7	C27—C28—N4	118.6 (7)
C11—C10—C15	117.8 (7)	C29—C28—N4	118.4 (6)
C11—C10—N2	121.7 (6)	C30—C29—C28	117.4 (6)
C15—C10—N2	120.5 (6)	C30—C29—H29	121.3
C12—C11—C10	121.9 (6)	C28—C29—H29	121.3
C12—C11—H11	119.0	C29—C30—C25	122.3 (6)
C10—C11—H11	119.0	C29—C30—H30	118.8
C11—C12—C13	118.7 (6)	C25—C30—H30	118.8
C11—C12—H12	120.6
C20—C21—N3—C24	133.4 (6)	C24—C25—C26—O3	−9.6 (13)
C21—N3—C24—C25	−171.5 (6)	C25—C26—O3—Pd1	−31.7 (13)
N3—C24—C25—C30	−166.9 (7)	C26—O3—Pd1—N2	−135.2 (7)
C5—C6—C9—N2	−176.7 (7)	O3—Pd1—N2—C9	−179.8 (5)
C6—C9—N2—C10	178.5 (6)	Pd1—N2—C9—C6	−2.8 (8)
C9—N2—C10—C15	−131.3 (7)	N2—C9—C6—C7	0.7 (9)
N3—C24—C25—C26	22.1 (10)	C1—N1—C3—C4	−179.2 (7)

(II) [4-(diethylamino)-N-(4-methoxyphenyl)salicylaldiminato]- {5-methoxy-2-[N-(4-methoxyphenyl)iminomethyl]phenyl}palladium(II), dichloromethane hemisolvate

Crystal data

[Pd(C14H11N2O3)(C18H21N2O2)]·0.5CH2Cl2	F(000) = 2872
Mr = 701.48	Dx = 1.516 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71069 Å
a = 31.582 (10) Å	Cell parameters from 24 reflections
b = 7.5847 (10) Å	θ = 8.5–11.8°
c = 26.557 (6) Å	µ = 0.74 mm^−1
β = 104.96 (3)°	T = 293 K
V = 6146 (3) Å^3	Prism, dark orange
Z = 8	0.5 × 0.1 × 0.06 mm

Data collection

Enraf-Nonius MACH3 diffractometer	3705 reflections with I > 2σ(I)
Radiation source: Enraf Nonius FR590	Rint = 0.060
Graphite monochromator	θmax = 28.0°, θmin = 1.3°
ω/θ scans	h = −41→40
Absorption correction: ψ scan (North et al., 1968)	k = 0→10
Tmin = 0.952, Tmax = 1.000	l = 0→34
7552 measured reflections	1 standard reflections every 120 min
7388 independent reflections	intensity decay: 1%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.151	H-atom parameters constrained
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0525P)^2] where P = (Fo^2 + 2Fc^2)/3
7388 reflections	(Δ/σ)max < 0.001
393 parameters	Δρmax = 0.66 e Å^−3
0 restraints	Δρmin = −0.75 e Å^−3

Special details

Experimental. Pd content in (1) and (2) was determined by thermogravimetric analysis (Mettler TG 50, scanning rate 20 C/min, air atmosphere). NMR analysis of (1) and (2), as well as of synthetic precursors, was performed on a Varian Gemini XL 200 Mhz spectrometer. UV-VIS spectra were recorded at ambient temperature with a Perkin Elmer Lambda 7 spectrometer. Transition temperatures were determined by DSC analysis (Perkin Elmer DSC-7 apparatus).

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. All H atoms were stereochemically positioned. For all H atoms refinement was by the riding model, with U_iso equal to U_eq of the carrier atom.

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

	x	y	z	Uiso*/Ueq
Pd1	0.192569 (16)	0.58907 (6)	0.151034 (17)	0.03280 (13)
N1	0.22485 (17)	0.6935 (7)	0.22168 (19)	0.0367 (12)
N2	0.02152 (19)	0.6326 (10)	0.1624 (3)	0.0604 (19)
N3	0.32671 (18)	0.0010 (7)	0.0894 (2)	0.0490 (15)
N4	0.15873 (16)	0.5164 (7)	0.07874 (18)	0.0356 (12)
O1	0.40472 (16)	0.7259 (7)	0.3076 (2)	0.0608 (14)
O2	−0.00407 (18)	0.6699 (12)	0.1875 (2)	0.112 (3)
O3	0.01069 (17)	0.5570 (9)	0.1214 (2)	0.0786 (18)
O4	0.24843 (13)	0.4736 (5)	0.13842 (16)	0.0385 (10)
O5	0.01872 (17)	0.8930 (8)	−0.0465 (2)	0.0714 (15)
C1	0.4236 (3)	0.6686 (12)	0.3592 (3)	0.074 (3)
H1A	0.4549	0.6815	0.3671	0.074*
H1B	0.4164	0.5469	0.3625	0.074*
H1C	0.4124	0.7383	0.3830	0.074*
C2	0.3606 (2)	0.7153 (9)	0.2899 (3)	0.0432 (16)
C3	0.3325 (2)	0.6591 (9)	0.3186 (3)	0.0448 (17)
H3	0.3433	0.6263	0.3533	0.045*
C4	0.2880 (2)	0.6521 (9)	0.2952 (3)	0.0424 (16)
H4	0.2690	0.6149	0.3146	0.042*
C5	0.2713 (2)	0.6983 (8)	0.2443 (2)	0.0356 (14)
C6	0.2993 (2)	0.7528 (9)	0.2151 (3)	0.0452 (16)
H6	0.2882	0.7815	0.1801	0.045*
C7	0.3437 (2)	0.7645 (9)	0.2380 (3)	0.0484 (17)
H7	0.3624	0.8053	0.2187	0.048*
C8	0.2001 (2)	0.7662 (8)	0.2476 (2)	0.0382 (15)
H8	0.2114	0.8248	0.2789	0.038*
C9	0.1536 (2)	0.7503 (7)	0.2244 (2)	0.0332 (14)
C10	0.1230 (2)	0.8063 (9)	0.2512 (2)	0.0430 (16)
H10	0.1322	0.8663	0.2827	0.043*
C11	0.0791 (2)	0.7715 (10)	0.2303 (3)	0.0487 (18)
H11	0.0581	0.8075	0.2470	0.049*
C12	0.0678 (2)	0.6819 (9)	0.1841 (3)	0.0420 (16)
C13	0.0973 (2)	0.6329 (8)	0.1556 (2)	0.0404 (16)
H13	0.0874	0.5780	0.1234	0.040*
C14	0.1414 (2)	0.6669 (8)	0.1757 (2)	0.0335 (14)
C15	0.3214 (3)	−0.3229 (10)	0.0817 (3)	0.085 (3)
H15A	0.3243	−0.4188	0.0593	0.085*
H15B	0.2920	−0.3199	0.0855	0.085*
H15C	0.3415	−0.3389	0.1153	0.085*
C16	0.3313 (2)	−0.1527 (9)	0.0584 (3)	0.0518 (19)
H16A	0.3610	−0.1569	0.0547	0.052*
H16B	0.3117	−0.1401	0.0239	0.052*
C17	0.3663 (2)	0.0518 (9)	0.1276 (3)	0.0513 (19)
H17A	0.3853	−0.0502	0.1362	0.051*
H17B	0.3587	0.0891	0.1591	0.051*
C18	0.3911 (2)	0.1990 (12)	0.1094 (3)	0.071 (2)
H18A	0.4169	0.2266	0.1363	0.071*
H18B	0.3727	0.3016	0.1016	0.071*
H18C	0.3993	0.1622	0.0786	0.071*
C19	0.2887 (2)	0.0929 (9)	0.0832 (2)	0.0386 (13)
C20	0.2864 (2)	0.2413 (8)	0.1132 (2)	0.0362 (15)
H20	0.3116	0.2782	0.1376	0.036*
C21	0.2475 (2)	0.3378 (8)	0.1083 (2)	0.0348 (14)
C22	0.2098 (2)	0.2863 (8)	0.0695 (2)	0.0374 (14)
C23	0.2131 (2)	0.1352 (8)	0.0391 (3)	0.0456 (17)
H23	0.1886	0.1007	0.0133	0.046*
C24	0.2501 (2)	0.0394 (9)	0.0459 (3)	0.0490 (18)
H24	0.2504	−0.0615	0.0261	0.049*
C25	0.1713 (2)	0.3859 (9)	0.0544 (2)	0.0386 (15)
H25	0.1521	0.3544	0.0228	0.039*
C26	0.1217 (2)	0.6140 (9)	0.0489 (2)	0.0379 (15)
C27	0.0839 (2)	0.5348 (10)	0.0198 (2)	0.0470 (17)
H27	0.0813	0.4129	0.0213	0.047*
C28	0.0504 (2)	0.6286 (10)	−0.0108 (3)	0.0522 (19)
H28	0.0252	0.5716	−0.0294	0.052*
C29	0.0541 (2)	0.8095 (11)	−0.0141 (3)	0.0541 (19)
C30	0.0907 (2)	0.8925 (10)	0.0160 (3)	0.0498 (17)
H30	0.0927	1.0148	0.0153	0.050*
C31	0.1246 (2)	0.7958 (9)	0.0474 (2)	0.0432 (16)
H31	0.1492	0.8530	0.0674	0.043*
C32	0.0226 (3)	1.0715 (13)	−0.0566 (4)	0.096 (3)
H32A	−0.0041	1.1129	−0.0796	0.096*
H32B	0.0464	1.0884	−0.0725	0.096*
H32C	0.0284	1.1363	−0.0245	0.096*
Cl1	0.0312 (3)	0.1473 (10)	0.3017 (3)	0.273 (3)
C33	0.0000	0.269 (3)	0.2500	0.260 (19)
H33B	0.0196	0.3445	0.2369	0.260*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.0413 (2)	0.0292 (2)	0.0299 (2)	0.0002 (3)	0.01264 (16)	−0.0033 (3)
N1	0.045 (3)	0.027 (3)	0.040 (3)	0.002 (2)	0.015 (2)	−0.001 (2)
N2	0.044 (4)	0.086 (6)	0.054 (4)	0.007 (3)	0.018 (3)	0.011 (4)
N3	0.049 (4)	0.034 (3)	0.066 (4)	−0.002 (3)	0.019 (3)	−0.023 (3)
N4	0.042 (3)	0.036 (3)	0.030 (3)	0.005 (2)	0.013 (2)	−0.001 (2)
O1	0.045 (3)	0.064 (4)	0.068 (4)	−0.001 (3)	0.005 (3)	−0.007 (3)
O2	0.048 (3)	0.214 (9)	0.079 (4)	0.000 (5)	0.021 (3)	−0.029 (5)
O3	0.058 (3)	0.103 (5)	0.073 (4)	−0.005 (3)	0.014 (3)	−0.016 (4)
O4	0.042 (2)	0.034 (2)	0.041 (2)	−0.001 (2)	0.014 (2)	−0.012 (2)
O5	0.064 (3)	0.068 (4)	0.074 (4)	0.010 (3)	0.002 (3)	0.022 (3)
C1	0.060 (5)	0.063 (6)	0.087 (6)	−0.008 (5)	−0.003 (5)	−0.011 (5)
C2	0.045 (4)	0.035 (4)	0.048 (4)	0.001 (3)	0.010 (3)	−0.009 (3)
C3	0.060 (5)	0.038 (4)	0.037 (4)	0.012 (3)	0.013 (3)	−0.005 (3)
C4	0.054 (4)	0.037 (4)	0.044 (4)	−0.001 (3)	0.025 (3)	−0.002 (3)
C5	0.046 (4)	0.027 (3)	0.036 (3)	−0.001 (3)	0.014 (3)	−0.006 (3)
C6	0.058 (4)	0.041 (4)	0.037 (3)	0.000 (3)	0.015 (3)	0.000 (3)
C7	0.055 (4)	0.042 (4)	0.051 (4)	−0.008 (4)	0.019 (3)	0.001 (3)
C8	0.055 (4)	0.028 (3)	0.030 (3)	−0.004 (3)	0.009 (3)	−0.005 (3)
C9	0.050 (4)	0.020 (3)	0.033 (3)	0.002 (3)	0.016 (3)	0.002 (2)
C10	0.053 (4)	0.044 (4)	0.033 (3)	0.011 (3)	0.012 (3)	−0.001 (3)
C11	0.058 (5)	0.050 (4)	0.045 (4)	0.023 (4)	0.028 (3)	0.011 (3)
C12	0.044 (4)	0.040 (4)	0.042 (4)	0.006 (3)	0.012 (3)	0.013 (3)
C13	0.048 (4)	0.035 (4)	0.042 (3)	−0.002 (3)	0.019 (3)	0.002 (3)
C14	0.040 (4)	0.025 (3)	0.038 (3)	0.004 (3)	0.016 (3)	0.004 (3)
C15	0.163 (10)	0.035 (5)	0.068 (6)	−0.010 (6)	0.050 (6)	−0.012 (4)
C16	0.067 (5)	0.045 (4)	0.054 (4)	0.001 (4)	0.036 (4)	−0.007 (3)
C17	0.051 (4)	0.045 (5)	0.060 (4)	0.021 (3)	0.018 (3)	0.006 (3)
C18	0.048 (5)	0.081 (6)	0.081 (6)	−0.004 (5)	0.011 (4)	−0.008 (5)
C19	0.046 (3)	0.027 (3)	0.048 (3)	0.002 (3)	0.023 (3)	0.000 (3)
C20	0.041 (4)	0.028 (3)	0.044 (4)	−0.006 (3)	0.018 (3)	−0.010 (3)
C21	0.043 (4)	0.032 (3)	0.036 (3)	−0.007 (3)	0.021 (3)	−0.002 (3)
C22	0.043 (4)	0.028 (3)	0.044 (4)	−0.002 (3)	0.017 (3)	−0.006 (3)
C23	0.046 (4)	0.038 (4)	0.050 (4)	−0.004 (3)	0.007 (3)	−0.020 (3)
C24	0.058 (4)	0.032 (4)	0.058 (4)	−0.003 (3)	0.018 (4)	−0.018 (3)
C25	0.044 (3)	0.044 (4)	0.027 (3)	−0.005 (3)	0.008 (3)	−0.001 (3)
C26	0.044 (4)	0.041 (4)	0.032 (3)	0.008 (3)	0.018 (3)	−0.001 (3)
C27	0.046 (4)	0.047 (4)	0.045 (4)	0.001 (3)	0.007 (3)	−0.002 (3)
C28	0.044 (4)	0.059 (5)	0.050 (4)	−0.004 (4)	0.005 (3)	−0.003 (4)
C29	0.044 (4)	0.061 (5)	0.052 (4)	0.002 (4)	0.004 (3)	0.001 (4)
C30	0.062 (4)	0.033 (4)	0.055 (4)	0.004 (4)	0.017 (3)	0.007 (4)
C31	0.041 (4)	0.042 (4)	0.045 (4)	0.000 (3)	0.009 (3)	−0.002 (3)
C32	0.069 (6)	0.089 (8)	0.122 (8)	0.001 (6)	0.011 (5)	0.040 (7)
Cl1	0.363 (9)	0.213 (6)	0.314 (8)	0.011 (6)	0.214 (7)	0.000 (6)
C33	0.58 (6)	0.074 (15)	0.16 (2)	0.000	0.16 (3)	0.000

Geometric parameters (Å, º)

Pd1—C14	1.984 (6)	C13—C14	1.382 (8)
Pd1—N4	2.018 (5)	C13—H13	0.9300
Pd1—N1	2.049 (5)	C15—C16	1.499 (10)
Pd1—O4	2.073 (4)	C15—H15A	0.9600
N1—C8	1.291 (7)	C15—H15B	0.9600
N1—C5	1.434 (8)	C15—H15C	0.9600
N2—O3	1.201 (8)	C16—H16A	0.9700
N2—O2	1.205 (8)	C16—H16B	0.9700
N2—C12	1.474 (9)	C17—C18	1.513 (10)
N3—C19	1.362 (8)	C17—H17A	0.9700
N3—C17	1.443 (8)	C17—H17B	0.9700
N3—C16	1.456 (8)	C18—H18A	0.9600
N4—C25	1.298 (7)	C18—H18B	0.9600
N4—C26	1.436 (8)	C18—H18C	0.9600
O1—C2	1.352 (8)	C19—C20	1.392 (8)
O1—C1	1.414 (9)	C19—C24	1.416 (9)
O4—C21	1.300 (7)	C20—C21	1.407 (8)
O5—C29	1.377 (8)	C20—H20	0.9300
O5—C32	1.392 (10)	C21—C22	1.414 (8)
C1—H1A	0.9600	C22—C25	1.399 (8)
C1—H1B	0.9600	C22—C23	1.421 (8)
C1—H1C	0.9600	C23—C24	1.349 (9)
C2—C3	1.380 (9)	C23—H23	0.9300
C2—C7	1.395 (9)	C24—H24	0.9300
C3—C4	1.383 (9)	C25—H25	0.9300
C3—H3	0.9300	C26—C27	1.381 (9)
C4—C5	1.362 (8)	C26—C31	1.383 (9)
C4—H4	0.9300	C27—C28	1.357 (9)
C5—C6	1.382 (8)	C27—H27	0.9300
C6—C7	1.380 (9)	C28—C29	1.381 (11)
C6—H6	0.9300	C28—H28	0.9300
C7—H7	0.9300	C29—C30	1.375 (10)
C8—C9	1.441 (8)	C30—C31	1.385 (9)
C8—H8	0.9300	C30—H30	0.9300
C9—C14	1.401 (8)	C31—H31	0.9300
C9—C10	1.406 (8)	C32—H32A	0.9600
C10—C11	1.378 (9)	C32—H32B	0.9600
C10—H10	0.9300	C32—H32C	0.9600
C11—C12	1.368 (9)	Cl1—C33	1.736 (13)
C11—H11	0.9300	C33—Cl1^i	1.736 (12)
C12—C13	1.395 (9)	C33—H33B	0.9701
C14—Pd1—N4	96.9 (2)	C16—C15—H15C	109.5
C14—Pd1—N1	80.6 (2)	H15A—C15—H15C	109.5
N4—Pd1—N1	173.1 (2)	H15B—C15—H15C	109.5
C14—Pd1—O4	168.2 (2)	N3—C16—C15	113.2 (6)
N4—Pd1—O4	89.70 (18)	N3—C16—H16A	108.9
N1—Pd1—O4	93.91 (18)	C15—C16—H16A	108.9
C8—N1—C5	117.4 (5)	N3—C16—H16B	108.9
C8—N1—Pd1	115.2 (4)	C15—C16—H16B	108.9
C5—N1—Pd1	127.4 (4)	H16A—C16—H16B	107.8
O3—N2—O2	122.6 (7)	N3—C17—C18	113.5 (6)
O3—N2—C12	119.8 (6)	N3—C17—H17A	108.9
O2—N2—C12	117.6 (7)	C18—C17—H17A	108.9
C19—N3—C17	121.7 (5)	N3—C17—H17B	108.9
C19—N3—C16	123.7 (6)	C18—C17—H17B	108.9
C17—N3—C16	114.6 (6)	H17A—C17—H17B	107.7
C25—N4—C26	115.3 (5)	C17—C18—H18A	109.5
C25—N4—Pd1	121.8 (4)	C17—C18—H18B	109.5
C26—N4—Pd1	122.7 (4)	H18A—C18—H18B	109.5
C2—O1—C1	117.2 (6)	C17—C18—H18C	109.5
C21—O4—Pd1	123.3 (4)	H18A—C18—H18C	109.5
C29—O5—C32	118.0 (7)	H18B—C18—H18C	109.5
O1—C1—H1A	109.5	N3—C19—C20	121.3 (6)
O1—C1—H1B	109.5	N3—C19—C24	120.7 (6)
H1A—C1—H1B	109.5	C20—C19—C24	118.0 (6)
O1—C1—H1C	109.5	C19—C20—C21	122.8 (6)
H1A—C1—H1C	109.5	C19—C20—H20	118.6
H1B—C1—H1C	109.5	C21—C20—H20	118.6
O1—C2—C3	125.4 (6)	O4—C21—C20	118.3 (6)
O1—C2—C7	115.2 (6)	O4—C21—C22	123.3 (6)
C3—C2—C7	119.4 (6)	C20—C21—C22	118.3 (6)
C2—C3—C4	119.3 (6)	C25—C22—C21	124.4 (6)
C2—C3—H3	120.4	C25—C22—C23	117.3 (6)
C4—C3—H3	120.4	C21—C22—C23	117.7 (6)
C5—C4—C3	121.6 (6)	C24—C23—C22	123.2 (6)
C5—C4—H4	119.2	C24—C23—H23	118.4
C3—C4—H4	119.2	C22—C23—H23	118.4
C4—C5—C6	119.6 (6)	C23—C24—C19	119.9 (6)
C4—C5—N1	120.1 (6)	C23—C24—H24	120.1
C6—C5—N1	120.3 (6)	C19—C24—H24	120.1
C7—C6—C5	119.8 (6)	N4—C25—C22	128.6 (6)
C7—C6—H6	120.1	N4—C25—H25	115.7
C5—C6—H6	120.1	C22—C25—H25	115.7
C6—C7—C2	120.3 (6)	C27—C26—C31	118.1 (6)
C6—C7—H7	119.8	C27—C26—N4	123.2 (6)
C2—C7—H7	119.8	C31—C26—N4	118.7 (6)
N1—C8—C9	115.3 (5)	C28—C27—C26	122.3 (7)
N1—C8—H8	122.4	C28—C27—H27	118.9
C9—C8—H8	122.4	C26—C27—H27	118.9
C14—C9—C10	122.8 (6)	C27—C28—C29	119.5 (7)
C14—C9—C8	116.0 (5)	C27—C28—H28	120.2
C10—C9—C8	121.1 (5)	C29—C28—H28	120.2
C11—C10—C9	119.4 (6)	C30—C29—O5	125.2 (7)
C11—C10—H10	120.3	C30—C29—C28	119.4 (7)
C9—C10—H10	120.3	O5—C29—C28	115.4 (7)
C12—C11—C10	117.3 (6)	C29—C30—C31	120.6 (7)
C12—C11—H11	121.4	C29—C30—H30	119.7
C10—C11—H11	121.4	C31—C30—H30	119.7
C11—C12—C13	124.3 (6)	C26—C31—C30	120.0 (7)
C11—C12—N2	118.6 (6)	C26—C31—H31	120.0
C13—C12—N2	117.1 (6)	C30—C31—H31	120.0
C14—C13—C12	119.2 (6)	O5—C32—H32A	109.5
C14—C13—H13	120.4	O5—C32—H32B	109.5
C12—C13—H13	120.4	H32A—C32—H32B	109.5
C13—C14—C9	116.9 (5)	O5—C32—H32C	109.5
C13—C14—Pd1	129.9 (5)	H32A—C32—H32C	109.5
C9—C14—Pd1	112.7 (4)	H32B—C32—H32C	109.5
C16—C15—H15A	109.5	Cl1—C33—Cl1^i	115.6 (14)
C16—C15—H15B	109.5	Cl1—C33—H33B	108.3
H15A—C15—H15B	109.5	Cl1^i—C33—H33B	108.3
C16—N3—C19—C20	−178.6 (6)	N1—C8—C9—C10	172.9 (6)
C23—C22—C25—N4	172.1 (6)	O4—C21—C22—C25	8.5 (9)
C22—C25—N4—C26	168.5 (6)	C21—C22—C25—N4	−16.6 (10)
C25—N4—C26—C31	−130.0 (6)	C22—C25—N4—Pd1	−6.2 (9)
C6—C5—N1—C8	−131.0 (6)	N1—C8—C9—C14	−3.3 (8)
C5—N1—C8—C9	−177.0 (5)	C8—C9—C14—Pd1	0.4 (7)

Symmetry code: (i) −x, y, −z+1/2.