Bis{2-[(3,5-diphenyl-1H-pyrrol-2-yl­idene-κN)amino]-3,5-di­phenyl­pyrrol-1-ido-κN}palladium(II): a homoleptic four-coordinate tetra­phenyl­aza­di­pyrromethene complex of palladium

The structural chemistry of the title compound, [Pd(C₃₂H₂₂N₃)₂], at 173 K is described. The compound is com­prised of two deprotonated (3,5-diphenyl-1H-pyrrol-2-yl)(3,5-di­phenyl­pyrrol-2-yl­idene)amine ligands coordinated to a central Pd^II cation, which lies on an inversion centre and has distorted square-planar geometry. The Pd—N bond lengths range from 2.008 (4) to 2.014 (4) Å and the bite angle is 84.16 (14)°. The chelate plane makes a dihedral angle of 45.3 (2)° with respect to the central PdN₄ plane, giving a stepped conformation to the mol­ecule. The complex displays simple intra­molecular C—H...N hydrogen bonds, while the unit cell consists of discrete monomeric Pd(C₃₂H₂₂N₃)₂ units which display inter­molecular C—H...π inter­actions and limited intra- and inter­molecular π–π stacking.

S1. Introduction

Bidentate aza­dipyrromethenes are a developing class of organic ligands valued for their spectroscopic properties as chromophores in the visible red and near-infrared (NIR) spectroscopic regions (Teets et al., 2008, 2009; Palma et al., 2009). The use of this class of compound as a framework for coordination of a BF₂ chelate confers sufficient structural rigidity on the resultant compound, thereby limiting radiation-less transitions and allowing the exploitation of their excited states (Hall et al., 2005, 2006; McDonnell & O'Shea, 2006). In particular, the excellent photostability, high extinction coefficients and high fluorescence quantum yields observed in BF₂-chelated tetra­aryl­aza­dipyrromethenes have encouraged their study and potential application in photodynamic therapy, fluorescent chemosensors and in vitro fluoro­phores (Killoran et al., 2002; McDonnell & O'Shea, 2006; Loudet et al., 2008; Frimannsson et al., 2010; Palma et al., 2011, and references therein). It is these photophysical characteristics and the ability readily to incorporate other metals into the organic framework that has led to the exploration of their transition metal complexes in efforts to attune the photophysical properties and lead to new potential catalysts, and optical data storage and electrochromic devices (Teets et al., 2008, 2009; Palma et al., 2009). However, despite being known in the literature [the tetra­aryl­aza­dipyrromethene used in this study was first reported by Rogers (1943)], and unlike the analogous dipyrrin class of compounds (Wood & Thompson, 2007), metal complexes of tetra­aryl­aza­dipyrromethenes remain limited in the literature to a few examples of tricoordinate group 11 (Cu^I, Ag^I and Au^I) (Teets et al., 2009) and first row bidentate (Co^II, Cu^II, Ni^II and Zn^II) complexes (Teets et al., 2008; Palma et al., 2009; Bessette et al., 2012). In the latter case, the aim of the study was to detect any potential impact of inter-ligand and metal–ligand sterics and subsequent effects on spectroscopic properties. Herein, we describe an extension of this early work in the synthesis and structural chemistry of the first structurally characterized Pd^II tetra­aryl­aza­dipyrromethene complex, the title compound, (II).

S2. Experimental

S2.1. Synthesis and crystallization

Pd(OAc)₂ (30 mg, 0.134 mmol, 1.03 equivalents) was added to a stirred solution of ligand (I) (58 mg, 0.130 mmol, 1 equivalent) in AcOH (5 ml) and heated at 373 K for 2 h with vigorous stirring. The dark-coloured solution was then cooled to room temperature, CH₂Cl₂ (25 ml) and H₂O (25 ml) were added, the product was extracted with CH₂Cl₂ (2 × 15 ml) and the combined organic phases were dried over MgSO₄. The solution was filtered and the solvent removed in vacuo, and the product was purified by flash column chromatography on silica gel with cyclo­hexane–EtOAc (19:1 v/v) to give the product, (II), as a green–blue solid [metallic brown given in CIF tables - please clarify] (yield 41 mg, 63%). R_F = 0.15 (cyclo­hexane–EtOAc; 19:1 v/v). Spectroscopic analysis: ¹H NMR (300 MHz, CDCl₃, δ, p.p.m.) 6.91 (1H, s), 7.15–7.19 (3H, m), 7.39 (1H, t, J = 7.5 Hz), 7.53 (2H, t, J = 7.5 Hz), 7.72–7.78 (2H, m), 8.39 (2H, d, J = 7.5 Hz); (ES⁺) m/z 554 [M - L]⁺, 554 (C₃₂H₂₂N₃¹⁰⁶Pd 554); UV–Vis: (CH₂Cl₂): λ max 611 nm.

Obtaining a crystal of (II) suitable for X-ray analysis was challenging, but one was grown by the slow evaporation of a CH₂Cl₂ solution of (II). The majority of the compound failed to give crystals and was obtained as a noncrystalline gum.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were placed in calculated positions and refined using a riding model, with fixed C—H distances of 0.95 (Csp²—H) and 0.98 Å (CH₃), and with U_iso(H) = 1.2U_eq(Csp²) or 1.5U_eq(Csp³). Attempts to refine the disorder using restraints in the phenyl ring including atoms C8, C9 and C10 led to unreasonably high correlations. It was thus decided to leave the model with single sites for these atoms. Data collection was based on pre-experiment and data collected at the start of the data collections, to the point where it appeared that it did not diffract any further. Upon completion of the data collection at the time of the experiment it was not recognized that additional data collection might have been warranted.

S3. Results and discussion

The molecular structure of (II) and the atom-labelling scheme are shown in Fig. 1(a), with selected geometric parameters listed in Table 2. Complex (II) crystallizes as brown prism-shaped crystals in the space group P2₁/c (No. 14) with two inverted N,N'-bidentate chelating tetra­aryl­aza­dipyrromethene ligands. The Pd^II cation is located on a crystallographic inversion centre (with one half of the molecule residing in the asymmetric unit), tetra­coordinated by two pyrrole N atoms of each ligand.

In spite of the two sterically bulky ligands, a distorted square-planar geometry is observed at the metal centre, with angles falling into the range 84–95° for various groupings of N—M—N angles (Table 2). In order to maintain this preferred square-planar geometry, the N1/C1/N2/C17/N3 chelation plane is splayed back, forming a dihedral angle of 45.3 (2)° with the mean metal coordination plane (PdN₄), giving the complex a stepped configuration (Fig. 1b). This stepped geometry has been observed in structurally analogous Pd^II dipyrrin and di­pyridyl­iminate complexes (Freeman & Snow, 1965; March et al., 1971; Wood & Thompson, 2007; Hall et al., 2010), with such a geometry predicted to be favoured over the distorted tetra­hedron detected in Ni^II and Zn^II analogues of this ligand (Teets et al., 2008; Palma et al., 2009).

The phenyl substituents of the pyrrole rings are parallel with respect to each other and show dihedral angles of 41.4 (2) and 62.95 (17)° (pyrrole positions C2 and C18), and 53.64 (15) and 56.55 (16)° (pyrrole positions C4 and C20), with the PdN₄ plane, respectively. Additionally, the phenyl substituents on the pyrrole C4 and C20 positions are almost planar with respect to the chelation plane, showing dihedral angles of 8.51 (17) and 11.31 (18)°, respectively. This gives an indication that the stepped geometry of this structure can overcome the inter­molecular steric repulsions of the bulky phenyl substituents used in this study and may allow further modification of the ligand to tune the desired properties without compromising an ideal structural conformation. However, slight deviation of the ligand from planarity is detected (Fig. 1c), with a folding of the two pyrrole rings away from chelation plane (N1/C1/N2/C17/N3) by 15.72 (18) and 16.48 (8)° along the N1—C1 and N3—C17 bonds, respectively. The chelate ring shows very minor puckering, with atom N3 lying out of the mean N1/C1/N2/C17 plane by 0.035 (9) Å, while the PdN₄ coordination plane is planar. The Pd—N bond lengths of 2.014 (4) and 2.008 (4) Å observed for (II) are typical for Pd^II complexes of this type and are related to those detected in structurally characterized palladium(II) dipyrrin, dipyrromethene and metallo-tetra­pyrrole complexes (March et al.,1971, 1972; Stolzenberg et al., 1992; Lord et al., 2000; Wood & Thompson, 2007).

Comparison of the data for the free (3,5-di­phenyl-1H-pyrrol-2-yl)(3,5-di­phenyl­pyrrol-2-yl­idene)amine ligand, (I) (Bandi et al., 2013) and its Pd^II complex, (II), shows minor structural differences in bond lengths and angles. As a representative sample, a deviation of only 0.034 Å is detected in the bond lengths of the pyrrole rings between (I) and (II). As observed in (I), the five-membered pyrrole rings (N1/C1–C4 and N3/C17–C20) are essentially planar, with the largest deviations being 0.024 (7) and 0.012 (9) Å for atoms C1 and C17, respectively. The backbone C1—N2—C17 bond angle (where N2 is the bridging N atom not involved in metal ligation) of 122.6 (4)° in (II) is comparable with the value in (I) [122.93 (11)°], larger than that reported for the analogous BF₂–aza­dipyrromethene compound [191.7 (1)°; Li et al., 2010] but smaller than in the corresponding previously reported metal(II) bis-chelates of (I) [124.9 (3)–129.3 (2)°; Palma et al., 2009]. These larger angles in the metal-coordinated systems indicate flexibility in the coordinated ligand. It is of inter­est that the C—N bond lengths of the ligand are comparable for (II) and the analogous Ni^II complex (Palma et al., 2009), suggesting the dominant feature for the ligand may be π-delocalisation, irrespective of any deformation of the ligand in the complex (March et al., 1971).

The unit cell of (II) (Fig. 2) consists of discrete monomeric Pd(C₃₂H₂₂N₃)₂ units [the shortest Pd···Pd distance being 9.197 (6) Å] that pack into two anti­parallel running stacks which are off-set to accommodate the torsion angle of the aromatic rings in the molecule. Limited π–π stacking between adjacent pyrrole–aryl rings and aryl–aryl rings, with perpendicular ring-to-ring distances of ca 3.6 Å, completes the host of weaker inter­molecular inter­actions detected in (II).

Examination of the structure with PLATON (Spek, 2009) shows the presence of two intra­molecular phenyl C—H···N hydrogen bonds (C10—H10···N2 and C26—H26···N2), two longer (weaker) C—H···π(arene) and two C—H···Pd inter­actions (Table 3). Both C—H···π(arene) inter­actions are inter­molecular, with phenyl atoms C13 and C29 acting as donors to the N1/C1–C4 and C21–C26 rings of adjacent molecules, thereby linking molecules in the unit cell into extended chains. The two C—H···Pd inter­actions are both intra­molecular and connect atoms H16 and H32 of the phenyl rings adjacent to the Pd metal centre, with H···Pd lengths of 2.76 and 2.79 Å, respectively (Table 3). Brookhart et al. (2007) categorized such M—H—C bonds as anagostic inter­actions (M—H ≈ 2.3–2.9 Å), largely electrostatic in nature and typical of square-planar d⁸ transition metal centres.

Related literature

For related literature, see: Bandi et al. (2013); Bessette et al. (2012); Brookhart et al. (2007); Freeman & Snow (1965); Frimannsson et al. (2010); Hall et al. (2005, 2006, 2010); Killoran et al. (2002); Li et al. (2010); Lord et al. (2000); Loudet et al. (2008); March et al. (1971, 1972); McDonnell & O'Shea (2006); Palma et al. (2009, 2011); Rogers (1943); Spek (2009); Stolzenberg et al. (1992); Teets et al. (2008, 2009); Wood & Thompson (2007).

Computing details

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

Fig. 1. (a) The molecular structure of (II), showing the atom-numbering scheme. Displacement elipsoids are drawn at the 50% probability level. (b) A view of the PdN₄ coordination plane and the N—C—N—C—N chelation plane geometry, showing the stepped configuration between the chelation planes of the ligands and the Pd atom (middle). (c) A view looking down the N1/N3 vector, showing the puckering of the pyrrolide rings with respect to the chelation plane. [Symmetry code: (i) -x + 2, -y + 2, -z.]

Fig. 2. The unit-cell packing in (II), viewed down a. The N and Pd atoms are represented by [small] ellipsoids drawn at the 50% probability level, while C atoms are represented by [large] spheres of arbitary size. H atoms have been omitted for clarity.

Bis{2-[(3,5-diphenyl-1H-pyrrol-2-ylidene-κN)amino]-3,5-diphenylpyrrol-1-ido-κN}palladium(II)

Crystal data

[Pd(C32H22N3)2]	F(000) = 1032
Mr = 1003.45	Dx = 1.443 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 3352 reflections
a = 13.9269 (4) Å	θ = 3.2–62.1°
b = 11.9137 (3) Å	µ = 3.64 mm^−1
c = 14.0158 (5) Å	T = 100 K
β = 96.665 (3)°	Prism, metallic brown
V = 2309.80 (12) Å^3	0.06 × 0.03 × 0.02 mm
Z = 2

Data collection

Agilent SuperNova Dual diffractometer (Cu at zero) with Atlas detector	3515 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	2879 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.040
Detector resolution: 10.3196 pixels mm^-1	θmax = 62.2°, θmin = 3.2°
ω scans	h = −15→15
Absorption correction: analytical [CrysAlis PRO (Agilent, 2011), based on expressions derived by Clark & Reid (1995)]	k = −10→13
Tmin = 0.842, Tmax = 0.945	l = −10→15
8633 measured reflections

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.125	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0552P)^2 + 3.8109P] where P = (Fo^2 + 2Fc^2)/3
3515 reflections	(Δ/σ)max < 0.001
322 parameters	Δρmax = 0.90 e Å^−3
0 restraints	Δρmin = −0.54 e Å^−3

Special details

Experimental. CrysAlisPro, Agilent Technologies, Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET) (Agilent, 2011). Analytical numerical absorption correction using a multifaceted crystal model based on expressions derived by R. C. Clark & J. S. Reid. [Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887–897].

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	1.0000	1.0000	0.0000	0.02687 (17)
N1	0.9128 (3)	1.0647 (3)	0.0910 (3)	0.0320 (9)
C1	0.8223 (3)	1.0169 (4)	0.0881 (3)	0.0295 (10)
C2	0.7580 (4)	1.0975 (4)	0.1268 (3)	0.0331 (11)
C5	0.6546 (4)	1.0846 (4)	0.1340 (4)	0.0369 (12)
C6	0.5998 (4)	1.1781 (5)	0.1495 (5)	0.0515 (15)
H6	0.6299	1.2498	0.1538	0.062*
C7	0.5018 (4)	1.1698 (5)	0.1590 (5)	0.0551 (16)
H7	0.4670	1.2350	0.1735	0.066*
C8	0.4559 (5)	1.0713 (5)	0.1482 (6)	0.068 (2)
H8	0.3876	1.0663	0.1467	0.082*
C9	0.5123 (6)	0.9766 (7)	0.1391 (11)	0.144 (6)
H9	0.4825	0.9048	0.1383	0.173*
C10	0.6084 (5)	0.9831 (6)	0.1314 (8)	0.104 (4)
H10	0.6440	0.9162	0.1240	0.125*
C3	0.8158 (4)	1.1873 (4)	0.1574 (3)	0.0325 (11)
H3	0.7955	1.2527	0.1882	0.039*
C4	0.9107 (4)	1.1657 (4)	0.1351 (3)	0.0318 (11)
C11	0.9966 (4)	1.2354 (4)	0.1586 (3)	0.0315 (11)
C12	0.9869 (4)	1.3505 (4)	0.1777 (3)	0.0363 (12)
H12	0.9243	1.3823	0.1766	0.044*
C13	1.0667 (4)	1.4171 (4)	0.1977 (4)	0.0396 (12)
H13	1.0587	1.4948	0.2098	0.048*
C14	1.1589 (4)	1.3730 (4)	0.2006 (4)	0.0407 (12)
H14	1.2139	1.4201	0.2139	0.049*
C15	1.1700 (4)	1.2598 (4)	0.1839 (3)	0.0374 (12)
H15	1.2331	1.2289	0.1863	0.045*
C16	1.0903 (4)	1.1906 (4)	0.1637 (3)	0.0330 (11)
H16	1.0991	1.1127	0.1533	0.040*
N2	0.7998 (3)	0.9102 (3)	0.0687 (3)	0.0290 (9)
C17	0.8660 (4)	0.8326 (4)	0.0579 (3)	0.0313 (11)
N3	0.9649 (3)	0.8522 (3)	0.0556 (3)	0.0294 (9)
C18	0.8506 (4)	0.7130 (4)	0.0668 (3)	0.0331 (11)
C21	0.7585 (4)	0.6580 (4)	0.0767 (3)	0.0321 (11)
C22	0.7557 (4)	0.5630 (4)	0.1357 (4)	0.0373 (12)
H22	0.8141	0.5348	0.1688	0.045*
C23	0.6702 (4)	0.5102 (4)	0.1465 (4)	0.0463 (14)
H23	0.6701	0.4458	0.1864	0.056*
C24	0.5841 (4)	0.5502 (5)	0.0994 (4)	0.0480 (14)
H24	0.5247	0.5138	0.1068	0.058*
C25	0.5859 (4)	0.6440 (5)	0.0417 (4)	0.0464 (14)
H25	0.5270	0.6723	0.0096	0.056*
C26	0.6715 (4)	0.6969 (4)	0.0299 (4)	0.0397 (12)
H26	0.6711	0.7609	−0.0106	0.048*
C19	0.9418 (3)	0.6654 (4)	0.0728 (3)	0.0310 (11)
H19	0.9560	0.5877	0.0801	0.037*
C20	1.0102 (3)	0.7518 (4)	0.0662 (3)	0.0286 (10)
C27	1.1155 (3)	0.7385 (4)	0.0765 (3)	0.0299 (10)
C28	1.1572 (4)	0.6353 (4)	0.0589 (3)	0.0339 (11)
H28	1.1169	0.5737	0.0378	0.041*
C29	1.2559 (4)	0.6211 (4)	0.0716 (4)	0.0416 (13)
H29	1.2829	0.5498	0.0604	0.050*
C30	1.3153 (4)	0.7090 (5)	0.1003 (4)	0.0417 (13)
H30	1.3835	0.6989	0.1088	0.050*
C31	1.2755 (4)	0.8140 (4)	0.1171 (4)	0.0403 (12)
H31	1.3168	0.8755	0.1359	0.048*
C32	1.1771 (3)	0.8286 (4)	0.1064 (3)	0.0324 (11)
H32	1.1505	0.8997	0.1192	0.039*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.0311 (3)	0.0168 (3)	0.0332 (3)	−0.0002 (2)	0.00588 (18)	−0.0007 (2)
N1	0.033 (2)	0.018 (2)	0.045 (2)	0.0000 (18)	0.0040 (18)	0.0040 (17)
C1	0.035 (3)	0.022 (3)	0.032 (3)	0.002 (2)	0.0042 (19)	0.0019 (19)
C2	0.040 (3)	0.026 (3)	0.035 (3)	0.005 (2)	0.009 (2)	0.003 (2)
C5	0.035 (3)	0.027 (3)	0.050 (3)	0.005 (2)	0.011 (2)	0.003 (2)
C6	0.043 (3)	0.031 (3)	0.080 (4)	0.003 (3)	0.003 (3)	−0.010 (3)
C7	0.045 (4)	0.049 (4)	0.072 (4)	0.014 (3)	0.007 (3)	−0.007 (3)
C8	0.042 (4)	0.044 (4)	0.126 (6)	0.007 (3)	0.038 (4)	0.015 (4)
C9	0.062 (5)	0.046 (5)	0.341 (18)	−0.018 (4)	0.092 (8)	−0.032 (7)
C10	0.053 (4)	0.045 (4)	0.226 (11)	0.000 (4)	0.061 (6)	−0.021 (5)
C3	0.042 (3)	0.021 (2)	0.035 (3)	0.004 (2)	0.007 (2)	−0.0019 (19)
C4	0.042 (3)	0.021 (2)	0.033 (3)	−0.001 (2)	0.005 (2)	0.0016 (19)
C11	0.044 (3)	0.024 (2)	0.026 (2)	−0.003 (2)	0.003 (2)	0.0002 (19)
C12	0.050 (3)	0.024 (3)	0.036 (3)	0.006 (2)	0.006 (2)	0.000 (2)
C13	0.057 (4)	0.026 (3)	0.035 (3)	−0.004 (3)	0.002 (2)	−0.002 (2)
C14	0.050 (3)	0.032 (3)	0.039 (3)	−0.008 (3)	0.001 (2)	−0.003 (2)
C15	0.041 (3)	0.032 (3)	0.039 (3)	−0.002 (2)	0.004 (2)	0.003 (2)
C16	0.040 (3)	0.027 (3)	0.032 (3)	0.000 (2)	0.002 (2)	0.001 (2)
N2	0.031 (2)	0.024 (2)	0.033 (2)	−0.0027 (18)	0.0067 (17)	0.0010 (16)
C17	0.040 (3)	0.022 (2)	0.031 (3)	0.004 (2)	0.001 (2)	0.0004 (19)
N3	0.029 (2)	0.024 (2)	0.035 (2)	−0.0009 (17)	0.0041 (17)	−0.0022 (16)
C18	0.039 (3)	0.024 (2)	0.035 (3)	−0.002 (2)	0.000 (2)	0.000 (2)
C21	0.039 (3)	0.020 (2)	0.037 (3)	−0.004 (2)	0.008 (2)	−0.0020 (19)
C22	0.042 (3)	0.023 (3)	0.046 (3)	0.002 (2)	0.002 (2)	−0.004 (2)
C23	0.058 (4)	0.029 (3)	0.054 (3)	−0.013 (3)	0.018 (3)	0.002 (2)
C24	0.041 (3)	0.043 (3)	0.062 (4)	−0.015 (3)	0.014 (3)	−0.002 (3)
C25	0.031 (3)	0.042 (3)	0.066 (4)	−0.002 (3)	0.004 (3)	0.001 (3)
C26	0.039 (3)	0.029 (3)	0.051 (3)	−0.002 (2)	0.006 (2)	−0.001 (2)
C19	0.040 (3)	0.016 (2)	0.036 (3)	−0.004 (2)	0.003 (2)	−0.0002 (19)
C20	0.036 (3)	0.016 (2)	0.034 (3)	0.002 (2)	0.005 (2)	0.0000 (18)
C27	0.037 (3)	0.020 (2)	0.032 (3)	0.000 (2)	0.005 (2)	0.0003 (19)
C28	0.041 (3)	0.023 (3)	0.038 (3)	−0.003 (2)	0.007 (2)	0.001 (2)
C29	0.049 (3)	0.031 (3)	0.046 (3)	0.010 (3)	0.010 (2)	0.002 (2)
C30	0.034 (3)	0.043 (3)	0.049 (3)	0.007 (3)	0.007 (2)	−0.001 (2)
C31	0.043 (3)	0.035 (3)	0.043 (3)	−0.005 (2)	0.007 (2)	−0.001 (2)
C32	0.034 (3)	0.027 (3)	0.037 (3)	0.004 (2)	0.006 (2)	0.000 (2)

Geometric parameters (Å, º)

Pd1—N3^i	2.008 (4)	C15—H15	0.9500
Pd1—N3	2.008 (4)	C16—H16	0.9500
Pd1—N1	2.014 (4)	N2—C17	1.326 (6)
Pd1—N1^i	2.014 (4)	C17—N3	1.402 (6)
N1—C4	1.354 (6)	C17—C18	1.448 (6)
N1—C1	1.380 (6)	N3—C20	1.352 (6)
C1—N2	1.330 (6)	C18—C19	1.385 (7)
C1—C2	1.459 (6)	C18—C21	1.461 (7)
C2—C3	1.377 (7)	C21—C26	1.389 (7)
C2—C5	1.463 (7)	C21—C22	1.405 (7)
C5—C10	1.369 (8)	C22—C23	1.369 (7)
C5—C6	1.381 (7)	C22—H22	0.9500
C6—C7	1.390 (8)	C23—C24	1.384 (8)
C6—H6	0.9500	C23—H23	0.9500
C7—C8	1.337 (9)	C24—C25	1.381 (8)
C7—H7	0.9500	C24—H24	0.9500
C8—C9	1.388 (10)	C25—C26	1.376 (7)
C8—H8	0.9500	C25—H25	0.9500
C9—C10	1.357 (10)	C26—H26	0.9500
C9—H9	0.9500	C19—C20	1.413 (6)
C10—H10	0.9500	C19—H19	0.9500
C3—C4	1.416 (7)	C20—C27	1.465 (7)
C3—H3	0.9500	C27—C28	1.394 (6)
C4—C11	1.463 (7)	C27—C32	1.407 (7)
C11—C16	1.404 (7)	C28—C29	1.376 (7)
C11—C12	1.406 (6)	C28—H28	0.9500
C12—C13	1.367 (7)	C29—C30	1.365 (8)
C12—H12	0.9500	C29—H29	0.9500
C13—C14	1.383 (8)	C30—C31	1.399 (7)
C13—H13	0.9500	C30—H30	0.9500
C14—C15	1.381 (7)	C31—C32	1.372 (7)
C14—H14	0.9500	C31—H31	0.9500
C15—C16	1.384 (7)	C32—H32	0.9500
N3^i—Pd1—N3	180.0	C15—C16—H16	119.9
N3^i—Pd1—N1	95.85 (14)	C11—C16—H16	119.9
N3—Pd1—N1	84.16 (14)	C17—N2—C1	122.6 (4)
N3^i—Pd1—N1^i	84.15 (14)	N2—C17—N3	125.8 (4)
N3—Pd1—N1^i	95.84 (14)	N2—C17—C18	124.3 (4)
N1—Pd1—N1^i	180.0	N3—C17—C18	108.8 (4)
C4—N1—C1	108.2 (4)	C20—N3—C17	107.3 (4)
C4—N1—Pd1	132.5 (3)	C20—N3—Pd1	133.4 (3)
C1—N1—Pd1	116.1 (3)	C17—N3—Pd1	116.1 (3)
N2—C1—N1	126.4 (4)	C19—C18—C17	105.3 (4)
N2—C1—C2	124.4 (4)	C19—C18—C21	128.3 (4)
N1—C1—C2	108.4 (4)	C17—C18—C21	126.1 (4)
C3—C2—C1	105.3 (4)	C26—C21—C22	117.6 (5)
C3—C2—C5	127.2 (4)	C26—C21—C18	122.2 (4)
C1—C2—C5	127.5 (4)	C22—C21—C18	120.2 (5)
C10—C5—C6	116.7 (5)	C23—C22—C21	121.3 (5)
C10—C5—C2	123.7 (5)	C23—C22—H22	119.4
C6—C5—C2	119.5 (5)	C21—C22—H22	119.4
C5—C6—C7	121.6 (5)	C22—C23—C24	120.4 (5)
C5—C6—H6	119.2	C22—C23—H23	119.8
C7—C6—H6	119.2	C24—C23—H23	119.8
C8—C7—C6	120.9 (6)	C25—C24—C23	118.9 (5)
C8—C7—H7	119.5	C25—C24—H24	120.5
C6—C7—H7	119.5	C23—C24—H24	120.5
C7—C8—C9	117.1 (6)	C26—C25—C24	121.0 (5)
C7—C8—H8	121.5	C26—C25—H25	119.5
C9—C8—H8	121.5	C24—C25—H25	119.5
C10—C9—C8	122.3 (7)	C25—C26—C21	120.8 (5)
C10—C9—H9	118.8	C25—C26—H26	119.6
C8—C9—H9	118.8	C21—C26—H26	119.6
C9—C10—C5	120.9 (6)	C18—C19—C20	108.5 (4)
C9—C10—H10	119.6	C18—C19—H19	125.7
C5—C10—H10	119.6	C20—C19—H19	125.7
C2—C3—C4	108.5 (4)	N3—C20—C19	110.0 (4)
C2—C3—H3	125.8	N3—C20—C27	123.8 (4)
C4—C3—H3	125.8	C19—C20—C27	126.1 (4)
N1—C4—C3	109.4 (4)	C28—C27—C32	118.2 (4)
N1—C4—C11	123.1 (4)	C28—C27—C20	120.7 (4)
C3—C4—C11	127.4 (4)	C32—C27—C20	121.0 (4)
C16—C11—C12	118.0 (5)	C29—C28—C27	121.0 (5)
C16—C11—C4	121.8 (4)	C29—C28—H28	119.5
C12—C11—C4	120.2 (5)	C27—C28—H28	119.5
C13—C12—C11	120.7 (5)	C30—C29—C28	120.4 (5)
C13—C12—H12	119.6	C30—C29—H29	119.8
C11—C12—H12	119.6	C28—C29—H29	119.8
C12—C13—C14	121.0 (5)	C29—C30—C31	119.8 (5)
C12—C13—H13	119.5	C29—C30—H30	120.1
C14—C13—H13	119.5	C31—C30—H30	120.1
C15—C14—C13	119.2 (5)	C32—C31—C30	120.3 (5)
C15—C14—H14	120.4	C32—C31—H31	119.8
C13—C14—H14	120.4	C30—C31—H31	119.8
C14—C15—C16	120.9 (5)	C31—C32—C27	120.2 (5)
C14—C15—H15	119.6	C31—C32—H32	119.9
C16—C15—H15	119.6	C27—C32—H32	119.9
C15—C16—C11	120.1 (5)
N3^i—Pd1—N1—C4	−27.3 (5)	C1—N2—C17—N3	−6.8 (7)
N3—Pd1—N1—C4	152.7 (5)	C1—N2—C17—C18	159.7 (5)
N3^i—Pd1—N1—C1	129.5 (3)	N2—C17—N3—C20	166.0 (4)
N3—Pd1—N1—C1	−50.5 (3)	C18—C17—N3—C20	−2.3 (5)
C4—N1—C1—N2	−165.5 (5)	N2—C17—N3—Pd1	−31.7 (6)
Pd1—N1—C1—N2	32.3 (6)	C18—C17—N3—Pd1	160.0 (3)
C4—N1—C1—C2	4.4 (5)	N1—Pd1—N3—C20	−153.4 (4)
Pd1—N1—C1—C2	−157.8 (3)	N1^i—Pd1—N3—C20	26.6 (4)
N2—C1—C2—C3	166.0 (4)	N1—Pd1—N3—C17	50.1 (3)
N1—C1—C2—C3	−4.1 (5)	N1^i—Pd1—N3—C17	−129.9 (3)
N2—C1—C2—C5	−12.5 (8)	N2—C17—C18—C19	−166.5 (4)
N1—C1—C2—C5	177.4 (5)	N3—C17—C18—C19	2.0 (5)
C3—C2—C5—C10	−158.3 (7)	N2—C17—C18—C21	8.2 (8)
C1—C2—C5—C10	19.8 (10)	N3—C17—C18—C21	176.6 (4)
C3—C2—C5—C6	18.1 (8)	C19—C18—C21—C26	−150.7 (5)
C1—C2—C5—C6	−163.7 (5)	C17—C18—C21—C26	35.9 (7)
C10—C5—C6—C7	−1.9 (10)	C19—C18—C21—C22	29.9 (7)
C2—C5—C6—C7	−178.6 (6)	C17—C18—C21—C22	−143.5 (5)
C5—C6—C7—C8	−3.8 (10)	C26—C21—C22—C23	0.3 (7)
C6—C7—C8—C9	7.8 (12)	C18—C21—C22—C23	179.7 (5)
C7—C8—C9—C10	−6.7 (18)	C21—C22—C23—C24	−0.4 (8)
C8—C9—C10—C5	1 (2)	C22—C23—C24—C25	0.0 (8)
C6—C5—C10—C9	3.0 (15)	C23—C24—C25—C26	0.5 (9)
C2—C5—C10—C9	179.6 (10)	C24—C25—C26—C21	−0.6 (8)
C1—C2—C3—C4	2.3 (5)	C22—C21—C26—C25	0.2 (7)
C5—C2—C3—C4	−179.2 (5)	C18—C21—C26—C25	−179.2 (5)
C1—N1—C4—C3	−2.9 (5)	C17—C18—C19—C20	−1.0 (5)
Pd1—N1—C4—C3	155.2 (4)	C21—C18—C19—C20	−175.5 (5)
C1—N1—C4—C11	174.3 (4)	C17—N3—C20—C19	1.7 (5)
Pd1—N1—C4—C11	−27.6 (7)	Pd1—N3—C20—C19	−156.3 (3)
C2—C3—C4—N1	0.3 (6)	C17—N3—C20—C27	−174.0 (4)
C2—C3—C4—C11	−176.8 (5)	Pd1—N3—C20—C27	28.0 (7)
N1—C4—C11—C16	−19.2 (7)	C18—C19—C20—N3	−0.4 (5)
C3—C4—C11—C16	157.4 (5)	C18—C19—C20—C27	175.1 (4)
N1—C4—C11—C12	161.3 (4)	N3—C20—C27—C28	−160.9 (4)
C3—C4—C11—C12	−22.1 (7)	C19—C20—C27—C28	24.1 (7)
C16—C11—C12—C13	1.9 (7)	N3—C20—C27—C32	20.5 (7)
C4—C11—C12—C13	−178.6 (4)	C19—C20—C27—C32	−154.5 (5)
C11—C12—C13—C14	−0.6 (7)	C32—C27—C28—C29	0.9 (7)
C12—C13—C14—C15	−0.6 (8)	C20—C27—C28—C29	−177.8 (4)
C13—C14—C15—C16	0.5 (7)	C27—C28—C29—C30	−1.2 (8)
C14—C15—C16—C11	0.9 (7)	C28—C29—C30—C31	0.2 (8)
C12—C11—C16—C15	−2.1 (7)	C29—C30—C31—C32	1.1 (8)
C4—C11—C16—C15	178.4 (4)	C30—C31—C32—C27	−1.3 (7)
N1—C1—N2—C17	6.4 (7)	C28—C27—C32—C31	0.4 (7)
C2—C1—N2—C17	−161.9 (5)	C20—C27—C32—C31	179.0 (4)

Symmetry code: (i) −x+2, −y+2, −z.

Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of the N1/C1–C4 five-membered ring and Cg2 is the centroid of the C21–C26 phenyl ring. Atom C10 is involved in an unrefined disorder. Symmetry codes: (ii) -x + 2, y + 1/2, -z + 1/2; (iii) -x + 2, -y + 1 -z.

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···N2	0.95	2.39	3.029 (9)	124
C26—H26···N2	0.95	2.67	3.115 (6)	109
C13—H13···Cg1^ii	0.95	2.93	3.528 (6)	122
C29—H29···Cg2^iii	0.95	2.90	3.710 (6)	144
C16—H16···Pd1	0.95	2.76	3.366 (5)	122
C32—H32···Pd1	0.95	2.79	3.409 (4)	123