Synthesis and crystal structure of a PdII complex of ortho-xylylenebis(pyridyl­triazole)

Pokharel, U.; Naquin, A.; Fronczek, F.

doi:10.1107/S2414314623003620

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 8| Part 4| April 2023| x230362

https://doi.org/10.1107/S2414314623003620

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Synthesis and crystal structure of a Pd^II complex of ortho-xylylenebis(pyridyltriazole)

Uttam Pokharel,^a ^* Aaron Naquin ^a and Frank Fronczek ^b

^aDepartment of Chemistry and Physical Sciences, Nicholls State University, 906 E. 1st St., Thibodaux, Louisiana 70301, USA, and ^bDepartment of Chemistry, Louisiana State University, Choppin Hall, Baton Rouge, Louisiana 70803, USA
^*Correspondence e-mail: uttam.pokharel@nicholls.edu

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 5 April 2023; accepted 20 April 2023; online 25 April 2023)

A tetradentate ligand, namely, ortho-xylylenebis(pyridyltriazole), o-xpt, was synthesized using the `click' method and complexed with Pd(BF₄)₂. In the title complex, bis{μ-1,1′-(o-xylylene)bis[4-(pyridin-2-yl)triazole]-κN³:N^3′}dipalladium(II) tetrakis(tetrafluoridoborate)–dimethylformamide–diethyl ether (1/2/1), as the BF₄ salt, and including dimethylformamide and diethyl ether solvent molecules, with stoichiometry [Pd₂(C₂₂H₁₈N₈)₂](BF₄)₄·2C₃H₇NO·C₄H₁₀O, the Pd complex and the disordered diethyl ether molecule lie on inversion centers. The ligand coordinates to the Pd^II centers with square-planar geometry, forming a dimeric macrocycle. The Pd⋯Pd separation in the complex [Pd₂(o-xpt)₂]⁴⁺ cation is 3.6184 (4) Å. In the crystal, the complex molecules are stacked along the b axis, with π–π interactions between the pyridyltriazole ligands of two molecules.

Keywords: o-xylylenebispyridyltriazole; Pd^II complex; X-ray crystallography; metal–organic supramolecules; square-planar geometry.

CCDC reference: 2257865

Structure description

The self-assembly of polydentate ligands with transition-metal ions to create functional metal–organic supramolecules has been of great interest in recent years. In particular, the complexation of 2-pyridyl-1,2,3-triazole chelating pockets with transition-metal ions has intensified due to the ease of synthesis of the ligands through the copper-catalyzed azide–alkyne cycloaddition (CuAAC) reaction (Crowley & McMorran, 2012 ). We and others have studied the complexation of ortho-, meta-, and para-xylylene-bridged pyridyltriazole tetradentate ligand with Cu^II (Pokharel et al., 2013 , 2014 ), Ni^II (Pokharel et al., 2020b ), Fe^II (Vellas et al., 2013 ), Ag^I (Gower & Crowley, 2010 ), and Cu^I (Zhao et al., 2013 ). We have recently studied the crystal structure of 1,1-bis(pyridyltriazoylmethyl)ferrocene and its complexation with Cu^I (Pokharel et al., 2020a ). As an extension of this work, we were also interested in studying the complexation of ortho-xylylenebis(pyridyltriazole), o-xpt, with Pd^II. Herein, we report the synthesis and crystal structure of the title compound.

The structure of the title compound consists of the cationic Pd^II complex [Pd₂(o-xpt)₂]⁴⁺ lying on an inversion center, two BF₄⁻ anions in general positions, a dimethylformamide solvent molecule in a general position and a diethyl ether solvent molecule disordered about an inversion center (Fig. 1). In the complex, two Pd^II cations are coordinated by two tetradentate o-xpt ligands, giving a dimeric macrocycle. The two pyridyltriazole units are coordinated to each metal center in a trans fashion. The Pd^II centers are tetracoordinated in a square-planar geometry defined by four (N1, N2, N7 and N8) atoms of two pyridyltriazole moieties. The N—Pd—N chelating angles are N1—Pd1—N2 = 79.46 (8)° and N7—Pd1—N8 = 79.75 (8)°. The N(py)—Pd bonds [py is pyridine; average 2.055 (2) Å] are slightly longer than N(trz)—Pd bonds [trz is triazole; average 1.995 (2) Å], suggesting the triazolium N atom coordinates more strongly to the Pd center than the pyridyl N atom of the ligand. These values are typical for the reported mononuclear Pd^II complex of pyridyltriazole ligands (Kilpin et al., 2011 ). The Pd⋯Pd separation in the complex is 3.6184 (4) Å. Two phenylene moieties in the complex are in an antiparallel orientation, with an interplanar separation of 7.802 Å.

Figure 1
The molecular structure of the title compound with the atom numbering. Displacement ellipsoids are drawn at the 50% probability level, and H atoms and disordered solvent molecules have been omitted for clarity.

In the crystal packing, the pyridyltriazole units between two adjacent molecules are associated in a head-to-tail arrangement (the electron-rich pyridyl group of one molecule stacks over the electron-deficient triazole group of the other molecule) with an average interplanar distance of 3.364 Å, indicating π–π interaction between the molecules; this is shown along the b axis in Fig. 2.

Figure 2
A view along the b axis of the crystal packing of the title compound. Disordered diethyl ether molecules have been omitted for clarity.

Synthesis and crystallization

To a stirred solution of [Pd(CH₃CN)₄]BF₄ (0.112 mg, 0.253 mol) in acetonitrile (5 ml), o-xpt (0.100 g, 0.253 mmol) in acetonitrile (5 ml) was added dropwise. The solution was stirred for 1 h at room temperature. The volatiles were removed in vacuo. The residue was washed with dichloromethane (2 ml), followed by methanol (2 ml), and dried under vacuum to give [Pd₂(o-xpt)₂](BF₄)₄ (0.126 mg, 74%) as a pale-yellow solid. Crystals suitable for X-ray analysis were obtained by slow vapor diffusion of diethyl ether into a dimethylformamide (DMF) solution of the complex at room temperature. Our attempts to obtain a clean ¹H NMR spectrum in DMSO-d₆ were not successful, possibly due to the labile nature of the complex in solution. High resolution ESI–MS analysis showed a monocationic signal at m/z 1255.1478 {calculated 1255.1540 for [Pd₂(o-xpt)₂(BF₄)₄]⁺}.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were located in difference maps and thereafter treated as riding in geometrically idealized positions, with C—H = 0.95 Å for Csp², 0.98 Å for methyl, and 0.99 Å for CH₂. U_iso(H) values were assigned as 1.2U_eq for the attached atom (1.5 for methyl). A torsional parameter was refined for each methyl group, except for those of the diethyl ether molecule, which were staggered with respect to CH₂. The diethyl ether solvent molecule is disordered about an inversion center with two half-populated sites. A number of distance and displacement parameter restraints were necessary to model the disorder.

Table 1
Experimental details

Crystal data
Chemical formula	[Pd₂(C₂₂H₁₈N₈)₂](BF₄)₄·2C₃H₇NO·C₄H₁₀O
M_r	1569.24
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	90
a, b, c (Å)	8.3546 (4), 12.4468 (5), 15.4504 (6)
α, β, γ (°)	85.540 (2), 79.660 (2), 76.997 (2)
V (Å³)	1538.86 (11)
Z	1
Radiation type	Cu Kα
μ (mm⁻¹)	5.68
Crystal size (mm)	0.08 × 0.04 × 0.01

Data collection
Diffractometer	Bruker Kappa APEXII CCD DUO
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.765, 0.945
No. of measured, independent and observed [I > 2σ(I)] reflections	17544, 5427, 4983
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.076, 1.03
No. of reflections	5427
No. of parameters	456
No. of restraints	34
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.68, −0.41
Computer programs: APEX2 and SAINT (Bruker, 2016 ), SHELXT2014 (Sheldrick, 2015a ), SHELXL2017 (Sheldrick, 2015b ), Mercury (Macrae et al., 2020 ), and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2257865

Crystal structure: contains datablocks I, glonal. DOI: https://doi.org/10.1107/S2414314623003620/xu4050sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314623003620/xu4050Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis{µ-1,1'-(o-xylylene)bis[4-(pyridin-2-yl)triazole]-κN³:N^3'}dipalladium(II) tetrakis(tetrafluoridoborate)–dimethylformamide–diethyl ether (1/2/1) top

Crystal data top

[Pd₂(C₂₂H₁₈N₈)₂](BF₄)₄·2C₃H₇NO·C₄H₁₀O	Z = 1
M_r = 1569.24	F(000) = 790
Triclinic, P1	D_x = 1.693 Mg m⁻³
a = 8.3546 (4) Å	Cu Kα radiation, λ = 1.54184 Å
b = 12.4468 (5) Å	Cell parameters from 7868 reflections
c = 15.4504 (6) Å	θ = 2.9–68.3°
α = 85.540 (2)°	µ = 5.68 mm⁻¹
β = 79.660 (2)°	T = 90 K
γ = 76.997 (2)°	Fragment, pale yellow
V = 1538.86 (11) Å³	0.08 × 0.04 × 0.01 mm

Data collection top

Bruker Kappa APEXII CCD DUO diffractometer	5427 independent reflections
Radiation source: IµS microfocus	4983 reflections with I > 2σ(I)
QUAZAR multilayer optics monochromator	R_int = 0.039
φ and ω scans	θ_max = 68.5°, θ_min = 3.7°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −9→10
T_min = 0.765, T_max = 0.945	k = −14→10
17544 measured reflections	l = −18→18

Refinement top

Refinement on F²	34 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.029	H-atom parameters constrained
wR(F²) = 0.076	w = 1/[σ²(F_o²) + (0.0428P)² + 1.022P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
5427 reflections	Δρ_max = 0.68 e Å⁻³
456 parameters	Δρ_min = −0.41 e Å⁻³

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Pd1	0.62296 (2)	0.54481 (2)	0.40085 (2)	0.01235 (8)
N1	0.4910 (3)	0.67202 (18)	0.33215 (15)	0.0177 (5)
N2	0.5621 (3)	0.46128 (17)	0.31114 (14)	0.0154 (4)
N3	0.5861 (3)	0.35595 (17)	0.29813 (14)	0.0154 (4)
N4	0.5089 (3)	0.34974 (17)	0.23042 (14)	0.0156 (4)
N5	0.2946 (3)	0.26548 (17)	0.41317 (14)	0.0145 (4)
N6	0.3668 (3)	0.26845 (17)	0.48321 (14)	0.0157 (4)
N7	0.3247 (3)	0.37183 (17)	0.50545 (14)	0.0144 (4)
N8	0.2416 (3)	0.58271 (17)	0.53220 (14)	0.0152 (4)
C1	0.4641 (4)	0.7791 (2)	0.34815 (19)	0.0218 (6)
H1	0.506819	0.800711	0.395483	0.026*
C2	0.3757 (4)	0.8589 (2)	0.2975 (2)	0.0310 (7)
H2	0.358914	0.934618	0.309918	0.037*
C3	0.3116 (5)	0.8291 (3)	0.2290 (2)	0.0378 (8)
H3	0.248716	0.883448	0.194498	0.045*
C4	0.3410 (4)	0.7178 (2)	0.2113 (2)	0.0294 (7)
H4	0.299455	0.694820	0.164041	0.035*
C5	0.4312 (3)	0.6413 (2)	0.26347 (18)	0.0189 (5)
C6	0.4704 (3)	0.5227 (2)	0.25314 (17)	0.0173 (5)
C7	0.4363 (3)	0.4500 (2)	0.20031 (17)	0.0175 (5)
H7	0.375086	0.466634	0.152977	0.021*
C8	0.5148 (3)	0.2393 (2)	0.19970 (18)	0.0176 (5)
H8A	0.580939	0.182775	0.235508	0.021*
H8B	0.572049	0.233842	0.137765	0.021*
C9	0.3437 (3)	0.2151 (2)	0.20577 (17)	0.0171 (5)
C10	0.2720 (4)	0.2300 (2)	0.12980 (18)	0.0212 (6)
H10	0.329220	0.257654	0.077049	0.025*
C11	0.1185 (4)	0.2050 (2)	0.12995 (19)	0.0255 (6)
H11	0.070824	0.216010	0.077702	0.031*
C12	0.0348 (4)	0.1642 (2)	0.20627 (19)	0.0252 (6)
H12	−0.069897	0.146220	0.206446	0.030*
C13	0.1041 (3)	0.1494 (2)	0.28270 (18)	0.0206 (6)
H13	0.046137	0.121030	0.334933	0.025*
C14	0.2570 (3)	0.1754 (2)	0.28398 (17)	0.0161 (5)
C15	0.3232 (3)	0.1588 (2)	0.36990 (17)	0.0171 (5)
H15A	0.266954	0.107126	0.409490	0.021*
H15B	0.444077	0.125712	0.358676	0.021*
C16	0.2068 (3)	0.3655 (2)	0.39066 (16)	0.0146 (5)
H16	0.144232	0.383836	0.343930	0.018*
C17	0.2283 (3)	0.4345 (2)	0.45040 (16)	0.0148 (5)
C18	0.1818 (3)	0.5523 (2)	0.46399 (17)	0.0154 (5)
C19	0.0907 (3)	0.6280 (2)	0.41110 (17)	0.0176 (5)
H19	0.049619	0.604355	0.364009	0.021*
C20	0.0605 (3)	0.7394 (2)	0.42825 (18)	0.0198 (6)
H20	−0.000657	0.793352	0.392719	0.024*
C21	0.1214 (3)	0.7704 (2)	0.49825 (18)	0.0198 (5)
H21	0.102035	0.846091	0.511181	0.024*
C22	0.2102 (3)	0.6906 (2)	0.54896 (17)	0.0178 (5)
H22	0.250380	0.712569	0.597095	0.021*
B1	0.7437 (5)	0.3502 (4)	−0.0041 (2)	0.0341 (8)
F1	0.8450 (3)	0.2509 (2)	−0.03601 (14)	0.0497 (5)
F2	0.7818 (2)	0.43622 (19)	−0.06116 (12)	0.0442 (5)
F3	0.7724 (2)	0.36416 (16)	0.07958 (11)	0.0324 (4)
F4	0.5762 (2)	0.34747 (19)	−0.00012 (12)	0.0429 (5)
B2	0.7718 (4)	0.9939 (3)	0.3743 (3)	0.0305 (8)
F5	0.8893 (3)	0.94186 (17)	0.30537 (14)	0.0536 (6)
F6	0.7324 (2)	1.10683 (13)	0.35316 (12)	0.0273 (4)
F7	0.8434 (3)	0.97815 (15)	0.45036 (12)	0.0394 (5)
F8	0.6308 (3)	0.95332 (18)	0.3871 (2)	0.0773 (9)
O1	0.9776 (3)	0.49882 (17)	0.27263 (13)	0.0280 (5)
N9	0.8519 (3)	0.6141 (2)	0.17162 (16)	0.0248 (5)
C23	0.9211 (3)	0.5157 (2)	0.20272 (19)	0.0239 (6)
H23	0.927928	0.453656	0.169054	0.029*
C24	0.8557 (4)	0.7145 (3)	0.2135 (2)	0.0314 (7)
H24A	0.857946	0.698513	0.276396	0.047*
H24B	0.756191	0.771129	0.205856	0.047*
H24C	0.955517	0.741219	0.186200	0.047*
C25	0.8014 (4)	0.6276 (3)	0.0849 (2)	0.0364 (8)
H25A	0.876235	0.665880	0.044140	0.055*
H25B	0.686950	0.671119	0.089651	0.055*
H25C	0.807063	0.554943	0.062787	0.055*
O2	0.4535 (11)	0.9884 (7)	1.0054 (7)	0.067 (3)	0.5
C26	0.3717 (19)	1.0268 (16)	0.9327 (11)	0.072 (4)	0.5
H26A	0.441392	0.995410	0.877955	0.086*	0.5
H26B	0.353021	1.108211	0.926463	0.086*	0.5
C27	0.2032 (17)	0.9910 (10)	0.9481 (10)	0.094 (4)	0.5
H27A	0.145357	1.017146	0.898066	0.141*	0.5
H27B	0.222622	0.910310	0.953778	0.141*	0.5
H27C	0.134518	1.022771	1.002139	0.141*	0.5
C28	0.6073 (17)	1.0284 (14)	0.9992 (12)	0.067 (3)	0.5
H28A	0.580069	1.110043	0.999418	0.081*	0.5
H28B	0.680609	1.006214	0.942838	0.081*	0.5
C29	0.699 (2)	0.9832 (15)	1.0748 (12)	0.086 (5)	0.5
H29A	0.801333	1.011668	1.068363	0.129*	0.5
H29B	0.628024	1.006203	1.130644	0.129*	0.5
H29C	0.728516	0.902423	1.074091	0.129*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.01319 (11)	0.00994 (11)	0.01434 (11)	−0.00127 (7)	−0.00446 (7)	−0.00152 (7)
N1	0.0181 (11)	0.0147 (11)	0.0203 (11)	−0.0029 (9)	−0.0039 (9)	−0.0016 (9)
N2	0.0137 (10)	0.0129 (10)	0.0187 (11)	−0.0014 (8)	−0.0024 (9)	−0.0003 (8)
N3	0.0146 (10)	0.0140 (10)	0.0183 (11)	−0.0027 (8)	−0.0038 (9)	−0.0033 (8)
N4	0.0164 (11)	0.0157 (11)	0.0156 (10)	−0.0035 (9)	−0.0041 (9)	−0.0039 (8)
N5	0.0162 (11)	0.0131 (10)	0.0154 (10)	−0.0024 (8)	−0.0052 (8)	−0.0034 (8)
N6	0.0168 (11)	0.0130 (10)	0.0181 (11)	−0.0023 (8)	−0.0055 (9)	−0.0023 (8)
N7	0.0144 (10)	0.0134 (10)	0.0150 (10)	−0.0019 (8)	−0.0024 (8)	−0.0006 (8)
N8	0.0155 (11)	0.0145 (10)	0.0161 (10)	−0.0026 (8)	−0.0030 (9)	−0.0035 (8)
C1	0.0275 (15)	0.0146 (13)	0.0239 (14)	−0.0032 (11)	−0.0067 (12)	−0.0026 (11)
C2	0.0466 (19)	0.0138 (13)	0.0343 (17)	−0.0009 (13)	−0.0178 (15)	−0.0021 (12)
C3	0.059 (2)	0.0178 (15)	0.0375 (18)	0.0055 (14)	−0.0276 (17)	−0.0004 (13)
C4	0.0412 (18)	0.0213 (14)	0.0272 (16)	0.0004 (13)	−0.0188 (14)	−0.0006 (12)
C5	0.0213 (13)	0.0167 (13)	0.0187 (13)	−0.0022 (11)	−0.0056 (11)	−0.0014 (10)
C6	0.0177 (13)	0.0168 (13)	0.0174 (13)	−0.0028 (10)	−0.0048 (10)	0.0002 (10)
C7	0.0192 (13)	0.0175 (13)	0.0160 (12)	−0.0027 (10)	−0.0049 (10)	−0.0020 (10)
C8	0.0187 (13)	0.0141 (12)	0.0205 (13)	−0.0021 (10)	−0.0044 (11)	−0.0045 (10)
C9	0.0178 (13)	0.0129 (12)	0.0208 (13)	−0.0013 (10)	−0.0043 (10)	−0.0050 (10)
C10	0.0257 (14)	0.0183 (13)	0.0200 (13)	−0.0042 (11)	−0.0048 (11)	−0.0027 (10)
C11	0.0239 (15)	0.0297 (15)	0.0252 (15)	−0.0044 (12)	−0.0107 (12)	−0.0032 (12)
C12	0.0189 (14)	0.0300 (15)	0.0298 (15)	−0.0071 (12)	−0.0073 (12)	−0.0061 (12)
C13	0.0198 (13)	0.0194 (13)	0.0226 (14)	−0.0040 (11)	−0.0019 (11)	−0.0049 (11)
C14	0.0187 (13)	0.0112 (11)	0.0180 (13)	0.0009 (10)	−0.0055 (10)	−0.0056 (9)
C15	0.0224 (13)	0.0109 (12)	0.0182 (13)	−0.0014 (10)	−0.0055 (11)	−0.0030 (10)
C16	0.0143 (12)	0.0143 (12)	0.0154 (12)	−0.0024 (10)	−0.0034 (10)	−0.0009 (9)
C17	0.0128 (12)	0.0150 (12)	0.0150 (12)	−0.0010 (10)	−0.0009 (10)	−0.0002 (9)
C18	0.0148 (12)	0.0118 (12)	0.0185 (13)	−0.0007 (10)	−0.0010 (10)	−0.0045 (10)
C19	0.0170 (13)	0.0187 (13)	0.0169 (13)	−0.0011 (10)	−0.0045 (10)	−0.0024 (10)
C20	0.0224 (14)	0.0150 (13)	0.0209 (13)	0.0009 (11)	−0.0068 (11)	−0.0009 (10)
C21	0.0232 (14)	0.0139 (12)	0.0217 (14)	−0.0015 (10)	−0.0046 (11)	−0.0018 (10)
C22	0.0180 (13)	0.0162 (13)	0.0182 (13)	−0.0015 (10)	−0.0017 (10)	−0.0044 (10)
B1	0.0245 (18)	0.057 (2)	0.0206 (17)	−0.0070 (16)	−0.0061 (14)	0.0010 (16)
F1	0.0433 (12)	0.0655 (14)	0.0374 (11)	−0.0002 (10)	−0.0085 (9)	−0.0133 (10)
F2	0.0301 (10)	0.0731 (15)	0.0282 (10)	−0.0117 (10)	−0.0081 (8)	0.0160 (9)
F3	0.0284 (9)	0.0488 (11)	0.0214 (9)	−0.0099 (8)	−0.0073 (7)	0.0014 (8)
F4	0.0256 (10)	0.0762 (15)	0.0305 (10)	−0.0159 (9)	−0.0090 (8)	0.0007 (9)
B2	0.0278 (18)	0.0158 (15)	0.050 (2)	−0.0031 (13)	−0.0145 (16)	0.0013 (14)
F5	0.0783 (16)	0.0320 (11)	0.0404 (11)	0.0168 (10)	−0.0169 (11)	−0.0069 (9)
F6	0.0243 (8)	0.0179 (8)	0.0408 (10)	−0.0040 (7)	−0.0110 (7)	0.0029 (7)
F7	0.0525 (12)	0.0270 (9)	0.0368 (10)	0.0019 (8)	−0.0169 (9)	0.0014 (8)
F8	0.0483 (14)	0.0306 (11)	0.166 (3)	−0.0230 (10)	−0.0454 (17)	0.0217 (15)
O1	0.0344 (12)	0.0262 (11)	0.0247 (11)	−0.0014 (9)	−0.0149 (9)	−0.0006 (8)
N9	0.0210 (12)	0.0313 (13)	0.0234 (12)	−0.0070 (10)	−0.0079 (10)	0.0047 (10)
C23	0.0200 (14)	0.0287 (15)	0.0234 (14)	−0.0045 (12)	−0.0060 (11)	0.0003 (12)
C24	0.0302 (16)	0.0278 (16)	0.0364 (17)	−0.0059 (13)	−0.0081 (14)	0.0030 (13)
C25	0.0362 (18)	0.050 (2)	0.0264 (16)	−0.0138 (15)	−0.0149 (14)	0.0119 (14)
O2	0.077 (7)	0.041 (4)	0.071 (3)	−0.004 (5)	0.013 (5)	−0.006 (3)
C26	0.091 (9)	0.048 (6)	0.067 (7)	0.000 (6)	−0.007 (6)	−0.004 (5)
C27	0.100 (9)	0.057 (7)	0.121 (11)	−0.028 (6)	0.021 (8)	−0.038 (7)
C28	0.077 (7)	0.041 (4)	0.071 (3)	−0.004 (5)	0.013 (5)	−0.006 (3)
C29	0.107 (13)	0.047 (8)	0.082 (9)	0.011 (9)	0.007 (10)	0.002 (6)

Geometric parameters (Å, º) top

Pd1—N2	1.994 (2)	C16—C17	1.369 (4)
Pd1—N7ⁱ	2.007 (2)	C16—H16	0.9500
Pd1—N1	2.055 (2)	C17—C18	1.451 (4)
Pd1—N8ⁱ	2.056 (2)	C18—C19	1.384 (4)
N1—C1	1.336 (4)	C19—C20	1.390 (4)
N1—C5	1.364 (3)	C19—H19	0.9500
N2—N3	1.307 (3)	C20—C21	1.389 (4)
N2—C6	1.360 (3)	C20—H20	0.9500
N3—N4	1.339 (3)	C21—C22	1.381 (4)
N4—C7	1.346 (3)	C21—H21	0.9500
N4—C8	1.477 (3)	C22—H22	0.9500
N5—N6	1.337 (3)	B1—F3	1.387 (4)
N5—C16	1.350 (3)	B1—F2	1.389 (4)
N5—C15	1.485 (3)	B1—F4	1.398 (4)
N6—N7	1.311 (3)	B1—F1	1.400 (5)
N7—C17	1.357 (3)	B2—F8	1.360 (4)
N8—C22	1.346 (3)	B2—F7	1.394 (4)
N8—C18	1.356 (3)	B2—F6	1.396 (4)
C1—C2	1.379 (4)	B2—F5	1.401 (5)
C1—H1	0.9500	O1—C23	1.240 (3)
C2—C3	1.379 (4)	N9—C23	1.325 (4)
C2—H2	0.9500	N9—C24	1.459 (4)
C3—C4	1.392 (4)	N9—C25	1.462 (4)
C3—H3	0.9500	C23—H23	0.9500
C4—C5	1.378 (4)	C24—H24A	0.9800
C4—H4	0.9500	C24—H24B	0.9800
C5—C6	1.453 (4)	C24—H24C	0.9800
C6—C7	1.372 (4)	C25—H25A	0.9800
C7—H7	0.9500	C25—H25B	0.9800
C8—C9	1.512 (4)	C25—H25C	0.9800
C8—H8A	0.9900	O2—C26	1.415 (14)
C8—H8B	0.9900	O2—C28	1.465 (12)
C9—C10	1.393 (4)	C26—C27	1.543 (14)
C9—C14	1.408 (4)	C26—H26A	0.9900
C10—C11	1.385 (4)	C26—H26B	0.9900
C10—H10	0.9500	C27—H27A	0.9800
C11—C12	1.381 (4)	C27—H27B	0.9800
C11—H11	0.9500	C27—H27C	0.9800
C12—C13	1.388 (4)	C28—C29	1.515 (16)
C12—H12	0.9500	C28—H28A	0.9900
C13—C14	1.390 (4)	C28—H28B	0.9900
C13—H13	0.9500	C29—H29A	0.9800
C14—C15	1.510 (3)	C29—H29B	0.9800
C15—H15A	0.9900	C29—H29C	0.9800
C15—H15B	0.9900

N2—Pd1—N7ⁱ	177.57 (8)	N5—C16—C17	104.4 (2)
N2—Pd1—N1	79.46 (8)	N5—C16—H16	127.8
N7ⁱ—Pd1—N1	100.55 (8)	C17—C16—H16	127.8
N2—Pd1—N8ⁱ	100.27 (8)	N7—C17—C16	107.1 (2)
N7ⁱ—Pd1—N8ⁱ	79.75 (8)	N7—C17—C18	116.8 (2)
N1—Pd1—N8ⁱ	179.01 (9)	C16—C17—C18	136.0 (2)
C1—N1—C5	119.1 (2)	N8—C18—C19	122.4 (2)
C1—N1—Pd1	125.63 (18)	N8—C18—C17	113.5 (2)
C5—N1—Pd1	115.24 (17)	C19—C18—C17	124.0 (2)
N3—N2—C6	111.1 (2)	C18—C19—C20	118.7 (2)
N3—N2—Pd1	132.75 (17)	C18—C19—H19	120.7
C6—N2—Pd1	116.02 (17)	C20—C19—H19	120.7
N2—N3—N4	105.32 (19)	C21—C20—C19	118.8 (2)
N3—N4—C7	112.2 (2)	C21—C20—H20	120.6
N3—N4—C8	118.0 (2)	C19—C20—H20	120.6
C7—N4—C8	129.8 (2)	C22—C21—C20	119.6 (2)
N6—N5—C16	112.4 (2)	C22—C21—H21	120.2
N6—N5—C15	118.5 (2)	C20—C21—H21	120.2
C16—N5—C15	129.2 (2)	N8—C22—C21	121.9 (2)
N7—N6—N5	105.12 (19)	N8—C22—H22	119.0
N6—N7—C17	111.1 (2)	C21—C22—H22	119.0
N6—N7—Pd1ⁱ	134.09 (16)	F3—B1—F2	110.5 (3)
C17—N7—Pd1ⁱ	114.81 (17)	F3—B1—F4	109.4 (3)
C22—N8—C18	118.5 (2)	F2—B1—F4	109.3 (3)
C22—N8—Pd1ⁱ	126.47 (17)	F3—B1—F1	109.2 (3)
C18—N8—Pd1ⁱ	115.02 (16)	F2—B1—F1	108.6 (3)
N1—C1—C2	121.5 (3)	F4—B1—F1	109.7 (3)
N1—C1—H1	119.2	F8—B2—F7	110.6 (3)
C2—C1—H1	119.2	F8—B2—F6	109.4 (3)
C3—C2—C1	120.1 (3)	F7—B2—F6	108.7 (3)
C3—C2—H2	120.0	F8—B2—F5	111.1 (3)
C1—C2—H2	120.0	F7—B2—F5	108.4 (3)
C2—C3—C4	118.7 (3)	F6—B2—F5	108.5 (3)
C2—C3—H3	120.6	C23—N9—C24	120.9 (2)
C4—C3—H3	120.6	C23—N9—C25	121.0 (3)
C5—C4—C3	118.9 (3)	C24—N9—C25	116.9 (3)
C5—C4—H4	120.6	O1—C23—N9	124.7 (3)
C3—C4—H4	120.6	O1—C23—H23	117.7
N1—C5—C4	121.7 (2)	N9—C23—H23	117.7
N1—C5—C6	113.4 (2)	N9—C24—H24A	109.5
C4—C5—C6	124.9 (3)	N9—C24—H24B	109.5
N2—C6—C7	106.7 (2)	H24A—C24—H24B	109.5
N2—C6—C5	115.9 (2)	N9—C24—H24C	109.5
C7—C6—C5	137.4 (2)	H24A—C24—H24C	109.5
N4—C7—C6	104.7 (2)	H24B—C24—H24C	109.5
N4—C7—H7	127.7	N9—C25—H25A	109.5
C6—C7—H7	127.7	N9—C25—H25B	109.5
N4—C8—C9	112.7 (2)	H25A—C25—H25B	109.5
N4—C8—H8A	109.1	N9—C25—H25C	109.5
C9—C8—H8A	109.1	H25A—C25—H25C	109.5
N4—C8—H8B	109.1	H25B—C25—H25C	109.5
C9—C8—H8B	109.1	C26—O2—C28	111.7 (9)
H8A—C8—H8B	107.8	O2—C26—C27	108.8 (12)
C10—C9—C14	119.1 (2)	O2—C26—H26A	109.9
C10—C9—C8	118.1 (2)	C27—C26—H26A	109.9
C14—C9—C8	122.7 (2)	O2—C26—H26B	109.9
C11—C10—C9	121.0 (3)	C27—C26—H26B	109.9
C11—C10—H10	119.5	H26A—C26—H26B	108.3
C9—C10—H10	119.5	C26—C27—H27A	109.5
C12—C11—C10	119.8 (3)	C26—C27—H27B	109.5
C12—C11—H11	120.1	H27A—C27—H27B	109.5
C10—C11—H11	120.1	C26—C27—H27C	109.5
C11—C12—C13	119.9 (3)	H27A—C27—H27C	109.5
C11—C12—H12	120.1	H27B—C27—H27C	109.5
C13—C12—H12	120.1	O2—C28—C29	111.9 (12)
C12—C13—C14	121.0 (3)	O2—C28—H28A	109.2
C12—C13—H13	119.5	C29—C28—H28A	109.2
C14—C13—H13	119.5	O2—C28—H28B	109.2
C13—C14—C9	119.1 (2)	C29—C28—H28B	109.2
C13—C14—C15	118.0 (2)	H28A—C28—H28B	107.9
C9—C14—C15	122.9 (2)	C28—C29—H29A	109.5
N5—C15—C14	110.7 (2)	C28—C29—H29B	109.5
N5—C15—H15A	109.5	H29A—C29—H29B	109.5
C14—C15—H15A	109.5	C28—C29—H29C	109.5
N5—C15—H15B	109.5	H29A—C29—H29C	109.5
C14—C15—H15B	109.5	H29B—C29—H29C	109.5
H15A—C15—H15B	108.1

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

We are thankful for the support of the Department of Chemistry and Physical Sciences at Nicholls State University and the X-ray Diffraction Laboratory at Louisiana State University, Baton Rouge. The upgrade of the diffractometer was made possible by a grant administered by the Louisiana Board of Regents.

Funding information

Funding for this research was provided by: Louisiana Board of Regents Support Fund (contract No. LEQSF(2011-12)-ENH-TR-01).

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