cis-(2,2′-Bipyridine-κ2N,N′)bis­(isonicotinamide-κN1)palladium(II) bis­(hexa­fluoridophosphate)

Adrian, R.A.; Quintela, B.; Powell, D.R.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536812043036

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 11| November 2012| Pages m1390-m1391

doi:10.1107/S1600536812043036

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cis-(2,2′-Bipyridine-κ²N,N′)bis(isonicotinamide-κN¹)palladium(II) bis(hexafluoridophosphate)

Rafael A. Adrian,^a ‡ Brayan Quintela,^a Douglas R. Powell,^b Seik Weng Ng ^c,^d and Edward R. T. Tiekink ^c ^*

^aDepartment of Chemistry, University of the Incarnate Word, San Antonio, TX 78209, USA, ^bDepartment of Chemistry & Biochemistry, University of Oklahoma, Norman, OK 73019, USA, ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^dChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: edward.tiekink@um.edu.my

(Received 12 October 2012; accepted 15 October 2012; online 20 October 2012)

In the title salt, [Pd(C₁₀H₈N₂)(C₆H₆NO)₂](PF₆)₂, the Pd^II atom is in a slightly distorted square-planar coordination environment by N atoms derived from two 4-pyridinecarboxamide ligands, in a cis disposition, and a chelating 2,2′-bipyridine molecule. The monodentate ligands are nearly orthogonal to each other [dihedral angle = 85.7 (5)°] and to the PdN₄ plane [dihedral angles = 79.3 (3) and 78.7 (3)°]. The amide O atoms lie to opposite sides of the PdN₄ plane. The most notable feature of the crystal packing is a linear supramolecular chain orientated approximately along [310] and formed via 16-membered {⋯HNCO}₄ motifs. These are connected into a three-dimensional network by amide–H⋯O, F interactions. Both PF₆⁻ anions are disordered over two positions of equal occupancy in respect of the F atoms.

Related literature

For the synthesis of compounds with supramolecular structures involving carboxamides as ligands, see: Sun et al. (2011 ); Moncol et al. (2007 ). For related palladium(II) complexes with isonicotinamide, see: Galstyan et al. (2011 ); Fujimura et al. (2004 ); Qin et al. (2001 ). For hydration of palladium-coordinated nitriles, see: Sanchez et al. (2000 ).

Experimental

Crystal data

[Pd(C₁₀H₈N₂)(C₆H₆NO₂)₂](PF₆)₂
M_r = 796.78
Monoclinic, C 2/c
a = 22.5920 (14) Å
b = 13.8299 (8) Å
c = 17.9092 (12) Å
β = 95.269 (8)°
V = 5572.0 (6) Å³
Z = 8
Cu Kα radiation
μ = 7.55 mm⁻¹
T = 100 K
0.46 × 0.16 × 0.15 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ) T_min = 0.126, T_max = 0.401
30116 measured reflections
5182 independent reflections
3944 reflections with I > 2σ(I)
R_int = 0.072

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.147
S = 1.01
5182 reflections
520 parameters
144 restraints
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.78 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N⋯O2ⁱ	0.88	2.29	3.031 (11)	142
N2—H1N⋯O2ⁱⁱ	0.88	2.37	3.032 (11)	132
N2—H2N⋯F9ⁱⁱⁱ	0.88	2.24	3.037 (15)	151
N2—H2N⋯F11′ⁱⁱⁱ	0.88	2.38	3.220 (14)	159
N4—H3N⋯F7′^iv	0.88	2.52	3.175 (19)	132
N4—H3N⋯F8^iv	0.88	2.55	3.10 (2)	121
N4—H4N⋯O1^v	0.88	1.97	2.836 (11)	168
Symmetry codes: (i) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x, -y+1, z+{\script{1\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (v) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812043036/su2513sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812043036/su2513Isup2.hkl

checkCIF report

Comment top

Carboxamides have been used for the synthesis of supramolecular structures due to their ability to hydrogen bond as shown by Sun et al. (2011) and Moncol et al. (2007). With that in mind we sought to crystallize palladium(II) complexes with 4-pyridinecarboxamide ligands, similar to those created by Galstyan et al., (2011), Fujimura et al. (2004) and Qin et al. (2001). The title compound can be synthesized by the reaction of the 2,2'-bipyridine palladium(II) metal centre with the 4-pyridinecarboxamide ligand or by the palladium-catalyzed hydration of the 2,2'-bipyridine palladium(II) 4-cyanopyridine analog complex in a similar reaction to the one reported by Sanchez et al. (2000).

The complex cation of the title compound, Fig. 1, features a square planar palladium(II) centre with a cis disposition of the N-bound 4-pyridinecarboxamide ligands. No systematic trends are evident in the Pd—N bond lengths (Table 1). The 4-pyridinecarboxamide ligands are almost orthogonal to each other, the dihedral angle being 85.7 (5)°, and to the PdN₄ plane with dihedral angles of 79.3 (3) [N1-ligand] and 78.7 (3)°; a similar situation was found in the BF₄^- analogue (Qin et al., 2001). Each of the amide groups lies out of the plane of the pyridyl ring to which it is connected as seen in the C2—C3—C6—O1 and C8—C9—C12—O2 torsion angles of -166.0 (8) and 171.5 (8)°, respectively. The 2,2'-bipyridine ring is almost planar the dihedral angle between the pyridyl rings being 4.7 (4)°. The amide-O atoms lie to opposite sides of the PdN₄ plane.

A detailed analysis of the crystal packing is not possible owing to the disorder in the two PF₆^- anions. However, the most notable feature of the crystal packing is a supramolecular chain orientated approximately along [3 1 0] arising from centrosymmetric 16-membered {···HNCO}₄ synthons constructed by four interacting amide groups (Fig. 2 and Table 2). A three-dimensional architecture arises from additional amide-H···O, F interactions (Table 2).

Related literature top

For the synthesis of supramolecular structures with carboxamides as ligands, see: Sun et al. (2011); Moncol et al. (2007). For related palladium(II) complexes with isonicotinamide, see: Galstyan et al. (2011); Fujimura et al. (2004); Qin et al. (2001). For hydration of palladium-coordinated nitriles, see: Sanchez et al. (2000).

Experimental top

Pd(bpy)(PF₆)₂ [bpy = 2,2'-bipyridine] was prepared by adding solid AgPF₆ to an acetonitrile suspension of Pd(bpy)Cl₂ (0.050 g, 0.15 mmol). After being stirred for 2 h, the mixture was filtered to remove AgCl. Isonicotinamide (0.037 g, 0.30 mmol) was added to the Pd(bpy)(PF₆)₂ solution and the solution was heated at 323 K for 3 h. Crystals were obtained by vapour diffusion of diethyl ether over an acetonitrile solution of the title complex [0.083 g, 85% yield; M.pt: 513 K (dec.), 523 K (melting)].

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the cation in the title salt showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. A view of the linear supramolecular chain mediated by N—H···O hydrogen bonds (orange dashed lines) along [13 5 -1] - see Table 1 for details.

cis-(2,2'-Bipyridine-κ²N,N')bis(isonicotinamide- κN¹)palladium(II) bis(hexafluoridophosphate) top

Crystal data top

[Pd(C₁₀H₈N₂)(C₆H₆NO₂)₂](PF₆)₂	F(000) = 3152
M_r = 796.78	D_x = 1.900 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -C 2yc	Cell parameters from 4302 reflections
a = 22.5920 (14) Å	θ = 3.8–68.1°
b = 13.8299 (8) Å	µ = 7.55 mm⁻¹
c = 17.9092 (12) Å	T = 100 K
β = 95.269 (8)°	Rod, colourless
V = 5572.0 (6) Å³	0.46 × 0.16 × 0.15 mm
Z = 8

Data collection top

Bruker APEX CCD diffractometer	5182 independent reflections
Radiation source: fine-focus sealed tube	3944 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.072
ϕ and ω scans	θ_max = 69.8°, θ_min = 3.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	h = −26→26
T_min = 0.126, T_max = 0.401	k = −16→16
30116 measured reflections	l = −21→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.147	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0879P)² + 9.8993P] where P = (F_o² + 2F_c²)/3
5182 reflections	(Δ/σ)_max = 0.001
520 parameters	Δρ_max = 0.67 e Å⁻³
144 restraints	Δρ_min = −0.78 e Å⁻³

Crystal data top

[Pd(C₁₀H₈N₂)(C₆H₆NO₂)₂](PF₆)₂	V = 5572.0 (6) Å³
M_r = 796.78	Z = 8
Monoclinic, C2/c	Cu Kα radiation
a = 22.5920 (14) Å	µ = 7.55 mm⁻¹
b = 13.8299 (8) Å	T = 100 K
c = 17.9092 (12) Å	0.46 × 0.16 × 0.15 mm
β = 95.269 (8)°

Data collection top

Bruker APEX CCD diffractometer	5182 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	3944 reflections with I > 2σ(I)
T_min = 0.126, T_max = 0.401	R_int = 0.072
30116 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	144 restraints
wR(F²) = 0.147	H-atom parameters constrained
S = 1.01	Δρ_max = 0.67 e Å⁻³
5182 reflections	Δρ_min = −0.78 e Å⁻³
520 parameters

Special details top

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Pd	0.667091 (18)	0.53803 (3)	0.62000 (2)	0.03743 (15)
P1	0.70718 (7)	0.64260 (15)	0.84670 (11)	0.0532 (4)
P2	0.57543 (8)	0.73478 (13)	0.41320 (11)	0.0519 (4)
F1	0.7509 (5)	0.6745 (11)	0.7858 (7)	0.086 (3)	0.50
F2	0.7240 (7)	0.7410 (9)	0.8898 (9)	0.118 (4)	0.50
F3	0.6661 (5)	0.6128 (12)	0.9038 (7)	0.093 (4)	0.50
F4	0.6999 (6)	0.5423 (8)	0.8021 (6)	0.084 (3)	0.50
F5	0.6557 (5)	0.6892 (10)	0.7948 (8)	0.087 (4)	0.50
F6	0.7629 (4)	0.5972 (6)	0.8934 (6)	0.052 (2)	0.50
F7	0.5623 (7)	0.6485 (8)	0.4674 (6)	0.088 (3)	0.50
F8	0.5449 (7)	0.8077 (15)	0.4605 (11)	0.081 (5)	0.50
F9	0.5970 (6)	0.8181 (7)	0.3611 (7)	0.077 (3)	0.50
F10	0.6113 (4)	0.6573 (8)	0.3638 (6)	0.052 (2)	0.50
F11	0.6403 (4)	0.7503 (9)	0.4640 (6)	0.078 (3)	0.50
F12	0.5198 (4)	0.7132 (10)	0.3636 (7)	0.087 (3)	0.50
F1'	0.7399 (10)	0.5757 (17)	0.7956 (11)	0.160 (7)	0.50
F2'	0.7296 (7)	0.7305 (12)	0.8075 (9)	0.118 (5)	0.50
F3'	0.6705 (6)	0.7100 (9)	0.8982 (6)	0.089 (3)	0.50
F4'	0.6788 (7)	0.5562 (9)	0.8956 (8)	0.095 (4)	0.50
F5'	0.6495 (6)	0.6323 (10)	0.7903 (7)	0.082 (3)	0.50
F6'	0.7612 (9)	0.6409 (15)	0.9077 (11)	0.136 (7)	0.50
F7'	0.5639 (7)	0.8201 (13)	0.4737 (11)	0.065 (4)	0.50
F8'	0.6250 (4)	0.7947 (9)	0.3815 (7)	0.066 (3)	0.50
F9'	0.5184 (6)	0.6781 (9)	0.4411 (7)	0.094 (3)	0.50
F10'	0.5814 (6)	0.6529 (10)	0.3528 (7)	0.081 (3)	0.50
F11'	0.5277 (4)	0.7880 (9)	0.3518 (6)	0.081 (3)	0.50
F12'	0.6163 (6)	0.6839 (10)	0.4707 (6)	0.094 (3)	0.50
O1	0.5848 (2)	0.0479 (3)	0.5984 (4)	0.0706 (16)
O2	0.9674 (2)	0.4298 (4)	0.6755 (4)	0.0730 (16)
N1	0.6458 (2)	0.3976 (4)	0.6254 (3)	0.0426 (11)
N2	0.5616 (5)	0.0829 (6)	0.7123 (5)	0.105 (3)
H1n	0.5465	0.0249	0.7176	0.126*
H2n	0.5616	0.1254	0.7488	0.126*
N3	0.7528 (2)	0.4988 (4)	0.6136 (3)	0.0393 (11)
N4	0.9639 (3)	0.4321 (6)	0.5525 (5)	0.086 (2)
H3n	1.0022	0.4192	0.5553	0.103*
H4n	0.9437	0.4393	0.5085	0.103*
N5	0.5835 (2)	0.5845 (4)	0.6278 (3)	0.0459 (12)
N6	0.6826 (2)	0.6815 (4)	0.6218 (3)	0.0407 (11)
C1	0.6372 (4)	0.3601 (5)	0.6929 (4)	0.0602 (19)
H1	0.6435	0.3999	0.7361	0.072*
C2	0.6201 (4)	0.2674 (5)	0.7010 (4)	0.0586 (18)
H2	0.6160	0.2428	0.7498	0.070*
C3	0.6084 (3)	0.2081 (4)	0.6399 (4)	0.0455 (15)
C4	0.6180 (5)	0.2470 (6)	0.5720 (5)	0.077 (3)
H4	0.6113	0.2087	0.5280	0.092*
C5	0.6369 (4)	0.3400 (6)	0.5663 (5)	0.068 (2)
H5	0.6440	0.3644	0.5184	0.082*
C6	0.5854 (3)	0.1070 (5)	0.6467 (5)	0.0577 (18)
C7	0.7775 (3)	0.5003 (8)	0.5506 (5)	0.071 (2)
H7	0.7535	0.5146	0.5055	0.085*
C8	0.8376 (4)	0.4816 (8)	0.5470 (5)	0.074 (3)
H8	0.8545	0.4856	0.5005	0.089*
C9	0.8717 (3)	0.4578 (4)	0.6095 (4)	0.0468 (15)
C10	0.8457 (4)	0.4501 (9)	0.6735 (6)	0.097 (4)
H10	0.8684	0.4304	0.7182	0.116*
C11	0.7862 (4)	0.4707 (9)	0.6746 (5)	0.090 (3)
H11	0.7684	0.4646	0.7205	0.108*
C12	0.9376 (3)	0.4405 (5)	0.6127 (5)	0.0546 (18)
C13	0.5341 (3)	0.5284 (5)	0.6259 (5)	0.0560 (17)
H13	0.5372	0.4608	0.6179	0.067*
C14	0.4796 (3)	0.5682 (6)	0.6354 (5)	0.068 (2)
H14	0.4451	0.5286	0.6333	0.081*
C15	0.4755 (3)	0.6653 (6)	0.6479 (6)	0.082 (3)
H15	0.4384	0.6936	0.6560	0.098*
C16	0.5259 (3)	0.7221 (6)	0.6486 (5)	0.068 (2)
H16	0.5236	0.7898	0.6569	0.082*
C17	0.5794 (3)	0.6798 (5)	0.6372 (4)	0.0497 (16)
C18	0.6345 (3)	0.7349 (5)	0.6329 (4)	0.0435 (14)
C19	0.6381 (3)	0.8338 (5)	0.6376 (4)	0.0520 (16)
H19	0.6037	0.8706	0.6452	0.062*
C20	0.6913 (3)	0.8800 (5)	0.6313 (4)	0.0558 (17)
H20	0.6939	0.9485	0.6336	0.067*
C21	0.7415 (3)	0.8240 (5)	0.6214 (4)	0.0545 (17)
H21	0.7791	0.8536	0.6178	0.065*
C22	0.7353 (3)	0.7249 (5)	0.6170 (4)	0.0437 (14)
H22	0.7692	0.6863	0.6104	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd	0.0313 (2)	0.0397 (2)	0.0422 (3)	−0.00218 (17)	0.00854 (15)	0.00002 (19)
P1	0.0333 (8)	0.0718 (11)	0.0553 (11)	0.0101 (7)	0.0084 (7)	0.0075 (9)
P2	0.0489 (10)	0.0513 (9)	0.0566 (11)	−0.0045 (7)	0.0104 (7)	−0.0003 (8)
F1	0.052 (5)	0.120 (8)	0.085 (7)	−0.023 (5)	0.009 (4)	0.023 (6)
F2	0.135 (8)	0.078 (6)	0.133 (9)	0.028 (6)	−0.024 (7)	−0.028 (6)
F3	0.074 (6)	0.141 (9)	0.069 (6)	0.002 (6)	0.034 (5)	0.002 (7)
F4	0.096 (7)	0.077 (6)	0.076 (6)	−0.036 (5)	−0.006 (5)	−0.024 (5)
F5	0.057 (6)	0.116 (8)	0.085 (7)	0.031 (6)	−0.007 (5)	0.019 (7)
F6	0.041 (4)	0.042 (4)	0.069 (5)	0.010 (3)	−0.005 (3)	0.002 (4)
F7	0.118 (8)	0.082 (6)	0.067 (6)	−0.025 (6)	0.027 (6)	0.011 (5)
F8	0.078 (9)	0.091 (8)	0.078 (8)	0.009 (7)	0.023 (7)	−0.031 (6)
F9	0.119 (8)	0.039 (4)	0.074 (6)	−0.011 (5)	0.022 (6)	0.000 (4)
F10	0.044 (4)	0.055 (5)	0.057 (5)	0.008 (4)	0.000 (4)	−0.001 (4)
F11	0.057 (5)	0.100 (7)	0.076 (6)	−0.001 (5)	−0.006 (4)	−0.021 (5)
F12	0.048 (5)	0.112 (7)	0.098 (7)	0.010 (5)	−0.003 (5)	−0.015 (6)
F1'	0.158 (10)	0.174 (11)	0.155 (10)	0.065 (9)	0.050 (8)	−0.009 (8)
F2'	0.122 (9)	0.118 (8)	0.115 (9)	−0.037 (7)	0.016 (7)	0.042 (7)
F3'	0.118 (7)	0.084 (6)	0.068 (6)	0.025 (6)	0.020 (5)	−0.010 (5)
F4'	0.122 (8)	0.068 (6)	0.096 (8)	−0.010 (6)	0.008 (6)	0.018 (6)
F5'	0.075 (6)	0.104 (7)	0.066 (6)	−0.011 (6)	0.001 (5)	0.001 (6)
F6'	0.098 (9)	0.172 (11)	0.134 (10)	−0.014 (9)	−0.002 (7)	0.031 (9)
F7'	0.063 (7)	0.063 (6)	0.071 (7)	−0.003 (5)	0.016 (6)	−0.014 (5)
F8'	0.045 (5)	0.081 (6)	0.075 (6)	−0.013 (4)	0.019 (4)	−0.019 (5)
F9'	0.091 (7)	0.097 (7)	0.095 (7)	−0.034 (6)	0.018 (6)	0.012 (6)
F10'	0.118 (8)	0.064 (5)	0.063 (6)	−0.011 (7)	0.012 (7)	−0.002 (5)
F11'	0.049 (5)	0.109 (7)	0.083 (6)	0.015 (5)	0.002 (4)	0.028 (5)
F12'	0.101 (7)	0.107 (7)	0.073 (6)	0.040 (6)	0.001 (5)	0.009 (6)
O1	0.058 (3)	0.043 (3)	0.115 (5)	−0.003 (2)	0.031 (3)	−0.020 (3)
O2	0.049 (3)	0.063 (3)	0.106 (5)	0.008 (2)	0.002 (3)	−0.007 (3)
N1	0.031 (2)	0.051 (3)	0.047 (3)	0.002 (2)	0.012 (2)	−0.004 (2)
N2	0.158 (9)	0.066 (5)	0.101 (7)	−0.041 (5)	0.058 (6)	−0.016 (4)
N3	0.035 (2)	0.038 (2)	0.046 (3)	0.0011 (19)	0.011 (2)	0.001 (2)
N4	0.051 (4)	0.109 (6)	0.101 (6)	0.006 (4)	0.025 (4)	−0.022 (5)
N5	0.037 (3)	0.047 (3)	0.053 (3)	−0.006 (2)	0.002 (2)	−0.001 (2)
N6	0.025 (2)	0.050 (3)	0.047 (3)	−0.0016 (19)	0.0054 (19)	0.000 (2)
C1	0.077 (5)	0.053 (4)	0.052 (5)	−0.016 (4)	0.018 (4)	−0.011 (3)
C2	0.073 (5)	0.048 (4)	0.055 (5)	−0.013 (3)	0.007 (3)	0.001 (3)
C3	0.037 (3)	0.033 (3)	0.066 (5)	0.004 (2)	0.007 (3)	−0.006 (3)
C4	0.114 (8)	0.058 (4)	0.061 (6)	−0.015 (5)	0.019 (5)	−0.023 (4)
C5	0.099 (6)	0.060 (4)	0.049 (5)	−0.024 (4)	0.022 (4)	−0.008 (3)
C6	0.051 (4)	0.048 (4)	0.075 (5)	0.004 (3)	0.010 (3)	−0.009 (4)
C7	0.045 (4)	0.122 (7)	0.047 (5)	0.019 (4)	0.013 (3)	−0.005 (4)
C8	0.053 (4)	0.123 (8)	0.049 (5)	0.027 (5)	0.017 (3)	−0.008 (4)
C9	0.038 (3)	0.037 (3)	0.066 (4)	−0.005 (2)	0.009 (3)	−0.009 (3)
C10	0.047 (5)	0.170 (12)	0.074 (6)	0.026 (6)	0.010 (4)	0.037 (7)
C11	0.047 (5)	0.167 (11)	0.059 (6)	0.007 (5)	0.018 (4)	0.035 (6)
C12	0.044 (4)	0.042 (3)	0.078 (5)	−0.001 (3)	0.009 (3)	−0.010 (3)
C13	0.036 (3)	0.056 (4)	0.075 (5)	−0.008 (3)	0.001 (3)	0.005 (3)
C14	0.040 (4)	0.066 (5)	0.098 (7)	−0.006 (3)	0.010 (4)	−0.004 (4)
C15	0.039 (4)	0.069 (5)	0.139 (9)	0.006 (4)	0.020 (4)	−0.005 (5)
C16	0.038 (4)	0.059 (4)	0.111 (7)	0.007 (3)	0.016 (4)	0.000 (4)
C17	0.032 (3)	0.058 (4)	0.060 (4)	−0.004 (3)	0.009 (3)	0.006 (3)
C18	0.033 (3)	0.047 (3)	0.051 (4)	−0.003 (2)	0.006 (2)	−0.002 (3)
C19	0.041 (3)	0.042 (3)	0.073 (5)	0.003 (3)	0.004 (3)	−0.008 (3)
C20	0.050 (4)	0.042 (3)	0.075 (5)	−0.003 (3)	0.004 (3)	−0.005 (3)
C21	0.043 (4)	0.049 (4)	0.071 (5)	−0.010 (3)	0.005 (3)	−0.003 (3)
C22	0.034 (3)	0.045 (3)	0.052 (4)	0.000 (2)	0.003 (2)	0.002 (3)

Geometric parameters (Å, º) top

Pd—N1	2.005 (5)	N5—C17	1.332 (9)
Pd—N3	2.024 (5)	N5—C13	1.357 (8)
Pd—N5	2.013 (5)	N6—C22	1.343 (7)
Pd—N6	2.014 (5)	N6—C18	1.346 (8)
P1—F3	1.501 (11)	C1—C2	1.351 (10)
P1—F2'	1.514 (13)	C1—H1	0.9500
P1—F1'	1.538 (16)	C2—C3	1.374 (10)
P1—F5	1.561 (11)	C2—H2	0.9500
P1—F6'	1.562 (19)	C3—C4	1.365 (11)
P1—F6	1.577 (9)	C3—C6	1.501 (9)
P1—F5'	1.580 (13)	C4—C5	1.362 (11)
P1—F2	1.593 (13)	C4—H4	0.9500
P1—F3'	1.596 (10)	C5—H5	0.9500
P1—F1	1.599 (11)	C7—C8	1.391 (10)
P1—F4	1.602 (10)	C7—H7	0.9500
P1—F4'	1.646 (12)	C8—C9	1.340 (11)
P2—F12'	1.494 (11)	C8—H8	0.9500
P2—F12	1.500 (10)	C9—C10	1.339 (12)
P2—F8	1.522 (19)	C9—C12	1.504 (9)
P2—F8'	1.542 (11)	C10—C11	1.376 (12)
P2—F10'	1.580 (13)	C10—H10	0.9500
P2—F7	1.583 (10)	C11—H11	0.9500
P2—F9	1.587 (11)	C13—C14	1.373 (10)
P2—F9'	1.626 (11)	C13—H13	0.9500
P2—F7'	1.639 (19)	C14—C15	1.366 (12)
P2—F11'	1.642 (10)	C14—H14	0.9500
P2—F10	1.650 (11)	C15—C16	1.382 (11)
P2—F11	1.667 (10)	C15—H15	0.9500
O1—C6	1.189 (9)	C16—C17	1.374 (9)
O2—C12	1.266 (10)	C16—H16	0.9500
N1—C5	1.325 (9)	C17—C18	1.467 (8)
N1—C1	1.345 (9)	C18—C19	1.372 (9)
N2—C6	1.376 (11)	C19—C20	1.375 (9)
N2—H1n	0.8800	C19—H19	0.9500
N2—H2n	0.8800	C20—C21	1.398 (10)
N3—C7	1.303 (9)	C20—H20	0.9500
N3—C11	1.329 (10)	C21—C22	1.380 (9)
N4—C12	1.282 (10)	C21—H21	0.9500
N4—H3n	0.8800	C22—H22	0.9500
N4—H4n	0.8800

N1—Pd—N5	94.3 (2)	C11—N3—Pd	120.4 (5)
N1—Pd—N6	174.40 (19)	C12—N4—H3n	120.0
N5—Pd—N6	81.2 (2)	C12—N4—H4n	120.0
N1—Pd—N3	88.8 (2)	H3n—N4—H4n	120.0
N5—Pd—N3	176.8 (2)	C17—N5—C13	120.2 (6)
N6—Pd—N3	95.66 (19)	C17—N5—Pd	113.6 (4)
F2'—P1—F1'	90.4 (10)	C13—N5—Pd	126.2 (5)
F3—P1—F5	92.6 (8)	C22—N6—C18	119.8 (6)
F3—P1—F6'	90.7 (9)	C22—N6—Pd	126.4 (4)
F2'—P1—F6'	93.6 (10)	C18—N6—Pd	113.7 (4)
F1'—P1—F6'	91.1 (11)	N1—C1—C2	121.9 (7)
F5—P1—F6'	156.2 (10)	N1—C1—H1	119.0
F3—P1—F6	92.5 (7)	C2—C1—H1	119.0
F5—P1—F6	174.9 (7)	C1—C2—C3	121.1 (7)
F2'—P1—F5'	93.9 (8)	C1—C2—H2	119.4
F1'—P1—F5'	88.8 (10)	C3—C2—H2	119.4
F6'—P1—F5'	172.5 (9)	C4—C3—C2	116.1 (6)
F3—P1—F2	92.3 (9)	C4—C3—C6	121.7 (7)
F5—P1—F2	93.9 (8)	C2—C3—C6	122.2 (7)
F6—P1—F2	86.6 (6)	C5—C4—C3	121.0 (7)
F2'—P1—F3'	90.8 (9)	C5—C4—H4	119.5
F1'—P1—F3'	177.4 (11)	C3—C4—H4	119.5
F6'—P1—F3'	91.1 (9)	N1—C5—C4	122.3 (8)
F5'—P1—F3'	88.9 (7)	N1—C5—H5	118.9
F3—P1—F1	179.9 (10)	C4—C5—H5	118.9
F5—P1—F1	87.4 (7)	O1—C6—N2	118.3 (7)
F6—P1—F1	87.6 (6)	O1—C6—C3	124.2 (7)
F2—P1—F1	87.7 (8)	N2—C6—C3	117.4 (7)
F3—P1—F4	93.5 (8)	N3—C7—C8	122.3 (8)
F5—P1—F4	91.3 (7)	N3—C7—H7	118.9
F6—P1—F4	87.8 (6)	C8—C7—H7	118.9
F2—P1—F4	172.1 (8)	C9—C8—C7	119.8 (7)
F1—P1—F4	86.6 (7)	C9—C8—H8	120.1
F2'—P1—F4'	173.2 (9)	C7—C8—H8	120.1
F1'—P1—F4'	96.4 (11)	C10—C9—C8	118.1 (7)
F6'—P1—F4'	86.3 (9)	C10—C9—C12	117.8 (7)
F5'—P1—F4'	86.3 (7)	C8—C9—C12	124.1 (7)
F3'—P1—F4'	82.4 (7)	C9—C10—C11	120.1 (8)
F12—P2—F8	93.7 (8)	C9—C10—H10	120.0
F12'—P2—F8'	94.8 (8)	C11—C10—H10	120.0
F12'—P2—F10'	92.7 (7)	N3—C11—C10	122.1 (8)
F8'—P2—F10'	91.3 (6)	N3—C11—H11	119.0
F12—P2—F7	91.1 (7)	C10—C11—H11	119.0
F8—P2—F7	92.2 (10)	O2—C12—N4	119.1 (8)
F12—P2—F9	94.7 (7)	O2—C12—C9	119.7 (7)
F8—P2—F9	91.4 (9)	N4—C12—C9	121.1 (8)
F10'—P2—F9	93.9 (6)	N5—C13—C14	120.8 (7)
F7—P2—F9	172.9 (8)	N5—C13—H13	119.6
F12'—P2—F9'	91.1 (8)	C14—C13—H13	119.6
F8'—P2—F9'	174.1 (7)	C15—C14—C13	119.2 (7)
F10'—P2—F9'	89.1 (7)	C15—C14—H14	120.4
F12'—P2—F7'	90.6 (8)	C13—C14—H14	120.4
F8'—P2—F7'	91.2 (7)	C14—C15—C16	119.5 (7)
F10'—P2—F7'	175.7 (8)	C14—C15—H15	120.2
F9'—P2—F7'	88.0 (7)	C16—C15—H15	120.2
F12'—P2—F11'	177.2 (7)	C17—C16—C15	119.4 (8)
F8'—P2—F11'	88.1 (6)	C17—C16—H16	120.3
F10'—P2—F11'	87.4 (7)	C15—C16—H16	120.3
F9'—P2—F11'	86.0 (6)	N5—C17—C16	120.8 (6)
F7'—P2—F11'	89.2 (8)	N5—C17—C18	116.0 (6)
F12—P2—F10	88.8 (5)	C16—C17—C18	123.2 (7)
F8—P2—F10	177.5 (7)	N6—C18—C19	120.8 (6)
F7—P2—F10	88.1 (6)	N6—C18—C17	115.1 (6)
F9—P2—F10	88.0 (6)	C19—C18—C17	124.1 (6)
F12—P2—F11	174.5 (6)	C18—C19—C20	120.4 (6)
F8—P2—F11	91.8 (7)	C18—C19—H19	119.8
F7—P2—F11	88.1 (7)	C20—C19—H19	119.8
F9—P2—F11	85.7 (7)	C19—C20—C21	118.6 (6)
F10—P2—F11	85.8 (5)	C19—C20—H20	120.7
C5—N1—C1	117.5 (6)	C21—C20—H20	120.7
C5—N1—Pd	124.3 (5)	C22—C21—C20	118.6 (6)
C1—N1—Pd	118.2 (4)	C22—C21—H21	120.7
C6—N2—H1n	120.0	C20—C21—H21	120.7
C6—N2—H2n	120.0	N6—C22—C21	121.8 (6)
H1n—N2—H2n	120.0	N6—C22—H22	119.1
C7—N3—C11	117.4 (6)	C21—C22—H22	119.1
C7—N3—Pd	122.2 (5)

N5—Pd—N1—C5	99.2 (6)	C8—C9—C10—C11	−2.9 (16)
N3—Pd—N1—C5	−81.7 (6)	C12—C9—C10—C11	176.3 (10)
N5—Pd—N1—C1	−77.7 (5)	C7—N3—C11—C10	4.4 (16)
N3—Pd—N1—C1	101.4 (5)	Pd—N3—C11—C10	−175.3 (9)
N1—Pd—N3—C7	103.1 (7)	C9—C10—C11—N3	−0.2 (19)
N6—Pd—N3—C7	−80.3 (7)	C10—C9—C12—O2	−7.7 (11)
N1—Pd—N3—C11	−77.2 (7)	C8—C9—C12—O2	171.5 (8)
N6—Pd—N3—C11	99.4 (7)	C10—C9—C12—N4	169.4 (9)
N1—Pd—N5—C17	170.8 (5)	C8—C9—C12—N4	−11.5 (12)
N6—Pd—N5—C17	−5.9 (5)	C17—N5—C13—C14	−1.6 (12)
N1—Pd—N5—C13	−7.8 (6)	Pd—N5—C13—C14	176.9 (6)
N6—Pd—N5—C13	175.6 (6)	N5—C13—C14—C15	−0.9 (14)
N5—Pd—N6—C22	−178.6 (6)	C13—C14—C15—C16	1.8 (16)
N3—Pd—N6—C22	2.1 (6)	C14—C15—C16—C17	−0.4 (15)
N5—Pd—N6—C18	4.9 (5)	C13—N5—C17—C16	3.0 (11)
N3—Pd—N6—C18	−174.4 (5)	Pd—N5—C17—C16	−175.6 (6)
C5—N1—C1—C2	−0.3 (12)	C13—N5—C17—C18	−175.6 (6)
Pd—N1—C1—C2	176.9 (6)	Pd—N5—C17—C18	5.8 (8)
N1—C1—C2—C3	−2.4 (13)	C15—C16—C17—N5	−2.0 (13)
C1—C2—C3—C4	3.0 (12)	C15—C16—C17—C18	176.5 (8)
C1—C2—C3—C6	−175.9 (7)	C22—N6—C18—C19	1.5 (10)
C2—C3—C4—C5	−1.2 (13)	Pd—N6—C18—C19	178.2 (5)
C6—C3—C4—C5	177.7 (8)	C22—N6—C18—C17	−180.0 (6)
C1—N1—C5—C4	2.1 (13)	Pd—N6—C18—C17	−3.3 (7)
Pd—N1—C5—C4	−174.8 (8)	N5—C17—C18—N6	−1.7 (9)
C3—C4—C5—N1	−1.4 (16)	C16—C17—C18—N6	179.7 (7)
C4—C3—C6—O1	15.2 (12)	N5—C17—C18—C19	176.7 (7)
C2—C3—C6—O1	−166.0 (8)	C16—C17—C18—C19	−1.8 (12)
C4—C3—C6—N2	−162.3 (9)	N6—C18—C19—C20	−0.2 (11)
C2—C3—C6—N2	16.6 (11)	C17—C18—C19—C20	−178.6 (7)
C11—N3—C7—C8	−5.4 (14)	C18—C19—C20—C21	−1.1 (12)
Pd—N3—C7—C8	174.2 (8)	C19—C20—C21—C22	1.1 (12)
N3—C7—C8—C9	2.4 (16)	C18—N6—C22—C21	−1.5 (10)
C7—C8—C9—C10	2.0 (14)	Pd—N6—C22—C21	−177.7 (5)
C7—C8—C9—C12	−177.2 (8)	C20—C21—C22—N6	0.1 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N···O2ⁱ	0.88	2.29	3.031 (11)	142
N2—H1N···O2ⁱⁱ	0.88	2.37	3.032 (11)	132
N2—H2N···F9ⁱⁱⁱ	0.88	2.24	3.037 (15)	151
N2—H2N···F11′ⁱⁱⁱ	0.88	2.38	3.220 (14)	159
N4—H3N···F7′^iv	0.88	2.52	3.175 (19)	132
N4—H3N···F8^iv	0.88	2.55	3.10 (2)	121
N4—H4N···O1^v	0.88	1.97	2.836 (11)	168

Symmetry codes: (i) x−1/2, y−1/2, z; (ii) −x+3/2, y−1/2, −z+3/2; (iii) x, −y+1, z+1/2; (iv) x+1/2, y−1/2, z; (v) −x+3/2, −y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	[Pd(C₁₀H₈N₂)(C₆H₆NO₂)₂](PF₆)₂
M_r	796.78
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	22.5920 (14), 13.8299 (8), 17.9092 (12)
β (°)	95.269 (8)
V (Å³)	5572.0 (6)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	7.55
Crystal size (mm)	0.46 × 0.16 × 0.15

Data collection
Diffractometer	Bruker APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2007)
T_min, T_max	0.126, 0.401
No. of measured, independent and observed [I > 2σ(I)] reflections	30116, 5182, 3944
R_int	0.072
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.147, 1.01
No. of reflections	5182
No. of parameters	520
No. of restraints	144
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.78

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N···O2ⁱ	0.88	2.29	3.031 (11)	142
N2—H1N···O2ⁱⁱ	0.88	2.37	3.032 (11)	132
N2—H2N···F9ⁱⁱⁱ	0.88	2.24	3.037 (15)	151
N2—H2N···F11'ⁱⁱⁱ	0.88	2.38	3.220 (14)	159
N4—H3N···F7'^iv	0.88	2.52	3.175 (19)	132
N4—H3N···F8^iv	0.88	2.55	3.10 (2)	121
N4—H4N···O1^v	0.88	1.97	2.836 (11)	168

Symmetry codes: (i) x−1/2, y−1/2, z; (ii) −x+3/2, y−1/2, −z+3/2; (iii) x, −y+1, z+1/2; (iv) x+1/2, y−1/2, z; (v) −x+3/2, −y+1/2, −z+1.

Footnotes

‡Additional correspondence author, e-mail: adrian@uiwtx.edu.

Acknowledgements

The authors appreciate the support of the Chemistry Department at the University of the Incarnate Word. The authors thank the National Science Foundation (grant CHE-0130835) and the University of Oklahoma for funds to purchase the X-ray instrument and computers. We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR-MOHE/SC/12).

References

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