Bis(2,2′-bipyrimidine-κ2N1,N1′)palladium(II) bis­(tetra­fluoro­borate) acetonitrile monosolvate

Duong, A.; Wuest, J.D.; Maris, T.

doi:10.1107/S1600536812041591

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Pages m1347-m1348

doi:10.1107/S1600536812041591

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Bis(2,2′-bipyrimidine-κ²N¹,N^1′)palladium(II) bis(tetrafluoroborate) acetonitrile monosolvate

Adam Duong,^a James D. Wuest ^a and Thierry Maris ^a ^*

^aDépartement de Chimie, Université de Montréal, 2900 Boulevard Édouard-Montpetit, Montréal, Québec, Canada H3C 3J7
^*Correspondence e-mail: thierry.maris@umontreal.ca

(Received 18 September 2012; accepted 4 October 2012; online 13 October 2012)

The reaction of [Pd(MeCN)₄](BF₄)₂ with 2,2′-bipyrimidine (bpm) in MeCN–CHCl₃ afforded the title compound, [Pd(C₈H₆N₄)₂](BF₄)₂·C₂H₃N. The asymmetric unit contains two half complexes, with the Pd^II atoms both lying on a twofold axis. Each metal atom adopts a tetrahedrally distorted square-planar geometry. In the crystal, [Pd(bpm)₂] dications are linked by C—H⋯N hydrogen bonds, forming chains parallel to the b axis. The chains are further linked by C—H⋯F and C—H⋯N interactions involving the tetrafluoroborate anions and acetonitrile molecules. In this way, each chain interacts with six surrounding chains to generate the observed three-dimensional structure.

Related literature

Similar Pd(bpm)₂ complexes are unknown, but the subject of related dicationic adducts of Pd^II with 2,2′-bipyridyl (bpy) has been reviewed by Constable (1989 ) and McKenzie (1971 ), and the structures of representative analogues have been reported by Chieh (1972 ), Duong et al. (2011 ), Gao et al. (2010 ), Geremia et al. (1992 ), Hinamoto et al. (1972 ), Maeda et al. (1986 ), Milani et al. (1997 ), Stoccoro et al. (2002 ), Wehman et al. (1994 ) and Yue et al. (2008 ).

Experimental

Crystal data

[Pd(C₈H₆N₄)₂](BF₄)₂·C₂H₃N
M_r = 637.41
Monoclinic, C 2/c
a = 18.0686 (4) Å
b = 18.1126 (4) Å
c = 14.8351 (3) Å
β = 108.613 (1)°
V = 4601.13 (17) Å³
Z = 8
Cu Kα radiation
μ = 7.38 mm⁻¹
T = 200 K
0.20 × 0.11 × 0.10 mm

Data collection

Bruker SMART 6000 diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.311, T_max = 0.478
31076 measured reflections
4246 independent reflections
4006 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.081
S = 1.03
4246 reflections
347 parameters
H-atom parameters constrained
Δρ_max = 1.07 e Å⁻³
Δρ_min = −0.75 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯N11ⁱ	0.95	2.62	3.460 (4)	148
C6—H6⋯N15ⁱⁱ	0.95	2.45	3.237 (4)	140
C14—H14⋯N16ⁱⁱⁱ	0.95	2.40	3.228 (4)	146
C2—H2⋯F7ⁱⁱⁱ	0.95	2.38	3.282 (3)	159
C3—H3⋯F2^iv	0.95	2.44	3.240 (3)	142
C8—H8⋯F3^v	0.95	2.45	3.270 (4)	145
C13—H13⋯F6^vi	0.95	2.37	2.982 (3)	122
C15—H15⋯F8^iv	0.95	2.52	3.408 (4)	155
C18—H18B⋯F5^vii	0.98	2.55	3.373 (5)	142
Symmetry codes: (i) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x, -y+1, z-{\script{1\over 2}}]$ ; (v) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (vi) $[-x, y, -z+{\script{1\over 2}}]$ ; (vii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: SMART (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Materials Studio (Accelrys, 2002 ); software used to prepare material for publication: UdMX (Maris, 2004 ) and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812041591/rz5009sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812041591/rz5009Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812041591/rz5009Isup3.cdx

checkCIF report

Comment top

The title compound was obtained and characterized in the course of a study of complexes of Pd(II) with chelating heterocyclic ligands (Duong et al., 2011). In the crystal structure, each Pd^II center is coordinated by two 2,2'-bipyrimidine (bpm) ligands to form two different distorted square-planar complexes (Figure 1). Distortions in such complexes arise because a normal square-planar geometry, which is inherently preferred by d⁸ metals, is opposed by steric interactions of the two ligands. As a result, related complexes of 2,2'-bipyridine (bpy) typically adopt one of two characteristic conformations: a so-called twisted geometry (involving a tetrahedral distortion of the metal center) and a bow-step deformation of the ligands themselves, as described by Constable (1989) and Milani et al. (1997). In the title compound, each of the two observed complexes incorporates approximately planar bpm ligands (maximum r. m. s. deviation 0.089 Å), and the geometry of coordination is twisted, with angles α of 21.52 (16)° and 25.80 (18)° between the N—Pd—N planes of the ligands. These values of α are similar to those found in analogous dicationic Pd^II(bpy)₂ complexes with twisted geometries, as reported by Chieh (1972), Geremia et al. (1992), Hinamoto et al. (1972), Milani et al. (1997), Stoccoro et al. (2002), and Wehman et al. (1994). In addition, the average Pd—N distance is normal [2.030 (2) Å] (McKenzie, 1971).

The structure consists of chains of Pd^II(bpm)₂ dications linked along the b-axis by C—H···N hydrogen bonds involving uncoordinated atoms of nitrogen (mean C—H···N distance: 3.348 (4) Å; Table 1), as shown in Figure 2. Within each chain, adjacent dications are arranged in an approximately orthogonal way (the dihedral angle between the N₄ coordination cores is 89.01 (6)°). The tetrafluoroborate counterions are located between the chains and bridge them via weak C—H···F contacts to create the three-dimensional packing. Included molecules of MeCN are located close to the Pd^II centers, fill remaining volume, and engage in additional C—H···N interactions (Figure 3).

Related literature top

Similar Pd(bpm)₂ complexes are unknown, but the subject of related dicationic adducts of Pd^II with 2,2'-bipyridyl (bpy) has been reviewed by Constable (1989) and McKenzie (1971), and the structures of representative analogues have been reported by Chieh (1972), Duong et al. (2011), Gao et al. (2010), Geremia et al. (1992), Hinamoto et al. (1972), Maeda et al. (1986), Milani et al. (1997), Stoccoro et al. (2002), Wehman et al. (1994) and Yue et al. (2008).

Experimental top

Solid [Pd(MeCN)₄](BF₄)₂ (71 mg, 0.16 mmol) was added at 25 °C to a stirred mixture of MeCN (2.5 ml) and CHCl₃ (2.5 ml) containing 2,2'-bipyrimidine (50 mg, 0.32 mmol). The resulting mixture quickly turned yellow, and a yellow solid began to precipitate. After the suspension had been stirred for 2 h, volatiles were removed by evaporation under reduced pressure, and the residual yellow solid was washed with MeCN. Crystals of the title complex were obtained in 70% yield by allowing vapors of MeCN to diffuse slowly into a solution of the yellow solid in DMSO.

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Materials Studio (Accelrys, 2002); software used to prepare material for publication: UdMX (Maris, 2004) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure of the title compound, with atomic labels and 50% probability displacement ellipsoids for non-hydrogen atoms. Hydrogen atoms are drawn as a sphere of arbitrary radius. Unlabelled atoms in the cationic complexes are related by the symmetry operations 1 - x, y, -z + 1/2 for Pd1 and -x, y, -z + 1/2 for Pd2.
	Fig. 2. View along the a-axis of a chain of cationic complexes, with C—H···N interactions shown as broken lines.
	Fig. 3. View along the b-axis of the unit-cell content. C—H···N and C—H···F contacts are shown as dashed lines.

Bis(2,2'-bipyrimidine-κ²N¹,N^1')palladium(II) bis(tetrafluoroborate) acetonitrile monosolvate top

Crystal data top

[Pd(C₈H₆N₄)₂](BF₄)₂·C₂H₃N	F(000) = 2512
M_r = 637.41	D_x = 1.840 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -C 2yc	Cell parameters from 20829 reflections
a = 18.0686 (4) Å	θ = 3.6–68.8°
b = 18.1126 (4) Å	µ = 7.38 mm⁻¹
c = 14.8351 (3) Å	T = 200 K
β = 108.613 (1)°	Block, yellow
V = 4601.13 (17) Å³	0.20 × 0.11 × 0.10 mm
Z = 8

Data collection top

Bruker SMART 6000 diffractometer	4246 independent reflections
Radiation source: Rotating anode	4006 reflections with I > 2σ(I)
Montel 200 optics monochromator	R_int = 0.031
Detector resolution: 5.5 pixels mm^-1	θ_max = 68.9°, θ_min = 3.6°
ω scans	h = −21→21
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	k = −20→21
T_min = 0.311, T_max = 0.478	l = −17→17
31076 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.081	w = 1/[σ²(F_o²) + (0.0458P)² + 11.6117P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.002
4246 reflections	Δρ_max = 1.07 e Å⁻³
347 parameters	Δρ_min = −0.75 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.000355 (19)

Crystal data top

[Pd(C₈H₆N₄)₂](BF₄)₂·C₂H₃N	V = 4601.13 (17) Å³
M_r = 637.41	Z = 8
Monoclinic, C2/c	Cu Kα radiation
a = 18.0686 (4) Å	µ = 7.38 mm⁻¹
b = 18.1126 (4) Å	T = 200 K
c = 14.8351 (3) Å	0.20 × 0.11 × 0.10 mm
β = 108.613 (1)°

Data collection top

Bruker SMART 6000 diffractometer	4246 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	4006 reflections with I > 2σ(I)
T_min = 0.311, T_max = 0.478	R_int = 0.031
31076 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.081	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0458P)² + 11.6117P] where P = (F_o² + 2F_c²)/3
4246 reflections	Δρ_max = 1.07 e Å⁻³
347 parameters	Δρ_min = −0.75 e Å⁻³

Special details top

Experimental. X-ray crystallographic data for I were collected from a single-crystal sample, which was mounted on a loop fiber. Data were collected using a Bruker Platform diffractometer, equipped with a Bruker SMART 4 K Charged-Coupled Device (CCD) Area Detector using the program APEX2 and a Nonius FR591 rotating anode equipped with Montel 200 optics. The crystal-to-detector distance was 5.0 cm, and the data collection was carried out in 512 x 512 pixel mode. The initial unit-cell parameters were determined by a least-squares fit of the angular setting of strong reflections, collected by a 10.0 degree scan in 33 frames over four different parts of the reciprocal space (132 frames total). One complete sphere of data was collected to better than 0.80 Å resolution.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l. s. planes) were estimated using the full covariance matrix. The cell e.s.d.'s were 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 were only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s was 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 and 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
Pd1	0.5000	0.336135 (12)	0.2500	0.02227 (10)
N1	0.44850 (12)	0.40551 (11)	0.13874 (15)	0.0244 (4)
C1	0.46387 (15)	0.47710 (14)	0.13047 (19)	0.0294 (5)
H1	0.5006	0.5018	0.1821	0.035*
C2	0.42721 (17)	0.51534 (15)	0.0482 (2)	0.0359 (6)
H2	0.4374	0.5662	0.0422	0.043*
C3	0.37529 (18)	0.47724 (17)	−0.0249 (2)	0.0408 (7)
H3	0.3476	0.5032	−0.0812	0.049*
N3	0.36210 (15)	0.40471 (13)	−0.01994 (16)	0.0369 (5)
C4	0.39986 (14)	0.37213 (14)	0.06120 (17)	0.0277 (5)
C5	0.38836 (14)	0.29190 (14)	0.07200 (17)	0.0269 (5)
N5	0.42993 (12)	0.26406 (11)	0.15719 (15)	0.0271 (4)
C6	0.41328 (16)	0.19506 (14)	0.1769 (2)	0.0364 (6)
H6	0.4384	0.1749	0.2381	0.044*
C7	0.35997 (17)	0.15308 (15)	0.1090 (2)	0.0399 (7)
H7	0.3477	0.1041	0.1223	0.048*
C8	0.32526 (15)	0.18455 (16)	0.0217 (2)	0.0367 (6)
H8	0.2909	0.1555	−0.0272	0.044*
N8	0.33807 (13)	0.25488 (13)	0.00285 (16)	0.0340 (5)
Pd2	0.0000	0.339164 (12)	0.2500	0.02379 (10)
N9	0.06638 (12)	0.25370 (11)	0.23195 (15)	0.0278 (4)
C9	0.13999 (16)	0.25769 (15)	0.2297 (2)	0.0349 (6)
H9	0.1621	0.3045	0.2248	0.042*
C10	0.18357 (18)	0.19496 (17)	0.2344 (2)	0.0429 (7)
H10	0.2356	0.1974	0.2327	0.051*
C11	0.14925 (18)	0.12859 (16)	0.2417 (2)	0.0433 (7)
H11	0.1779	0.0844	0.2428	0.052*
N11	0.07683 (15)	0.12380 (12)	0.24733 (18)	0.0382 (5)
C12	0.03914 (15)	0.18649 (14)	0.24370 (18)	0.0287 (5)
N12	0.04299 (12)	0.42452 (11)	0.19429 (15)	0.0257 (4)
C13	0.07712 (16)	0.42029 (14)	0.12669 (19)	0.0314 (6)
H13	0.0896	0.3733	0.1070	0.038*
C14	0.09431 (17)	0.48312 (16)	0.0854 (2)	0.0364 (6)
H14	0.1184	0.4806	0.0372	0.044*
C15	0.07533 (17)	0.54960 (16)	0.1164 (2)	0.0393 (6)
H15	0.0890	0.5937	0.0909	0.047*
N15	0.03809 (14)	0.55468 (12)	0.18145 (17)	0.0349 (5)
C16	0.02226 (14)	0.49198 (13)	0.21627 (18)	0.0274 (5)
B1	0.2913 (2)	0.4231 (2)	0.2178 (3)	0.0447 (9)
F1	0.27658 (12)	0.46150 (13)	0.13349 (14)	0.0621 (5)
F2	0.36425 (10)	0.43957 (11)	0.27788 (13)	0.0496 (5)
F3	0.28788 (19)	0.34813 (14)	0.19523 (19)	0.0962 (10)
F4	0.23745 (14)	0.4387 (3)	0.26137 (17)	0.1125 (13)
B2	0.0691 (2)	0.24786 (18)	0.5158 (2)	0.0373 (7)
F5	0.09817 (13)	0.24491 (16)	0.44108 (15)	0.0749 (7)
F6	0.00661 (12)	0.29637 (11)	0.49624 (17)	0.0644 (6)
F7	0.04445 (17)	0.17898 (12)	0.5299 (2)	0.0885 (9)
F8	0.12677 (16)	0.27183 (14)	0.59487 (17)	0.0869 (8)
N16	0.35521 (18)	0.04534 (18)	0.5904 (2)	0.0563 (8)
C17	0.3079 (2)	0.08800 (18)	0.5644 (2)	0.0446 (7)
C18	0.2469 (2)	0.1432 (2)	0.5312 (4)	0.0771 (13)
H18A	0.2098	0.1274	0.4703	0.116*
H18B	0.2703	0.1905	0.5229	0.116*
H18C	0.2195	0.1489	0.5781	0.116*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.02316 (15)	0.01678 (15)	0.02304 (15)	0.000	0.00197 (10)	0.000
N1	0.0241 (10)	0.0227 (10)	0.0262 (10)	0.0030 (8)	0.0075 (8)	0.0017 (8)
C1	0.0293 (12)	0.0249 (13)	0.0352 (14)	0.0010 (10)	0.0118 (11)	0.0013 (10)
C2	0.0417 (15)	0.0280 (14)	0.0422 (15)	0.0048 (11)	0.0193 (13)	0.0103 (11)
C3	0.0503 (17)	0.0391 (16)	0.0316 (14)	0.0103 (13)	0.0112 (12)	0.0129 (12)
N3	0.0430 (13)	0.0380 (13)	0.0259 (11)	0.0062 (10)	0.0055 (10)	0.0034 (9)
C4	0.0266 (12)	0.0297 (13)	0.0269 (12)	0.0028 (10)	0.0086 (10)	−0.0010 (10)
C5	0.0244 (12)	0.0282 (13)	0.0277 (12)	0.0023 (10)	0.0076 (10)	−0.0030 (10)
N5	0.0262 (10)	0.0215 (10)	0.0294 (10)	0.0004 (8)	0.0030 (8)	−0.0033 (8)
C6	0.0362 (14)	0.0235 (13)	0.0415 (15)	−0.0010 (11)	0.0014 (12)	0.0010 (11)
C7	0.0330 (15)	0.0244 (13)	0.0557 (18)	−0.0030 (11)	0.0050 (13)	−0.0044 (12)
C8	0.0276 (13)	0.0324 (14)	0.0448 (16)	−0.0021 (11)	0.0041 (11)	−0.0160 (12)
N8	0.0284 (11)	0.0375 (13)	0.0320 (11)	0.0020 (9)	0.0039 (9)	−0.0083 (10)
Pd2	0.02831 (16)	0.01530 (15)	0.03000 (16)	0.000	0.01245 (11)	0.000
N9	0.0341 (11)	0.0218 (10)	0.0297 (10)	0.0020 (9)	0.0133 (9)	0.0000 (8)
C9	0.0360 (14)	0.0297 (14)	0.0423 (15)	0.0015 (11)	0.0169 (12)	0.0030 (11)
C10	0.0393 (16)	0.0415 (17)	0.0533 (18)	0.0082 (13)	0.0224 (14)	0.0001 (14)
C11	0.0466 (17)	0.0298 (15)	0.0564 (18)	0.0111 (12)	0.0204 (14)	−0.0024 (13)
N11	0.0448 (13)	0.0221 (11)	0.0487 (14)	0.0042 (10)	0.0161 (11)	−0.0022 (10)
C12	0.0351 (14)	0.0219 (12)	0.0296 (13)	−0.0001 (10)	0.0109 (10)	−0.0011 (10)
N12	0.0276 (11)	0.0205 (10)	0.0288 (10)	−0.0008 (8)	0.0084 (9)	0.0008 (8)
C13	0.0348 (14)	0.0276 (13)	0.0332 (14)	0.0006 (10)	0.0129 (11)	0.0015 (10)
C14	0.0379 (14)	0.0366 (15)	0.0375 (14)	−0.0008 (12)	0.0161 (12)	0.0067 (12)
C15	0.0422 (15)	0.0306 (14)	0.0464 (16)	−0.0036 (12)	0.0161 (13)	0.0106 (12)
N15	0.0413 (13)	0.0222 (11)	0.0414 (13)	−0.0026 (9)	0.0136 (10)	0.0031 (9)
C16	0.0291 (12)	0.0197 (12)	0.0303 (12)	−0.0006 (10)	0.0049 (10)	−0.0003 (10)
B1	0.0313 (17)	0.070 (2)	0.0338 (17)	−0.0178 (16)	0.0122 (14)	−0.0100 (16)
F1	0.0564 (12)	0.0816 (15)	0.0497 (11)	0.0054 (11)	0.0191 (9)	0.0139 (10)
F2	0.0344 (9)	0.0654 (12)	0.0463 (10)	−0.0109 (8)	0.0090 (8)	−0.0200 (9)
F3	0.128 (2)	0.0692 (16)	0.0691 (16)	−0.0514 (16)	−0.0002 (15)	−0.0088 (12)
F4	0.0420 (12)	0.251 (4)	0.0502 (13)	0.0151 (18)	0.0228 (11)	−0.0055 (18)
B2	0.0413 (17)	0.0302 (16)	0.0408 (17)	0.0011 (13)	0.0135 (14)	0.0002 (13)
F5	0.0584 (13)	0.119 (2)	0.0545 (12)	0.0111 (13)	0.0274 (10)	0.0160 (13)
F6	0.0525 (12)	0.0496 (12)	0.0871 (15)	0.0149 (9)	0.0167 (11)	0.0021 (11)
F7	0.105 (2)	0.0334 (10)	0.157 (3)	−0.0061 (12)	0.084 (2)	−0.0008 (14)
F8	0.0868 (17)	0.0793 (17)	0.0655 (14)	0.0202 (13)	−0.0165 (12)	−0.0219 (12)
N16	0.0577 (18)	0.070 (2)	0.0405 (15)	0.0225 (16)	0.0146 (13)	−0.0056 (14)
C17	0.0408 (17)	0.052 (2)	0.0403 (17)	0.0031 (14)	0.0113 (14)	−0.0006 (13)
C18	0.047 (2)	0.060 (2)	0.117 (4)	0.0100 (19)	0.017 (2)	0.030 (3)

Geometric parameters (Å, º) top

Pd1—N5ⁱ	2.022 (2)	C9—H9	0.9500
Pd1—N5	2.022 (2)	C10—C11	1.372 (5)
Pd1—N1	2.047 (2)	C10—H10	0.9500
Pd1—N1ⁱ	2.047 (2)	C11—N11	1.340 (4)
N1—C1	1.340 (3)	C11—H11	0.9500
N1—C4	1.348 (3)	N11—C12	1.316 (3)
C1—C2	1.375 (4)	C12—C12ⁱⁱ	1.485 (5)
C1—H1	0.9500	N12—C13	1.337 (3)
C2—C3	1.372 (4)	N12—C16	1.348 (3)
C2—H2	0.9500	C13—C14	1.374 (4)
C3—N3	1.341 (4)	C13—H13	0.9500
C3—H3	0.9500	C14—C15	1.371 (4)
N3—C4	1.318 (3)	C14—H14	0.9500
C4—C5	1.484 (4)	C15—N15	1.345 (4)
C5—N8	1.316 (3)	C15—H15	0.9500
C5—N5	1.345 (3)	N15—C16	1.316 (3)
N5—C6	1.339 (3)	C16—C16ⁱⁱ	1.471 (5)
C6—C7	1.378 (4)	B1—F4	1.357 (4)
C6—H6	0.9500	B1—F2	1.368 (4)
C7—C8	1.369 (4)	B1—F1	1.381 (4)
C7—H7	0.9500	B1—F3	1.396 (5)
C8—N8	1.340 (4)	B2—F7	1.363 (4)
C8—H8	0.9500	B2—F8	1.368 (4)
Pd2—N12	2.021 (2)	B2—F5	1.371 (4)
Pd2—N12ⁱⁱ	2.021 (2)	B2—F6	1.386 (4)
Pd2—N9	2.028 (2)	N16—C17	1.125 (4)
Pd2—N9ⁱⁱ	2.028 (2)	C17—C18	1.452 (5)
N9—C9	1.343 (3)	C18—H18a	0.9800
N9—C12	1.345 (3)	C18—H18b	0.9800
C9—C10	1.372 (4)	C18—H18c	0.9800

N5ⁱ—PD1—N5	99.59 (11)	N9—C9—H9	119.6
N5ⁱ—PD1—N1	165.94 (8)	C10—C9—H9	119.6
N5—PD1—N1	79.78 (8)	C9—C10—C11	117.6 (3)
N5ⁱ—PD1—N1ⁱ	79.78 (8)	C9—C10—H10	121.2
N5—PD1—N1ⁱ	165.94 (8)	C11—C10—H10	121.2
N1—PD1—N1ⁱ	104.24 (11)	N11—C11—C10	122.4 (3)
C1—N1—C4	117.0 (2)	N11—C11—H11	118.8
C1—N1—PD1	127.87 (17)	C10—C11—H11	118.8
C4—N1—PD1	114.69 (16)	C12—N11—C11	116.4 (2)
N1—C1—C2	120.9 (2)	N11—C12—N9	125.4 (2)
N1—C1—H1	119.6	N11—C12—C12ⁱⁱ	119.74 (16)
C2—C1—H1	119.6	N9—C12—C12ⁱⁱ	114.78 (14)
C3—C2—C1	117.5 (3)	C13—N12—C16	117.6 (2)
C3—C2—H2	121.2	C13—N12—PD2	126.33 (17)
C1—C2—H2	121.2	C16—N12—PD2	114.94 (17)
N3—C3—C2	122.5 (3)	N12—C13—C14	120.7 (2)
N3—C3—H3	118.7	N12—C13—H13	119.6
C2—C3—H3	118.7	C14—C13—H13	119.6
C4—N3—C3	116.1 (2)	C15—C14—C13	117.5 (3)
N3—C4—N1	125.8 (2)	C15—C14—H14	121.2
N3—C4—C5	119.2 (2)	C13—C14—H14	121.2
N1—C4—C5	115.0 (2)	N15—C15—C14	122.5 (2)
N8—C5—N5	125.5 (2)	N15—C15—H15	118.8
N8—C5—C4	120.0 (2)	C14—C15—H15	118.8
N5—C5—C4	114.4 (2)	C16—N15—C15	116.3 (2)
C6—N5—C5	117.2 (2)	N15—C16—N12	125.1 (2)
C6—N5—PD1	126.12 (18)	N15—C16—C16ⁱⁱ	120.10 (15)
C5—N5—PD1	115.98 (16)	N12—C16—C16ⁱⁱ	114.78 (14)
N5—C6—C7	120.6 (3)	F4—B1—F2	109.5 (3)
N5—C6—H6	119.7	F4—B1—F1	111.5 (3)
C7—C6—H6	119.7	F2—B1—F1	110.3 (3)
C8—C7—C6	117.6 (3)	F4—B1—F3	109.5 (3)
C8—C7—H7	121.2	F2—B1—F3	109.1 (3)
C6—C7—H7	121.2	F1—B1—F3	106.9 (3)
N8—C8—C7	122.4 (2)	F7—B2—F8	110.8 (3)
N8—C8—H8	118.8	F7—B2—F5	108.5 (3)
C7—C8—H8	118.8	F8—B2—F5	108.8 (3)
C5—N8—C8	116.3 (2)	F7—B2—F6	109.2 (3)
N12—PD2—N12ⁱⁱ	80.22 (12)	F8—B2—F6	109.0 (3)
N12—PD2—N9	102.08 (8)	F5—B2—F6	110.6 (3)
N12ⁱⁱ—PD2—N9	163.44 (9)	N16—C17—C18	179.7 (4)
N12—PD2—N9ⁱⁱ	163.44 (9)	C17—C18—H18A	109.5
N12ⁱⁱ—PD2—N9ⁱⁱ	102.08 (8)	C17—C18—H18B	109.5
N9—PD2—N9ⁱⁱ	80.47 (12)	H18A—C18—H18B	109.5
C9—N9—C12	117.3 (2)	C17—C18—H18C	109.5
C9—N9—PD2	126.46 (18)	H18A—C18—H18C	109.5
C12—N9—PD2	114.67 (17)	H18B—C18—H18C	109.5
N9—C9—C10	120.7 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N11ⁱⁱⁱ	0.95	2.62	3.460 (4)	148
C6—H6···N15^iv	0.95	2.45	3.237 (4)	140
C14—H14···N16^v	0.95	2.40	3.228 (4)	146
C2—H2···F7^v	0.95	2.38	3.282 (3)	159
C3—H3···F2^vi	0.95	2.44	3.240 (3)	142
C8—H8···F3^vii	0.95	2.45	3.270 (4)	145
C13—H13···F6ⁱⁱ	0.95	2.37	2.982 (3)	122
C15—H15···F8^vi	0.95	2.52	3.408 (4)	155
C18—H18B···F5^viii	0.98	2.55	3.373 (5)	142

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

Experimental details

Crystal data
Chemical formula	[Pd(C₈H₆N₄)₂](BF₄)₂·C₂H₃N
M_r	637.41
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	200
a, b, c (Å)	18.0686 (4), 18.1126 (4), 14.8351 (3)
β (°)	108.613 (1)
V (Å³)	4601.13 (17)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	7.38
Crystal size (mm)	0.20 × 0.11 × 0.10

Data collection
Diffractometer	Bruker SMART 6000 diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.311, 0.478
No. of measured, independent and observed [I > 2σ(I)] reflections	31076, 4246, 4006
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.605

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.081, 1.03
No. of reflections	4246
No. of parameters	347
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0458P)² + 11.6117P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.07, −0.75

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and Materials Studio (Accelrys, 2002), UdMX (Maris, 2004) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N11ⁱ	0.95	2.62	3.460 (4)	147.6
C6—H6···N15ⁱⁱ	0.95	2.45	3.237 (4)	139.7
C14—H14···N16ⁱⁱⁱ	0.95	2.40	3.228 (4)	145.5
C2—H2···F7ⁱⁱⁱ	0.95	2.38	3.282 (3)	159.2
C3—H3···F2^iv	0.95	2.44	3.240 (3)	142.3
C8—H8···F3^v	0.95	2.45	3.270 (4)	145
C13—H13···F6^vi	0.95	2.37	2.982 (3)	121.9
C15—H15···F8^iv	0.95	2.52	3.408 (4)	154.8
C18—H18B···F5^vii	0.98	2.55	3.373 (5)	141.8

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

Acknowledgements

We are grateful to the Natural Sciences and Engineering Research Council of Canada, the Ministère de l'Éducation du Québec, the Canada Foundation for Innovation, the Canada Research Chairs Program, and the Université de Montréal for financial support.

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