metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
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ISSN: 2056-9890
Volume 68| Part 11| November 2012| Pages m1347-m1348

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

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 PdII 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 PdII with 2,2′-bipyridyl (bpy) has been reviewed by Constable (1989[Constable, E. C. (1989). Adv. Inorg. Chem. 34, 1-63.]) and McKenzie (1971[McKenzie, E. D. (1971). Coord. Chem. Rev. 6, 187-216.]), and the structures of representative analogues have been reported by Chieh (1972[Chieh, P. C. (1972). J. Chem. Soc. Dalton Trans. pp. 1643-1646.]), Duong et al. (2011[Duong, A., Maris, T. & Wuest, J. D. (2011). Inorg. Chem. 50, 5605-5618.]), Gao et al. (2010[Gao, E. J., Zhang, Y. X., Zhu, M. C., Liu, H. Y., Huang, Y., Zhang, M., Su, M., Guo, M. J., Guan, F., Gao, X. N. & Wang, M. L. (2010). Russ. J. Coord. Chem. 36, 853-858.]), Geremia et al. (1992[Geremia, S., Randaccio, L., Mestroni, G. & Milani, B. (1992). J. Chem. Soc. Dalton Trans. pp. 2117-2118.]), Hinamoto et al. (1972[Hinamoto, M., Ooi, S. & Kuroya, H. (1972). J. Chem. Soc. Chem. Commun. pp. 356-357.]), Maeda et al. (1986[Maeda, S., Nishida, Y., Okawa, H. & Kida, S. (1986). Bull. Chem. Soc. Jpn, 59, 2013-2014.]), Milani et al. (1997[Milani, B., Anzilutti, A., Vicentini, L., Sessanta o Santi, A., Zangrando, E., Geremia, S. & Mestroni, G. (1997). Organometallics, 16, 5064-5075.]), Stoccoro et al. (2002[Stoccoro, S., Alesso, G., Cinellu, M. A., Minghetti, G., Zucca, A., Bastero, A., Claver, C. & Manassero, M. (2002). J. Organomet. Chem. 664, 77-84.]), Wehman et al. (1994[Wehman, P., Dol, G. C., Moorman, E. R., Kamer, P. C. J., van Leeuwen, P. W. N. M., Fraanje, J. & Goubitz, K. (1994). Organometallics, 13, 4856-4869.]) and Yue et al. (2008[Yue, C.-Y., Jiang, F.-L., Yuan, D.-Q., Chen, L., Wu, M.-Y. & Hong, M.-C. (2008). Chin. J. Struct. Chem. 27, 467-470.]).

[Scheme 1]

Experimental

Crystal data
  • [Pd(C8H6N4)2](BF4)2·C2H3N

  • Mr = 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[Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.]) Tmin = 0.311, Tmax = 0.478

  • 31076 measured reflections

  • 4246 independent reflections

  • 4006 reflections with I > 2σ(I)

  • Rint = 0.031

Refinement
  • R[F2 > 2σ(F2)] = 0.030

  • wR(F2) = 0.081

  • S = 1.03

  • 4246 reflections

  • 347 parameters

  • H-atom parameters constrained

  • Δρmax = 1.07 e Å−3

  • Δρmin = −0.75 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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⋯F2iv 0.95 2.44 3.240 (3) 142
C8—H8⋯F3v 0.95 2.45 3.270 (4) 145
C13—H13⋯F6vi 0.95 2.37 2.982 (3) 122
C15—H15⋯F8iv 0.95 2.52 3.408 (4) 155
C18—H18B⋯F5vii 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[Bruker (2003). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2003[Bruker (2003). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and Materials Studio (Accelrys, 2002[Accelrys (2002). Materials Studio. Accelrys Inc., San Diego, California, USA.]); software used to prepare material for publication: UdMX (Maris, 2004[Maris, T. (2004). UdMX. Université de Montréal, Montréal, Québec, Canada.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


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 PdII 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 PdII(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 PdII(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 PdII 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 PdII 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.

Refinement top

All H-atoms were placed in calculated positions (C—H 0.95–0.98 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2Ueq(C) for hydrogen atoms bonded to sp2-hybridized carbon atoms and 1.5Ueq(C) for hydrogen atoms bonded to sp3-hybridized carbon atoms.

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
[Figure 1] 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.
[Figure 2] Fig. 2. View along the a-axis of a chain of cationic complexes, with C—H···N interactions shown as broken lines.
[Figure 3] 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,N1')palladium(II) bis(tetrafluoroborate) acetonitrile monosolvate top
Crystal data top
[Pd(C8H6N4)2](BF4)2·C2H3NF(000) = 2512
Mr = 637.41Dx = 1.840 Mg m3
Monoclinic, C2/cCu Kα radiation, λ = 1.54178 Å
Hall symbol: -C 2ycCell parameters from 20829 reflections
a = 18.0686 (4) Åθ = 3.6–68.8°
b = 18.1126 (4) ŵ = 7.38 mm1
c = 14.8351 (3) ÅT = 200 K
β = 108.613 (1)°Block, yellow
V = 4601.13 (17) Å30.20 × 0.11 × 0.10 mm
Z = 8
Data collection top
Bruker SMART 6000
diffractometer
4246 independent reflections
Radiation source: Rotating anode4006 reflections with I > 2σ(I)
Montel 200 optics monochromatorRint = 0.031
Detector resolution: 5.5 pixels mm-1θmax = 68.9°, θmin = 3.6°
ω scansh = 2121
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
k = 2021
Tmin = 0.311, Tmax = 0.478l = 1717
31076 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.081 w = 1/[σ2(Fo2) + (0.0458P)2 + 11.6117P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.002
4246 reflectionsΔρmax = 1.07 e Å3
347 parametersΔρmin = 0.75 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.000355 (19)
Crystal data top
[Pd(C8H6N4)2](BF4)2·C2H3NV = 4601.13 (17) Å3
Mr = 637.41Z = 8
Monoclinic, C2/cCu Kα radiation
a = 18.0686 (4) ŵ = 7.38 mm1
b = 18.1126 (4) ÅT = 200 K
c = 14.8351 (3) Å0.20 × 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)
Tmin = 0.311, Tmax = 0.478Rint = 0.031
31076 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.081H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0458P)2 + 11.6117P]
where P = (Fo2 + 2Fc2)/3
4246 reflectionsΔρmax = 1.07 e Å3
347 parametersΔρmin = 0.75 e Å3
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
xyzUiso*/Ueq
Pd10.50000.336135 (12)0.25000.02227 (10)
N10.44850 (12)0.40551 (11)0.13874 (15)0.0244 (4)
C10.46387 (15)0.47710 (14)0.13047 (19)0.0294 (5)
H10.50060.50180.18210.035*
C20.42721 (17)0.51534 (15)0.0482 (2)0.0359 (6)
H20.43740.56620.04220.043*
C30.37529 (18)0.47724 (17)0.0249 (2)0.0408 (7)
H30.34760.50320.08120.049*
N30.36210 (15)0.40471 (13)0.01994 (16)0.0369 (5)
C40.39986 (14)0.37213 (14)0.06120 (17)0.0277 (5)
C50.38836 (14)0.29190 (14)0.07200 (17)0.0269 (5)
N50.42993 (12)0.26406 (11)0.15719 (15)0.0271 (4)
C60.41328 (16)0.19506 (14)0.1769 (2)0.0364 (6)
H60.43840.17490.23810.044*
C70.35997 (17)0.15308 (15)0.1090 (2)0.0399 (7)
H70.34770.10410.12230.048*
C80.32526 (15)0.18455 (16)0.0217 (2)0.0367 (6)
H80.29090.15550.02720.044*
N80.33807 (13)0.25488 (13)0.00285 (16)0.0340 (5)
Pd20.00000.339164 (12)0.25000.02379 (10)
N90.06638 (12)0.25370 (11)0.23195 (15)0.0278 (4)
C90.13999 (16)0.25769 (15)0.2297 (2)0.0349 (6)
H90.16210.30450.22480.042*
C100.18357 (18)0.19496 (17)0.2344 (2)0.0429 (7)
H100.23560.19740.23270.051*
C110.14925 (18)0.12859 (16)0.2417 (2)0.0433 (7)
H110.17790.08440.24280.052*
N110.07683 (15)0.12380 (12)0.24733 (18)0.0382 (5)
C120.03914 (15)0.18649 (14)0.24370 (18)0.0287 (5)
N120.04299 (12)0.42452 (11)0.19429 (15)0.0257 (4)
C130.07712 (16)0.42029 (14)0.12669 (19)0.0314 (6)
H130.08960.37330.10700.038*
C140.09431 (17)0.48312 (16)0.0854 (2)0.0364 (6)
H140.11840.48060.03720.044*
C150.07533 (17)0.54960 (16)0.1164 (2)0.0393 (6)
H150.08900.59370.09090.047*
N150.03809 (14)0.55468 (12)0.18145 (17)0.0349 (5)
C160.02226 (14)0.49198 (13)0.21627 (18)0.0274 (5)
B10.2913 (2)0.4231 (2)0.2178 (3)0.0447 (9)
F10.27658 (12)0.46150 (13)0.13349 (14)0.0621 (5)
F20.36425 (10)0.43957 (11)0.27788 (13)0.0496 (5)
F30.28788 (19)0.34813 (14)0.19523 (19)0.0962 (10)
F40.23745 (14)0.4387 (3)0.26137 (17)0.1125 (13)
B20.0691 (2)0.24786 (18)0.5158 (2)0.0373 (7)
F50.09817 (13)0.24491 (16)0.44108 (15)0.0749 (7)
F60.00661 (12)0.29637 (11)0.49624 (17)0.0644 (6)
F70.04445 (17)0.17898 (12)0.5299 (2)0.0885 (9)
F80.12677 (16)0.27183 (14)0.59487 (17)0.0869 (8)
N160.35521 (18)0.04534 (18)0.5904 (2)0.0563 (8)
C170.3079 (2)0.08800 (18)0.5644 (2)0.0446 (7)
C180.2469 (2)0.1432 (2)0.5312 (4)0.0771 (13)
H18A0.20980.12740.47030.116*
H18B0.27030.19050.52290.116*
H18C0.21950.14890.57810.116*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.02316 (15)0.01678 (15)0.02304 (15)0.0000.00197 (10)0.000
N10.0241 (10)0.0227 (10)0.0262 (10)0.0030 (8)0.0075 (8)0.0017 (8)
C10.0293 (12)0.0249 (13)0.0352 (14)0.0010 (10)0.0118 (11)0.0013 (10)
C20.0417 (15)0.0280 (14)0.0422 (15)0.0048 (11)0.0193 (13)0.0103 (11)
C30.0503 (17)0.0391 (16)0.0316 (14)0.0103 (13)0.0112 (12)0.0129 (12)
N30.0430 (13)0.0380 (13)0.0259 (11)0.0062 (10)0.0055 (10)0.0034 (9)
C40.0266 (12)0.0297 (13)0.0269 (12)0.0028 (10)0.0086 (10)0.0010 (10)
C50.0244 (12)0.0282 (13)0.0277 (12)0.0023 (10)0.0076 (10)0.0030 (10)
N50.0262 (10)0.0215 (10)0.0294 (10)0.0004 (8)0.0030 (8)0.0033 (8)
C60.0362 (14)0.0235 (13)0.0415 (15)0.0010 (11)0.0014 (12)0.0010 (11)
C70.0330 (15)0.0244 (13)0.0557 (18)0.0030 (11)0.0050 (13)0.0044 (12)
C80.0276 (13)0.0324 (14)0.0448 (16)0.0021 (11)0.0041 (11)0.0160 (12)
N80.0284 (11)0.0375 (13)0.0320 (11)0.0020 (9)0.0039 (9)0.0083 (10)
Pd20.02831 (16)0.01530 (15)0.03000 (16)0.0000.01245 (11)0.000
N90.0341 (11)0.0218 (10)0.0297 (10)0.0020 (9)0.0133 (9)0.0000 (8)
C90.0360 (14)0.0297 (14)0.0423 (15)0.0015 (11)0.0169 (12)0.0030 (11)
C100.0393 (16)0.0415 (17)0.0533 (18)0.0082 (13)0.0224 (14)0.0001 (14)
C110.0466 (17)0.0298 (15)0.0564 (18)0.0111 (12)0.0204 (14)0.0024 (13)
N110.0448 (13)0.0221 (11)0.0487 (14)0.0042 (10)0.0161 (11)0.0022 (10)
C120.0351 (14)0.0219 (12)0.0296 (13)0.0001 (10)0.0109 (10)0.0011 (10)
N120.0276 (11)0.0205 (10)0.0288 (10)0.0008 (8)0.0084 (9)0.0008 (8)
C130.0348 (14)0.0276 (13)0.0332 (14)0.0006 (10)0.0129 (11)0.0015 (10)
C140.0379 (14)0.0366 (15)0.0375 (14)0.0008 (12)0.0161 (12)0.0067 (12)
C150.0422 (15)0.0306 (14)0.0464 (16)0.0036 (12)0.0161 (13)0.0106 (12)
N150.0413 (13)0.0222 (11)0.0414 (13)0.0026 (9)0.0136 (10)0.0031 (9)
C160.0291 (12)0.0197 (12)0.0303 (12)0.0006 (10)0.0049 (10)0.0003 (10)
B10.0313 (17)0.070 (2)0.0338 (17)0.0178 (16)0.0122 (14)0.0100 (16)
F10.0564 (12)0.0816 (15)0.0497 (11)0.0054 (11)0.0191 (9)0.0139 (10)
F20.0344 (9)0.0654 (12)0.0463 (10)0.0109 (8)0.0090 (8)0.0200 (9)
F30.128 (2)0.0692 (16)0.0691 (16)0.0514 (16)0.0002 (15)0.0088 (12)
F40.0420 (12)0.251 (4)0.0502 (13)0.0151 (18)0.0228 (11)0.0055 (18)
B20.0413 (17)0.0302 (16)0.0408 (17)0.0011 (13)0.0135 (14)0.0002 (13)
F50.0584 (13)0.119 (2)0.0545 (12)0.0111 (13)0.0274 (10)0.0160 (13)
F60.0525 (12)0.0496 (12)0.0871 (15)0.0149 (9)0.0167 (11)0.0021 (11)
F70.105 (2)0.0334 (10)0.157 (3)0.0061 (12)0.084 (2)0.0008 (14)
F80.0868 (17)0.0793 (17)0.0655 (14)0.0202 (13)0.0165 (12)0.0219 (12)
N160.0577 (18)0.070 (2)0.0405 (15)0.0225 (16)0.0146 (13)0.0056 (14)
C170.0408 (17)0.052 (2)0.0403 (17)0.0031 (14)0.0113 (14)0.0006 (13)
C180.047 (2)0.060 (2)0.117 (4)0.0100 (19)0.017 (2)0.030 (3)
Geometric parameters (Å, º) top
Pd1—N5i2.022 (2)C9—H90.9500
Pd1—N52.022 (2)C10—C111.372 (5)
Pd1—N12.047 (2)C10—H100.9500
Pd1—N1i2.047 (2)C11—N111.340 (4)
N1—C11.340 (3)C11—H110.9500
N1—C41.348 (3)N11—C121.316 (3)
C1—C21.375 (4)C12—C12ii1.485 (5)
C1—H10.9500N12—C131.337 (3)
C2—C31.372 (4)N12—C161.348 (3)
C2—H20.9500C13—C141.374 (4)
C3—N31.341 (4)C13—H130.9500
C3—H30.9500C14—C151.371 (4)
N3—C41.318 (3)C14—H140.9500
C4—C51.484 (4)C15—N151.345 (4)
C5—N81.316 (3)C15—H150.9500
C5—N51.345 (3)N15—C161.316 (3)
N5—C61.339 (3)C16—C16ii1.471 (5)
C6—C71.378 (4)B1—F41.357 (4)
C6—H60.9500B1—F21.368 (4)
C7—C81.369 (4)B1—F11.381 (4)
C7—H70.9500B1—F31.396 (5)
C8—N81.340 (4)B2—F71.363 (4)
C8—H80.9500B2—F81.368 (4)
Pd2—N122.021 (2)B2—F51.371 (4)
Pd2—N12ii2.021 (2)B2—F61.386 (4)
Pd2—N92.028 (2)N16—C171.125 (4)
Pd2—N9ii2.028 (2)C17—C181.452 (5)
N9—C91.343 (3)C18—H18a0.9800
N9—C121.345 (3)C18—H18b0.9800
C9—C101.372 (4)C18—H18c0.9800
N5i—PD1—N599.59 (11)N9—C9—H9119.6
N5i—PD1—N1165.94 (8)C10—C9—H9119.6
N5—PD1—N179.78 (8)C9—C10—C11117.6 (3)
N5i—PD1—N1i79.78 (8)C9—C10—H10121.2
N5—PD1—N1i165.94 (8)C11—C10—H10121.2
N1—PD1—N1i104.24 (11)N11—C11—C10122.4 (3)
C1—N1—C4117.0 (2)N11—C11—H11118.8
C1—N1—PD1127.87 (17)C10—C11—H11118.8
C4—N1—PD1114.69 (16)C12—N11—C11116.4 (2)
N1—C1—C2120.9 (2)N11—C12—N9125.4 (2)
N1—C1—H1119.6N11—C12—C12ii119.74 (16)
C2—C1—H1119.6N9—C12—C12ii114.78 (14)
C3—C2—C1117.5 (3)C13—N12—C16117.6 (2)
C3—C2—H2121.2C13—N12—PD2126.33 (17)
C1—C2—H2121.2C16—N12—PD2114.94 (17)
N3—C3—C2122.5 (3)N12—C13—C14120.7 (2)
N3—C3—H3118.7N12—C13—H13119.6
C2—C3—H3118.7C14—C13—H13119.6
C4—N3—C3116.1 (2)C15—C14—C13117.5 (3)
N3—C4—N1125.8 (2)C15—C14—H14121.2
N3—C4—C5119.2 (2)C13—C14—H14121.2
N1—C4—C5115.0 (2)N15—C15—C14122.5 (2)
N8—C5—N5125.5 (2)N15—C15—H15118.8
N8—C5—C4120.0 (2)C14—C15—H15118.8
N5—C5—C4114.4 (2)C16—N15—C15116.3 (2)
C6—N5—C5117.2 (2)N15—C16—N12125.1 (2)
C6—N5—PD1126.12 (18)N15—C16—C16ii120.10 (15)
C5—N5—PD1115.98 (16)N12—C16—C16ii114.78 (14)
N5—C6—C7120.6 (3)F4—B1—F2109.5 (3)
N5—C6—H6119.7F4—B1—F1111.5 (3)
C7—C6—H6119.7F2—B1—F1110.3 (3)
C8—C7—C6117.6 (3)F4—B1—F3109.5 (3)
C8—C7—H7121.2F2—B1—F3109.1 (3)
C6—C7—H7121.2F1—B1—F3106.9 (3)
N8—C8—C7122.4 (2)F7—B2—F8110.8 (3)
N8—C8—H8118.8F7—B2—F5108.5 (3)
C7—C8—H8118.8F8—B2—F5108.8 (3)
C5—N8—C8116.3 (2)F7—B2—F6109.2 (3)
N12—PD2—N12ii80.22 (12)F8—B2—F6109.0 (3)
N12—PD2—N9102.08 (8)F5—B2—F6110.6 (3)
N12ii—PD2—N9163.44 (9)N16—C17—C18179.7 (4)
N12—PD2—N9ii163.44 (9)C17—C18—H18A109.5
N12ii—PD2—N9ii102.08 (8)C17—C18—H18B109.5
N9—PD2—N9ii80.47 (12)H18A—C18—H18B109.5
C9—N9—C12117.3 (2)C17—C18—H18C109.5
C9—N9—PD2126.46 (18)H18A—C18—H18C109.5
C12—N9—PD2114.67 (17)H18B—C18—H18C109.5
N9—C9—C10120.7 (3)
Symmetry codes: (i) x+1, y, z+1/2; (ii) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···N11iii0.952.623.460 (4)148
C6—H6···N15iv0.952.453.237 (4)140
C14—H14···N16v0.952.403.228 (4)146
C2—H2···F7v0.952.383.282 (3)159
C3—H3···F2vi0.952.443.240 (3)142
C8—H8···F3vii0.952.453.270 (4)145
C13—H13···F6ii0.952.372.982 (3)122
C15—H15···F8vi0.952.523.408 (4)155
C18—H18B···F5viii0.982.553.373 (5)142
Symmetry codes: (ii) x, y, z+1/2; (iii) x+1/2, y+1/2, z; (iv) x+1/2, y1/2, z+1/2; (v) x+1/2, y+1/2, z+1/2; (vi) x, y+1, z1/2; (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
Mr637.41
Crystal system, space groupMonoclinic, C2/c
Temperature (K)200
a, b, c (Å)18.0686 (4), 18.1126 (4), 14.8351 (3)
β (°) 108.613 (1)
V3)4601.13 (17)
Z8
Radiation typeCu Kα
µ (mm1)7.38
Crystal size (mm)0.20 × 0.11 × 0.10
Data collection
DiffractometerBruker SMART 6000
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2004)
Tmin, Tmax0.311, 0.478
No. of measured, independent and
observed [I > 2σ(I)] reflections
31076, 4246, 4006
Rint0.031
(sin θ/λ)max1)0.605
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.081, 1.03
No. of reflections4246
No. of parameters347
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0458P)2 + 11.6117P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
C1—H1···N11i0.952.623.460 (4)147.6
C6—H6···N15ii0.952.453.237 (4)139.7
C14—H14···N16iii0.952.403.228 (4)145.5
C2—H2···F7iii0.952.383.282 (3)159.2
C3—H3···F2iv0.952.443.240 (3)142.3
C8—H8···F3v0.952.453.270 (4)145
C13—H13···F6vi0.952.372.982 (3)121.9
C15—H15···F8iv0.952.523.408 (4)154.8
C18—H18B···F5vii0.982.553.373 (5)141.8
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x+1/2, y1/2, z+1/2; (iii) x+1/2, y+1/2, z+1/2; (iv) x, y+1, z1/2; (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.

References

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