supplementary materials
Tetrakis(pyridine-![[kappa]](/logos/entities/kappa_rmgif.gif)
N)palladium(II) bis(tetrafluoridoborate)
A solution of 0.070 g (0.308 mmol) [PdCl2(CH3CN)2] was dissolved in a
mixture of CH2Cl2 (10 ml) and methanol (10 ml). About 0.1230 g, (0.625 mmol) of pyridine was added to a solution. Then, a solution of 0.070 g, (0.625 mmol) of NaBF4 in methanol (2 ml) was added dropwise with vigorous stirring.
After 2 h, stirring was stopped, and the product precipitated as yellow solid,
was filtered, washed with diethylether, and dried under vacuum. Crystals were
obtained by evaporation of acetonitrile solution. Yield: 0.15 g, (81%) -
C20H20B2F8N4Pd (596.42). (%): C, 40.27; H, 3.38; N, 9.39; found: C,
40.26; H, 3.37; N, 9.39. Conductivity (Ω-1 cm2 mol-1, 1.03 x
10-3 M in acetonitrile): 279. IR(KBr, cm-1): ν(C=C)py;
ν(C=N)py 1603, δ(C=C)py; δ(C=N)py 1448, ν(B—F) 1068,
δ(C—H)oop 769, 695. IR (polyethylene, cm-1): ν(Pd—N)as(py) 472. 1H
NMR (250 MHz, [D3]-acetonitrile solution) δ = 7.58–7.43 (m, 8H, py),
8.85–8.72 (m, 8H, py), 8.04–7.90 (m, 4H, py). 13C NMR (63 MHz,
[D3]-acetonitrile solution) δ = 128–126(py), 142–140(py), 154–152(py).
Data collection: CAD-4-PC (Kretschmar, 1996); cell refinement: CAD-4-PC; data reduction: WinGX-PC (Farrugia, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP (Brueggemann & Schmid, 1990); software used to prepare material for publication: PLATON (Spek, 2003).
Tetrakis(pyridine-
κN)palladium(II) bis(tetrafluoridoborate)
top
Crystal data top
| [Pd(C5H5N)4](BF4)2 | F(000) = 1184 |
| Mr = 596.42 | Dx = 1.643 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 25 reflections |
| a = 15.640 (7) Å | θ = 9–18° |
| b = 10.886 (7) Å | µ = 0.85 mm−1 |
| c = 15.711 (7) Å | T = 295 K |
| β = 115.63 (3)° | Prism, yellow |
| V = 2412 (2) Å3 | 0.18 × 0.15 × 0.11 mm |
| Z = 4 | |
Data collection top
Enraf–Nonius CAD-4
diffractometer | Rint = 0.064 |
| Radiation source: fine-focus sealed tube | θmax = 30.0°, θmin = 2.4° |
| graphite | h = −21→21 |
| ω/2θ' scans | k = −14→15 |
| 6864 measured reflections | l = −22→12 |
| 3521 independent reflections | 3 standard reflections every 120 min |
| 1872 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.154 | H atoms treated by a mixture of independent and constrained refinement |
| S = 0.97 | w = 1/[σ2(Fo2) + (0.0885P)2]
where P = (Fo2 + 2Fc2)/3 |
| 3521 reflections | (Δ/σ)max = 0.001 |
| 217 parameters | Δρmax = 0.96 e Å−3 |
| 20 restraints | Δρmin = −0.52 e Å−3 |
Crystal data top
| [Pd(C5H5N)4](BF4)2 | V = 2412 (2) Å3 |
| Mr = 596.42 | Z = 4 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 15.640 (7) Å | µ = 0.85 mm−1 |
| b = 10.886 (7) Å | T = 295 K |
| c = 15.711 (7) Å | 0.18 × 0.15 × 0.11 mm |
| β = 115.63 (3)° | |
Data collection top
Enraf–Nonius CAD-4
diffractometer | Rint = 0.064 |
| 6864 measured reflections | θmax = 30.0° |
| 3521 independent reflections | 3 standard reflections every 120 min |
| 1872 reflections with I > 2σ(I) | intensity decay: none |
Refinement top
| R[F2 > 2σ(F2)] = 0.046 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.154 | Δρmax = 0.96 e Å−3 |
| S = 0.97 | Δρmin = −0.52 e Å−3 |
| 3521 reflections | Absolute structure: ? |
| 217 parameters | Flack parameter: ? |
| 20 restraints | Rogers parameter: ? |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top| | x | y | z | Uiso*/Ueq | Occ. (<1) |
| Pd | 0.2500 | 0.2500 | 0.5000 | 0.04425 (17) | |
| N1 | 0.3643 (3) | 0.3627 (3) | 0.5562 (3) | 0.0524 (10) | |
| N2 | 0.2482 (3) | 0.2718 (3) | 0.3707 (3) | 0.0515 (10) | |
| C1 | 0.3518 (4) | 0.4830 (5) | 0.5591 (5) | 0.0706 (16) | |
| H1 | 0.281 (4) | 0.507 (6) | 0.540 (4) | 0.085* | |
| C2 | 0.4256 (5) | 0.5640 (5) | 0.5942 (5) | 0.090 (2) | |
| H2 | 0.4145 | 0.6479 | 0.5939 | 0.107* | |
| C3 | 0.5147 (5) | 0.5201 (7) | 0.6291 (6) | 0.107 (3) | |
| H3 | 0.5662 | 0.5730 | 0.6560 | 0.128* | |
| C4 | 0.5284 (5) | 0.3985 (8) | 0.6246 (7) | 0.119 (3) | |
| H4 | 0.5897 | 0.3678 | 0.6460 | 0.142* | |
| C5 | 0.4529 (4) | 0.3202 (5) | 0.5888 (5) | 0.081 (2) | |
| H5 | 0.466 (6) | 0.234 (5) | 0.602 (5) | 0.097* | |
| C6 | 0.3069 (5) | 0.2063 (5) | 0.3457 (4) | 0.0618 (14) | |
| H6 | 0.339 (4) | 0.159 (5) | 0.392 (4) | 0.074* | |
| C7 | 0.3078 (5) | 0.2172 (6) | 0.2601 (5) | 0.0747 (19) | |
| H7 | 0.359 (4) | 0.175 (6) | 0.251 (4) | 0.090* | |
| C8 | 0.2451 (5) | 0.2970 (7) | 0.1942 (5) | 0.0736 (17) | |
| H8 | 0.246 (5) | 0.302 (6) | 0.139 (5) | 0.088* | |
| C9 | 0.1841 (5) | 0.3641 (5) | 0.2183 (4) | 0.0753 (17) | |
| H9 | 0.130 (4) | 0.420 (6) | 0.181 (4) | 0.090* | |
| C10 | 0.1872 (5) | 0.3496 (5) | 0.3071 (5) | 0.0682 (15) | |
| H10 | 0.139 (4) | 0.375 (5) | 0.328 (4) | 0.082* | |
| B | 0.4188 (3) | 0.0789 (4) | 0.0683 (3) | 0.0520 (13) | |
| F1 | 0.3608 (6) | 0.1363 (7) | 0.1009 (6) | 0.087 (4) | 0.50 |
| F1' | 0.3416 (6) | 0.1358 (9) | 0.0789 (9) | 0.126 (6) | 0.50 |
| F2 | 0.4665 (5) | 0.1591 (5) | 0.0370 (5) | 0.074 (2) | 0.50 |
| F2' | 0.4267 (10) | 0.1392 (11) | −0.0085 (7) | 0.209 (9) | 0.50 |
| F3 | 0.3647 (5) | −0.0047 (5) | −0.0055 (5) | 0.078 (2) | 0.50 |
| F3' | 0.3989 (8) | −0.0435 (5) | 0.0473 (11) | 0.171 (8) | 0.50 |
| F4 | 0.4867 (5) | 0.0047 (7) | 0.1429 (4) | 0.095 (3) | 0.50 |
| F4' | 0.5011 (6) | 0.0967 (14) | 0.1496 (6) | 0.206 (8) | 0.50 |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Pd | 0.0444 (3) | 0.0326 (2) | 0.0633 (3) | −0.0010 (3) | 0.0304 (2) | −0.0053 (3) |
| N1 | 0.047 (2) | 0.0369 (19) | 0.075 (3) | 0.0015 (16) | 0.028 (2) | 0.0004 (18) |
| N2 | 0.056 (2) | 0.037 (2) | 0.069 (2) | −0.0016 (15) | 0.034 (2) | −0.0049 (16) |
| C1 | 0.064 (3) | 0.037 (2) | 0.107 (5) | 0.000 (2) | 0.033 (3) | 0.002 (3) |
| C2 | 0.089 (5) | 0.036 (3) | 0.135 (6) | −0.014 (3) | 0.041 (5) | −0.014 (4) |
| C3 | 0.070 (4) | 0.070 (4) | 0.149 (7) | −0.031 (4) | 0.018 (4) | 0.019 (5) |
| C4 | 0.046 (3) | 0.093 (6) | 0.184 (9) | 0.002 (4) | 0.020 (4) | 0.028 (6) |
| C5 | 0.053 (3) | 0.049 (3) | 0.131 (6) | 0.001 (2) | 0.032 (4) | 0.011 (3) |
| C6 | 0.073 (4) | 0.048 (2) | 0.082 (4) | 0.001 (2) | 0.050 (3) | −0.002 (3) |
| C7 | 0.087 (4) | 0.068 (4) | 0.094 (5) | −0.013 (3) | 0.063 (4) | −0.018 (3) |
| C8 | 0.091 (5) | 0.069 (3) | 0.071 (4) | −0.018 (3) | 0.044 (4) | −0.011 (3) |
| C9 | 0.094 (4) | 0.055 (3) | 0.069 (4) | −0.002 (3) | 0.027 (3) | 0.001 (3) |
| C10 | 0.084 (4) | 0.045 (3) | 0.084 (4) | 0.005 (3) | 0.044 (3) | 0.001 (3) |
| B | 0.057 (3) | 0.050 (3) | 0.053 (3) | −0.009 (3) | 0.027 (3) | 0.000 (2) |
| F1 | 0.106 (7) | 0.068 (7) | 0.130 (8) | 0.010 (6) | 0.092 (7) | −0.010 (6) |
| F1' | 0.087 (7) | 0.124 (12) | 0.189 (13) | −0.034 (7) | 0.079 (8) | −0.083 (10) |
| F2 | 0.083 (5) | 0.050 (4) | 0.123 (7) | −0.013 (3) | 0.076 (5) | 0.007 (4) |
| F2' | 0.31 (2) | 0.232 (19) | 0.121 (11) | 0.107 (17) | 0.131 (13) | 0.071 (11) |
| F3 | 0.075 (5) | 0.051 (4) | 0.096 (5) | −0.010 (4) | 0.026 (4) | −0.032 (4) |
| F3' | 0.166 (12) | 0.038 (4) | 0.39 (2) | −0.003 (6) | 0.201 (15) | −0.006 (9) |
| F4 | 0.097 (6) | 0.101 (7) | 0.062 (5) | 0.015 (5) | 0.013 (4) | 0.020 (5) |
| F4' | 0.139 (11) | 0.25 (2) | 0.138 (11) | 0.006 (13) | −0.023 (8) | −0.043 (12) |
Geometric parameters (Å, °) top
| Pd—N1i | 2.028 (4) | C6—C7 | 1.357 (9) |
| Pd—N1 | 2.028 (4) | C6—H6 | 0.85 (6) |
| Pd—N2i | 2.033 (5) | C7—C8 | 1.382 (11) |
| Pd—N2 | 2.033 (5) | C7—H7 | 0.99 (6) |
| N1—C1 | 1.328 (6) | C8—C9 | 1.379 (9) |
| N1—C5 | 1.335 (7) | C8—H8 | 0.88 (7) |
| N2—C10 | 1.342 (7) | C9—C10 | 1.384 (9) |
| N2—C6 | 1.348 (7) | C9—H9 | 1.00 (6) |
| C1—C2 | 1.365 (8) | C10—H10 | 0.99 (6) |
| C1—H1 | 1.05 (6) | B—F1 | 1.370 (6) |
| C2—C3 | 1.344 (10) | B—F2 | 1.371 (5) |
| C2—H2 | 0.9300 | B—F3' | 1.375 (6) |
| C3—C4 | 1.348 (11) | B—F4' | 1.380 (7) |
| C3—H3 | 0.9300 | B—F2' | 1.425 (7) |
| C4—C5 | 1.365 (9) | B—F3 | 1.428 (6) |
| C4—H4 | 0.9300 | B—F1' | 1.430 (7) |
| C5—H5 | 0.96 (6) | B—F4 | 1.441 (6) |
| | | |
| N1i—Pd—N1 | 180.00 (17) | N2—C6—C7 | 122.9 (6) |
| N1i—Pd—N2i | 89.63 (17) | N2—C6—H6 | 108 (4) |
| N1—Pd—N2i | 90.37 (17) | C7—C6—H6 | 129 (4) |
| N1i—Pd—N2 | 90.37 (17) | C6—C7—C8 | 119.3 (6) |
| N1—Pd—N2 | 89.63 (17) | C6—C7—H7 | 117 (4) |
| N2i—Pd—N2 | 180.0 | C8—C7—H7 | 123 (4) |
| C1—N1—C5 | 118.2 (5) | C9—C8—C7 | 118.6 (6) |
| C1—N1—Pd | 119.8 (4) | C9—C8—H8 | 123 (5) |
| C5—N1—Pd | 122.0 (4) | C7—C8—H8 | 118 (5) |
| C10—N2—C6 | 118.1 (5) | C8—C9—C10 | 119.3 (6) |
| C10—N2—Pd | 121.1 (4) | C8—C9—H9 | 132 (4) |
| C6—N2—Pd | 120.8 (4) | C10—C9—H9 | 108 (4) |
| N1—C1—C2 | 122.7 (6) | N2—C10—C9 | 121.8 (6) |
| N1—C1—H1 | 113 (4) | N2—C10—H10 | 109 (3) |
| C2—C1—H1 | 124 (4) | C9—C10—H10 | 128 (3) |
| C3—C2—C1 | 118.8 (6) | F1—B—F2 | 113.2 (4) |
| C3—C2—H2 | 120.6 | F1—B—F3 | 109.8 (4) |
| C1—C2—H2 | 120.6 | F2—B—F3 | 109.7 (4) |
| C2—C3—C4 | 119.2 (6) | F1—B—F4 | 109.0 (4) |
| C2—C3—H3 | 120.4 | F2—B—F4 | 109.0 (4) |
| C4—C3—H3 | 120.4 | F3—B—F4 | 105.8 (4) |
| C3—C4—C5 | 120.4 (7) | F3'—B—F4' | 112.4 (4) |
| C3—C4—H4 | 119.8 | F3'—B—F2' | 109.7 (4) |
| C5—C4—H4 | 119.8 | F3'—B—F1' | 109.4 (4) |
| N1—C5—C4 | 120.7 (6) | F4'—B—F2' | 109.4 (4) |
| N1—C5—H5 | 121 (5) | F4'—B—F1' | 109.1 (4) |
| C4—C5—H5 | 117 (5) | F2'—B—F1' | 106.6 (4) |
| Symmetry codes: (i) −x+1/2, −y+1/2, −z+1. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C4—H4···Cg1ii | 0.93 | 2.97 | 3.800 (10) | 150 |
| Symmetry codes: (ii) x+1/2, −y+1/2, z−1/2. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C4—H4···Cg1i | 0.93 | 2.97 | 3.800 (10) | 150 |
| Symmetry codes: (i) x+1/2, −y+1/2, z−1/2. |
Braga, D., Grepioni, F. & Desiraju, G. R. (1998). Chem. Rev. 98, 1375–1406.
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Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Holzbock, J., Sawodny, W. & Thewalt, U. (2000). Z. Anorg. Allg. Chem. 626, 2563–2568.
Kretschmar, M. (1996). CAD-4-PC. Version 2.0. PC version of CAD-4 Software Version 5.0. University of Tübingen, Germany.
Lehn, J. M. (1995). Supramolecular Chemistry: Concepts and Perspectives. New York: VCH.
Liqing et al. (2005).
Lutz, M., Spek, A. L., Kleij, A. W. & van Koten, G. (2000). Crystallographic Cambridge Data Centre, CCDC 147242. Private communication.
Ma, L., Smith, R. C. & Protasiewicz, J. D. (2005). Inorg. Chim. Acta, 358, 3478–3482.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
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F interactions (involving disordered BF4- anions) [range 2.988 (12)-3.431 (10) Å], together with C-H![[pi]](/logos/entities/pi_rmgif.gif)
(pyridine) interactions. The F atoms are disordered equally over two positions.![[Figure 1]](./gg2027fig1thm.gif)
The design of supramolecular coordination compounds by self-assembly is a developing research area (Lehn, 1995, Braga et al., 1998). Four-coordinate PdII complexes with square-planar geometry and four pyridine ligands, in particular, is a potentially useful building block for producing an array of interesting molecular architectures by means of C—H···π-ring interactions, thanks to the mobility of pyridine planes. It is for that reason that we have tried to prepare the title compound (I) to be able to compare the results with the structure of the same compound with acetone solvate (Lutz et al., 2000).
Normally, the tetrakis(pyridine-N)palladium(II) ion has a square-planar coordination, with the anion occupying the apical positions of an octahedron. Pd···X lengths are 4.299 (5) Å in (I) (X = B); 4.028 (7) Å (X = B, Lutz et al., 2000); 4.4759 (11) Å in the orthorhombic phase and 4.100 (2) Å in the triclinic phase (X = I, Tebbe et al., 1996); 3.112 (2) Å (X = O, Liqing et al. 2005) and 3.079 (4) or 3.031 (3) Å (X = F, Holzbock et al., 2000). The packing will come defined by the solvate presence and the size of the anion which will alter, in addition, the dihedral angle between the pyridine planes. This angle is equal to 89.53 (19)° in (I), 89.62° in the Liqing structure, a range of 85.73 to 81.13° in the Holzbock structure, 85.33° in orthorhombic phase and 83.37° in triclinic phase of the Tebbe structure and 78.25 to 58.13° in the Lutz structure. The C—H···π-(ring) interaction only takes place in (I) and the triclinic phase of the Tebbe structure producing a one-dimensional-structure. The data for C4—H4···N2 (pyridine ring) (symmetry = 1/2 + x, 1/2 - y, 1/2 + z) are H-centroid distance 2.97 Å, γ = 20.28°. This fact suggests that the solvate absence and a dihedral angle between the pyridine planes next to 90° facilitate this interaction.