Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807034411/gg2027sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807034411/gg2027Isup2.hkl |
CCDC reference: 657593
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).
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.
For related literature, see: Braga et al. (1998); Holzbock et al. (2000); Lehn (1995); Liqing et al. (2005); Lutz et al. (2000); Ma et al. (2005); Tebbe et al. (1996).
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).
[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 |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.064 |
Radiation source: fine-focus sealed tube | θmax = 30.0°, θmin = 2.4° |
Graphite monochromator | 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 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 |
[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)° |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.064 |
6864 measured reflections | 3 standard reflections every 120 min |
3521 independent reflections | intensity decay: none |
1872 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.046 | 20 restraints |
wR(F2) = 0.154 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.97 | Δρmax = 0.96 e Å−3 |
3521 reflections | Δρmin = −0.52 e Å−3 |
217 parameters |
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 |
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) |
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 code: (i) −x+1/2, −y+1/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···Cg1ii | 0.93 | 2.97 | 3.800 (10) | 150 |
Symmetry code: (ii) x+1/2, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Pd(C5H5N)4](BF4)2 |
Mr | 596.42 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 295 |
a, b, c (Å) | 15.640 (7), 10.886 (7), 15.711 (7) |
β (°) | 115.63 (3) |
V (Å3) | 2412 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.85 |
Crystal size (mm) | 0.18 × 0.15 × 0.11 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6864, 3521, 1872 |
Rint | 0.064 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.154, 0.97 |
No. of reflections | 3521 |
No. of parameters | 217 |
No. of restraints | 20 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.96, −0.52 |
Computer programs: CAD-4-PC (Kretschmar, 1996), CAD-4-PC, WinGX-PC (Farrugia, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP (Brueggemann & Schmid, 1990), PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···Cg1i | 0.93 | 2.97 | 3.800 (10) | 150 |
Symmetry code: (i) x+1/2, −y+1/2, z−1/2. |
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.