metal-organic compounds
(2,2′-Bipyridine-κ2N,N′)diiodidopalladium(II)
aSchool of Applied Chemical Engineering, The Research Institute of Catalysis, Chonnam National University, Gwangju 500-757, Republic of Korea
*Correspondence e-mail: hakwang@chonnam.ac.kr
The 2(C10H8N2)], contains one half of the formula unit. The Pd2+ ion is located on a twofold rotation axis and is four-coordinated in a slightly distorted square-planar environment by two N atoms of the chelating 2,2′-bipyridine ligand and two iodide ions. The compound displays intermolecular π–π interactions between the pyridine rings of the ligand, the shortest centroid–centroid distance being 4.220 (4) Å.
of the title complex, [PdIRelated literature
For the crystal structures of [PdX2(bipy)] (bipy = 2,2′-bipyridine; X = Cl or Br), see: Maekawa et al. (1991); Smeets et al. (1997). For the crystal structures of [PdX2(bipy)]·CH2Cl2 (X = Cl or Br), see: Vicente et al. (1997); Kim et al. (2009); Kim & Ha (2009).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2000); cell SAINT (Bruker, 2000); 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 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536809047771/is2486sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809047771/is2486Isup2.hkl
To a solution of Na2PdCl4 (0.1991 g, 0.677 mmol) in H2O (20 ml) were added KI (1.1230 g, 6.765 mmol) and 2,2'-bipyridine (0.1057 g, 0.677 mmol), and refluxed for 3 h. The precipitate obtained was separated by filtration, and washed with water and acetone, and dried at 70 °C, to give a red-brown powder (0.2999 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a CH3CN solution.
H atoms were positioned geometrically and allowed to ride on their respective parent atoms [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C)].
Data collection: SMART (Bruker, 2000); cell
SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).[PdI2(C10H8N2)] | F(000) = 936 |
Mr = 516.38 | Dx = 2.831 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 550 reflections |
a = 17.232 (4) Å | θ = 2.4–24.4° |
b = 9.8273 (19) Å | µ = 6.60 mm−1 |
c = 7.6868 (15) Å | T = 293 K |
β = 111.438 (3)° | Needle, brown |
V = 1211.6 (4) Å3 | 0.25 × 0.05 × 0.05 mm |
Z = 4 |
Bruker SMART 1000 CCD diffractometer | 1240 independent reflections |
Radiation source: fine-focus sealed tube | 1049 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ϕ and ω scans | θmax = 26.4°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −21→13 |
Tmin = 0.139, Tmax = 0.719 | k = −11→12 |
3458 measured reflections | l = −9→9 |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.071 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0328P)2] where P = (Fo2 + 2Fc2)/3 |
1240 reflections | (Δ/σ)max < 0.001 |
69 parameters | Δρmax = 0.60 e Å−3 |
0 restraints | Δρmin = −0.65 e Å−3 |
[PdI2(C10H8N2)] | V = 1211.6 (4) Å3 |
Mr = 516.38 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 17.232 (4) Å | µ = 6.60 mm−1 |
b = 9.8273 (19) Å | T = 293 K |
c = 7.6868 (15) Å | 0.25 × 0.05 × 0.05 mm |
β = 111.438 (3)° |
Bruker SMART 1000 CCD diffractometer | 1240 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1049 reflections with I > 2σ(I) |
Tmin = 0.139, Tmax = 0.719 | Rint = 0.025 |
3458 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.071 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.60 e Å−3 |
1240 reflections | Δρmin = −0.65 e Å−3 |
69 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are 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 are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is 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, 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. |
x | y | z | Uiso*/Ueq | ||
Pd1 | 0.0000 | −0.19021 (5) | 0.2500 | 0.03813 (17) | |
I1 | 0.10045 (3) | −0.37899 (4) | 0.43052 (5) | 0.06273 (19) | |
N1 | 0.0755 (3) | −0.0277 (4) | 0.3822 (6) | 0.0431 (10) | |
C1 | 0.1524 (4) | −0.0339 (6) | 0.5132 (7) | 0.0546 (14) | |
H1 | 0.1767 | −0.1188 | 0.5499 | 0.066* | |
C2 | 0.1966 (4) | 0.0802 (7) | 0.5952 (9) | 0.0655 (17) | |
H2 | 0.2495 | 0.0725 | 0.6871 | 0.079* | |
C3 | 0.1617 (4) | 0.2050 (6) | 0.5399 (9) | 0.0656 (18) | |
H3 | 0.1902 | 0.2837 | 0.5944 | 0.079* | |
C4 | 0.0840 (4) | 0.2128 (6) | 0.4029 (9) | 0.0611 (17) | |
H4 | 0.0597 | 0.2972 | 0.3627 | 0.073* | |
C5 | 0.0418 (4) | 0.0954 (5) | 0.3248 (8) | 0.0446 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.0378 (3) | 0.0339 (3) | 0.0385 (3) | 0.000 | 0.0091 (2) | 0.000 |
I1 | 0.0636 (3) | 0.0471 (3) | 0.0633 (3) | 0.01213 (18) | 0.0064 (2) | 0.00869 (16) |
N1 | 0.043 (2) | 0.043 (2) | 0.045 (2) | −0.002 (2) | 0.018 (2) | −0.0005 (19) |
C1 | 0.046 (3) | 0.062 (4) | 0.050 (3) | −0.003 (3) | 0.012 (3) | −0.004 (3) |
C2 | 0.050 (4) | 0.087 (5) | 0.056 (4) | −0.019 (4) | 0.016 (3) | −0.015 (3) |
C3 | 0.065 (4) | 0.060 (4) | 0.082 (4) | −0.029 (4) | 0.039 (4) | −0.028 (3) |
C4 | 0.067 (4) | 0.050 (3) | 0.074 (4) | −0.018 (3) | 0.036 (4) | −0.015 (3) |
C5 | 0.050 (3) | 0.039 (3) | 0.056 (3) | −0.001 (2) | 0.033 (3) | −0.002 (2) |
Pd1—N1 | 2.076 (4) | C2—C3 | 1.364 (9) |
Pd1—N1i | 2.076 (4) | C2—H2 | 0.9300 |
Pd1—I1i | 2.5704 (6) | C3—C4 | 1.370 (9) |
Pd1—I1 | 2.5704 (6) | C3—H3 | 0.9300 |
N1—C1 | 1.341 (7) | C4—C5 | 1.378 (7) |
N1—C5 | 1.345 (6) | C4—H4 | 0.9300 |
C1—C2 | 1.372 (8) | C5—C5i | 1.480 (12) |
C1—H1 | 0.9300 | ||
N1—Pd1—N1i | 79.4 (2) | C3—C2—C1 | 119.0 (6) |
N1—Pd1—I1i | 175.85 (12) | C3—C2—H2 | 120.5 |
N1i—Pd1—I1i | 96.48 (12) | C1—C2—H2 | 120.5 |
N1—Pd1—I1 | 96.48 (12) | C2—C3—C4 | 119.0 (6) |
N1i—Pd1—I1 | 175.85 (12) | C2—C3—H3 | 120.5 |
I1i—Pd1—I1 | 87.61 (3) | C4—C3—H3 | 120.5 |
C1—N1—C5 | 118.5 (5) | C3—C4—C5 | 120.0 (6) |
C1—N1—Pd1 | 127.1 (4) | C3—C4—H4 | 120.0 |
C5—N1—Pd1 | 114.4 (4) | C5—C4—H4 | 120.0 |
N1—C1—C2 | 122.6 (6) | N1—C5—C4 | 120.9 (6) |
N1—C1—H1 | 118.7 | N1—C5—C5i | 115.9 (3) |
C2—C1—H1 | 118.7 | C4—C5—C5i | 123.2 (4) |
N1i—Pd1—N1—C1 | −178.7 (6) | C2—C3—C4—C5 | 0.8 (9) |
I1—Pd1—N1—C1 | 2.1 (5) | C1—N1—C5—C4 | −2.1 (8) |
N1i—Pd1—N1—C5 | 0.5 (3) | Pd1—N1—C5—C4 | 178.6 (4) |
I1—Pd1—N1—C5 | −178.7 (3) | C1—N1—C5—C5i | 177.9 (6) |
C5—N1—C1—C2 | 2.3 (9) | Pd1—N1—C5—C5i | −1.4 (7) |
Pd1—N1—C1—C2 | −178.5 (4) | C3—C4—C5—N1 | 0.6 (9) |
N1—C1—C2—C3 | −0.9 (10) | C3—C4—C5—C5i | −179.4 (6) |
C1—C2—C3—C4 | −0.6 (10) |
Symmetry code: (i) −x, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [PdI2(C10H8N2)] |
Mr | 516.38 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 17.232 (4), 9.8273 (19), 7.6868 (15) |
β (°) | 111.438 (3) |
V (Å3) | 1211.6 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 6.60 |
Crystal size (mm) | 0.25 × 0.05 × 0.05 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.139, 0.719 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3458, 1240, 1049 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.071, 1.06 |
No. of reflections | 1240 |
No. of parameters | 69 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.60, −0.65 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009).
Pd1—N1 | 2.076 (4) | Pd1—I1 | 2.5704 (6) |
N1—Pd1—N1i | 79.4 (2) |
Symmetry code: (i) −x, y, −z+1/2. |
Acknowledgements
This work was supported by a Korea Research Foundation Grant funded by the Korean Government (MOEHRD) (KRF-2007–412-J02001).
References
Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Kim, N.-H. & Ha, K. (2009). Acta Cryst. E65, m1292. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kim, N.-H., Hwang, I.-C. & Ha, K. (2009). Acta Cryst. E65, m615–m616. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Maekawa, M., Munakata, M., Kitagawa, S. & Nakamura, M. (1991). Anal. Sci. 7, 521–522. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Smeets, W. J. J., Spek, A. L., Hoare, J. L., Canty, A. J., Hovestad, N. & van Koten, G. (1997). Acta Cryst. C53, 1045–1047. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vicente, J., Abad, J. A., Rink, B. & Arellano, M. C. R. (1997). Private communication (refcode PYCXMN02). CCDC, Cambridge, England. Google Scholar
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The title complex, [PdI2(bipy)] (where bipy is 2,2'-bipyridine, C10H8N2), is isomorphous with [PdBr2(bipy)] (Smeets et al., 1997), whereas [PdCl2(bipy)] crystallized in the orthorhombic space group C2221 (Maekawa et al., 1991).
The asymmetric unit of the title complex contains one half of the formula unit. The complex is disposed about a twofold rotation axis through Pd atom with the special position at (0, y, 1/4) (Wyckoff letter e). The Pd2+ ion is four-coordinated in a slightly distorted square-planar environment by two N atoms of the chelating 2,2'-bipyridine ligand and two iodide ions (Fig. 1). The main contribution to the distortion is the tight N1—Pd1—N1a [symmetry code: (a) -x, y, 1/2 - z] chelate angle [79.4 (2)°], which results in non-linear trans arrangement [<N1—Pd1—I1a = 175.85 (12)°]. The complex displays intermolecular π-π interactions between adjacent pyridine rings of the lignad (the symmetry operation for second plane x, -y, -1/2 + z), with a shortest centroid-centroid distance of 4.220 (4) Å (Fig. 2).