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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): m1588.
Published online 2009 November 14. doi:  10.1107/S1600536809047771
PMCID: PMC2971767

(2,2′-Bipyridine-κ2 N,N′)diiodido­palladium(II)

Abstract

The asymmetric unit of the title complex, [PdI2(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.

Related literature

For the crystal structures of [PdX 2(bipy)] (bipy = 2,2′-bipyridine; X = Cl or Br), see: Maekawa et al. (1991 [triangle]); Smeets et al. (1997 [triangle]). For the crystal structures of [PdX 2(bipy)]·CH2Cl2 (X = Cl or Br), see: Vicente et al. (1997 [triangle]); Kim et al. (2009 [triangle]); Kim & Ha (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-m1588-scheme1.jpg

Experimental

Crystal data

  • [PdI2(C10H8N2)]
  • M r = 516.38
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1588-efi2.jpg
  • a = 17.232 (4) Å
  • b = 9.8273 (19) Å
  • c = 7.6868 (15) Å
  • β = 111.438 (3)°
  • V = 1211.6 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 6.60 mm−1
  • T = 293 K
  • 0.25 × 0.05 × 0.05 mm

Data collection

  • Bruker SMART 1000 CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.139, T max = 0.719
  • 3458 measured reflections
  • 1240 independent reflections
  • 1049 reflections with I > 2σ(I)
  • R int = 0.025

Refinement

  • R[F 2 > 2σ(F 2)] = 0.032
  • wR(F 2) = 0.071
  • S = 1.06
  • 1240 reflections
  • 69 parameters
  • H-atom parameters constrained
  • Δρmax = 0.60 e Å−3
  • Δρmin = −0.65 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Selected geometric parameters (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809047771/is2486sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809047771/is2486Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by a Korea Research Foundation Grant funded by the Korean Government (MOEHRD) (KRF-2007–412-J02001).

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

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)].

Figures

Fig. 1.
The structure of the title complex, with displacement ellipsoids drawn at the 50% probability level for non-H atoms [Symmetry code: (a) -x, y, 1/2 - z].
Fig. 2.
Crystal packing of the title complex.

Crystal data

[PdI2(C10H8N2)]F(000) = 936
Mr = 516.38Dx = 2.831 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 550 reflections
a = 17.232 (4) Åθ = 2.4–24.4°
b = 9.8273 (19) ŵ = 6.60 mm1
c = 7.6868 (15) ÅT = 293 K
β = 111.438 (3)°Needle, brown
V = 1211.6 (4) Å30.25 × 0.05 × 0.05 mm
Z = 4

Data collection

Bruker SMART 1000 CCD diffractometer1240 independent reflections
Radiation source: fine-focus sealed tube1049 reflections with I > 2σ(I)
graphiteRint = 0.025
[var phi] and ω scansθmax = 26.4°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2000)h = −21→13
Tmin = 0.139, Tmax = 0.719k = −11→12
3458 measured reflectionsl = −9→9

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.071H-atom parameters constrained
S = 1.06w = 1/[σ2(Fo2) + (0.0328P)2] where P = (Fo2 + 2Fc2)/3
1240 reflections(Δ/σ)max < 0.001
69 parametersΔρmax = 0.60 e Å3
0 restraintsΔρmin = −0.65 e Å3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Pd10.0000−0.19021 (5)0.25000.03813 (17)
I10.10045 (3)−0.37899 (4)0.43052 (5)0.06273 (19)
N10.0755 (3)−0.0277 (4)0.3822 (6)0.0431 (10)
C10.1524 (4)−0.0339 (6)0.5132 (7)0.0546 (14)
H10.1767−0.11880.54990.066*
C20.1966 (4)0.0802 (7)0.5952 (9)0.0655 (17)
H20.24950.07250.68710.079*
C30.1617 (4)0.2050 (6)0.5399 (9)0.0656 (18)
H30.19020.28370.59440.079*
C40.0840 (4)0.2128 (6)0.4029 (9)0.0611 (17)
H40.05970.29720.36270.073*
C50.0418 (4)0.0954 (5)0.3248 (8)0.0446 (12)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Pd10.0378 (3)0.0339 (3)0.0385 (3)0.0000.0091 (2)0.000
I10.0636 (3)0.0471 (3)0.0633 (3)0.01213 (18)0.0064 (2)0.00869 (16)
N10.043 (2)0.043 (2)0.045 (2)−0.002 (2)0.018 (2)−0.0005 (19)
C10.046 (3)0.062 (4)0.050 (3)−0.003 (3)0.012 (3)−0.004 (3)
C20.050 (4)0.087 (5)0.056 (4)−0.019 (4)0.016 (3)−0.015 (3)
C30.065 (4)0.060 (4)0.082 (4)−0.029 (4)0.039 (4)−0.028 (3)
C40.067 (4)0.050 (3)0.074 (4)−0.018 (3)0.036 (4)−0.015 (3)
C50.050 (3)0.039 (3)0.056 (3)−0.001 (2)0.033 (3)−0.002 (2)

Geometric parameters (Å, °)

Pd1—N12.076 (4)C2—C31.364 (9)
Pd1—N1i2.076 (4)C2—H20.9300
Pd1—I1i2.5704 (6)C3—C41.370 (9)
Pd1—I12.5704 (6)C3—H30.9300
N1—C11.341 (7)C4—C51.378 (7)
N1—C51.345 (6)C4—H40.9300
C1—C21.372 (8)C5—C5i1.480 (12)
C1—H10.9300
N1—Pd1—N1i79.4 (2)C3—C2—C1119.0 (6)
N1—Pd1—I1i175.85 (12)C3—C2—H2120.5
N1i—Pd1—I1i96.48 (12)C1—C2—H2120.5
N1—Pd1—I196.48 (12)C2—C3—C4119.0 (6)
N1i—Pd1—I1175.85 (12)C2—C3—H3120.5
I1i—Pd1—I187.61 (3)C4—C3—H3120.5
C1—N1—C5118.5 (5)C3—C4—C5120.0 (6)
C1—N1—Pd1127.1 (4)C3—C4—H4120.0
C5—N1—Pd1114.4 (4)C5—C4—H4120.0
N1—C1—C2122.6 (6)N1—C5—C4120.9 (6)
N1—C1—H1118.7N1—C5—C5i115.9 (3)
C2—C1—H1118.7C4—C5—C5i123.2 (4)
N1i—Pd1—N1—C1−178.7 (6)C2—C3—C4—C50.8 (9)
I1—Pd1—N1—C12.1 (5)C1—N1—C5—C4−2.1 (8)
N1i—Pd1—N1—C50.5 (3)Pd1—N1—C5—C4178.6 (4)
I1—Pd1—N1—C5−178.7 (3)C1—N1—C5—C5i177.9 (6)
C5—N1—C1—C22.3 (9)Pd1—N1—C5—C5i−1.4 (7)
Pd1—N1—C1—C2−178.5 (4)C3—C4—C5—N10.6 (9)
N1—C1—C2—C3−0.9 (10)C3—C4—C5—C5i−179.4 (6)
C1—C2—C3—C4−0.6 (10)

Symmetry codes: (i) −x, y, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS2486).

References

  • Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
  • Kim, N.-H. & Ha, K. (2009). Acta Cryst. E65, m1292. [PMC free article] [PubMed]
  • Kim, N.-H., Hwang, I.-C. & Ha, K. (2009). Acta Cryst. E65, m615–m616. [PMC free article] [PubMed]
  • Maekawa, M., Munakata, M., Kitagawa, S. & Nakamura, M. (1991). Anal. Sci. 7, 521–522.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Smeets, W. J. J., Spek, A. L., Hoare, J. L., Canty, A. J., Hovestad, N. & van Koten, G. (1997). Acta Cryst. C53, 1045–1047.
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]
  • Vicente, J., Abad, J. A., Rink, B. & Arellano, M. C. R. (1997). Private communication (refcode PYCXMN02). CCDC, Cambridge, England.

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