(2,2′-Bipyridine-κ2N,N′)diiodido­palladium(II)

Ha, K.

doi:10.1107/S1600536809047771

metal-organic compounds

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Volume 65| Part 12| December 2009| Page m1588

doi:10.1107/S1600536809047771

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(2,2′-Bipyridine-κ²N,N′)diiodidopalladium(II)

Kwang Ha ^a ^*

^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

(Received 10 November 2009; accepted 11 November 2009; online 14 November 2009)

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 [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

[PdI₂(C₁₀H₈N₂)]
M_r = 516.38
Monoclinic, C 2/c
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 ) 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[F² > 2σ(F²)] = 0.032
wR(F²) = 0.071
S = 1.06
1240 reflections
69 parameters
H-atom parameters constrained
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Pd1—N1	2.076 (4)
Pd1—I1	2.5704 (6)

N1—Pd1—N1ⁱ	79.4 (2)
Symmetry code: (i) $[-x, y, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: 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

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

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

checkCIF report

Comment top

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—N1^a [symmetry code: (a) -x, y, 1/2 - z] chelate angle [79.4 (2)°], which results in non-linear trans arrangement [<N1—Pd1—I1^a = 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).

Related literature top

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 top

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.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: 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).

Figures top

	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.

(2,2'-Bipyridine-κ²N,N')diiodidopalladium(II) top

Crystal data top

[PdI₂(C₁₀H₈N₂)]	F(000) = 936
M_r = 516.38	D_x = 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

Data collection top

Bruker SMART 1000 CCD diffractometer	1240 independent reflections
Radiation source: fine-focus sealed tube	1049 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ϕ and ω scans	θ_max = 26.4°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −21→13
T_min = 0.139, T_max = 0.719	k = −11→12
3458 measured reflections	l = −9→9

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.071	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0328P)²] where P = (F_o² + 2F_c²)/3
1240 reflections	(Δ/σ)_max < 0.001
69 parameters	Δρ_max = 0.60 e Å⁻³
0 restraints	Δρ_min = −0.65 e Å⁻³

Crystal data top

[PdI₂(C₁₀H₈N₂)]	V = 1211.6 (4) Å³
M_r = 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)°

Data collection top

Bruker SMART 1000 CCD diffractometer	1240 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1049 reflections with I > 2σ(I)
T_min = 0.139, T_max = 0.719	R_int = 0.025
3458 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.071	H-atom parameters constrained
S = 1.06	Δρ_max = 0.60 e Å⁻³
1240 reflections	Δρ_min = −0.65 e Å⁻³
69 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)]
M_r	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)
T_min, T_max	0.139, 0.719
No. of measured, independent and observed [I > 2σ(I)] reflections	3458, 1240, 1049
R_int	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
Δρ_max, Δρ_min (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).

Selected geometric parameters (Å, º) top

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

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