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Acta Cryst. (2007). E63, m2585    [ doi:10.1107/S1600536807045722 ]

Bis(di-2-pyridylmethanediol-[kappa]2N,N')palladium(II) bis(perchlorate)

Y.-M. Li, X.-W. Zhao and J.-L. Zhang

Abstract top

In the title compound, [Pd(C11H10N2O2)2](ClO4)2, the PdII atom, which lies on an inversion centre, adopts square-planar coordination, binding to the two N atoms of each of the two di-2-pyridylmethanediol ligands. In the crystal structure, molecules are linked by a network of O-H...O hydrogen bonds involving the hydroxyl groups and the O atoms of the perchlorate anions to form columns down a.

Comment top

The crystal structure of (I) consists of [Pd(C11H10N2O2)2]2+ cations and ClO4- anions (Fig. 1). In the cation, the metal atom lies on an inversion centre and binds to two N,N'-chelated di-2-pyridylmethanediol ligands in a square planar geometry. The Pd—N bond lengths are 2.025 (3) and 2.031 (3) Å. The N1—Pd—N2 angles are 86.97 (12) and 93.03 (12). A similar Pd(II) complex has already been reported by Sommerer et al. (1997).

In the crystal structure, there is a complex hydrogen-bonding network among the hydroxyl groups and the O atoms of the perchlorate anions, (Table 1, Fig. 2).

Related literature top

A similar PdII square-planar complex of di-2-pyridylmethanediol has been reported by Sommerer et al. (1997).

Experimental top

The title complex was synthesized by refluxing a mixture of Pd(OAc)2 (0.449 g, 2 mmol) and di-2-pyridylketone (0.185 g, 1 mmol) in ethanol/water (20 ml; 3:1 v/v) for 1 h with stirring. After cooling, solid NaClO4·H2O (0.210 g, 1.5 mmol) was added and the solution filtered. Yellow crystals of (I) suitable for X-ray analysis were obtained as plates by slow evaporation of the filtrate over two weeks.

Refinement top

H atoms were positioned geometrically and treated as riding atoms, with C—H distances of 0.93 Å and O—H distances of 0.82 Å, with Uiso(H) = 1.2 Ueq(C) and Uiso(H) = 1.5 Ueq(O).

Computing details top

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalClear (Rigaku, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms. Atoms with the A suffix are generated by the symmetry code (−x, 1 − y, −z).
[Figure 2] Fig. 2. A view of the crystal packing along the a axis. Hydrogen bonds are shown as dashed lines.
Bis(di-2-pyridylmethanediol-κ2N,N')palladium(II) bis(perchlorate) top
Crystal data top
[Pd(C11H10N2O2)2](ClO4)2F000 = 712
Mr = 709.72Dx = 1.833 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2779 reflections
a = 7.677 (3) Åθ = 3.1–27.5º
b = 13.929 (5) ŵ = 1.00 mm−1
c = 12.173 (5) ÅT = 293 (2) K
β = 99.008 (5)ºPlate, yellow
V = 1285.7 (8) Å30.40 × 0.20 × 0.08 mm
Z = 2
Data collection top
Rigaku Mercury CCD
diffractometer		2925 independent reflections
Radiation source: fine-focus sealed tube2518 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.027
T = 293(2) Kθmax = 27.5º
ω scansθmin = 3.1º
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2000)		h = −9→9
Tmin = 0.858, Tmax = 1.000k = −16→17
9661 measured reflectionsl = −12→15
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.107  w = 1/[σ2(Fo2) + (0.0431P)2 + 1.6859P]
where P = (Fo2 + 2Fc2)/3
S = 1.12(Δ/σ)max < 0.001
2925 reflectionsΔρmax = 0.62 e Å−3
187 parametersΔρmin = −0.60 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Pd(C11H10N2O2)2](ClO4)2V = 1285.7 (8) Å3
Mr = 709.72Z = 2
Monoclinic, P21/nMo Kα
a = 7.677 (3) ŵ = 1.00 mm−1
b = 13.929 (5) ÅT = 293 (2) K
c = 12.173 (5) Å0.40 × 0.20 × 0.08 mm
β = 99.008 (5)º
Data collection top
Rigaku Mercury CCD
diffractometer		2925 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2000)		2518 reflections with I > 2σ(I)
Tmin = 0.858, Tmax = 1.000Rint = 0.027
9661 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.046187 parameters
wR(F2) = 0.107H-atom parameters constrained
S = 1.12Δρmax = 0.62 e Å−3
2925 reflectionsΔρmin = −0.60 e Å−3
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
xyzUiso*/Ueq
Pd10.00000.50000.00000.03376 (13)
Cl1−0.15333 (17)0.38024 (9)−0.41355 (9)0.0642 (3)
C10.3177 (5)0.4007 (3)−0.0473 (3)0.0456 (9)
H1A0.29520.36150.01070.055*
C20.4601 (5)0.3814 (3)−0.0988 (4)0.0582 (11)
H2A0.53300.3293−0.07670.070*
C30.4931 (6)0.4395 (4)−0.1826 (4)0.0671 (13)
H3A0.58870.4270−0.21890.081*
C40.3849 (6)0.5173 (4)−0.2141 (4)0.0594 (12)
H4A0.40810.5579−0.27070.071*
C50.2432 (5)0.5337 (3)−0.1610 (3)0.0433 (8)
C60.1147 (6)0.6181 (3)−0.1892 (3)0.0490 (9)
C70.0762 (5)0.6930 (3)0.0970 (3)0.0459 (9)
H7A0.04110.66480.15920.055*
C80.1333 (6)0.7865 (3)0.1033 (4)0.0560 (11)
H8A0.13900.82100.16920.067*
C90.1817 (6)0.8280 (3)0.0109 (4)0.0633 (12)
H9A0.21870.89160.01320.076*
C100.1758 (6)0.7757 (3)−0.0853 (4)0.0543 (10)
H10A0.20970.8034−0.14820.065*
C110.1187 (5)0.6813 (3)−0.0876 (3)0.0410 (8)
N10.2095 (4)0.4751 (2)−0.0785 (2)0.0378 (7)
N20.0696 (4)0.6408 (2)0.0028 (2)0.0376 (6)
O1−0.0599 (4)0.5845 (2)−0.2184 (2)0.0600 (8)
H1B−0.05970.5349−0.25460.090*
O20.1675 (5)0.6744 (2)−0.2722 (3)0.0781 (11)
H2B0.14140.6475−0.33250.117*
O3−0.2926 (7)0.4402 (4)−0.4044 (7)0.164 (3)
O4−0.1980 (10)0.2889 (3)−0.3818 (5)0.166 (3)
O5−0.0060 (6)0.4159 (3)−0.3402 (3)0.0981 (13)
O6−0.1158 (11)0.3796 (8)−0.5176 (4)0.236 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.0400 (2)0.0271 (2)0.0341 (2)0.00115 (15)0.00552 (14)−0.00030 (15)
Cl10.0799 (8)0.0667 (7)0.0469 (6)−0.0032 (6)0.0133 (5)−0.0136 (5)
C10.045 (2)0.036 (2)0.054 (2)0.0021 (16)0.0036 (17)−0.0038 (17)
C20.044 (2)0.054 (3)0.075 (3)0.0073 (19)0.005 (2)−0.016 (2)
C30.051 (2)0.082 (4)0.073 (3)0.002 (2)0.022 (2)−0.020 (3)
C40.061 (3)0.072 (3)0.049 (2)−0.012 (2)0.019 (2)−0.003 (2)
C50.055 (2)0.0387 (19)0.0360 (18)−0.0066 (17)0.0056 (16)−0.0055 (16)
C60.070 (3)0.041 (2)0.0345 (18)−0.0004 (19)0.0032 (17)0.0061 (16)
C70.047 (2)0.042 (2)0.049 (2)0.0009 (17)0.0074 (17)−0.0119 (17)
C80.055 (2)0.045 (2)0.068 (3)−0.0016 (19)0.006 (2)−0.023 (2)
C90.069 (3)0.031 (2)0.089 (3)−0.006 (2)0.008 (3)−0.010 (2)
C100.071 (3)0.036 (2)0.056 (2)−0.0048 (19)0.009 (2)0.0049 (18)
C110.048 (2)0.0318 (18)0.0414 (19)0.0000 (15)0.0018 (16)0.0016 (15)
N10.0423 (16)0.0341 (15)0.0372 (15)0.0008 (12)0.0069 (12)−0.0038 (12)
N20.0438 (15)0.0294 (15)0.0388 (15)−0.0012 (13)0.0040 (12)−0.0023 (12)
O10.071 (2)0.0484 (16)0.0521 (17)0.0097 (14)−0.0167 (14)−0.0082 (13)
O20.135 (3)0.0552 (19)0.0451 (17)−0.007 (2)0.0183 (19)0.0136 (15)
O30.109 (4)0.096 (4)0.297 (9)0.020 (3)0.066 (5)0.006 (5)
O40.246 (7)0.054 (3)0.171 (5)−0.029 (3)−0.049 (5)−0.009 (3)
O50.107 (3)0.095 (3)0.085 (3)−0.013 (2)−0.007 (2)−0.034 (2)
O60.235 (8)0.432 (13)0.052 (3)−0.126 (9)0.055 (4)−0.075 (5)
Geometric parameters (Å, °) top
Pd1—N12.025 (3)C5—N11.351 (5)
Pd1—N1i2.025 (3)C5—C61.538 (6)
Pd1—N2i2.031 (3)C6—O21.389 (5)
Pd1—N22.031 (3)C6—O11.411 (5)
Cl1—O61.342 (5)C6—C111.515 (5)
Cl1—O31.375 (5)C7—N21.352 (4)
Cl1—O41.389 (5)C7—C81.373 (6)
Cl1—O51.416 (4)C7—H7A0.9300
C1—N11.345 (5)C8—C91.366 (7)
C1—C21.370 (6)C8—H8A0.9300
C1—H1A0.9300C9—C101.374 (6)
C2—C31.357 (7)C9—H9A0.9300
C2—H2A0.9300C10—C111.385 (5)
C3—C41.382 (7)C10—H10A0.9300
C3—H3A0.9300C11—N21.342 (5)
C4—C51.370 (6)O1—H1B0.8200
C4—H4A0.9300O2—H2B0.8200
N1—Pd1—N1i180.0O2—C6—C11107.1 (3)
N1—Pd1—N2i93.03 (12)O1—C6—C11107.2 (3)
N1i—Pd1—N2i86.97 (12)O2—C6—C5110.1 (4)
N1—Pd1—N286.97 (12)O1—C6—C5110.7 (3)
N1i—Pd1—N293.03 (12)C11—C6—C5109.4 (3)
N2i—Pd1—N2180.0N2—C7—C8121.8 (4)
O6—Cl1—O3111.4 (6)N2—C7—H7A119.1
O6—Cl1—O4110.8 (5)C8—C7—H7A119.1
O3—Cl1—O4107.8 (4)C9—C8—C7118.7 (4)
O6—Cl1—O5109.2 (4)C9—C8—H8A120.6
O3—Cl1—O5106.9 (4)C7—C8—H8A120.6
O4—Cl1—O5110.7 (3)C8—C9—C10120.0 (4)
N1—C1—C2121.6 (4)C8—C9—H9A120.0
N1—C1—H1A119.2C10—C9—H9A120.0
C2—C1—H1A119.2C9—C10—C11119.3 (4)
C3—C2—C1118.9 (4)C9—C10—H10A120.4
C3—C2—H2A120.6C11—C10—H10A120.4
C1—C2—H2A120.6N2—C11—C10120.7 (4)
C2—C3—C4120.1 (4)N2—C11—C6116.9 (3)
C2—C3—H3A120.0C10—C11—C6122.3 (4)
C4—C3—H3A120.0C1—N1—C5119.6 (3)
C5—C4—C3119.2 (4)C1—N1—Pd1120.0 (3)
C5—C4—H4A120.4C5—N1—Pd1120.4 (3)
C3—C4—H4A120.4C11—N2—C7119.4 (3)
N1—C5—C4120.6 (4)C11—N2—Pd1119.9 (2)
N1—C5—C6115.9 (3)C7—N2—Pd1120.6 (3)
C4—C5—C6123.5 (4)C6—O1—H1B109.5
O2—C6—O1112.2 (3)C6—O2—H2B109.5
Symmetry codes: (i) −x, −y+1, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1B···O50.822.032.842 (5)169
O2—H2B···O6ii0.821.842.636 (6)162
Symmetry codes: (ii) −x, −y+1, −z−1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1B···O50.822.032.842 (5)169
O2—H2B···O6i0.821.842.636 (6)162
Symmetry codes: (i) −x, −y+1, −z−1.
Acknowledgements top

The authors thank Henan University for financial support and Professors X.-T. Wu, T.-L. Sheng and J.-J. Zhang for their help.

references
References top

Rigaku (2000). CrystalClear. Version 1.3. Rigaku Corporation, Tokyo, Japan.

Sheldrick, G. M. (1997). SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Sommerer, S. O., Jircitano, A. J., Westcott, B. L., Abboud, K. A. & Krause Bauer, J. A. (1997). Acta Cryst. C53, 707–710.